ORALS

SESSION: PhysicalThuAM-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Thu Oct, 24 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Antonio de Lucas Consuegra; Dimitrios Niakolas; Session Monitor: TBA

11:20: [PhysicalThuAM01] Plenary
Neutrinos and Electrons/Positrons: The Building Elements and Catalysts of our Universe
Constantinos Vayenas¹ ; ¹University of Patras, Patras, Greece;
Paper Id: 353 [Abstract]

Inspection of the decay product Tables of Hadrons, Mesons and Bosons [1,2] shows that all these composite particles decay eventually to neutrinos, antineutrinos, electrons and positrons. Conversely, these leptons can be used to synthesize all known composite particles by forming, via gravitational confinement, rotating rings of super relativistic neutrinos in the cases of Hadrons and Mesons [2,3] and mixed superrelativistic electron/positron – neutrino rings in the case of bosons [4-7]. As shown recently, [2-7] the masses of these composite particles, i.e. hadrons, mesons and bosons, can be computed within typically 1% from first principles by constructing Bohr-type rotating lepton models using special relativity and gravity as the centripetal force and achieving quantization via the de Broglie wavelength equations [2-7]. These models do not contain adjustable parameters. Recent work has shown that the use of General Relativity (GR) instead of Special Relativity (SR) leads to the same conclusions [8,9]. Also, [10] it was recently shown that the formation of these rotational structures is very strongly catalyzed by positrons or electrons which, via their much larger rest mass than that of neutrinos, accelerate neutrinos to strongly relativistic velocities, thus dramatically increasing their relativistic and gravitational mass and facilitating the formation of the neutrino rotational rings. Bosons forced via electron-neutrino pairs also facilitate hadronization [5,6,7,10]. The main hadronization reaction, i.e. proton formation from three neutrinos and a positron, 3ν_e+e⁺ → p, is extremely exothermic (some 20 times more exothermic than H fusion) and may thus have played a significant role in the Big Bang. It could also, in principle, play a role for future terrestrial power production under controlled conditions. In conclusion, it appears that quarks are polarized relativistic neutrinos, that the Strong Force is relativistic gravity between neutrinos, and that the Weak Force is relativistic gravity between electrons/positrons and neutrinos. It also appears that electrons and positrons have played a key role in the formation of our Universe as we know it today by catalyzing the strongly exothermic hadronization reactions leading to the formation of protons, neutrons and, eventually, atoms.

References:
[1] D. Griffiths, Introduction to Elementary Particles. (2nd ed. Wiley-VCH Verlag GmbH & Co. KgaA, Weinheim, 2008).\n[2] C. G. Vayenas, S. N.-A. Souentie, Gravity, special relativity and the strong force: A Bohr-Einstein-de Broglie model for the formation of hadrons. (Springer, NY, 2012).\n[3] C.G. Vayenas, S. Souentie, A. Fokas, “A Bohr-type model of a composite particle using gravity as the attractive force”. Physica A, 405, 360-379 (2014).\n[4] C.G. Vayenas, A.S. Fokas, D. Grigoriou, “On the structure, masses and thermodynamics of the W bosons”. Physica A, 450, 37-48 (2016).\n[5] A.S. Fokas, C.G. Vayenas, “On the structure, mass and thermodynamics of the Zo bosons”. Physica A, 464, 231-240 (2016).\n[6] A.S. Fokas, C.G. Vayenas, D.P. Grigoriou, “On the mass and thermodynamics of the Higgs boson”. Physica A, 492, 737-746 (2018).\n[7] C.G. Vayenas, “Thermodynamics and catalysis of the generation of mass”, Proceedings of the Academy of Athens, 93A, 97-133 (2018).\n[8] D. Grigoriou, C.G. Vayenas, “Schwarzschild geodesics and the Strong Force” in Proc. of the 18th Lomonosov conference, in “Particle Physics at the Year of 25th Anniversary of the Lomonosov Conferences”, p. 374, (2019).\n[9] A. Fokas, “Ultra-relativistic gravity has properties associated with the strong force”, Eur. Phys. J. C, 79, 271 (2019).\n[10] C.G. Vayenas, A.S. Fokas, D. Grigoriou, “Catalysis and autocatalysis of chemical synthesis and of hadronization”. Appl. Catal. B, 203, 582-590 (2017).

11:45: [PhysicalThuAM02] Plenary
Gravity, Relativity and the Bohr Model
Ilan Riess¹ ; ¹Technion Israel Institute of Technology Faculty of Physics, Haifa, Israel;
Paper Id: 31 [Abstract]

The wealth of particles generated in high energy collisions are explained by the standard model. In this model there are sixteen particles which are considered elementary. To that one has to add a seventeen one, the Higgs particle. The force acting between elementary particles is the strong force mediated by gluons, the weak force mediated by the bosons W⁺, W^- and Z⁰ and the electromagnetic interaction, mediated by photons. The gravitational force, though present, is so weak that it is neglected.
About a decade ago Prof. Vayenas [1,2] suggested that the strong force is generated by rapidly moving particles with a velocity, v, very close to that of light, c. This results in a significant increase in the Lorentz factor (1-vv/cc)^-1/2 hence also in the effective mass of the moving particles. The Lorentz factor was introduced into the gravitational force expression. An existing experimental report showed that the proton contains three components and it originally led to the three-quark model of the proton and neutron. Prof. Vayenas suggested, that the proton and neutron are composed of three particles rotating at a high speed very close to c and are interacting through the gravitational force. Solving for the bound states of the rotating particles, in analogy to the Bohr model, led to a LOrentz factor ~10¹⁰ and a rest mass of 0.0437 eV/c² for the rotating particles which, at the time, was of the order of the upper limit for the neutrino and is now known experimentally to be very close to the measured mass of the neutrino. Thus, in this model the strong force does not require the existence of gluons and the quarks are presented as moving neutrinos. The mass of the particles composed of three rotating neutrinos is of the order of 1 GeV/c² or more. An outstanding success of the new theory is a calculation of the pressure inside a proton. in full agreement with an experimental value recently reported.[3] In recent years Prof. Vayenas extended this analysis to other particles generated in high energy collisions. Thus in the new model the list of elementary particles reduces to only electrons and positrons and neutrinos. All the rest are either superfluous (the gluons), are replaced by neutrinos (quarks) or are a combination of neutrinos and electrons. This drastically simplifies the model of matter and our understanding of the universe along the line of thinking of Albert Einstein that was looking for a unification of the forces in nature.

References:
[1] C.G. Vayenas, S.N.-A. Souentie, A. Fokas, Physica A 405 (2014) 360.\n\n[2] C.G. Vayenas, S.N.-A. Souentie, Gravity, Special Relativity and the Strong Force, Springer, 2012.\n[3] C.G. Vayenas, D. Grigoriu and E. Martino, J. Mech. Behav. Mater., (accepted).

12:10: [PhysicalThuAM03] Keynote
Electrochemical Promotion of Catalysis in Hydrogen Production Reactions
José Luis Valverde¹ ; Fernando Dorado² ; Estela Ruiz Lopez³ ; Antonio De Lucas Consuegra³ ; ¹University of Castilla la Mancha, 13071, Spain; ²University of Castilla La Mancha, 13071, Spain; ³University of Castilla La Mancha, Ciudad Real, Spain;
Paper Id: 55 [Abstract]

Hydrogen is a very important feedstock in the industry and a promising energy carrier with a main application in internal combustion engines and in fuel cell technology, as a clean and efficient alternative to the massive consumption of fossil fuels. Among the different methods for hydrogen production, catalytic routes are the most interesting ones, for instance via reforming and partial oxidation of hydrocarbons and biomass. In this sense, the addition of electronic promoters chemically (chemical promotion) or electrochemically (electrochemical promotion or EPOC) induces very significant and similar effects on catalytic hydrogen production reactions [1]. Both kinds of promotional phenomena follow the same general mechanism but the usefulness of the latter is highlighted. Hence the EPOC effect is based on the modification of the chemisorption properties of a metal catalyst by the electrochemical migration of promoter ions from a solid electrolyte support (via application of an electric current or potential) [2-3]. Hence, while in chemical promotion, a specific amount of a promoter is added during the preparation step of the catalyst. In the case of the electrochemical promotion, promoter ions are electrochemically pumped between the metal catalyst and the solid electrolyte in a controlled and reversible way during the reaction step [3]. Then, the electrochemical promotion presents several additional advantages, such as the possibility of optimizing the promoter coverage on the catalyst surface at different reaction conditions and the in-situ enhancement of the catalytic activity and selectivity. In this communication, the most important and recent contributions of our group in the electrochemical promotion of different hydrogen production reactions are reviewed. The functional similarities and operational differences between both promotion ways are pointed out, and their impact on the hydrogen production technology is discussed. By this method, the EPOC effects have shown a great interest in H₂ production technology by improving catalytic activity and selectivity under working reaction conditions. In addition, the in-situ catalyst regeneration from carbon deposition, and the possibility of applying the EPOC in the field of H₂ storage, among other novel contributions, lead EPOC to new opportunities in the H₂ technology. For these purposes, novel catalyst films were developed by means of different preparation techniques and also by means of operando surface analysis techniques such as in-situ near-ambient pressure photoemission (NAPP) spectroscopy have been used in order to investigate the origin and mechanism of this phenomenon.

References:
[1] J. Gonzalez-Cobos, J.L. Valverde , A. de Lucas-Consuegra, International Journal of Hydrogen Energy 42 (2017) 13712-13723
[2] P. Vernoux, L. Lizarraga, M. N. Tsampas, F. Sapountzi, A. De Lucas-Consuegra, J.L. Valverde JL, et al. Ionically conducting ceramics as active catalyst supports. Chem Rev. 113 (2013) 8192-260
[3] C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda, Tsiplakides D. Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion and Metal-Support Interactions. New York: Kluwer Academic Publishers/Plenum Press; 2001.

12:35: [PhysicalThuAM04]
Transition Metal Elements as Ni/GDC Dopants for the H2O Electrolysis Process in SOECs; Fe-Ni vs Au-Mo-Ni Interaction
Dimitrios Niakolas¹ ; Stylianos G. Neophytides² ; Evangelia Ioannidou¹ ; Charalampos Neofytidis¹ ; ¹Foundation for Research and Technology, Institute of Chemical Engineering Sciences (FORTH/ICEHT), Patras, Greece; ²FORTH ICE-HT, PATRAS, Greece;
Paper Id: 146 [Abstract]

High quality H₂ can be produced through water electrolysis at low or high temperatures. In this respect, solid oxide electrolysis cells (SOECs) are a promising and fast growing technology [1, 2] for H₂O electrolysis above 500°C. SOECs have identical configuration with SOFCs, but reverse operations and currently novel modified Ni-based fuel electrodes are under investigation for H₂O, CO₂ and H₂O⁺ CO₂ electrolysis applications [1, 3]. The presented study focuses on the effect of transition metal elements as dopants of the commercial NiO/GDC powder for the Solid Oxide H₂O electrolysis. Specifically, the experimental comparison is between Au [1], Mo and Fe doping. Comparative electrocatalytic measurements with I-V curves and electrochemical impedance spectra (EIS) analyses are presented in the range of 800-900°C between electrolyte-supported cells with Ni/GDC, 3Au-Ni/GDC [1], 3Mo-Ni/GDC, 3Au-3Mo-Ni/GDC, 2Fe-Ni/GDC and 0.5Fe-Ni/GDC, as the fuel electrode. Complementary physicochemical characterization was also performed both in the form of powders and as half cells with ex-situ and in-situ techniques, including specific redox stability measurements in the presence of H₂O. In summary, the cell comprising the ternary 3Au-3Mo-Ni/GDC electrode and that with 0.5Fe-Ni/GDC performed significantly better compared to the rest. The superior performance of the ternary sample is primarily ascribed to the enrichment of the surface with Au [1] and of the bulk phase with Mo, through the formation of Ni-Au-Mo solid solution [3, 4]. The involved elements act in synergy and modify the physicochemical properties of the electrode, improving the: (i) H₂O re-oxidation rate, (ii) electronic conductivity and (iii) electrochemical interface. In regards to Fe-doping, the wt.% content in iron is one key parameter. The 0.5wt.% loading of Fe results in an electrode of similar high performance to that of the Au-Mo-Ni electrode, having the great advantage of not containing gold in its composition.

References:
[1] E. Ioannidou, Ch. Neofytidis, L. Sygellou, D.K. Niakolas, Applied Catalysis B: Environmental 236 (2018) 253-264.
[2] P. Mocoteguy, A. Brisse, Int. J. Hydrogen Energy 38 (2013) 15887-15902.
[3] Ch. Neofytidis, E. Ioannidou, L. Sygellou, M. Kollia and D.K. Niakolas, Journal of Catalysis (2019), Accepted, In Press.
[4] D.K. Niakolas, C.S. Neofytidis, S.G. Neophytides, Frontiers in Environmental Science 5 (78) (2017) 1-20.

14:25: [PhysicalThuPM106] Keynote
How Transient and Isotopic Techniques Advance the Design of Catalytic Materials for Industrial Dry Reforming of Methane to Syngas
Angelos Efstathiou¹ ; Michalis Vasiliades¹ ; Constantinos Damaskinos¹ ; ¹University of Cyprus, Nicosia, Cyprus;
Paper Id: 162 [Abstract]

During the last decades, several natural gas (NG) reservoirs were found to be rich in CO₂ (> 40 vol%), and this led to an intense effort for the development of a dry reforming of methane (DRM) catalytic technology (CH₄ + CO₂ to 2 CO + 2 H₂) with a favorable H₂/CO gas ratio for liquid fuels (Gas To Liquid, GTL) and other useful chemicals (e.g., DME, MeOH, acetic acid) by the catalysis research community and related industries [1]. Biogas (a renewable energy source) can also be a suitable feedstock for the DRM catalytic technology [2]. Practical problems related to the irreversible coking phenomena, especially on the less-costly attractive Ni-based catalysts, remain one of the main obstacles for the catalytic DRM technology to find industrial applications. It is well known that an in-depth understanding of the elementary steps related to carbon deposition and removal chemistry on Ni or other relevant metal supported catalytic systems along with their micro-kinetic analysis is a key factor for the future development of highly active and <br />carbon - resistant DRM catalytic systems, preferably at temperatures lower than 750 ^oC. This keynote lecture will present the use of various transient and isotopic experiments (use of ¹⁸O₂, ¹³CO₂ and ¹³CH₄) to elucidate the role of metal cation dopant in Ce_1-xM_xO₂ (M = Ti⁴⁺, Pr³⁺) used as support of Ni, and the use of Pt in the NiPt alloy supported on Ce_0.8Pr_0.2O₂, in reducing the carbon accumulation to a remarkable extent during DRM at 750^oC. In particular, the importance of carbon gasification by labile oxygen of support to the formation of CO(g), the contribution of oxygen vacant sites of support to the CO₂ dissociation rate and re-oxidation of support, and the quantification of the origin of carbon accumulation (CH₄ vs CO₂ activation route) will be elucidated [3, 4]. Other experimental approaches reported in the literature for the understanding of carbon deposition and removal chemistry on supported Ni and other metals will be presented. Experimental results from the SSITKA technique (use of ¹³CO₂ or ¹³CH₄) will be presented to demonstrate the effect of metal dopant on support and Pt on the active carbon that is strictly associated with the rate of reaction.

References:
[1] S. Afzal, D. Sengupta, A. Sarkar, M. El-Halwagi, N. Elbashir, ACS Sustainable Chem. Eng. 6 (2018) 7532-7544.\n[2] Ch. Papadopoulou, H. Matralis, X. Verykios, in:, L. Guczi, A. Erdohelyi (Eds.), Catal. Altern. Energy Gener., Springer New York, New York, NY, 2012, pp. 57-127.\n[3] C.M. Damaskinos, M.A. Vasiliades, A.M. Efstathiou, Appl. Catal. A: Gen., in press (doi.org/10.1016/j.apcata.2019.04.023).\n[4] M.A. Vasiliades, C.M. Damaskinos, K.K. Kyprianou, M. Kollia, A.M. Efstathiou, Catal. Today, in press (doi.org/10.1016/j.cattod.2019.04.022).

14:50: [PhysicalThuPM107] Keynote
The Role of the Promoting Ionic Species in Electrochemical Promotion and in Metal-Support Interactions. The Case of CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; Hydrogenation on Ru Based Catalysts
Dimitrios Grigoriou¹ ; Dimitrios Zagoraios¹ ; Alexandros Katsaounis² ; Constantinos Vayenas¹ ; ¹University of Patras, Patras, Greece; ²Department of Chemical Engineering, University of Patras, Patras, Greece;
Paper Id: 105 [Abstract]

The reaction of CO₂ hydrogenation is of high environmental interest since it allows for the transformation of the logistically challenging H₂, gained from renewable sources, to the much more manageable hydrocarbons.<br />CO₂ hydrogenation takes place mainly through the following two reactions:<br />xCO₂ + (2x-z+y/2)H₂ --> C_xH_xO_z + (2x-z)H₂O<br />and<br />CO₂ + H₂ --> CO + H₂O The first reaction directly produces hydrocarbons whereas the second one, also known as RWGS, produces syngas which is useful in the synthesis of several hydrocarbons.<br />With CO₂ being a rather inert molecule, the reaction of CO₂ hydrogenation requires high pressures and temperatures, as well as the existence of a good catalyst. The development of an efficient catalyst is a requirement for the extensive application of a strategy where renewable energy is stored as HCs. An important parameter for the development of an efficient catalyst is the metal-support interactions. Those interactions have been closely identified as the underlying reason for Electrochemical Promotion of Catalysis [1-5]. Conversely, EPOC has proven itself as a valuable tool for the study of metal support interactions. Promoters of catalysts alter the catalytic activity and selectivity by modifying the bonds of the reactants on the active sites and the work function of the catalytic surface. Electropositive promoters enhance the chemisorption of electron-acceptors and weaken the bonds of electron donors. Electronegative promoters have the opposite effect [1-5]. Ruthenium is a catalyst widely used to produce methane from CO₂. In this study, we present an example of how electrochemical promotion of catalysis (EPOC) can elucidate the role of solid electrolytes (YSZ, BZY), supporting Ru porous films or nanoparticles.<br />The results of the study have shown that the electrolytic features of the support (anionic or cationic or mixed conductor) can have a very pronounced and dominant effect on the activity and selectivity of the supported metal nanoparticles. The mechanism of the interaction can be studied conveniently via EPOC and then the support can be chosen accordingly. Nucleophilic EPOC behavior suggests that the reaction will be enhanced when using an anionic catalyst support, such as YSZ, and electrophilic EPOC behavior suggests that the reaction will be enhanced using a cationic support, such as BZY. Thus, one may conclude, again, that EPOC (or NEMCA effect) and MSI are functionally identical and only operationally different [1, 2] since they both rely on ion spillover. The use of EPOC can significantly facilitate the choice of catalyst support.

References:
[1] C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda, D. Tsiplakides, Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion and Metal-Support Interactions, Kluwer Academic/Plenum Publishers, New York, 2001.\n[2] P. Vernoux, L. Lizarraga, M.N. Tsampas, F.M. Sapountzi, A. De Lucas-Consuegra, J.-L. Valverde, S. Souentie, C.G. Vayenas, D. Tsiplakides, S. Balomenou, E.A. Baranova, Ionically Conducting Ceramics as Active Catalyst Supports, Chemical Reviews, 113 (2013) 8192-8260.\n[3] A. Katsaounis, Recent developments and trends in the electrochemical promotion of catalysis (EPOC), Journal of Applied Electrochemistry, 40 (2010) 885-902.\n[4] D. Tsiplakides, S. Balomenou, Milestones and perspectives in electrochemically promoted catalysis, Catalysis Today, 146 (2009) 312-318.\n[5] A. De Lucas-Consuegra, J. Gonzalez-Cobos, Y. Garcia-Rodriguez, A. Mosquera, J.L. Endrino, J.L. Valverde, Enhancing the catalytic activity and selectivity of the partial oxidation of methanol by electrochemical promotion, Journal of Catalysis, 293 (2012) 149-157.

15:15: [PhysicalThuPM108]
Image Quality Improvement of Steel Cracks Inspection using MicroCT Allied to Mathematical Filters
Ricardo Lopes¹ ; Olga Araujo¹ ; Alessandra Machado¹ ; Davi Oliveira¹ ; ¹Federal University of Rio de Janeiro, Rio de Janeiro, Brazil;
Paper Id: 211 [Abstract]

Microcomputed Tomography has become a powerful and widely used tool for non-destructive testing and can be used for mapping the complex 3D structures of cracks and their interactions. The materials of most oil and gas transport pipes, buried or submerged, such as high strength low alloy steels, for example, are likely to suffer corrosion, degradation and fracture due to the corrosive environment. Similarly, cracks are one of the most severe types of discontinuities in a welded joint because they are strong stress concentrators. High tensile stresses develop in the weld region as a result of the localized thermal expansion and contraction associated with the welding thermal cycle. To better characterize the cracking behavior, it is important to gain information about the evolution of the 3D crack network. The search for improving image quality in the inspection of steel samples using X-ray beams, however, is still challenging because of spreading effects that can cause noise in the 3D image. For this purpose, we performed microCT tests to verify cracks due to corrosion, loss of weld adhesion, and cracks applying to mathematical filters to improve the final image quality. To enhance details of the greyscale micro-CT image, the image was filtered using anisotropic diffusion (AD) and unsharp mask (UM) filters [1], which have been found to be highly effective for enhancement of digital fractured media [2,3]. AD is an edge-preserving noise reduction filter that has been shown to enhance the signal-to-noise ratio of tomographic images in a variety of contexts while preserving edges [4]. UM is highly effective at sharpening edges without excessively strengthening the noise [1]. It was possible to verify cracks around 0.66 mm for corrosion cracks and 2.67 mm for cracks due to loss of weld adhesion. Also, observation of the continuities of the cracks in the 3D visualization of the inspected materials was possible.

References:
[1] A.P. Sheppard, R.M. Sok, H. Averdunk Techniques for image enhancement and segmentation of tomographic images of porous materials Phys. A: Stat. Mech. Appl., 339 (2004), pp. 145-151
[2] H.L. Ramandi, P. Mostaghimi, R.T. Armstrong Digital rock analysis for accurate prediction of fractured media permeability J. Hydrol., 554 (2017), pp. 817-826
[3] H.L. Ramandi, M. Liu, S. Tadbiri, P. Mostaghimi Impact of dissolution of syngenetic and epigenetic minerals on coal permeability Chem. Geol. (2018)
[4] R.C. Gonzales, R.E. Woods Digital Image Processing
(3rd edition ed.), Addison & Wesley Publishing Company, MA(1987)

SESSION: PhysicalThuPM2-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Thu Oct, 24 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Vasileios Kyriakou; Dimitrios Zagoraios; Session Monitor: TBA

15:55: [PhysicalThuPM209] Keynote
High Temperature Proton and Co-Ionic Electrochemical Membrane Reactors a) Co2/H2o Co-Electrolysis and b) Nh3 Synthesis
Ioannis Garagounis¹ ; Vasileios Kyriakou² ; Anastasios Vourros¹ ; Demetrios Stoukides¹ ; Michael Stoukides¹ ; ¹Aristotle University, Thessaloniki, Greece; ²Dutch Institute for Fundamental Energy Research (DIFFER), Eindhoven, Netherlands;
Paper Id: 46 [Abstract]

Solid state proton conductors can operate at high temperatures (> 500 ^oC) and have been applied in the construction of sensors, fuel cells and hydrogen separators. In the past two decades, they have also been used in the construction of electrochemical membrane reactors. The advantage of high temperature conductors, versus those operating at low temperatures, is that they operate in the temperature range within which a large number of industrially important catalytic hydro-reactions and dehydrogenation reactions take place. In most of the earlier applications of electrochemical membrane reactors in catalytic research, the reaction of interest took place on the working electrode while the counter electrode served for the formation of protons from a hydrogen containing compound. These electrochemical reactors, however, would become more competitive if useful chemicals were produced on both, working and counter electrodes [1, 2]. Results on two reaction systems in which both, cathode and anode were properly utilized are presented here. The first is the production of methanol and oxygen from CO₂ and H₂O. Steam and CO₂ are introduced at the anode and cathode side, respectively, of a co-ionic (H⁺ and O^2-) conductor. Steam is electrolyzed to form O₂ and protons (H⁺). The latter are transferred to the cathode and react with CO₂ to form CH₃OH. The second system is an electrochemical Haber-Bosch (H-B) Process [3]. A mixture of steam and methane is fed to the anode chamber. Nitrogen is fed over the cathodic electrode. Hydrogen produced at the anode is "pumped" electrochemically (in the form of protons) to the cathode, where it reacts with N₂ to produce NH₃. A preliminary energy analysis indicates that, at faradaic efficiencies above 30% and at cell bias as low as 0.4 V, the electrochemical H-B becomes more efficient than the conventional H-B Process with respect to both, energy consumption and CO₂ emissions.

References:
[1] S.H. Morejudo, R. Zanon, S. Escolastico, I. Yuste, H. Malerød-Fjeld, P.K. Vestre, W.G. Coors, A. Martínez, T. Norby, J.M. Serra, C. Kjølseth, Science, 353 (2016) 563-566.
[2] A.Vourros, V. Kyriakou, I. Garagounis, E. Vasileiou, M. Stoukides, Solid State Ionics, 306 (2017) 76-81.
[3] V. Kyriakou, I. Garagounis, E. Vasileiou, A. Vourros, M. Stoukides, Catalysis Today, 286 (2017) pp. 2-13.

16:20: [PhysicalThuPM210] Keynote
New Low Loading Pt Based Nano-Materials for Fuel Cell Applications
Stylianos G. Neophytides¹ ; Maria Daletou² ; ¹FORTH ICE-HT, PATRAS, Greece; ²FORTH-ICE/HT, patras, Greece;
Paper Id: 159 [Abstract]

Pt supported on carbon electrocatalysts are the most efficient and stable materials for both the oxygen reduction reaction (ORR) at the cathode and the hydrogen oxidation reaction (HOR) at the anode of polymer electrolyte membrane fuel cells (PEMFCs) (1). In this respect, there is increasing demand to reduce cost and therefore, the amounts of Pt used. This can be achieved by increased catalyst activity and/or utilization (2). To reach this goal, there are two approaches: (a) enhancing the specific activity or (b) increasing the specific surface area of the catalyst by forming a fine dispersion. The performance and stability of the (electro) catalysts strongly depends on the physicochemical characteristics, such as the surface area, the crystalline structure, the size and shape of the particles, and the interactions with the support. Both approaches for Pt reduction can be followed separately or combined by exploiting the differentiations induced to the metal by the surface chemistry of the support to result in customized properties and control its performance. When the dispersion of the metal is high, its metal atom is accessible to reactants and available for catalysis, maximizing the efficiency of the metal and minimizing the cost. Reducing the size of the metal in atoms or small groups of atoms can significantly increase both the active surface and the activity of the catalyst through diversification or strengthening of the metal-support interactions3. In this work, we have developed Pt/f-MWCNTs (f-MWCNTs=covalently functionalized MWCNTs) based electrocatalysts with different surface functionalities and Pt loadings. The deposition of the metal was achieved by using the polyol synthetic procedure: reduction of metal precursor salts in an ethylene glycol solution. Through a structural and chemical characterization study of the materials, the introduction of certain groups on the sidewalls of the carbon support resulted in differentiation of the properties, not only in terms of quantitative deposition and dispersion, but also with respect to metal-support interactions, platinum crystal properties and/or oxidative states. The present work addresses scientific issues regarding the most challenging core component of a PEM fuel cell: the Pt based electrocatalyst. This work proposes a comprehensive effort to explore a new approach and exploit the differentiations induced on the metal by the surface chemistry of the support. The introduction of pyridines on the sidewalls of the carbon support can differentiate the metal deposition, not only in terms of dispersion and the obtained morphology, but also with respect to metal-support interactions on platinum properties and its oxidative state. The aim is the interpretation of the catalyst’s electrochemical behavior through a structural and physicochemical characterization study. It is shown that the substrate can play a decisive role on the size and functionality of the electrochemical interface. This approach constitutes a promising route for developing materials with innovative features aiming to a serious reduction in the Pt loads, thus resulting into increased catalyst activity and metal utilization.

References:
1. Yang C., Costamagna P., Srinivasan S., Benziger J., Bocarsly A.B. (2001). J Power Sources, 103:1-9.
2. Notter A D., Kouravelou K., Karachalios T., Daletou M.K., Haberland N.T. (2015). Energy Environ Sci, 8:1969-1985.
3. Flytzani-Stephanopoulos M., Gates B.C. (2012). Annu. Rev. Chem. Biomol. Eng., 3:545-574.

16:45: [PhysicalThuPM211]
Exsolution of Transition Metal Nanoparticles for Solid Oxide Co-Electrolysis of CO2-H2O
Vasileios Kyriakou¹ ; Dragos Neagu² ; Michail Tsampas³ ; ¹Dutch Institute for Fundamental Energy Research (DIFFER), Eindhoven, Netherlands; ²Newcastle University, Newcastle, United Kingdom; ³DIFFER, Eindhoven, Netherlands;
Paper Id: 112 [Abstract]

The production of synthetic fuels from renewable energy could be a more efficient solution for a sustainable future without the need of huge investments for modifications in the existing infrastructure [1,2]. The raw material of synthetic fuels via the Fischer-Tropsch process is syngas (H²⁺CO) and is primarily generated by fossil fuels. The co-electrolysis of carbon dioxide and steam in a solid oxide electrolysis cells (SOECs) is an emerging route to produce syngas and thus store renewable electricity in the form of chemical bonds [2]. The commonly employed materials for fuel electrodes (cathode) in the process are Ni based cermets that exhibit high ionic-electronic conductivity and electrocatalytic activity. Nevertheless, Ni-YSZ electrodes suffer from coarsening under redox conditions and coking under carbon rich environments [3]. To circumvent coarsening, a reducing agent, such as hydrogen or carbon monoxide, is always co-fed with CO₂-H₂O in order to keep Ni in a reducing state [2]. Perovskite oxide ceramics (ABO3) are the most promising alternative fuel electrodes. Perovskites exhibit mixed ionic-electronic conductivity as single phases and can accommodate several kinds of defects under redox conditions, allowing them to adapt to various external conditions and therefore maintain stability and functionality under redox environments [4]. Lanthanum titanates constitute an intriguing class of perovskites, exhibiting chemical, dimensional, thermal and mechanical stability. By controlling deficiency of the A-site, transition metal nanoparticles may be exsolved to the surface from the perovskite oxide backbone under reducing environments. The grown particles are uniformly dispersed as well as anchored to the perovskite scaffold, thus rendering them more catalytically active and chemically stable compared to the oxide supported counterparts prepared by infiltration [5-7]. Along these lines, here we report on the electrochemical performance of (LaCa)(MTi)O₃ (M=transition metal) as fuel electrodes for high temperature CO₂-H₂O co-electrolysis. The cells are characterized and tested at 800-850°C under several feed mixtures (CO₂/H₂O, H₂O/H₂, CO₂/ H₂O/H₂, CH₄/H₂O-CO₂) and applied voltages.

References:
[1] J.A.Ritter, A.D, Ebner, Separation Science and Technology 2007, 42, 1123-1193.
[2] S. D. Ebbesen, R. Knibbe, M. Mogensen, Journal of Electrochemical Society 2012, 159, F482-F489. P. Hjalmarsson,
[3] S. D. Ebbesen, C. Graves, A. Hauch, S. H. Jensen, M. Mogensen, Journal of the Electrochemical Society 2010, 157, B1419-B1429.
[4] Y. Zheng, J. Wang, B. Yu, W. Zhang, J. Chen, J. Qiao, J. Zhang, Chem. Soc. Rev.
46 (2017) 1427-1463.
[5] D. Neagu, G. Tsekouras, D.N, Miller, H,Menard, J.T.S. Irvine, Nature Chemistry 2013, 11, 916-923.
[6] J-H. Myung, D. Neagu, D.N, Miller, J.T.S. Irvine, Nature 2016, 537 (7621), 528-531.
[7] L. Ye, M. Zhang, P. Huang, G. Guo, M. Hong, C. Li, J.T.S. Irvine, K. Xie, Nature Communications 2017, 8, 14785, doi: 10.1038/ncomms14785.

17:10: [PhysicalThuPM212]
Electrochemical Promotion of Methane Oxidation over Nanodispersed Pd/Co3O4 Catalysts
Dimitrios Zagoraios¹ ; Dimitrios Zagoraios² ; Alexandros Katsaounis³ ; Angel Caravaca⁴ ; Ioanna Kalaitzidou⁴ ; Athanasia Athanasiadi⁵ ; Spyros Ntais⁴ ; Philippe Vernoux⁶ ; Constantinos Vayenas² ; ¹University of Patras, Dept. of Chemical Engineering, Patras, Greece; ²University of Patras, Patras, Greece; ³Department of Chemical Engineering, University of Patras, Patras, Greece; ⁴University of Lyon, Lyon, France; ⁵University of Patras Dept. of Chemical Enginnering, Patras, Achaia, Greece; ⁶University LYON 1, Lyon, France;
Paper Id: 59 [Abstract]

During the last two decades, the Electrochemical Promotion of Catalysis (EPOC) phenomenon has been studied extensively for many catalytic reactions, including hydrocarbon oxidation reactions and hydrogenations [1-3]. The EPOC effect is based on the modification of the work function of a metal, which also serves as a working electrode, leading to an alteration in the chemisorption bond strength of the reactants. This effect is observed when small currents or potentials are applied to a catalyst deposited on a solid electrolyte. In the majority of the studies, the catalysts/electrodes consisted of porous noble metal films (Pt, Pd, Rh) prepared, for instance, by calcination of organometallic pastes [4]. This results in low metal dispersion and low active surface area, therefore limiting the overall catalytic activity. In view of further practical application of the EPOC phenomenon to industrial catalysts, we should be able to enhance the activity of nanodispersed materials. In this study, for the very first time, we observed an enhanced catalytic activity of a Pd nanodispersed catalyst supported on a porous Co₃O₄ semiconductor film. The Pd/Co₃O₄ composite powder was deposited on an yttria-stabilized zirconia (YSZ) solid electrolyte without the presence of an interlayer film. The observed enhancement was non-Faradaic, with apparent Faradaic efficiency values as high as 80. The Pd/Co₃O₄ catalyst was characterized thoroughly by means of a wide variety of physicochemical techniques, such as TEM, SEM, TGA, ICP and BET. Using supported catalysts as catalytic films for electrochemical promotion studies may lead to the practical utilization of EPOC in the chemical industry or in gas exhaust treatment.

References:
[1] C.G. Vayenas, S. Bebelis, I.V. Yentekakis, H.G. Lintz, Catal. Today. 11 (1992) 303-438.\n[2] C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda, D. Tsiplakides Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion and Metal-Support Interactions, Kluwer Academic/Plenum Publishers, New York, 2001.\n[3] C.G. Vayenas, J. Solid State Electrochem. 7-8 (2011) 1425-1435.\n[4] C. Jimenez-Borja, S. Brosda, F. Matei, M. Makri, B. Delgado, F. Sapountzi, D. Ciuparu, F. Dorado, J.L. Valverde, C.G. Vayenas, Appl. Catal. B Environ. 128 (2012) 48-54.

SESSION: PhysicalFriAM-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Fri Oct, 25 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Ioannis Yentekakis; Philippe Vernoux; Session Monitor: TBA

11:20: [PhysicalFriAM01] Plenary
Electrochemical Promotion of Catalysis over Dispersed Nanoparticles
Philippe Vernoux¹ ; ¹University LYON 1, Lyon, France;
Paper Id: 10 [Abstract]

Electrochemical Promotion of Catalysis (EPOC) or non-Faradaic electrochemical modification of catalytic activity (NEMCA) is a promising concept for boosting catalytic processes and advancing the frontiers of catalysis. This innovative field, discovered by the group of Professor C.G. Vayenas in the early 80s [1], aims to modify operando both the activity and the selectivity of catalysts, in a reversible and controlled manner. More than 80 different catalytic systems (total and partial oxidations, hydrogenations, dehydrogenations, isomerisations, and decompositions) have been electrochemically promoted on metal or metal oxide catalysts supported on different ionic conductors [2,3]. These include reaction systems of critical importance in diverse fields of chemical synthesis including the production of commodity and fine chemicals and in the abatement of automotive emissions. EPOC utilises solid electrolyte materials (ionically conducting ceramics) as catalytic carriers. Ions contained in these electrolytes are electrochemically supplied to the catalyst surface and act as promoting agents to modify the electronic properties of the catalyst in order to achieve optimal catalytic performance. Different types of ions such as O^2-, Na⁺, H⁺, K⁺ have been successively used in the literature to boost catalytic properties of catalytic materials. It thus provides a unique means of varying promoter levels at the metal surface under reaction conditions by simply changing the potential of the catalyst film. Therefore, EPOC can be considered as an electrically controlled catalyst-support interaction in which promoting ionic agents are accurately supplied onto the catalytic surface by electrical potential control. The main technological issue of EPOC is related with the use of continuous metallic coatings interfaced onto dense solid electrolyte supports. On that account, the metallic dispersion of the catalyst-electrodes, and therefore their catalytic activity, is usually far lower than that of commercial dispersed catalysts. In addition, the thermal stability of continuous metallic coatings is rather low to the sintering phenomenon, especially when using transition metals. This explains why most of the EPOC studies reported in the literature have been performed on Platinum Group Metals (Pt, Pd, Rh) and to a lesser extent on Ag, Ru and Ir. The utilization of pure precious metals catalytic layers is not economically reliable. Furthermore, the thermal stability of pure transition metals coatings deposited on dense solid electrolyte supports is too low to be realistically implemented for catalytic processes. Therefore, some research efforts are focused to achieve EPOC over catalytic dispersed nanoparticles. This plenary lecture will give an overview of recent advances in the quest of electro-promoted nanoparticles including innovative architectures of catalyst-electrodes.

References:
[1] M. Stoukides and C.G. Vayenas, J. Catal., 70 (1981) 137.
[2] C.G. Vayenas, Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion, and Metal-Support Interactions, Springer, 2001.
[3] P. Vernoux, L. Lizarraga, M.N. Tsampas, F.M. Sapountzi, A. De Lucas-Consuegra, J.L. Valverde, S. Souentie, C.G. Vayenas, D. Tsiplakides, S. Balomenou, E.A. Baranova, Chem. Rev. 113 (2013) 8192.

11:45: [PhysicalFriAM02] Keynote
Electrochemical Promotion of Catalysis: A Journey Through the Past Thirty Years
Symeon Bebelis¹ ; Constantinos Vayenas² ; ¹Department of Chemical Engineering, University of Patras, Patras, Greece; ²University of Patras, Patras, Greece;
Paper Id: 109 [Abstract]

Electrochemical promotion of catalysis (EP or EPOC) or non-faradaic electrochemical modification of catalytic activity (NEMCA) corresponds to the induced reversible modification of the catalytic behavior of metal or metal oxide catalyst-electrodes deposited on solid electrolytes or mixed ionic-electronic conductors (MIEC), resulting from polarization of the electrode/electrolyte interface [1-3]. This electrochemically induced catalytic effect has been attributed to electrochemical pumping of mobile promoter ionic species (e.g. O^2-, H⁺, Na⁺, depending on the solid electrolyte or MIEC) to or from the gas exposed electrode surface under reaction conditions. This results in modification of the electronic properties of the electrode and, concomitantly, to the alteration of its catalytic properties [1-3].<br />Electrochemical promotion has been demonstrated for a very large number of combinations of solid electrolytes or MIEC, electrodes and catalytic reactions [1-7]. It is an effect of fundamental importance, bridging electrochemistry and heterogeneous catalysis [3], whereas, as it allows for <i>in situ</i> reversible tuning of catalyst performance, it opens up new possibilities for practical application in the fields of heterogeneous catalysis and applied electrochemistry [3-7]. <br />This work highlights key landmarks in electrochemical promotion over the past three decades, with emphasis on the origin and mechanistic understanding of this effect, on the rules of electrochemical promotion and on its functional equivalence to metal support interactions. Moreover, current activities and trends in electrochemical promotion, as well as obstacles to overcome for commercial applications, are also discussed.

References:
[1] C.G. Vayenas, S. Bebelis, S. Ladas, Nature 343 (1990) 625-627.\n[2] C.G. Vayenas, S. Bebelis, C. Pliangos, S. Brosda, D. Tsiplakides, Electrochemical Activation of Catalysis: Promotion, Electrochemical Promotion and Metal-Support Interactions, Kluwer Academic/Plenum Publishers, New York (2001).\n[3] C.G. Vayenas, J. Solid State Electrochem. 15 (2011) 1425-1435.\n[4] D. Tsiplakides, S. Balomenou, Catal. Today 146 (2009) 312-318.\n[5] A. Katsaounis, J. Appl. Electrochem. 40 (2010) 885-902.\n[6] P. Vernoux, L. Lizarraga, M.N. Tsampas, F.M.Sapountzi, A. De Lucas-Consuegra, J.L. Valverde, S. Souentie, C.G. Vayenas, D. Tsiplakides, S.Balomenou, E.A. Baranova, Chem. Rev. 113 (2013) 8192-8260.\n[7] A. De Lucas-Consuegra, Catal. Surv. Asia 19 (2015) 25-37.|

12:10: [PhysicalFriAM03] Keynote
Novel Method for Determining Series of Elementary Steps in Oxygen Reduction Processes Using Isotope Exchange.
Ilan Riess¹ ; ¹Technion Israel Institute of Technology Faculty of Physics, Haifa, Israel;
Paper Id: 30 [Abstract]

A novel method is discussed for determining series of elementary steps in the reduction process of oxygen on an oxide.[1,2] The method is based on exposure of the oxide, first to ¹⁶O₂, and then to ¹⁸O₂ while monitoring the rate at which ¹⁶O¹⁸O molecules are generated and evaporate into the gas stream, under short time conditions. The parameters to be changed are oxygen partial pressure, P(O₂) (being the same for both isotopes) and acceptor doping level [A] of the oxide. ¹⁸O₂can be applied in the form of a pulse or a step function. The rate of ¹⁶O¹⁸O generation is shown to depend on P(O₂)^m1 [A] ^m2. Another parameter that can be determined is J₀, the rate of the forward reaction in the slow step of the series which depends on P(O₂)^m3 [A] ^m4. The indices {m₁,m₂, m₃, m₄} are, in most cases, typical for a particular series of elementary steps. The series to be identified consist of fast steps ending with a relative slow one. This method is then different from the one based on the time dependence of the concentrations of ¹⁶O₂, ¹⁶O¹⁸O and ¹⁸O₂ in the gas phase.[3,4] The method is quite sensitive and even changing the source for electrons from the valence band to the conduction band changes the value of the exponents {m1,…,m4}. The analysis assumes that the dependence of the concentrations of point defects (oxygen vacancies and electrons) in the outer most layer of the oxide on P(O₂) and [A], is known. The method was applied so far under the conditions that the P(O₂) and [A] dependence is the same as in the deep, neutral bulk. This is shown to be indeed the case under many prevailing conditions.[5] Other P(O₂) and [A] dependence of the concentrations of point defects in the outer most layer of the oxide bulk are also presented.[5] Thus it is possible to determine series of elementary steps on all type of oxides which are undoped or acceptor doped. The method is not limited to oxygen isotope exchange and can readily be extended to other isotopes e.g. ³⁵Cl₂ and ³⁷Cl₂ exchange. Exchange of H₂ and D₂ requires special attention due to the mass effect on the chemistry of hydrogen and we show how to cope with it.[2]

References:
1. I. Riess, Solid State Ionics, 280 (2015) 51.
2. I. Riess, Solid State Ionics, 302 (2017) 7.
3. K. Klier et al. J. Catal. 2 (1963) 479.
4. G.K. Boreskov, Adv. Catal. 15, (1964) 285.
5. I. Riess, Solid State Ionics, 329 (2019) 95.

SESSION: PhysicalFriPM1-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Fri Oct, 25 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Katerina Aifantis; Eftychia Martino; Session Monitor: TBA

14:00: [PhysicalFriPM105] Plenary
Gradient Theory and Mg-Alloys
Elias Aifantis¹ ; ¹Aristotle University of Thessaloniki, Thessaloniki, Greece;
Paper Id: 444 [Abstract]

Vayenas et al have proposed an unexpectedly simple but extremely powerful method for elementary particle physics. It is based upon a straightforward synthesis of quantum mechanics and special relativity. The central idea is to replace Newton’s classical gravitational law with the expression (where is the rest mass of neutrino and the Lorentz factor) for the rotating neutrino model (RNM) which was invented to describe the strong force in the nucleus. Here, an attempt is made to revisit ideas used in continuous media for dealing with singularities, in order to modify in a different way the classical gravitational potential. The resulting modified gravitational potential is used for the RNM configuration, Vayenas results are recovered.

References:
[1] E.C. Aifantis, Internal length gradient (ILG) material mechanics across scales and disciplines, Adv. Appl. Mech. 49, pp. 1-110, 2016.

[2] E.C. Aifantis, Weak nonlocal extension of classical material models, Frontiers in Physics, 2019 (in press).

14:25: [PhysicalFriPM106] Plenary
Induced Electrochemical Codeposition of Rhenium and Tungsten Alloys with Iron-Group (and other) Metals
Noam Eliaz¹ ; Eliezer Gileadi² ; ¹Dept. Materials Science and Engineering, Tel-Aviv University, Tel Aviv, Israel; ²School of Chemistry, Tel-Aviv University, Tel Aviv 6997801, Israel;
Paper Id: 12 [Abstract]

The term "induced codeposition" was already coined by Brenner in 1963 to describe a process where certain elements such as tungsten (W),that cannot be deposited alone from their aqueous solutions, are readily codeposited with iron-group metals. Indeed, alloys of W with iron-group metals can readily be formed using, for example, a solution of NiSO₄ and Na₂WO₄, with citric acid added as a complexing agent. In this particular case, it was shown that the NiW alloy is deposited from an adsorbed complex containing both metals, while Ni is also deposited in parallel reactions from its complex with citrate. The term induced codeposition may also be used to describe a process where a metal, that can barely be deposited alone, with a low current efficiency (FE) and poor adherence of the deposit, is readily deposited in the presence of other metal ions. This is the case of rhenium (Re), which can be electroplated alone at FE a ≤ 7% and poor coating quality. By adding a suitable iron-group metal salt to the bath, we have obtained coatings with a Re content as high as 93 at.% and a FE as high as 96%. In this plenary presentation, we review our study of the electrodeposition and electroless plating of Re-based alloys. Issues such as the catalytic effect of iron-group metals on the deposition of Re, the early stages of deposition, the effects of bath additives and pulse plating, electroless plating, and the associated microstructures are discussed. We also discuss the effect of other alloying elements (e.g. Sn or Ir) on the resulting deposition process and microstructure. Similarities and differences compared to induced codeposition of W are discussed. The fundamental aspects are complemented by some applied aspects, e.g. with respect to thermal barrier coatings and catalysis.

References:
1) N. Eliaz, T.M. Sridhar and E. Gileadi, Electrochim. Acta, 50(14) (2005) 2893-2904.
2) N. Eliaz and E. Gileadi, Chapter 4, in Modern Aspects of Electrochemistry, Vol. 42, eds. C.G. Vayenas, R.E. White and M.E. Gamboa-Aldeco, Springer, New York (2008) 191-301.
3) A. Naor, N. Eliaz and E. Gileadi, J. Electrochem. Soc., 157(7) (2010) D422-D427.
4) A. Naor-Pomerantz, N. Eliaz and E. Gileadi, Electrochim. Acta, 56 (2011) 6361-6370.
5) O. Berkh, N. Eliaz and E. Gileadi, J. Electrochem. Soc., 161(5) (2014) D219-D226.
*** The first ever open-access manuscript of the Journal of the Electrochemical Society.
6) T. Nusbaum, B.A. Rosen, E. Gileadi and N. Eliaz, J. Electrochem. Soc., 162(7) (2015) D250-D255.
7) A. Duhin, A. Inberg, N. Eliaz and E. Gileadi, Electrochim. Acta, 174 (2015) 660-666.
8) B.A. Rosen, E. Gileadi and N. Eliaz, Catal. Commun., 76 (2016) 23-28.
9) S.I. Baik, A. Duhin, P.J. Phillips, R.F. Klie, E. Gileadi, D.N. Seidman and N. Eliaz, Adv. Eng. Mater., 18(7) (2016) 1133-1144.
10) N. Eliaz and E. Gileadi, Physical Electrochemistry: Fundamentals, Techniques, and Applications, Wiley-VCH, 2nd Edition. ISBN: 978-3-527-34139-9 (2019).

14:50: [PhysicalFriPM107] Invited
Next Generation Electrodes for Na-Ion Batteries
Katerina Aifantis¹ ; Pu Hu² ; ¹University of Florida, Gainesville, United States; ²Univ of Florida, Gainesville, Greece;
Paper Id: 324 [Abstract]

Na-ion batteries are the most promising energy sources for stationary applications. Numerous electrode materials that are used in Li-ion cells seem promising for use in Na-ion cells as well. A stable long term capacity, however, is yet to be achieved by these electrode materials. The present talk will compare the differences between the sodiation and lithiation mechanisms of TiS₂ which can serve as a cathode material. X-ray diffraction and electron microscopy illustrate that cycling with respect to lithium results in long term electrochemical stability, whereas with respect to sodium, irreversible phases and cracks form, giving rise to a capacity decay. The experimental results are supported with continuum mechanics studies on stress evolution during cycling.

15:15: [PhysicalFriPM108]
Experimental Investigation and Mathematical Modeling of Triode PEM Fuel Cells
Eftychia Martino¹ ; Alexandros Katsaounis² ; Constantinos Vayenas³ ; ¹University of Patras, Dept. of Chemical Engineering, Patras, Achaia, Greece; ²Department of Chemical Engineering, University of Patras, Patras, Greece; ³University of Patras, Patras, Greece;
Paper Id: 58 [Abstract]

Triode operation of fuel cells is an alternative approach for enhancing fuel cells’ power output under severe poisoning conditions which lead to high overpotentials. This innovation was developed and applied firstly on SOFCs and later on PEMFCs [1-4]. In a triode fuel cell, in addition to the anode and the cathode, there is a third auxiliary electrode in contact with the solid electrolyte (e.g. polymer electrolyte membrane in the case of PEMFCs). This electrode forms, together with the cathode, a second (auxiliary) electric circuit operating in parallel with the conventional main circuit of the fuel cell. The auxiliary circuit runs in the electrolytic mode, pumping ions (i.e. protons in the case of a PEMFC) from the cathode to the auxiliary electrode. This way, imposition of a potential difference between the auxiliary electrode and the cathode permits the primary circuit of the fuel cell to operate under previously inaccessible, i.e larger than 1.23 V, anode - cathode potentials. The triode operation of humidified PEM fuel cells has been investigated both with pure H₂ and with CO poisoned H₂ feed over commercial Vulcan supported Pt(30%)-Ru(15%) anodes. It was found that triode operation, which involves the use of a third, auxiliary, electrode, leads to up to 400% power output increase with the same CO poisoned H₂ gas feed. At low current densities, the power increase is accompanied by an increase in overall thermodynamic efficiency. A mathematical model, based on Kirchhoff’s laws, has been developed which is in reasonably good agreement with the experimental results. In order to gain some additional insight into the mechanism of triode operation, the model has been also extended to describe the potential distribution inside the Nafion membrane via the numerical solution of the Nernst-Planck equation. Both models and experiments have shown the critical role of minimizing the auxiliary-anode or auxiliary-cathode resistance, and this has led to improved comb-shaped anode or cathode electrode geometries.

References:
[1] S.P. Balomenou, C.G. Vayenas, Triode Fuel Cells and Batteries, J. Electrochem. Soc. 151 (2004) A1874. doi:10.1149/1.1795511.
[2] S.P. Balomenou, F. Sapountzi, D. Presvytes, M. Tsampas, C.G. Vayenas, Triode fuel cells, Solid State Ionics. 177 (2006) 2023-2027. doi:10.1016/j.ssi.2006.02.046.
[3] F.M. Sapountzi, S.C. Divane, M.N. Tsampas, C.G. Vayenas, Enhanced performance of CO poisoned proton exchange membrane fuel cells via triode operation, Electrochim. Acta. 56 (2011) 6966-6975. doi:10.1016/j.electacta.2011.06.012.
[4] E. Martino, G. Koilias, M. Athanasiou, A. Katsaounis, Y. Dimakopoulos, J. Tsamopoulos, C.G. Vayenas, Experimental investigation and mathematical modeling of triode PEM fuel cells, Electrochim. Acta. 248 (2017) 518-533. doi:10.1016/j.electacta.2017.07.168.

SESSION: PhysicalFriPM2-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Fri Oct, 25 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Ilan Riess; Pasquale Bosso; Session Monitor: TBA

15:55: [PhysicalFriPM209]
Computation of the Neutrino Flavor Masses via the Rotating Lepton Model of Hadrons and Bosons
Dionysios Tsousis¹ ; Constantinos Vayenas¹ ; Dimitrios Grigoriou¹ ; ¹University of Patras, Patras, Greece;
Paper Id: 65 [Abstract]

The rotating lepton model (RLM) of composite particles [1-3], a combination of Gravity, Special Relativity and Quantum Mechanics, is used to compute analytically the masses of two out of the three neutrino flavors on the basis of the masses of hadrons, without any unknown parameters. The results are in good agreement with the Normal Hierarchy of the neutrino flavor masses, which have not been measured independently yet. The computed masses are then used to derive formulae for the masses of the three bosons and the equilibrium pressures inside hadrons and bosons, which were recently measured via deeply virtual Compton scattering. Comparison with the experimental values shows a semiquantitative agreement (within 1%) and supports the idea that the strong force is a gravitational attraction between relativistic neutrinos.

References:
1. "Gravity, special relativity and the strong force: A Bohr-Einstein-de Broglie model for the formation of hadrons", Constantinos G. Vayenas, Stamatios N.-A. Souentie, Springer, NY, ISBN 978-1-4614-3935F-6 (2012). \n2. "A Bohr-type model of a composite particle using gravity as the attractive force", C.G. Vayenas, S. Souentie, A. Fokas, Physica A, 405, 360-379 (2014).\n3."On the structure, masses and thermodynamics of the W +- bosons". C.G. Vayenas, A.S. Fokas, D. Grigoriou, Physica A, 450, 37-48 (2016).

16:45: [PhysicalFriPM211] Invited
Quantum Gravity Phenomenology from the Generalized Uncertainty Principle
Pasquale Bosso¹ ; ¹University of Lethbridge, Lethbridge, Canada;
Paper Id: 288 [Abstract]

The fundamental physical description of Nature is based on two mutually incompatible theories: Quantum Mechanics and General Relativity. Their union in a theory of Quantum Gravity remains one of the main challenges of theoretical physics. A common feature of candidate theories of Quantum Gravity is the existence of a minimal observable length of the order of the Planck length [1]. This prediction, though, is in contradiction with Heisenberg's Uncertainty Principle. In fact, according to this principle, it is possible to observe any length while increasing the uncertainty in momentum. In the context of Quantum Gravity Phenomenology, that studies quantum-gravitational effects in low-energy systems, Heisenberg's principle is then modified into the Generalized Uncertainty Principle (GUP) [2]. The GUP then imposes a minimal uncertainty in position and predicts a deformed commutation relation between position and momentum [3]. In this talk, after introducing the basics of the Uncertainty Principle, I will show how the GUP can change known aspects of standard Quantum Mechanics, leading to ways to test theories of Quantum Gravity.

References:
[1] L. J. Garay, "Quantum gravity and minimum length," <i>International Journal of Modern Physics A</i> <b>10</b> no. 02, (Jan, 1995) 145-165.\n[2] A. Kempf, G. Mangano, and R. B. Mann, "Hilbert space representation of the minimal length uncertainty relation," <i>Physical Review D</i> <b>52</b> no. 2, (Jul, 1995) 1108-1118.\n[3] P. Bosso, "Generalized Uncertainty Principle and Quantum Gravity Phenomenology,'' Ph.D. Thesis, University of Lethbridge, (Aug, 2017).

SESSION: PhysicalSatAM-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Sat Oct, 26 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Michael Stoukides; Costas Galiotis; Session Monitor: TBA

11:20: [PhysicalSatAM01] Plenary
Graphene Synthesis and Applications
Costas Galiotis¹ ; ¹University of Patras School of Engineering, Patras, Greece;
Paper Id: 282 [Abstract]

Graphene is a perfect 2D crystal of covalently bonded carbon atoms and forms the basis of all graphitic structures with superior properties [1] that can be exploited in many research areas. Nevertheless, these structures cannot have significant impact until efficient production techniques develop to harvest their unique properties in global applications and devices. Chemical Vapor Deposition (CVD) is the most well-known method of graphene growth [2]. The fabrication process is rather complex, as it involves multiple steps such as hydrocarbon decomposition, carbon adsorption and subsequently, diffusion on the catalytic substrate, the generation of the nucleation point and finally, the growth. As the nucleation happens at random places on the surface, this method by default results in micro-meter sized multi-domain layers. Moreover, the separation and transport steps add further defects and contaminations, which further impair the ideal physical properties of these materials. In contrast to a solid catalytic substrate, graphene growing on Liquid Metal Catalysts (LMCat) might be a solution for the production of defect-free single graphene domains at high synthesis speeds due to the enhanced atomic mobility, homogeneity, and fluidity of a LMCat. In-situ monitoring of such a complex procedure is of paramount importance for the control of graphene growth and the understanding of growing kinetics. Among other optical techniques, Raman spectroscopy has been used extensively for studying nanomaterials in general and graphene in particular. Performing in situ Raman spectroscopy at high temperatures, however, needs special considerations, otherwise the weak Raman signal could be easily dominated by the intense thermal radiation. In our case, a UV laser line at 405 nm was used to reduce the black body radiation effect. Raman spectra were acquired on liquid Cu during growth and it verified the existence of graphene even at its primary stages. This result is of paramount importance since it is the first time that a chemically sensitive technique like Raman spectroscopy was implemented for the in-situ monitoring of graphene growth. Beside Raman spectroscopy, a novel metrology system based on reflectance spectroscopy for the in-situ monitoring of surface changes during graphene growth by taking advantage of reflectance variations was developed. Simultaneously, reflectance fluctuations on the surface of copper are monitored and analyzed. The results indicated that the growth rate of graphene can be estimated from the measured differential reflectance. We will present processing strategies for the production of macro-scale CVD-graphene/polymer nanolaminates based on the combination of ultra-thin casting, wet transfer and floating deposition [3, 4]. These composites possess excellent mechanical and electrical properties and can be employed as coatings for EMI shielding or electro-active displays in a variety of applications. This can assist in the protection of membranes, art objects and particularly paintings. Finally, the use of large transparent graphene veils for the protection of art works will also be covered in this presentation.

References:
[1] Novoselov K. S. et al., Proc. Natl. Acad. Sci., 102, 10451, 2005
[2] Bae S. et al., Nat. Nanotechnology, 5, 574, 2010
[3] Vlassiouk I et al., ACS Appl Mater Interfaces, 20, 10702, 2015
[4] Pavlou Ch. al, submitted

12:10: [PhysicalSatAM03]
Proton Internal Pressure Distribution Suggests a Simple Proton Structure
Dimitrios Grigoriou¹ ; Eftychia Martino² ; Constantinos Vayenas¹ ; ¹University of Patras, Patras, Greece; ²University of Patras, Dept. of Chemical Engineering, Patras, Achaia, Greece;
Paper Id: 89 [Abstract]

Understanding the origin of quark confinement in hadrons remains one of the most challenging problems in modern physics. Recently, the pressure distribution inside the proton was measured via deeply virtual Compton scattering. Surprisingly, strong repulsive pressure up to 10³⁵ pascals, the highest so far measured in our universe, was obtained near the center of the proton up to 0.6 fm, combined with strong binding energy at larger distances. We show here that this profile can be derived semi-quantitatively without any adjustable parameters using the rotating lepton model of composite particles (RLM), i.e. a proton structure comprising a ring of three gravitationally attracting rotating ultrarelativistic quarks. The RLM synthesizes Newton's gravitational law, Einstein's special relativity, and de Broglie's wavelength expression, thereby conforming to quantum mechanics. This also yields a simple analytical formula for the proton radius and for the maximum measured pressure which are in excellent agreement with the experimental values.

References:
1. V.D. Burkert, L. Elouadrhiri & F.X. Girod, <i> Nature</i>,<b> 557</b>, 396 (2018).
2. C.G. Vayenas, S. Souentie Gravity, special relativity and the strong force: A Bohr-Einstein-de-Broglie model for the formation of hadrons. (Springer, New York, 2012).
3. C.G. Vayenas, S. Souentie, & A. Fokas, Physica A, <b>405</b>, 360 (2014).

12:35: [PhysicalSatAM04]
Consequences of Important Parameters on the Effect of Water on Fischer-Tropsch Synthesis Rate and Selectivity
Klito C. Petallidou¹ ; Enrique Iglesia² ; Angelos Efstathiou³ ; ¹University of California at Berkeley, University of Cyprus, Nicosia, Cyprus; ²University of California at Berkeley, Berkeley, United States; ³University of Cyprus, Nicosia, Cyprus;
Paper Id: 195 [Abstract]

Water is one of the main products of Fischer-Tropsch (FT) synthesis and its effect on the FT rate has been reported to be positive [1], negative [2], or negligible [1]. The void structure plays an important role on the effect of water on the FT rate [1]. Catalysts with large void structures show positive effects of water on the turnover rate, while catalysts with small void structure show negligible effects. In the case of small void structures, the condense H₂O phase may already exist, while large void structures, require higher water pressure for intrapore condensation [1, 3]. Also, it has been reported that these enhancement rates with increasing water pressure are due to stabilization of kinetically-relevant step through H-transfer [4]. Kinetic and spectroscopic experiments were used to address the influence of the void structure on the effect of water on the rate and selectivity of FT synthesis over Cobalt-based catalysts and the consequences of (i) Cobalt particle size, (ii) extent of reduction of Cobalt, (iii) total pressure of CO/H₂ and (iv) reaction temperature. The consequences of these important parameters on the influence of void structure on the effect water remain unanswered until now. The present study provides a useful and important contribution to the state-of-the-art important kinetic and mechanistic aspects of FT synthesis. These rate enhancements caused by water are independent of the particle size and the extent of reduction of cobalt. Water plays an important role on the reaction temperature and the total pressure of reactants. Catalysts with large void structures show positive effects of water on the turnover rate at lower reaction temperatures and higher pressures, while at higher reaction temperatures and lower pressures minor effects are observed. Catalysts with small void structure show negligible effects of water on the rate in all experimental conditions. In all cases (small and large void structure), CH₄ selectivity decreases and C₅⁺ selectivity increases with increasing the water partial pressure, except at higher temperatures and lower pressures, where the selectivities are constant. These results reinforce the previous proposal for intrapore condensation of liquid water.

References:
[1] E. Iglesia, Appl. Catal. A: Gen. 161 (1997) 59-78.
[2] A.M. Hilmen, D. Schanke, K.F. Hanssen, A. Holmen, Appl. Catal. A: Gen. 186 (1999) 169-188.
[3] S. Krishnamoorthy, M. Tu, M.P. Ojeda, D. Pinna, E. Iglesia, J. Catal. 211 (2002) 422-433.
[4] D.D. Hibbitts, B.T. Loveless, M. Neurock, E. Iglesia, Angew. Chem. Int. Ed. 20 (2013) 12273-12278.

SESSION: PhysicalSatPM1-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Sat Oct, 26 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Pavlos Stephanou; Session Monitor: TBA

14:00: [PhysicalSatPM105] Plenary
Single Metal Atom Catalysts: a New Frontier in Heterogeneous Catalysis
Maria Flytzani Stephanopoulos¹ ; ¹Tufts University, Medford, United States;
Paper Id: 280 [Abstract]

Novel catalyst designs aiming at the development of energy-efficient, low-cost and sustainable processes are of great interest for applications to fuel and chemical production, and to environmental pollution abatement. Identification of the active catalytic site and design of catalysts with 100% atom efficiency has been a long-standing goal in heterogeneous catalysis. A promising approach to reaching this goal through the controlled preparation of isolated single-atom heterogeneous catalysts has emerged in recent literature. For catalytic metals, atomic dispersion affords better utilization, different (often better) selectivity than the extended metal, as well as new prospects for low-cost and green process development. Isolated supported metal atoms may be viewed as species bonded to a support, the latter serving as a ligand. An analogy between a homogeneous and a heterogeneous single-site catalytic center can thus be made. Single atom sites catalyze some, but not all reactions. It is crucial to understand the mechanisms behind catalysis by supported single metal atoms, as this will guide new, improved catalyst designs. In this presentation, suitably stabilized catalytic sites as single metal atoms/cations on various supports will be showcased by drawing examples from a variety of reactions: the low-temperature water-gas shift reactions, methanol and ethanol dehydrogenation and steam reforming reactions, the direct methane conversion to oxygenates, and selective hydrogenation reactions on single-atom alloys. Reaction mechanisms involving single metal atoms/cations often transcend support structure and composition, thus allowing flexibility in the choice of the support. A unique "signature" of the metal (Au, Pt, Pd, Ni, etc.) at the atomic state is preserved, distinct however from the corresponding extended metal catalyst. A new class of single-atom heterogeneous catalysts will be presented, namely single-atom alloys that comprise of catalytically active elements like Pt, Pd and Ni alloyed in a more inert host metal like Cu, Au or Ag at the single-atom limit. Single-atom alloys offer a unique approach towards rational catalyst design, one that combines surface science, catalysis and theory in a most efficient way. Model surfaces and nanoparticles that can host isolated atoms in the surface layers behave similarly in escaping the linear scaling relationships and allow for the rational fine-tuning of activity and selectivity. Good stability is imparted by the strong metal-metal bonds between the host, the minority metal, and atomic dispersion. This can be maintained at high temperatures. Resistance to CO poisoning and coking are additional advantages of these promising materials, as will be shown in the presentation where examples will be drawn from alkyne and alkadiene hydrogenation, and alkane dehydrogenation. Novel synthesis methods and the stability of single-atom metal catalysts in various supports and reaction environments will be discussed.

14:25: [PhysicalSatPM106]
Multiscale Modeling and Simulation of the Viscoelasticity of Complex, Microstructured Fluids Guided from Nonequilibrium Thermodynamics
Vlasios Mavrantzas¹ ; Pavlos Stephanou² ; ¹1. University of Patras, Department of Chemical Engineering 2. ETH Zurich, Department of Mechanical and Process Engineering, Zurich, Switzerland; ²Cyprus University of Technology, Limassol, Cyprus;
Paper Id: 84 [Abstract]

Soft microstructured materials is the class of materials where computer simulations have enjoyed the most rapid advances in the last two decades due to the development of several innovative molecular simulation techniques (such as multiple-time step Molecular Dynamics, chain connectivity altering Monte Carlo, and coarse-grained schemes), the introduction of advanced, very accurate force fields and the use of graphics processing units (GPUs) which has revolutionized the field.<br />In our presentation, we will highlight all these extraordinary developments, we will stress the importance specifically of atomistic simulations in substantially improving our understanding of the structure-property-processing relationship in materials with a highly complex internal microstructure [1], and we will show how molecular modelling can be used as a true design tool for new multifunctional materials by unravelling the fundamental physicochemical properties governing the performance of the final product in actual applications [2].<br />In particular, we will demonstrate how we can get help from nonequilibrium thermodynamics [3, 4] to design novel methodologies that can lead to the efficient computation of the viscoelastic properties of complex fluids or to the formulation of more accurate constitutive models describing their flow behavior as a function of their internal microstructure [5, 6].

References:
[1] D.G. Tsalikis, P.V. Alatas, L.D. Peristeras, V.G. Mavrantzas, Scaling laws for the conformation and viscosity of ring polymers in the crossover region around Me from detailed molecular dynamics simulations, ACS Macro Lett. 2018, 7, 916-920.\n
[2] F.D. Tsourtou, E.N. Skountzos, S.D. Peroukidis, V.G. Mavrantzas, Molecular simulation of the high temperature phase behaviour of a-unsubstituted sexithiophenea, Soft Matter 2018, 14, 8253- 8266.\n
[3] A.N. Beris, B.J. Edwards, Thermodynamics of flowing systems with internal microstructure, Oxford University Press, New York (1994).\n[4] H.C. Oettinger, Beyond equilibrium thermodynamics, Wiley-Interscience, Hoboken, New Jersey (2004).\n
[5] C. Baig, V.G. Mavrantzas, H.C. Oettinger, On Maxwell's Relations of Thermodynamics for Polymeric Liquids away from Equilibrium, Macromolecules 2011, 44, 640-646.\n
[6] Ch. Tsimouri, P.S. Stephanou, V.G. Mavrantzas, A constitutive rheological model for agglomerating blood derived from nonequilibrium thermodynamics, Physics of Fluids 2018, 30, 030710.

14:50: [PhysicalSatPM107] Plenary
Sorption and Catalytic Chemistry in Crowded Environments
Johannes A. Lercher¹ ; Yue Liu² ; ¹Technical University of Munich, Garching, Germany; ²Technical University of Munich, Garching bei München, Germany;
Paper Id: 128 [Abstract]

Molecular sized pores are not only critical for ion exchange and sorption, but they also provide a unique chemical and steric environment for catalysis. Regular dimensions allow stability of ground and transition states of reacting molecules better than that of larger pore oxide and organic porous materials. This enhances interaction strength and lowers the standard free energies of transition states in a highly selective manner. These properties are analog to qualities that are critical for the high activity of enzymes, for the local constraints and for the local chemical environment at active sites. Many reactions in petroleum chemistry, such as cracking or isomerization, occur under conditions where the concentration of reacting molecules is low and excellent models to understand reactive interactions under such conditions have been developed. The search for more efficient reactions at lower temperatures, such as eliminations, carbon-carbon bond formation, and the presence of the liquid phase induce complex ordering of reactants, intermediates and products, enabling a subtle way to direct sorption and catalysis. The ordering in protic solvents, such as water, especially leads to new chemistry as acid zeolites transform into a polar oxide environment with hydrated hydronium ions as the stable active site. The lecture will address the chemical consequences of such an environment and compare it with the environment created in molecular organic frameworks. We will show how water and protic solvent molecules self-organize in this environment and how they impact the thermodynamic state of the sorbed and reacting molecules. It will be shown that the interactions can be designed and controlled via direct synthesis (changing pore sizes and concentration of sites), as well as via the addition of cations, oxidic clusters or organic fragments. Such interactions will be compared to interactions reacting molecules have with coordination compounds and enzyme sites. As examples for catalytic transformations, the lecture will compare elimination reactions of alcohols, alkylation of aromatic molecules and oligomerization of olefins. Experimental methods to define the state of the reacting molecules, combined with detailed kinetic analysis and theory, will be used to explain the principal contributions of the interactions and the confinement to determine reaction rates. We will discuss how reaction rates and pathways can be tailored using the space available for a transition state and the chemical constituents around the active site.

15:15: [PhysicalSatPM108]
The Mechanics of the Space-Time Fabric of Space
Mark F. Horstemeyer¹ ; ¹Liberty University, Virgina, United States;
Paper Id: 445 [Abstract]

An elastic constitutive model of gravity where we identify physical space with the mid-hypersurface of an elastic hyperplate called the “cosmic fabric” and spacetime with the fabric’s world volume. Using a Lagrangian formulation, we show that the fabric’s behavior as derived from Hooke’s Law is analogous to that of spacetime per the Field Equations of General Relativity (GR). The study is conducted in the limit of small strains, or analogously, in the limit of weak and nearly static gravitational fields. The Fabric’s Lagrangian outside of inclusions is shown to have the same form as the Einstein–Hilbert Lagrangian for free space. Properties of the fabric such as strain, stress, vibrations and elastic moduli are related to properties of gravity and space, such as the gravitational potential, gravitational acceleration, gravitational waves and the energy density of free space. By introducing a mechanical analogy of GR, we enable the application of Solid Mechanics tools to address problems in Cosmology. Finally, because the cosmos acts as a continuum body with external tractions according to Cauchy’s Law, the existence of God is proven as exemplified by the tractions on the outside surface of the cosmos.

SESSION: PhysicalSatPM2-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Sat Oct, 26 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Renat Sultanov; Libor Kvitek; Session Monitor: TBA

15:55: [PhysicalSatPM209] Plenary
Ultra-Relativistic Post-Minkowskian General Relativity, the Strong Force, and the Vayenas Model
Athanassios Fokas¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 133 [Abstract]

The post-Minkowskian approximation of the N-body problem of general relativity has been recently analysed by Luc Blanchet and the speaker[1]. The ultrarelativistic limit of the above formulation in the particular case of two equal masses yields a formula for the underlying force which has characteristics of the strong force, including confinement and asymptotic freedom[2]. This result is consistent with the iconoclastic model of particle physics of C Vayenas.

References:
[1] Blanchet, L., & Fokas, A. S. (2018). Equations of motion of self-gravitating N-body systems in the first post-Minkowskian approximation. Physical Review D, 98(8), 084005.

[2] Fokas, A. S. (2019). Ultra-relativistic gravity has properties associated with the strong force. The European Physical Journal C, 79(3), 271.

16:20: [PhysicalSatPM210] Plenary
Reaction Mechanisms in Electrocatalysis: Insights from Electrochemical Methods, Kinetic Modeling and Operando Spectroscopies
Elena Savinova¹ ; ¹University of Strasbourg, Strasbourg, France;
Paper Id: 11 [Abstract]

Electrocatalysis plays a pivotal role in electrochemical energy conversion devices such as fuel and electrolysis cells by decreasing the overpotential of electrode reactions. Understanding mechanisms of the electrode reactions and the nature of active sites and intermediates is an important clue in designing efficient and durable electrode materials for practical applications. Various approaches can be utilized in order to obtain information regarding the mechanisms of electrocatalytic reactions and the nature of the active sites; among them are electrochemical methods, operando spectroscopies, ab initio calculations and kinetic modeling. In this presentation, we will illustrate these approaches by considering reactions of outstanding practical importance [1-6] such as the oxygen reduction (ORR) and the oxygen evolution reaction (OER), the hydrogen evolution (HER) and the hydrogen oxidation reaction (HOR).

References:
[1] D. Salmazo, M.F. Juarez, A.G. Oshchepkov, O.V. Cherstiouk, A. Bonnefont, S.A. Shermukhamedov, R.R. Nazmutdinov, W. Schmickler, E. R. Savinova, Electrochimica Acta (2019).
[2] A. Bonnefont, A. S. Ryabova, T. Schott, G. Karanguaven, S. Ya. Istomin, E. V. Antipov, E. R. Savinova, Current Opinion in Electrochemistry, , 14 (2019) 23-31.
[3] V. A. Nikitina, A. A. Kurilovich, A. Bonnefont, A. S. Ryabova, R. R. Nazmutdinov, E. R. Savinova, G. A. Tsirlina, J. Electrochem. Soc. 165 (2018) J3199-J3208.
[4] V. A. Saveleva, L. Wang, D. Teschner, T. Jones, A. S. Gago, K. A. Friedrich, S. Zafeiratos, R.Schloigl, E. R. Savinova, ., J. Phys. Chem. Lett, 9 (2018), 3154-3160.
[5] V. A. Saveleva, L. Wang, W. Luo, S. Zafeiratos, C. Ulhaq-Bouillet, A. S. Gago, K. A. Friedrich, E. R. Savinova, .J.Phys.Chem.Lett. 7 (2016) 3240-3245.
[6] A. S. Ryabova, F. S. Napolskiy, T. Poux, S. Ya. Istomin, A. Bonnefont, D. Antipin, A. Ye. Baranchikov, E. E. Levin, A. M. Abakumov, G. Karanguaven, E. V. Antipov, G. A. Tsirlina, E. R. Savinova, Electrochimica Acta, 187 (2016) 161-172.

16:45: [PhysicalSatPM211] Invited
Interplay between Coulomb and Nuclear Forces in Low-Energy Atomic, Muonic and Anti-protonic Few-Body Systems
Renat Sultanov¹ ; ¹Department of Mathematics and Engineering, Odessa College, Odessa, Texas, Odessa, United States;
Paper Id: 20 [Abstract]

In this lecture we will focus on low-energy, non-relativistic quantum-mechanical three- and four-charge-particle systems which are of a significant interest in different fields of atomic, muonic and molecular physics. Some of the particles in the few-body systems may have additional nuclear strong interactions between them. An appropriate inclusion of these forces in calculations and estimation of their influence on the properties of the few-body systems is an important but challenging task. We will present different Coulomb three-body systems, which are related to the problems of the muon-Catalyzed-Fusion cycle (muCF-cycle). Secondly, certain few-body systems and problems in the field of the low-energy antiproton physics and anti-hydrogen formation and annihilation reactions will also be considered and discussed [1]. Additionally, we will present various theoretical methods and few-body techniques, which are based on the three-body Faddeev [2] and/or modified Faddeev-type equations [1]. Special attention will be given to comparison between theoretical results and available experimental data. Other theoretical numerical methods such as variational, adiabatic, and hyper-spherical will be briefly introduced and discussed as well.

References:
1. Sultanov R. A., Guster D. (2013) J. Phys. B 46, 215204.
2. Faddeev L. D. (1960) Zh. Eksp. Teor. Fiz. 39 1459; (1961) Sov. Phys.-JETP 12 1014.

17:10: [PhysicalSatPM212]
Hydrogenation of Carbon Dioxide on the Iron Based Nanocatalyst
Libor Kvitek¹ ; Martina Kubikova¹ ; Robert Prucek² ; Ales Panacek² ; Manoj B. Gawande¹ ; ¹Palacky University in Olomouc, Olomouc, Czech Republic; ²Palacky University, Olomouc, Czech Republic;
Paper Id: 274 [Abstract]

Global warming triggered by growing of the greenhouse gases concentration in the atmosphere actually represents the biggest world ecology problem. Carbon dioxide is one of the most important greenhouse gases because it is the main reason for global warming [1] Therefore, effective solutions to the global warming problem should be connected with the lowering of the carbon dioxide concentration in the atmosphere. One of the feasible protocols is to employ carbon dioxide as starting material and to convert it to the valuable compounds in various industrial processes which are very important. [2] For this purpose, iron-based materials act as a one of the most effective catalytic materials for carbon dioxide hydrogenation to methane, methanol and other simple important hydrocarbons. [3] Heterogeneous catalysis is connected with the active surface of catalysts. Therefore, the subject of the presented study is to investigate the influence of the catalyst’s physical state on its activity in hydrogenation of CO₂. Four types of iron oxide catalysts were prepared by high temperature decomposition of Iron (II) oxalate in the air. Afterword, its catalytic performance was studied at low pressure (1 bar) and low temperature (325°C) in the microreactor, Microactivity Effi, connected with a gas chromatograph for the detection of the reaction products. Depending on the order and rate of reaction, components mixing four different samples of the nanostructured iron oxide catalyst were prepared. After high temperature decomposition the composition of the prepared catalyst was determined by XRD and only hematite and magnetite in a various ratio between 90:10 down to 40:60 (hematite: magnetite) was observed in the emerging catalysts. Bigger differences between these catalysts were observed during reduction of the iron oxide in the hydrogen atmosphere by the XRD technique. Part of the samples produced zero valent iron but the second parts of the samples were reduced only to the form of pure magnetite. Also, observed catalytic activity of the prepared catalysts was different. The highest reaction rate, but also the lowest stability, was observed for catalysts which were reduced in the hydrogen atmosphere to zero valent irons, whereas catalysts which were reduced only to magnetite were substantially stable in selectivity of the production of methane in comparison with carbon monooxide. Unfortunately, total reaction rate was, in this case, slower. On the other hand, microstructured commercial Iron(II) oxide used as reference did not produce hydrocarbons (mainly methane), only carbon monoxide was observed as a carbon based product with this catalyst.

References:
References:\n[1] M. Aresta, A. Dibenedetto, Dalton Trans. 28 (2007) 2975-2992.\n[2] A. Rafiee, R. Khalilpour, D. Milani, M. Panahi, J. Environ. Chem. Eng. 6 (2018) 5771-5794.\n[3] C.-S.T. Chih-Hung Huang, T. Chung-Sung, Aerosol Air Qual. Res. 14 (2014) 480-499.

SESSION: PhysicalSatPM3-R10	Vayenas International Symposium on Physical Chemistry and its applications for sustainable development
Sat Oct, 26 2019 / Room: Aphrodite B (100/Gr. F)
Session Chairs: Dionysios Tsousis; Session Monitor: TBA

17:50: [PhysicalSatPM313]
Characterization of WOx-ZrO2/MWCNT: An Aqueous Phase Acid Catalyst for Alcohol Dehydration
Patrick Kelleher¹ ; Cyril Thomas² ; Hui Shi³ ; Gary Haller¹ ; ¹Yale University, New Haven, United States; ²Sorbonne Université, Paris, France; ³Department of Chemistry, Catalysis Research Center, Technische Universität München, Garching, Germany;
Paper Id: 32 [Abstract]

Tungstated zirconia supported on multi-walled carbon nanotubes (WO_x-ZrO₂/MWCNT) has been characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), NO_x temperature programmed desorption (NO_x-TPD) and probe reaction of cyclohexanol dehydration in liquid water. TEM and XRD establish that the ZrO₂ grafted to MWCNT are tetragonal crystalline nanoparticles of about 2 nm [1]. XAS and thermal gravimetric analysis indicates that the tungstated zirconia nanoparticles are hydrothermally stable at 200°C and NO_x-TPD [2] was used to measure the interaction of impregnated WO_x with ZrO₂/MWCNT; the WO_x preferentially interacts with the surface of ZrO₂ until about a monolayer (~4 W/nm²) of coverage is reached when a WO₃ particulate phase develops. At a coverage of 8 W/nm², WO₃ can be detected by XRD. The turnover frequencies (TOF) normalized per W atom for cyclohexanol dehydration at 215°C at W surface densities of 2, 4 and 8 W/nm² are 0.043, 0.029 and 0.027, respectively, compared to a commercial bulk WO_x-ZrO₂ with W surface density of 5 W/nm², where it is 0.021. Thus, the TOF of the WO_x-ZrO₂/MWCNT at 2 W/nm² is about twice that of unsupported WO_x-ZrO₂ and exceeds the bulk WO_x-ZrO₂ even when the W density is greater than that of unsupported WO_x-ZrO₂. Dividing the bulk 15.5 wt% WO_x-ZrO₂ TOF (based on acid site density) by the TOF (based on a W atom normalization) indicates that on average it requires 3.3 W atoms per acid site. Because the acid site is a hydronium ion in all cases [3], a better interpretation is that fewer W atoms per acid site are required on the low W density WO_x-ZrO₂/MWCNT. Thus we estimate that about 1.6 W atoms per acid site are required on the 2 W/nm² WO_x-ZrO₂/MWCNT.

References:
\n[1] C. Lui, S. Lee, D. Su et al., J. Phys. Chem. C, 116 (2012) 21742.\n[2] H. Y. Law, J. Blanchard, X. Carrier et al., J. Phys. Chem. C, 114 (2010) 9731.\n[3] H. Shi, S. Eckstein, A. Vjunov et al., nature Commun., 8 (2017) 15442.

SESSION: EnergyThuAM-R11	6th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Thu Oct, 24 2019 / Room: Coralino
Session Chairs: Manfred Mauntz; Harold Dodds; Session Monitor: TBA

11:20: [EnergyThuAM01]
Electricity Production Choices and Consequences-2019 Update
Harold Dodds¹ ; ¹University of Tennessee, Knoxville, United States;
Paper Id: 175 [Abstract]

With the world's population currently increasing from seven billion to approximately nine billion by the year 2040, achieving a healthy lifestyle for all people on earth will depend, in part, on the availability of affordable energy, especially electricity. This paper considers the various choices, or options, for producing electricity and the consequences associated with each option. The options are fossil, renewable, and nuclear energies. The consequences associated with these three options are addressed in five different areas: economics, environmental effects, public health and safety, sustainability, and politics. All options are needed, but some options may be better than others when compared in the five areas. This presentation is a brief summary of a short course entitled "Energy Choices and Consequences," which was created by the author several years ago and is continually updated. The presentation will provide updated information through October of 2019.

References:
"Energy Choices and Consequences," a short course for university honor students, developed and continually updated by H. L. Dodds, Professor Emeritus, University of Tennessee, Knoxville, Tennessee, USA

11:45: [EnergyThuAM02]
Continuous Online Monitoring of Dielectric Parameters for Engine Oils: Identification of Critical Operation Conditions of Efficient Diesel and Gas Engines for Live Time Enhancement
Manfred Mauntz¹ ; Jorn Peuser¹ ; ¹cmc Instruments GmbH, Eschborn, Germany;
Paper Id: 56 [Abstract]

The requirements of renewable energy for large industrial gearboxes as installed in wind turbines on and off shore rise. The same applies for efficient gas and diesel engines. A larger flexibility is required of these devices such as maximum operational reliability and a long lifetime. Thus, the requirements for oil and oil condition monitoring grow correspondingly. This presentation provides information about a novel online oil condition monitoring system that gives a solution to the mentioned priorities in the energy sector. The different mechanisms of oil parameter variation in gearboxes and engines are addressed; the data interpretation has to be redefined to the dominating effect. From this, the very sensitive measurement of conductivity kappa, relative permittivity epsilon, r, and temperature, T, enables the detection of small changes in the conductivity and dielectric constant of the corresponding oil composition. Therefore, the sensor system effectively controls the proper operation conditions of engines and gearboxes. 24/7 monitoring of the asset during operation enables specific preventive and condition-based maintenance which is independent of rigid inspection intervals.

References:
[1] P. Tchakoua, R. Wamkeue, M. Ouhrouche, F.S. Hasnaoui, T.A. Tameghe, G. Ekemb: Wind Turbine Condition Monitoring: State-of-the-Art Review, New Trends, and Future Challenges, Energies 2014,7, pp. 2595-2630, (2014)
[2] Noria Corporation: The critical role of additives in lubrication, Machinery Lubrication June 2012, (2012)
[3] M. Mauntz and U. Kuipers: Sensorsystem- Sensorsystem zur Messung von Komponenten der komplexen Impedanz elektrisch gering leitender und nichtleitender Fluide, dessen Realisierung und Anwendung, patent application no. 10 2008 047 366F.9, German Patent Office, Munich, (2008)
[4] M. Mauntz, U. Kuipers and J. Peuser: New oil condition monitoring system, WearSense enables continuous, online detection of critical operating conditions and wear damage, Malaysian International Tribology Conference 2015 - MITC2015, Penang, Malaysia on November 16-17, 2015, Conference Proceedings, ISBN: 978-967-13625F-0-1, S. 179-180, (2015)

12:10: [EnergyThuAM03]
Nuclear Education and Training at Harbin Engineering University, China
Puzhen Gao¹ ; ¹Harbin Engineering University, Harbin, China;
Paper Id: 78 [Abstract]

Nuclear Power is developing fast in China. Peaceful and safe use of nuclear energy requires not only advanced technology, but also an extensive and intensive safety culture. A large number of personnel with nuclear safety technology and nuclear safety vision are in demand. Universities play an important role in providing nuclear engineering professionals. The presentation will introduce the nuclear engineering education in China, specifically at Harbin Engineering University (HEU). HEU is a national key university. It has a long glorious history and good tradition. The nuclear major at HEU was founded in 1958. With the support of the Chinese government and the IAEA, the College of Nuclear Science and Technology (CNST) has become the largest nuclear engineering education and training base in China. CNST annually trains and outputs 300-350 students with different degrees. The presentation will cover: - Nuclear education and training at HEU, including application of simulators and virtual reality tools. -Teaching Labs, the nuclear power simulation center, and the virtual reality lab. - Student academic activities, International cooperation, and Student exchange.

References:
[1] College of Nuclear Science and Technology. http://cnst.hrbeu.edu.cn/en15/, (accessed on June 7 2019).
[2] School of Nuclear Science and Technology. http://cnst.hrbeu.edu.cn/, (accessed on June 7 2019).

12:35: [EnergyThuAM04] Keynote
Dynamic Probabilistic Risk Assessment of Nuclear Reactor Operation
Tunc Aldemir¹ ; ¹The Ohio state University, Columbus, United States;
Paper Id: 183 [Abstract]

Introduced in the 70s, the traditional approach to probabilistic risk assessment (PRA) of a nuclear reactor operation is the event-tree/fault-tree approach (ET/FT). The ET/FT approach only qualitatively accounts for the timing of events through their ordering. A new generation of methodologies is starting to receive attention for the nuclear reactor PRA. Often referred to as dynamic PRA (DPRA) methodologies¹, these methodologies explicitly account for the time element in the probabilistic system evolution and heavily incorporate plant analysis tools (e.g., RELAP², MELCOR³, MAAP5⁴) to model possible dependencies among failure events that may arise from hardware/software/firmware/process/ human interactions. DPRA methodologies are also capable of quantifying the effects of phenomenological variability and model uncertainties on the consequences of upset conditions. They can be particularly useful for the PRA modeling of passive safety systems, including representation of aging effects. An overview of the DPRA methodologies is presented, including system level applicable computational tools.

References:
1. T. Aldemir, "A Survey of Dynamic Methodologies for Probabilistic Safety Assessment of Nuclear Power Plants", Annals of Nuclear Engineering, 52, 113-124 (2013).
2. The RELAP5-3D Code Development Team, RELAP5-3D Code Manual, Volume I: Code Structure, System Models, and Solution Methods, INEEL-EXT-98-00834, June 2005.
3. R. O. Gauntt et al., "MELCOR Computer Code Manuals," NUREG/CR-6119, Vol.2, Rev. 3 (SAND2005-5713), U.S. Nuclear Regulatory Commission, Washington, D.C. (2005).
4. Modular Accident Analysis Program - MAAP5 v5.04 for Windows, 3002007340, EPRI, Palo Alto, CA. September 2016 (2016).

SESSION: EnergyThuPM1-R11	6th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Thu Oct, 24 2019 / Room: Coralino
Session Chairs: Udo Schwingenschlogl; Tunc Aldemir; Session Monitor: TBA

14:00: [EnergyThuPM105]
Proximity-Induced Spin-Valley Polarization in Silicene or Germanene on F-Doped WS2
Udo Schwingenschlogl¹ ; Shahid Sattar¹ ; Nirpendra Singh¹ ; ¹King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia;
Paper Id: 23 [Abstract]

Silicene and germanene are key materials for the field of valleytronics. Interaction with the substrate, however, which is necessary to support the electronically active medium, becomes a major obstacle. In the present work, we propose a substrate (F-doped WS₂) that avoids detrimental effects and, at the same time, induces the required valley polarization, so that no further steps are needed for this purpose. The behavior is explained by proximity effects on silicene or germanene, as demonstrated by first-principle calculations. Broken inversion symmetry due to the presence of WS₂ opens a substantial band gap in silicene or germanene. F doping of WS₂ results in spin polarization which, in conjunction with proximity-enhanced spin-orbit coupling, creates sizable spin-valley polarizations.

References:
Physical Review B 94, 205415 (2016)

14:25: [EnergyThuPM106]
Agri-Food Biomass Resources and Process Simulation for Bioenergy Production
⁰ ; Jonilda Llupa¹ ; Lorina Liçi² ; Ilirjan Malollari³ ; ¹PhD at Laboratory of Food Chemistry, Ioannina, Greece; ²Lecturer at Department of Energy Resources, Tirana, Albania; ³University of Tirana-Faculty of Natural Science, Tirana, Albania;
Paper Id: 460 [Abstract]

The present study was dedicated to introducing the agri-food residual biomass potential evaluated from the model calculation and for considering all possibilities of its utilization for heat and/or energy production. <br />Emphasis has been given to the agricultural and food industry wastes, as well as animal organic wastes, aimed to follow some technology tendency for performing a proper treatment of a mixture prepared from these organic wastes, in order to reach as much as possible biogas (bio-methane as a holder of bioenergy).<br />The most important way to reduce carbon emission is strongly depended firstly on how much local potential of each source can be collected and there is a number of factors such as the quality of waste chosen as a feedstock, conversion route, processing technology, its maturity and possibility to improve the efficiency of transformation into a bio-source of energy.<br />For this work has been chosen the biodegradation, but there are also other methods of preliminary waste treatment for disintegration such as composting or burning which however does not resolve definitely the issues related to the collection of such organic wastes, because from them still remains some residue after treatments. <br />For this study, it was performed a series of different transformation methods for agri-food and animal organic residues, as well as their combinations, so-called pretreatment process, which prepare conditions so the biomass to undergo to an easier process for anaerobic bio digestion or them. During these processes especially for the former one, play a key role some kind of specialized microorganisms which can produce a mixture of gases (Biogas composed of 65% methane and 35% carbon dioxide) and a mixture of liquid (which carries a high value of mineral nutrient elements like nitrogen, phosphorus, especially used as fertilizer additive, etc.

References:
[1] S. T. Merino and J. Cherry, “Progress and challenges in enzyme development for biomass utilization,” Advances in Biochemical Engineering/Biotechnology, vol. 108, pp. 95–120, 2007.
[2] N.Mosier,C.Wyman,B.Daleetal.,“Features of promising technologies for pretreatment of lignocellulosic biomass,” Bioresource Technology, vol. 96, no. 6, pp. 673–686, 2005..
[3] J. Zhu, C. Wan, and Y. Li, “Enhanced solid-state anaerobic digestion of corn stover by alkaline pretreatment,” Bioresource Technology, vol. 101, no. 19, pp. 7523–7528, 2010.
[4] A. T. W. M. Hendriks and G. Zeeman, “Pretreatments to enhance the digestibility of lignocellulosic biomass,” Bioresource Technology, vol. 100, no. 1, pp. 10–18, 2009.
[5] R. Sun, J. M. Lawther, and W. B. Banks, “Influence of alkaline pre-treatments on the cell wall components of wheat straw,” Industrial Crops and Products, vol. 4, no. 2, pp. 127–145,1995.
[6] J. Ruffell, B. Levie, S. Helle, and S. Duff, “Pretreatment and enzymatic hydrolysis of recovered fibre for ethanol production,” Bioresource Technology, vol. 101, no. 7, pp. 2267–2272, 2010.
[7] B.Du,L.N.Sharma,C.Beckeretal.,“Effect of varying feedstock-pretreatment chemistry combinations on the formation and accumulation of potentially inhibitory degradation products in biomass hydrolysates,” Biotechnology and Bioengineering, vol. 107, no. 3, pp. 430–440, 2010.
[8] B.C.Saha,L.B.Iten,M.A.Cotta,andY.V.Wu,“Dilute acid pretreatment, enzymatic saccharification, and fermentation of rice hulls to ethanol,” Biotechnology Progress, vol. 21, no. 3, pp. 816–822, 2005.
[9] A. Esteghlalian, A. G. Hashimoto, J. J. Fenske, and M. H. Penner, “Modeling and optimization of the dilute-sulfuric-acid pretreatment of corn stover, poplar and switchgrass,” Bioresource Technology, vol. 59, no. 2-3, pp. 129–136, 1997.
[10] L.da Costa Sousa,S.P.Chundawat,V.Balan,and B.E.Dale, “Cradle-to-grave’ assessment of existing lignocellulose pretreatment technologies,” Current Opinion in Biotechnology, vol. 20, no. 3, pp. 339–347, 2009.
[11] S. J. B. Duff and W. D. Murray, “Bioconversion of forest products industry waste cellulosics to fuel ethanol: a review,” Bioresource Technology, vol. 55, no. 1, pp. 1–33, 1996.
[12] L. Lin, R. Yan, Y. Liu, and W. Jiang, “In-depth investigation of enzymatic hydrolysis of biomass wastes based on three major components: cellulose, hemicellulose and lignin,” Bioresource Technology, vol. 101, no. 21, pp. 8217–8223, 2010.
[13] T. Eggeman and R. T. Elander, “Process and economic analysis of pretreatment technologies,” Bioresource Technology, vol. 96, no. 18, pp. 2019–2025, 2005.

14:50: [EnergyThuPM107]
MANAGEMENT SHIPPING, TRANSPORTATION AND STORAGE OF HAZARDOUS WASTE IN THE WESTERN BALKAN COUNTRIES
Sonja Stefanov¹ ; Rade Biocanin² ; ¹, Novi Sad, Serbia and Montenegro (formerly Yugoslavia); ²State University of Novi Pazar, Novi Pazar, Serbia and Montenegro (formerly Yugoslavia);
Paper Id: 155 [Abstract]

Waste management should be done in a way that does not endanger human health or the environment. In a general sense, under the definition of solid waste, we imply a solid, or a combination of solid wastes. The quantity, concentration, physical, chemical or infectious characteristics of this solid waste may cause or significantly contribute to increase in mortality, and present hazard to human health or the environment. In an aim to reduce negative effects, hazardous waste should be clasified in-situ by its physical and chemical caracteristics and state of aggregation, as well as by means of treatment. Prevention of waste is an important issue in the course of "clean" production, especially the development of clean technologies and the rational use of natural resources. It is important to eliminate the risk of the harmful effects of waste on human health, quality of life and the quality of the environment. Re- utilization of grit and recycling, separation of secondary raw materials and the use of waste as an energy source are also important to consider. Following the development of procedures and methods of waste disposal, remediation of uncontrolled landfills, monitoring existing and informal landfills, and raising awareness on waste management and public information should be accomplished. Transport of hazardous waste is done by the transport van plant, which includes loading, reloading and unloading waste. Only a person who has a license to transport waste issued by the proper authority may perform this transport. The waste is transported in a closed vehicle within a container or in another appropriate medium in order to prevent scattering, falling, loading and unloading during transport. This also prevents pollution of air, water and land. Transportation of waste can only be performed by ADR equipped vehicles and certified vehicles operated by drivers with a certificate of competency to transport cargo. Movement of Hazardous Wastes always requires appropriate documents with certification from the manufacturer, the owner and the person who receives hazardous waste. The producer or the owner of hazardous waste is required to permanently keep a copy of the document, certifying that the movement of waste is completed with a signature and stamp of the consignee of the waste .This paper presents legislation that defines an integrated hazardous waste permit for controlling and preventing pollution. This paper also points out the problems in obtaining permits for facilities for disposal or reuse of hazardous wastes. We will present what are considered the best available technology (techniques) that allow the minimization of hazardous waste.

References:
[1] R. Biočnin, S. Stefanov., Effects and Consequences of Pesticide Use and Biochemical Measures of Protection , 10th Anniversary International Scientific Conference, Gabrovo, Bugarska(2010).
[2] R. Biocanin, S.Stefanov, Ekološka bezbednost transporta opasnih materija i tereta, Treća reginalna naučno-stručna konferencija o upravlajnju industrijskim otpadom u sferi održivog razvoja, Kopaonik, (2011).
[3] R. Biočanin, S.Stefanov. Ekološka bezbednost opasnog transporta, International Quality Conference, Kragujevac (2011).
[4] S.Stefanov, R.Biocanin, M. Badic, S.Bancov. New techologies with economic and ecological aspects, , Međunarodna naučno-stručna konferencija EMoNT2011, u štampi, Kladovo, Serbia (2011)
[5] S. Stefanov, M. Vojinović Miloradov, R.Biočanin, Pasivni sempleri - monitoring industrijskih polutanata u složenim procesnim sistemima, I Simpozijum ekologa Republike Srpske, Banja Luka (2010).
[6] S.Stefanov, R.Cvejic, R.Biocanin. Modeling of pollutants at the landfill waste,I nternational scientific and methodological conference "Quality of education" management, certification, recognition, Kramatorsk, Ukraine,(2011).
[7] S.Stefanov, M.Vojinovic Miloradov, R.Biočanin. Inovaciona istraživanja za smanjenje koncentracija polutanata u složenim procesnim sistemima, I Simpozijum inovacionih istraživanja - SINOVIS-2011,Palata Srbije, Beograd (2011) 122-128
[8] S.Stefanov, R.Biocanin, Modeling of pollutants at the landfill waste, 15th Symposium of Thermal Science and Engineering of Serbia, Soko Banja,Book of abstracts, Serbia (2011) 24
[9] Stefanov S., Biočanin R., Pavlovic S.Modeling of polutants CO, PM, PAH in accidental fire at the landfill waste, XI International conference - RaDMI-2011, Sokobanja, Serbia Vol 1 (2011). tefanov S., Biočanin R., Vojinovic Miloradov M. Ecological modeling of industrial pollutants-Serbian case, Journal of Enironmental protection and Ecology, SciBulCom Ltd, Sofia, Bulgaria (2011) .
[10] S.Stefanov, M.Vojinovic Miloradov, R.Biocanin, Ecological modeliling of pollutants in process industry, ICET 2011 &PEC-9, Faculty of Engineering PSU, Thailand (2011) p.202-208
[11] S.Stefanov, M.Vojinovic Miloradov, R.Biočanin, Š.Bančov , Monitoring industrijskih polutanata u vazduhu, Simpozijum sa medunardonim uaešaem Zaštita vazduha 2010, Subotica (2010).
[12] S.Stefanov, M.Vojinovic Miloradov, R. Biocanin, S.Sokolovic, Š.Bancov, The best available technologies for the control and reduction of pollutation, 10th International Conference "Research and Development in Mechanical Industry" RaDMI 2010, Donji Milanovac, Vol 2. (2010).
[13] S.Stefanov, M.Vojinovic Miloradov, R. Biocanin, S.Sokolovic, Š.Bancov, Monitoring of industrial pollutants in Oil and Petrochemical industry, 10th International Conference, -Research and Development in Mechanical Industry-RaDMI 2010, Donji Milanovac.
[14] Ketin S., (2018) Transport and environment, CESNA B, Bezbednost u postmodernom ambijentu-Kniiga XXVI, p.133-138
[15] Ketin S, Dasic P, Neskovic S, Kostic B, The technological process of solidification for the treatment of hazardous waste, Fresenius Environmental Bulletin (2016),Vol. 25; No. 1

15:15: [EnergyThuPM108] Keynote
The Role of the Energy Corporation in Driving to a Sustainable Future
David Christian¹ ; ¹Dominion Energy, Richmond, United States;
Paper Id: 259 [Abstract]

An Oral Presentation will be made describing the role of Energy Companies as a driving force toward a more sustainable future. Environmentally responsible and sustainable energy production is a grand challenge that must be met and one that is a necessary condition for addressing other grand challenges such as poverty, disease, water, hunger, etc. To date, much of the effort to address climate change and sustainable development has been concentrated in the government policy arena. While government policies and the attendant allocation of resources for research and development in these areas are necessary, they may not be sufficient. Public corporations have long recognized their responsibilities for what they do<i> for </i>society and for their impacts <i>to</i> society. [Drucker] Corporations are increasingly assuming a role that transcends mere compliance with their respective regulatory and policy frameworks and assuming leadership roles in driving forward to a more sustainable future. This trend's progress can accelerate in curbing societal contributions to climate change drivers such as CO ₂ and CH ₄ emissions. The presentation will recognize actions of several companies, and will have a sharper focus on Dominion Energy where the author is a CEO and Chief Innovation Officer.

SESSION: EnergyThuPM2-R11	6th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Thu Oct, 24 2019 / Room: Coralino
Session Chairs: Puzhen Gao; Sonja Stefanov; Session Monitor: TBA

15:55: [EnergyThuPM209]
Artificial Cellulase Type Catalysts for Processing Cellulosic Biomass
Ananda Amarasekara¹ ; ¹Prairie View A&M University, Prairie View, United States;
Paper Id: 329 [Abstract]

Depolymerization of cellulosic biomass to sugars is a challenging step and is the primary obstacle for the large scale processing of cellulosic biomass to biofuels and renewable feedstocks. Ionic liquids are well known for their ability to dissolve cellulose and our interest in the search for efficient catalytic methods for saccharification of polysaccharides has led us to develop –SO₃H group functionalized Brønsted acidic ionic liquids (BAILs) as solvents as well as catalysts [1]. Later we found that these sulfuric acid derivatives can be used as catalysts in aqueous phase as well. For example, BAIL 1-(1-propylsulfonic)-3-methylimidazolium chloride aqueous solution was shown to be a better catalyst than H₂SO₄ of the same [H⁺] for the degradation of cellulose [2]. This observation is an important lead for the development of a BAIL based cellulase mimic type catalyst for depolymerization of cellulose [3]. In an attempt to develop recyclable, simple enzyme mimic type catalysts, we have studied quantitative structure activity relationships (QSAR) of a series of BAIL catalysts and found that activity with different cation types decreases in the order: imidazolium > pyridinium > triethanol ammonium [4]. Furthermore, we have investigated the effects of selected metal ions on 1-(1-propylsulfonic)-3-methylimidazolium chloride BAIL catalyzed hydrolysis of cellulose in water at 140-170 °C. The total reducing sugar (TRS) yields produced during the hydrolysis of cellulose (DP ~ 450) in aq. 1-(1-propylsulfonic)-3-methylimidazolium chloride solution at 140 - 170 °C using Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺ Ni²⁺, Cu²⁺, Zn²⁺, and La³⁺ chlorides as co-catalysts were studied. Cellulose samples heated with Mn²⁺, Fe³⁺, Co²⁺ as co-catalysts produce significantly higher TRS yields compared to the sample heated without the metal ions. The highest catalytic effect enhancement is observed with Mn²⁺ and produced TRS yields of 59.1, 78.4, 91.8, and 91.9 % at 140, 150, 160, and 170 °C respectively, whereas cellulose hydrolyzed without Mn²⁺ produced TRS yields of 9.8, 16.5, 28.0, and 28.7 % at the same four temperatures. This is a 503, 375, 228, and 220 % enhancement in TRS yield due to the addition of Mn²⁺ as a co-catalyst to BAIL catalyzed cellulose hydrolysis at 140, 150, 160 and 170°C respectively. This paper will present the development of BAIL based artificial cellulase type catalysts, QSAR studies, catalyst immobilizations, applications on lignocellulosic biomass materials (corn stover, switchgrass, poplar) and recycling studies.

References:
1. A.S. Amarasekara et al., Ind. Eng. Chem. Res., 2009, 48(22), 10152.
2. A.S. Amarasekara et al., Ind. Eng. Chem. Res., 2011, 50(21), 12276.
3. A.S. Amarasekara et al., Cat.. Sci. Tech., 2016, 6, 426.
4. A.S. Amarasekara et al., Sustain. Energ., 2014, 2(3), 102.

16:20: [EnergyThuPM210]
Hydrogen Production via the Glycerol Steam Reforming using Ce-La-xCu Catalysts pt.2
Ayesha Alkhoori¹ ; Kyriaki Polychronopoulou¹ ; ¹Khalifa University, Abu Dhabi, United Arab Emirates;
Paper Id: 505 [Abstract]

An unintended consequence of the drive towards replacing petro-based sources in the transport sector and the subsequent growth of the biodiesel industry is the co-production of large amounts of crude glycerol (C₃H₈O₃) which constitutes the main by-product of the transesterification process [1-3]. A promising solution is its steam reforming since every mol of C₃H₈O₃ can theoretically produce 7 mol of H₂. Thus, research efforts are directed towards the discovery of cheap (i.e., transition metal based), highly active and stable catalysts. In the work presented herein, a series of Ce-La-xCu, (x=3, 5, 7, 10, 20 at.%) catalysts were evaluated for the glycerol steam reforming reaction in the 400-750^oC temperature range. Stability tests were conducted at 650^oC for 12h. The catalysts were prepared by coupling microwave radiation with the sol-gel method and BET, XRD, Raman, NH₃-TPD, CO₂-TPD, H₂-TPR, SEM, HAADF-STEM and XPS. These were used in order to derive information regarding their textural, morphological and physic-chemical properties to elucidate their effect on catalytic performance. The results obtained show that C₃H₈O₃ conversion of over 85% can be achieved with values for H₂ selectivity and approaches the yield of the thermodynamically predicted ones. The liquid effluents produced contained differing amounts of acetol, acetone, acetic acid, acrolein, allyl alcohol and acetaldehyde depending on the reaction temperature. Time-on-stream results, which were undertaken at more severe conditions, showed that all catalysts maintain quite a stable performance.

References:
[1] Papageridis, K.N.; Charisiou, N.D.; Siakavelas, G.; Avraam, D.G.; Tzounis, L.; Kousi, K.; Goula, M.A. Comparative study of Ni, Co, Cu supported on gamma-alumina catalysts for hydrogen production via the glycerol steam reforming reaction. Fuel Process. Technol. 2016, 152, 156-175.\n[2] Bepari, S.; Pradhan, N.C.; Dalai, A.K. Selective production of hydrogen by steam reforming of glycerol over Ni/Fly ash catalyst. Catal. Today 2017, 291, 36-46.\n[3] Goula, M.A.; Charisiou, N.D.; Pandis, P.K.; Stathopoulos, V.N. Ni/apatite-type lanthanum silicate supported catalyst for the glycerol steam reforming reaction. RSC Adv. 2016, 6, 78954-78958.

16:45: [EnergyThuPM211]
Roles of Ni, Co and Cu Monometallic Catalysts Supported on ZrO2 for Green Diesel Production via the Palm Oil Hydrodeoxygenation
Nikolaos Charisiou¹ ; Steven J. Hinder² ; Mark A. Baker² ; Kyriaki Polychronopoulou³ ; Maria A. Goula¹ ; ¹Laboratory of Alternative Fuels and Environmental Catalysis, Department of Chemical Engineering, University of Western Macedonia, Kozani, Greece, Kozani, Greece; ²The Surface Analysis Laboratory, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford, UK, Guildford, United Kingdom; ³Khalifa University, Abu Dhabi, United Arab Emirates;
Paper Id: 249 [Abstract]

Energy demand in the world is expected to increase by 59% by the year 2035 [1]. In addition, liquid transportation fuels from renewable resources are urgently needed due to the depletion of fossil resources. During the last 10 years intensive research efforts on biofuels, among them only green diesel, which can be synthesized either via catalytic hydrodeoxygenation or deoxygenation of triglycerides and fats, exhibits the same fuel properties as conventional diesel, since it has a similar composition. On the other hand, ethanol and butanol exhibit lower heating values and can suffer from incomplete burning thus forming oxygenated, harmful, gaseous by-products [2]. Moreover, biodiesel consisting of fatty acid methyl esters (FAMEs) has low oxidative stability, high viscosity and poor cold weather performance and is incompatible for large-scale use in conjunction with fossil fuels [3]. In the present work, we prepared ZrO₂-supported Ni, Co and Cu monometallic catalysts for the production of green diesel via hydrodeoxygenation of palm oil. The catalysts were prepared by the wet impregnation method and had the same metal loading (8 wt.%). The physical and chemical properties were determined by applying several characterization techniques including BET, XRD, NH3/CO2-TPD, TPR, XPS and TEM. Catalytic deoxygenation experiments were carried out in a fixed bed reactor (Autoclave Engineers BTRS) equipped with an HPLC pump. The SDO experiments were conducted using different operating parameters for the Ni/Zr catalyst, as follows: T=250-375°C, P=20-30 bar, LHSV=1.2-2.4 h^-1 and H₂/oil=250-2000 cm³/cm³, while for the Cu/Zr and Co/Zr samples the following operating parameters were used: T=300-400^oC, P=30 bar, LHSV=1.2 h^-1 and H₂/oil=1000 cm³/cm³. The results shows that the recommended conditions for the Ni/Zr were: I�=300 I�C, P = 30 bar, LHSV = 1.2 h^-1, H₂/oil ratio = 1000 cm³/cm³. Specifically, Palm oil was totally converted at 300 &#o176;C and the main reaction products were C₁₅ and C₁₇, with yields of 16 and 49 mol%, respectively, while C₁₅-C₁₈ n-alkane's yield was equal to 88 mol%. By comparing the three catalysts the deoxygenation activity decreased in the order of C₁₅-C₁₈ n-alkane's yield Ni > Cu > Co when compared at the same reaction temperatures. Also, to understand the roles of the three catalysts on the activity and selectivity in the deoxygenation reaction, the contributions of HDO and deCOx were estimated based on the mole balance corresponding to fatty acids in the oil feed. The Ni and Cu catalysts were favorable to the deCOx routes, whereas HDO was dominant over the Co catalyst.

References:
[1] X. Li, X. Luo, Y. Jin, J. Li, H. Zhang, A. Zhang, J. Xie, Renew. Sustain. Energy Rev. 82 (2018) 3762-3797.
[2] S. Douvartzides, N.D. Charisiou, K. N. Papageridis, M.A. Goula, Energies 12(5), 809 (2019).
[3] N.D. Charisiou, K. Polychronopoulou, A. Asif, M.A. Goula, Surf. Coatings Technol. (2018).

17:10: [EnergyThuPM212] Keynote
Cement Clinker Burning Process Simulation For Using Addition Of Some Wastes As Alternative Fuels For Improving Material And Energy Balances
Dhurata Premti¹ ; Klevis Golloshi² ; Erald Karakashi³ ; Ilirjan Malollari⁴ ; ¹Lecturer at the Department of Industrial Chemistry, University of Tirana, Tirana, Albania; ²Chemical Engineer at Cement Plant Fushe-Kruja, Albania, Kruje, Albania; ³Plant Management Engineer,, Kruje, Albania; ⁴University of Tirana-Faculty of Natural Science, Tirana, Albania;
Paper Id: 458 [Abstract]

Cement technology is very traditional and the basic principles have remained unchanged for a long time. However, very profound changes in the production techniques were introduced recently, leading to the diminishing of energy consumption. <br />Energy cost has affected manufactures to evaluate the substitution of conventional fuels with alternative fuels, i.e. processed waste. To be able to use alternative fuels as; waste oils, plastics, waste tire, sewage sludge, etc. it is necessary to know the composition of these alternative materials. So, the usage of waste organic materials affects the thermal energy in the heated furnace. It was used as an example of applying the results of this study in a cement production plant in Albania, which has started a strategy for the real studies allowing to use other alternative fuels. <br />In this study was used Aspen Plus simulation software to test the possibility for improving the energy performance of cement clinker burning oven process, while maintaining the same product quality. <br />For this purpose, were used data from real production practice. Mixtures of various organic materials were tested with Aspen Plus simulation software. <br />The results of different alternative material were compared with conventional materials such as oil, diesel, heavy oil, gas, etc. On the other hand, from the simulation results, it was identified as the most effective fuel source to minimize the material and energy cost.

SESSION: BatteryFriAM-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katerina Aifantis; Rumen Tomov; Session Monitor: TBA

11:20: [BatteryFriAM01]
Future Thinking in Batteries
Vasant Kumar¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 336 [Abstract]

Given the massive shifts facing the future energy-environment paradigm, it is pertinent to evaluate the centrality of “New Thinking” within this energy-environment [1] nexus in the evolving scenario. This paper will look into aspects of energy storage, advanced materials [2] and environmental issues in electric grids, transportation, renewable energy, and resources. It is generally agreed that 2D-based materials have a bright future in electrochemical energy devices as they can combine good electrical conductivity & connectivity with a suitable porous structure that is able to facilitate rapid redox reactions. 2D materials are combined with other electroactive components for optimal synergy. A number of approaches for making the electrode structure will be presented. Recycling and recovery of upgraded materials from spent batteries are crucial considerations for the future use of batteries. A number of factors including future research trajectories and resources strategy issues will be considered.

References:
1. Leapfrogging to sustainable power, R.V. Kumar, Chapter in “Smart Villages: New Thinking for Off-Grid Communities Worldwide; Published by Banson (Lavenham Press, UK), 2015, pp. 35-41; ISBN 978-0-9932932-0-7(paperback); 978-0-9932932-1-4 (hardback)
2. “High Density Energy Lithium Batteries”; KE Aifantis, SA Hackney and RV Kumar (Editors), Wiley-VCH Verlag, 2010.

11:45: [BatteryFriAM02] Keynote
Flux-grown Crystals Science and Engineering toward Next-generation Batteries
Katsuya Teshima¹ ; ¹Shinshu University, Nagano, Japan;
Paper Id: 149 [Abstract]

Lithium ion batteries (LIBs) have been widely used as energy-storage systems for a variety of power devices. It is necessary to further develop LIBs toward high-functional devices, such as electric vehicles and mobile electronics. Nowadays, all-solid-state LIBs have been of much interest because of high energy densities and high safety. All solid-state LIBs gave a lot of advantages in terms of size, flexibility, cost, and performance. In the case of oxide-type all-solid-state LIBs, however, there are serious problems to be solved toward practical uses. For example, diffusion of lithium ions at their interfaces between different solid materials is still too poor to operate charge/discharge in batteries. Our group has studied high-quality crystals for applications as energy and environmental materials by using a flux method. The flux method is a nature-mimetic liquid-phase crystal growth technique. It is possible to construct a molten reaction field at any temperature with facile setup, and give a designed shape to crystals, including crystal faces, which has never been achieved using other methods like solid state reactions. Recently, we have proposed and applied the flux technique to battery materials to create “all-crystal (solid)-state LIBs”. We have expected that flux crystal growth gave (I) crystal-shape controls of active materials (and solid electrolytes), (II) construction of good interfaces in electrodes among cathodes, and (III) solid electrolytes and anodes. As a result, smooth ionic transportation through bulks and their interfaces would be realized in all-crystal (solid)-state LIBs. Our concept of using the flux crystal growth method would provide new aspects to make innovations in oxide-type all-solid-state LIBs as next-generation energy storage. The details of material and interfacial designs for next-generation batteries will be introduced in the SIPS2019. Acknowledgement: This research was partially supported by MEXT-Regional Innovation Ecosystems, JST-CREST (JPMJCR1322), JSPS Grant-in-Aid for Scientific Research (A) (25249089&17H01322) and JST-ALCA.

References:
(1) Hiromasa Shiiba, Nobuyuki Zettsu, Satoru Kida, Dae-wook Kim, Katsuya Teshima, Journal of Materials Chemistry A, 6 (2018) 22749-22757.
(2) Hiromasa Shiiba, Nobuyuki Zettsu, Miho Yamashita, Hitoshi Onodera, Randy Jalem, Masanobu Nakayama, Katsuya Teshima, The Journal of Physical Chemistry C, 122 (2018) 21755-21762.
(3) Dae-wook Kim, Shuhei Uchida, Hiromasa Shiiba, Nobuyuki Zettsu, Katsuya Teshima, Scientific Reports, 8 (2018) 11771_1-9.

12:10: [BatteryFriAM03] Invited
Na-Ion Batteries for Large Scale Applications: Challenges and Opportunities
Teofilo Rojo¹ ; ¹CIC energiGUNE, Vitoria-Gasteiz, Spain;
Paper Id: 92 [Abstract]

With the ever-increasing demands of modern societies, energy generation, storage, and distribution are becoming increasingly important research fields. Currently, one of the most promising areas of research and development is sodium ion battery (SiB) technology, which has a range of potential applications, but remains particularly suited for use in stationary systems. Here we will discuss SiB systems in terms of what may be considered its three most significant components: anodes, electrolytes, and cathodes. SiB anodes are mainly based on hard carbon materials, due to their attractive combination of low cost and high energy density. However, there has also been interest in other systems, such as intermetallic alloying materials and metal oxides, as well as exploitation of specific electrolyte co-solvation effects, so as to enable the use of graphite. In general, the SiB research community uses organic electrolytes which are analogous to already existing Lithium ion batteries (LiB). Recently, however, there has been growing interest in developing new electrolytes which are specifically tailored for use in SiBs, such as optimized liquid and solid electrolytes. At the present time, cathodes are one of the most explored SiB components with a plethora of options to choose from, including Prussian blue and organic materials. The most promising are polyanionic and layered materials, with their good combinations of electrochemical performance, low cost, stability and available constituents. Although interest in SiB technology is only relatively new, when compared to LiBs, it has been already developed at the prototyping level. A general overview of the most interesting electrode and electrolyte materials for Na-ion batteries, paying special attention to those related to the current prototypes, will be presented. By examining this topic in detail, it will be shown that there exists a strong drive to exploit this technology and that there are a wide range of opportunities to develop new and improved SiB technologies.

12:35: [BatteryFriAM04]
Novel Carbon - Ultrafine Silicon Composite Anode for High-Performance Lithium-Ion Batteries
Dmitry Yarmolich¹ ; Dzianis Yarmolich² ; Yaroslav Odarchenko³ ; Carmen Murphy⁴ ; Enrico Petrucco⁴ ; Vasant Kumar⁵ ; Rumen Tomov⁵ ; ¹Plasma App Ltd, OX11 0QX, United Kingdom; ²Plasma App Ltd, Oxford , OX11 0QX, United Kingdom; ³Plasma App Ltd, Oxford OX11 0QX, United Kingdom; ⁴Johnson Matthey Battery Materials, Reading RG4 9NH, United Kingdom; ⁵University of Cambridge, Cambridge, United Kingdom;
Paper Id: 352 [Abstract]

Silicon (Si) has been widely considered as potential high capacity anode material in Li-ion batteries due to its desirable properties: (i) high theoretical specific capacity (1672 mA h g-1), (ii) nontoxicity and (iii) low cost and natural abundance [1]. Despite its favourable comparison to commercial graphite anodes (theoretical capacity of 372 mA h g-1), the implementation of bulk Si anode has been hindered by the large volume change during the charging and discharging cycle (~ 300%). Such structural instability results in loss of contact with the other electrode constituents and self-destruction [2]. Another adverse feature is the limited Li⁺ ion diffusivity and electronic conductivity of bulk Si at room temperature. A scalable method of producing carbon (ultrafine silicon composite electrode) was developed using the Virtual Cathode Deposition technique [3]. As-deposited coatings contained silicon nano-crystallites encapsulated in a novel polymorph of mesoporous disordered carbon matrix. The architecture of the electrode offers close-order integration of both materials ensuring fast Li⁺ ion diffusivity and mixed-(ionic/electronic) conductivity as well as alleviating Si volume change during cycling. The composite carbon polymorph-silicon anode tested versus Li displayed a first cycle specific capacity of more than 2000 mAh g^-1 retaining in the following cycles ~1200 mAh g^-1 at a 0.1C rate. The good cyclability (over 80 cycles) demonstrated the effectiveness of such Si - carbon encapsulation, addressing the instability issues of Si-based anodes.

References:
[1] P. G. Bruce, S. A. Freunberger, L. J. Hardwick and J. M. Tarascon, Nat. Mater., 2012, 11, 19–29.
[2] Li B, Xiao Q, Luo Y (2018) A modified synthesis process of three dimensional sulfur/graphene aerogel as binder-free cathode for lithium-sulfur batteries. Mater Des 153:9–14
[3] D. Yarmolich, D. Virtual cathode deposition (vcd) for thin film manufacturing WO2016042530A1. (2015).

SESSION: BatteryFriPM1-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Guoran Li; Claudio Capiglia; Session Monitor: TBA

14:00: [BatteryFriPM105]
Feasibility of a Physical Vapor Deposition technology for battery electrode manufacturing
Dmitry Yarmolich¹ ; Rumen Tomov² ; Vasant Kumar² ; Carmen Murphy³ ; Yaroslav Odarchenko⁴ ; Dzianis Yarmolich⁵ ; Enrico Petrucco³ ; ¹Plasma App Ltd, OX11 0QX, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom; ³Johnson Matthey Battery Materials, Reading RG4 9NH, United Kingdom; ⁴Plasma App Ltd, Oxford OX11 0QX, United Kingdom; ⁵Plasma App Ltd, Oxford , OX11 0QX, United Kingdom;
Paper Id: 504 [Abstract]

The method of physical vapor deposition has been tested for the manufacture of electric vehicle lithium-ion battery anodes. The anode was fabricated using Virtual Cathode Deposition1 (VCD) which enables direct deposition of 20 μm thick carbon active material onto a 25 μm polypropylene separator, followed by deposition of a 2 μm copper current collector. Carbon polymorphism2 induced by the deposition process is responsible for active material high gravimetric and volumetric capacity allowing anode areal capacity up to 4.2 mAh/cm2 at the 0.1 C charge rate. The PVD process increases the purity of active materials and quality control compared to the state-of-the-art wet chemical3 method. Currently, the production of a 24 kWh Nissan Leaf’s battery pack requires about 25 MWh, more than 80% of which is spent on drying the electrodes and dry room conditioning. VCD eliminates use of solvents that saves the energy for electrode drying and increase the environmental safety of battery production.

References:
1. Yarmolich, D. Patent No. WO2016042530A1 (September 2014).
2. Zhao, C. X., Niu, Ch. Y., Qin, Z-J., Ren, X. Y., Wang, J-T., Cho J.H. and Jia, Y. H18Carbon: A New Metallic Phase with sp2-sp3 Hybridized Bonding Network. Sci. Rep. 6, 1–9 (2016).
3. A. Sakti , J. J. Michalek, E. R.H. Fuchs, Jay F. Whitacre., A techno-economic analysis and optimization of Li-ion batteries for light-duty passenger vehicle electrification. Journal of Power Sources 273 (2015)
4. C. Yuan, Ye. Deng, T. Li, F. Yang, Manufacturing energy analysis of lithium ion battery pack for electric vehicles, CIRP Annals - Manufacturing Technology 66 (2017)

14:25: [BatteryFriPM106] Keynote
NovoPb: A New, Complete and Sustainable Recycling Process for High-Purity Lead Oxide
Deise Menezes Santos¹ ; Francklin Jonas De Paula² ; Yandiara Larissa Barros³ ; Matheus Carvalho⁴ ; Wanderson Souza Da Silva⁵ ; Vasant Kumar⁶ ; ¹Universidade Federal do Espírito Santo, Vitoria, Brazil; ²Faculdade Pitagoras, Governador Valadares, Brazil; ³Instituto Federal do Espirito Santo, Vitoria, Brazil; ⁴Instituto Federal de Minas Gerais, Governador Valadares, Brazil; ⁵Universidade Federal do Espirito Santo, Vitoria, Brazil; ⁶University of Cambridge, Cambridge, United Kingdom;
Paper Id: 258 [Abstract]

Pyrometallurgical recycling of lead-acid battery (LAB) produces high-purity metallic lead (99.99% purity) through an energy-intensive and polluting process (1). The alternative hydrometallurgical method directly recovers lead oxide from spent lead paste, although many impurities may not be removed. We have experienced a breakthrough success in NovoPb, an ongoing project to implement a sustainable LAB recycling process in a 1 ton capacity pilot plant at Minas Gerais in Brazil(2). During NovoPb, a 3-step hydrometallurgical process was used for synthesis of high-purity leady oxide derived from spent LAB samples of industry pastes. Dessulfuration with NaOH, followed by acetic acid and H₂O₂ leaching of LAB paste removed the impurities and generated pure lead acetate solution (3), a blank canvas. A lead complex with citric acid(4) was formed to remove lead from the solution in order to produce a high-purity nanostructured leady oxide, by calcining it at a much lower temperature (350°C) than usual smelted lead (1200°C), saving energy and reducing hazardous gas emissions. The characterization of the 10 LAB pastes were performed by XRD, XRF, SEM/EDS and basic chemical analysis to successfully reproduce 20 recycling experiments at the laboratory. Factorial design was applied to determine optimal reaction conditions. 2.5 kg of lead citrate were synthesized and characterized by TGA, XRD, and SEM, then calcined to obtain leady oxide. Acid absorption, BET surface area, SEM/EDS, XRD and ICP-OES results show nanostructured leady oxide, 99,9% purity, with larger surface area and acid absorption than a lead oxide produced by traditional ball mill process. This research is part of the Embrapii project of the Vitoria Innovation Center of the Federal Institute of Espirito Santo, in partnership with the University of Cambridge, Innovate UK, Brazilian companies Tudor MG de Baterias, Antares Reciclagem LTDA, Embrapii and the British company, Aurelius Environmental.

References:
1. Ballantyne AD, Hallett JP, Jason D, Shah N, Payne DJ, Payne DJ. Lead acid battery recycling for the twenty-first century. Royal Society Open Science: 2018;
2. Ifes. Polo de Inovação firma convenio com empresas para implantar processo mais limpo na reciclagem de baterias [Internet]. 2018. Available from: https://www.ifes.edu.br/noticias/17758-polo-de-inovacao-firma-convenio-com-empresas-para-implantar-processo-mais-limpo-na-reciclagem-de-baterias
3. Yu W, Yang J, Li M, Hu Y, Hou H, Vasant R. A facile lead acetate conversion process for synthesis of high-purity alpha-lead oxide derived from spent lead-acid batteries. Society of Chemical Industry: 2018;(July).
4. Kumar RV. LEAD RECYCLING. UNITED KINGDOM; WO 2008/056125 A1, 2008. p. 35.

14:50: [BatteryFriPM107]
Adjustable Interlayer Spacing for Layered Titanate for Potassium Storage
Cheng-yen Lao¹ ; Vasant Kumar¹ ; Yingjun Liu¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 343 [Abstract]

Potassium-ion batteries (KIBs) are promising substitutes for lithium-ion batteries (LIBs) in grid-scale energy storage due to the Earth-abundancy of potassium [1]. Practical KIB applications, however, are hindered by slow diffusion kinetics and severe structural deterioration as the large cation is cycled in and out of the electrode, respectively leading to low specific capacity and short lifetime [2]. Herein we synthesize layered alkali titanates as electrode materials for KIBs by chemical reaction between nanoparticles and aqueous alkali hydroxides. By increasing the interlayer spacing of titanates, we show improvements in electrochemical performances in terms of specific capacity, charging rate and cycle life. Larger interlayer spacing allows quick and increased ion storage [3]. The adjustment of reaction temperature, concentration and types of hydroxides has direct effects on the interlayer spacing of these titanates. As a result, we have produced a range of alkali titanates with different interlayer spacing. Some as-prepared titanates with larger interlayer spacing deliver electrochemical performances for KIBs comparable to titanium-oxide based LIBs [4], [5]. Our work provides a method to design future energy storage electrode materials for large ions.

References:
[1] W. Zhang, Y. Liu, and Z. Guo, “Approaching high-performance potassium-ion batteries via advanced design strategies and engineering,” Sci. Adv., vol. 5, no. 5, p. eaav7412, May2019.
[2] T. A. Pham, K. E. Kweon, A. Samanta, V. Lordi, and J. E. Pask, “Solvation and dynamics of sodium and potassium in ethylene carbonate from ab Initio molecular dynamics simulations,” J. Phys. Chem. C, vol. 121, no. 40, pp. 21913–21920, Oct.2017.
[3] J. Yang et al., “Size-independent fast ion intercalation in two-dimensional titania nanosheets for alkali-metal-ion batteries,” Angew. Chemie Int. Ed., vol. 58, no. 26, pp. 8740–8745, Jun.2019.
[4] J. Liu, J. S. Chen, X. Wei, X. W. Lou, and X.-W. Liu, “Sandwich-like, stacked ultrathin titanate nanosheets for ultrafast lithium storage,” Adv. Mater., vol. 23, no. 8, pp. 998–1002, Dec.2010.
[5] J. Ma et al., “Layered lepidocrocite type structure isolated by revisiting the sol–gel chemistry of anatase TiO2: A new anode material for batteries,” Chem. Mater., vol. 29, no. 19, pp. 8313–8324, Oct.2017.

15:15: [BatteryFriPM108]
Inkjet Printing of PEDOT/PEO Semi-Interpenetrating Networks for Highly Scaleable Supercapacitor Electrodes
Paulina Librizzi¹ ; Vasant Kumar² ; ¹University of Cambridge - Department of Materials Science and Metallurgy, Cambridge, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom;
Paper Id: 411 [Abstract]

A semi-interpenetrating network of PEDOT and PEO was used as a highly effective supercapacitor electrode. Wang and co-authors in 2017[1] detailed a process in which an semi-interpenetrating polyethylenedioxythiophene/polyethylene oxide (PEDOT/PEO) network with mixed ionic and electronic conductivity could be synthesized in a simultaneous fashion[1]. The ionically conducting PEO was phase separated with the electronically conductive PEDOT, leading to a larger triple phase boundary and thus a higher capacity[1,2]. The phase separation of PEDOT and PEO also allowed for mechanical robustness and increased cycling ability[1]. While these films represent a significant step forward for flexible electronics, solution casting, the current fabrication process, is not suitable for large scale production. In this work, films of this interpenetrating polymer network were made through inkjet printing[3]. The viscosity of the polymer precursor is 31 cP, at the upper limit of what a typical inkjet printhead can handle (~20 cP)[3,4]. The raw prepolymer also displays shear thinning behavior, dropping linearly to 21 cP between shear rates of 130 and 210 s-1. To make a more suitable precursor for inkjet printing, ethanol was added to decrease the viscosity of the precursor. Ethanol is a commonly used solvent for inkjet printing as is has an optimal viscosity (1.1 cP at STP), low vapor pressure, and good wetting properties. Additionally, ethanol is not known to polymerize via free-radical polymerization[5] and will not compromise the chemical integrity of the interpenetrating network [5]. Ethanol is a relatively safe organic solvent and is soluble in the precursor. It is also soluble in methanol, which is used in the initial polymer processing to clear away excess unpolymerized precursor. Cyclic voltammograms of both neat and inkjet printed films in an aqueous LiClO4 electrolyte with a platinum counter electrode and an Ag/AgCl reference electrode were taken. The results of the two cyclic voltammograms were comparable and showed a similar capacitance.

References:
1. Fong, K. D., Wang, T., Kim, H.-K., Kumar, R. V. & Smoukov, S. K. Semi-Interpenetrating Polymer Networks for Enhanced Supercapacitor Electrodes. ACS Energy Lett. 2014–2020 (2017). doi:10.1021/acsenergylett.7b00466.
2. Ghosh, S. & Inganäs, O. Networks of Electron-Conducting Polymer in Matrices of Ion-Conducting Polymers Applications to Fast Electrodes. Electrochem. Solid-State Lett. 3, 213 (1999).
3. Magdassi, S. et al. The Chemistry of Inkjet Inks. (World Scientific Publishing Co. Pte. Ltd., 2009). doi:10.1142/6869
4. Magdassi, S. Ink Requirements and Formulations Guidelines. in The Chemistry of Inkjet Inks 19–41 doi:10.1142/9789812818225_0002.
5. Hazrati, H. D., Whittle, J. D. & Vasilev, K. A Mechanistic Study of the Plasma Polymerization of Ethanol. doi:10.1002/ppap.201300110

SESSION: BatteryFriPM2-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Katsuya Teshima; Deise Menezes Santos; Session Monitor: TBA

15:55: [BatteryFriPM209]
Production of Ultra-Pure Lead Citrate from Spent Lead-Acid Battery Paste using a Cost-Effective, Eco-Friendly Process
Vimalnath Selvaraj¹ ; Marcel Yiao¹ ; Robert Liu² ; Rumen Tomov¹ ; Vasant Kumar¹ ; Peter Knight¹ ; Steve Andrew² ; Spencer Lowe² ; Athan Fox³ ; Miles Freeman² ; Johdie Harris² ; ¹University of Cambridge, Cambridge, United Kingdom; ²Aurelius Environmental, Dudley, United Kingdom; ³Aurelius Environmental, Tipton, United Kingdom;
Paper Id: 415 [Abstract]

Abstract The recovery of Pb from the spent lead-acid battery paste is achieved conventionally through pyrometallurgical processes. This process requires relatively high temperature (~1,100 °C) for the decomposition of PbSO4 which is a dominant compound in the paste along with PbO2, PbO, metallic Pb and other impurities. The high-temperature pyrometallurgical process releases SO2 gas and Pb particulates into the environment, raising serious environmental concerns. The hydro-electro metallurgical process, which has been developed as an alternative, also consumes high energy and uses toxic acids like HBF4 or H2SiF6. The need for an eco-friendly and cost-effective recycling process for the recovery of spent battery paste [1,2,3,4], is not only critical but also very timely. Indeed, the market size of secondary lead-acid batteries is forecasted to reach over $95 billion USD by 2026 [5]. Within this market, the recycling of lead-acid batteries is a revenue stream worth around $14-16 billion USD by 2025 [6]. In this paper, we present our work towards a fully hydrometallurgical, eco-friendly and cost-effective process. The recovery of Pb is achieved through the synthesis of ultrapure lead-citrate, which is obtained directly from spent lead-acid battery paste via desulphurisation and treatment with organic acids. Unlike previous iterations of this process, we have optimised the conditions to achieve production of ultra-pure lead-citrate, 99.99%, with minimum consumption of reagents. This paper shows how it is possible to minimise production costs for the recycled lead compounds to the extent that the process is as cost-effective, if not superior economically, when compared to the incumbent technology. The scalability and economic improvement of the latest iteration of this now-patented hydrometallurgical process greatly facilitate the globalisation of this innovative technology. Keywords Lead, battery, recycling, lead citrate, hydrometallurgy, organic acids

References:
References
[1] Sonmez, M. S., and R. V. Kumar, Hydrometallurgy 95.1-2 (2009) 53-60.
[2] Sonmez, M. S., and R. V. Kumar, Hydrometallurgy 95.1-2 (2009) 82-86.
[3] Yang, Jiakuan, Ramachandran Vasant Kumar, and Deepak P. Singh, Journal of Chemical Technology & Biotechnology 87.10 (2012) 1480-1488.
[4] Zhu, X., He, X., Yang, J., Gao, L., Liu, J., Yang, D., Sun, X., Zhang, W., Wang, Q. and Kumar, R.V, Journal of Hazardous Materials 250 (2013) 387-396.
[5] https://www.reportsanddata.com (report ID RND_00104)
[6] https://www.cambridgeindependent.co.uk/business/cambridge-battery-recycling-technology-set-to-disrupt-global-market-9052189/

16:20: [BatteryFriPM210] Keynote
Overview on Lithium Sulphur Batteries Technologies
Claudio Capiglia¹ ; ¹Recruit R&D, Tokyo, Japan;
Paper Id: 15 [Abstract]

Li-ion technology might have reached its limit especially when it comes to the energy requirements for the next generation of electric vehicles (EVs) and hybrid electric vehicles (HEVs). Lithium-sulphur batteries could represent a good alternative because they have higher theoretical energy than conventional lithium-ion batteries and are a good candidate for application in the growing e-mobility and stationary market. There are, however, technical issues which should be properly addressed, such as the low conductivity and the large volume variation of sulphur, as well as the formation of polysulphides during cycling, especially, the back and forth movement of polysulphides between cathode and anode, known as the shuttle effect. In this presentation, a systematic description of the approach which aims at mitigating these issues is overviewed and the electrochemical performances associated with the different proposed solutions are discussed. To better understand the failure mechanisms of lithium-sulphur batteries, important novel characterization techniques applied to energy storage systems are also reviewed. Finally, the state of the art of lithium-sulphur batteries technology is presented from a geopolitical perspective by providing a comparison between the results achieved in this field by the main world industrial and academic actors, namely Asia, North America, and Europe [1,2]

References:
[1] A comprehensive understanding of lithium-sulphur battery technology" C. Capiglia et al. Journal Advanced Functional Materials. Submitted.
[2] Comprehensive understanding lithium-sulphur batteries: current status and outlooks, Advanced Battery Materials, Capiglia et al., 355-398, Chunwen Sun (ed.), 2019 WILEY-Scrivener Publishing LLC, USA.

16:45: [BatteryFriPM211] Invited
Size Effects in Nanostructured Li-Ion Batteries
Sundararajan Natarajan¹ ; Katerina Aifantis² ; ¹Indian Institute of Technology Madras, Chennai, India; ²University of Florida, Gainesville, United States;
Paper Id: 355 [Abstract]

Materials such as Si, Al and Sn are considered as active sites during the formation of Li-alloys. During the Li insertion, the volume of the active sites expands over 100\% at maximum capacity. As a result, large internal stresses are produced. The effect of stresses is widely acknowledged. As the size of these particles is small, however, the gradient effects cannot be ignored. In this paper, we present, for the first time, the size effects within a purely gradient elasticity framework. A coupled mechanical equilibrium and Li diffusion accounting for the effect of stress on diffusion and the effect of diffusion on stress are considered. We also consider the effect of concentration on the Young's modulus. As the constitutive equation involves higher order gradient terms, the conventional finite element method is not suitable. Moreover, the two-way coupling necessitates the need for higher order shape functions. In this study, we employ B-spline functions with the framework of the iso-geometric analysis for spatial discretization. The effect of internal characteristic length on the concentration evolution and the hydrostatic stresses are studied. It is observed that the internal length has significant impact on the stress amplitudes.

17:10: [BatteryFriPM212]
Graphene-based lithium-sulfur batteries
Liam Bird¹ ; Kai Xi¹ ; Cheng-yen Lao¹ ; Vasant Kumar¹ ; Andrea Ferrari¹ ; Caterina Ducati¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 453 [Abstract]

Lithium-sulfur (Li-S) batteries have a theoretical capacity of 1675 mAhg^-1[1], five times that of conventional Li-ion batteries[2], facilitated by the sulfur cathode undergoing a series of redox reactions to form lithium polysulfides (PS)[3]. However, the continuous diffusion of PS through the electrolyte results in progressive loss of electrical contact to the active material and hence poor capacity retention with repeated cycling[4, 5]. A lightweight, electrically conductive host framework compatible with scalable manufacture is therefore required to exploit sulfur’s low cost and abundance[6] in batteries with sustained high capacity. Templated mesoporous carbons, including CMK-3, are electronically conductive and have a hierarchical porous structure suitable for constraining PS[7]. However, graphene and related materials (GRMs) are compatible with higher throughput manufacturing processes[8]. In addition to high conductivity[8], mechanical strength[8], and surface area, GRMs offer opportunities for tunable functionalisation to increase PS binding energy to the host framework[9]. Here, we investigate the use of graphene nanoplatelets synthesised by microfluidization[10] (GNPs) and graphene oxide (GO) with CMK-3 as composite sulfur hosts for Li-S batteries. We find that a composite of GNPs and CMK-3 improves the capacity of Li-S batteries, and that a composite of GO and CMK-3 improves the capacity retention of batteries for the first ~100 cycles, compared to CMK-3 alone in identical conditions. The incorporation of GNPs appears to enhance the contribution of long-chain PS (Li2Sx for 4≤x≤8) to the cell’s capacity, demonstrating improved constraint of this active material in contact with the conducting host. This improves the cycling capability of Li-S batteries, facilitating their application in electric vehicles and grid-scale renewable energy storage.

References:
1 J. R. Akridge, et al. Solid State Ion. 175, 243 (2004)
2 K. Mizushima, et al. Mater. Res. Bull. 15, 783 (1980)
3 E. Peled, J. Electrochem. Soc., 136, 1621 (1989)
4 Y. V. Mikhaylik et al., J Electrochem. Soc. 151, A1969 (2004)
5 S.-E. Cheon, et al., J. Electrochem. Soc. 150, A796 (2003)
6 A. Manthiram, et al., Chem. Rev. 114, 11751 (2014)
7 X. Ji, K. T. Lee, L. F. Nazar, Nat. Mater. 8, 500 (2009)
8 A. C. Ferrari, et al. Nanoscale, 11, 4598 (2015)
9 X. Zhou at al. J. Power Sources 243, 993 (2013)
10 P. G. Karagiannidis et al. ACS Nano 11, 2742 (2017)

SESSION: BatteryFriPM3-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Fri Oct, 25 2019 / Room: Coralino
Session Chairs: Vimalnath Selvaraj; Teofilo Rojo; Session Monitor: TBA

17:50: [BatteryFriPM313] Plenary
Metallic 2D Materials for Energy Storage
Manish Chhowalla¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 406 [Abstract]

Two dimensional (2D) materials provide well-defined ion diffusion pathways for sodium and other ions, facilitating ion insertion and movement, which is difficult to achieve in conventional 3D electrode materials. As a result, high power densities can be achieved in 2D electrodes with rapid ion and electron transport. Although heavier than lithium, Na+ and K+ have key advantages in addition to their lower price – their lower desolvation energy, compared to smaller Li+, improves kinetics of ion insertion into the electrode and may lead to higher power. Multivalent ions, such as Mg2+ and Al3+, may store 2 – 3 electrons per ion, but their movement in 3D bulk or porous solids is restricted due to the limited lattice space, leading to slow charge/discharge processes and inferior stability of charge storage devices. Metallic 2D materials offer distinct advantages for battery electrodes. They are: i) highly conductive, with high density of states at the Fermi level and metal-like carrier densities; ii) chemically diverse and tailorable, allowing for systematic variation of both their intrinsic composition and their post-synthetically modified surface chemistry; iii) exceptionally rigid, with bending stiffness values comparable to graphene that are ideally suited for flexible energy storage devices; and iv) hydrophilic, allowing for co-assembly with polar species and enabling sustainable, green processability. These attributes make them especially promising for next-generation of rechargeable batteries with improved storage capability, faster charging and much longer lifetimes, even when combined with larger and higher charged ions. In this presentation, I will present our recent progress on synthesis of battery electrodes with metallic 2D materials and their performance as supercapacitors, electrochemical actuators and batteries.

18:15: [BatteryFriPM314] Invited
Molten Salt Preparation of Nanostructured Materials for Energy Applications
Ali Reza Kamali¹ ; ¹Energy and Environmental Materials Research Centre (E2MC), School of Metallurgy, Northeastern University, Shenyang 110819, China;
Paper Id: 417 [Abstract]

Molten salts are very promising fluids for their various properties, and have historically been used for industrial production of metals such as aluminum with an annual production of more than 60 million tons. During the recent 20 years, new generations of molten salt technologies have been developed through breakthrough in research. These technologies are very attractive since they offer scalable techniques for green and/or efficient production of advanced materials from metals and nanodiamonds to functional nanostructures for many high-value applications. In this talk, the molten salt preparation of graphene and graphene-based composites and their applications in energy storage devices are discussed. Particular attention will be paid to our recent experimental studies on facile preparation of high quality carbon nanostructures, and their composites for use as the electrode materials of supercapacitors and lithium ion batteries.

References:
1. A.R.Kamali, Carbon 123 (2017) 205.
2. A.R.Kamali, J. Ind. Eng. Chem.52 (2017) 18.
3. Z.K. He et al., J. Alloy. Compd. (2019) 1213.
4. A.R. Kamali, Green Chem. 18 (2016) 1952.
5. A.R. Kamali et al., J. Mater. Chem. A 5 (2017) 19126.
6. K.Xie, A.R.Kamali, Green Chem. 21 (2019)198.
7. A.R. Kamali, Appl. Surf. Sci.476 (2019) 539-551.

SESSION: BatterySatAM-R11	6th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Sat Oct, 26 2019 / Room: Coralino
Session Chairs: Vasant Kumar; Ali Reza Kamali; Session Monitor: TBA

11:20: [BatterySatAM01]
Surface and Interface phenomena for Electrochemical Energy Storage
Hervé Martinez¹ ; ¹Université de Pau et des Pays de l'Adour - IPREM CNRS UMR 5254, Pau, France;
Paper Id: 158 [Abstract]

The study of surfaces and interfaces is one of the main fields of material science. This domain requires specific techniques of surface analysis such as X-ray Photoelectron Spectroscopy (XPS), Auger Electron Spectroscopy (AES), Secondary Ion Mass spectrometry (TOF-SIMS) or Scanning Probe Microscopies (AFM a�� STM). In this field, surface and interface phenomena occurring in Li(Na, Mg, Ka��.) batteries during cycling (including liquid or solid electrolyte) play a key role for their performances. Solid Electrolyte Interphase (SEI) formed upon cycling leads to a double-edged problematic: its formation lowers the coulombic efficiency and causes irreversible capacity loss, but it also passivates the electrode from the electrolyte and prevents further aging processes. The present talk aims to obtain new sets of information on the in-depth spatial distribution of SEI species within the electrode over cycling by ToF-SIMS (surface and depth-profile experiments), XPS (using Ag source to increase the depth of analysis compared with the conventional Al source) and Auger Spectroscopy. Several systems were considered to illustrate this talk: First is the study of Full cells as Li4Ti5O12(LTO)/LiNi3/5Co1/5Mn1/5O2 (NMC) and LTO/LiMn2O4 (LMO). The interactions between the two electrodes during cycling are investigated, especially the deposition and insertion of metallic compounds within the LTO electrode, which can directly influence on the stability of the cells and their electrochemical performances. More specifically, we focus this presentation on the results obtained by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Although ToF-SIMS is a recent surface analysis method in the field of battery materials, measurements acquired with this technique could give in-depth elemental and molecular information about the interfacial layers through sputter-depth-profiling experiments. Thanks to a high sensitivity and 2 D and 3D imaging capability, it will be particularly useful to follow the deposition of low amounts of metallic species and especially manganese within the SEI layer. Moreover, the evolution of the SEI chemical composition and spatial distribution upon cycling is also reported to better understand the protective role of the SEI. Secondly, surface modification of LTO, by synthetizing a chemisorbed thin fluorinated layer upon Li4Ti5O12 (LTO) anode material is considered to manage the passivating power of the SEI leading to enhanced electrochemical performances. Overall, this talk presents the relation between electrochemical performances of Li batteries and surface and interface phenomena.

References:
Nicolas Gauthier et al. Journal of The Electrochemical Society, 165(13): A2925-A2934, 2018.

11:45: [BatterySatAM02] Invited
The Anode Electrodes for Potassium-Ion Batteries
Zelang Jian¹ ; ¹Wuhan University of Technology, Wuhan, China;
Paper Id: 441 [Abstract]

The poor lithium resources and high cost limited the application of lithium-ion batteries in energy storage. Due to the low cost and similar electrochemical performance with lithium-ion batteries, potassium ion batteries are the promising candidates for energy storage. We, for the first time, reported electrochemical potassium insertion in graphite in a nonaqueous electrolyte, which can exhibit a high reversible capacity of 273 mAh/g. Ex-situ XRD studies confirm that KC36, KC24, and KC8 sequentially form upon potassiation, whereas depotassiation recovers graphite through phase transformations in an opposite sequence. Graphite shows moderate rate capability and relatively fast capacity fading. To improve the performance of carbon K-ion anodes, we designed two low-density nongraphitic carbon: soft carbon and hard carbon. Those low-density carbons have large graphene layer, which has lots of benefits for high-performance potassium ion batteries. Firstly, the large graphene layer can accommodate large volume change, leading good cycling performance; secondly, K+ can fast extract/insert out/into the graphene layer. Therefore, both soft and hard carbons exhibit cyclability and rate capability much superior to that of graphite. Our work opened up a new paradigm toward rechargeable K-ion batteries. To get high capacity, carbon-coated Bi nanocomposite was designed as well. It exhibits a high capacity and extremely high rate ability. These works push forward the development of rechargeable K-ion battery

References:
1. Z. Jian, W. Luo and X. Ji, J. Am. Chem. Soc., 2015, 137, 11566
2. Z. Jian, Z. Xing, C. Bommier, Z. Li and X. Ji, Adv. Energy Mater., 2016, 6, 1501874.
3. Z. Jian, S. Hwang, Z. Li, A. S. Hernandez, X. Wang, Z. Xing, D. Su and X. Ji* Adv. Funct. Mater., 2017, 27, 1700324;

12:10: [BatterySatAM03]
Si-Polymer Nanocomposite Anodes for Li-Ion Batteries
Pu Hu¹ ; Utkarsh Ahuja² ; Bo Wang³ ; Katerina Aifantis⁴ ; ¹Univ of Florida, Gainesville, Greece; ²Uni. of Florida, Gainesville, United States; ³Univ. of Florid, Gainesville, United States; ⁴University of Florida, Gainesville, United States;
Paper Id: 325 [Abstract]

Si has recently been commerialized as an active material in anodes for Li-ion batteries. Due to large volume expansion, however, it experiences low amounts of graphite anodes during Li-insertion, resulting in a small capacity of increase over purely graphitic ones. The present talk illustrates new Si based anodes comprised of Si nanoparticles that are coated with polymers. These configurations allow for improved mechanical properties over those of pure Si nanoparticle anodes. A mechanics model is formulated that can predict and design criteria that can prolong the mechanical and electrochemical stability of high content Si based anodes. The model predictions are in agreement with the experimental observations and can also capture the size effect for which fractures can be avoided by tuning the particle diameter and polymer coating. Different polymers have been considered, including conductive and non-conductive ones, while in some cases, the binder was not added in producing the porous electrode.

12:35: [BatterySatAM04] Plenary
Non-carbon Matrix Sulfur Cathodes for High Volumetric Specific Energy Lithium-sulfur Batteries
Guoran Li¹ ; Xueping Gao¹ ; ¹Nankai University, Tianjin, China;
Paper Id: 440 [Abstract]

Lithium-sulfur battery is recognized as one of the most promising energy storage devices with high energy density, however, the application and commercialization are severely hindered by both the practical gravimetric and volumetric energy densities due to the low sulfur content and tap density with light-weight and nonpolar porous carbon materials as sulfur host. <br />Herein, we have developed some metal oxides and oxyhydroxides, i.g. NiCo2O4, NiFe2O4, and CoOOH, as carbon-free sulfur immobilizer to fabricate sulfur-based composite as cathode for lithium-sulfur battery. These non-carbon matrix materials for sulfur can accelerate the catalytic conversion kinetics of lithium polysulfides by strong chemical interaction, successfully alleviating the shuttle isuue and leading to a good cycle stability. The S/NiCo2O4 composite presents a high gravimetric capacity of 1125 mAh g-1-composite at 0.1C rate, and a low fading rate of 0.039% per cycle over 1500 cycles at 1C rate. In particular, the S/NiCo2O4 composite with the high tap density of 1.66 g cm-3 delivers a large volumetric capacity of 1867 mAh cm-3-composite, almost twice that of the conventional S/carbon composite. With ultrahigh sulfur content of 91.8 wt% and tap density of 1.26 g cm-3, the sulfur/CoOOH composite delivers high gravimetric capacity and volumetric capacity of 1199.4 mAh g-1-composite and 1511.3 mAh cm-3 at 0.1C rate, respectively. Meanwhile, the sulfur-based composite presents satisfactory cycle stability with a slow capacity decay rate of 0.09% per cycle within 500 cycles at 1C rate. The works provide a new strategy to realize the combination of gravimetric energy density, volumetric energy density and good electrochemical performance of lithium-sulfur battery.

References:
[1] Zhen-Yu Wang, Lu Wang, Sheng Liu, Guo-Ran Li, and Xue-Ping Gao,Adv. Funct. Mater. 2019, 1901051.\n[2] Ya-Tao Liu, Dian-Dian Han, Lu Wang, Guo-Ran Li, Sheng Liu, and Xue-Ping Gao, Adv. Energy Mater. 2019, 1803477.\n[3] Ze Zhang, Di-Hua, Wu, Zhen Zhou, Guo-Ran Li, and Xue-Ping Gao, Sci. China Mater., 2019, 62,74.

SESSION: NanomaterialsSatPM1-R11	6th Intl. Symp. on Synthesis and Properties of Nanomaterials for Future Energy Demands
Sat Oct, 26 2019 / Room: Coralino
Session Chairs: Marcos de Campos; Yoshio Kobayashi; Session Monitor: TBA

14:00: [NanomaterialsSatPM105]
The Steinmetz law: Theoretical considerations
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 432 [Abstract]

According to the Steinmetz hysteresis law, the power losses P vary as function of the induction B with an exponent n, where n typically is 1.6. This results in the formula P= k B^n, where k is a constant. However, the exponent n can be different according to the evaluated material. From theoretical considerations, it is expected an exponent n=2, because the Power losses are given approximately by 4 B H, for the case of square hysteresis. Here, H is the applied field. As B is the product of the permeability times the applied field H, then theoretically is expected P = K B^2. Reasons for n be lower than 2 are discussed. It is presented a model able to explain exponent n lower than 2. A better understanding of the Steinmetz law is useful for improvements of models able to predict the heating of steel laminations used in electric motors.

14:25: [NanomaterialsSatPM106]
Fabrication of Multi-Layered Gold-Silica-Gadolinium Compound Core-Shell Particles and their Applications to X-ray Imaging and Magnetic Resonance Imaging
Yuta Shindo¹ ; Tomoya Inose² ; Noriko Yamauchi¹ ; Kouichi Nakashima¹ ; Masayuki Tokunaga² ; Chihiro Kato² ; Kohsuke Gonda² ; Yoshio Kobayashi¹ ; ¹Ibaraki University, Hitachi, Japan; ²Tohoku University, Sendai, Japan;
Paper Id: 6 [Abstract]

Materials composed of components that have different properties should have multiple functions. Various composite particles with magnetism and X-ray absorption abilities have been developed. Based on the viewpoint for multi-functionalization of materials, particles containing gold (Au) and gadolinium compounds (GdC) will act as both the X-ray contrast agent and the MRI contrast agent. In our previous work [1], the silica (SiO₂)-coating of metallic Au nanoparticles has been performed by using a modified Stober method. Our other previous works have proposed methods for GdC-coating particles such as the SiO₂ [2] and SiO₂-coated quantum dot [3,4]. The present work proposes a method for preparing multi-layered core-shell particles composed of the core of Au, the first shell of SiO₂, and the second shell of GdC (Au/SiO₂/GdC), which is a combination of the various coating techniques developed in our previous works [1-4]. Imaging abilities based on both X-ray absorption and magnetic resonances of the multi-layered core-shell particle colloid solution were also studied in the present work. The Au nanoparticles were produced by reducing hydrogen tetrachloroaurate (III) trihydrate with trisodium citrate dihydrate. SiO₂-coated Au (Au/SiO₂) nanoparticles were fabricated by a sol-gel reaction in the presence of the Au nanoparticles. Multi-layered Au/SiO₂/GdC nanoparticles were fabricated by a homogeneous precipitation reaction in the presence of Au/SiO₂ nanoparticles. The Au nanoparticles, the Au/SiO₂ nanoparticles, and the multilayered Au/SiO₂/GdC nanoparticles had average sizes of 15.5, 38.0, and 43.8 nm, respectively. The computed tomography (CT) value of the Au/SiO₂/GdC colloid solution containing 4.3x10^-2 M Au was 606 HU: Its converted CT value (CT value divided by Au concentration) was 1.4x10⁴ HU M^-1. The longitudinal relaxation rate (r1) of the Au/SiO₂/GdC colloid solution was 2.3 mM^-1 s^-1. In conclusion, the Au/SiO₂/GdC colloid solution was found to function as the X-ray contrast agent and the MRI contrast agent.

References:
[1] Y. Kobayashi, H. Inose, T. Nakagawa, K. Gonda, M. Takeda, N. Ohuchi, A. Kasuya, J. Colloid Interface Sci. 358 (2011) 329-333.\n[2] Y. Kobayashi, J. Imai, D. Nagao, M. Takeda, N. Ohuchi, A. Kasuya, M. Konno, Colloids Surf. A 308 (2007) 14-19.\n[3] Y. Kobayashi, T. Nozawa, T. Nakagawa, K. Gonda, M. Takeda, N. Ohuchi, A. Kasuya, J. Sol-Gel Sci. Technol. 55 (2010) 79-85.\n[4] Y. Kobayashi, T. Nozawa, M. Takeda, N. Ohuchi, A. Kasuya, J. Chem. Eng. Jpn. 43 (2010) 490-493.

14:50: [NanomaterialsSatPM107]
Magnetostatic coupling in nanocrystalline magnetic materials
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 433 [Abstract]

Magnetic coupling can appear in samples with nanocrystalline structure, when two phases of different characteristics are mixed. In other, words, the coupling can happen when there are two phases: one magnetically hard and other magnetically soft. It is discussed the possiblity of occurrence of either, exchange coupling or magnetostatic coupling in nanocrystalline magnetic materials. Exchange coupling requires coherent lattice between the two phases. However, magnetostatic coupling can happen even for incoherent interfaces. As magnetostatic coupling is more general, and can happen in any situation of lattice coherency or incoherency, many of the observed coupling phenomena are due to magnetostatic interactions and not to exchange coupling. Criteria for occurrence of magnetostic coupling are discussed. Both phases should be single domain size, in order to happen magnetostatic coupling.

15:15: [NanomaterialsSatPM108]
Obtaining Carbon Structures Containing Reinforced Ceramic Materials Based on Alumina
Tinatin Kuchukhidze¹ ; ¹LEPL Ilia Vekua Sukhumi Institute of Physics and Technology, Tbilisi, Georgia;
Paper Id: 392 [Abstract]

The growing scientific-technological progress in modern civilization causes actuality of producing construction materials which can successfully work in conditions of high temperature, radiation, pressure, speed and chemically aggressive environment. Such extreme conditions can withstand very few types of materials and among them ceramic materials are in the first place.Corundum ceramics is the most useful material for creation of constructive nodes and products of various purposes for its low cost,easy accessibility to raw materials and good combination of physical-chemical properties.

SESSION: NanomaterialsSatPM2-R11	6th Intl. Symp. on Synthesis and Properties of Nanomaterials for Future Energy Demands
Sat Oct, 26 2019 / Room: Coralino
Session Chairs: Lucian Pintilie; Tetiana Prikhna; Session Monitor: TBA

15:55: [NanomaterialsSatPM209]
Iron Oxide Nanopowder Synthesized by Electroerosion Dispersion
Tetiana Prikhna¹ ; Mykola Monastyrov² ; Bernd Halbedel³ ; Semyon Ponomarov⁴ ; Fernand Marquis⁵ ; Athanasios Mamalis⁶ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Open International University of Human Development Ukraine, Kiev, Ukraine; ³Technische Universitat Ilmenau, Ilmenau, Germany; ⁴Institute of Semiconductor Physics, Kiev, Ukraine; ⁵San Diego State University, San Diego, United States; ⁶National Technical University of Athens, Athens, Greece;
Paper Id: 121 [Abstract]

In this work, we present a method for simple preparation of magnetic iron oxide nanopowders by electroerosion dispersion (EED) of carbon steel in water. Magnetic nanoparticles (MNP) have attracted considerable interest in many fields of research and applied science due to their impressive properties. In the past, in order to fix biomedical issues, the development of MNPs has been promoted. For technical applications, such as wastewater treatment and absorption of electromagnetic waves, the existing synthesis approaches are too expensive and/or the producible quantities are too low. We describe the synthesis method, the laboratory installation and discuss the structural, chemical and electromagnetic properties of the syn-thetized EED powders, as well as their applicability for microwave absorption compared to other available ferrite powders. The electromagnetic properties of the EED powder allow microwave absorption values like that of hexaferrite powders and values considerably larger than that of the commercially available iron oxide powder: Magsilica. The production of the EED powder, however, is much simpler. Modern applications with high-frequency electromagnetic fields (satellite-TV, mobile funk, WLAN technologies, radar for traffic and aerial supervision, microwave heating, drying, sintering, up to automotive and medical applications) require very low-cost absorbing materials. This allows reduction of the electromagnetic radiation exposure on biological systems, assures the safe operation of instruments and equipment (prevention of wireless signal leakages) or facilitates modern communication applications [1].

References:
[1] B. Halbedel, T. Prikhna/, P. Quiroz, J. Schawohl, T. Kups, M. Monastyrov Iron oxide nanopowder synthesized by electroerosion dispersion (EED) - Properties and potential for microwave applications // Current Applied Physics. - 2018. - Vol. 18. - P. 1410-1414

16:20: [NanomaterialsSatPM210]
How to Handle the Exchange Energy Term in Micromagnetic Models
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 204 [Abstract]

In the modelling of magnetic properties of magnetic materials, four energy terms need to be considered: (i) the Zeeman term, due the applied field, (ii) the term due to the magnetostic energy, (iii) the term due to the magnetocrystalline anisotorpy, and (iv) the term due to exchange energy. These four terms are considered in micromagnetic models. In the present study, different formulations for the exchange energy terms are compared [1]. The Heisenberg exchange interaction is usually described by a scalar product, which results in a term depending on the cosine function. The approximation of the 1- cosine function by a Taylor series gives a polynomial of order two, since other terms of the Taylor series expansion are neglected. Replacing a cosine funstion by a polynomial of order two, however, overestimates the exchange energy contribution significantly. It is shown that existence of antiferromagnetism can reduce the energy of system. Thus, the exchange energy term needs to consider all other neighbours because they can reduce the energy of the system. Thus, the exchange energy is more properly described by a Fourier series than by a polynomial of order two.

References:
[1] A.F. da Silva Jr ; M.F. de Campos, M.F. ; A. S. Martins. Domain Wall Structure in Metals: a New Approach to an Old Problem. JOURNAL OF MAGNETISM AND MAGNETIC MATERIALS, v. 442, p. 236-241, 2017.

16:45: [NanomaterialsSatPM211]
Magnetic Materials employed in Electric Vehicles
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 207 [Abstract]

A subject of recent interest nowadays is electric and hybrid cars. Most of the high-efficiency motors use magnets in the rotors because this saves the current used in the magnetization of the soft magnetic material. The IE4 European efficiency specification (Super Premium Efficiency) also request motors with magnets in order to achieve the specifications of the manufacturers. Thus, it is forecasted that the market of magnets for electric motors should increase considerably in the forthcoming years.
The electric vehicles industry put emphasis on the optimization of batteries and on the reduction of the weight of the cars. The increase of efficiency of the motors, however, has been much neglected, especially from the material point-of-view.
The idea presented here in this paper is that both the soft magnetic material and the hard magnetic material need to be optimized at the same time [1]. For example, by using a better soft magnetic material, the losses are reduced, and also, less heat is generated. Thus, a magnet without Dysprosium can be used since optimized electric steels are used. The recent motors designed for electric vehicles can work at very high frequencies. In this case, resistivity of the magnets is an issue. Axial flux machines are in development nowadays. Some of the prototypes of axial flux machines use strontium ferrite magnets. One reason for the choice of ferrites is that the resistivity of ferrites is much lower than in the case of NdFeB or SmCo magnets.
The automotive industry is a mass production industry and requests cheap materials. Thus, there is pressure for avoiding expensive magnets which use Dysprosium or Terbium. Most of the manufacturers of electric motors, however, need magnets with high coercivity which is specified in the motor design. In these motors, irreversible reversal of magnetization of even parts of the grains of the magnets is a big problem, resulting in reduction of motor performance. This motivates the choice of high coercivity NdPrFeB type magnets. SmCoFeCuZr would have excellent performance, but the high cost of cobalt makes its use avoidable.
In this paper, we discuss how to model the losses in soft magnetic materials (electric steels) and also on the magnets. One relevant result of the modeling is that rotors with surface mounted magnets expose the magnet to high fields and strong eddy currents. Thus, buried magnets are a better option. Several types of magnet configurations have been tested as the V type used in the Toyota Prius and Tesla Model 3, the double V used in the GM Chevy Volt and the Delta type used by the Nissan Leaf. Many manufacturers have opted for the V type, but the concept used by BMW i3, the Hybrid Synchronous motors, is a possibility. The motor of the Tesla Model 3 makes use of the Halbach effect, and the benefits of using the Halbach array will be discussed. The Halbach array allows the soft magnetic material (the electrical steel) to be magnetized at the fields near the magnetic saturation.

References:
[1] M. F. de Campos. Magnetic Materials for Motors of Electric Cars. In: Proceedings of 2018 Rare Earth Permanent Magnets and Advanced Magnetic Materials and Their Applications REPM 2018, Beijing, China, August 26-30, 2018. p. A0414-01-A0414-11.

17:10: [NanomaterialsSatPM212]
Recent Trends in the Battery Market and Applications
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 209 [Abstract]

Batteries are now seen as an essential subject for renewable energies. This is because the wind and sun are intermittent energy sources.
Europe, the United States and other countries are significantly increasing the production of wind energy. Also, solar energy generation needs batteries because, at night, energy production is not possible.
The electric energy produced by the wind and sun can be used for moving electric cars. This avoids petroleum importation which is a relevant issue for many countries. European environmental specifications should increase the market of hybrid and electric cars. The market of hybrid cars with cheap batteries, as the 48V mild hybrid vehicles market, is also expanding.
At the present time, hybrid cars present a better relationship with cost-benefit than full electric cars. This situation can change if the price of batteries continues to reduce [1].
Hybrid trucks have been considered as an alternative for the near future. It is difficult to make a full electric truck due to the high weight of batteries that need transportation with the vehicle.
Several main types of batteries are available. Nowadays, Lithium ion batteries, such as NMC (nickel-manganese-cobalt)are dominant. The cars of Tesla motors use NCA (nickel-cobalt-aluminium). Due to the high cost of cobalt, there is a big pressure for reducing cobalt usage in NMC batteries. This has been achieved by replacing cobalt by nickel.
China developed LiFePO₄ batteries, and these batteries have the big advantage of being environmentally friendly. The chinese electric car industry, however, is also moving to NMC batteries.
Other types of batteries, such as Na based or Al based batteries, continue to develop. Progress in batteries is slow due to the need of a long testing period for new products.
Vanadium redox batteries have been considered for trucks. Vanadium demand has increased, generating a peak of price. Application of vanadium in VRB redox batteries, however,is still quite limited. Most of the VRB batteries are prototypes. It is said that 90% of the market of Vanadium is for microalloyed steels, where FeV can easily be replaced by FeNb.
Solid State batteries are in development and some companies are making very optimistic predictions. The feasibility of commercial solid state batteries, however, continues to be a subject of discussion. An important subject of study is the quick charging of batteries.

References:
[1] Bjorn Nykvist, Frances Sprei, Mans Nilsson. Assessing the progress toward lower priced long range battery electric vehicles. Energy Policy Volume 124, January 2019, Pages 144-155

SESSION: NanomaterialsSatPM3-R11	6th Intl. Symp. on Synthesis and Properties of Nanomaterials for Future Energy Demands
Sat Oct, 26 2019 / Room: Coralino
Session Chairs: Chun Li; Session Monitor: TBA

17:50: [NanomaterialsSatPM313]
The Applicability of Combustion Synthesis Process to the Fabrication of MoSi2-SiC Composites
Manadana Adeli¹ ; Amir Tayebi Pak² ; ¹School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Tehran, Iran; ²Iran University of Science and Technology, Tehran, Iran;
Paper Id: 278 [Abstract]

Combustion synthesis is a novel low-cost, rapid, and energy-saving method for the production of high-temperature materials. The synthesis of products via this method is based on the formation of the desired compounds by making use of the exothermic reactions between the starting elemental powders. In this study, the synthesis of MoSi₂-SiC composites from the starting powder mixture of Mo+2Si and Si+C has been investigated. XRD, SEM-EDS, and Vickers microhardness tests have been used to characterize the products. The effect of Mo+2Si/Si+C weight ratio on the intensity of the reaction, as well as the formation of the products, was studied. It was found out that the desired products were formed in Mo+2Si powder mixtures containing 10wt.%Si+C samples. Using higher amounts of Si+C resulted in incomplete reactions which gave rise to remains of unreacted powder particles in the product microstructure. The MoSi₂-10wt.%SiC composite showed the highest values of mircrohardness

References:
1. M. Panneerselvam, Ankur Agrawal, K.J. Rao, "Microwave sintering of MoSi2-SiC composites", Materials Science and Engineering A356 (2003) 267-273.
2. Jianguang Xu, Huiqiang Li, Haijiang Wu, Fangling Lei, Preparation of MoSi₂/SiC composite by mechanical-assistant combustion synthesis method, Journal of Alloys and Compounds, 487 (2009) 326-330.
3. Subrahmanyam Jandhyala, "Thermochemical Evaluation of Combustion Synthesis of
MoSi,-Sic Composites" J. of the American Ceramic Society, vol. 76 (1993) 226-228.

SESSION: MoltenThuAM-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Thu Oct, 24 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Marcelle Gaune-Escard; Gregory McKenna; Session Monitor: TBA

11:20: [MoltenThuAM01] Plenary
Glassforming and Ionic Liquids
Austen Angell¹ ; ¹Arizona State University, Tempe, United States;
Paper Id: 454 [Abstract]

Glassforming liquids with emphasis on the ionic liquids have been on my mind, since my early graduate student days. At that time (1950’s) the molten silicates and sulfides of Chemical Metallurgy (where they served as scavengers for unwanted components in the metals extraction processes) were still regarded as molecular mixtures in institutions as august as MIT. Then John Bockris and students at Imperial College of Science, London, measured the ionic conductivity, and introduced the term “ionic liquids” for the first time. My M.Sc. Advisor in Chemical Metallurgy at Melbourne University, Mervyn Willis, told me this was the way to go, so I dropped the PbO-Fe2O3 -SiO2 4D phase diagram project I had been working on and joined Bockris’ group (then at the University of Pennsylvania) in 1956. That started a long journey through liquid silicates, molten salts, concentrated aqueous and non-aqueous solutions and molecular liquids and finally back to ionic liquids, touching many personalities and countries. I will try to give some feeling for the highlights of the journey.

11:45: [MoltenThuAM02] Plenary
20 Million Year Old Amber and Ultra-stable Amorphous Teflon and the Unexplored Region of Glassy Behavior
Gregory Mckenna¹ ; ¹Texas Tech University, Lubbock, United States;
Paper Id: 49 [Abstract]

A major question related to the glass transition event is whether there exists an ideal glass temperature <i>T_g,ideal</i> [1,2]. Because the laboratory glass transition <i>T_g</i> is some 40 to 100 K above the putative <i>T_g,ideal</i> it is virtually impossible to perform direct measurements that even approach the true equilibrium state at this temperature. Therefore, it is important to develop methods to finesse the problem and to work in the so-called "unexplored" region of glassy behavior [3] where the non-equilibrium response should be an upper bound to the dynamical behavior of the glass [4,5]. The framework for the study is that of the fictive temperature originally proposed by Tool [6] and that creates a solid framework for understanding the volume or enthalpy vs. temperature behaviors of glass-forming liquids as well as the evolution of the glassy properties during arbitrary thermal histories. In this framework, the fictive temperature <i>T_F</i> of the glass defines a point of intersection of the glass-like behavior with that of the equilibrium liquid. When the temperature <i>T</i> is below <i>T_F</i>, the dynamics are faster than those of the material in the equilibrium state. When <i>T</i>><i>T_F</i>, the dynamics are slower, i.e., provide an upper bound to the equilibrium relaxation times at <i>T</i>. At <i>T = T_F</i> the equilibrium response should, in principle, be obtained. Therefore, to test concepts such as the possibility that the relaxation times or viscosity diverge at a temperature above absolute zero (possibly at <i>T_g,ideal</i>), as seen in multiple models of glass-forming liquids, the goal became to find or to create glasses with fictive temperatures as far as possible below the glass transition temperature <i>T_g</i>. Then, if one can work in the ''window'' between <i>T_F</i> and <i>T_g</i>, the theoretical predictions or extrapolations from the known equilibrium behavior above <i>T_g</i> can be tested down to <i>T_F</i>. We have addressed this challenge by using a 20 million year old amber [4] having a fictive temperature some 43.6 K below the conventionally measured <i>T_g</i> and were able to determine upper bounds to the relaxation times in the relevant temperature window. We subsequently were able to create an ultra-stable amorphous Teflon through a vapor deposition process that had a <i>T_F</i> some 55 K below the <i>T_g</i> of the same material and very close to the nominal <i>T_g,ideal</i>. In this case, and unlike the amber for which the dynamics could be measured by macroscopic rheological methods, there was an additional challenge. Here the vapor deposition process made only micro-gram quantities of material, at least in a reasonable time of multiple hours. Therefore the challenge was to make dynamic measurements on these ultra-small quantities of material. This we did by using the TTU bubble inflation method [7] of viscoelastic measurements to determine the creep response in the temperature range from just below <i>T_F</i> to <i>T_g</i> and applying time-temperature superposition to estimate the temperature dependence of the relaxation times, again in the upper bound condition. Two important results came from these investigations. The first is that the temperature dependence of the dynamics was found to deviate significantly from the finite temperature divergence given by extrapolation of the equilibrium response obtained for temperatures greater than <i>T_g</i>, thus challenging the idea of an ideal glass transition, at least as seen in the temperature dependence of the dynamics. The second is that the data are good enough to permit the evaluation of more modern theories that do not predict diverging time scales at finite temperature. The comparison with several of these will be shown. It is also of interest that, in spite of the challenge to ideas of an ideal glass transition, the activation energies of these upper bound relaxation times are still extremely high, thus the ''turn over'' from super-Arrhenius to Arrhenius-like behavior does not resolve the conundrum of the high apparent activation energies of the relaxation processes in glass-forming liquids, one of the original motivating factors in the ongoing study of complex fluids [8-11].

References:
[1] C.A. Angell and J. Donnella, "Mechanical collapse vs ideal glass formation in slowly vitrified solutions: A plausibility test," J. Chem. Phys., 67, 4560-4563 (1977); https://doi.org/10.1063/1.434597
[2] C.A. Angell, "On the uncertain distinction between fast landscape exploration and second amorphous phase (ideal glass) interpretations of the ultrastable glass phenomenon," Journal of Non-Crystalline Solids, 407, 246-255 (2015); http://dx.doi.org/10.1016/j.jnoncrysol.2014.08.044
[3] G.B. McKenna and S.L. Simon, "50th Anniversary Perspective: Challenges in the Dynamics and Kinetics of Glass-Forming Polymers," Macromolecules, <b>50</b>, 6333-6361 (2017); DOI: 10.1021/acs.macromol.7b01014.
[4] J. Zhao, S.L. Simon, G. B. McKenna, "Using 20-million-year-old amber to test the super-Arrhenius behavior of glass-forming systems," Nature Communications, 4>, 1783-1 - 1783-6 (2013). DOI: 10.1038/ncomms2809
[5] A.J. Kovacs, "Transition Vitreuse dans les Polymeres Amorphes. Etude Phenomenologique," Fortschr. Hochpolym. Forsch., <b>3</b>, 394-507 (1963).
[6] A.Q. Tool, "Relation Between Inelastic Deformability and Thermal Expansion of Glass in Its Annealing Range," J. Am. Ceram. Soc., 29, 240-253 (1946); A.Q. Tool, "Viscosity and the Extraordinary Heat Effects in Glass," J. Research National Bureau of Standards (USA), <b>37</b>, 73-90 (1946).
[7]P.A. O'Connell and G.B. McKenna, "Novel Nanobubble Inflation Method for Determining the Viscoelastic Properties of Ultrathin Polymer Films," Rev. Sci. Inst., 78, 013901-1 - 013901-12 (2007).
[8] H. Vogel, "Das TemperaaturabhAngigkeitsgesetz der Viskositat Flussigkeiten," Phys. Z., 22, 645-646 (1921)
[9] G.S. Fulcher, "Analysis of recent measurements of the viscosity of glasses," J. Am.Ceram. Soc., 8, 339-355 (1925).
[10] G. Tammann, "Glasses as supercooled liquids," J. Soc. Glass Technol., 9 166-185 (1925).
[11] H. Le Chatelier, "Sur la viscosite du verre," Compt. Rendus, 179, 517-521 (1924); H. Le Chatelier, "Sur l'allotropie du verre," Compt. Rendus, 179, 718-723 (1924).

12:10: [MoltenThuAM03] Keynote
The Making of a Theory of the Vitreous Solid State: from 1 milli-K to 1 kilo-K
Giancarlo Jug¹ ; ¹DiSAT, Dip. Scienza e Alta Tecnologia, Università dell\'Insubria, Como (Italy), Como, Italy;
Paper Id: 102 [Abstract]

The vitreous state (bulk glasses and amorphous films) remains a challenging problem in physics owing to the lack of a regular crystalline background. Thus, most scientists approach this state from the liquid side, at high temperatures, where theoretical physics is quite well established. In this talk, I will present the embryo of an approach that looks at the glass transformation region from the low-temperature, solid-state side. I shall attempt, at the same time, to provide a reasonable description of the structure and ensuing physical properties of the glassy-state itself. This is mainly for silicates, but also for other classes of amorphous materials, including semiconductor films. The surprising picture that is emerging is that the vitreous state appears to be a novel type of solid state, rather than a "dynamically arrested" liquid state, in that an amount of residual quasi-regular structure is still remaining in the highly-disordered medium. This is seen, however, only at the mesoscopic scale where the amorphous solid appears to be rather like a failed poly-crystalline medium. Important differences with true poly-crystalline solids is that, in-between the grains, there appear to be remnants of liquid-like regions and the grains themselves are only quasi-ordered. This scenario is being investigated and developed by means of a phenomenological theory that takes its moves from the lowest temperatures phenomena, where bizarre magnetic effects have been reported which have been explained satisfactorily by means of this new theory. Presently, I have been able to conduct new experiments on glasses at temperatures up to 315 K and in a magnetic field. The analysis of the data corroborates the new approach and theory with surprising accuracy. I will review this new theory and scenario, surveying the results obtained so far at the lower temperatures, and present the new results at higher temperatures. An embryo of the new approach's resulting description of the glass transformation will also be presented.

References:
- G. Jug, M. Paliienko and S. Bonfanti, J. Non-Crystal. Solids 2014
- G. Jug, S. Bonfanti and W. Kob, Phil. Mag. 2016
- G. Jug, Ch. 13, Springer Book (A.V. Chalyi and L.A. Bulavin) 2018

12:35: [MoltenThuAM04] Keynote
NdBr3 - MBr binary systems (M = Li, Na, K, Rb, Cs) – an example for discussion of thermodynamic and transport properties of these LnX3-MX systems
⁰ ; Ida Chojnacka¹ ; Leszek Rycerz¹ ; Jan Kapala² ; ¹Wroclaw University of Science and Technology, Wroclaw, Poland; ²Faculty of Chemistry, Wroclaw University of Technology, Wroclaw, Poland;
Paper Id: 463 [Abstract]

All the NdBr₃-MBr binary systems (M = Li, Na, K, Rb, Cs) are characterized by negative enthalpies of mixing [1]. The minimum of molar mixing enthalpy is shifted towards the alkali bromide-rich composition and located in the vicinity of x(NdBr₃) of about 0.3-0.4. Ionic radius of the alkali metal influences the magnitude of mixing enthalpy as well as the minimum position. The smaller the alkali metal ionic radius, the smaller the absolute value of mixing enthalpy and the minimum more shifted towards the alkali bromide-rich composition. Comparison with other LnX₃-MX binary systems (Ln = lanthanide, X = Cl, Br, I) showed that mixing enthalpy depends also on lanthanide and halide ionic radii. Its absolute value increases with decrease of lanthanide ionic radius and decreases with increase of halide ionic radius. In all the NdBr₃-MBr binary systems, the value of interaction parameter λ, which represents energetic asymmetry of the melts under investigation, is negative. Its absolute value increases significantly with ionic radius of alkali metal cation. All the systems show more negative values of the interaction parameter in the alkali halide-rich compositions. Starting from potassium bromide a broad minimum appears to exist at a molar fraction of neodymium bromide x(NdBr₃) of about 0.2-0.3. This minimum can be undoubtedly ascribed to the formation of NdBr₆^3- octahedral complexes in the systems under investigation. Conclusion concerning octahedral complexes formation in investigated melts is confirmed by the results of electrical conductivity measurements of NdBr₃-MBr liquid mixtures. Temperatures and molar enthalpies of phase transitions of all the M₃NdBr₆ congruently melting compounds (M = K, Rb, Cs) were determined and compared with data obtained for analogous chloride and bromide compounds of other lanthanides [2]. This comparison showed that M₃NdBr₆ compounds could be divided into two groups: compounds, which are formed at higher temperatures from M₂NdBr₅ and MBr, and compounds, which are stable or metastable at ambient temperature. Moreover, compounds formed at higher temperatures can exist at ambient temperature as metastable phases when cooled with high rate. On subsequent heating thermograms exothermic effect related to the decomposition of “undercooled” decomposition occurs abruptly. The heat capacities of M₃NdBr₆ compounds were fitted by equations, which provides a satisfactory representation up to temperature of the Cp discontinuity [3]. Electrical conductivity of solid phase of M₃NdBr₆ compounds correlates well with their heat capacity [3]. Specific behavior of the heat capacity and electrical conductivity dependence on temperature of solid M₃NdBr₆ compounds is undoubtedly connected with disordering of cationic sublattice formed by alkali metal cations.

References:
M. Gaune-Escard, A. Bogacz, L. Rycerz, W. Szczepaniak, Formation enthalpies of the MBr - NdBr3 liquid mixtures (M = Li, Na, K, Rb, Cs), Thermochim. Acta, 279 (1996) 11-25
L.Rycerz, M.Gaune-Escard, Enthalpy of phase transitions and heat capacity of compounds formed in the NdBr3 - MBr systems (M = K,Rb,Cs), In "Progress in Molten Salt Chemistry 1, Prof.N.J.Bjerrum Special Volume",R.W.Berg,H.A.Hjuler Editors,Elsevier (2000), 461-465
L. Rycerz, Thermochemistry of lanthanide halides and their systems with alkali metal halides, Beau Bassin, LAP LAMBERT Academic Publishing, 2017

SESSION: MoltenThuPM1-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Thu Oct, 24 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Alois Loidl; Michel Armand; Session Monitor: TBA

14:00: [MoltenThuPM105] Keynote
Broadband Dielectric Spectroscopy on Supercooled Liquids and Ion Conductors
Peter Lunkenheimer¹ ; Alois Loidl² ; ¹University of Augsburg, 86135 Augsburg, Germany; ²Institute of Physics, University of Augsburg, Augsburg, Germany;
Paper Id: 126 [Abstract]

We shall review results of broadband dielectric spectroscopy on supercooled liquids and ion conductors. Our review will cover more than 15 decades of frequency ranging from millihertz to terahertz and in a wide range of temperatures from the low-viscosity liquid to rigid sub-Tg glass [1]. The access to this extremely broad frequency window allows a detailed study of the complexity of glassy freezing and of the ionic and/or molecular dynamics in a large variety of materials. This includes ionic conductors and plastic crystals. Dielectric spectroscopy not only documents the enormous slowing down of the structural relaxation when approaching the glass transition, but also reveals a variety of further dynamic processes. These processes are important to understand the physics of the transition from a supercooled liquid into a rigid glass. We exemplify the phenomenology of glassy dynamics as revealed by these broadband spectra: the structural relaxation, the Johari-Goldstein relaxation, the appearance of a fast process as proposed by the mode-coupling theory, and the boson peak, a well-defined feature in the dielectric loss at THz frequencies. We also will mention the importance of non-linear dielectric spectroscopy to unravel the mystery of the glass transition [2], the significance of sub-Tg experiments like ageing, or the search for fingerprints of the Gardner transition [3]. Finally, we will focus on the charge dynamics in new classes of ionic conductors, like ionic liquids [4], deep eutectic solvents [5], or plastic crystals [6]. Compared to conventional electrolytes, plastic crystals are considered superior concerning ease of preparation, low cost, sustainability, and biocompatibility. Finding better electrolytes is of prime importance for further development of energy-storage and energy-conversion devices like batteries, fuel cells, and super-capacitors. Thus, these devices are a key factor for ensuring the sustainable energy supply of tomorrow. Dielectric spectroscopy is an ideal tool to study the ionic charge transport in these materials and its correlation to their glassy freezing, and to the reorientational dynamics of molecular entities.

References:
References:\n[1] P. Lunkenheimer and A. Loidl, in "The Scaling of Relaxational Processes" (F. Kremer and A. Loidl, Eds.) Advances in Dielectrics, Springer, 2018, pp. 1 -21.\n[2] S. Albert, Th. Bauer, M. Michl, G. Biroli, J.-P. Bouchaud, A. Loidl, P. Lunkenheimer, R. Tourbot, C. Wiertel-Gasquet, F. Ladieu, Science 352 (2016) 1308-1311.\n[3] K. Geirhos, P. Lunkenheimer, A. Loidl, Phys. Rev. Lett. 120 (2018) 085705\n[4] P. Sippel, P. Lunkenheimer, S. Krohns, E. Thoms, A. Loidl, Sci. Rep. 5 (2015) 13922.\n[5] D. Reuter, C. Binder, P. Lunkenheimer, A. Loidl, Phys. Chem. Chem. Phys. 21 (2019) 6801-6909.\n[6] K. Geirhos, P. Lunkenheimer, M. Michl, D. Reuter, A. Loidl, J. Chem. Phys. 143 (2015) 081101.

14:25: [MoltenThuPM106] Plenary
Polymer Electrolytes, in Search for the Elusive Decoupling
Michel Armand¹ ; ¹CIC Energigune, Paris, France;
Paper Id: 73 [Abstract]

Polymer electrolytes have been an active field of research since the late 70's. This has culminated in the commercial launching of lithium metal polymer electrolytes batteries powering a fleet of cars since 2011 in different cities in France ^[1]. The poly(ethylene oxide) - PEO-based as 'solvent' for a low lattice energy salt has been the key to obtain decent conductivities. The operational temperature, however, is a ≈ 70°C, i.e. 10°C above the melting point of crystalline PEO and 100°C above the T_g of the resulting melt. These systems are coupled (diffusion with segmental motion) and can be called "fragile" according to Angell definition ^[2]. Besides, the fraction of the current carried by the cations (Li⁺, Na⁺), the only important species in the electrodes processes, expressed as T+, is only 0.2 to 0.3. <br />We will discuss here the strategies to improve the performances of such ionic conductors in the hopes to meet the requirement for the dearly sought after high energy density battery operating at/close to room temperature, and safer and longer cycling than the present ones using flammable liquid electrolytes technology. <br />Without resorting to modify PEO, the modification of the solute (salt) is one fruitful strategy. The introduction of the extensively delocalized fluorinated imides (R_fSO₂)₂N^- (R_f = F, CF₃) anions where the charge is spread on 5 centers and importantly possess a a"hinge", with the flexible S-N-S "pia" bonds lowering the T_g of the resulting solid solution with PEO, have revolutionized the field. This is also true for ionic liquids, in majority based on these anions.<br />The concept can be pushed further with the "super imide" family, where the charge is further delocalized and the number of "hinges" extended. The first example is [(CF₃SO₂N)₂S(O)(CF₃)] with two S-N-S "pi" bonds. The T_g for the polymer-salt complex is thus further lowered (Fox equation). Besides, when this salt is tethered to a polymer to immobilize the anion, this results in the highest conductivities reported for a single-ion conductor (T₊ = 1) ^[3]. <br />Manipulation of the simple anions, while still keeping the flexible imide linkage, allows the increase of T+ to ≈ 0.5 by simply removing one fluorine from (CF₃SO₂)₂N to (CF₂HSO₂)(CF₃SO₂)N , resulting in H bond formation with the ether oxygens, slowing the negative charge correspondingly ^[4]. Alternatively, the (CF₃SO₂)N( )SO₂- moiety can be kept, attached to either long alkyl chains or short EO units. The former anions result in nanophase separation with the formation of micelles; for the latter, the CH₂CH₂O units attached to the imide center plasticize the polymeric chains without participating in the solvation. Both systems results in much decreased anion mobility, keeping the Li⁺ diffusion at a high value. Both salts seem to, for the first time, exhibit some decoupling. <br />The salt aspect as well as that of new alternatives to PEO will be discussed.

References:
[1] http://www.bollore.com/en-us/activities/electricity-storage-and-solutions/electric-vehicles-solutions.\n[2] Angell, C. A. (1995). "Formation of Glasses from Liquids and Biopolymers". Science. 267: 1924 -1935.\n[3] Ma et al. https://doi.org/10.1002/anie.201509299\n[4] Zhang et al., DOI: 10.1002/anie.201813700

14:50: [MoltenThuPM107] Keynote
Reliable estimation of the hydrate vapour pressure of molten reactive halide systems important to electrolysis and metallothermic reduction
Georges Kipouros¹ ; ¹Materials Engineering, Dalhousie University, Halifax, Canada;
Paper Id: 131 [Abstract]

Most of reactive metals and their alloys are produced by fused salt electrolysis or metallothermic reduction in molten salts. The feed material for both of these processes is the anhydrous chloride of the metal under consideration produced by the dehydration of the form of hydrate. A critical step in the production of most reactive metals requires rigorous thermodynamic analysis. Thermodynamic data for most of the reactive metal chloride hydrates have not been measured. Improper dehydration of the metal chloride hydrate may lead to a prohibitive amount of hydroxychloride, oxychloride, and finally oxide. To prevent hydrolysis, a certain pressure of hydrogen chloride must be maintained to supress or reverse hydrolysis. In this investigation, it is demonstrated that by careful application of the phase rule, sigma function, and utilization of prediction and estimation techniques will lead to a reliable technique for the estimation of the hydrate vapour pressure. These techniques will also lead to prediction of the necessary hydrogen chloride presence to avoid hydrolysis. Thermodynamic data, including heat capacities, standard entropies, and enthalpies, are estimated/predicted for all conceivable intermediate hydrate compounds. Estimations are based on published data, as well as trends proven in similar systems. The thermodynamic estimations and predictions have been published for magnesium chloride, neodymium trichloride, dysprosium chloride and is a continuous program for rare earth metal chlorides.

References:
1. G.J. Kipouros and D.R. Sadoway, "The Chemistry and Electrochemistry of Magnesium Production" in Advances in Molten Salt Chemistry, Vol. 6, Edited by G. Mamantov, C.B. Mamantov and J. Braunstein, Elsevier, Amsterdam, pp. 127-209 (1987).
2. R.J. Roy and G.J. Kipouros, "Estimation of Vapour Pressures of Neodymium Trichloride Hydrates", Thermochimica Acta, 178, 169-183 (1991).
3. Judge and G.J. Kipouros, “Prediction of hydrogen chloride pressure to avoid hydrolysis in the dehydration of dysprosium trichloride hexahydrate (DyCl3.6H2O).” Can. Metall. Quart., 52,(3), 303-310 (2013).
4. G.J. Kipouros, “Dehydration of Magnesium Chloride Hexahydrate”, Ralph Lloyd Harris Memorial Symposium, Ed. Cameron L. Harris, Sina Kashani-Nejad and Matthew Kreuh, Materials Science and Technology (MS&T) 2013, 11-23 (Invited, keynote), (2013).

15:15: [MoltenThuPM108]
The Similarity Method, Critical Analysis of Specific Heat and the Hybrid Model to Describe Solid AIIIBV, AIIBVI and Fourth Group Compounds from 0 to 1500 K
Valery Vassiliev¹ ; Marcelle Gaune Escard² ; ¹Lomonossov Moscow State University, Moscow, Russian Federation; ²Aix-Marseille Universite/Polytech, CNRS/IUSTI UMR7343, Marseille, France;
Paper Id: 462 [Abstract]

Our previous review articles [1] evidenced the relation of thermodynamic data with the Periodic Law. A strict relationship could be established between the enthalpy of formation, melting point and the components atomic numbers in the semiconductor A^IIIB^V phases, with diamond-like structures of sphalerite and wurtzite types. The proposed model was used to critically assess the thermodynamic properties of isostructural compounds. The relationship between the reduced enthalpy, standard entropy, reduced Gibbs energy and the sum of the atomic numbers (Z_i = Z_A + Z_B) has been used to critically assess the thermodynamic properties of A^IIIB^V phases. For the A^IIIB^V in the solid-state, the Similarity method was applied to critically analyse heat capacities. For these A^IIIB^V phases (sphalerite and wurtzite types), heat capacities relationship with the logarithm of elements atomic numbers was used to estimate the continuum above 298 K [2]. The Similarity Method was also used for the specific heat critical analysis for the fourth group (C, Si, Ge, Sn), A^IIIB^V and A^IIB^VI isostructural phases in the solid-state. The dependence of the heat capacities from 0 to 1500 K follows certain regularity. Phases with the same element atomic numbers (Z) sum, such as BN (hex) Z=12 and glassy pure carbon Z=6; BP and AlN (Z=20); AlP (Z=28) and pure Si (Z=14); BAs and GaN (Z=38); AlAs and ZnS (Z=46); AlSb, GaAs, InP (Z=64) and pure Ge (Z=32); GaSb, InAs, and CdSe (Z=82); InSb, CdTe (Z=100) and pure grey Sn (Z=50); have the same heat capacity experimental values in the solid-state within the experimental uncertainty [3]. This rule can be applied to different isostructural compounds.

References:
1. V.P. Vassiliev, B. Legendre, V.P. Zlomanov. The critical analysis and mutual coherence of thermodynamic data of the AIIIBV phases. Intermetallics 19 (2011) 1891-1901.
2. V.P. Vassiliev, W.P. Gong, A.F. Taldrik, S.A. Kulinich. Method of the correlative optimization of heat capacities of isostructural compounds. J. Alloys and Comp. 552 (2013) 248-254.
3. V.P. Vassiliev , V.A. Lysenko , A.F. Taldrik , N.I. Ilynykh , L.G. Sevastyanova. 41st Conference on Phase Equilibria Book of Abstracts, JEEP. 2015. Coimbra.V.1.P.140, Portugal, Mars 23-25, 2015. Approximation of the Low-temperature Heat Capacity of AIIIBV Compounds by Linear Combination of Debye’s Functions

SESSION: MoltenThuPM2-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Thu Oct, 24 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Georges Kipouros; Giancarlo Jug; Session Monitor: TBA

15:55: [MoltenThuPM209] Plenary
Thermomechanical processing to extend the range of the glassy state
A. Lindsay Greer¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 248 [Abstract]

For conventional engineering alloys (which are of course polycrystalline), thermomechanical processing is routinely applied to change their microstructure and optimize their properties. Thermomechanical processing is not applied to conventional glasses, which are generally considered to be brittle. In contrast, metallic glasses formed by liquid quenching have a range of possible states. This range is remarkably extendable by thermomechanical processing [1]. Plastic deformation at room temperature leads to relaxation or rejuvenation. A notched sample in compression shows extreme rejuvenation at the notch root: locally, the hardness and enthalpy match those for a glass cooled at 10¹⁰ K/s, 10⁷-10⁸ times faster than for the original glass [2]. Effects of loading in the nominally elastic regime, whether quasi-static or cyclic, are also reviewed [3,4]. Cryogenic thermal cycling (CTC) reduces the initial yield load in nanoindentation and increases plasticity in macroscopic compression, partially reversing the effects of annealing [5]. Yet CTC has little effect on other properties such as elastic moduli. CTC may stimulate soft spots in a matrix that itself is largely unaffected. Combined treatments, e.g. annealing with CTC, can have dramatic effects, e.g. glasses that are harder and stiffer, yet more plastic. Prospects for further modification of metallic glasses will be considered, outlining useful property changes that may be achieved.

References:
References:\n[1] Y.H. Sun et al., Thermomechanical processing of metallic glasses: extending the range of the glassy state, Nature Rev. Mater. 1 (2016) 16039.\n[2] J. Pan et al., Extreme rejuvenation and softening in a bulk metallic glass, Nature Comm. 9 (2018) 560.\n[3] A.L. Greer & Y.H. Sun, Stored energy in metallic glasses due to strains within the elastic limit, Philos. Mag. 96 (2016) 1643-1663. \n[4] D.V. Louzguine-Luzgin et al., On room-temperature quasi-elastic mechanical behaviour of bulk metallic glasses, Acta Mater. 129 (2017) 343-351.\n[5] S.V. Ketov et al., Rejuvenation of metallic glasses by non-affine thermal strain, Nature 524 (2015) 200-203.

16:20: [MoltenThuPM210] Keynote
Luminescent and photocatalytically active carbon nitride nanocrystals dissolved in polar liquids
Paul F Mcmillan¹ ; Adam Clancy² ; Christopher Howard² ; Martin Wilding³ ; ¹University College London, London, United Kingdom; ²UCL, London, United Kingdom; ³Univ Manchester, Didcot, United Kingdom;
Paper Id: 106 [Abstract]

Layered carbon nitrides based on a polytriazine imide (PTI) sheet structure crystallize as 50-100 nm particles with hexagonal columnar morphology following synthesis from precursors such as dicyandiamide (DCDA) in molten salt (LiCl/KCl or LiBr/KBr eutectic) solutions [1,2]. When the crystals are exposed to aprotic polar liquids including DMSO, DMF and NMP as well as H₂O they dissolve spontaneously forming few-layered crystalline 2D nanosheets in solution. The solutions are photoluminescent and photocatalytically active [3,4]. Following solvent evaporation the layered nanomaterials re-stack in a crystalline arrangement giving rise to a broad range of emission wavelengths extending throughout the visible range [3,5]. We will present new results for the dissolution process and the 2D nanoparticles in solution using high energy X-ray and neutron scattering techniques. We also discuss the glass forming ability of the solutions to provide few-layered crystalline nanoparticles with tunable photoluminescence properties held in a solid matrix.

References:
[1] M.J. Bojdys et al, Chem Eur J 14 (2008) 8177
[2] E. Wirnhier et al, Chem Eur J 17 (2011) 3213
[3] T.S. Miller et al, Nano Letts 17 (2017) 5891
[4] K. Schwinghammer et al J Am Chem Soc 136 (2014) 1730
[5] T.M. Suter et al, Chem Sci 10 (2019) 2519

16:45: [MoltenThuPM211] Invited
Effect of additives on electrochemical properties of ionic liquids
Masahiro Yoshizawa Fujita¹ ; ¹Sophia University, Tokyo, Japan;
Paper Id: 168 [Abstract]

Lithium-ion batteries (LIBs) have been widely used in power devices. For further expanding the usage of LIBs, safety and energy densities must be improved. We have focused on zwitterions, which have positive charge and negative charge in the same molecule [1]. Lithium-ion transport was improved by adding a zwitterion to polymer gel electrolytes [2]. Recently, we found that adding a small amount of zwitterion improved not only the electrochemical stability of oligo-ether electrolytes up to about 5 V [3], but also the charge-discharge cycle stability of cells with oligo-ether electrolytes [4]. We also investigated the effect of zwitterions on electrochemical properties of ionic liquid (IL) electrolytes. Zwitterions showed positive effects in IL electrolytes containing Li salts. Li/LiCoO₂ cells containing the IL/zwitterion electrolyte system exhibited high capacities as compared with those of IL electrolytes without zwitterions [5,6]. The increase in the interfacial resistance between the electrolyte and cathode with cycling was suppressed. Recently, we have focused on the magnesium secondary battery, which has been attracting much attention as a next generation secondary battery. Magnesium metal has a high theoretical capacity density and low electrode potential, so it is expected to have high energy density. It is, however, difficult to control stripping and plating of Mg because of the formation of the passivation film. We will add zwitterions into IL/Mg electrolytes. The effect of zwitterions on the properties of IL/Mg electrolytes will be introduced.

References:
[1] H. Ohno, M. Yoshizawa-Fujita, Y. Kohno, Phys. Chem. Chem. Phys. 20 (2018) 10978.
[2] C. Tiyapiboonchaiya, J. M. Pringle, J. Sun, N. Byrne, P. C. Howlett, D. R. MacFarlane, M. Forsyth, Nat. Mater. 3 (2004) 29.
[3] M. Suematsu, M. Yoshizawa-Fujita, H. Zhu, M. Forsyth, Y. Takeoka, M. Rikukawa, Electrochim. Acta 175 (2015) 209.
[4] S. Yamaguchi, M. Yoshizawa-Fujita, H. Zhu, M. Forsyth, Y. Takeoka, M. Rikukawa, Electrochim. Acta 186 (2015) 471.
[5] S. Yamaguchi, M. Yoshizawa-Fujita, Y. Takeoka, M. Rikukawa, J. Power Sources 331 (2016) 308.
[6] S. Horiuchi, H. Zhu, M. Forsyth, Y. Takeoka, M. Rikukawa, M. Yoshizawa-Fujita, Electrochim. Acta 241 (2017) 272.

17:10: [MoltenThuPM212]
The relationship between the cohesive energy density, the internal pressure, and the surface tension of ionic liquids
Yizhak Marcus¹ ; ¹Hebrew University, Jerusalem, Israel;
Paper Id: 17 [Abstract]

The balance between the attractive and repulsive forces between the ions in room temperature ionic liquids (RTILs) and their high-melting molten salts (MSs) analogs is responsible for their cohesive energy density (ced), their internal pressures (P_int) and their surface tensions (σ). Therefore, definite relationships exist between these quantities pertaining to the ionic liquids. For 33 RTILs and 53 MSs for which all the data are available, the relationships are linear and take the form ced = a + b(σV^-1/3) and P_int= p + q(σV^-1/3). The quantity σV^-1/3, called the Gordon parameter, has the dimension of a pressure, as do ced and Pint. The slopes b ≈ 67 and q ≈ 25 are the same for these two kinds of ionic liquids, because the electrostatic interactions between the ions are the dominant attractive forces. The internal energy of the ionic liquid is inversely proportional not to its volume, but to a higher power of it, so that the cohesive (or internal) energy divided by the volume (the ced) is more than twice its volume derivative (the internal pressure, P_int). The established relationships can help estimate unknown quantities among the three dealt with here from the other two.

References:
Y. Marcus: The internal pressure and cohesive energy density of liquid metallic elements. Int. J. Thermophys. 38, 1-9 (2016).
Y. Marcus: The internal pressure and cohesive energy density of two inorganic liquids: bromine and carbon disulfide. J. Chem. Thermodyn., 98, 317-318 (2016).
Y. Marcus: Relationships between the internal pressure, the cohesive energy and the surface tension of liquids. Phys. Chem. Liq., 55, 522-531 (2017).
Y. Marcus: The structure of mixtures of water and methanol derived from their cohesive energy densities and internal pressures at 298 to 473 K. J. Phys. Chem B, 121, 863-866
(2017)

SESSION: MoltenThuPM3-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Thu Oct, 24 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Kyoko FUJITA; Florian Maier; Session Monitor: TBA

17:50: [MoltenThuPM313] Keynote
Extreme Fragilities in Liquids: From super-Strong to super-Fragile
Alexei Sokolov¹ ; ¹University of Tennessee and Oak Ridge National Laboratory, Knoxville, United States;
Paper Id: 110 [Abstract]

In this talk we overview broad literature on temperature dependence of structural relaxation (fragility) in molecular and polymeric systems. We emphasize broad range of known fragility index, from extremely low m~14 in supercooled water to extremely high m ~ 150-200 in many polymers. We ascribe the former to significant quantum effects in dynamics of water [1,2]. To understand better microscopic origin of fragility in non-polymeric systems we performed detailed analysis of the static structure factor S(Q). This analysis reveals that the temperature variations of the width of the main diffraction peak DQ(T) correlates with fragility of these liquids [3]. This observation suggests a direct connection between rather subtle changes in static structure and sharp slowing down of structural relaxation in glass forming liquids. We show that this observation can be rationalized using the Adam-Gibbs approach, through a connection between temperature variations of structural correlation length, lc, and the size of cooperatively rearranging regions. Then we discuss specific case of polymers where chain connectivity leads to many deviations from regularities observed for small molecules [4]. We demonstrate that while segmental relaxation in many polymers exhibits extremely high fragility, the temperature dependence of molecular scale relaxation (chain relaxation in case of polymers) exhibits fragility in the range usual for molecuklar systems, m < 100 [4,5]. We ascribe the extremely high segmental fragility in polymers to non-ergodicity of these systems on segmental time scale [4,5]. At the end we summarize the major microscopic parameters controling steepness of the temperature dependence of structural relaxation in glassforming liquids.

References:
[1] C. Gainaru, et al., PNAS 111, 17402 (2014).
[2] A. L. Agapov, et al., Phys. Rev. E 91, 022312 (2015).
[3] D.N Voylov, et al., Phys. Rev. E 94, 060603(R) (2016).
[4] C. Dalle-Ferrier, et al., J. Chem. Phys. 145, 154901 (2016).
[5] A. L. Agapov, et al., Macromolecules 51, 4874 (2018).

18:15: [MoltenThuPM314]
Overview of the Long-Term Experience of the Scientific as well as Technological Research in the Field of Molten Salt Reactors (MSR)
Miloslav Hron¹ ; ¹, Praha, Czech Republic;
Paper Id: 161 [Abstract]

The principal ideas will first be reminded. Then, the basic scientific research steps will be clarified in the very beginning of the first nuclear era, in the repetition of this effort in the so-called renaissance of this scientific region, in the frame of global collaboration, and also in the national research area in the Czech Republic (former Czechoslovakia). The first stage is the period from the 1940s up to the 1960s, when this field of research was mostly performed in the USA, namely in the Oak Ridge National Laboratory [1]. The second stage is the period from the 1960s up to the 1980s, when higher activity in this field started during that time in the Soviet Union. The Soviet Union was closely collaborating with Czechoslovakia, namely in the field of spent nuclear fuel reprocessing. The developed regeneration process was based on the fluorination of uranium and plutonium by elementary fluorine to volatile hexafluoride. This process has been developed to fit the level of the demonstration laboratory equipment, where mechanically disintegrated spent fuel in powder form is converted, by fluorination, to UF₆ and PuF₆. Volatile and non-volatile fission products are separated by fluorination or by distillation of UF₆. The whole technological line is operated in the hot chamber with a remote control. The capacity of the entire technological equipment is 1-2 kg of heavy metal / day. The fluorinator of the flamboyant type, including the entire device, is made by nickel, resp. by MoNel metal. The condensers, separation columns, and distillation are provided with control elements, valves, flow meters, and pressure gauges. This allows remote control directly from the control panel. The principle of technology and the entire procedure, including the operational experience, are applicable to reprocessing of spent fuel from reactors operating in the thorium-uranium fuel cycle. This activity was stopped after the Chernobyl accident and started again in the 1990s when a renaissance of this effort started in the US Los Alamos National Laboratory, in the frame of the so called ADTT (Accelerator Driven Transmutation Technology) [2]. The scientific and technological research of this concept based on MSR systems was performed in the frame of a close collaboration of the scientific capacity of the USA, Russian Federation, and the Czech Republic. Since the beginning of the 2000s, it was incorporated in the global activity of the development of the nuclear reactors of the 4^th generation [3] and the preparation of the entrance in the second nuclear era.

References:
[1] A. Weinberg, E. Wigner: "The Physical theory of Neutron Chain Reactorsa", The University of Chicago Press (1958).
[2] C. D. BOWMAN, "Accelerator-Driven Systems for Nuclear Waste Transmutation," Annual Review of Nuclear and Particle Science, 48, 505-556 (December 1998).
[3] U.S. DEPARTMENT OF ENERGY, A Technology Roadmap for Generation IV Nuclear Energy Systems, Nuclear Energy Advisory Committee and the Generation IV International Forum (2002).

SESSION: MoltenFriAM-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Fri Oct, 25 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Masayoshi Watanabe; Andrzej Grzybowski; Session Monitor: TBA

11:20: [MoltenFriAM01] Keynote
A Close Look at Ionic Liquid Interfaces in Ultrathin Films by X-Ray Photoelectron Spectroscopy
Matthias Lexow¹ ; Florian Maier¹ ; Hans-peter Steinrück¹ ; ¹Chair Physical Chemistry II, FAU University Erlangen-Nürnberg, Erlangen, Germany;
Paper Id: 148 [Abstract]

Solid-liquid and gas-liquid interfaces play a crucial role in catalysis, electrochemistry, coatings, and separation technology, to name only a view. The extremely low volatility of ionic liquids (ILs) and molten salt systems enables the use of ultra-high vacuum based surface science methods that were originally developed for solids. X-ray photoelectron spectroscopy (XPS) turned out to be a very powerful tool for IL reaction studies, particularly due the possibility to follow changes in chemical state of the IL via XPS chemical shifts. Moreover, angle-resolved XPS (ARXPS) allows for varying the information depth from about 7-9 nm (0° electron emission angle, more bulk-sensitive) down to 1-1.5 nm (80°, more surface-sensitive); in the latter case, about 80% of the overall XPS intensity arises solely from the outermost IL layer. Thus, differences between the top-most layer and the layers underneath can be accessed in great detail by ARXPS. Within the last years, we demonstrated that a large variety of phenomena such as reactions [1] and ion exchange processes [2] at interfaces are accessible when using ARXPS in combination with physical vapor deposition of ILs. The work presented here focuses on processes such as selective adsorption, film growth and stability in ultrathin IL binary mixture films and in IL/porphyrin films grown <i>in situ</i> on solid surfaces. Furthermore, we address the roles of surface free energy versus interface adsorption energy by comparing the surface compositions in the film and the macroscopic mixture systems. Such studies play an important role with respect to thin film / nanoscale applications of ionic systems.

References:
[1] F. Maier, I. Niedermaier, H.-P. Steinrück, "Perspective: Chemical reactions in ionic liquids monitored through the gas (vacuum)/liquid interface", J. Chem. Phys. 146 (2017), 170901.\n\n[2] M. Lexow, B. S. J. Heller, G. Partl, R. G. Bhuin, F. Maier, H.-P. Steinrück, "Cation Exchange at the Interfaces of Ultrathin Films of Fluorous Ionic Liquids on Ag(111)" Langmuir 35 (2019), 398-405.

11:45: [MoltenFriAM02] Invited
Hydrated Ionic Liquids for Solubilisation and Refolding of Aggregated Proteins
Kyoko Fujita¹ ; Roka Nakano² ; Risa Nakaba¹ ; Hiroyuki Ohno² ; Nobuhumi Nakamura² ; Kimiyoshi Ichida¹ ; ¹Tokyo University of Pharmacy and Life Sciences, Tokyo, Japan; ²Tokyo University of Agriculture and Technology, Tokyo, Japan;
Paper Id: 123 [Abstract]

Misfolded proteins form protein aggregates and it is hard to dissolve in aqueous buffer solutions. Some denaturants such as guanidine hydrochloride and urea are usually used to dissolve these protein aggregates in the refolding process. Excess amount of denaturants, however, prevent proteins from refolding, and prevent activity recovery even after dialysis or dilution. Furthermore, re-aggregation of protein occurs at high rate in the dialysis step. Development of re-naturation methods have been desired for a long time. Hydrated ionic liquids (Hy ILs), which have been reported as a potential solvent to stabilize proteins and enzymes [1], are expected to provide a matrix for re-naturation of aggregated proteins [2]. In this study, we have analysed the effects of component ion and water content on the dissolution followed by refolding behaviour of aggregated proteins in Hy ILs. Aggregated concanavaline A (Con A), a sugar chain recognition protein, was prepared by heating at 70°C for 10 minutes. ILs, which have different component structures, were mixed with aggregated Con A. The solubility and folding state of Con A in Hy ILs were measured with fluorescence spectroscopy. The solubility of aggregated Con A was affected by cation structure. Furthermore, the solubility of aggregated Con A was decreased with the increase of water molecules in Hy ILs [3]. In Hy ILs composition of selected cations and anions resulted in the aggregation of Con A, showing strong solubility properties, as well as refolding behaviour. Dissolved Con A in some Hy ILs showed recovery of the binding ability of the sugar chain after dilution with the buffer.

References:
1. K. Fujita, D. R. McFarlane, M. Forsyth, Chem Commun (2005) 4804-4806.
2. K. Fujita, M. Kajiayma, Y. Liu, N. Nakamura, and H. Ohno, Chem Commun 52 (2016) 13491-13494.
3. K. Fujita, R. Nakano, R. Nakaba, N. Nakamura, and H. Ohno, Chem Commun 55 (2019) 3563-3676.

12:10: [MoltenFriAM03] Keynote
Enhancing the Li/Na-Ion Battery Performances by Disorder/Order Engineering
Yuanzheng Yue¹ ; ¹Aalborg University, Aalborg, Denmark;
Paper Id: 120 [Abstract]

We are facing big challenges in developing full-solid Li/Na ion batteries concerning the limited performances and problems of electrodes and solid electrolytes. There are, however, potential possibilities to overcome these challenges. In this presentation, we demonstrate a different route, that is, our disorder/ordering engineering concept [1] to develop high performance cathode/anode/electrolyte materials. The disorder/order engineering refers to two aspects. First, part of the disordered or glass structure in cathode/anode materials is transformed into the ordered domains. Second, the long-range ordered solids are transformed into disordered or amorphous ones. In this talk, we present three case studies concerning the effect of the disorder/order engineering on the electrochemical performances of cathodes, anodes, and solid electrolytes, respectively, for Li/Na-ion batteries. <br />Case 1: A series of vanadium-tellurite glasses with various V/Te ratios were synthesized via melt-quenching [1,2]. Then, the glass was pulverized and mixed with carbon to make Li-ion battery anodes. The anodes underwent discharging/charging cycles. During cycling, a fascinating phenomenon was observed, i.e., nanocrystals formed in glass matrix. As a consequence, the cycling stability and electronic/ionic conductivity of the anodes were enhanced. This kind of nanocrystal formation has a fundamentally different origin compared to the thermally induced crystallization [1,3].<br />Case 2: NaFePO₄ with maricite structure, which is a thermodynamically stable phase, was considered to be electrochemically inactive for sodium-ion storage. Recently, we succeeded in creating disorder in the NaFePO4 cathode by a mechanochemical route to enhance electrochemical performances of Na-ion batteries [4]. The derived NaFePO₄ cathodes containing both amorphous and maricite phases exhibit much improved sodium storage performance with an initial capacity of 115 mA h g^-1 at 1 C and an excellent cycling stability of capacity retention of 91.3% after 800 cycles.<br />Case 3: The crystalline Ag₃PS₄ was transformed into amorphous state via a chemo-mechanical milling process. The Ag⁺ conductivity of the amorphous sample was found to be about three orders of magnitude higher than that of the crystalline counterpart. The amorphous sample exhibits lower activation energy (<i>E</i>_a) for the Ag⁺ migration, and hence, lower Ag+ conductivity compared to the crystalline one. By performing structural characterizations, we explored the origin of the enhanced Ag⁺ conductivity of the amorphous sample. The present study provides valuable information for developing solid electrolytes.

References:
1. Y.F. Zhang, P.X. Wang, T. Zheng, D.M. Li, G.D. Li, Y.Z. Yue. Enhancing Li-ion battery anode performances via disorder/order engineering. Nano Energy 49 (2018) 596-602.\n2. J. Kjeldsen, Y.Z. Yue, C.B. Bragatto, A.C.M. Rodrigues. Electronic Conductivity of Vanadium-Tellurite Glass-Ceramics. J. Non-Cryst. Solids 378 (2013) 196-200.\n3. Y.F. Zhang, P.X. Wang, G.D. Li, J.H. Fan, C.W. Gao, Z.Y. Wang, Y.Z. Yue, Clarifying the charging induced nucleation in glass anode of Li-ion batteries and its enhanced performances, Nano Energy 57 (2019) 592-599.\n4. F.Y. Xiong, Q.Y. An, L.X. Xia, Y.Zhao, L.Q. Mai, H.Z. Tao, Y.Z. Yue, Revealing the atomistic origin of the disorder-enhanced Na-storage performance in NaFePO₄ battery cathode, Nano Energy 57 (2019) 608-615.

12:35: [MoltenFriAM04]
Physico-chemical justification of electrochemical synthesis of carbonaceous materials in molten salts.
Inessa Novoselova¹ ; ¹Institute of General and Inorganic Chemistry, Kyiv, Ukraine;
Paper Id: 43 [Abstract]

Carbon nanomaterials have been widely used in modern devices and high tech [1-2]. This is the reason why the obtaining of carbonaceous materials in molten salts has attracted great interest among researchers. Various carbon products such as carbon nanotubes, carbon nanofibers, carbon nanoparticles, and graphene have been successfully prepared in molten salts by electrochemical reduction processes [3-5].
This paper is devoted to the physicochemical substantiation of the choice of composition of the electrolytic bath and the electrode materials for the generation of carbon nanostructures of different morphologies from molten salts, based on the thermodynamic calculation of the decomposition voltages of various carbonates and analysis of the metal - carbon, and metal carbide - carbon state diagrams.
An analysis of the decomposition voltages of lithium, sodium, potassium, calcium, barium, and magnesium carbonates with different versions of cathode products (elemental carbon, carbon monoxide, metal and carbide) in the range of 300-1900 K have showed that for K₂CO₃ deposition of alkali metals on the cathode is a most energetically profitable process at all temperatures. For Na₂CO₃, it is possible to obtain carbon at T < 1000 K. With temperature increase, the predominant process is the reduction of alkali metals. For Li₂CO₃, CaCO₃, BaCO₃, and MgCO₃ at T < 950 K, carbon deposition will be more advantageous at higher temperatures including reduction up to CO. The decomposition of CO₂ flows at more positive potentials compared with carbonate systems. However, low activity of CO₂ in carbonate-containing melts will prevent the significant contribution of this reaction to the electrode process. Thermodynamic calculations of the dependence of the carbon deposition potentials from carbonate anion on the acidity of the melt (concentration of oxide ions) show the possibility of displacing this potential up to 0.8 V. This can be done by changing the acid-base properties of the melt. On the basis of the analysis of binary phase diagrams of Me-C and MeC-C, criteria for selecting the cathode material for generation of the tubular structure of graphite are established. The diagrams should contain: (1) solid solutions of C-Me at a temperature of 700-900°C and sufficient solubility of carbon (up to ~ 1 at.%) in the metal should be observed; (2) after saturation of the solid solution with carbon, the precipitation of graphite from the metal should occur without the formation of intermediate carbide phases; (3) in the case of the formation of carbides, the diffusion of carbon in the solid С-Ме solution, and in the MeС carbide phase should flow with high speed and quickly reach the concentration of carbon saturation for graphite deposition.

References:
[1] C. Liu, F. Li, L.P. Ma, H.M. Cheng, Adv.Mater. 22 (2010) E28-E62.\n[2] S.L. Candelaria, Y. Shao, W. Zhou, X. Li, J. Xiao, J.G. Zhang, Y. Wang, J. Liu, J. Li, G. Cao, Nano Energy 1 (2012) 195-220.\n[3] C. Schwandt, A.T. Dimitrov, D.J. Fray, Carbon 50 (2012) 1311-1315.\n[4] I.A. Novoselova, N.F. Oliinyk, S.V. Volkov, A.A. Konchits, I.B. Yanchuk, V.S. Yefanov, S.P. Kolesnik, M.V. Karpets, Phys. E Low-dimen. Syst. Nanostruct. 40 (2008) 2231-2237.\n[5] I.A. Novoselova, S.V. Kuleshov, S.V. Volkov, V.N. Bykov, Electrochimica Acta 211 (2016) 343-355.

SESSION: MoltenFriPM1-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Fri Oct, 25 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Yizhak Marcus; Yuanzheng Yue; Session Monitor: TBA

14:00: [MoltenFriPM105] Invited
Powerful Predictive Capabilities of Density Scaling: From New Invariants to the Arrhenius Law Breakdown in both the Normal and Supercooled Liquid States
Andrzej Grzybowski¹ ; Erik Thoms¹ ; Agnieszka Jedrzejowska¹ ; Sebastian Pawlus¹ ; Marian Paluch¹ ; ¹Institute of Physics, University of Silesia in Katowice, Chorzow, Poland;
Paper Id: 19 [Abstract]

Since the beginning of this century, an important idea of density scaling (DS) has been developing successfully. This idea relates macroscopic properties of supercooled liquids to an effective short-range intermolecular Lennard-Jones-type potential and bears hallmarks of universality in cases of different quantities (structural relaxation time, viscosity, segmental relaxation time, Debye-like relaxation time, conductivity relaxation time, dc-conductivity, and diffusivity) and various materials. This includes van der Waals liquids, polymer melts, protic and aprotic ionic liquids, and liquid crystals[1]. According to the basic DS law, the dynamic quantities typically measured in isobaric or/and isothermal conditions can be plotted onto one master curve as a single-variable function <i>f</i>(<i>Gamma</i>), where the scaling variable <i>Gamma</i>=<i>density^gamma</i>/<i>temperature</i> and the scaling exponent, gamma, is a material constant related to the exponent of the repulsive part of the effective intermolecular potential. An additional advantage of the DS law consists in its powerful predictive capabilities, remaining in effect in both the supercooled and normal liquid states [1-3]. Recently, we have shown that the DS based transformation from the temperature-pressure domain to the temperature-density domain enables to reveal some invariant quantities, including a new invariant that is the ratio of dynamic and thermodynamic moduli in both the supercooled and normal liquid states [1,2]. Very recently, we have established that the inflection points observed in isothermal dependences of dynamic quantities, reported first by Herbst et al. in Nature in 1993, can be numerically predicted for different materials from the DS law [1,3]. This surprising finding has resulted in an even more spectacular outcome that is a breakdown of the Arrhenius law regarded, since the end of the 19th century, as a standard rule. This rule is valid for various physicochemical processes, including the thermodynamic evolution of dynamic quantities (such as primary relaxation time, viscosity, and dc-conductivity) in the normal liquid state in isobaric conditions. Combining numerical and analytical arguments based on experimental data measured at ambient and high pressures, we have justified that the standard Arrhenius law, log(<i>X</i>) ~ <i>E_act</i>/<i>temperature</i>, considered for a dynamic quantity <i>X</i> on the assumption of constant apparent activation energy <i>E_act</i>, cannot generally be valid, not only in the supercooled liquid state characterized by super-Arrhenian cooperative molecular dynamics, but also between the boiling and melting points in isobaric conditions, including ambient pressure, at least if the DS law is satisfied [1,3].

References:
[1] A. Grzybowski, M. Paluch, Universality of Density Scaling, p. 77-120 in The Scaling of Relaxation Processes, (Eds) F. Kremer, A. Loidl, Springer Nature 2018.\n[2] A. Jedrzejowska, A. Grzybowski, M. Paluch, Phys. Chem. Chem. Phys. 19 (2017) 18348-18355. \n[3] E. Thoms, A. Grzybowski, S. Pawlus, M. Paluch, J. Phys. Chem. Lett. 9 (2018) 1783-1787.

14:25: [MoltenFriPM106] Plenary
From Ionic Liquids to Solvate Ionic Liquids and Beyond
Masayoshi Watanabe¹ ; ¹Yokohama National University, Yokohama, Japan;
Paper Id: 34 [Abstract]

Certain molten solvates of Li salts can be regarded as solvate ionic liquids [1, 2]. A typical example is equimolar mixtures of glymes (G3: triglyme and G4: tetraglyme) and Li[TFSA]([TFSA]=[NTf₂]) ([Li(glyme)][TFSA]). The amount of free glyme estimated by Raman spectroscopy and MD simulation was found to be a few percent in [Li(glyme)][TFSA]^-, and thereby could be regarded as solvate ionic liquids. The activity of Li⁺ in the glyme-Li salt mixtures was also evaluated by measuring the electrode potential of Li/Li⁺ as a function of concentration. At a higher concentration of Li salt, the amount of free glyme diminished in the solvate ionic liquids, leading to a drastic increase in the electrode potential. Unlike conventional electrolytes, the solvation of Li⁺ by the glyme forms stable and discrete solvate ions ([Li(glyme)]⁺) in the solvate ionic liquids. This anomalous Li⁺ solvation had a great impact on the electrolyte properties and electrode reactions [1]. The electrochemical oxidation of glyme in [Li(glyme)][TFSA] is greatly enhanced due to the donation of lone pairs of ether oxygen atoms to the Li⁺ cation, resulting in the HOMO energy level lowering of a glyme molecule. This anomalous Li⁺ solvation induces interesting transport properties when interfacial electrochemical reactions proceed, which is not transport of solvated ions based on Stokes' law but a ligand (solvent)-exchange transport. Another intriguing aspect of the solvate ionic liquids is unusual solubility, which leads to the stable operation of the Li-S battery due to very low solubility of the discharge products (Li₂S_x). Li⁺-intercalated graphite was electrochemically formed in [Li(G3)₁][TFSA]. In contrast, the cointercalation of G3 and Li+ (intercalation of solvate [Li(G3)₁]⁺ cation) into graphite occurred in [Li(G3)_x][TFSA] electrolytes containing excess G3 (x > 1). In the solvate ionic liquid, the activity of the free solvent is very low, which would make the solvate ion unstable and the desolvation possible at the interface. Very recently, we demonstrate that Li⁺ hopping conduction, which cannot be explained by conventional Stokes' law, emerges in highly concentrated molten solvate electrolytes composed of LiBF₄ and sulfolane (SL) [3]. In the concentrated electrolytes with molar ratios of SL/LiBF₄ < 3, Li⁺ diffused faster than SL and BF₄^-, and thus the evolution of Li⁺ hopping conduction was found.

References:
[1] M. Watanabe, K. Dokko, K. Ueno, M.L. Thomas, From Ionic Liquids to Solvate Ionic Liquids: Challenges and Opportunities for Next Generation Battery Electrolytes, Bull. Chem. Soc. Jpn., 91 (2018) 1660-1682.
[2] M. Watanabe, M.L. Thomas, S. Zhang, K. Ueno, T. Yasuda, K. Dokko, Application of Ionic Liquids to Energy Storage and Conversion Materials and Devices, Chem. Rev., 117 (2017) 7190-7239.
[3] K. Dokko, D. Watanabe, Y. Ugata, M.L. Thomas, S. Tsuzuki, W. Shinoda, K. Hashimoto, K. Ueno, Y. Umebayashi, M. Watanabe, Direct Evidence for Li Ion Hopping Conduction in Highly Concentrated Sulfolane-Based Liquid Electrolyte, J. Phys. Chem. B, 122 (2018) 10736-10745.

14:50: [MoltenFriPM107]
Forecast of geometrical structure for T-x-y-z diagram Li,Na,Th,U||F
Vasily Lutsyk¹ ; Anna Zelenaya¹ ; Maria Parfenova² ; Marina Lamueva³ ; ¹Institute of Physical Materials Science SB RAS, Ulan-Ude, Russian Federation; ²Tomsk State University of Control Systems and Radio-electronics, Tomsk, Russian Federation; ³Institute of Physical Materials Science, Ulan-Ude, Russian Federation;
Paper Id: 173 [Abstract]

Geometric structure of four T-x-y diagrams, forming the T-x-y-z diagram of the quaternary system Li,Na,Th,U||F have been thoroughly analyzed, and 3D models of 4 space diagrams have been assembled. On the basis of data for the structure of the bounding binary and ternary systems, a scheme of mono and invariant states for the quaternary system has been formed. This scheme is the basis for the topological forecast of the geometrical structure of the Т-х-y-z diagram for LiF-NaF-ThF₄ -UF₄ (А-B-C-D) system. Nineteen binary compounds R(J) and 30 invariant transformations (2 peritectic, 20 quasiperitectic and 8 eutectic ones) are characterized this quaternary diagram. It is expected that within the quaternary system, 10 invariant reactions involving the melt (6 of quasiperitectic type and 4 of peritectic type) should run. The Т-х-y-z diagram will be formed by 17 hypersurfaces of liquidus. Seven of them correspond to the primary crystallization of lithium and sodium fluorides (A and B) and solid solutions С(D), R2(R11), R4(R12), R7(R15), R8(R16). Ten of them correspond to the primary crystallization of compounds R1, R3, R5, R6, R9, R10, R13, R14, R17, R18. Compound R10 on the edge LiF-UF4 (A-D) has, in both ternary adjoining systems, LiF-NaF-UF4 (A-B-D) and LiF-ThF4-UF4 (А-C-D), the liquidus surfaces of the wedge type. Compound R10 participates only in 2 phase reactions Q14: L+R10→A+R2(R11) and E7: L→A+R10+R2(R11). Therefore, it is assumed that in the Т-х-у-z diagram, the dots Q14 and E7 are joined without the quaternary invariant dot. On the scheme of mono and invariant states, they are joined by a line, corresponding to the reaction L→A+R10+R2(R11). Thus, a liquidus hypersurface of the compound R10 has a counter eR10R11pAR10E7Q14.

References:
1. Beneš O. Thermodynamics of molten salts for nuclear applications. Dissertation. Prague. 2008. 205 p.
2. Beneš O., Beilmann M., Konings R.J.M. Thermodynamic assessment of the LiF-NaF-ThF4-UF4 system // Journal of Nuclear Materials. 2010. Vol. 405. P. 186-198.
3. Phase Diagrams of Nuclear Reactor Materials. ORNL-2548 / ed. by Тhoma R.E. 1956. 205 p.

15:15: [MoltenFriPM108]
Creation of Functional Materials in Molten Salts Through Surface Engineering and Their Application
Sergey Kuznetsov¹ ; ¹Institute of Chemistry, Kola Science Centre RAS, Apatity, Russian Federation;
Paper Id: 224 [Abstract]

For the production of materials of various functional application based on rare refractory metals, broad prospects are opened when using molten salts. Technological processes have been developed and equipment has been created for obtaining coatings of refractory metals by the electrolytic method in molten salts. Using this method, a unique rotor design of a cryogenic gyroscope has been created. It consists of a carbopyroceram sphere with a special cut at the equator covered with a superconducting niobium layer of high purity [1]. Biomedical material nitinol/tantalum was obtained by stationary and pulsed electrolysis. The adhesion of tantalum coatings, their porosity, and the corrosion resistance of the nitinol/tantalum composition were measured. Highly active, stable catalysts of the new generation in the form of nanostructured Mo ₂ C coatings on molybdenum for the water-gas shift reaction (operating temperature 200-550°С) were obtained [2]. A composite material MoSi ₂ -MoB ₄ was created to protect molybdenum microreactors from oxidation in air-water vapor at a temperature of 500-700°C. By the electrochemical method were produced: carrying devices from copper alloy with a less porous niobium coating for a long-term operation at temperatures up to 1000°С in a high vacuum; Cu-Hf high-temperature solders for diffusion soldering of various refractory metals; heat-resistant material made of niobium alloy with hafnium on borosilicated graphite for operation in an oxidizing environment with an operating temperature of 1700-2200°C [3].

References:
1. A. Dubrovskiy, M. Okunev, O Makarova., S. Kuznetsov, Coatings 8 (2018) 213.
2. A. Dubrovskiy, O. Makarova, S. Kuznetsov, Coatings 8 (2018) 442.
3. S.A Kuznetsov, Chemical Papers, 66 (2012), 511-518.

SESSION: MoltenFriPM2-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Fri Oct, 25 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Rasmus Fehrmann; Masahiro Yoshizawa-Fujita; Session Monitor: TBA

15:55: [MoltenFriPM209] Keynote
Poly(ionic liquids) as a platform for CO2 capture and transformation
Sandra Einloft¹ ; Franciele Bernard¹ ; ¹PUCRS, Porto Alegre, Brazil;
Paper Id: 116 [Abstract]

The largest anthropogenic contribution to climate change is the fossil fuel burning resulting in huge carbon dioxide (CO₂) emissions. Reduction of CO₂ emissions is imperative to mitigate environmental impacts. CO₂ separation can help global warming mitigation as well as provide CO₂ for other processes such as carbon capture and utilization (CCU) and enhanced oil recovery (EOR). Yet CO₂ is an abundant nontoxic resource that can be used in several applications. Chemical absorption processes for CO₂ capture using aqueous amine solutions have been extensively studied and used in industry for decades. They have, however, some operational drawbacks. Ionic liquids have been proposed as the next generation of solvents for a selective CO₂ separation. These compounds are versatile and less harmful to the environment than conventional organic solvents. They present unique properties such as negligible vapor pressure, non-flammability, high thermal stability, and tunability (myriad of possible combinations of cations and anions). Nevertheless, these solvents suffer from high viscosity and high production costs when compared to aqueous amines solutions. Poly(ionic liquid)s (PILs) appear as an alternative to RTIL for CO₂ capture and utilization. PILs represent an emerging subclass of the polyelectrolytes, were each repeating unit is ionic and connected through a polymeric backbone forming a macromolecular structure[1]. PILs combine the good features of RTILs with good mechanical stability, processing and tunable macromolecular design of polymeric material. PILs present higher CO₂ sorption capacity and sorption/desorption velocity than RTIL. PILs, materials with smart designs, can be used for CO₂ separation from the flue gas (CO₂/N₂), and natural gas purification (CO₂/CH₄), besides being active as catalyst for cyclic carbonate production from the reaction of CO₂ and epoxide. The aim of this presentation is to give a concise overview of PILs described in literature, as well as the research published by our group[1-5]. In addition, PLIs syntheses routes, as well as the influence of PILs backbone, anions type, and modification in CO₂ sorption capacity and catalyst activity will be discussed.

References:
1- Einloft, S.; Bernard, F. L.; Dalla Vecchia, F. In Polymerized Ionic Liquids; Eftekhari, A., Ed.; 2017; pp 489-514.
2- Bernard, F. L.; Polesso, B. B.; Cobalchini, F. W.; Donato, A. J.; Seferin, M.; Ligabue, R.; Chaban, V. V.; do Nascimento, J. F.; Dalla Vecchia, F.; Einloft, S. Polymer (Guildf). 2016, 102, 199-208.
3- Magalhaes, T. O.; Aquino, A. S.; Dalla Vecchia, F.; Bernard, F. L.; Seferin, M.; Menezes, S. C.; Ligabue, R.; Einloft, S. RSC Adv. 2014, 4, 18164-18170.
4- Bernard, F. L.; Duczinski, R. B.; Rojas, M. F.; Fialho, M. C. C.; Carreño, L. Á.; Chaban, V. V.; Vecchia, F. D.; Einloft, S. Fuel 2018, 211, 76-86.
5- Bernard, F. L.; Polesso, B. B.; Cobalchini, F. W.; Chaban, V. V.; do Nascimento, J. F.; Dalla Vecchia, F.; Einloft, S. Energy & Fuels 2017, 31, 9840-9849.

16:20: [MoltenFriPM210]
Variants of T-x-y-z Diagrams for Subsystems LiF-LiCl-NaCl-UCl3, LiF-NaF-NaCl-UC3, 7NaF-6UF4-LiF-UF4-UCl3, 3NaF-UF4-LiF-NaF-UCl
Vasily Lutsyk¹ ; Vera Vorob'eva¹ ; Maria Parfenova² ; Marina Lamueva³ ; ¹Institute of Physical Materials Science SB RAS, Ulan-Ude, Russian Federation; ²Tomsk State University of Control Systems and Radio-electronics, Tomsk, Russian Federation; ³Institute of Physical Materials Science, Ulan-Ude, Russian Federation;
Paper Id: 125 [Abstract]

Previously, [1] the possible options for the system Li,Na,U||F,Cl polyhedration were considered. The system LiF-NaCl is eutectical [1] (eutectic 0.415 mole LiF at 685°С), so within the reciprocal system Li,Na,U||F,Cl , diagonal LiF-NaCl is stable. It is also known [2, Р. 88] that a NaF-UF4 system is characterized by 3 eutectics (0.215 mole UF4 at 618°С; 0.28 mole UF4 at 623°С and 0.56 mole UF4 at 680°С), 2 peritectics (0.325 mole UF4 at 648°С and 0.37 mole UF4 at 673°С, 2 congruently melting compounds (R1=3NaF-UF₄, R2=7NaF-6UF₄), and 2 incongruently melting ones (2NaF-UF₄, 5NaF-3UF₄). As a result, it is possible to consider 3 variants of polyhedration: two with the stable diagonal LiF-UCl₃ (LiF-UCl₃, NaF-UCl₃ and LiF-UCl₃, NaCl-UF4), and one with the diagonals LiCl-UF₄, NaCl-UF₄. In the case of polyhedration with the stable diagonals LiF-UCl₃ and 3 diagonals from the apex NaCl, the initial prism of the reciprocal system consists of 5 tetrhedra: LiF-NaF-NaCl-R₁, LiF-UF₄-NaCl-UCl₃, LiF-UF₄--NaCl-R₂, LiF-LiCl-NaCl-UCl₃, and LiF-NaCl-R₁-R₂. When all stable diagonals are of the eutectic type, then the tetrahedron LiF-LiCl-NaCl-UCl₃ is bounded by 5 eutectic binary systems and by LiCl-NaCl. This includes the continuous rows of solid solutions. Systems LiF-NaF-NaCl-R₁, LiF-NaF-NaCl-UCl₃ , and LiF-NaF-UCl₃-R₁ are bounded by 6 binary and 4 ternary eutectic systems. This work has been performed under the program of fundamental research SB RAS (project 0336-2016-0006) and partially supported by the RFBR project 17-08-00875.

References:
1. V. Lutsyk, V. Vorob'еva, M. Parfenova, M. Lamueva. Materials for the Nuclear Reactors of Generation IV: Polyhedration of the Chloride-Fluoride Reciprocal Systems // Sustainable Industrial Processing Summit & Exhibition SIPS-2018. Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing. - Id Paper: 96 https://www.flogen.org/sips2018/technical_program.php?a=c51ce410c124a10e0db5e4b97fc2af3 2. Gabcova J., Peschl J., Malinovsky M. et al // Chemicke Zvesti (Chemical Papers). 1976. V. 30. No 6. P. 796-804.
3. Thoma R.E., Editor. Phase Diagrams of Nuclear Reactor Materials, Union Carbide Corp., Oak Ridge, Tennessee, 1959, 205 pp.

16:45: [MoltenFriPM211] Keynote
Catalysis and Gas Separation by Supported Ionic Liquids
Rasmus Fehrmann¹ ; Leonard Schill¹ ; Anders Riisager² ; Jakob Marinkovic³ ; ¹DTU Chemistry, Lyngby, Denmark; ²DTU Chemistry, Kgs. Lyngby, Denmark; ³Technical University of Denmark, Department of Chemistry, Lyngby, Denmark;
Paper Id: 312 [Abstract]

Ionic liquids are thermally stable, low-melting salts (mp. below 100°C), which typically consist of mixed organic and inorganic halogen-containing or halogen–free ions. The exceptionally low melting temperatures are obtained as result of low ion charge densities, which reduce intermolecular forces between the ions. Ionic liquids are unique compared to all other commonly applied liquids, as they are generally non-volatile and thermally stable in their whole liquid range (often 25-400°C), i.e. below their decomposition temperature. These characteristics enable their replacement for common volatile organic solvents (VOCs), thereby facilitating more environmentally friendly and sustainable technologies. The non-volatile property of most ionic liquids makes it possible to maintain the liquid intact on the surface of a porous support. This is impossible with almost all other solvents since they will evaporate during use, a scenario that has made a very limited number of industrial SLP (Supported Liquid Phase) catalysts successful so far. Here we demonstrate that such Supported Ionic Liquid-Phase (SILP) materials, with the catalyst dissolved in the ionic liquid, make heterogenized, homogeneous catalytic processes possible. This is done by turning the cumbersome batch operation into a continuous flow process design without compromising the traditionally high selectivity and heat transfer properties. Thus SILP catalyst processes regarding hydroformylation and alkoxycarbonylation of alkenes, as well as carbonylation of alcoholes, will be highlighted. In addition, our research shows that due to environmental and climate concern, the gases CO₂, NO and SO₂ can be reversible and selectively absorbed using different ILs and that SILP absorbers. These ILs and SILP absorbers are promising materials for industrial flue gas cleaning, natural and biogas sweetening, and selective separation of gas mixtures. Absorption/desorption efficiency can be tuned by design of the ionic liquid, temperature, pressure and gas concentrations. The SILP technology dramatically improves the overall kinetics of both catalysis and the gas absorption and desorption processes compared to bulk ionic liquid performance.

References:
1. A. Riisager, R. Fehrmann, S. Flicker, M. Haumann, P. Wasserscheid\nAngew. Chem. Int. Ed. 2005, 44, 815 (VIP)\n2. A.J. Kunov-Kruse, P. Thomassen, S. Mossin, A. Riisager, R. Fehrmann, \nChemistry: A European Journal, 22, 11745, 2016\n3 Supported Ionic Liquids, Eds. R. Fehrmann, A. Riisager, M. Haumann,\nWiley-VCH Verlag GmbH, 2014

17:10: [MoltenFriPM212]
Carbon Dioxide Capture and Transformation in Ionic Liquids
Jairton Dupont¹ ; Muhammad Qadir¹ ; Nathalia Simon¹ ; Marcileia Zanatta¹ ; ¹UFRGS, Porto Alegre, Brazil;
Paper Id: 151 [Abstract]

Despite a growing number of climate change mitigation policies and increasing investments associated with the capture and storage technologies for CO₂, the anthropogenic emissions of this gas are inexorably growing. [1] Hence, there is a growing interest in finding large-scale commercially viable end-use opportunities for CO₂ utilization. In the last decade, thermal, electrochemical, and photo-reduction of carbon dioxide to CO and/or hydrocarbon derivatives has grown into a blooming field of research. [2, 3] A simple combination of sunlight, aqueous solutions saturated with carbon dioxide, and appropriate photocatalysts may yield CO (reverse semi-combustion) and/or hydrocarbon derivatives (reverse combustion). [4, 5] Ionic liquids (ILs) are known to solubilize and, in some cases, to activate carbon dioxide by stabilizing radical/anionic species [6, 7] and hence, constitute an attractive material for CO₂ capture/reduction.[8] We will present the most recent aspects on CO₂ capture by ILs. This involves the formation of bicarbonate, and its hydrogenation promoted metal nanoparticles to hydrocarbons and formic acid, as well as orgono-photocatalytic and electrocatalytic reduction to carbon monoxide. The basic aspects of the multi-roles of ionic liquids in these transformations will be detailed based on experimental and theoretical evidence, particularly in IL aqueous solutions.

References:
[1] Lewis, R. J., Sr., Hazardous Chemicals, Desk Reference, 5th Ed, Wiley-Interscience, New York, (2002).
[2] Mac Dowell, N.; Fennell, P. S.; Shah, N.; Maitland, G. C., Nature Clim. Change 7 (2017) 243-249.
[3] J. L. White, M. F. Baruch, J. E. Pander Iii, Y. Hu, I. C. Fortmeyer, J. E. Park, T. Zhang, K. Liao, J. Gu, Y. Yan, T. W. Shaw, E. Abelev and A. B. Bocarsly, Chem. Rev., 115 (2015) 12888-12935.
[4] Y. Chen, G. Ji, S. Guo, B. Yu, Y. Zhao, Y. Wu, H. Zhang, Z. Liu, B. Han and Z. Liu, Green Chem., 19 (2017) 5777-5781.
[5] Rosen, B. A.; Salehi-Khojin, A.; Thorson, M. R.; Zhu, W.; Whipple, D. T.; Kenis, P. J.; Masel, R. I, Science. 334 (2011) 643-644.

SESSION: MoltenSatAM-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Sat Oct, 26 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Anders Riisager; Adam Clancy; Session Monitor: TBA

11:20: [MoltenSatAM01] Keynote
Capture and Transformation of Carbon Dioxide Confined in Ionic Liquids
Jairton Dupont¹ ; ¹UFRGS, Porto Alegre, Brazil;
Paper Id: 13 [Abstract]

Despite a growing number of climate change mitigation policies and increasing investments associated with the capture and storage technologies for CO₂, the anthropogenic emissions of this gas are inexorably growing. [1] Hence, there is a growing interest in finding large-scale commercially viable end-use opportunities for CO₂ utilization. In the last decade, thermal, electrochemical, and photo-reduction of carbon dioxide to CO and/or hydrocarbon derivatives has grown into a blooming field of research. [2, 3] A simple combination of sunlight, aqueous solutions saturated with carbon dioxide, and appropriate photocatalysts may yield CO (reverse semi-combustion) and/or hydrocarbon derivatives (reverse combustion). [4, 5] Ionic liquids (ILs) are known to solubilize and, in some cases, to activate carbon dioxide by stabilizing radical/anionic species [6, 7] and hence, constitute an attractive material for CO₂ capture/reduction.[8] We will present the most recent aspects on CO₂ capture by ILs. This involves the formation of bicarbonate, and its hydrogenation promoted metal nanoparticles to hydrocarbons and formic acid, as well as orgono-photocatalytic and electrocatalytic reduction to carbon monoxide. The basic aspects of the multi-roles of ionic liquids in these transformations will be detailed based on experimental and theoretical evidence, particularly in IL aqueous solutions.

References:
[1] N. Mac Dowell, P.S. Fennell, N. Shah, G.C. Maitland, The role of CO2 capture and utilization in mitigating climate change, Nature Clim. Change, 7 (2017) 243-249.
[2] T.A. Faunce, W. Lubitz, A.W. Rutherford, D. MacFarlane, G.F. Moore, P. Yang, D.G. Nocera, T.A. Moore, D.H. Gregory, S. Fukuzumi, K.B. Yoon, F.A. Armstrong, M.R. Wasielewski, S. Styring, Energy and environment policy case for a global project on artificial photosynthesis, Energ. Environ. Sci., 6 (2013) 695-698.
[3] K. Li, B. Peng, T. Peng, Recent Advances in Heterogeneous Photocatalytic CO2 Conversion to Solar Fuels, ACS Catal., 6 (2016) 7485-7527.
[4] J.L. White, M.F. Baruch, J.E. Pander Iii, Y. Hu, I.C. Fortmeyer, J.E. Park, T. Zhang, K. Liao, J. Gu, Y. Yan, T.W. Shaw, E. Abelev, A.B. Bocarsly, Light-Driven Heterogeneous Reduction of Carbon Dioxide: Photocatalysts and Photoelectrodes, Chem. Rev., 115 (2015) 12888-12935.
[5] S.N. Habisreutinger, L. Schmidt-Mende, J.K. Stolarczyk, Photocatalytic reduction of CO2 on TiO2 and other semiconductors, Angew. Chem. Int. Ed., 52 (2013) 7372-7408.
[6] B.A. Rosen, A. Salehi-Khojin, M.R. Thorson, W. Zhu, D.T. Whipple, P.J. Kenis, R.I. Masel, Ionic liquid-mediated selective conversion of CO(2) to CO at low overpotentials, Science, 334 (2011) 643-644.
[7] V. Strehmel, Radicals in Ionic Liquids, ChemPhysChem, 13 (2012) 1649-1663.
[8] S. Wang, X. Wang, Imidazolium Ionic Liquids, Imidazolylidene Heterocyclic Carbenes, and Zeolitic Imidazolate Frameworks for CO2 Capture and Photochemical Reduction, Angew. Chem. Int. Ed., 55 (2016) 2308-2320.

11:45: [MoltenSatAM02]
Computer Simulation of the Anion Effect in Gas Absortpion of Ionic Liquids
Hubert Stassen¹ ; ¹Instituto de Química - Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil;
Paper Id: 257 [Abstract]

Ionic liquids are currently investigated as promising materials for the absorption, storage, and separation of gases, such as CO2 [1], and H₂S [2] among others. Ionic liquids based on the imidazolium cation are intensively studied for these purposes [3]. The possibility of combining distinct cations with different anions permits an easy design of ionic liquids. In an attempt to extract the structure-gas absorption relationship, we performed molecular dynamics computer simulations [4] on ionic liquids containing the 1-butyl-3-methylimidazolium cation and several anions (acetate, prolinate, BF₄^-, Br^-) interacting under typical experimental conditions (298 K, 10 bar gas pressure) with different gases (CO₂, N₂, methane, H₂ S). Two series of simulations have been carried out to characterize the physical absorption of the gases: i) ionic liquids containing 0.25 molar fractions of the gases, and ii) pure ionic liquids interacting with the gas phase. The first series of simulations revealed that the structure of the ionic liquids is essentially maintained when the gas is dissolved. N₂ and methane are only found in the apolar domains of the ionic liquids presenting a tendency of separating phases, whereas CO₂ and H₂S also enter the polar domains of the ionic liquid producing stable solutions. The second series of simulations demonstrated that the ionic liquids only weakly absorb N₂ and methane, but are able to capture large amounts of CO₂ and, especially, H₂S from the gas phase. In this process of physical absorption of the gases, the small BF₄^- anion, offering several coordination sides for the gas molecules, performs best.

References:
[1] S. Zeng, X. Zhang, L. Bai, X. Zhang, H. Wang, J. Wang, D. Bao, M. Li, X. Liu, S. Zhang, Chem. Rev. 117 (2017), 9625-9673.
[2] M.S. Shah, M. Tsapatsis, J.I. Siepmann, Chem. Rev. 117 (2017), 9755-9803.
[3] N.M. Simon, M. Zanatta, J. Neumann, A.L. Girard, G. Marin, H. Stassen, J. Dupont, Chem. Phys. Chem 19 (2018), 2879-2884.
[4] J. de Andrade, E.S. Böes, H. Stassen, J. Phys. Chem. B 106 (2002), 3546-3548 and 13344-13351.

12:10: [MoltenSatAM03]
Selective recovery of Neodynium from NdFeB magnets in molten salts
Patrick J. Masset¹ ; Mickael Mery² ; ¹Technallium Engineering & Consulting, Steinberg am See, Germany; ²Fraunhofer UMSICHT, Sulzbach-Rosenberg, Germany;
Paper Id: 268 [Abstract]

Rare earths (RE) elements are becoming very important for current and future industrial products, such as computers, LCD screens and lasers, but also for so-called "green technologies", such as wind turbines, electric cars and bicycles [1]. Due to highly volatile markets, the high environmental impacts, and the geopolitical challenges of raw material supply and production, many efforts are made worldwide to develop new recycling processes. Only a few countries have access to neodymium; China dominates the world production with above 90 % of the whole market. According to a recent study of the European Union [2] and the US Department of Energy [3], the RE elements are the most critical raw material resource. Despite extensive research activities in this field, only about 1 % of the RE elements are currently recycled. [4] Currently, different processes are used or investigated for the recovery of neodymium, such as hydrometallurgy, glass-based method, and direct melting. In this work, we investigate the selective recovery of neodymium by using pyrochemical based processes. Anodically, Nd is dissolved selectively from the NdFeB matrix and metallic Nd is recovered at the cathode. It was shown that electrolyte composition is crucial as it impacts the electrolysis efficiency significantly. Mass balance and Nd recovered analysis confirms the results of the electrochemical investigations and electrolysis runs.

References:
[1] NDR, Neodym: Das schmutzige Geheimnis sauberer Windräder, Pressemitteilung des Norddeutschen Rundfunks, http://www.ndr.de/unternehhmen/presse/pressemitteillungen/pressemeldungndr8137.html.
[2] Commission, Critical raw materials for the EU, Report of the Ad-hoc Working Group on defining critical raw materials, 2010.
[3] U.S. Department of Energy, Critical materials strategy, 2011.
[4] K. Binnemans, P. T. Jones, B. Blanpain, T. Van Gerven, Y. Yang, A. Walton and M. Buchert, J. Clean. Prod., 2013, 51, 1-22.

12:35: [MoltenSatAM04] Keynote
Like likes like in ionic liquids: When cooperative hydrogen bonding overcomes Coulomb repulsion between ions of like charge
Ralf Ludwig¹ ; ¹University of Rostock, Rostock, Germany;
Paper Id: 85 [Abstract]

"Unlike charges attract, but like charges repel". We recently challenged This conventional wisdom for ionic liquids (ILs). Here, we show that like-charged ions attract each other despite the powerful opposing electrostatic forces. In principle, cooperative hydrogen bonding between ions of like-charge can overcome the repulsive Coulomb interaction while pushing the limits of chemical bonding [1-11]. The key challenge of this solvation phenomenon is to establish design principles for the efficient formation of clusters of like-charged ions in ionic liquids. For that purpose, we combined weakly coordinating anions with polarizable cations, which are all equipped with hydroxyl groups for possible H-bonding. The formation of H-bonded cationic clusters can be controlled by the interaction strengths of the counterions and the delocalization of the positive charge on the cations [1-4]. Strongly interacting anions and localized charges on the cations result in hydrogen bonded ions of opposite charge, whereas weakly coordinating anions and delocalized charge on the cations lead to the formation of H-bonded cationic clusters up to cyclic tetramers. If we increase the distance between the hydroxyl groups and the positive charge centre on the cation we can further support the cationic cluster formation. These clusters are observed by bulk infrared (FT-IR) and cryogenic vibrational spectroscopy, and interpreted by density functional theory (DFT) calculations on neutral and ionic clusters [1-11]. The formation of cationic clusters is also reflected in NMR coupling parameters and relaxation times. Additional molecular dynamics simulations (MD) provide information about the lifetimes of the hydrogen bonds in the cationic clusters compared to those in the typical ion pairs [9]. Moreover, we show that cationic clustering influences the phase behavior of ionic liquids. These ILs can be supercooled and form glasses.[6]

References:
[1] A. Knorr, K. Fumino, A.-M. Bonsa, R. Ludwig, Phys. Chem. Chem. Phys. 17, 30978 (2015).
[2] A. Knorr, R. Ludwig, Sci. Rep. 5, 17505 (2015).
[3] A. Knorr, P. Stange, K. Fumino, F. Weinhold, R. Ludwig, ChemPhysChem 17, 458 (2016).
[4] A. Strate, T. Niemann, D. Michalik, R. Ludwig, Angew. Chem. Int. Ed. 56, 496 (2017).
[5] A. Strate, T. Niemann, R. Ludwig, Phys. Chem. Chem. Phys. 19, 18854 (2017).
[6] T. Niemann, D. Zaitsau, A. Strate, A. Villinger, R. Ludwig, Sci. Rep. 8, 14753 (2018).
[7] F. Menges, H. Zeng, P. Kelleher, O. Gorlova, M. Johnson, T. Niemann, A. Strate, R. Ludwig, J. Phys. Chem. Lett. 9, 2979 (2018).
[8] T. Niemann, A. Strate, R. Ludwig, F. Menges, H. Zeng, P. Kelleher, O. Gorlova, M. Johnson, Angew. Chem. Int. Ed. 75, 15364 (2018).
[9] A. Strate, J. Neumann, V. Overbeck, A.-M. Bonsa, D. Michalik, D. Paschek, R. Ludwig, J. Chem. Phys. 148, 193843 (2018).
[10] T. Niemann, P. Stange, A. Strate, R. Ludwig, ChemPhysChem, 19, 1691 (2018)
[11] T. Niemann, P. Stange, A. Strate, R. Ludwig, Phys. Chem. Chem. Phys., DOI: 10.1039/C8CP06417B (2019)

SESSION: MoltenSatPM1-R1	Angell International Symposium on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability (7th Intl. Symp. on Molten Salt, Ionic & Glass-forming Liquids: Processing and Sustainability).
Sat Oct, 26 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Vasily Lutsyk; Pierre Lucas; Session Monitor: TBA

14:00: [MoltenSatPM105] Invited
Tuning the kinetics in phase-change materials
Shuai Wei¹ ; ¹RWTH Aachen University, Aachen, Germany;
Paper Id: 118 [Abstract]

The phase-change materials (PCMs) such as Ge-Sb-Te alloys can be reversibly switched between amorphous and crystalline states on a timescale of nanoseconds. The phase switch provides the material basis for next-generation non-volatile phase-change memory devices. I show experimental studies of PCM kinetics spanning over 1000 K in temperature and 16 orders of magnitude in timescales. In the (supercooled) liquid states, this class of materials exhibits a variety of anomalous behaviors in thermodynamics and kinetics, such as heat capacity and density maxima, dynamic crossovers, and a breakdown of the Stokes-Einstein relations. These anomalies are related to a high- to low-density and metal-to-semiconductor liquid-liquid transition hidden below the melting temperature obscured by fast crystallization. I will bring the idea of tuning this transition through adjusting metallicities to attain desired switching kinetics for faster and more reliable phase-change memory applications.

References:
1.Wei, S., Evenson, Z., Stolpe, M., Lucas, P. & Angell, C. A. Breakdown of the Stokes-Einstein relation above the melting temperature in a liquid phase-change material. Science Advances 4, eaat8632 (2018).
2.Wei, S., Coleman, G. J., Lucas, P. & Angell, C. A. Glass Transitions, Semiconductor-Metal Transitions, and Fragilities in Ge-V-Te (V=As, Sb) Liquid Alloys: The Difference One Element Can Make. Phys. Rev. Applied 7, 034035 (2017).
3.Wei, S., Lucas, P. & Angell, C. A. Phase change alloy viscosities down to Tg using Adam-Gibbs-equation fittings to excess entropy data: A fragile-to-strong transition. J. Appl. Phys. 118, 034903 (2015).

14:25: [MoltenSatPM106]
Proton shuttling in protic ionic liquid fuel cells
Darren Walsh¹ ; Daniel Smith¹ ; ¹University of Nottingham, Nottingham, United Kingdom;
Paper Id: 254 [Abstract]

The conventional polymer-electrolyte membranes used in low-temperature fuel cells are limited to operating temperatures below about 120 celsius, as they must be fully hydrated to facilitate proton transport. Protic ionic liquids (PILs) are ionic liquids formed by transferring protons from Brønsted acids to Brønsted bases, and it has recently been shown that some ammonium-based PILs inherently exhibit high proton conductivities. Consequently, PILs have been proposed for use as electrolytes in non-humidified fuel cells that can operate above 120 celsius (at intermediate temperatures).^1-3 While they nominally consist entirely of ions, however, PILs can often contain a significant quantity of neutral species (either molecules or ion clusters) that can affect the physicochemical properties of the liquids.<br />In this contribution, we first describe an electroanalytical method for detecting and quantifying residual Brønsted acids in a series of ammonium-based PILs. Ultramicroelectrode voltammetry reveals that some of the accepted methods for synthesizing PILs can readily result in the formation of nonstoichiometric PILs containing up to 230 mmol/L residual acid. We will then show that residual acids in PILs can have a drastic effect on the electrocatalytic oxygen reduction reaction (ORR) in the PILs. For example, the potential at which the ORR occurs at Pt in the PIL diethylmethylammonium trifluoromethanesulfonate, [dema][TfO], decreases linearly as the strength of the proton donor in the liquid decreases. In pure [dema][TfO], in which the proton donors during the ORR are the cations of the PIL (p<i>K</i>_a = 10), the onset potential of the ORR is the same as that of the hydrogen oxidation reaction (HOR) in the PIL. These observations have significant implications for the use of PILs as electrolytes in fuel cells and indicate that the best PILs are highly "acidic" liquids that can support oxygen reduction at high potentials.

References:
1. M. Watanabe, M. L. Thomas, S. Zhang, K. Ueno, T. Yasuda, K. Dokko, Chem. Rev. 2017, 117, 7190-7239.\n2. J. Thomson, P. Dunn, L. Holmes, J.-P. Belieres, C. A. Angell, D. Gervasio, ECS Trans.\n2008, 13, 21-29.\n3. D. R. MacFarlane, N. Tachikawa, M. Forsyth, J. M. Pringle, P. C. Howlett, G. D. Elliott,\nJ. H. Davis Jr., M. Watanabe, P. Simon, C. A. Angell, Energy Environ. Sci. 2014, 7, 232-250.

14:50: [MoltenSatPM107] Invited
Structure and dynamics of tetrahedral ionic glass-forming liquids
Pierre Lucas¹ ; ¹University of Arizona, Tucson, United States;
Paper Id: 75 [Abstract]

Molten halide salts are of interest for applications as heat transport fluids (HTF) in concentrated solar power plants due to their excellent resilience at high temperatures. Application as HTF requires a combination of properties including high heat capacity, low vapor pressure and low viscosity to optimize fluid flow through heat-exchanger networks. A fundamental understanding of viscous behavior in halide salts in relation to their structure is therefore of interest for optimizing HTF formulations. Here we perform a combination of modeling (ab-initio molecular dynamics) [1] and spectroscopic analysis (Raman) [2] of tetrahedral zinc chloride melts as a function of temperature. It is found that the ratio of edge- to corner-sharing tetrahedra varies with temperature and that it can be correlated with the viscous behavior through configurational entropy considerations. More interestingly, it is observed that a fragile-to-strong transition occurs at high temperature which can also be correlated with a change in structural behavior [3]. This behavior is compared with that of other tetrahedral melts and found to be related to changes in multiple physical properties such as heat-capacity, density, compressibility etc.

References:
[1] A.Q. Alsayoud, M. Venkateswara Rao, A.N. Edwards, P.A. Deymier, K. Muralidharan, B.G. Potter, K. Runge, P. Lucas, Structure of ZnCl2 Melt. Part I: Raman Spectroscopy Analysis Driven by Ab Initio Methods, J. Phys. Chem. B, 120 (2016) 4174-4181.
[2] P. Lucas, G.J. Coleman, M. Venkateswara Rao, A.N. Edwards, C. Devaadithya, S. Wei, A.Q. Alsayoud, B.G. Potter, K. Muralidharan, P.A. Deymier, Structure of ZnCl2 Melt. Part II: Fragile-to-Strong Transition in a Tetrahedral Liquid, J. Phys. Chem. B, 121 (2017) 11210-11218.
[3] P. Lucas, Fragile-to-Strong transitions in Glass Forming Liquids, J. Non-Cryst. Solids, (2019) in print.

SESSION: RecyclingSatPM2-R1	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Ambrosia A (77/RF)
Session Chairs: Shrenivas Ashrit; Elsayed Mousa; Session Monitor: TBA

15:55: [RecyclingSatPM209]
Development and implementation of the oxidized copper ores' heap leaching processes in the Republic of Kazakhstan
Larissa Kushakova¹ ; Yevgeniy Startsev¹ ; Natalya Sizikova¹ ; ¹VNIItsvetmet, Ust-Kamenogorsk, Kazakhstan;
Paper Id: 44 [Abstract]

Nowadays, it is obvious that the share of the hydrometallurgical operations in the global volumes of non-ferrous metals production is gradually increasing [1]. This trend is specific to the Republic of Kazakhstan as well. Rapid development of the copper hydrometallurgy based on the processes of heap leaching (HL), solvent extraction (EX) and electrowinning (EW) resulting in getting highly-pure copper cathodes and economic efficiency has been specific to the country during recent years. <br />The Eastern mining-and-metallurgical research institute for non-ferrous metals (VNIItsvetmet) has been running the researches on application of HL-EX-EW processes for processing of copper-bearing ores of Kazakhstan deposits since 1997. The heap leaching tests include study of the ores’ material composition, bottle roll and column tests, selection of the optimal extractant for each pregnant leaching solution (PLS), etc. Research results can be used to come up with the feasibility studies, Process Procedures, basic design, and detailed engineering of the ore-processing plants [2]. <br />There is a number of plants operating nowadays in Kazakhstan under HL-SX-EW technology which were designed and constructed on the basis of VNIItsvetmet research results. There are, for example, ore-processing plants at the deposits of Kounrad (annual capacity of 13 thousand tons of copper cathodes), Ayak-Kodzhan (annual capacity of 3 thousand tons of copper cathodes), Aktogay (annual capacity of 15 thousand tons of copper cathodes) and others [3].

References:
[1] Mark. E. Schlesinger, Mattew J. King, Kathryn C. Sole, William G. Davenport. Extractive Metallurgy of Copper (2011) 481.\n[2] L. Kushakova, N. Sizikova. Process aspects of Kazakhstan copper ores’ heap leaching, Intensification of hydrometallurgical processes of recycling of natural and technogenic raw materials, St. Petersburg (2018), 143-146.\n [3] Larissa Kushakova, Yevgeniy Startsev. Ore processing under SX-EW technology - Kazakhstan experience // Lix Users’ Conference 2017 by BASF, Santa-Cruz, Chile, November 13th-15th, 2017.

16:20: [RecyclingSatPM210]
Using zinc cake flotation in columnar type equipment for increasing of Waelz Process Efficiency
A. Panshin¹ ; Pavel Kozlov² ; Mark Viduetskiy³ ; ¹LLC "UMMC-Holding", Verkhnyaya Pyshma, Russian Federation; ²UMMC-Holding, Moscow, Russian Federation; ³Institute of of Material Science and Metallurgy, Ural Federal University, Yekaterinburg, Russian Federation;
Paper Id: 144 [Abstract]

The Chelyabinsk Zinc Plant carried out the pilot tests of flotation technology removal of sulfur from zinc cake on pilot pneumatic flotation machine CFM-180. A key principle of the operation of pneumatic machines CFM is pulp oxygenation with finely dispersed air bubbles in the ejector, which reduces flotation time and increases its selectivity. Technological schemes of testing include basic flotation of original cake, control flotation of the chamber product, and two cleaner flotations of froth product. In comparison with mechanical flotation machine, the following indicators increase during flotation of cake on CFM: - Initial feed performance (by 4 times); - Sulfur recovery into flotation concentrate (by 1.4 times); - Silver recovery into flotation concentrate (by 1.2 times). The washed chamber product (0.06% of sulfide sulfur and 2.98% of sulphate sulfur) and foam product (18.1% of sulfide sulfur) were obtained during testing. The results of laboratory studies of the processing of the flotation products are presented. The flotation and zinc cake washing can reduce zinc cake output by 20-25%, which allows increase of the processing volumes of oxidized imported raw materials by the Waelz-process. Processing of chamber flotation product (zinc cake with low sulfur content) by the Waelz-process can improve the Waelz kiln performance and reduce the coke breeze consumption. Foam product can be used as a sulfurizing additive under independent processing of copper plant dust with zinc, lead, and tin extraction into fumes. On the basis of the carried out tests, the project of the processing site of zinc cakes by flotation on the basis of industrial machines CFM-600 and CFM -1400 has been realized.

References:
[1] Kozlov P.A., Kazanbaev L.A., Ivakin D.A. et al., Forecast calculation of yield of zinc, copper and cobalt cakes. Russian Journal of Non-Ferrous Metals. 2006.No.4.pp.6-13.
[2] Kozlov P.A., Waelz-process. Moscow: "Ore and Metals" Publishing House, 2002.
[3] Panshin A.M., Kozlov P.A., Ivakin D.A., Research of thermaltechnical peculiarities of operation of pipe furnaces with Waelz-processing of metallurgy wastes., Non-Ferrous Metals. 2013. No.8, pp. 48-50.

16:45: [RecyclingSatPM211]
Potential of briquetting in sustainable recycling of residues in steel industry
Elsayed Mousa¹ ; ¹Swerim AB, Luleå, Sweden;
Paper Id: 147 [Abstract]

Iron and steel making is accompanied by generations of various types of by-products and waste materials which usually need some pre-treatment to be usable [1]. The resource efficiency, environmental, and economic benefits are vital keys to motivate the re-circulation of steel mill residues and recovery of their associated minerals as far as possible to save the virgin resources and reduce material sent to landfills. Nowadays, the steel industry pays more attention to adopt a circular economy model to reach zero waste through reuse and recycling of all by-products. In this context, briquetting can play an important role in residues re-circulation in the steel industry and circular economy [2-5]. The developed briquettes should have adequate chemical composition and mechanical strength to be suitable for usage in iron and steel production units [6, 7]. In the present study, the residues rich with lime and metallic iron are selected for developing briquettes suitable for basic oxygen furnace (BOF) implementation. The briquetting is performed with binders which have low sulfur content to enhance the recycling efficiency. Various recipes are designed and produced using lab scale hydraulic press and pilot scale roller press. The mechanical strength of the developed briquettes is evaluated using cold compression strength device and drop test. The potential of the developed briquettes on saving lime and scrap will be addressed. The gained knowledge can contribute to the enhancement of residues re-circulation in other metallurgical sectors.

References:
[1] Fact Sheet- Steel Industry by-products; https://www.worldsteel.org/en/dam/jcr:1b916a6d-06fd-4e84-b35d-c1d911d18df4/Fact_By-products_2016.pdf; [accessed on 18 January 2018].
[2] L. Sundqvist, K.O. Jonsson, H.O. Lampinen, L.E. Eriksson: Committee on Raw Materials-Seminar, Proc. International Iron and Steel Institute (IISI), (1999), Brussels.
[3] K. Kundvist, M. Braimming, J. Riesbeck, A. Wedholm: New methods for waste minimization in an integrated steel site; Chem. Eng. Trans. (2015), No. 45, 739-44.
[4] S. Maneesh: Studies on the cement bonded-briquettes of iron and steel plant by-products as burden material for blast furnaces (2002) PhD thesis, Chemical and Metallurgical Engineering/Process Metallurgy, Luleå University of Technology. ISRN: LTU-DT-02/50-SE.
[5] A. Andersson, M. Andersson, E. Mousa, A. Kullerstedt, H. Ahmed, B. Bjairkman, L. Sundqvist-Aikvist: The potential of recycling the high-zinc fraction of upgraded BF sludge to the desulfurization plant and basic oxygen furnace; Metals (2018), No. 8, 1-13.
[6] C. Coenraets, J. Banchet: Binder-free compaction: a new technology to enhance efficient recycling of by-products, 8th European Oxygen Steelmaking Conference, 10-12 October 2018, Taranto, Italy.
[7] E.A. Mousa, H.M. Ahmed, C. Wang: Novel approach towards biomass lignin utilization in ironmaking blast furnace; ISIJ Int. 57 (2017), No. 10, 788-1796.

17:10: [RecyclingSatPM212]
EFFECT OF NON-STATIONARY ELECTRIC CURRENT ON CHEMICAL REACTIONS AT THE METAL / ELECTROLYTE INTERFACE
Essen Suleimenov¹ ; ¹Kazakh British Technical University, Almaty, Kazakhstan;
Paper Id: 260 [Abstract]

Modern experimental material has given reason to believe that the key points in the development of scientific concepts about the nature and mechanism of physicochemical processes are the following provisions of M Faraday: the identity of energy manifestations in the interaction of material objects and the discrete nature of electric current. Developed without taking into account the work of M. Faraday, the theory allowed not to take into account the identity of energy manifestations in the interaction of material objects. Hence, there was a lack of work to determine the real mechanism of heat transfer between material objects. This circumstance influenced the lack of attention to the use of the discontinuity of electric current for practical use. We have shown that a change in a wide range of electrical signal parameters can promote unusual chemical reactions and physicochemical processes at the interface and in condensed systems. Phase transitions in an oxide melt can occur without noticeable thermal effects. That is, the structure of this liquid does not only depend on the chemical composition and temperature. Under the influence of electromagnetic fields, the conductivity of the melts may decrease with increasing temperature and change at a constant temperature. Crossed electromagnetic fields cause phase and quantitative division of melts of both synthetic oxide melts, and oxide-sulfide multicomponent systems, etc. The possibility of dissolving metallic molybdenum in alkaline solutions has been established experimentally. The dissolution rate is not proportional to the frequency of the current and the dissolution stops as the current frequency increases. Dissolution ceases at any current parameters and concentrations of potassium oxide at temperatures above 75 ^oC. The dissolution of molybdenum does not occur at any current parameters if the concentration of potassium oxide exceeds 9%. It was shown that the electrical signal at the metal aluminum / aluminate solution interface accelerates the decomposition of the aluminate solution by at least 4 times (in some cases, from 45 hours to 8 hours). Studies have been conducted on the use of a sulfurgraphite composite electrode for organizing a parallel process for the formation of a leaching agent (sulfuric acid, sodium thiosulfate, etc.) and for the extraction of metals into a solution from various metal-containing raw materials. These and our other experimental data can serve as a basis for revising some theoretical concepts in the natural sciences and creating effective technological processes.

SESSION: RecyclingSatPM3-R1	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Ambrosia A (77/RF)
Session Chairs: TBA Session Monitor: TBA

17:50: [RecyclingSatPM313]
Turning the Extractive-Waste Problems Into a Resource-Recovery Opportunity
Teodor Velea¹ ; Alexandra-georgiana Vatui² ; Ionut Macarescu² ; Ioana Andreea Chirea² ; Mika Paajanen³ ; Lieven Machiels⁴ ; Carlos Frias Gomez⁵ ; Vasile Predica⁶ ; Manuel Sevilla⁷ ; ¹National Research- Development Institute for Nonferrous and Rare Metals- IMNR Bucharest, Romania, Pantelimon, Romania; ²National Research- Development Institute for Nonferrous and Rare Metals- IMNR Bucharest, Romania, ILFOV, Romania; ³VTT TECHNICAL RESEARCH CENTRE OF FINLAND LTD, Tampere, Finland; ⁴, Heverlee, Belgium; ⁵Cobre las Cruces, S.A., Sevilla, Spain; ⁶National Research & Development Institute for Non-Ferrous and Rare Metals, Ilfov, Romania; ⁷COBRE LAS CRUCES (CLC), Seville, Spain;
Paper Id: 243 [Abstract]

Apart from metals, the mining and metallurgical processing of non-ferrous metals such as Cu, Pb, Zn, Au, Ag produces large volumes of waste [3]. A particular challenge is generated by waste containing residual sulphides, like pyrite, as sulphides can, upon oxidation, cause so-called acid mine drainage. This paper presents the results of experiments for advanced removal of sulphur in order to obtain near zero-waste and valuable metals products as well as other by-products [5]. The main process applied is leaching under pressure in an alkaline media (K₂CO₃, Na₂CO₃, KOH, NaOH) using air or oxygen at low to moderate temperatures and pressure (120-155^oC and 4-8 atm.) [1-2][4]. Results show that more than 96-99% of sulphur can be removed by leaching of pyrite in one stage while from an alkaline solution (coming from pressure leaching), pure crystals of K₂SO₄ / Na₂SO₄ were obtained as valuable by-products. This paper is part of the NEMO project which has received funding from the European Union, EU Horizon 2020 Programme under Grant Agreement No. 776846 - https://h2020-nemo.eu/.

References:
[1] T. Velea, V. Predica, L. Gherghe, The Sixth International Copper-Cobre Conference, Toronto 2007, Symposium on Copper Hydrometallurgy, vol. 4, pg. 221-230.\n[2] T. Velea, V. Predica, L Gherghe, International Conference Copper Metallurgy, Krakow, Poland 2011.\n[3] INTMET Project no. 689515/2015-2019 financed by EU in Horizon 2020 programme.\n[4] T. Velea, V. Predica, D. Taloi, S. Onisei Proceeding of the XV Balkan Minerals Proceeding Congress, Sozopol, Bulgaria, p 12-26, 2013.\n[5] NEMO Project Horizon 2020- No. 776846, 2018-2022, funding from EU

18:15: [RecyclingSatPM314]
Gastrointestinal Simulation Reactor System For Bioaccessibility Determination Of Potentially Toxic Elements
Thalia Garcia Rodriguez¹ ; Daniel Quiroz Vivanco² ; Margarita Gutierrez Ruiz¹ ; Maria Fernanda Mehle Jordan³ ; Benjamin Varela Orozco⁴ ; Violeta Andrea Uribe Castillo⁵ ; ¹UNAM, Mexico, Mexico; ²Universidad Nacional Autónoma de México (UNAM), Ciudad de México, Mexico; ³Comisión Reguladora de Energía, Ciudad de Mexico, Mexico; ⁴Instituto de Ciencias Aplicadas y Tecnología, Universidad Nacional Autónoma de Mexico, Ciudad de Mexico, Mexico; ⁵Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Ciudad de Mexico, Mexico;
Paper Id: 122 [Abstract]

Recently an innovative, patent pending reactor system based on the PBET method [1] (LABQA-RSGB), which simulates the human gastrointestinal tract, was developed and metal bioaccessibility was evaluated for mining waste solid samples [2]. Results obtained with this system are on par with those of US EPAs equipment from SW-846 Test Method 1340 [3].<br />The LABQA-RSGB system simulates stomach and small bowel conditions, while allowing for monitoring, pH adjustments and development of kinetic studies without interrupting the process nor altering the reactors’ temperature.<br />The current paper describes the improvements carried out on the LABQA-RSGB, in order to minimize systematic errors and potential sources of cross contamination, as well as allow design and reactor operation optimization [4]. Results of the bioaccessible fraction extracted with the new equipment (LABQA-SRSGB) were compared with those of the original LABQA-RSGB and US EPA equipments, using a reference material, internal controls and samples.<br />Coupled with continuous and simultaneous monitoring of pH, temperature and stirring within each reactor, the enhancements implemented in the LABQA-RSGB provide reliable results for various potentially toxic elements in different matrices.

References:
[1] M.W. Ruby, A. Davis, R. Schoof, S. Eberle, and C.M. Sellstone,"Estimation of Lead and Arsenic Bioavailability Using a Physiologically Based Extraction Test, "Environ. Sci. Technol. 30(2): 422-430, 1996.\n[2] Garcia Rodriguez, T. Gutierrez Ruiz M. E., Quiroz Vivanco D. Ceniceros Gomez A. Tavares T. Aguirre Gomez A. Determination of Bioaccessibility of As and Pb in Soils Polluted With Mining Wastes: A New Equipment That Simplifies the Gastric and Intestinal Phases Measurements. Sustainable Industrial Processing Summit & Exhibition, 4-7 November 2018, Rio Othon Palace, Rio De Janeiro, Brazil.\n[3] U.S. EPA, "Method 1340 in vitro bioaccessibility assay for lead in soil", Revision 1, February 2017, Update VI. EPA publication SW-846.\n[4] Quiroz Vivanco Daniel, (2018), Diseno de un equipo para realizar pruebas y analisis de bioaccesibilidad de metales en suelos, tesis de pregrado, Facultad de Quimica, Universidad Nacional Autonoma de Mexico, Ciudad de Mexico, Mexico.

SESSION: ManufacturingThuAM-R2	2nd Intl. Symp.on Advanced Manufacturing for Sustainable Development
Thu Oct, 24 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Fernand Marquis; Nikoloz Chikhradze; Session Monitor: TBA

11:20: [ManufacturingThuAM01] Keynote
Advances in Synthesis and Densification of Heterogeneous Ultrafine and Nanostructured Materials and Applications in Components and Devices
Fernand D. S. Marquis¹ ; Nikoloz Chikhradze² ; Tetiana Prikhna³ ; Eugene Olevsky¹ ; ¹San Diego State University, San Diego, United States; ²G. Tsulukidze Mining Institute, Tbilisi, Georgia; ³Institute for Superhard Materials, Kiev, Ukraine;
Paper Id: 456 [Abstract]

Because the strength, toughness and other engineering properties of heterogeneous materials are strong dependent on their grain size and density, the quest to achieve simultaneously dense and fine, ultrafine and nanostructured grain size materials has been one of the most important in materials science and engineering. In this work we explore novel approaches for producing dense and fine, ultrafine and nanostructured heterogeneous materials. Typical approaches consist of acoustic cavitation, high energy planetary ball milling, reaction synthesis, and shock synthesis and modified spark plasma synthesis, followed by dynamic and static consolidation and densification pre and post reaction synthesis. Typical heterogeneous multiphase, multi microstructural constituent materials covered in this work consist of tungsten heavy alloys, coated graphite powders, metal silicide and aluminides and ceramic composites. The synthesized and densified materials were fully characterized by OM, SEM, TEM, EDX analysis, quantitative image analysis, X-Ray diffraction and mechanical testing. This paper presents and discusses the effect of reaction and processing parameters on the microstructure, densification, strength and toughness of typical heterogeneous materials and their application into the manufacture of advanced components and devices.

11:45: [ManufacturingThuAM02]
Nuclear Fusion, Advantages and Disadvantages of Inertial Methods
Jerzy Pisarek¹ ; ¹Jan Dlugosz Univ. Faculty of Mathematics and Natural Science, Czestochowa, Poland;
Paper Id: 225 [Abstract]

The polish way of nuclear fusion will be described. The author will present some historical experiments performed by S.Kaliski’s team and some new alternative methods for nuclear fission, including his proposals of plasma stabilisation methods in plasma-focus arrangements. The high speed gas jet and some effects of laser-plasma interaction are used. Contrary to experiments led in Warsow by S.Kaliski, low-cost experiments led by the author had only one distinctive character and were realized at low energy densities. Obtained results, however, suggest the desirability of further research which would be performed in conditions that approach high-energetic systems of plasma-focus or laser-plasma-focus. With the sentence of the author, new mathematical tools will perform the essential role of designing new experiments. Their closer characteristics will become contained in the monograph prepared for the publication in the next year. The obtainment of the fusion reaction is not a critical problem for thermonuclear energetics today. The fusion reaction was obtained on the laboratory-scale, using both the inertial method (in Warsow, Sylwester Kaliski team) and in low-pressure-arrangements of Tokamak (in Nagoya Noria Aray team). The lifetime of the reactor and its economic profitability is a current problem. Inertial reactors, especially reactors of the plasma-focus type, are more permanent and significantly cheaper from reactors of the TOKAMAK type. Several ideas, probably leading to further increase of the durability of the inertial reactor elements, will be presented in the paper. Unfortunately, the several problems waiting for solutions must also be presented. In spite of the success of the experiments realized in Warsaw in the years 1974-78, works on the construction of the reactor able to have practical meaning were not undertaken. The most persons from prof. Kaliski’s team are not alive. The proposed presentation is dedicated to their memory.

References:
[1] S.Kaliski - "Lasery, synteza jadrowa" , Wiedza powszechna 1982\n[2] W.Nowak, J.Pisarek - "Use of CO₂ Laser Beam to Control of Arc Plasma Focus" - RAN98 2-nd International Symp. On Advanced Energy Conversion System and Related Technologies, Nagoya 1998, Japan, p. 332-333

12:10: [ManufacturingThuAM03] Keynote
Constrained Crystal Growth During Solidification of Particles and Splats in Uniform Droplet Sprays
Haris Doumanidis¹ ; Yiannos Ioannou² ; Hiroki Fukuda³ ; Teiichi Ando⁴ ; Claus Rebholz⁵ ; Yiliang Liao⁶ ; ¹Vin University, Hanoi, Viet Nam; ²Montanuniversitat Leoben, Leoben, Austria; ³Fukuda Metal Foil & Powder Co Ltd, Kyoto, Japan; ⁴Northeastern University, Boston, United States; ⁵University of Cyprus, Nicosia, Cyprus; ⁶University of Nevada Reno, Reno, United States;
Paper Id: 152 [Abstract]

Crystallite size is a primary determinant of the mechanical properties in solidified alloy deposits, and thus it is in need of predictive modeling. This project reports on employing uniform droplet spraying (UDS) [1] as a paradigm for solidification modeling of mono-size solid droplets in an oil bath, as well as planar and globular splats on a cooling substrate for AZ₉₁D and Mg₉₇ZnY₂ alloys [2]. The model combines a nucleation and dendrite fragmentation description from solidification theory with a framework for constrained growth of crystalline domains confined by adjacent developing ones [3]. The latter is based on differential attributes of the dynamic temperature field during solidification, derived from semi-analytical expressions for the simple droplet and splat geometries above. The model parameters are calibrated and its predictions are validated against measured domain size distributions on section micrographs, and found to be within a -10% to +14% estimation error range. Further improvement of the model via numerical thermal descriptions for off-line material design and optimization in additive manufacturing is discussed [4], along with its use as a real-time structural observer for closed-loop control based on temperature measurements in UDS-based processes.

References:
[1] Chun, J.-H., Passow, C.H., " Production of Charged Uniformly Sized Metal Droplets ", Massachusetts Institute of Technology, US Patent 5,266,098 (1992).\n[2] Fukuda, H, "Droplet-Based Processing of Magnesium Alloys for the Production of High-Performance Bulk Materials", PhD Thesis, MIE Dept, Northeastern University, Boston, MA (2009).\n[3] DiVenuti, A.G., Ando, T., " Free Dendritic Growth Model Accommodating Curved Phase Boundaries and High Peclet Number Conditions " Metallurgical and Materials Transactions A: Physical Metallurgy and Materials Science 29A (12) (1998): 3047-3056.\n[4] Wang, P., Sun, H., Wong, P.Y., Fukuda, H., Ando, T., " Modeling of Droplet-Based Processing for the Production of High-performance Particulate Materials Using Level Set Method ", Proc. of IMECE2008, ASME, Boston, MA (2008).

12:35: [ManufacturingThuAM04] Invited
Laser Induced Forward Transfer of Nanocomposites for Sensor and Biosensor Fabrication
Alexandra Palla Papavlu¹ ; Anca Bonciu¹ ; Mihaela Filipescu² ; Maria Dinescu² ; ¹National Institute for Lasers, Plasma and Radiation Physics, MAGURELE, Romania; ²National Institute for Lasers, Plasma and Radiation Physics, Magurele, Romania;
Paper Id: 215 [Abstract]

For many years, the detection of explosives and illegal drugs has been a major challenge which aligns with the speeding process of globalization. In particular, the illicit drug market is in continuous growth, as indicated by the 2.4 million drug seizures made by law enforcement. Therefore, the demand for alarm technologies that can be effectively used for developing illicit drug and explosives detection sensors becomes even more urgent. Under this point of view, electronic nose (e-nose) technologies meet all the above requirements, combining the data obtained by a sensor array selected for target application with computational intelligence to make an efficient chemical detection system. Of the various e-noses developed, the ones based on surface acoustic wave (SAW) devices are among the most sensitive. In addition, SAW vapor sensors are fast, highly sensitive and reversible. Their fabrication methods are compatible with standard integrated circuit technology, which makes them suitable for volume production and, hence, for cost reduction. Nowadays, however, e-noses based on SAW vapor sensors are used only for some very specific applications like detection of explosives and warfare agents. One of the main reasons for lack of a commercial development of SAW e-noses could be related to the available deposition techniques for the sensitive layers. In fact, SAW sensors require a uniform (i.e. continuous, uniform in thickness and hole-free) active layer along the wave propagation path in order to prevent high attenuation and degradation of the Q-factor. In this work, we will show that we can use different nanocomposites, i.e. polymers (for example poly[3-(6-carboxyhexyl)thiophe-2,5-diyl]) : graphene, as active materials. These could be printed solvent free by the laser (no clogging of nozzles or creating of special inks) and show sensitivities below 100 Hz/ppm for dimethyl methylphosphonate (a simulant for sarin gas), dichloromethane and ethyl acetate. The SAW e-nose system is based on an array configuration composed of six SAW resonators coated with five different polymers, plus an uncoated SAW device used as reference. In particular, laser-induced forward transfer was applied for the coating of SAW sensors with different nanocomposite layers. The nanocomposites as active materials detect different chemical interaction affinities of the vapors in a manner in which pattern recognition methods succeed in discrimination between target vapor classes and interferents.

References:
[1] M. Benetti, D. Cannata, E. Verona, A. Palla-Papavlu, V. Dinca, T. Lippert, M. Dinescu, F. Di Pietrantonio, Highly selective surface acoustic wave e-nose implemented by laser direct writing, Sensors and Actuators B: Chemical (2019)
[2] A. Palla Papavlu, T. Mattle, U. Lehmann, A. Hintennach, A. Griesel, A. Wokaun, T. Lippert, Scientific Reports 6, 25144 (2016)
[3] A. Palla Papavlu, M. Filipescu, S. Vizireanu, L. Vogt, S. Antohe, M. Dinescu, A. Wokaun, T. Lippert, Applied Surface Science 374, 312-317 (2016)

SESSION: ManufacturingThuPM1-R2	2nd Intl. Symp.on Advanced Manufacturing for Sustainable Development
Thu Oct, 24 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Jerzy Pisarek; Session Monitor: TBA

14:00: [ManufacturingThuPM105] Keynote
Modeling, Structure and Properties of Aluminum Dodecaboride and Boron Carbide-Based Ceramics
Tetiana Prikhna¹ ; Pavlo Barvitskiy¹ ; Richard Haber² ; Volodymyr Kushch³ ; Leonid Devin³ ; Sergey Dub¹ ; Myroslav Karpets¹ ; Semyon Ponomarov⁴ ; Florian Kongoli⁵ ; Fernand Marquis⁶ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Department of Materials Science and Engineering, Rutgers, The State University of New Jersey, New Brunswick, United States; ³Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev, Ukraine; ⁴Institute of Semiconductor Physics, Kiev, Ukraine; ⁵FLOGEN Technologies Inc., Mont-Royal, Canada; ⁶San Diego State University, San Diego, United States;
Paper Id: 119 [Abstract]

The results of the study of structures and mechanical properties of ceramic materials will be discussed. These ceramic materials were obtained by hot pressing from the submicron AlB₁₂C₂ and AlB₁₂ powder [1], with and without the addition of TiC, as well as from B₄C, without and with SiC additions. Temperature, pressure and composition of the starting powder are optimized to obtain sintered bodies with desired high mechanical characteristics. X-ray diffraction, scanning electron microscopy and Raman microspectroscopy are utilized to investigate phase composition and microstructure of the sintered ceramics. High compression strength (1551 MPa for B₄C, 1878 MPa for B₄C-SiC-based material and 795 MPa for AlB₁₂C₂-TiB₂ based material) together with high bending strength, hardness, fracture toughness, and a light weight make the synthesized and sintered ceramics very promising as a shock-wave resistant material. The effect of C, TiC and SiC additions on the properties of the resultant composites and the particularities of the ceramics destruction under shock loading will be discussed. The results of the modeling of ballistic characteristics will be discussed. The performed ballistic tests of 10 mm thick plates from the developed ceramic had a 2.63 g/cm³ density as well as a composition of 78 wt.% of B₄C and 22 wt.% of SiC according to X-ray diffraction analysis. According to SEM microprobe X-ray analysis, stoichiometries B_3.64CSi_0.01 and SiC_1.07, respectively, showed that the plates can withstand the shot of a B32 bullet with kinetic energy of 3.7 kJ from a 10 m distance.

References:
[1] T.A. Prikhna, R. A. Haber, P.P. Barvitskiy, V.B. Sverdun, S.N. Dub, V.B. Muratov, V. Domnich, M.V. Karpets, V.E. Moshchil, M.G. Loshak, V.V. Kovylaev and O.O. Vasiliev Synthesis, sintering, structure and properties of AlB₁₂C₂-based materials //Proceedings of the 41st international conference on advanced ceramics and composites: ceramic engineering and science proceedings (January 22-27, 2017. - Daytona Beach, Fla.) (eds J. Salem, J. C. LaSalvia, R. Narayan, D. Zhu), John Wiley & Sons, Inc., Hoboken, NJ, USA. - 2018. - Vol. 38, Is. 2. - Р. 195-203. doi: 10.1002/9781119474678.ch19

14:25: [ManufacturingThuPM106] Keynote
Present Status and Future Directions of Sustainable Machining
M. Helmi Attia¹ ; ¹Adj Professor, Mechanical Engineering, McGill University / National Research Council Canada (NRC), Montreal, Canada;
Paper Id: 164 [Abstract]

Manufacturing remains the largest and most important wealth generating sector. Within this sector, material removal is a key technology in the aerospace and automotive industries, contributing to more than $200 billion of the economy in North America on an annual basis. The demand for high productivity and high accuracy is steadily increasing, along with the increasing attention to the impact on the environment. In this work, only conventional machining processes are discussed. A system approach to the machining system is presented in terms of its elements (machine, tool, workpiece and fixture), properties (materials, configuration, contact interfaces) and interactions (dynamic, tribological, thermal, thermo-elastic) to set the framework for predicting the system response (quality attributes and machining-induced defects) to the operational input. This input describes controlled cutting conditions and uncontrolled dynamic-tribo-thermo-elastic self-induced changes. The impacts of this new approach on the environment will be explored. The paper provides a critical assessment of the current status of removal technologies of sustainable material. The paper also assesses the research effort towards the development of new and hybrid sustainable machining strategies and processes for: (a) high speed/high performance machining and tool life management, (b) machining of composites and stacked materials, (c) high performance/superabrasive advanced grinding and polishing, and (d) physics-based modeling and simulation of the machining system to achieve a virtual machining environment for the realization of sustainable development philosophy. Life cycle analyses of these technologies, which proved to be effective for applications that involve aggressive metal removal, especially for hard-to-cut materials, are discussed and compared to flood machining. They are compared in terms of their environmental impact on human health, ecosystem quality and natural resources (materials and energy). The effect of MQL and cryogenic machining on the surface integrity of machined surfaces and the reduction in cutting forces, surface roughness and tool wear are presented.

References:
1. Damir, A., Shi, B, and Attia, M. H., "Flow Characteristics of Optimized Hybrid Cryogenic-Minimum Quantity Lubrication Cooling in Machining of Aerospace Materials," accepted for publication in CIRP Annals - Manufacturing Technology, 2019. \n2. Shi, B., Elsayed, A., Damir, A., Attia, M. H., and Ma'Saoubi, R., "A Hybrid Modelling Approach for Characterization and Simulation of Cryogenic Machining of Ti-6Al4V Alloy," Trans. ASME, Journal of Manufacturing Science and Engineering, Vol. 141, p. 021021-1-8, 2019.\n3. Jawahir, I.S., Attia, M. H., Biermann, D., Duflou, J., Klocke, F., Meyer, D., et al., "Cryogenic Manufacturing Processes," Keynote Paper, CIRP Annals - Manufacturing Technology, vol. 65, pp. 713-736, 2016.\n4. Damir, A., Sadek, A., and Attia, M.H., "Characterization of Machinability and Environmental Impact of Cryogenic Turning of Ti-6Al-4V," Procedia CIRP, 69: p. 893-898, 2018.\n5. Dam, A., Sadek, A., Attia, M. H., and Tendolkar, A., "Characterization and Optimization of Machinability and Environmental Impact of Machining of Ti-6Al-4V with Minimum Quantity Lubrication," International Journal of Robotics and Mechatronics, 4(1): p. 1-7, 2017.\n6. Attia, M. H., "Sustainable Manufacturing: A Dilemma or Window of Opportunity?" 3rd International Symposium Aerospace Materials and Manufacturing, Montreal, Canada, 2006.

SESSION: AdvancedMaterialsThuPM2-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Thu Oct, 24 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Fernand Marquis; Udo Schwingenschlogl; Session Monitor: TBA

15:55: [AdvancedMaterialsThuPM209] Plenary
Perspectives on the Role of Transformative Materials and Technologies in Energy, Environment and Sustainability
Fernand D. S. Marquis¹ ; ¹San Diego State University, San Diego, United States;
Paper Id: 455 [Abstract]

Sustainable development is a comprehensive and complex system of systems requiring multidisciplinary and interdisciplinary science and technology inputs with economic, environment and social objectives. The trade space is very wide, and the multitude of trade-offs generate considerable challenges and make it often difficult to achieve an effective balance. During the last sixty years the planet’s population has grown exponentially, from 2.5 to 7.5 billion people, and the technological progress achieved has been tremendous, especially in the industrialized countries. These trends are expected to continue, even at faster rates. All these associated technological activities in the pursuit of better living standards have created a considerable depletion of resources and pollution of land, water and air. Thus, and because most of our resources are limited, it is imperative that we achieve more with less. In broad terms, sustainable development is achieved when the present needs and challenges are met without placing in jeopardy the ability of future generations to meet their own needs and challenges. The global energy demand is expected to increase exponentially, associated with the increase in the global population. The three main reserves of fossil fuels: oil, natural gas and coal are decreasing very rapidly and will not always be available to meet the global demands soon. The continuation of fossil fuel emissions will be environmentally deleterious, and there is already a need to remediate some of the deleterious effects already sustained by the environment. Energy security has become a major and critical issue as fossil fuels are confined to a few areas in the world and their availability is controlled by political, economic and ecological factors. This means that in a short term, considerable energy efficiencies and savings must be achieved, and alternative and renewable sources of energy must be developed. To enable all these technologies considerable advances in energy storage and conversion materials and technologies such as batteries, super capacitors and fuel cells must be achieved. The transportation industry has by far the largest share of global oil consumption and is now the major producer of global greenhouse gas emissions in most industrialized countries. Mobility projections show that it is expected to triple by 2050 with associated energy use and environmental impact. Considerable achievements have recently been obtained in the development of new and advanced materials such as light weight metallic alloys, metal matrix composites, intermetallic and carbon fiber composites and hybrid materials. Nano, nano-structured and nano-hybrid materials systems and nanotechnologies have also been deployed with significant impact. In addition, component redesign using a materials and functional systems integration approach is being used resulting in considerable system improvements and energy efficiency. This resulted in their introduction in the energy, transportation and manufacturing industries in a wide variety of devices and components with considerable technological, economic, environment and social impacts. Keywords: Transformative materials and technologies, nano,

16:20: [AdvancedMaterialsThuPM210] Keynote
Elemental 2D Materials beyond Graphene: Insights from Computational Theory
Udo Schwingenschlogl¹ ; ¹King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia;
Paper Id: 50 [Abstract]

The presentation will address recent developments related to elemental 2-D materials beyond graphene, with a focus on silicene, germanene, and arsenene. Several examples will be discussed in order to illustrate how computational theory based on first-principles calculations can contribute to the understanding of basic physical and chemical phenomena in 2-D condensed matter. Silicene is of particular interest due to its compatibility with established Si technology. Regrettably, strong interaction with common substrates eliminates the Dirac states. Alternative substrates will be analyzed and the effects on silicene will be evaluated with respect to technological requirements. Germanene attracts more and more attention because the effects of spin-orbit coupling are accessible in contrast to lighter 2-D materials. While the same is true for arsenene, the material's strongly buckled structure is not compatible with Dirac physics. Recovering the sp² bonding, on the other hand, makes it possible to realize unusual properties.

References:
1. ACS Applied Materials & Interfaces 6, 11675-11681 (2014)
2. Journal of Materials Chemistry C 3, 3946-3953 (2015)
3. 2D Materials 2, 045004 (2015)
4. Physical Review B 93, 045312 (2016)
5. Physical Review B 94, 205415 (2016)

16:45: [AdvancedMaterialsThuPM211] Invited
An Efficient Flexible Self-powered System Integrating Organic Solar Cells and Supercapacitors
Ruiyuan Liu¹ ; Masahito Takakuwa² ; Kilho Yu² ; Zhi Jiang² ;⁰ ; Shinjiro Umezu³ ; Kenjiro Fukuda² ; Takao Someya² ; ¹Center for Emergent Matter Science (CEMS), RIKEN, Wako, Japan; ²Center for Emergent Matter Science (CEMS), RIKEN, Japan, Wako, Japan; ³Waseda University, Tokyo, Japan;
Paper Id: 404 [Abstract]

Nontoxic flexible solar cells are by far the best candidates for meeting the ever-growing energy consumption demand of wearable devices, portable electronics, and the Internet of Things, while the output of solar cells is intrinsically restricted by the fluctuation of sunlight from ambient factors such as weather and day-night cycle. Self-powered integrated energy devices consisting of photovoltaic cells and energy storage units can serve as sustainable and portable distributed power sources that simultaneously generate and store electric energy without the need for external charging circuits and wires.
Previously, we have developed ultra-flexible organic photovoltaics (OPVs) with a total thickness of a few micrometers that could realize superior mechanical stretchability and environmental stability (water, heat, light et al.) while maintaining high power conversion efficiency (over 10%). With this ultra-thin OPVs as direct power sources that can be well attached onto objects, we have successfully developed self-powered ultra-flexible electronic devices that can precisely measure biometric signals on skin or other tissues. To further extent the application of such kind of solar cells in wearable electronics, a compatible energy storage units is needed to ensure a stable power supply.
However, the complexity of power management, device compatibility design and materials engineering optimization in the flexible integrated device results in low total conversion and storage efficiency (~2%), large device thickness (~mm) and poor operation stability. In this talk, we will report an efficient, ultra-thin, and flexible self-powered system integrating OPVs with supercapacitors that addresses the above issues. Introducing carbon nanotubes content into conducting polymers along with a chemical treatment yields dramatically increased electrode surface area, decreased charge-transfer resistances, and enhanced mechanical robustness, thus improving the specific capacities of supercapacitors, reducing the device thickness into a few tens of micrometers while maintaining excellent stability. Through the optimization of carbon nanotube-polymer composite electrodes, high total energy conversion and storage efficiency has been achieved in the long-term stable ultra-flexible integrated devices.

References:
1. Takao Someya et al. High Operation Stability of Ultraflexible Organic Solar Cells with Ultraviolet-Filtering Substrates. Adv.Mater.2019, 31, 1808033.\n2. Takao Someya et al. Self-powered ultra-flexible electronics via nanograting-patterned organic photovoltaics. Nature 2018, 561, 516-521.\n3. Takao Someya et al.Thermally stable, highly efcient, ultrafexible organic photovoltaics. Proc. Natl Acad. Sci. USA 2018, 115, 4589-4594. \n4. Takao Someya et al. Stretchable and waterproof elastomer-coated organic photovoltaics for washable electronic textile applications. Nat. Energy 2017, 2, 780-785.

17:10: [AdvancedMaterialsThuPM212]
Contrast Experiment Research of Cementitious Materials to an Iron Mine
Li Xin¹ ; ¹BGRIMM Technology Group, BEIJING, China;
Paper Id: 436 [Abstract]

The method of stage vacant place and subsequent filling has been used in an iron mine in Anhui province, but the effect of underground filling with local cement is not good. Therefore, the cementitious material was developed which suitable for the actual situation of the mine. In this paper, the basic properties, fluidity of filling slurry and strength of filling body between local cement and cementitious materials are compared and studied. The experimental results show that the diffusion of filling slurry with new cementitious material is higher 37.93% than the filling slurry with local cement, and the compressive strength of filling body is higher 75.82% than the filling body with local cement. The testing indexes of the new cementitious material are better than the local cement. Therefore, the new cementitious material for mining can be well adapted to the cemented filling of tailings in this mine. Through the comparative experimental study in this paper, the data support and theoretical basis of performance evaluation and industrial application are provided for mine filling cementitious materials.

References:
[1] Tikov B, Mostafa B. Design and application of underground mine paste backfill technology[J]. Geotechnical and Geological Engineering, 2008, 26(2): 147−174.
[2] Yu Runcang. Development and innovation of cemented filling technology in China[J]. China Mine Engineering, 2010, 39(5): 1-3．
[3] Zhang Qinli, Wang Xin-ming. Hydraulic calculation of gravity transportation pipeline system for backfill slurry[J]. Journal of Central South University of Technology, 2008, 15(5):645−649.
[4] Wang Xinming, LI Jian-xiong, FAN Ping-zhi. Applied technique of the cemented fill with fly ash and fine sands[J].Journal of Central South University of Technology, 2001, 8(3):189−192.
[5] Zhang Qinli, Li Xieping, Yang Wei. Optimization of filling slurry ratio in a mine based on back-propagation neural network[J]. Journal of Central South University: Science and Technology，2013，44(7) : 2868-2874．
[6] Deng X，Mirzalan A．Competitive robot mapping homogeneous markers[J]. IEEE Trans on Robotics Automation, 1996, 12 ( 4) : 532-542．
[7] Jiang Xiuxiang, Bai Zhongmin. Study and practice on a new type of binder used in underground stope backfilling[J]. West-China Exploration Engineering, 2002, 14(5) : 71-72．
[8] Zhang Haijun, Chen Huaili, Liang Tingdong. Study on improving the early strength of filling[J]. Metal Mine, 2009: 284-286．
[9] Rudd M, Nagaratnam S. Geotechnical properties of cemented paste backfill from Cannington Mine, Australia[J]. Geotechnical and Geological Engineering, 2007(25): 383-393.
[10] Ercikdi B，Kesimal A，Cihangir F. Cemented paste backfill of sulphide-rich tailings: Importance of binder type and dosage[J]. Cement and Concrete Composites, 2009, 31(4): 268-274．
[11] Deng Daiqiang，Gao Yongtao，Wu Shunchuan. The multivariate analysis of cement classified tailings filling material with orthogonal experiment[J]. Journal of Shandong University of Science and Technology, 2010, 29(1) : 48-57．

SESSION: AdvancedMaterialsThuPM3-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Thu Oct, 24 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Anka Trajkovska Petkoska; Ivana Barisic; Session Monitor: TBA

17:50: [AdvancedMaterialsThuPM313]
Improved Efficiency of PVT Collector
Anka Trajkovska Petkoska¹ ; Ilija Nasov² ; ¹Assoc. Prof., Veles, Macedonia (Former Yugoslav Republic of Macedonia); ²CEO PLasma, Skopje, Macedonia (Former Yugoslav Republic of Macedonia);
Paper Id: 293 [Abstract]

The increased concern for global warming, climate changes and rising energy prices has led to a high level of political and social motivation for energy-efficient, eco-friendly and sustainable energy production. Solar energy has the potential to play a leading role in renewable energy solutions. It addresses the energy problem from human health and environmental perspectives to economic perspectives. Moreover, solar energy is capable of satisfying both the electrical and thermal needs of industries and households by means of photovoltaic (PV) and solar thermal (ST) technologies respectively or by using hybrid photovoltaic-thermal (PVT) collectors. Actually, PVT collectors incorporate both thermal and electrical energy generations that can be used as a cooling system for the PV system in order to enhance the electrical energy efficiency and, at the same time, produce thermal energy that can be used in other applications (e.g. for water heating, space heating, etc.). This integration of PV and thermal collectors does not only enhance PV effectiveness; it also produces more energy for a certain area than a singular PV cell or solar collector alone. The combination of these systems offers few benefits such as: (i) An increase of photovoltaic cell effectiveness (cooling through the solar thermal system), (ii) A reduction in space utilisation (attractive in the case when the available roof surface is limited), (iii) Replacement of the roofing material with the PVT system that can reduce the payback period, (iv) Reduction of greenhouse gas emissions by utilisation of renewable energies. PVT collectors have become an important research topic in the last four decades and have attracted many interests. Research on PVT collectors started with the main focus on increasing the PV efficiency. In this work, the authors present a few innovative steps that increase PVT efficiency as well. Namely, low soiling coating on the top cover glass of PVT assembly enables the system to have a clean surface for a longer period of time. It extends the time efficiency of this system because the top glass transmittance is not decreased over a certain time period and consequently, produces more energy compared to PVT systems that do not have such a coating. This protective coating could offer a combination of antireflective, antistatic, anti-corrosion and, in some cases, photocatalytic effects. The second innovation is related to usage of thermal conductive adhesives that bond together the PV module to the ST’s absorber. Namely, the PV backsheet is directly adhered to the Al absorber surface and the heat taken from the PV module is transferred towards the ST absorber. To enhance the heat conductivity in this system, thermally conductive dopants were used. A variety of adhesive systems were investigated and the best one was selected. Finally, ST absorbers’ pipes are protected with inner anti-corrosive coating, so the PVT system could be considered for usage in salty (corrosive) regions or in direct water-circulation systems (e.g. for pool heating). This project is supported by the Fund of innovation and technology development of R. North Macedonia, 2018-2020.

18:15: [AdvancedMaterialsThuPM314]
Agricultural and Industrial Waste Materials as Low-Cost Sorbents for Environmental Pollutants
Anka Trajkovska Petkoska¹ ; Anna Maria Petkoska² ; Andrea Leng³ ; Anita Trajkovska Broach⁴ ; ¹Assoc. Prof., Veles, Macedonia (Former Yugoslav Republic of Macedonia); ²Yahya Kemal High School, Skopje, R. North Macedonia, Skopje, Macedonia; ³Blacksburg High School, Blacksburg, United States; ⁴Scientist/Consultant, CSI: Create. Solve. Innovate. LLC, Blacksburg, United States;
Paper Id: 304 [Abstract]

Landfill sites are on the rise and are competing for a spot on Earth whose population is rapidly growing. The dangerous gasses released from the landfills, in addition to other pollutants in the air and water, are “responsible” for the scary statistics reporting that 3 % of the deaths worldwide are due to drinking polluted water, while 7 million deaths each year are due to the air pollution (WHO, 2013). The PoSH™ (Porous Shells and Husks) project offers a great potential to give a “second chance” to the waste by utilizing it for a good cause and contributing towards a cleaner world. Various types of waste materials disposed from households, restaurants, farms and industries were tested for their efficiency to adsorb environmental pollutants, viz. heavy metals – lead, nickel, zinc, copper and others. These waste materials are collectively referred to as PoSH™ materials here and include such materials as egg shells, peanut husks, rice husks, corn cobs and husks, nut shells, peels and many others. The findings showed that, without any prior treatment, most of the tested waste efficiently adsorbs heavy metals from contaminated water. Most of the agricultural waste adsorbed more than 70% of the present pollutants within an hour of contact with the contaminated water. The effects of contact time, surface area of the adsorbent and concentration of the sorption efficacy of the waste material toward heavy metals were investigated, as well. The project is in progress and it is expected to have a huge impact on increasing public awareness for re-using waste before it is thrown and decomposed in landfills. The project is supported by the Virginia Tech (VT) National Center for Earth and Environmental Nanotechnology Infrastructure (NanoEarth), a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is in turn supported by NSF (ECCS 1542100). The support by CSI: Create. Solve. Innovate. LLC is also appreciated.

SESSION: AdvancedMaterialsFriAM-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Fri Oct, 25 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Nikoloz Chikhradze; Ivanka Netinger Grubesa; Session Monitor: TBA

11:20: [AdvancedMaterialsFriAM01]
Polyoxometalate Chemistry in Carbon Nanotubes
Graham Newton¹ ; Jack Jordan¹ ; Andrei Khlobystov¹ ; Darren Walsh¹ ; ¹University of Nottingham, Nottingham, United Kingdom;
Paper Id: 253 [Abstract]

Polyoxometalates (POMs) have received considerable attention in recent years due to their rich redox properties and potential applications in energy storage.[1] Due to their discrete nature, the use of POMs as components in energy storage devices relies on their stable combination with conductive supports.[2] Carbon nanotubes (CNTs) are stable, hollow cylinders made entirely of carbon. These nanostructured carbons are highly conductive, mechanically strong and can be functionalized.[3] By encapsulating molecular materials within CNTs, their properties can be enhanced. This work describes the first report of the encapsulation of the Keggin [PW₁₂O₄₀]^3- and Wells-Dawson [P₂W₁₈O₆₂]^6- heteropolyanions within carbon nanotubes (CNTs), along with detailed structural, chemical and electronic characterizations. Transmission electron microscopy (TEM) confirms the presence of encapsulated POMs, as well as provides the necessary energy to perform observable chemical transformations within the CNTs. Access to POM redox properties from within the CNT upon encapsulation is described. The POM electrochemistry is shown to be stabilized across a greater range of conditions and cycles than typically possible. Using Raman spectroscopy, investigations probe the electronic coupling between the host and guest, showing electron transfer between the two.

References:
1. Sadakane, M.; Steckhan, E., Electrochemical Properties of Polyoxometalates as Electrocatalysts. Chem. Rev. 1998, 98 (1), 219-238.
2. Song, Y.-F.; Tsunashima, R., Recent advances on polyoxometalate-based molecular and composite materials. Chem. Soc. Rev. 2012, 41 (22), 7384-7402.
3. Miners, S. A.; Rance, G. A.; Khlobystov, A. N., Chemical reactions confined within carbon nanotubes. Chem. Soc. Rev. 2016, 45 (17), 4727-4746.

11:45: [AdvancedMaterialsFriAM02] Invited
Bioinspired Materials with Micro and Nanostructured Gradient Surfaces to Control Dynamic Wettability
Yongmei Zheng¹ ; ¹Beihang University, Beijing, China;
Paper Id: 77 [Abstract]

Biological surfaces in nature (e.g., spider silk, cactus spine, beetle back, butterfly wing, lotus leaf, etc.) have inspired us to design functional materials and surfaces [1-5]. Inspired by the structures of spider silk for directional water collecting ability, a series of bioinspired gradient fibers has been designed by integrating fabrication methods and technologies, e.g., dip-coating, Rayleigh instability break-droplets, electrospinning, and wet-assembly, etc.. Thus, this allows roughness and curvature, gradient spindle-knots, a star-shape wettable pattern, etc. for droplet transport and harvesting. Inspired by cactus spines, the conical spines with periodic roughness or micro- and nanostructures can achieve high-efficiency condensed-droplet transport. Some dynamic gradient surfaces are also designed, e.g., photo-thermal organogel surfaces for control of droplet transport in various routes via light radiation, and magnetic-induced dynamic tilt-angle pillar array for driving of the droplet shedding-off in directions. The bioinspired gradient surfaces can be further designed to exhibit robust transport and control of droplets. These bioinspired gradient surfaces would be promising applications into anti-icing, liquid transport, anti-fogging/self-cleaning, water harvesting, etc.

References:
[1] Zheng. Y. Bioinspired wettability surfaces: Development in micro- and nanostructures, Pan Stanford Publishing. 2015, 0-216.
[2] Zheng, Y. et al., Directional water collection on wetted spider silk, Nature 2010, 463, 640-463.
[3] Xu, T. et al., High-efficiency fog collector: water unidirectional transport on heterogeneous rough conical wires. ACS Nano 2016, 10, 10681-10688.
[4] C Gao, et al., Droplets Manipulated on Photothermal Organogel Surfaces. Adv. Funct. Mater. 2018, 1803072.
[5] Y. Lin, et al., Magnetically Induced Low Adhesive Direction of Nano/ Micropillar Arrays for Microdroplet Transport. Adv. Funct. Mater. 2018, 1800163.

12:10: [AdvancedMaterialsFriAM03]
AGRICULTURAL BIOMASS ASH IN CIVIL ENGINEERING - FROM ENERGY TO SUSTAINABLE DEVELOPMENT
Ivana Barisic¹ ; Ivanka Netinger Grubesa² ; Tihomir Dokšanović³ ; Hrvoje Draganić³ ; Mirjana Malešev⁴ ; Slobodan Supic⁴ ; Miroslava Radeka⁴ ; Vlastimir Radonjanin⁴ ; ¹INTERREG IPA CBC Croatia-Serbia ECO Build HR-RS38, Osijek, Croatia; ²Faculty of Civil Engineering and Architecture Osijek, VAT HR04150850819, INTERREG IPA CBC Croatia-Serbia ECO Build HR-RS38, Osijek, Croatia; ³Faculty of Civil Engineering and Architecture Osijek, University in Osijek, Osijek, Croatia; ⁴Department of Civil Engineering and Geodesy, Faculty of Technical Sciences, University in Novi Sad, Novi Sad, Serbia and Montenegro;
Paper Id: 40 [Abstract]

Every year in the world, millions of tons of harvest residues are generated, such as, corn stalks and corn cob blanks, wheat, soy and rice straw, sunflowers, and rice husk. Those harvest residues can be used as a replacement for fossil fuels and represents a renewable energy source. Ash, which is generated by combustion of harvest residues, is usually deposited in landfills, causing environmental pollution and potential human health risks. These risks are caused by non-existent bio-ash management and the absence of pollution control [1]. In order to promote biomass as an energy source, the available quantities of agricultural biomass in Croatia and Serbia are presented. Its heating power is determined and compared to the heating power of standard energy sources. The possibilities of using biomass ash as a waste material in the building industry are outlined. As presented in [2-4], different kind of biomass ashes can be successfully used to replace cement in mortars and concrete and have positive influence on geotechnical properties of the soil. Preliminary results of ash suggest that these ashes exhibit the potential for use in the building industry, but because of the differences in their characteristics, each of them needs to be investigated in more detail.

References:
1. Carević, I., Banjad Pečur, I., Štirmer, N., Milovanović, Bojan; Baričević, A.: Potencijal biopepela i stanje u Republici Hrvatskoj, Sabor hrvatskih graditelja 2016 - EU i hrvatsko graditeljstvo - zbornik radova / Lakušić, Stjepan (Ed.), Hrvatski savez građevinskih inženjera, Zagreb, 2016., 133-142 (in Croatian)\n2. Antonio P., Ryan Y.,Ellie F., Taher Abu-L.: Investigating effects of introduction of corncob ash into portland cements concrete: mechanical and thermal properties, American Journal of Engineering and Applied Sciences, 7, 2014., 137-148\n3. Biricik, H., Akoz, F., Turker, F., Berktay, I.: Resistance to magnesium sulfate and sodium sulfate attack of mortars containing wheat straw ash, Cement and Concrete Research, 30(8), 2000., 1189-1197\n4. Singh, M., Sharma, R.: Soill stabilization using industrial waste (wheat husk and sugarcane straw ash), International Research Journal of Engineering and Technology, 4(9), 2017., 589-596

12:35: [AdvancedMaterialsFriAM04]
Surface Tailored Organic Molecule Copolymerized Silica Nanoparticles
Gabor Patonay¹ ; Eman Alsolmy¹ ; Gala Chapman¹ ; Walid Abdelwahab¹ ; ¹Georgia State University, Atlanta, United States;
Paper Id: 24 [Abstract]

Surface-modified silica nanoparticles that are copolymerized with one or more types of small organic molecules can be synthesized using a wide range of organic molecules, fluorescent or non-fluorescent, including near-infrared dyes due to the wide availability of modified reactive TEOS analogues. These silica nanoparticles that are copolymerized with dye molecules can be utilized as bright fluorescence labels or sensors. In addition, covalently surface bonded moieties can be added to silica nanoparticles to custom tailor the surface behavior of the silica nanoparticles. These surface modifiers can serve many purposes, such as molecular recognition. For example, introducing hydrophobic molecules to the surface of silica nanoparticles facilitates binding of the particle to hydrophobic molecules and surfaces. Fluorescence intensity of a single molecular label can be relatively weak requiring larger amounts of chemicals. One way to achieve sustainability during manufacturing or any chemical applications is to significantly reduce the amount of chemicals used. Another way to reduce the environmental impact of chemicals is to incorporate the molecules in a more environmentally friendly shield that effectively prevents the less desirable molecules from leaching out in the environment. All these can be achieved by encapsulating fluorophores in silica nanoparticles. The outside of surface tailored silica nanoparticles can be designed for any chemistry to make them more environmentally friendly. The encapsulated dye can serve as a simple reporting label, as a sophisticated molecular probe or as a tracer. Due to the large number of molecules that can be encapsulated in a single silica nanoparticle, the number of labels is very small, requiring minimal amount of chemicals. This presentation discusses the facile synthesis of silica nanoparticles using modified TEOS. Using the re-growth technique for surface modification, copolymerized fluorophores and surface bound moieties are introduced. Practical applications of these particles including environmental, forensic and analytical applications will be discussed. Surface modification examples will be given to achieve any desired behavior of the silica nanoparticle.

References:
1. Patonay, G., Chapman, G. Beckford, G, Henary M., Ellis, H. Proc. SPIE. 8956, 89560U/1-89560U/11 (2014)
2. Krauss, T. D.; Peterson, J. J. Nature Mater. 2012, 11, 14-16.
3. Medintz, I.L.; Uyeda, H.T.; Goldman, E.R.; Mattoussi, H. Nature Mater. 2005, 4, 435
4. Chou, K.-S.; Chen, C.-C. Ceram. Int. 2008, 34, 1623-1627.
5. Chapman, G. Solomon, I. Patonay, G. Henary, M. J. of Heterocyc Chem (52) 3, 861-872 (2015).

SESSION: AdvancedMaterialsFriPM1-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Fri Oct, 25 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Lev Rapoport; Teofilo Rojo; Session Monitor: TBA

14:00: [AdvancedMaterialsFriPM105] Keynote
Low Cost, Corrosion Resistant and Microwave-Absorbing Coatings
Tetiana Prikhna¹ ; Mykola Monastyrov² ; Fernand Marquis³ ; Viktor Moshchil¹ ; Olena Prysiazhna⁴ ; Bernd Halbedel⁵ ; Pavlo Barvitskiy¹ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Open International University of Human Development Ukraine, Kiev, Ukraine; ³San Diego State University, San Diego, United States; ⁴Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev, Ukraine; ⁵Technische Universitat Ilmenau, Ilmenau, Germany;
Paper Id: 117 [Abstract]

New low cost masking coatings have been developed. These coatings are based on corrosion resistant polyurethane and acrylic-urethane priming varnishes and paints of Ukrainian manufacture (InterGasSinthez). In addition, the coatings are also based on nanopowders of polyvalent iron oxides obtained by electroerosion dispersion [1], carbon, omega spheres (based on silica and alumina), and basalt fibers demonstrating high absorption abilities (90-99%) of microwaves in a wide range of frequencies (10-70 GHz, wavelength 0,03-0,0043 m) with their reflection close to zero (-10 Db - - 23 Db or 10% -0.5%). Polymeric bases of the developed coatings are used to protect against corrosion of metal structures in all macroclimatic areas, in sea and fresh water, in saline solutions, and in oil and oil products that are resistant to ultraviolet radiation, aggressive media. They demonstrate high mechanical performance (adhesion, strength, elasticity) and long service life. The coatings can be used for painting of ships, deck structures, containers, building constructions and buildings, auto and railway transports, parts and mechanisms, etc.

References:
[1] B. Halbedel, T. Prikhna/, P. Quiroz, J. Schawohl, T. Kups, M. Monastyrov Iron oxide nanopowder synthesized by electroerosion dispersion (EED), Properties and potential for microwave applications // Current Applied Physics. - 2018. - Vol. 18. - P. 1410-1414

14:25: [AdvancedMaterialsFriPM106]
Evolution of Microstructure of Surface Layers of Silver, Copper, Nickel and Aluminum Under Friction in Lubricated Conditions
Lev Rapoport¹ ; Alexey Moshkovich² ; Inna Popov³ ; Lev Rapoport⁴ ; ¹Holon Institute of technology, Holon, Israel; ², Holon, Israel; ³The Hebrew University of Jerusalem, Jerusalem, Israel; ⁴Holon Institute of Technology, Holon, Israel;
Paper Id: 373 [Abstract]

The objectives of this work are: to study the evolution of the microstructure of four face-centered cubic metals (Ag, Cu, Ni and Al) after friction in lubricated conditions, to evaluate the effect of stacking fault energy (SFE) on grain size and wear loss [1, 2]. Methods: The deformed microstructures after friction were carefully examined with a field emission scanning electron microscope. Cross sectional transmission electron microscopy. (TEM) lamellae were prepared using a focused ion beam (FIB). Results: Deformation twinning followed by a limited recovery within the surface of Ag led to the formation of relatively thick top layer of ultrafine equiaxial grains. Thermally activated processes for the rearrangement and annihilation of dislocations are accelerated during friction of Cu and Ni due to middle and high SFE and relatively high contact temperature. Steady state values of grain size, ds, and hardness, Hs, during friction are explained by the balance between hardening and dynamic recovery in surface layers, and they strongly depend on the SFE and temperature. Conclusions: The best wear properties of fcc studied metals are determined by high strength and ductility of surface layers during friction.

References:
[1]A. Moshkovich, I. Lapsker, Y. Feldman, L. Rapoport, Severe plastic deformation of four FCC metals during friction under lubricated conditions, Wear, 386-387 (2017) 49-57.
[2] I. Popov, A. Moshkovich, S. R. Cohen, V. Perfilyev, A. Vakahy, L Rapoport, Microstructure and nanohardness of Ag and Ni under friction in boundary lubrication, Wear 404–405 (2018) 62–70.

14:50: [AdvancedMaterialsFriPM107] Invited
Advanced Materials for Na-Ion Batteries: A Promising Technology
Nicholas Drewett¹ ; Nagore Ortiz Vitoriano¹ ; Elena Gonzalo¹ ; Galceran Montserrat¹ ; Damien Saurel¹ ; Miguel Angel Munoz Marquez¹ ; Juan Luis Gomez Camer¹ ; Teofilo Rojo¹ ; ¹CIC energiGUNE, Vitoria-Gasteiz, Spain;
Paper Id: 170 [Abstract]

As modern society's demands for energy storage technologies increases, it becomes necessary to develop new approaches to meeting the challenges of the future. One of the most promising areas of current research and development is that of sodium ion batteries (SIB) which potentially offer, in comparison to existing technologies, low cost, environmentally friendly technologies from earth abundant resources. While (SIBs) have many potential applications, they are particularly well suited to stationary storage.[1] In this work, we will offer an overview of SIB technology before exploring key advances and highlighting important factors affecting their properties. In order to do this, we will discuss SIBs in terms of their three most significant components: anodes, electrolytes, and cathodes. SIB anodes are mainly based on hard carbon materials, due to their attractive combination of low cost and high energy density, though there has also been interest in other systems (e.g. intermetallic alloying materials and metal oxides), as well as interest in exploiting specific electrolyte co-solvation effects so as to enable the use of graphite.[2,4] The SIB research community typically uses organic electrolytes analogous to those developed for lithium ion batteries (LIBs) to exploit their analogous natures. Recently, however, there has also been increasing interest in developing new electrolytes specifically tailored to SIBs, such as optimized liquid and solid electrolytes.[5,6] At the present time, cathodes are one of the most explored (SIB) components - with a plethora of options to choose from, including prussian blue and organic materials. The most promising, however, are polyanionic and layered materials because of their good combinations of electrochemical performance, low cost, stability and available constituents.[1,7,8] Although interest in SIB technology is only relatively new, when compared to LIBs it has been already developed at the prototyping and demonstrators' levels. A general overview of the most interesting electrode and electrolyte materials for Na-ion batteries - with a strong focus on those related to the current prototypes - will be presented. By examining this topic in detail, we will demonstrate the considerable potential of this new technology, and highlight some of the most promising opportunities for developing new and improved SIB technologies.

References:
[1] V. Palomares, M. Casas-Cabanas, E. Castillo-Martínez, M.H. Han, T. Rojo, Energy Environ. Sci. 6 (2013) 2312-2337.
[2] B. Jache, J.O. Binder, T. Abe, P. Adelhelm, Phys. Chem. Chem. Phys. 18 (2016) 14299-14316.
[3] M.A. Muñoz-Márquez, D. Saurel, J.L. Gómez-Cámer, M. Casas-Cabanas, E. Castillo-Martínez, T. Rojo, Adv. Energy Mater. 7 (2017) 1700463.
[4] D. Saurel, B. Orayech, B. Xiao, D. Carriazo, X. Li, T. Rojo, Adv. Energy Mater. 8 (2018) 1703268.
[5] C. Bommier, X. Ji, Small. 14 (2018) 1703576.
[6] W. Hou, X. Guo, X. Shen, K. Amine, H. Yu, J. Lu, Nano Energy. 52 (2018) 279-291.
[7] N. Ortiz-Vitoriano, N.E. Drewett, E. Gonzalo, T. Rojo, Energy Environ. Sci. 10 (2017) 1051-1074.
[8] E. Gonzalo, N. Ortiz-Vitoriano, N.E. Drewett, B. Acebedo, J.M. López del Amo, F.J. Bonilla, T. Rojo, J. Power Sources. 401 (2018) 117-125.

15:15: [AdvancedMaterialsFriPM108]
Coupling of Mechanochemical Synthesis with Enhanced Microwave Chemistry towards Biogas Dry Reforming Catalysts
Kyriaki Polychronopoulou¹ ; Sara Alkhoori¹ ; Aseel Hussien² ; ¹Khalifa University, Abu Dhabi, United Arab Emirates; ²Khalifa University of Science and Technology, Abu Dhabi, United Arab Emirates;
Paper Id: 252 [Abstract]

In the present study, enhanced microwave (EMW) synthesis, where microwave radiation is coupled with reflux conditions, was used to prepare CeO₂, CeO₂-La₂O₃, and CeO₂-La₂O₃-10% Cu catalysts. Ceria has become a promising material that features high redox properties, high population of oxygen vacancies [Ovac], that are crucial for hydrocarbon catalytic reactions such as CO₂ reformation of methane (dry reforming of biogas) [1-3]. This is crucial in the sense that they contribute to coke reduction. Post synthetically, the catalyst CeO₂-La₂O₃-10% Cu was ball milled under both, wet and dry conditions. The ball milling technique is expected to further improve the oxygen vacancies and give higher efficiency for uniform multi-component mixed oxides in consideration of time and energy usage. The prepared catalysts were characterized using x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Remarkably, the EMW synthesis conditions affect the crystallinity of the catalysts (XRD) and the crystal growth, generating particles with crystallite size in the ranges of ~11-19 nm. The ball-milled catalysts exhibited a smaller crystallite size ~9.5 nm (XRD), which corresponds to larger surface area (m²/g). This, in fact, enhances oxygen mobility in the ceria support lattice and yields to the formation of more O vacancies.

References:
[1] ND Charisiou, G Siakavelas, L Tzounis, V Sebastian, A Monzon, MA Baker, SJ Hinder,
K Polychronopoulou, IV Yentekakis, MA Goula, International Journal of Hydrogen Energy
43 (41), 18955-18976
[2] ND Charisiou, K Polychronopoulou, A Asif, MA Goula Surface and Coatings Technology 352, 92-111
[3] ND Charisiou, A Iordanidis, K Polychronopoulou, IV Yentekakis, MA Goula
Materials Today: Proceedings 5 (14), 27607-27616

SESSION: AdvancedMaterialsFriPM2-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Fri Oct, 25 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Tetiana Prikhna; Ruiyuan Liu; Session Monitor: TBA

15:55: [AdvancedMaterialsFriPM209] Keynote
High Temperature Stability in Oxygen and Hydrogen Environments and Wear Resistance of Ti,Nb-Al-C MAX Phases
Tetiana Prikhna¹ ; Tetiana Serbenyuk² ; Vladimir Sverdun² ; Fernand Marquis³ ; Orest Ostash⁴ ; Viktoriya Podhurska⁵ ; Alexander Kuprin⁶ ; Myroslav Karpets¹ ; Semyon Ponomarov⁷ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev, Ukraine; ³San Diego State University, San Diego, United States; ⁴Karpenko Physical-Mechanical Institute of the National Academy of Sciences of Ukraine, Lviv, Ukraine; ⁵Physico-Mechanical Institute of the National Academy of Sciences of Ukraine, Lviv, Ukraine; ⁶National Science Center Kharkov Institute of Physics and Technology, Kharkov, Ukraine; ⁷Institute of Semiconductor Physics, Kiev, Ukraine;
Paper Id: 107 [Abstract]

MAX phases of Ti-Al-C system are the most examined and perspective for high temperature applications; they are light, electro conductive, having high damping and low friction abilities, etc. But despite the combination of unique properties they did not find yet wide spread application (it is difficult to synthesize single phased material, they should combine a set of properties and even the singlephased materials can have very different characteristics because of synthesis parameters) [1]. The bulk Ti₂AlC, Ti₃AlC₂ and (Ti,Nb)₃AlC₂ developed by us are promising for the manufacture of interconnects of solid hydrogen fuel cells, pantograph, as damping substrates under the incisors, and others. The films with an approximate stoichiometry of Ti^3.3-3.9AlC_1.4-1.6 (5 I�m thick) deposited on Ti substrate using a vacuum-arc method from the hota�� pressed target (Ti₂AlC (57 wt.%) +Ti₃AlC₂ (43 wt.%)) were extremely promising for high-temperature applications, in particular for interconnects fuel cells and as cavitation resistant coatings on turbines. After 1000 h heating at 600 ^oC the surface electrical conductivity of the films only slightly decreased from 0.01 to 0,01-3 Ohm while the surface of pure Ti after 250 h in the same conditions totally oxidized and lost conductivity. Investigation of the influence of H₂ for 3 - 40 h and oxidation up to 1000 h at 600 ^oC, as well as thermocycling in air up to 600 ^oC on the bending strength and mass change of Ti₃AlC₂, (Ti,Nb)₃AlC₂, Ti₂AlC showed that the highest absolute value demonstrated Ti₂AlC and it was the most stable in the oxide medium (seems due to presence of some oxygen in the structure - Ti_2.2AlC_0.9O_0.17). The bending strength of the Ti₃AlC₂ and (Ti,Nb)₃AlC₂ even increased after heating in H₂. The addition of Nb allowed increasing the stability of the MAX phase in H₂, and in air (the oxide film was twice thinner than that on the samples without Nb after 1000 h heating at 600 ^oC). The high temperature X-rays showed that Ti₂AlC was oxidized more intensive than Ti₃AlC₂ at higher temperatures (Ti₂AlC was stable up to 700- 750 ^oC and Ti₃AlC₂ - up to 1050-1100 ^oC). The most stable at thermal cycling to 1200 ^oC was a high-density material based on the MAX phase Ti₃AlC₂, obtained by two-stage technology (synthesis in vacuum with subsequent compression by hot pressing at 30 MPa). The oxidized layer of specimens contained ~100% of Ti₃AlC₂but synthesized by one-stage hot pressing at 15-30 MPa for 10-30 min was twice thicker. The wear of Ti₃AlC₂ materials obtained at 30 MPa according to the one- and two-stage technologies was very low (as compare to silumin), but the wear of the copper in contact with them was rather high. Significant reduction of wear of copper was achieved when the manufacturing pressure was reduced to 15 MPa: during friction in pair with copper its wear resistance in comparison with traditionally used silumin was 40 times higher, and the wear of copper was 14 times smaller (after 6 km of the way); Besides, Ti₃AlC₂demonstrated much higher arc resistance.

References:
[1] T. Prikhna, O. Ostash, V. Sverdun, M. Karpets, T. Zimych, A. Ivasyshin, T. Cabioca��h, P. Chartier, S. Dub, L. Javorska, V. Podgurska, P. Figel, J. Cyboroń, V. Moshchil, V. Kovylaev, S. Ponomaryov, V. Romaka, T. Serbenyuk, A. Starostina Presence of oxygen in Ti-Al-C MAX phases-based materials and their stability in oxidizing environment at elevated temperatures // Acta Physica Polonica A. - 2018. - Vol. 133, a�� 4. - P. 789-793

16:20: [AdvancedMaterialsFriPM210] Keynote
A Convenient Way to Synthesize of Nanosized Catalysts in Quasi-intramolecular Solid Phase Redox Reactions
Laszlo Kotai¹ ; Fernanda Paiva Franguelli² ; Kende Beres³ ; Hanna Solt¹ ; Peter Nemeth¹ ; Zoltan Homonnay⁴ ; Istvan E. Sajo⁵ ; ¹Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, Hungary; ²Hungary and Budapest University of Technology and Economics, Budapest, Hungary; ³Hungary and Institute of Chemistry, ELTE Eotvos Lorand University, Budapest, Hungary; ⁴Institute of Chemistry, ELTE Eotvos Lorand University, Budapest, Hungary; ⁵Janos Szentagothai Research Centre, University of Pecs, Budapest, Hungary;
Paper Id: 289 [Abstract]

Nanosized mixed-metal-oxide catalysts are used in various industrially relevant processes like Fischer-Tropsch synthesis or NOx removal from gases. Transition metal ions, coordinated by reducible ligands (NH₃, pyridine or urea) that make salts with oxometalate anions (MnO₄^-, CrO₄^2-, Cr₂O₇^2-), are used to prepare nano-sized mixed spinel-type metal-oxides with pre-selected composition, properties, and structure. The applicability of a mixed oxide catalyst is determined by the distribution of the two metals among valence states, and crystallographic positions (in spinels T-4 and OC-6). The methods currently used for the synthesis of mixed metal-oxides do not allow the control of these properties. This is because the methods used for synthesis of mixed metal-oxides include processes that take place at high temperatures, where the mobility of atoms leads to the formation of a thermodynamically stable structure. This stable structure is characterized by its unique distribution of metal atoms among positions and valence states. The unique feature of the catalyst synthesis method developed by us [1-4] is based on the thermal decomposition of tetraoxometalates of transition metal ions, coordinated by reducible ligands at relatively low temperatures (100-200 ^oC). The thermal decomposition of tetraoxometalates then releases gas-phase products formed from the ligands. This is a solid-phase reaction which forms mixed oxides with metastable structures because at low temperatures, the metal ions remain in the crystallographic positions of the precursor salt. For example, hexaaquairon(III) permanganate results in (Fe,Mn)O type and (Fe,Mn)₃O₄ type mixed oxides, depending on the atmosphere and temperature of decomposition. Furthermore, the original spinel structure can be oxidized into defect-spinel structures and finally to (Fe,Mn)₂O₃ type oxides.<br /> <br />[Fe(urea)₆(MnO₄)₃] --> (Fe,Mn)₃O₄ --> (Fe,Mn)₃O_4.5 --> (Fe,Mn)₂O₃<br /> --> (Fe,Mn)O<br /> Due to a large number of crystal defects, nanocrystallites are formed which is favorable for catalysis. Our method enables one to set the ratio of the metal ions arbitrarily by starting from an isomorphous solid solution in which we partially replaced the metal ion by another one, and/or the anion by another tetraoxometalate or by an "innocent" anion (which forms gaseous products due to the lack of metal atoms, e.g., MnO₄^- by ClO₄^-).<br />[Fe(urea)₆](MnO₄)₃ -- (Fe,Mn)-oxides with Fe:Mn=1:3 overall ratio<br />[Fe(urea)₆(MnO₄)₂(ClO₄)₂ -- (Fe,Mn)-oxides with Fe:Mn=1:2 overall ratio<br />[Fe(Urea)₆](MnO₄)(ClO₄)₂ -- (Fe,Mn)-oxides with Fe:Mn=1:1 overall ratio<br />[(Fe_0.5Cr_0.5)(urea)₆](MnO₄)_0.5(ClO₄)_2.5-- (Fe,Cr,Mn) oxides with Fe:Cr:Mn=1:1:1 overall ratio

References:
[1] Sajó I.E., Bakos P. Szilágyi I.M., Lendvay Gy., Magyari J., Mohai M., Szegedi A., Farkas A., Jánosity A., Klébert Sz., Kótai L., Inorg. Chem., 2018, 57(21), 13679-13692.\n[2] Kotai, L., Banerji, K. K., Sajo, I., Kristof, J., Sreedhar, B., Holly, S., Keresztury, G., Rockenbauer, A.\nHelv. Chim. Acta, 2002, 85<span class="fon_main_wrapper"><span phone-source="(8) 2316-2327" class="fon-phone-wrap fon-hightlighted active-call" id="fon-phone-te9Y5gzl8q">(8) 2316-2327</span><a phone-source="(8) 2316-2327" href="#" class="fonCallLinkButton active-call"><img src="data:image/png;base64,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" alt="F"/></a></span>\n[3] Kotai L., Fodor J., Jakab E., Sajo I., Szabo P., Lonyi F., Valyon J., Gacs, I., Argay G., Banerji K., Trans. Metal Chem., 2006, 31(1) 30-34\n[4] Sajó I. E., Kotai L., Keresztury G., Gacs I., Pokol Gy., Kristóf J., Soptrayanov B., Petrusevski V. M., Timpu D., Sharma P. K., Helv. Chim. Acta 2008, 91, 1646

16:45: [AdvancedMaterialsFriPM211] Invited
Materials Research Society of Serbia and International Institute for the Science of Sintering Fostering Materials Research in Serbia
Dragan Uskokovic¹ ; ¹Materials Research Society of Serbia, Belgrade, Serbia and Montenegro;
Paper Id: 194 [Abstract]

Research in the field of material science and engineering has had a long history and tradition in Serbia. The seminal steps were made in the early 1950s, first at the University of Belgrade and the Institute of Nuclear Sciences in Vinča, after which important contributions were made by the associates of the Institute of Technical Sciences of the Serbian Academy of Sciences and Arts. The International Institute for the Science of Sintering (IISS) is certainly one of the most beautiful examples of how a very successful international scientific organization can be formed in a small country and how it can encourage the development of this discipline. The IISS was founded in 1968 in Belgrade, and the founding conference was held in Herceg-Novi, Montenegro in 1969. It was organized by 15 scientists from around the world who all agreed to develop this area with joint forces. The IISS had the important role of bringing together scientists in this field from a variety of international institutions, taking advantage of the fact that Yugoslavia, at the time, was a rare meeting place for the scientists from the East and from the West. Today, the IISS counts 12 honorable members, 45 full members, 16 correspondent members and 33 inactive members from 20 countries from all over the globe. The IISS has organized 10 international conferences on sintering (World Round Table Conferences on Sintering, WRTCS), all at the territory of former Yugoslavia. The IISS has also organized 7 international topical symposia on sintering, only the first of which was held in Herceg-Novi in former Yugoslavia and all others were held around the world: Warsaw in 1979, New Delhi in 1983, Tokyo in 1987, Vancouver in 1991, Haiko in 1995, and New Delhi in 2000. The IISS has been also publishing its Science of Sintering Journal for 50 years now. The Materials Research Society of Serbia (MRS-Serbia) was established in 1997 to promote multidisciplinary, goal-oriented research in material science and engineering, similarly to other MRS societies in the world. The main task and objective of MRS-Serbia is to encourage creativity in researching materials and model the evolution of this field in Serbia according to the analogous activities elsewhere in the world. MRS-Serbia has held twenty conferences so far and all of them, starting from the first one in 1995, were organized in Herceg-Novi in Montenegro. On average, 200 scientific presentations are given per conference, with more than 4 000 works being presented so far in total. This includes 500 plenary lectures by world-renowned researchers from some of the world’s most famous universities. The research program on "Molecular Designing of Nanoparticles and Functional Materials" [1] has been conducted throughout the last ten years within this environment. Since the methods for producing nanoparticles are at the basis of advanced materials science and engineering, a particular emphasis in this program is placed on soft, eco-friendly, bottom-up and easily technologically transferable fabrication methods. The materials that are the topics of our investigation can be potentially applicable in numerous technological fields: electronics, energy-storage, sensors, optics, catalysis, and biomedicine. Research activities such as those deployed in our labs may prove to be relevant for ensuring a sustainable development of humanity in energy, health, environment, water and other global sectors [2-5].

References:
[1] N. Ignjatovic, S. Markovic, D. Jugovic, D. Uskokovic, " Molecular designing of nanoparticles and functional materials", Journal of the Serbian Chemical Society, 2017, https://doi.org/10.2298/JSC1612070011I.
[2] Vuk Uskokovic and Dragan P.Uskokovic (eds.), Nanotechnologies in Preventive and Regenerative Medicine, Elsevier, 2018, 614 p.
[3] D. Jugovic, D. Uskokovic, "A review of recent developments in the synthesis procedures of LiFePO4 powders", Journal of Power Sources, vol. 180, no. 2 (2009) 538-544,doi:10.1016/j.jpowsour.2009.01.074.
[4] N. L. Ignjatovic, K. M. Penov-Gaši, J. J. Ajdukovic, V. V. Kojić, S. B. Marković, D. P. Uskoković, "The effect of the androstane lung cancer inhibitor content on the cell-selective toxicity of hydroxyapatite-chitosan-PLGA nanocomposites", Materials Science and Engineering C, 89 (2018) 371-377, https://doi.org/10.1016/j.msec.2018.04.028.
[5] Lj. Veselinovic, M. Mitric, M. Avdeev, S. Markovic, D. Uskokovic, "New insights into BaTi1-xSnxO3 (0 ? x ? 0.20) phase diagram from neutron diffraction data", Journal of Applied Crystallography, 49, 5 (2016) 1726-1733, https://doi.org/10.1107/S1600576716013157.

17:10: [AdvancedMaterialsFriPM212]
Cycloaddition of Carbon Dioxide to Cyclic Carbonate Catalyzed by Silica Xerogel Functionalized with Imidazolium-Based Ionic Liquids
Daniela Rodrigues¹ ; Leonardo Dos Santos¹ ; Franciele Bernard¹ ; Ingrid Pinto¹ ; Sandra Einloft¹ ; ¹PUCRS, Porto Alegre, Brazil;
Paper Id: 66 [Abstract]

The increase in carbon dioxide (CO₂) emissions from burning fossil fuels is the largest contributor to global warming of anthropic origin. Nevertheless, CO₂ is a nontoxic, nonflammable, and renewable feedstock. CO₂ utilization for the production of cyclic carbonates has gained great notoriety in the last decades because it is an environmentally benign alternative to reduce CO₂ emissions. Cyclic carbonates can be used as intermediates in the synthesis of fine chemicals, as monomers in polymerization reactions and as aprotic polar solvents. Cyclic carbonate is produced by cycloaddition of CO₂ with epoxides in the presence of catalysts due to CO₂ thermodynamical stability. Currently, the exploration of efficient catalysts for CO₂ coupling reactions is still necessary to promote an efficient reaction [1]. Ionic liquids (ILs) are salts composed of organic cations and organic or inorganic anions with melting point lower than 100°C [2]. These compounds have been proposed as homogeneous catalysts. The high price of ILs, however, and the difficulty to separate ILs from reaction media represent a barrier to implement them in the industry [3]. One solution for overcoming this disadvantage is silica xerogel functionalization with ILs [4]. In this study, a series of silica xerogels functionalized with imidazolium-based ILs ([BMIM][Cl], [BMIM][NTf2], [MBMIM][NTf2], [EMIM][NTf2], [EMIM][MSO₃] and [EMIM] [CF₃SO₃]) were synthesized by sol gel method and characterized by BET, RAMAN, TGA, FESEM and TEM. The catalytic performance of these compounds for CO₂ chemical transformation into cyclic carbonates by cycloaddition of CO₂ with epoxides was investigated. All cycloaddition reactions were performed at 40 bars and 110°C during six hours in a 120 cm³ titanium reactor equipped with magnetic stirring and temperature controller. The highest yield was obtained with [BMIM][Cl] (82.6%) and [EMIM][MSO3] (91.6%), both showing 99% selectivity. These results highlight the potential of these compounds as new catalysts.

References:
[1] L. Liu, S. M. Wang, Z. B. Han, M. Ding, D. Q. Yuan and H. L. Jiang, Inorganic Chemistry, 2016, 55, 3558-3565.
[2] R. M. Cuéllar-Franca and A. Azapagic, Journal of CO2 Utilization, 2015, 9, 82-102.
[3] A. Cherian, K. Robin, B. Jose and T. Roshith, Catalysis Surveys from Asia, 2015, 19, 223-235.
[4] Vidinha P, Augusto V, Almeida M, et al. Sol-gel encapsulation: An efficient and versatile immobilization technique for cutinase in non-aqueous media. J Biotechnol 2006, 121:23-33.

SESSION: AdvancedMaterialsFriPM3-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Fri Oct, 25 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Anka Trajkovska Petkoska; Yongmei Zheng; Session Monitor: TBA

17:50: [AdvancedMaterialsFriPM313]
Nitrite Elimination by Pd-Based Catalysts using Formic Acid as a Reducing Agent
Thiago Favarini Beltrame¹ ; Fernanda Zoppas² ; Marco Antonio Siqueira Rodrigues³ ; Vanina Aghemo⁴ ; Eduardo Miro² ; Fernanda Albana Marchesini² ; Andrea Moura Bernardes¹ ; Salatiel Wohlmuth Da Silva⁵ ; ¹UFRGS, Porto Alegre, Brazil; ²UNL, Santa Fe, Argentina; ³FEEVALE, Porto Alegre, Brazil; ⁴Instituto de Investigaciones en Catálisis y Petroquímica INCAPE, UNL, CONICET, Santa Fe, Argentina; ⁵Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil;
Paper Id: 68 [Abstract]

In recent years, the contamination of drinking water with nitrogen compounds is increasing due to the poor disposal of animal waste and excessive consumption of fertilizer. Nitrates and nitrites present in water produce serious problems for human health. Acceptable limits for nitrate, nitrite, and ammonium in drinking water were set by the World Health Organization at 50 ppm, 3 ppm and 0.5 ppm respectively [1]. The past few years have seen diverse technologies for nitrate and nitrite elimination, such as reverse osmosis, electrodialysis, ion exchange, catalytic abatement and biodenitrification. Among them, for the nitrite case, the catalytic reduction results in attraction due to easy accessibility, low investment costs, no need of additional treatment, and so on. In catalytic technology, a noble metal catalyst is used, like Pd, supported on a different massive oxide (i.e. alumina, silica Si:Al30). H₂ (g) is used as reducing agent for promoting the nitrite reduction to gaseous nitrogen. In this sense, formic acid (FA) has been considered as a way to store H₂ (g) and it could be used as a reducing agent for nitrite reduction [2]. To the best of our knowledge, there are no studies of catalytic removal of nitrite using formic acid as a reducing agent. Since this agent is suitable for the removal of nitrate, the study of this agent in nitrite removal deserves attention. The objective of this study was to investigate the behavior of formic acid as a hydrogen source in the catalytic reduction of nitrite (100 N-ppm) present in drinking or waste water.
Pd catalysts, supported on alumina, silica, and a mixture of Si:Al30, were synthesized by wet impregnation and evaluated for nitrite removal in a batch reactor. Palladium chloride (PdCl₂) was used as a precursor.
The results obtained show that in the presence of FA and without a catalyst, nitrite was 80% oxidized to nitrate. This reaction follows a chemical equilibrium between these two compounds [3]. In all tests, nitrate formation occurred. On the other side, it was found that using catalysts, the formation of nitrate is lower, in comparison with its formation without a catalyst. The catalyst which shows the best selectivity to N₂ in the same conversion rate (95%) was the one supported in alumina (55%). The nitrate selectivities obtained in the same conversion (95%) are 80%, 55%, 45% and 65% for formic acid, PdSi:Al30, alpha-Al₂O₃, PdSiO₂ respectively. Also, in the same order, the ammonium selectivities obtained in the same conversion (95%) are: 0%, 0.9%, 0% and 0%, respectively. Therefore, alpha-Al₂O₃ promotes a better selectivity to gaseous compounds, making it the most promising support among those evaluated for this reaction. The use of FA shows a promising result, which must be optimized for its future use in catalytic nitrogen removal processes.

References:
[1] WHO, Nitrate and Nitrite in Drinking-water, Switzerland, 2016.\n[2] Y. Ding, W. Sun, W. Yang, Q. Li, Formic acid as the in-situ hydrogen source for catalytic reduction of nitrate in water by PdAg alloy nanoparticles supported on amine-functionalized SiO2, Applied Catalysis B: Environmental, 203 (2017) 372-380.\n[3] A. Garron, F. Epron, Use of formic acid as reducing agent for application in catalytic reduction of nitrate in water, Water Res, 39 (2005) 3073-3081.

18:15: [AdvancedMaterialsFriPM314] Keynote
Application of Powerful Catalyzing agent for Chemical and Biological Processes Based on Flying Jet Plasma Torch
Wameath Abdul Majeed¹ ; ¹University of Nizwa, Nizwa, Oman;
Paper Id: 25 [Abstract]

Non-thermal plasma (NTP), also referred to as a cold plasma, is a unique tool with different applications where the temperature of electrons typically ranges from 10000 K to 250000 K while the hot gas exists at room temperature. These highly energetic electrons produce free radicals from parent molecules in multi-step physical and chemical processes, leading to high destructive ability. NTP is currently applied in different applications such as health sectors, environmental remediation, removal of volatile organic pollutants, simultaneous removal of NOx and soot in diesel exhaust and sterilization of air and water. Plasma jets, a category of NTP which can deliver plasma up to a few meters distance, are unique in producing reactive chemistry at room temperature. Therefore, it has attracted much attention in different applications due to their versatility and low-cost operation. Jet plasma has a privilege of lower shock risk, compared with DBD and corona discharge, which can penetrate and propagate inside small holes and flexible dielectric tubes. This is quite useful in different applications. In this sense, we developed a flying jet plasma torch (FJPT) and used it as an impetus in wide spectrum research. Those were dedicated to investigate FJPT as a sole and assisting catalyzing agent for: (1) Biodiesel production from fresh and wasted vegetable oil; (2) Treatment of domestic wastewater; (3) Treatment of raw polymers (polypropylene, polystyrene, and polyethylene) before end use process; (4) Activation of carbon derived from peat soil towards simple way of carbon nano tubes production; (5) Application of jet plasma in health sector (inactivation of wide range pathogens). Recent researches were devoted to utilizing our developed FJPT on: regeneration of reforming spent catalysts, treatment and conversion of land fill leachate towards biofuel production, and production of methanol from wasted steam plasmolysis. So far, a bunch of results of the aforementioned researches were published in refereed journals, while others will be in the near future.

References:
1. Wameath S. Abdul-Majeed, Khamis O. Al-Riyami 2019. Activation of peat soil carbon and production of carbon nanostructures using a flying jet cold plasma torch. Environmental Chemistry Letters (First online 6 March 2019, DOI: 10.1007/s10311-019-00869F-x).
2. Wameath S. Abdul-Majeed, Abdullatif Khan, Ahmed Al-Harrasi 2018. Application of Flying jet Plasma Torch in Wastewater treatment. Journal of Engineering Science and Military Technologies 2 (3), 101-108.
3. Wameath S. Abdul-Majeed, Ibtisam M. AL-Handhali, Shima H. AL-Yaquobi, Khamis O. Al-Riyami 2017. Application of Novel Polymeric Surface Remediation Technique Based on Flying Jet Plasma Torch. Industrial and Engineering Chemistry Research, 56 (39), 11352-11358
4. Wameath S. Abdul-Majeed , Ghanim S. AAl-Thani, Jamal N. Al-Sabahi 2016. Application of Flying Jet Plasma for Production of Biodiesel Fuel from Wasted Vegetable Oil. Plasma Chemistry and Plasma Processing, 36 (6), 1517-1531.

SESSION: AdvancedMaterialsSatAM-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Sat Oct, 26 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Monika Janowicz; Agnieszka Ciurzyńska; Session Monitor: TBA

11:20: [AdvancedMaterialsSatAM01] Invited
Silver Nanoparticles as Potential Antibacterial Agent: how Silver can overcome Antibiotic Resistance and how Bacteria can Resist Silver
Ales Panacek¹ ; Libor Kvitek² ; Milan Kolar¹ ; Renata Vecerova¹ ; ¹Palacky University, Olomouc, Czech Republic; ²Palacky University in Olomouc, Olomouc, Czech Republic;
Paper Id: 270 [Abstract]

Silver nanoparticles (NPs) exhibit significant antimicrobial activity against a broad range of bacteria and fungi at concentrations ranging from a few ppm to tens of ppm that are not cytotoxic to human cells [1,2]. Silver NPs also strongly enhance antibacterial activity against multiresistant, beta-lactamase and carbapenemase-producing Enterobacteriaceae when combined with antibiotics such as cefotaxime, ceftazidime, meropenem, ciprofloxacin and gentamicin [3]. All the antibiotics, when combined with silver NPs, showed enhanced antibacterial activity at concentrations far below the minimum inhibitory concentrations (tenths to hundredths of one ppm) of individual antibiotics and silver NPs. As a result, silver NPs have already been successfully applied in various biomedical and antimicrobial technologies and products used in every-day life as an alternative to conventional antimicrobials. While bacterial resistance to antibiotics has been discussed extensively in the literature, the possible development of resistance to silver NPs after repeated long-term exposure has not been fully explored. We report that the Gram-negative bacteria can develop resistance to silver NPs after prolonged exposure. The observed resistance stems from the production of the adhesive flagellum protein flagellin, which triggers the aggregation of silver NPs and eliminates their antibacterial effects. The resistance mechanism cannot be overcome by stabilization of silver NPs, by polymers or by surfactants. It is possible, however, to suppress it by inhibiting flagellin production with pomegranate rind extract [4].

References:
[1] Panacek A., Kvitek L., Prucek R. et al., J. Phys. Chem. B 110, 33 (2006) 16248-16253.\n[2] Panacek A., Kolar M., Vecerova R. et al., Biomaterials 30, 31 (2009) 6333-6340.\n[3] Panacek A., Smekalova M., Vecerova R., et al., Colloids Surf., B 142 (2016) 392-399.\n[4] Panacek A., Kvitek L., Smekalova M. et al., Nature Nat. 13, (2018) 65-72.

11:45: [AdvancedMaterialsSatAM02]
Architecture of Hybrid Materials Produced by Severe Plastic Deformation for Industrial Applications
Anibal De Andrade Mendes Filho¹ ; Rimma Lapovok² ; ¹CECS, Federal University of ABC | UFABC, Brazil, São Paulo, Brazil; ²Deakin University (Australia), Technion (Israel), Carnegie, Melbourne, Australia;
Paper Id: 71 [Abstract]

Significant enhancement of properties may be achieved through hybrid materials produced by newly emerging techniques of shear mixing [1]. It was shown that properties obtained by severe plastic co-deformation of dissimilar metallic materials are far outside of the expected properties of composite materials due to several physical phenomena observed, such as extension of solid solubility in immiscible metals, formation of non-equilibrium phases and reduction of grain size to a range of 10-20 nm near the interface. This level of nanostructuring that is accessible in hybrid materials is shown to be unreachable in single constituent materials. The idea of manufacturing material hybrids with simultaneous nanostructuring by SPD to reach new levels of properties is quite appealing. The architecture of hybrid materials is based not only on the design of the constituents and their volume fraction, but also on optimisation of the width and composition of the interface zone. Moreover, the understanding of physical mechanisms involved in interface formation and triggered by severe shear deformation under hydrostatic pressure is crucial for the architecture of hybrid materials with enhanced properties. One of the important factors for lightweight application examples is focused on shear-assisted interface formation in composite sheets of Interstitial-Free steel with Al or Cu interlayers [2, 3]. Al-IF steel and Cu-IF steel, multilayered composite sheets with different volume fractions of aluminium or copper, were produced by accumulative roll bonding (ARB) and Asymmetric Accumulative Roll Bonding (AARB), the latter introducing additional shear strain. The IF steel and Al/Cu alloy sheets were stacked in a sandwich-like structure and roll-bonded by two passes with varying roll diameter ratios (dr) equal to 1 and 2 for ARB and AARB processes, respectively. This work shows the effect of shear strain on the formation of the interface zone. The interface zone thickness, formed by intermixing and diffusion, was characterised by several different techniques, such as STEM EDX line scan, HRTEM and Atom Probe. Furthermore, finite element simulations of both processes were conducted to determine the level of interfacial shear strain. Conclusions: - Severe Plastic Deformation (SPD) processes were shown to be a useful tool to produce hybrid materials with concurrent nano-structuring of the constituents. - Shear strain, hydrostatic pressure and temperature of SPD processing play an important role in enhancement of the formation and properties of measurable interfaces. - The width of the interfacial zone correlates directly with the magnitude of the shear strain and architecture of the hybrid material. - The volume fraction and the nature of the interfaces play a decisive role in the improvement of mechanical and physical properties of a hybrid material.

References:
[1] Y. Beygelzimer, Y. Estrin, R. Kulagin, Synthesis of Hybrid Materials by Severe Plastic Deformation: A New Paradigm of SPD Processing, Advanced Engineering Materials, 17:12 (2015), 1853-1861.
[2] A. Mendes, I. Timokhina, A. Molotnikov, P. Hodgson, R. Lapovok, Role of Shear in Interface Formation of Aluminium-Steel Multilayered Composite Sheets, Material Science & Engineering A, 705 (2017), 142-152.
[3] A. Mendes, A. Molotnikov, P. Hodgson, R. Lapovok, Interface Formation in Copper-Steel Multilayered Sheets under Severe Shear Strain, Advanced Engineering Materials, (2019), https://doi.org/10.1002/adem.201900029

12:10: [AdvancedMaterialsSatAM03]
Self-Assembly in Intermediate Phase Region (fluctuation driven) from the UV-Visible Data and Coherence Correlation from X-ray Structural Data across GexSe1-x Chalcogenide Glass series
Deepak Sharma¹ ; ¹scriet meerut, meerut, India;
Paper Id: 82 [Abstract]

In this article, we are reporting conclusive experimental evidence from UV-Visible data for the existence of self-assembly structures in intermediate phase region which lays between 2.4 ≤ < r > < 2.54 across the Ge_xSe_1-x glass series. Various experimental studies were performed on chalcogenide glasses since 1996 until 2019 by many groups on modulated differential scanning calorimetry (MDSC). These studies have shown the presence of the intermediate phase, the so-called self-organized phase. Investigations on the compositional dependencies of the optical bandgap have revealed a non-monotonical trend in increase of bandgap due to nanocluster formation of different sizes. This gives rise to the intermediate phase region of the fluctuation driven bandgap and existence of the rigidity percolation threshold at < r > = 2.4. Glasses in the intermediate phase region are supposed to be stress free and homogenous. The results in the intermediate phase region are discussed and correlated with X-ray structural coherence data (D=2π/Δk from FSDP) which shows deviation from the mean field, from fluctuation-driven behavior in terms of network topologies and from percolative arguments. Irregular disorder in the compositional range plays a vigorous role for the manifestation of intermediate phase regions at room temperature. Our results extricate between triphase structural seclusion of the system across the Ge_xSe_1-x glass series.

References:
1. Sharma D; Sampath S; Lalla N.P; Awasthi A.M; Physica B 2005, 357,290
2. Sharma.D; Ingale. Alka; Awasthi A.M.; Solid State Communications 2005,134,653
3. Kirchner A.Katelyn and Mauro, C. John, Frontiers in Materials 2019, 6(11),1

12:35: [AdvancedMaterialsSatAM04]
Donor-Acceptor Molecular Materials as Emitters and Hosts for Organic Light Emitting Diodes
Ramin Pashzadeh¹ ; Eigirdas Skuodis¹ ; Ausra Tomkeviciene¹ ; Dmytro Volyniuk¹ ; Jurate Simokaitiene¹ ; Egle Jatautiene¹ ; Ramunas Lygaitis¹ ; Juozas Vidas Grazulevicius¹ ; ¹Kaunas University of Technology, Kaunas, Lithuania;
Paper Id: 83 [Abstract]

Molecular materials containing donor and acceptor moieties recently synthesized at the laboratories of the presenting author, and applied in organic light emitting diodes (OLEDs) as emitters and hosts will be reported. The derivative of 3-(trifluoromethyl)benzonitrile and 3,3' -bicarbazole was found to exhibit both delayed fluorescence and exciplex-forming properties [1]. Warm-white OLED based on this material showed external quantum efficiency (EQE) of ca. 20 %. The derivative of acridan and dicyanobenzene was found to be an efficient emitter, exhibiting both thermally activated delayed fluorescence (TADF) and aggregation induced emission enhancement. Green OLED fabricated using this emitter exhibited maximum current, power efficiency and EQE of 68 cd/m², 62 lm/W and 22.5 %, respectively [2]. A series of carbazole-quinoxaline-carbazole derivatives exhibiting TADF and mechanochromic luminescence properties were synthesized and studied. Green-blue to green-yellow TADF OLEDs fabricated by solution processing demonstrated EQE up to 10.9% and luminance of 16760 cd m^-2 [3]. Deep-blue OLED based on triplet-triplet annihilation with EQE of 14.1% was fabricated [4]. This was done by utilization of the derivatives cyanophenyl and ditertbutylcarbazolyl which were substituted with triphenylbenzene and different substitution patterns as hosts and guests of the emissive layer. This research was funded by the European Social Fund according to the activity "Improvement of researchers" qualification by implementing world-class R&D projects of Measure No. 09.3.3-LMT-K-712.

References:
[1] G. Grybauskaite-Kaminskiene et al. J. Mater. Chem. C, 6 (2018) 1543.
[2] Skuodis E. et al. Org. Electron., 63 (2018)29 (2018).
[3] Pashazadeh R. et al. J. Phys. Chem. Lett., 9 (2018) 1172.
[4] Kukhta N. et al. J. Phys. Chem. Lett.2017, 8 (2017) 6199.

SESSION: AdvancedMaterialsSatPM1-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Sat Oct, 26 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Gabor Patonay; Adriana Estokova; Session Monitor: TBA

14:00: [AdvancedMaterialsSatPM105]
Polypropylene Based Nanocomposite Membrane with a Self-Assembled Coating for Seawater Treatment via Membrane Distillation
Rajesha Kumar¹ ; Mansour Ahmed¹ ; Garudachari Bhadrachari¹ ; Jibu Thomas¹ ; ¹Kuwait Institute for Scientific Research, Kuwait, Kuwait;
Paper Id: 188 [Abstract]

Polypropylene based nanocomposite membrane with a self-assembled coating for seawater treatment via membrane distillation Rajesha Kumar1, Mansour Ahmed1, Garudachari Bhadrachari1, Jibu Thomas1 1Water Research Center, Kuwait Institute for Scientific Research, P.O. Box, 24885, 13109 Safat, Kuwait, Tel: +965 97920482 * e-mail: rajeshakumar15@yahoo.com Abstract. A novel approach of self-assembly techniques has been used for the coating of superhydrophobic layer over the microporous polypropylene (PP) support. The hydrophobic fluorinated silica nanoparticles were synthesized and isolated by reacting tetraethyl orthosilicate (TEOS) with excess heptadeca- fluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane. The hydrophobic silica particles (HSP) were dispersed in the coating solution consisted of trimesoyl chloride, trimethylamine and hexane compositions. The coating layer thickness was limited to 100-150 I�m by selecting the proper compositions of the TEA and TMC. The coating layer with HSP was effectively formed over the PP support via self-assembly of the hydrolyzed TMC molecules (trimesic acid (TMA) molecules). The high dispersion of HSP particles was achieved in the coating solution consisted of TMA leading to smooth and superhydrophic membrane surfaces with a contact angle of >150A�. The porosity of the surface was well in control with an average pore size of ~0.2 I�m. The application of membranes was tested for membrane distillation application in direct contact membrane distillation (DCMD) configuration. The hot feed of 35 g/L aqueous sodium chloride solution, and cold deionized water as permeate. The maximum transmembrane permeate flux of 46.7 kg/m2h with >99% salt rejection was obtained at 80 A�C demonstrating the future potential application towards seawater desalination. Keywords: seawater treatment, nanocomposite membrane, membrane distillation, self-assembly

References:
References
Behera, D, Banthia, AK, (2007) BisGMA/TiO2 organic-inorganic hybrid nanocomposite. Polymer-plastics Technology and Engineering 26(1):10-12. DOI: 10.1080/03602550701575821
Rittigstein, P, Priestley RD, Broadbelt, LJ, Torkelson JM, (2007) Model polymer nanocomposites with known interlayer spacing provide understanding of confinement effects in real nanocomposites. Nature Materials 6(1):278-282. DOI: 10.1038/nmat1870
Hongxia W, Jian F, Tong C, Jie D, Liangti Q, Liming D, Xungai W, Tong L, (2008) One-step coating of fluoro-containing silica nanoparticles for universal generation of surface superhydrophobicity. Chemical Communications 0 (2008) 877a��879. DOI: 10.1039/B714352D

14:25: [AdvancedMaterialsSatPM106] Invited
Strongly Luminescent Silver Complexes with Very Short and Very Long Excited State Lifetimes
Rafal Czerwieniec¹ ; ¹Universität Regensburg, Regensburg, Germany;
Paper Id: 114 [Abstract]

The design of transition metal complexes with high emission quantum yields and other photophysical and chemical properties, optimized for particular applications, is a challenge. For organic light emitting devices (OLEDs), among other requirements, a short emission decay time is advantageous for reduction of saturation effects. On the contrary, for up-conversion, highly sensitive oxygen sensing and long-lived excited states of photocatalysis are preferred. Structurally related silver complexes (1) Ag(dbp)(P₂-nCB) [1,2] and (2) Ag(dmp)(dpep)PF₆ [3], with dbp = 2,9-di-<i>n</i>-butyl-1,10-phenanthroline, P₂-nCB = nido-carboranebis(diphenylphosphine), dmp = 2,9-dimethyl-1,10-phenanthroline, and dpep = bis[(2-diphenylphosphino)phenyl] ether, respectively, are strongly luminescent with the emission quantum yields (PLQY) at ambient temperatures, approaching 100 % for 1 and 50 % for 2. The excited state (radiative) lifetimes differ drastically. For complex 1, an unprecedentedly short time is measured for this kind of luminescent materials' emission decay time of 1.4 microseconds (at PLQY = 100 %). For complex 2, the decay time (at PLQY = 50 %) is as long as 0.11 s. The short-lived emission of complex 1 originates from the efficient thermally activated delayed fluorescence (TADF) process, whereas the long-lived emission of complex 2 represents phosphorescence. The distinctly different photophysical properties of these structurally similar compounds demonstrate the high variability of the molecular electronic structures and emission mechanisms. Using these compounds as extreme case examples, general trends and "recipes" for engineering of luminescent materials for defined applications can be elucidated.

References:
[1] M. Z. Shafikov, A. F. Suleymanova, R. Czerwieniec, H. Yersin, Chem. Mater. 29 (2017) 1708-1715.\n[2] M. Z. Shafikov, A. F. Suleymanova, R. Czerwieniec, H. Yersin, Inorg. Chem. 56 (2017) 13274-13285.\n[3] M. Z. Shafikov, A. F. Suleymanova, R. Czerwieniec, H. Yersin, Dalton Trans. 48 (2019) 2802-2806.

14:50: [AdvancedMaterialsSatPM107]
Quinoxalinophenanthrophenazine Compounds in Organic Optoelectronic Applications
Bilal Kaafarani¹ ; ¹American University of Beirut, Beirut, Lebanon;
Paper Id: 203 [Abstract]

Fused, ladder-type organic materials have inherent advantages, such as extended Pi-frameworks, favorable stacking behavior in the solid state, conductivity, and high field-effect mobility. We have reported a wide range of quinoxalinophenanthrophenazine (TQPP) compounds. The introduction of nitrogen atoms in the TQPP core decreases the HOMO-LUMO gap, making the compounds of more interest in electronic applications. Besides, the planarity of the core in the TQPP compounds facilitates the efficient cofacial stacking of the materials in the solid state and increases the intermolecular Pi-orbital overlap. Combining the electronic properties of the electron-deficient TQPP chromophore with the predisposition of the TQPP compounds to self-organize into efficient self-assembled Pi-Pi columnar stacks in a single molecule offers an interesting combination of physical properties and, perhaps, a route to new materials for electronic applications. In this talk, we will discuss the different properties and features of the TQPP compounds.

References:
1. Kaafarani, B. R.; El-Assaad, T. H.; Smith, W. A.; Ryno, S. M.; Hermerschmidt, F.; Lyons, J.; Patra, D.; Wex, B.; List-Kratochvil, E. J. W.; Risko, C.; Barlow, S.; Marder, S. R. “Bis(tercarbazole) pyrene and tetrahydropyrene derivatives: photophysical and electrochemical properties, theoretical modeling, and OLEDs”, J. Mater. Chem. C 2019, 7, 5009 - 5018.
2. Taing, H.; Cassar, A. M.; Ocheje, M. U.; Rondeau-Gagne, S.; El-Assaad, T. H.; Sharabati, C. A.; Kaafarani, B. R.; Eichhorn, S. H. “Self-assembly of Board-shaped Diketopyrrolopyrrole and Isoindigo Mesogens Into Columnar Pi-Pi Stacks”, ChemPlusChem 2019, 84, 103-106.
3. Fratczak, E. Z.; Makowski, T.; Moustafa, R. M.; El-Assaad, T. H.; Moneta, M. E.; Uznanski, P.; Kaafarani, B. R. “Spectroscopic Characterization of Structural Properties of Quinoxalinophenanthrophenazines Thin Films”, J. Mater. Chem. C 2018, 6, 781-789.
4. Wex, B.; Kaafarani, B. R. “Perspective on Carbazole-Based Organic Compounds as Emitters and Hosts in TADF Applications”, J. Mater. Chem. C 2017, 5, 8622-8653.
5. Altarawneh, S.; Nahar, S.; Arachchige, I. U.; El-Ballouli, A. O.; Hallal, K. M.; Kaafarani, B. R.; Rabbani, M. G.; El-Kaderi, H. M. “Highly Porous and Photoluminescent QuinoxalinoPhenanthroPhenazine-Derived Benzimidazole-Linked Polymers”, J. Mater. Chem. A 2015, 3, 3006-3010.
6. El-Ballouli, A. O.; Kayal, H.; Shuai, C.; Zeidan, T. A.; Raad, F. S.; Leng, S.; Wex, B.; Cheng, S. Z. D.; Eichhorn, S. H.; Kaafarani, B. R. “Lateral Extension Induces Columnar Mesomorphism in Crucifix Shaped Quinoxalinophenanthrophenazines”, Tetrahedron 2015, 71, 308-314.
7. Makowski, T.; Moustafa, R. M.; Uznanski, P.; Zajaczkowski, W.; Pisula, W.; Tracz, A.; Kaafarani, B. R. “Structural, Thermo-Optical, and Photophysical Properties of Highly Oriented Thin Films of Quinoxalinophenanthrophenazine Derivative”, J. Phys. Chem. C 2014, 118, 18736-18745.
8. Chen, S.; Raad, F. S.; Ahmida, M.; Kaafarani, B. R.; Eichhorn, H. S. “Columnar Mesomorphism of Fluorescent Board-Shaped Quinoxalinophenanthrophenazine Derivatives With Donor-Acceptor Structure”, Org. Lett. 2013, 15, 558-561.
9. Kaafarani, B. R. “Discotic Liquid Crystals for Opto-Electronic Applications”, Chem. Mater. 2011, 23, 378-396.

15:15: [AdvancedMaterialsSatPM108] Keynote
Fabrication of High Entropy Alloys Shock Wave Consolidation of Ti-Ni-Fe-W-Cu Powders
Nikoloz Chikhradze¹ ; Fernand Marquis² ; Mikheil Chikhradze³ ; Guram Abashidze¹ ; Davit Tsverava⁴ ; ¹G. Tsulukidze Mining Institute, Tbilisi, Georgia; ²San Diego State University, San Diego, United States; ³Georgian Technical University, Tbilisi, Georgia; ⁴LEPL Grigol Tsulukidze Mining Institute/M.Sc. Student of Georgian Technical University, Tbilisi, Georgia;
Paper Id: 337 [Abstract]

High Entropy Alloys are characterized with specific properties, including high hardness, wear-resistance, high strength, structural stability, corrosion and oxidation-resistance [1-5]. The complex of desired properties defines the increasing interest for the application in different fields of engineering. In spite of the interest towards High Entropy Alloys/materials, most of the traditional methods do not allow the fabrication the desired varieties of composites due to the technological limitation. On the other hand, investigations towards high entropy materials are increasing as there are some properties that have to be studied and validated in multi-component systems. The goal of the current investigations is to carry out experiments and define synthesis regimes for Ti-Ni-Fe-W-Cu system powders by mechanical alloying and establish the technological parameters for the formation of High Entropy Alloys. The other goal of the work is to make experimental investigations for the synthesis of bulk materials by an explosive consolidation technique. The paper describes the preliminary theoretical investigations and initial experimental results of mechanical alloying and explosive compaction of the Ti-Ni-Fe-W-Cu multi-component system. As a result, the preliminary investigations establish the technological parameters for mechanical alloying. The blend with different percentages of content of powders was prepared. The high energetic planetary ball mill was used for blend processing, mechanical alloying, and amorphization ultrafine/nanopowder production. The time of processing varied in the range of 1-28 h. Selected Ball milled blends were compacted by explosive consolidation technology. For shock wave generation, the industrial explosives and new explosives obtained from decommissioned weapons were used in the experiments. The technological parameters of the explosive consolidation have been studied and are discussed in this paper.

References:
1. Yeh J. et al, Nanostructured high entropy alloys with multiple principal elements: novel alloy design concepts and outcomes, Adv. Eng. Mater. V. 6., #5, 2004
2. Michael C. Cao, Jien-Wei-Yeh, Peter K. Liaw, Youg Zhang, eBook: High-Entropy Alloys, Fundamentals and Applications, Springer, 2016
3. High-Entropy Alloys, JOM, An official publication of The Minerals, Metals & Materials Society, Springer, November 2017
4. Cantor B. et al., Materials Science and Engineering: A, 375-377, 213-218, 2004,
5. He Q. F. et al, Design of High-Entropy Alloy: A Perspective from Nonideal Mixing, JOM, v.69., # 11, p. 2092-2098, 2017

SESSION: AdvancedMaterialsSatPM2-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Sat Oct, 26 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Nadezda Stevulova; Liudmila Lisitsyna; Session Monitor: TBA

15:55: [AdvancedMaterialsSatPM209]
Low-Cost Thermochemical Heat Storage by Using Cement-Based Composite Materials
Matteo Pavese¹ ; Luca Lavagna¹ ; Davide Burlon¹ ; Roberto Nistico¹ ; Vincenza Brancato² ; Andrea Frazzica² ; Eliodoro Chiavazzo¹ ; ¹Politecnico di Torino, Torino, Italy; ²Consiglio Nazionale delle Ricerche, Messina, Italy;
Paper Id: 265 [Abstract]

In Europe, heating is responsible for the most part of the residential energy demand [1]. To reduce energy consumption, thermochemical materials (TCMs) coupled with renewable heat production (e.g. solar thermal) seem a very promising option for seasonal heat storage. Among the TCMs, salt hydrates provide the highest energy density [2], but has poor mass and heat transport properties. On the contrary, highly porous materials like zeolites present good mass and energy transfer, but have high cost and rather low energy density [3]. The coupling of a porous material and a salt hydrate would be an optimal solution to guarantee both transfer properties and energy density, provided that the cost issue is addressed. In this work, we developed a composite TCM, based on hydrated cement for the porous matrix and on calcium chloride or magnesium sulfate as salt hydrates, that allows a significant reduction of the cost per unit energy stored. Usually, the conditions of cement hydration are chosen to obtain a low porosity material, to provide high mechanical properties. By increasing the water-to-cement (w/c) ratio in the cement paste, however, the hydrated cement becomes highly porous. Thus, the first part of the work was to characterize cement at very high w/c ratios by density measurements, N₂ physisorption analyses, microscopy and mechanical testing. Once the best preparation conditions for porous cement were selected, two techniques were used to prepare the composite materials: the standard impregnation method from aqueous solutions and a novel one-step technique where cement was hydrated with a concentrated solution of the chosen salt instead of distilled water. The energy density of the composites was estimated by DSC analysis and a preliminary calorimetric characterization was performed by monitoring the temperature of the samples during hydration with liquid water. The observed temperature lift was a measure of the heat generated during the hydration step. The most interesting materials were finally characterized by equilibrium water vapor adsorption isobars. A preliminary economic analysis, based on thermal energy cycles at a maximum temperature of 80°C and 140°C (common flat-plate or evacuated-tube solar collectors, respectively), was also performed. The price per stored kWh was calculated for literature-based materials and for the cement-based composites. The results showed a three-fold reduction of price per stored kWh with respect to zeolite-based systems [4].

References:
[1] "Communication from the Commission to the European Parliament, the Council, the European Economic and Social Committee and the Committee of the Regions on an EU Strategy for Heating and Cooling", European Commission, Brussels, 16.2.2016
[2] K. Visscher, J. Veldhuis, Ninth International IBPSA Conference Proceedings, Montreal, Canada, August 15-18, 2005.
[3] L. Scapino, H. Zondag, J. Van Bael, J. Diriken, C. Rindt, Applied Energy 190 (2017), 920-948.
[4] S. Hongois, F. Kuznik, P. Stevens, J.J. Roux, Solar Energy Materials and Solar Cells 95 (2011) 1831-1837.

16:20: [AdvancedMaterialsSatPM210]
Modular Pavements Application Areas and their specifications
Audrius Vaitkus¹ ; Judita Grazulyte² ; ¹Road Research Institute, Vilnius Gediminas technical university, Vilnius, Lithuania; ², Vilnius, Lithuania;
Paper Id: 90 [Abstract]

Roads and other trafficked areas' infrastructure start to deteriorate as far as it is opened to traffic. Thus, it has to be timely repaired and reconstructed. Any interruption to traffic by implementing repair and rehabilitation works, however, leads to users' discomfort and traffic congestion. Modular pavements, also known as precast concrete pavements, can be constructed at night; consequently, they eliminate or reduce traffic flow issues related to repairs. They consist of prefabricated concrete slabs that are transported to the construction site only after the curing period, when the desirable concrete strength is achieved and installed on a prepared foundation. The prefabrication of slabs in a plant results in better concrete quality, controlled concrete curing conditions, and wider periods for pavement construction. It also reduces time before opening to traffic, and eliminates early-age failures and material segregation which may occur during concrete or asphalt mixture transportation to the project site and laying. Despite these advantages, modular pavements are barely used in Europe. In order to enhance the usage of modular pavements in Europe, this paper focuses on the identification of the most promising modular pavement application areas and their types of selection. The most promising application areas, such as motorways and arterial streets, were identified on the basis of the conducted survey among high-qualified researchers. Low volume roads, private roads, and bicycle and pedestrian paths could be included as special application areas to modular pavements using a slightly different approach.

16:45: [AdvancedMaterialsSatPM211]
Hydrotalcite Derived Nano-Catalysts in Dry Reforming of Methane Process
Djamilla. Halliche¹ ; Patrick J. Masset² ; Zoulikha Abdelsadek³ ; ¹Laboratory of Chemistry and Natural Gas, Faculty of Chemistry, USTHB, Algiers, Algeria; ²Technallium Engineering & Consulting, Steinberg am See, Germany; ³Laboratory of Chemistry and Natural Gas, Faculty of Chemistry, USTHB, Institute of Electrical and Electronics Engineering, University of M’hamed Bougara, ALgiers, Algeria;
Paper Id: 199 [Abstract]

In the frame of the reduction of greenhouse gases, hydrotalcite nano-catalysts become a key component in the process of the dry reforming of methane (DRM). This process is now intensely investigated, both academically and industrially. The DRM reaction leads to the production of syngas with a lower H₂/CO ratio (= 1) which is appropriate for the Fischer-Tropsch and methanol syntheses. The use of hydrotalcite at the industrial level, however, faces key issues such as the sintering of the active phase and the deactivation of catalysts by carbon deposits. This presentation provides an understanding of the overview of the key issues of the use of hydrotalcite in the DRM process. This will be illustrated by some examples including selection of materials, catalyst synthesis, alternative materials and synthesis routes, their characterisation, performance in term of conversion efficiency, and ageing ability regarding the DRM process. Finally, a comprehensive review of the developed materials so far and current trends in the development of material combination will be provided.

References:
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17:10: [AdvancedMaterialsSatPM212]
Photoluminescence of Phosphors Containing W-O Emission Complexes
Aida Tulegenova¹ ; Liudmila Lisitsyna² ; ¹2Al-Farabi Kazakh National University, Almatу,, Kazakhstan; ²Tomsk State University of Architecrure and Building, Tomsk,, Russian Federation;
Paper Id: 93 [Abstract]

Natural phosphors like MeWO₄, possessing high light emissions at small volumes, are considered to be a promising material for X rays and γ-scintillators. Nanostructured MeWO₄ materials are promising candidates for photoluminescence. During the past decade, unique properties of these materials such as photocatalytic activity, photochromism and electrochromism have attracted the attention of researchers. Photoluminescence in ZnWO₄ crystals, WO₃ crystalline micropowders, as well as in LiF crystals and MgF₂ ceramics doped with tungsten trioxide, was researched at 300 K. Prepared As phosphors were not transparent in the range ≥4 eV (WO₃, ZnWO₄), or they became opaque in this range after doping with tungsten trioxide (LiF crystals, MgF₂ ceramics). Emission was excited by photons with 6>E_ph ≥ 4 eV. The focus of these studies is on the emissions of phosphors with different types of matrices. What they have in common is that the lattices contain W-O polyhedrons. The following was revealed: - Spectral-kinetic characteristics of the phosphors' photoluminescence in the visible range (band at 2.6-2.7 eV) are independent of the width of the band gap (from 13 till 3.8 eV), of the lattice structure of phosphorus matrices and of the method of preparing the materials (grown in air, sintering, laser ablation). - The emission characteristics of phosphors: spectral position of emission band, the value of long-lived time decay, the emission band FWHW and the value of the Stokes shift are similar to those in the WO₃ crystalline micropowder. It looks as if emission centers were created under UV irradiation in specific areas of phosphors with the same properties in all materials under research. - The work deals with a hypothesis according to which the presence of the WO₃ phase in phosphor matrices defines the structure of emission centers (oxygen-depleted polyhedron W⁶⁺nO^2-) and high sensitivity to UV irradiation. The latter is due to the small width of the band gap of the WO₃ lattice (3.8 eV) compared with those in the researched phosphorus matrix lattices. - The emission in the WO₃ material is of a recombination nature. It means that wide-gap dielectric phosphors doped with WO₃ (LiF and MgF₂), free electrons, and holes are created when E_ph<E_g in the matrices. Perhaps, in this case, photocatalytic activity, photochromic, and electrochromic properties are inherent properties of many oxides of transition metals revealed in WO₃-containing materials [1, 2].

References:
[1] J. Grabis, D. Jankovica, M. Kodols, D. Rasmane. Latvian J. Chem., 1/2 (2012) 93-98
[2] G. Huang, Y. Zhu. J. Phys. Chem. C, 111 (2007) 11952-1195

SESSION: AdvancedMaterialsSatPM3-R2	5th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Sat Oct, 26 2019 / Room: Leda (99/Mezz. F)
Session Chairs: Natia Jalagonia; Roba Saab; Session Monitor: TBA

17:50: [AdvancedMaterialsSatPM313]
Modified Graphene Oxide as Reinforcement for Alumina Based Composite
Natia Jalagonia¹ ; Ekaterine Sanaia² ; Guram Bokuchava³ ; Tinatin Kuchukhidze⁴ ; Nino Darakhvelidze² ; Tamari Archuadze⁵ ; ¹Ilia Vekua Sokhumi Institute of Physics and Technology, Tbilisi, Georgia; ², Tbilisi, Georgia; ³Ilia Vekua Sukhumi Institute of Physics and Technology, Tbilisi, Georgia; ⁴LEPL Ilia Vekua Sukhumi Institute of Physics and Technology, Tbilisi, Georgia; ⁵Ilia Vekua Institute of Physics and technology, Tbilisi, Georgia;
Paper Id: 185 [Abstract]

Discovery of graphene as important materials carried out the coup in nanotechnology. Great interest to graphene testifies lots of articles, which are published monthly in the scientific literature. It seems that less attention is paid to chemical properties of carbon nanostructures. Carbon nanostructures have different functional groups that have the ability to react with various organic and inorganic compounds [1]. That is why it is possible to modify the carbon nanostructures by different compounds and then obtain organic and inorganic composites based on the above mentioned modified nanoparticles [2]. For the purpose of obtaining hard ceramic materials, graphene oxide was functionalized by organic compounds (polyvinyl alcohol (PVA), polyethylene glycol (PEG).Then, functionalized graphene oxide was added in alumina and the homogenization process was carried out in nanomill during 24 hours. Organic compounds are allocated from graphene oxide at high temperatures during sintering, leading to reduction of graphene oxide. This kind reduced graphene oxide has mostly similar properties as graphene, which have influence over the physical-mechanical properties of ceramics. Concentration of modified graphene oxide is 1.5%w in composite. The obtained mixture is dried and then consolidated in a high temperature vacuum furnace at 1600°C under pressure at 478 kg/sm₂. The microhardness is 15.41 GPa (loading - 200 g) of the obtained ceramic materials in Fig 1. The microhardness is 12.025 GPa of the ceramic materials obtained from pure alumina under the same conditions. Testing was carried out using the Oliver-Pharr method according to the ISO-14577 standard. We are continuing works to determine optimal concentration of modified graphene oxide and we are researching other physical-mechanical properties [3].

References:
[1] Lee, C. et al. Elastic and Frictional Properties of Graphene. Phys. Stat. Solidi. B 246, 2562-2567 (2009);
[2] Natia Jalagonia, Fernand Marquis, Karlo Barbakadze, Ekaterine Sanaia, Guram Bokuchava, Tinatin Kuchukhidze. Materials Science Forum, ISSN: 1662-9752, Vol. 900, 101-104; doi:10.4028/www.scientific.net/MSF. 900.101; 2017 Trans Tech Publications, Switzerland;
[3] Hyo Jin Kim, Sung-Min Lee1, Yoon-Suk Oh, Young-Hwan Yang, Young Soo Lim, Dae Ho Yoon,Changgu Lee, Jong-Young Kim, Rodney S. Ruoff. DOI: 10.1038/srep05176;

18:15: [AdvancedMaterialsSatPM314]
Hierarchical Porous Materials towards a Novel Hydrocracking Catalyst
Roba Saab¹ ; Kyriaki Polychronopoulou¹ ; Andreas Schiffer¹ ; ¹Khalifa University, Abu Dhabi, United Arab Emirates;
Paper Id: 246 [Abstract]

The use of heavy oils as fuel is becoming less favorable due to the environmental concerns associated with them, and thus, it is highly recommended to convert them into lighter high-value products. An important process in the conversion of such fuels is hydro-cracking, a process by which heavy chemicals are converted into lighter and added value products [1]. The development of zeolites as catalysts in hydrocracking has caused a major breakthrough due to their superior activity, stability, and gasoline selectivity as compared to amorphous silica-alumina catalysts [2]. Y-type zeolites with uniform crystal pore sizes and strong Brønsted acidity arising from the bridging OH groups are widely used as catalysts in industrial processes such as, hydrocracking, isomerization, and alkylation [3]. Nonetheless, carbon-zeolite composites seem to be interesting catalysts for hydrocracking in which the zeolite serves as a support for metal nanoparticles and provides an acidic cracking function. Meanwhile, the CNTs and graphene provide high thermal stability and conductivity, as well as a large specific surface area. To further increase the performance of existing hydrocracking catalysts, we demonstrate a novel approach for the synthesis of hybrid catalysts composed of Y-type zeolite, nickel nanoparticles and nano-carbon material (CNTs, Graphene). The zeolites, having a SiO₂/Al₂O₃ ratio of 30, were loaded with Ni, in 5 wt. %, using the wet impregnation method, and were hyberdized with CNTs. Despite their unique properties of high surface area and thermal conductivity, CNTs shall also add mesoporosity to the microporous zeolites, forming a hierarchical porous material. The synthesized catalyst was later tested for heptane hydrocracking at two different temperatures, 350°C and 400°C for 20 hours of time-on-stream.

References:
[1] H. B. Park, K. D. Kim, and Y. K. Lee, “Promoting asphaltene conversion by tetralin for hydrocracking of petroleum pitch,” Fuel, vol. 222, no. February, pp. 105-113, 2018.
[2] C. L. Hemler and L. F. Smith, “UOP fluid catalytic cracking Process,” in Hand book of Petroleum refining Processes, Third., McGraw-Hill, 2004.
[3] G. Busca, “Acidity and basicity of zeolites: A fundamental approach,” Microporous Mesoporous Mater., vol. 254, no. June 2016, pp. 3-16, 2017.

SESSION: SISAMThuAM-R3 A: Magnetic materials today	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Thu Oct, 24 2019 / Room: Dr. Christian Bernard
Session Chairs: Jean-Marie Dubois; Session Monitor: TBA

11:20: [SISAMThuAM01] Plenary
Magnetic Materials in the Current Global Environmental Issues
Jean-marie Dubois¹ ; Spomenka Kobe² ; ¹Institut Jean Lamour, Nancy, France; ²Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 471 [Abstract]

Critical magnetic materials in the current global environmental issues have been one of the main research fields of Prof. Spomenka Kobe, who is being honored with the current symposium for her distinguished work and her lifetime achievements. These magnets, based on Nd-Fe-B alloys, are dominating the field already 36 years and their vital importance is nowadays mainly in e-mobility and e-energy power supply. Professor Kobe is the pioneer of modern magnetic materials in Slovenia. Over her career, she has achieved a number of breakthroughs in the area of these sustainable materials. The last to date is the reduction by a factor of at least 15 times less amount of heavy rare earth (HRE) needed to maintain high coercivity in engineered magnets with the largest possible magnetization, such as the ones used in wind generators or car engines. Nd-Fe-B magnets are at the forefront of sustainability. Due to the constant presence of possibly repeated restrictions on raw materials from the leading supplier, it is of vital importance to search for the ways how to avoid the next feasible crisis. In August 2019, the Chinese government cut the resource tax on companies mining heavy rare earths to 20 percent from 27 percent, as part of its efforts to support the vital sector and maintain the country’s dominance. Millions of end of life (EoL) devices, especially the wind generators, are a great source of raw materials. The new frontiers in Europe are now focused on the recycling of magnetic materials from tens of thousands of those magnets. By using the latest technologies developed in Europe, we can use short-loop circular economy routes to re-integrate the metals into new products for the European market1. The basic and applied research of the Magnetic Group (Department for Nanostructured Materials, Jožef Stefan Institute) in the field of Nd-Fe-B magnets, as well as possible alternatives, will also be briefly introduced and later on presented by the members of the group.

References:
SUSMAGPRO European Project Horizon 2020 programme of the European Commission (Coordinated by Prof. Carlo Burkhardt)

11:45: [SISAMThuAM02] Plenary
Advances in Permanent Magnets
George Hadjipanayis¹ ; ¹University of Delaware, Newark, United States;
Paper Id: 427 [Abstract]

In this presentation, the current trends and the latest developments in the field of the permanent magnets will be reviewed. Two powerful factors shape the current developments of the rare-earth magnets, the rapidly growing demand for high-energy-density magnets operating at 150 – 200 °C and the echo of the 2010-11 rare earths supply crisis. The incentive for increasing the operating temperature of the Nd-Fe-B magnets using smaller amounts of heavy rare earths has resulted in the development of localized alloying techniques, in which Dy or Tb are delivered to the exact locations in the magnet through grain-boundary infiltration. Moreover, the same infiltration approach as well as a more refined micro-alloying now allows for sintered and die-upset Nd-Fe-B magnets exhibiting a coercivity as high as 20 kOe without any use of the heavy rare earths. To address the sustainability challenge, researchers and manufacturers are also partially replacing even the light rare earths, Nd and Pr, with the more abundant Ce and La. The Sm-Co magnets had their maximum energy product recently increased to 35 MGOe, primarily through a greater Fe substitution for Co. The ThMn12-type compounds, notable for their naturally low rare earth content see a renewed interest. Although 1:12 alloys with excellent fundamental properties – rivaling those of the Nd2Fe14B compound – have been synthesized and processed by different approaches ranging from sintering followed by infiltration to mechanochemistry, there has not yet been a breakthrough in preparation of practical 1:12 magnet. Such breakthrough apparently happened this year for the most developed rare-earth-free permanent magnet material (not counting the prohibitively expensive FePt). Magnetic-field annealing of a properly alloyed MnBi alloy, after it has been subjected to melt spinning and warm compaction, produced magnets exhibiting a maximum energy product of 11-12 MGOe, which is 40% greater than those obtained via the traditional powder metallurgy and which must be sufficient to replace the lower grades of the rare earth magnets.

12:10: [SISAMThuAM03]
Interaction Of Ferromagnetic And Superconducting Permanent Magnets: Basics And Applications Of Passively Stable Quantum Levitation
Ludwig Schultz¹ ; ¹TU Dresden, Dresden, Germany;
Paper Id: 94 [Abstract]

Superconducting magnetic levitation is passively stable without any electronic control except with attracting and repelling forces to suspend a vehicle pendant or standing upright. Due to this intrinsic stability, the levitation itself does not consume any energy. These are perfect conditions for a rail-bound system like Hyperloop. Individual transport with cabins for 4 to 5 passengers is requested call by call. They will levitate without noise over a track made of rare-earth permanent magnets, saving energy and travel time. A big step forward in this vision has been made in Dresden. The world’s largest research and test facility for transport systems using bulk high-temperature superconducting material in the levitation and guidance system, in combination with a permanent magnet track, was put into operation. A vehicle for 2 passengers, equipped with linear drive propulsion, noncontact energy supply, second braking system, and various test and measurement systems runs on an 80 m long oval driveway. In the presentation, the principle of superconducting levitation by flux pinning in bulk high-temperature superconductors will be described. Based on this, an overview of the SupraTrans II research facility and future directions of superconductivity-based magnetic levitation and bearing for automation technology, transportation, and medical treatment under enhanced gravity will be given. Also, the physics behind the "Back to the Future II " superconducting hoverboard, recently presented by Lexus, will be described.

References:
no additonal references

12:35: [SISAMThuAM04] Invited
Recent Developments in R-Fe-X Permanent Magnets
Takahiko Iriyama¹ ; Masato Sagawa² ; ¹Corporate R&D Center, Daido Steel Co., Ltd., Nagoya, Japan; ²Daido Steel Co. Ltd., Nagoya, Japan;
Paper Id: 192 [Abstract]

The demand for high-performance rare-earth-iron permanent magnets in various applications such as motors/sensors for automotive, electronic devices, or home appliances has increased in recent years. Sintered or hot-deformed Nd-Fe-B magnets [1, 2] are the most attractive choice because they have the highest (BH)max value among all the commercial magnetic materials. The addition of heavy rare earth elements (HREEs), such as Dy or Tb, is a common way to increase the coercivity of Nd-Fe-B magnets thus allowing the use of such magnets at high temperatures. The problem with the HREE addition, however, is the reduction of (BH)max. Another problem, which is even more serious, is the supply risk of HREEs due to geo-political and environmental issues. Accordingly, efforts to reduce HREE use have been undertaken all over the world. Fabrication processes utilizing grain boundary diffusion (GBD) have recently been developed to effectively reduce HREE usage by more than 50%. The ultimate goal, however, is the creation of HREE-free Nd-Fe-B magnets with high coercivities. It is well known that decreasing the grain size increases coercivity. The hot-deformed magnet has a fine microstructure that is one order of magnitude finer than that of the conventional sintered magnet. Thus, hot-deformed Nd-Fe-B is a promising material to create high performance HREE-free magnets. The PLP (Press-less Process) proposed by one of the authors also realized a fine-grained sintered Nd-Fe-B magnet. This is because the atmosphere in the PLP process is inert throughout the processes and the resulting magnets contain a low level of oxygen inclusions [3]. By optimizing the fabrication processes and microstructures, high coercivities of about 1600 kA/m (20 kOe) have been obtained for HREE-free magnets made with the above two types of fine-grained magnets [3, 4]. Sm-Fe-N materials also have demonstrated excellent magnetic properties and corrosion resistance when used as bonded magnets [5]. It is important to expand the market for the Sm-Fe-N from the resource management point of view because Sm is one of the surplus rare-earth elements. Various studies to improve the magnetic properties are now being conducted by many research groups. In this symposium, recent developments for the above R-Fe-X permanent magnets will be presented.

References:
[1] M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto, and Y. Matsuura, J. Appl. Phys., 55 (1984) 2083.
[2] J. F. Herbst, J. J. Croat, F. E. Pinkerton and W. B. Yelon, Phys. Rev., 29 (1984) 4176.
[3] M. Sagawa, Proceedings of the 21st International Workshop on Rare-Earth Permanent Magnets and their Applications, (2010) 183.
[4] K. Hioki, A. Hattori, and, T. Iriyama, J. Magn. Soc. Jpn., 38 (2014) 79.
[5] T. Iriyama, K. Kobayashi, N. Imaoka, T. Fukuda, H. Kato, Y. Nakagawa, IEEE Trans. Magn. 28 (1992) 2326-2331.

SESSION: SISAMThuPM1-R3 B: Bio is beautiful	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Thu Oct, 24 2019 / Room: Dr. Christian Bernard
Session Chairs: Saso Sturm; Session Monitor: TBA

14:00: [SISAMThuPM105] Keynote
Engineering of Nanoparticle-based Magnetic Resonance Imaging Contrast Agents
Nina Kostevšek¹ ; Igor Serša² ; Calvin Cheung³ ; Wafa Al Jamal⁴ ; ¹Jozef Stefan Institute, ljubljana, Slovenia; ²Jozef Stefan Institute, Ljubljana, Slovenia; ³School of Pharmacy Queen’s University Belfast, Belfast, United Kingdom; ⁴School of Pharmacy, Queen's University Belfast, Belfast, United Kingdom, Belfast, United Kingdom;
Paper Id: 307 [Abstract]

The majority of the iron oxide-based clinically approved contrast agents for magnetic resonance imaging (MRI) have been withdrawn from the market either due to safety concerns or lack of profits.[1] Therefore, there is a need for novel imaging agents with high safety margins and superior MRI properties. Several factors influence the relaxation of water molecules in the vicinity of the magnetic centres, such as NP's magnetization and surface coatings.[2], [3] The latter can affect the relaxation of water molecules in various forms, such as diffusion, retention, hydration, and hydrogen bonding.[3], [4] In the first part, it will be demonstrated how size and clustering influence nanoparticles’ magnetic properties and consequently relaxivity r2 values. In the second part, the focus will be on coating optimization with a description of all the parameters that influence r2 values and thus the performance of NPs as T2 MRI contrast agents. [2], [3] Proper surface coating endows NPs with good colloidal stability and protects them from undesired degradation or aggregation. The effect of different coating material and thickness on the r2 values will be discussed. Moreover, a surface that favors diffusion and retention of water molecules within the second sphere is preferred. Taking all these parameters into account, the case study made on different phospholipids as optimal coating material will be presented. In conclusion, the in vitro MRI measurements revealed that use of magneto liposomes as contrast agents leads to an improvement in the contrast and an easier distinction between the healthy and the cancerous tissues. This proves that the developed liposomes have a high potential to be used as MRI contrast agents, even at very low concentration.

References:
[1] S. M. Dadfar et al., Adv. Drug Deliv. Rev.138 (2019) 302–325.\n[2] Y. Lin et al., J. Mater. Chem. B 5702 (2015) 5702–5710.\n[3] W. Zhang et al., Theranostics 8 (2018) 2521–2548.\n[4] J. Huang et al. Theranostics 2 (2012) 86–102.

14:25: [SISAMThuPM106]
Improving Soft-Magnetic And Biodegradable Metallic Materials By Means Of Severe Plastic Deformation
Michael J. Zehetbauer¹ ; Sheraz Khakwani¹ ; Monika Antoni² ; Alexander Rabensteiner² ; Roland Groessinger³ ; Andrea Ojdanic¹ ; Jelena Horky⁴ ; Erhard Schafler¹ ; Dmytro Orlov⁵ ; ¹University of Vienna, Wien, Austria; ²Technical University Vienna, Wien, Austria; ³Vienna University of Technology, Faculty of Physics, Wien, Austria; ⁴Austrian Institute of Technology, Seibersdorf, Austria; ⁵Division Mater.Engineering, Dep. Mech. Engineering, Lund University, Lund, Sweden;
Paper Id: 113 [Abstract]

The magnetic properties of soft magnetic materials such as Fe-3wt%Si and Fe-6.5wt%Si studied here can be strongly improved by nanocrystallization if the grain size is smaller than the magnetic moment exchange length [1]. Recent top-down techniques like those of Severe Plastic Deformation (SPD), in particular of High Pressure Torsion (HPT), allow for the production of bulk nanocrystalline soft magnetic materials, as they are capable to reach grain and/or subgrain sizes well below 100-10 nm [2], thus underrunning the exchange length of magnetic moments. This fact should lead to a significant decrease of coercive force (Hc) and finally of the hysteresis losses (P/f with f as the frequency), being an inherent goal of soft magnetic materials research. HPT-induced changes of Hc and P/f were found to be in parallel; they could be related to the changes of two most important parameters such as the subgrain size (D), and the dislocation density (N). In both cases, only decreases of D or N led to decreases of Hc. At least the first result confirms that Hc is indeed dominated by exchange coupling within the magnetic domains, their size exceeding that of the subgrains. Since HPT can only achieve decreases of D and concomitant increases of N, thermal treatments were applied after HPT-processing, in order to decrease N while keeping D unchanged. A maximum decrease of Hc could only be reached when a strong increase of D or N during HPT-processing or during thermal treatment could be avoided. Other conditions are that neither the HPT-induced strain is too large nor the processing temperature applied is too low; otherwise nanostructures become resistant to the thermal treatment. Theories from literature [3] which predict a change of the Hc ~ D6law for large-angle misoriented grains, to a law with distinctly lower exponent Hc ~ D3 or D2 in the case of small-angle misoriented subgrains, were confirmed by the experiments [4]. Another example of successful application of SPD to functional nanomaterials is the improvement in functional properties of biodegradable binary and ternary Mg-Zn-Ca alloys achieved by High-Pressure Torsion (HPT)-processing and subsequent heat treatment. These procedures have been applied in order to strengthen the alloy and to limit the corrosion rate [5]. Two paths of HPT-processing fulfilled these conditions; these were (i) low temperature-low strain HPT, or (ii) high temperature-high strain HPT of the solid solution state, both followed by subsequent thermal treatment at 373 K [6]. While treatment (i) yielded strength increases till 250% mainly due to generation of HPT-induced defects including those of vacancies, treatment (ii) produced precipitates with strength increases of only 60% but much higher ductility [6]. In conclusion, SPD-processing achieved different nanostructures with individual extents of strength, ductility and corrosion resistance, thus meeting the specific requirements of different biodegradable implants and prostheses.

References:
[1] G. Herzer, Mater.Sci.Eng. A 133 (1991) 1\n[2] Bulk Nanostructured Materials, eds. M. J.Zehetbauer and Y.T.Zhu, Wiley VCH, Weinheim (2009)\n[3] K. Suzuki, N. Ito, J.S. Garitaonandia, J.D. Cashion, G. Herzer, J.Non Cryst.Solid 354 (2008) 5089\n[4] S. Khakwani, PhD Thesis, Technical Univ. Vienna, Austria (2019)\n[5] A. Ojdanic, E. Schafler, D. Orlov, M. Zehetbauer, Magnesium Technology, eds. D. Orlov, V. Joshi, K. Solanki, N. Neelameggham, Springer, 267-282 (2018)\n[6] A. Ojdanic, PhD Thesis, University of Vienna, Austria (2019)

14:50: [SISAMThuPM107]
Towards The Sustainability of Implantable Medical Devices
Richard Kouitat Njiwa¹ ; Pierre Bravetti² ; M'barek Taghite³ ; Gael Pierson⁴ ; ¹Institut Jean Lamour (UMR 7198 CNRS-Université de Lorraine), Nancy, France; ²Institut Jean Lamour (UMR 7198 CNRS-Uninersite de lorraine), Nancy, France; ³, Laxou, France; ⁴Institut Jean Lamour, Nancy, France;
Paper Id: 137 [Abstract]

Whether for therapeutic or aesthetic purposes, implantable medical devices have to be biocompatible and functional. Their implementation requires surgery that can be considered as a cumbersome procedure as it depends on the patient. Additionally, the osseointegration of these implantable devices has to be sustinable. Considering the example of dental implants, there are two types of implants: endosseous axial implants and supraosseous basal with lateral fixation implants on maxillofacial skeleton girders. These axial implants are manufactured by machines with standard diameters and lengths defined for all implant brands. It is the same for basal plate implants. The sustainability of these devices, in contact with living media, seems to be related to the mechanical and surface characteristics of implanted parts. The development of periodontal diseases like peri-implantites, caused by a bacterial grip, leads to the removal of the implant due to the long term destruction of the oxide layer and the bacterial corrosion of titanium. In order to understand the sustainability of dental implants, an experimental study was conducted on the determination of elastic and surface properties (roughness parameters) of various materials and for different surface conditions. The results show that the knowledge of these characteristics alone is insufficient to understand the sustainability of implanted devices. A biological improvement of the surface condition is necessary to avoid the loss of osseointegration by bacterial attack.

References:
CharalampakasisG., Rabe P. Leonhardt A, Dahlen G, A follow-up study of prei-implantitis cases after treatment. J. Clin. Periodontol 38-9(2011) 864-871
Maloney WJ, Smith RL, Castro F, Schuman DJ, Fibroblat response to mettalic debris in vitro. Enzyme infuction cell proliferation and toxicity. J. Bone Joint Surg. Am 75-6(1993) 835-844

15:15: [SISAMThuPM108]
A Surface Mechanical Approach of the Sustainability of Implantable Medical Devices
Richard Kouitat Njiwa¹ ; ¹Institut Jean Lamour (UMR 7198 CNRS-Université de Lorraine), Nancy, France;
Paper Id: 186 [Abstract]

Many therapeutic fields use implantable medical devices. This usually involves replacing a whole organ or a defective part of an organ by a biocompatible substitute. Knee prostheses, hip prostheses, dental prostheses and breast prostheses are among the best-known implantable medical devices. These biomedical materials are intended to be in long-term contact with biological materials. Cells contained in these biological materials detect and react to their environment. This mechano-transduction process greatly influences the physiological processes involved in development, health and disease. The mechanical function of cells impacts, among other things, the processes of healing, differentiation of stem cells, and cancer metastases [1]-[4]. The impact of the contact forces developed between the implant and the biological tissue on changes in the behavior of the tissue has not yet received much attention from the scientific community. This is mainly because the mechanical constitutive equation of biological tissues is not available due to their complex microstructure. We believe that biological tissues can be considered as micromorphic media. It is actually the most achieved phenomenological top-down approach. The effectiveness of this modelling is investigated by considering the examples of an implant/bone system and a stent/artery system. The presented study is completely numerical and supported by clinical observations.

References:
[1] D. E. Discher, "Tissue Cells Feel and Respond to the Stiffness of Their Substrate", Science, vol. 310, no 5751, p. 1139-1143, nov. 2005.
[2] D. E. Jaalouk et J. Lammerding, "Mechanotransduction gone awry", Nature Reviews Molecular Cell Biology, vol. 10, no 1, p. 63-73, janv. 2009.
[3] A. Mammoto et al., "A mechanosensitive transcriptional mechanism that controls angiogenesis", Nature, vol. 457, no 7233, p. 1103-1108, févr. 2009.
[4] P. Friedl, Y. Hegerfeldt, et M. Tusch, "Collective cell migration in morphogenesis and cancer", The International Journal of Developmental Biology, vol. 48, no 5-6, p. 441-449, 2004.

SESSION: SISAMThuPM2-R3 C: Processing	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Thu Oct, 24 2019 / Room: Dr. Christian Bernard
Session Chairs: Carlo Burkhardt; Session Monitor: TBA

15:55: [SISAMThuPM209] Invited
Net Shape 3D Printed NdFeB Permanent Magnet
Jacim Jacimovic¹ ; ¹ABB Corporate research, Baden-Daetwill, Switzerland;
Paper Id: 115 [Abstract]

Nd₂Fe₁₄B hard magnets are a strategic material in determining the efficiency and size of both existing and future electrical and electronics devices. To meet the strict device requirements, these magnets are often doped with expensive heavy rare-earth elements like Dy, and Tb. In our research, we combined machine design and material development to produce the permanent magnets in the shape required to eliminate the dependency of those two chemical elements. At this conference we will present firstly that expensive Dy-rich, high coercivity magnet compositions may not be required throughout the full magnets within electrical machines, and the steps in experimental realization of such magnet geometry will be discussed. Second, we will show that the emerging technology named 3D metal printing by selective laser melting can be used produce hard magnets in various shapes. The magnetic properties of 3D printed magnet are superior to those prepared by other means, like injection molding and spark plasma sintering. It is demonstrated that the fast melting and solidification process provided by this fabrication method enables an internal microstructure not achievable by any other production means, resulting in an increase of magnetic performance. Finally, 3D printing brings to the magnet novel functionality. For example, a cooling channel extends its application range and, very importantly, reduces the magnetic dependence on Dy and Tb.

16:20: [SISAMThuPM210]
Powder Metallurgy: An old technique became a sustainable component of the additive metal manufacturing
Georges Kipouros¹ ; ¹Materials Engineering, Dalhousie University, Halifax, Canada;
Paper Id: 132 [Abstract]

Powder metallurgy has been established in the past sixty years as an old technique, deriving its roots from ancient civilizations, to produce ferrous, copper and zinc products. It was only twenty years ago that it was demonstrated in our laboratory for the first time that it is possible to produce aluminum powder metallurgy parts by using a small addition of magnesium in pure aluminum. It has now become an industry of its own, producing millions of parts used in automotive applications. In this presentation, attempts to extend the powder metallurgy to magnesium metal and its alloys will be discussed. In the last decade, the machine design and its artificial intelligence led to the utilization of 3D metal printing or additive manufacturing. The emphasis has been shifted to the computer aspects of the process although there are still fundamental difficulties on sintering metals.

References:
1. W.D. Judge and G.J. Kipouros, “Aluminum PM Alloys: Structure and Porosity”, in Encyclopedia of Aluminum and Its Alloys (EAIA), Ed. G.E. Totten, M. Tiryakioglu and O. Kessler, CRC Press, Taylor and Francis, pp. 1977-1995, (2018).
2. P. Burke, Y. G. Kipouros, W.D. Judge and G. J. Kipouros, Surprises and Pitfalls on the Development of Magnesium Powder Metallurgy Alloys, in Magnesium and Its Alloys: Technology and Applications, Ed. G.E. Totten, L. Dobrzanski, Taylor & Francis (in print) (2019).
3. P. Burke, G. J. Kipouros, D. Fancelli and V. Laverdiere, “Sintering Fundamentals of Magnesium Powders”, Can. Metall. Q., 48(2), 123-132 (2009).
4. P. Burke and G.J. Kipouros, “Powder Metallurgy of Magnesium: Is it Feasible?”, Magnesium Technology 2010, Ed. Sean R. Agnew, et. al., The Minerals, Metals & Materials Society, 115-120 (2010).

16:45: [SISAMThuPM211]
Review of melt-spun RE-Fe-B powders and their bonded and fully-dense magnets for automotive applications
Zhongmin Chen¹ ; ¹Neo Performance Materials (Singapore) Pte Ltd, Singapore, Singapore;
Paper Id: 156 [Abstract]

RE-Fe-B permanent magnets have been increasingly used for motor applications in automotive industry. Higher performance magnets are always in demand as they enable the motor to achieve high efficiency, high power density and smaller size. It is well known that rapid solidification technology has the advantage of producing nanoscale fine-grained RE-Fe-B material and therefore enabling higher magnetic performance. For past several years, melt-spun RE-Fe-B powders and their bonded magnets and fully-dense magnets have found more and more applications in the automotive industry. In this presentation, we will review Magnequench’s latest R&D efforts in RE-Fe-B product development for automotive applications. These include isotropic melt-spun MQP and MQU powders, and anisotropic MQA powders. MQ1 bonded magnets made from MQP or MQA powders, and fully-dense MQ2 and MQ3 magnets made from MQU powders will also be discussed. An emphasis will be put on their processing-microstructure-performance relationships, especially microstructure uniformity and its importance on magnetic performance.

17:10: [SISAMThuPM212]
Effective Eectrochemical and Physical Reprocessing of Nd-Fe-B and Sm-Co Permanent Magnets, Approaching the Zero Waste Economy
Kristina Zuzek Rozman¹ ; Xuan Xu¹ ; Awais Ikram¹ ; Farhan Mehmood¹ ; Richard Sheridan² ; Allan Walton² ; Muhammad Awais² ; Anas Eldosoukey³ ; Spomenka Kobe⁴ ; Saso Sturm⁵ ; ¹Jozef Stefan Institute, Ljubljana, Slovenia; ²University of Birmingham, Birmingham, United Kingdom; ³Magneti LJubljana, d.d., Ljubljana, Slovenia; ⁴Josef Stefan Institute, Ljubljana, Slovenia; ⁵Head of Department for Nanostructured Materials, Ljubljana, Slovenia;
Paper Id: 189 [Abstract]

Currently, less than 1% of the rare-earth elements (REEs) that reach the end of their useful lives are recycled. This is a very small percentage, especially if we consider that the recycling of end-of-life (EoL) (Dy, Nd)-Fe-B magnets is an important strategy for reducing the environmental dangers associated with rare-earth mining, and overcoming the well-documented supply risks associated with the REEs. We report on possibilities of direct electrochemical recycling and electrochemical reprocessing of Nd-Fe(B)-based magnets. Previous attempts to deposit alloys of rare earths from solutions at mild temperatures have met little success. Excitingly, in this investigation, we were able to electrodeposit Nd-Fe from the 1-ethyl-3-methylimidizolium dicyanamide ([EMIM][DCA]) ionic liquid. We observed that Nd(III) cannot be reduced independently, although it can be co-deposited inductively as substrate with the addition of Fe(II), proven by electron-energy-loss spectroscopy. Further, we propose a new concept of recycling the sintered (Dy, Nd)-Fe-B magnets by directly recovering the (Dy, Nd)₂Fe₁₄B matrix phase. Via an electrochemical etching method, we are able to recover pure individual(Dy, Nd)₂Fe₁₄B grains that can be re-used for new types of magnet production. In terms of energy consumption, the proposed electrochemical recycling route is comparable to the established direct re-use methods. These direct methods are considered as the most economical and ecological ways for recycling the sintered (Dy, Nd)-Fe-B magnets. In the frame of physical reprocessing, we have successfully synthesised new magnets out of hydrogen-recycled stocks with contemporary sintering technique of pulsed electric current sintering. The SmCo₅ magnets for recycling were first decrepitated by hydrogen gas to produce the powder. The sample sintered at 900°C showed the best internal coercivity (jHc) of higher than 1500 kA/m with high remanence (Br) value of 0.47 T. The optimal SPS conditions yielded fully dense Nd-Fe-B magnets with the coercivity Hc = 1060 kA/m, which was boosted to 1160 kA/m after the post-SPS thermal treatment. The Br and Hc were tackled further, and increased applied pressures of 100-150 MPa resulted in Br = 1.01 T. Via the addition of DyF₃, 17.5% higher coercivity than the optimally SPS-ed magnet was obtained due to Dy substituting the Nd in the matrix Nd₂Fe₁₄B phase. We showed that with a fine tune of the SPS and post annealing, together with variations in Br and Hc, it is possible to revitalize the recycled Nd-Fe-B and Sm-Co magnets.

SESSION: SISAMThuPM3-R3 C: Processing cont.	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Thu Oct, 24 2019 / Room: Dr. Christian Bernard
Session Chairs: Allan Walton; Session Monitor: TBA

17:50: [SISAMThuPM313]
Effect of grain size on the coercive field of hard and soft magnetic materials
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 208 [Abstract]

Several models for predicting the effect of grain size on the coercive field are presented and discussed. For small grain size, near the mono domain grain size, a law Hc ~ 1 / D0.5 has been observed [1]. Here, Hc is the coercive field and D is the grain size. For sintered NdFeB and Strontium ferrites, the Hc ~ 1 / D0.5 law has been experimentally confirmed. For very large grain size, however, a case of soft magnetic materials as electric steels, a Hc ~ 1 / D is observed [2]. The origin of these different behaviors is discussed [3]. We also discuss how to evaluate the effect of grain size on the coercive field by means of a nucleation model.

References:
[1] M. F de Campos. Effect of Grain Size on the Coercivity of Sintered NdFeB Magnets. Materials Science Forum, v. 660, p. 284-289, 2010.\n[2] M. F. de Campos. A General Coercivity Model for Soft Magnetic Materials. Materials Science Forum, v. 727-728, p. 157-162, 2012.\n[3] M. F. de Campos. Coercivity Mechanism in Hard and Soft Sintered Magnetic Materials. Materials Science Forum , v. 802, p. 563-568, 2014.

18:15: [SISAMThuPM314]
A Success Story for more than 30 years: From Basic Research to the Industrial Innovation of Magnet Materials at Jožef Stefan Institute, Slovenia
Benjamin Podmiljsak¹ ; Kristina Zuzek Rozman¹ ; Saso Sturm² ; Spomenka Kobe³ ; ¹Jozef Stefan Institute, Ljubljana, Slovenia; ²Head of Department for Nanostructured Materials, Ljubljana, Slovenia; ³Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 356 [Abstract]

At the Jožef Stefan Institute, a leading Slovenian research organisation in the field of natural sciences and technology, has conducted a systematic and consistent research of permanent magnets, tracing way back to the 1980s. In the last twenty years, this initiative has concentrated within the Department for Nanostructured Materials, within a research group specialised on magnetism, magnetic materials, and magnetic characterisation. The fact that a world-wide recognised research group on magnetic materials is present in a relatively small country of Slovenia is in many ways associated with an exceptionally high concentration of companies focused on the production and implementation of various types of permanent magnets. The research collaboration has always been motivated by the ongoing strategy of industry-driven basic research close to industrial innovation. It is therefore not surprising that during the rare earth crises approximately ten years ago, where Europe’s magnet industrial sector was nearly collapsing, all of the related Slovenian companies not only survived, but also strengthened their positon in the European region and worldwide. In this presentation, we will uncover historical backgrounds and current research strategies which led to the ongoing miracle of the magnet industry in Slovenia which will be shown through the prism of various success stories from basic-research driven industrial innovation, to the high impact implementation of the circular economy and problem-solving approaches during the production of different magnet types. These research strategies include, but are not restricted to, development of high-end corrosion protection for magnetic powder, failure analysis during the magnet production and the development of novel magnetic materials for state-of-the-art magnetic traction sensors for the robotic industry.

SESSION: SISAMFriAM-R3 D: Sustainable resources	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Fri Oct, 25 2019 / Room: Dr. Christian Bernard
Session Chairs: George Hadjipanayis; Session Monitor: TBA

11:20: [SISAMFriAM01] Keynote
Enabling a circular economy ecosystem for NdFeB magnets: Which measures are needed and what is really feasible?
Carlo Burkhardt¹ ; Spomenka Kobe² ; Benjamin Podmiljsak³ ; ¹Pforzheim University, Pforzheim, Germany; ²Josef Stefan Institute, Ljubljana, Slovenia; ³Jozef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 124 [Abstract]

Magnets are one of the most crucial materials necessary for modern Europe, as they are integral to energy conversion across the renewable energy and electric mobility sectors [1]. Unfortunately, even though the alloying constituents of NdFeB magnets have been classified as EU Critical Raw Materials and 90% are produced outside of the EU, there is still no circular economy to reuse and capture value for these types of materials [2]. With the prediction that the need for RE magnets will double in the next 10 years [3,4], this problem becomes even more urgent. At present, the only way to recover end of life (EOL) magnets from waste streams of electric and electronic equipment is by shredding and recycling by chemicals and pyrometallurgical routes, which is expensive and energy intensive [5]. Another problem is that the quality of the recollected materials varies significantly, especially with respect to alloying constituents and state of corrosion and employed corrosion protection, with no classification system for recyclate grades of EOL NdFeB magnets. To enable a circular economy ecosystem for NdFeB magnets, a whole range of measures is necessary: a) the development of an eco-labelling system for newly produced RE permanent magnets to clearly identify different magnets types and qualities in order to categorise the EOL NdFeB magnets by technical pre-processing requirements, b) using the highly effective HPMS process (Hydrogen Processing of Magnetic Scrap) for re-processing extracted materials directly from NdFeB alloy, c) better treatments to eliminate pre-processing residue which contaminates the HPMS process, d) upgrading the magnetic properties of EOL NdFeB magnets by tailoring the microstructure, phase ratio and phase composition, and e) developing industrial up-scalability, including thorough life cycle assessments. The feasibility of the above proposed measures will be discussed and illustrated with actual results generated in the EU-funded projects Maxycle and SUSMAGPRO. These projects will have a great impact by overcoming existing low recycling rates due to poor collection, high leakages of collected materials into non-suitable channels, and inappropriate interface management between logistics, mechanical pre-processing, and metallurgical metals recovery.

References:
[1] European Commission. Critical Raw Materials. http://ec.europa.eu/growth/sectors/raw-materials/specific-interest/critical_en (retrieved May 29, 2019).
[2] Sprecher, B., Xiao, Y.,Walton, A., Speight, J.D., Harris, I.R., Kleijn, R., Visser, G., Kramer, G.J.; Life Cycle Inventory of the Production of Rare Earths and the Subsequent Production of Nd-Fe-B Rare Earth Permanent Magnets. Environmental Science and Technology (2014) 3951-3958.
[3] Constantinides, S.; Market Outlook for Ferrite, Rare Earth and other Permanent Magnets. International Forum on Magnetic Applications, Technologies & Materials. 21-22 January 2016, Jacksonville, USA
[4]International Energy Agency. Energy, Climate Change & Environment: 2016 Insights
[5] DOI: 10.1021/es404596q

11:45: [SISAMFriAM02]
Transmission Electron Microscopy for efficient recycling of Nd-Fe-B permanent magnets
Saso Sturm¹ ; Awais Ikram² ; Xuan Xu² ; Spomenka Kobe³ ; Kristina Zuzek Rozman² ; Farhan Mehmood² ; ¹Head of Department for Nanostructured Materials, Ljubljana, Slovenia; ²Jozef Stefan Institute, Ljubljana, Slovenia; ³Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 281 [Abstract]

The transition towards future green and e-mobility technologies, based on permanent magnets, is unavoidably linked to a stable supply of (heavy) rare earth elements. In the recent past, the transition towards green and e-mobility technologies has been hindered due to various geo-political and economic reasons. One promising way to address this problem is to develop strategies for various efficient magnet recycling and reprocessing routes that turn magnet waste into new functional magnets with little or negligible loss of overall magnetic performance [1]. The current recycling techniques, however, such as hydrogenation disproportionation desorption recombination (HDDR) processing, remelting, spark plasma sintering (SPS) and electrochemical deposition, inevitably perturb the desired microstructure. Detecting and understanding the underlying chemical and physical mechanisms is thus the key to optimize the overall magnetic performance of the recycled/reprocessed magnets. These mechanisms are typically associated with the structural/chemical properties of different crystal phases and defects, including dislocations, grains, and interphase boundaries. In recent years, state-of-the-art Transmission Electron Microscopy, which typically includes Scanning Transmission Electron Microscopy (STEM) with different spectroscopy techniques, such as Energy Dispersive X-ray Spectroscopy (EDXS) and Electron Energy-Loss Spectroscopy (EELS), has become an indispensable tool for characterization of rare earth-based permanent magnets. Transmission Electron Microscopy has become indispensable since it provides correlative structural and chemical information along with atomic-scale spatial resolution. In this presentation the above-described analytical techniques will be demonstrated against the most challenging research problems that were encountered during the development of two conceptually different recycling routes. In one approach, end-of-life Nd-Fe-B permanent magnets were first transformed in powder form by a HDDR process. The HDDR process was further used to fabricate initial dense reprocessed bulk magnet by spark plasma sintering (SPS) at different temperatures (ranging from 650⁰C to 850⁰C).Finally, a conventional heat treatment route at 750⁰C for 15 minutes was used on the bulk magnet that was fabricated. By applying advanced TEM, i.e. atomic-scale Z-contrast STEM, combined with EDXS and EELS, the resulting magnetic properties were critically assessed against various types of structural and compositional discontinuities down to the atomic-scale. We believe these discontinuities control the microstructure evolution during the SPS processing route. An alternative reprocessing route for Nd-Fe-based magnets that we have developed is based on electro-co-deposition of Nd and Fe from an ionic-liquid (1-ethyl-3-methylimidizolium dicyanamide) electrolyte. In order to reveal the deposition mechanism, the chemistry and phase composition of the deposit were investigated by means of analytical TEM. This showed that Nd(III) is reduced to Nd(0) during the electrodeposition process. Furthermore, we were able to confirm that the deposition of the Nd–Fe starts with the sole deposition of Fe, followed by the co-deposition of Nd–Fe. These new insights into the electrodeposition process represent an important step closer to efficient recycling of rare earths in metallic form at a mild temperature. This is a sustainable and economically viable route based on the green-chemistry approach, thus providing a genuine alternative to high-temperature molten-salt electrolysis.

References:
[1] This work was supported by the European Union's EU Framework Programme for Research and Innovation Horizon 2020 under Grant Agreement No 674973 (DEMETER).

12:10: [SISAMFriAM03] Keynote
Sustainable and efficient use of rare earth magnets
Allan Walton¹ ; ¹University of Birmingham, Birmingham, United Kingdom;
Paper Id: 410 [Abstract]

In recent years there has been significant price volatility for rare earth magnets based upon neodymium iron boron (NdFeB), which has stemmed from possible supply constraints from the main supplier (China). The Magnetic Materials Group (MMG) has been developing recycling strategies for these materials to mitigate at least some of the supply risk as well as investigating efficient methods of manufacture for fully dense NdFeB magnets. In this presentation Prof Walton will outline the problems encountered when recycling rare earth magnets from end of life products, including identification of magnet type, ease of extraction, problems for purification and complications for re-processing into new materials. He will then propose solutions to these problems including new sensor technologies for identifying magnets in waste, robotic disassembly of magnet containing products and hydrogen based technologies for extraction and reprocessing of sintered magnets. In the second part of the presentation Prof Walton will outline a new method for producing fully dense NdFeB magnets called the Hydrogen Ductilisation Process (HyDP ref- 1,2,3). During HyDP solid cast NdFeB alloys can be converted into a ductile material at room temperature. This is achieved by converting the cast alloy into a disproportionated structure containing -Fe, NdH2 and Fe2B by processing in hydrogen at between 1-2 bar pressure and > 600^oC. The disproportionated material can be pressed at room temperature and on recombination this produces a small grained anisotropic NdFeB magnetic material. The HyDP process could be used to reduce the yield loss for producing thin magnets compared to conventional sintering processes, it may be possible to process in air which would reduce cost and it could be used to make complex geometries.

References:
1) GB Patent Application -
GB1511553.8. 2015

2) O.Brooks, A.Walton, W. Zhou and I.R.Harris, The Hydrogen Ductilisation Process (HyDP) for shaping NdFeB magnets, Journal of Alloys and Compounds 703 (2017) 538-547

3) O. Brooks, A. Walton, W. Zhou, D. Brown, I.R. Harris, Complete ductility
in NdFeB-type alloys using the Hydrogen Ductilisation Process (HyDP), Acta Materialia (2018), doi:10.1016/j.actamat.2018.04.055.

12:35: [SISAMFriAM04]
Current Trends In Recycling, Usage and Market of Rare-Earths
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 198 [Abstract]

Here is presented an overview on the usage and application of rare-earths, and also of the rare-earth market. This overview will focus on recent trends.
The low price of rare-earths have discouraged some mining projects, such as that of Brazilian company CBMM which decided to keep focusing on niobium production. Serra Verde, a Brazilian mining company, however, promised to start production in the next decade of heavy rare-earths as dysprosium.
The Mountain Pass Californian mine returned to produce rare-earths, and now has an annual production of similar size as the Australian mine Lynas. Both Lynas and Mountain Pass focus on light rare-earths. Mountain Pass sends the rare-earth concentrate for further processing in China. Myanmar also had significant production of rare-earths last year, with an amount near that of Lynas and Mountain Pass. The Neodymium oxide prices have decreased 10% since the beginning of 2019.

Both Neodymium and Praseodymium are seen as essential for electric cars. Each electric car uses ~1 -1.5 kg of NdPr-Fe-B type magnets [1]. Giant wind turbines, constructed without gearbox, which avoids maintenance problems, need tons of NdPr-Fe-B magnets.
The Europium price is low at the present time, and has been below the Holmium price. Both Gadolinium and Holmium have been used as alloying elements in rare-earth magnets.
Terbium is in high demand, which is attributed to the application of Tb in Terbium-diffused magnets. Dysprosium also is seen as necessary to increase the temperature of operation of the magnets.
Cerium and Lanthanum are in large oversupply. Application of Cerium as red pigment (Ce₂S₃) has been proposed. Use of cerium base red pigments would avoid use of cadmium or molybdenum-chromium.
Recycling of fluorescent lightbulbs for recovering Europium and Terbium is possible, but the low price of Europium is a problem for economic feasibility. Now, LED lightbulbs, which use much less are-earths than fluorescent lightbulbs, are dominating the market.
Recycling of Magnets is possible, since there is standardization of commercial magnets. An enormous amount of energy is spent in the magnet production. If only the rare-earth oxide, such as neodymium oxide, is recovered, the energy used in the process is lost. The re-use of magnets is the best option for rare-earth magnet recycling.

References:
[1] MF de Campos. Magnetic Materials for Motors of Electric Cars. In: Proceedings of the 25th International Workshop on Rare Earth Permanent Magnets and Advanced Magnetic Materials and Their Applications REPM 2018, Beijing, China, August 26-30, 2018. p. A0414-01-A0414-11.

SESSION: SISAMFriPM1-R3 E: Complexity in materials	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Fri Oct, 25 2019 / Room: Dr. Christian Bernard
Session Chairs: Mariana Calin; Session Monitor: TBA

14:00: [SISAMFriPM105]
Designing Metallic Glasses and Heterophase Materials for Engineering Applications
Juergen Eckert¹ ; ¹Erich Schmid Institute of Materials Science, Leoben, Austria;
Paper Id: 70 [Abstract]

The structure of glasses is generally taken to be isoconfigurational, although it is well-known that the details of structure arrangement strongly depend on the temperature-time history experienced while establishing the glassy state. Recent studies of glass-forming metallic systems have revealed intriguing complexity, e.g. unusual shifts in radial distribution functions with temperature change or upon mechanical loading in the elastic or plastic regime. Nearest neighbour distances and medium-range order structural arrangements appear to change, e.g. shorten upon heating or become larger with decreasing temperature. Concomitantly, temperature changes as well as static or dynamic mechanical loading within the nominally elastic regime can trigger significant changes in glass properties, which are directly correlated with local non-reversible configurational changes due to non-affine elastic or anelastic displacements. All these findings strongly suggest that the characteristics of the atomic structure decisively determine the properties of the glass and of nanostructured materials derived from glass-forming systems. Recent findings and developments along this line will be summarized. Results from high-energy synchrotron x-ray radiation investigations at different temperatures and after mechanical loading will be related to the atomic structure of the material. It will also be related to its dependence on temperature, mechanical load as well as intrinsic heterogeneities and length-scale modulation to elucidate the correlation between atomic arrangement and mechanical or magnetic properties.

References:
1. Ashby, M.F., Greer, A.L.: Metallic glasses as structural materials. Scripta Materialia 54, 321 (2006).
2. Cubuk, E.D., et al: Structure-property relationships from universal signatures of plasticity in disordered solids. Science 358, 1033 (2017).
3. Scudino, S., Shakur Shahabi, H., Stoica, M., Kaban, I., Escher, B., Kühn, U., Vaughan, G.B.M., Eckert, J.: Structural features of plastic deformation in bulk metallic glasses. Applied Physics Letters 106, 031903 (2015).
4. Sarac, B., Zhang, L., Kosiba, K., Pauly, S., Stoica, M., Eckert, J.: Towards the better: Intrinsic property amelioration in bulk metallic glasses. Scientific Reports 6, 27271 (2016).
5. Bian, X.L., Wang, G., Yi, J., Jia, Y.D., Bednarcik, J., Zhai, Q.J., Kaban, I., Sarac, B., Mühlbacher, M., Spieckermann, F., Keckes, J., Eckert, J.: Atomic origin for rejuvenation of a Zr-based metallic glass at cryogenic temperature. Journal of Alloys and Compounds 718, 254 (2017).
6. Sarac, B., Ivanov, Y.P., Chuvilin, A., Schöberl, T., Stoica, M., Zhang, Z., Eckert, J.: Origin of large plasticity and multiscale effects in iron-based metallic glasses, Nature Communications 9, 1333 (2018).

14:25: [SISAMFriPM106]
Nanocrystal-amorphous dispersions in Al-based and high-entropy alloys
A. Lindsay Greer¹ ; Akihisa Inoue² ; ¹University of Cambridge, Cambridge, United Kingdom; ²Tianjin University, Tianjin, China;
Paper Id: 250 [Abstract]

We review recent advances in the development of two types of rapidly quenched alloys that show promise as structural materials. In each case, the focus of interest is the dispersions of nanocrystals in the residual amorphous matrix that can be achieved by treating initially fully amorphous melt-spun ribbons.
The first alloy type is Al-based with compositions such as Al₉₀Y₁₀ (at.%) and Al₈₄Y_8.5Ni₄Co₂Pd₁Fe_0.5 [1,2]. Remarkably, when amorphous ribbons are cold-rolled, this induces partial crystallization to nanoscale fcc-Al (alpha-Al). By contrasting this crystallization with the apparently similar crystallization induced by annealing, progress has been made in understanding the mechanisms of hardening and softening. Polymorphic crystallization induced by cold-rolling avoids the formation of compound phases associated with brittleness, and is therefore promising for the development of high-solute Al-based alloys as structural materials.
The second alloy type is metal-metalloid, with a complex (high-entropy) mixture of metals and relatively low metalloid content. An example is the alloy series (Fe_0.25Co_0.25Ni_0.25Cr_0.125Mo_0.125)_86-89B_11-14 [3]. Initially amorphous alloys when annealed show complex crystallization sequences. Nanoscale (5-15 nm) particles of fcc and bcc phases are formed and show very high thermal stability (resistance to coarsening). It is of particular interest that ultrahigh hardness of 1500-1550 Hv can be achieved without the formation of any boride phases. The hardening and thermal stability are unusually high for such low boron content and encouraging for the development of ultrahard coatings.
Prospects for further alloy development are considered.

References:
1. F.F. Han, A. Inoue, Y. Han, F.L. Kong, S.L. Zhu, E. Shalaan, F. Al-Marzouki, A.L. Greer, Novel heating-induced reversion during crystallization of Al-based glassy alloys, Sci. Reports 7 (2017) 46113.\n2. H.W. Bi, A. Inoue, F.F. Han, Y. Han, F.L. Kong, S.L. Zhu, E. Shalaan, F. Al-Marzouki, A.L. Greer, Novel deformation-induced polymorphic crystallization and softening of Al-based amorphous alloys, Acta Mater. 147 (2018) 90-99.\n3. F. Wang, A. Inoue, F.L. Kong, S.L. Zhu, E. Shalaan, F. Al-Marzouki, W.J. Botta, C.S. Kiminami, Yu.P. Ivanov, A.L. Greer, Formation, stability and ultrahigh strength of novel nanostructured alloys by partial crystallization of high-entropy (Fe_0.25Co_0.25Ni_0.25Cr_0.125Mo_0.125)_86-89B_11-14 amorphous phase, Acta Mater. 170 (2019) 50-61.

14:50: [SISAMFriPM107] Invited
Amorphous and metastable gold-based alloys as precursors for nanoporous gold synthesis for Surface Enhanced Raman Spectroscopy applications.
Paola Rizzi¹ ; Federico Scaglione² ; Deepti Raj² ; Livio Battezzati² ; ¹Università di Torino, Dipartimento di Chimica, Torino, Italy; ²Università di Torino, Torino, Italy;
Paper Id: 29 [Abstract]

Nanoporous gold (NPG) can be produced by dealloying [1], a process in which the less noble elements in an alloy are chemically or electrochemically dissolved into an electrolyte, leaving on the surface the noble element to form ligaments and pores with size of tens or hundreds of nanometers. The dealloying process can be performed from a crystalline or an amorphous precursor [2, 3] with a consequent change in the dealloying mechanism. This way, when amorphous precursors are used, ligaments result to be highly rough with nanometric holes that enable excellent optical and electrochemical properties. Nanoporous gold is produced in a large variety of morphologies and it can be modified by electrodeposition of Au nanoparticles on the ligament surface in order to enhance electrochemical or SERS (Surface Enhanced Raman Spectroscopy) activity. In this work, the production of nanoporous gold via dealloying of Au-based amorphous precursors is outlined and compared with nanoporous gold produced from Fe-Au system, an innovative precursor that can allow a sensitive reduction in NPG production costs. For this purpose, Au-based amorphous alloys and Fe-Au crystalline alloys were chemically dealloyied in a solution of 2, 5, 10 and 14.4 M HNO₃ plus 0.5 M HF for different times. The surface morphology of de-alloyed samples was observed by scanning electron microscopy. SERS measurements were performed on NPG samples synthesised following different routes in order to determine the morphology leading to the higher SERS activity. Bipyridine and melamine were used as probe molecules achieving detection limit down to 10-14 M. The enhancement of SERS effect on nanoporous gold is attributed to the localized enhanced electromagnetic fields around nanopores and to the electromagnetic coupling between ligaments. Ligaments constituted by several nanocrystals with random orientation and separated by grain boundaries leads to further enhancement of the SERS effect.

References:
[1] J. Erlebacher, M.J. Aziz, a. Karma, N. Dimitrov, K. Sieradzki, Evolution of nanoporosity in dealloying, Nature 410 (2001) 450-453\n[2] F. Scaglione, P. Rizzi, F. Celegato, L. Battezzati, Synthesis of nanoporous gold by free corrosion of an amorphous precursor, J. Alloys Compd. 615 (2014) S142-S147\n[3] E.M. Paschalidou, F. Celegato, F. Scaglione, P. Rizzi, L. Battezzati, A. Gebert, S. Oswald, U. Wolff, L. Mihaylov, T. Spassov, The mechanism of generating nanoporous Au by de-alloying amorphous alloys, Acta Mater. 119 (2016) 177-183

15:15: [SISAMFriPM108]
Continuous 3D graphene-like networks formation from cellulose nanofibers in ceramic matrices
Andraz Kocjan¹ ; Ana Lazar² ; Eduardo Ruiz Hitzky³ ; Bernd Wicklein⁴ ; ¹Jozef Stefan Institute, Ljubljana, Slovenia; ²Jožef Stefan Institute, Ljubljana, Slovenia; ³Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas (CSIC), Madrid, Spain; ⁴Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Cientificas (CSIC), Madrid, Spain;
Paper Id: 18 [Abstract]

Establishing a 3D electrically percolating network in an insulating ceramic matrix is key to numerous engineering and functional applications. Using hydrophobic carbon nanofillers like graphene or carbon nanotubes is tempting, but still results in suboptimal performance due to processing challenges including colloidal instabilities in aqueous media. Here, we demonstrate an alternative, sustainable way by a small addition of cellulose nanofibers (CNF), which render highly homogeneous aqueous ceramic dispersions due to the increased hydrophilicity character and facilitates green machining of the consolidated green bodies. During sintering the natural CNF`s [1] can be in situ transformed into graphene-like sheets connected to a 3D network enhancing both the transport and the mechanical properties of sintered Al2O3 and yttria-stabilised ZrO2 (YSZ) ceramic matrices [2] [3]. The advantage presented here is the colloidal processing in water of CNF hydrogels with ceramic powder suspensions, which guarantees uniform and homogeneous properties from the bulk scale down to the nanoscale. The network architecture of the few-layered graphene (FLG) sheets also permits the decoupling of electrical and thermal conductivities, which represents a major obstacle in attaining efficient thermoelectric materials. The microstructure of the resulting materials was characterised by electron microscopy and spectroscopy (STEM/EELS), while the electrical and dielectrical properties were analysed by impedance spectroscopy. The materials showed high electrical conductivity at only 2 % initial CNF content, while the FLG-YSZ nanocomposites exhibited mixed ionic-electronic conduction at a��1% CNF, which is interesting for electrode materials in solid-oxide fuel cells. Besides the transport properties, the incorporated CNF improve the (green) mechanical properties and also enable the use of technologically important machining methods for electro-conductive ceramics. We envisage that our results can advance the processing science and technology to provide the improved hierarchical graphene composite materials needed for advanced applications in fields like energy and telecommunications.

References:
[1] B. Wicklein, A. Kocjan, G. Salazar-Alvarez, F, Carosio, G. Camino, M. Antonietti and L. BergstrA�m, Thermally insulating and fire-retardant lightweight anisotropic foams based on nanocellulose and graphene oxide, Nature. Nanotech. 10 (2015) 277a��84.
[2] A. Kocjan, R. Schimdt, A. Lazar, J. Prado-Gonjal, J. KovaA�, M. Logar, F. j. Mompean, M. Garcia-Hernandez, E. Ruiz-Hitzky, B. Wicklein, In situ generation of 3D graphene-like networks from cellulose nanofibres in sintered ceramics, Nanoscale. 10 (2018) 10488a��97.
[3] A. Kocjan, B. Wicklein, E. Ruiz-Hitzky, Patent PCT/EP2017/078239.

SESSION: SISAMFriPM2-R3 F: Metastability & sustainability	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Fri Oct, 25 2019 / Room: Dr. Christian Bernard
Session Chairs: Michael J. Zehetbauer; Session Monitor: TBA

15:55: [SISAMFriPM209] Plenary
The Role of Science and Materials in Saving Our Planet and Ourselves (Part 1)
Richard Wheeler¹ ; ¹Jozef Stefan Institute (Slovenia), (and) European Sustainable Energy Innovation Alliance (Austria), (and) Balkan Institute for Labour and Social Policy (Bulgaria), Edinburgh, United Kingdom;
Paper Id: 74 [Abstract]

<b>We live in a time of unprecedented global change, and face a very near future of climate chaos, mass migration, and sociopolitical upheaval. </b>We now have only about eight years to radically improve the ecological conditions on the planet to avoid mass extinctions, and at most twenty years to master the emerging field of geotechnical or planetary, engineering. If civilization is going to exist for our grandchildren, we must become very good at planetary-scale engineering, and quickly. How do we move whole cities? How do we radically regenerate ocean and atmospheric health? What should future civilizations look like, and does humanity have the strength, courage, and ingenuity to rise to these challenges, or have we doomed life on the planet to extinction? What role might physics and the material sciences play, and what special responsibilities does the research community have? What decisions should the EU and its nations make now to ensure their future survival? <i>Are we as scientists acting rationally, and what should we do next?</i>

References:
(none)

16:20: [SISAMFriPM210]
The Role of Science and Materials in Saving Our Planet and Ourselves (Part 2)
Richard Wheeler¹ ; ¹Jozef Stefan Institute (Slovenia), (and) European Sustainable Energy Innovation Alliance (Austria), (and) Balkan Institute for Labour and Social Policy (Bulgaria), Edinburgh, United Kingdom;
Paper Id: 472 [Abstract]

We live in a time of unprecedented global change, and face a very near future of climate chaos, mass migration, and sociopolitical upheaval. We now have only about eight years to radically improve the ecological conditions on the planet to avoid mass extinctions, and at most twenty years to master the emerging field of geotechnical or planetary, engineering. If civilization is going to exist for our grandchildren, we must become very good at planetary-scale engineering, and quickly. How do we move whole cities? How do we radically regenerate ocean and atmospheric health? What should future civilizations look like, and does humanity have the strength, courage, and ingenuity to rise to these challenges, or have we doomed life on the planet to extinction? What role might physics and the material sciences play, and what special responsibilities does the research community have? What decisions should the EU and its nations make now to ensure their future survival? Are we as scientists acting rationally, and what should we do next?

16:45: [SISAMFriPM211] Invited
Towards High Coercivities in Heavy Rare Earth Free Nd-Fe-B Ribbons
Marko Soderžnik¹ ; Matic Korent² ; Urska Ročnik³ ; Boris Saje⁴ ; Spomenka Kobe⁵ ; ¹Jožef Stefan Institute, Ljubljana, Slovenia; ²Jozzef Stefan Institute, LJUBLJANA, Slovenia; ³Department for Nanostructured Materials, Jožef Stefan Institute, Ljubljana, Slovenia; ⁴Kolektor Magnet Technology GmbH, Essen, Germany; ⁵Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 367 [Abstract]

Reasonable magnetic performance to weight ratio makes polymer-bonded magnets indispensable in automotive applications [i]. The magnetic powders, used for bonded magnets are mainly produced by the gas atomization and melt-spinning [ii]. Several magnetic powders can be used for such purposes, namely ferrites, SmCo, Sm-Fe-N, Nd-Fe-B and/or combinations of all of them. Since the magnetic powder is blended with non-magnetic binder, the remanent magnetization is diluting as the volume percent of the binder is increasing. Therefore, they can be classified as medium-performance isotropic bonded magnets. The coercivity of the magnet, however, is not related to the magnetic powder/non-magnetic binder ratio but to the chemistry and microstructural features. Melt-spun ribbons of Nd-Fe-B material are composed of randomly oriented Nd₂Fe₁₄B grains within the size of single magnetic domain [iii]. Therefore, they have a huge potential for higher coercivity compared to sintered Nd-Fe-B magnets in which a typical grain size is measured in microns [iv]. There exist several ways to improve the coercivity of Nd-Fe-B magnets. One way is to decouple the Nd2Fe14B grains by infiltration of low eutectic Nd-based alloys which we propose within this study. Detailed microstructural analyses showed that non-ferromagnetic Nd₇₀Cu₃₀ was successfully infiltrated between the grains, which prevented the physical contact between the grains leading to weaker intergrain exchange coupling. The results of such a process show more than 20 % improvement in coercivity while the remanence is increased as expected due to the lower amount of the ferro-magnetic phase. Significant increase in coercivity compensates lower remanence, and the energy product is also increased. In comparison to the basic powder, the coercivity at 150 °C is significantly improved, which enables these magnets to be used at a higher temperature.

References:
[i] J. J. Croat, 8-Major applications for rapidly solidified NdFeB permanent magnets, Woodhead Publishing Series in Electronic and Optical Materials (2018) 325–361.\n[ii] G. Sarriegui, J. M. Martín, M. Ipatov, A. P. Zhukov, J. Gonzalez, Magnetic Properties of NdFeB Alloys Obtained by Gas Atomization Technique, IEEE Trans. Magn. 54 (2018) 2103105.\n[iii] J. D. Livingston, Magnetic domains in sintered Fe-Nd-B magnets, J. Appl. Phys. 57 (1985) 4137–4139.\n[iv] M. Soderžnik, M. Korent, K. Žagar Soderžnik, M. Katter, K. Üstüner, S. Kobe, Acta Mat. 115 (2016) 178–284.

17:10: [SISAMFriPM212] Invited
Between metastability and equilibrium in Fe-Ga functional alloys
Igor S. Golovin¹ ; Valeria V. Palacheva¹ ; Abdelkariem Mohamed¹ ; Anatoly M. Balagurov² ; Ivan A. Bobrikov² ; ¹National University of Science and Technology 'MISiS', Moscow, Russian Federation; ²Joint Institute of Nuclear Research, Dubna, Russian Federation;
Paper Id: 150 [Abstract]

The equilibrium phase diagram does not reflect the real structure of Fe-Ga alloys neither in the as cast state nor after annealing followed by air-cooling or furnace-cooling. Functional properties of the Fe-Ga alloys are extremely sensitive to particular details of the phase transition from the metastable (as-cast, as-quenched) state with A2 or D0₃ structures with positive magnetostriction to the equilibrium state with L1₂ structure and negative magnetostriction. They are also sensitive to short range ordering of the A2 metastable phase including the formation of local martensite-like structures. In the present study, we have investigated the time-dependence and temperature-dependence of the transition of as-cast metastable Fe-(9-33at.%)Ga ‘Galfenol’ alloys to the equilibrium state along with corresponding changes in their functional properties and anelastic effects that accompany these transitions. To characterize such a time-temperature-transition diagram we used both long-time isochronal annealing (up to 300 hrs) and instant heating treatments with different temperature protocols. In-situ neutron diffraction at instant heating-cooling and isochronal annealing, XRD, DSC, VSM, SEM-EBSD, Mössbauer and mechanical spectroscopy techniques were used to study first and second order phase transitions, structure, and functional properties of Galfenols.

References:
[1] I.S. Golovin, А.M. Balagurov, V.V. Palacheva, I.A. Bobrikov, V.B Zlokazov.
Materials and Design, 98 (2016) 113-119
[2] V.V. Palacheva, A. Emdadi, F. Emeis, I.A. Bobrikov, A.M. Balagurov, S.V. Divinski, G. Wilde, I.S. Golovin. Acta Materialia 130 (2017) 229-239
[3] M.V. Matyunina, M.A. Zagrebin, V.V. Sokolovskiy, O.O. Pavlukhina, V.D. Buchelnikov, A.M. Balagurov, I.S. Golovin. Phase Transitions. 92 (2019) n.2, 101-116

SESSION: SISAMFriPM3-R3 I: Crystals	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Fri Oct, 25 2019 / Room: Dr. Christian Bernard
Session Chairs: Kristina Zuzek-Rozman; Session Monitor: TBA

17:50: [SISAMFriPM313] Invited
Lanthanum Silicate for High-Dielectric Gate Insulator
Hiroshi Iwai¹ ; ¹Tokyo Institute of Technology, Yokohama, Japan;
Paper Id: 80 [Abstract]

Progress of microprocessors or logic integrated circuits has been conducted by the continuous miniaturization of Si MOSFETs. In the course of the miniaturization, the gate length and the gate oxide thickness have been reduced with the same ratio. Silicon dioxide (SiO₂) has been used as the gate insulator for many years. In order to decrease the equivalent gate oxide thickness (EOT) to less than 1 nm, high-dielectric material is necessary [1] and hafnium dioxide (HfO₂) [2] was chosen to replace SiO₂. For further decreasing of the EOT to sub-0.5 nm, lanthanum oxide (La₂O₃) is supposed to be one of the best candidates among many materials when considering the band-offset and dielectric constant values [3]. Then, La silicate is expected to be even better because La silicate has some good properties similar to SiO₂. In this paper, excellent MOSFET characteristics with 0.4 nm EOT gate oxide are demonstrated by introducing La silicate as the gate dielectrics. After the n⁺ source and drain formation on the p-Si substrate, the La₂O₃gate oxide film was deposited by an ultra-high vacuum evaporation method, followed by tungsten (W) and tantalum nitride (TaN) gate electrode film deposition by in situ RF sputtering under ultra-high vacuum conditions. After the gate electrode patterning, 3% forming gas annealing was performed for 30 minutes. After the annealing, a thin La silicate gate insulator was created with a smooth interface. The diffusion of oxygen into the gate oxide and the resulting increase of the EOT were almost completely suppressed by the combination of the stacked TaN and W gate electrode and the ambient forming gas during the annealing. The minimum EOT value obtained by C-V measurement was 0.4 nm. Very low values for the interface state density for the La silicate MOS capacitor of less than 10¹¹cm^-2eV^-1 were observed during the forming gas annealing performed above 850^oC. The fixed charge density evaluated by the flat-band voltage was 1.0 X 10¹¹cm^-2. La silicate films are composed of good glass network structures as those of SiO₂ and have high viscosity at high temperatures. The movement of the atoms at a high temperature recovers the defects at the interfaces and in the films. This is the reason for the low interface state and fixed charge densities. Good I_d - V_d characteristics of a 0.4 nm EOT MOSFET were confirmed because of the excellent interfacial property. Due to the high band offset value between the conduction-bands of the Si channel and the La silicate gate insulator, the tunneling leakage current was almost completely suppressed down to EOT = 0.4 nm.

References:
[1] C. Fiegna, H. Iwai, T. Wada, T. Saito, E. Sangiorgi, B. Ricco, Dig. Tech. Symp. on VLSI Tech. (1993) 33-34.\n[2] K. Mistry et al., IEDM Tech. Dig. (2007), 247 - 250.\n[3] T. Hattori, T. Yoshida, T. Shiraishi, K. Takahashi, H. Nohira, S. Joumori, K. Nakajima, M. Suzuki, K. Kimura, I. Kashiwagi, C. Ohshima, S. Ohmi, H. Iwai, Microelectronic Engineering 72 (2004) 283 - 287.

18:15: [SISAMFriPM314] Keynote
Recent Results and New Functionalities in Ferroelectric Based Structures
Lucian Pintilie¹ ; Ioana Pintilie¹ ; ¹National Institute of Materials Physics, Magurele, Romania;
Paper Id: 241 [Abstract]

Ferroelectrics are materials with a wide range of applications, an important one being non-volatile memories [1]. Efforts were made to obtain epitaxial films by pulsed laser deposition (PLD). There are still debates, however, regarding the intrinsic properties of ferroelectrics. Here we report new results regarding intrinsic properties of single crystal PbZr_0.2Ti_0.8O ₃ (PZT) layers manufactured on single crystal SrTiO₃ substrates with bottom and top SrRuO₃ electrodes, as well new functionalities in PZT-based multi-layers of the PZT-interlayer-PZT type. The main findings are:<br />- The dielectric constant in ultra-thin epitaxial PZT layers, of 20-25, is very low. This was evidenced by a new method of recording the voltage dependence of capacitance named "static" C-V characteristics and was explained in relation with the structural quality of the epitaxial films, showing that films with structural defects have a larger dielectric constant.<br />- The relation between hysteresis loops and the C-V characteristic is discussed. It is shown that a negative capacitance effect can be obtained during polarization switching at around P=0. This is a transitory effect and is explained by a sudden increase of the electrical conductivity when the charges involved in the compensation of the depolarization field change places from one electrode interface to the other.<br />- New functionalities were found in tri-layer structures such as the PZT-interlayer-PZT, with a semiconducting or insulating interlayer. These layers can consist of multiple polarization states that can be used in memory cells with multiple states or of multiple capacitance states that can be used as non-destructive readout methods for FeRAMs. It was also found that tri-layer structures can be used for logic operations but can also function as memcapacitors.

References:
[1] J. F. Scott, Annu. Rev. Mater. Sci. 28 (1998) 79-100

SESSION: SISAMSatAM-R3 G: Nanoscale(s)	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Sat Oct, 26 2019 / Room: Dr. Christian Bernard
Session Chairs: Ludwig Schultz; Session Monitor: TBA

11:20: [SISAMSatAM01]
Comprehensive Modeling of Cu-Ni Nanoparticle Phase-Diagrams Based on Modified Cohesion and Coordination-Dependent Bond Energies
Micha Polak¹ ; Leonid Rubinovich¹ ; ¹Ben-Gurion University of the Negev, Beer-Sheva, Israel;
Paper Id: 104 [Abstract]

Cu-Ni alloys have gained interest as bulk and nanoparticles (NPs) primarily due to their catalytic and magnetic properties. Different modeling methods employed before for computations of chemical-order were limited to Cu-Ni NPs consisting of few hundred atoms. The present study uses the highly efficient statistical-mechanical free-energy concentration expansion method (FCEM [1]), combined with coordination-dependent bond-energy variations (CBEV [2]), and the coarse-grained layer (CGLM [3]) models for the case of CuNi truncated-octahedrons (TO). This quite efficient semi-analytical methodology enables the exploration of chemical-order configurations and transitions between them in much larger particle sizes and over broad ranges of composition and temperature. Furthermore, in spite of free-atom electronic-relaxation contributions to transition-metal cohesive-energies, numerous studies have misused the latter instead of using genuine bond-energies in modeling NP properties [4].Using the corresponding modified cohesive-energies, and depending strongly on size and composition, the following findings regarding chemical-order configurations are obtained: due to the CBEV, asymmetric Janus-like configuration (JA) is expected to be the most stable for all compositions only for the 201, 586 and 1029-atom TO sizes. At elevated temperatures, they transform into quasi-mixed configurations (QM). For larger TOs, core-shell (CS) configurations start to stabilize in narrow ranges of elevated temperatures and intermediate compositions, and become progressively stable at increasingly wider ranges. Three types of transitions are revealed: JA-CS, CS-QM, and JA-QM, yielding the first comprehensive Cu-Ni nanophase-separation diagrams. The use of unmodified cohesive energies leads to significantly altered transition temperatures, demonstrating the importance of the commonly ignored modification. Preliminary results for Cu-Ni-Pd TOs reveal a considerable impact of Pd alloying on the chemical-order diagrams, particularly the suppression of JA in favor of CS configurations.

References:
[1] M. Polak and L. Rubinovich, Surf. Sci. Reports 38 (2000) 127-194.
[2] L. Rubinovich and M. Polak, Phys. Rev. B 80 (2009) 045404.
[3] M. Polak and L. Rubinovich, Phys. Chem. Chem. Phys., 17 (2015) 28211-28218.
[4] M. Polak, L. Rubinovich, J. Phys.: Condens. Matter, 31 (2019) 215402.

11:45: [SISAMSatAM02]
Surface Structure and Properties of Complex Intermetallics
Vincent Fournée¹ ; ¹Institut Jean Lamour, CNRS-Université de Lorraine, NANCY, France;
Paper Id: 318 [Abstract]

Quasiperiodic structures exhibit long-range order like normal crystals, but lack translational symmetry. Quasicrystals were first discovered as a new class of intermetallic compounds, now comprising hundreds of members in binary and ternary systems. They usually adopt either the icosahedral or the decagonal point group symmetry. Later, quasicrystals were also found in soft matter systems and more recently, in a two-dimensional perovskite oxide thin film grown on a periodic substrate. The discovery of quasicrystals has led to a paradigm shift in crystallography and has attracted a large interest in the material science community, motivated by unexpected physical properties that could be linked to quasiperiodicity. This remarkable class of materials has also challenged our understanding of metal surfaces. An atomic scale description of their surfaces is especially important, as it forms the basis for understanding and predicting phenomena such as gas adsorption, metal epitaxy, and friction. Here we will review some key results on the characteristics of their surface structure and their physo-chemical properties [1-4].

References:
[1] J. Ledieu, V. Fournée, Comptes Rendus de l’Académie des Sciences, Physique, 15 (2014) 48-57.
[2] J. Ledieu, É. Gaudry, V. Fournée. Sci. Technol. Adv. Mater. 15 (2014) 034802.
[3] V. Fournée. “Surface properties and engineering of complex intermetallics”. Book series on Complex Metallic Alloys – Vol. III., E. Belin-Ferré Eds., World Scientific, Singapore, 2010, ISBN: 13-<span class="fon_main_wrapper"><span phone-source="978-981-4304" class="fon-phone-wrap fon-hightlighted active-call" id="fon-phone-64CEjepxaT">978-981-4304</span><a phone-source="978-981-4304" href="#" class="fonCallLinkButton active-call"><img src="data:image/png;base64,iVBORw0KGgoAAAANSUhEUgAAABAAAAAQCAMAAAAoLQ9TAAADAFBMVEUAAACfn58+u2cGBgb+/f3H69LHx8fPzc2hoaHI7NMer0wns1SioqLDwMAfsE3u7e0JCQlWVlZ9fX3o9u3T8t3v7u6kpKTx8fHU894LCwvNzc1YWFilpaXW09MMDAzz8/PY1dXNzc3Nzc2K1qKC05yC05319fXL7db////29vYZrUh70Zc2NjaDg4PPzc1dXV3z8fHMysqrq6v08vLY1dUSEhL5+fmc3LGU2arEwcE7uWTU1NTU0dH7+/v3/vmIiIhiYmLDw8PT09P9/f0crkuKior+/v7p+u6Li4v28vQVrEb///8esEwNqT8/Pz/U0dGNjY1nZ2fOy8u2trbQ7tmQkJCA0ppERESRkZHJ7NXb2dnv7e4QqkFtbW3t7Ozq6Ojw7u7y8fHLyspISEiVlZX08/OD053X09OYmJjl5eXE6tCZmZkrtFdzc3PAwMAAAAAbrkr08fLZ2Nibm5v7+vqdnZ2e3bLRz88AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAlXTQeAAABAHRSTlMA////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////////Cpf0PAAAAAlwSFlzAAAXEgAAFxIBZ5/SUgAAAAd0SU1FB94KAQ0qFGuFIz0AAAAHdEVYdEF1dGhvcgCprsxIAAAADHRFWHREZXNjcmlwdGlvbgATCSEjAAAACnRFWHRDb3B5cmlnaHQArA/MOgAAAA50RVh0Q3JlYXRpb24gdGltZQA19w8JAAAACXRFWHRTb2Z0d2FyZQBdcP86AAAAC3RFWHREaXNjbGFpbWVyALfAtI8AAAAIdEVYdFdhcm5pbmcAwBvmhwAAAAd0RVh0U291cmNlAPX/g+sAAAAIdEVYdENvbW1lbnQA9syWvwAAAAZ0RVh0VGl0bGUAqO7SJwAAAF9JREFUGJVjCBfKRYbhDEIsLFkSLHCQCxJgKkMICEEFxJ2cnDKRBYJNBcOF7JAFdNG0BMc6RaFpSQ7PZcGrRQhdIBdNgJ0RTQDVpdqoAuIswuJAlh0I2YkLMYTHooBcALNHHdnKWUyEAAAAAElFTkSuQmCC" alt="F"/></a></span>-76-4. pp. 183-229.
[4] V. Fournée, J. Ledieu, J.Y. Park. “Surface Science of Complex Metallic Alloys”. in “Complex Metallic Alloys: Fundamentals and Applications”, J.M. Dubois, E. Belin-Ferré Eds., Wiley, Berlin, 2011, ISBN: 978-3-527-32523-8. pp 155-207.

12:10: [SISAMSatAM03]
Machine learning for permanent magnet optimization
Thomas Schrefl¹ ; ¹Danube University Krems, Wiener Neustadt, Austria;
Paper Id: 33 [Abstract]

In addition to the intrinsic magnetic properties, the microstructure is of utmost importance for the performance of a permanent magnet. We show how to use machine learning methods in order obtain a deeper understanding of the influence of the granular structure on the coercive field of permanent magnets. Using machine learning, we can identify the weak spots in a magnet where magnetization reversal is initiated. Tailored improvement of the magnet's structure or the intrinsic magnetic properties at regions where the switching field was identified to be low can sufficiently improve the magnet. Work supported by the European Union's Horizon 2020 NMBP23-2015 research No 686056.

References:
Fischbacher, J., Kovacs, A., Gusenbauer, M., Oezelt, H., Exl, L., Bance, S., & Schrefl, T. (2018). Micromagnetics of rare-earth efficient permanent magnets. Journal of Physics D: Applied Physics, 51(19), 193002.
Exl, L., Fischbacher, J., Kovacs, A., Oezelt, H., Gusenbauer, M., Yokota, K., ... & Schrefl, T. (2018). Magnetic microstructure machine learning analysis. Journal of Physics: Materials, 2(1), 014001.

12:35: [SISAMSatAM04] Invited
Magnetic shape memory turns to nano: the crucial role of microstructure engineering
Franca Albertini¹ ; Milad Takhsha Ghahfarokhi¹ ; Francesca Casoli¹ ; Simone Fabbrici¹ ; Lucia Nasi¹ ; Marco Campanini² ; Cesar Magen³ ; Gabriele Barrera⁴ ; Federica Celegato⁵ ; Paola Tiberto⁵ ; ¹IMEM-CNR, Parma, Italy; ²EMPA, Dubendorf, Switzerland; ³Instituto de Nanociencia de AragOn, Zaragoza, Spain; ⁴INRIM,, Torino, Italy; ⁵INRIM, Torino, Italy;
Paper Id: 264 [Abstract]

Magnetic shape memory Heuslers are an important class of ferroic materials for next-generation remote actuation and energy conversion (i.e. solid-state cooling and energy harvesting), arising from giant multifunctional effects (e.g. thermo/magneto-mechanical, magneto/elasto-caloric) that can be driven by external stimuli (i.e magnetic field, temperature, pressure and stress) [1]. Low-dimensional materials, mainly thin films, have recently attracted much interest for their great potential in applications (e.g. microactuators, solid-state microrefrigerators, microvalves) [2]. With respect to the bulk, they offer the further possibility of tuning properties by exploiting the epitaxial growth on suitable substrates and underlayers. Patterned films and 2D nanostructures are nowadays a vast and almost unexplored field. This talk is focused on microstructure engineering of continuous and patterned NiMnGa thin films, and free standing nanodisks. By a thorough multiscale magnetic and structural study ,we will show that martensitic microstructure is sensitive to size confinement and can also be easily tuned by tuning growth parameters and performing suitable post-growth treatments (magnetic field, T, stress) [3, 4]. Microstructure engineering can be exploited for the optimization of the multifunctional properties. As an example, we demonstrate the possible actuation of free standing nanodisks by the combined application of temperature and magnetic fields, giving rise to areal strain (up to 5.5%) whose intensity and sign is ruled by a martensitic microstructure [5]. On the other hand, such "microstructure flexibility" makes magnetic shape memory materials a unique system, among magnetic materials, for the "magnetic flexibility"; magnetism can be easily manipulated at the different length-scales by taking advantage of martensitic microstructure and strong spin-lattice coupling.

References:
[1] M. Acet, et al., Handbook of Magnetic Materials vol. 19, Elsevier, Amsterdam, 2011.
[2] A. Backen et al., Adv. Eng. Mat. 14,(2012) 696.
[3] P. Ranzieri et al., Acta Mater. 61 (2013) 263.
[4] P. Ranzieri et al., Adv. Mater. 32, (2015) 4760.
[5] M. Campanini et al. Small 14 (2018) 1803027.

SESSION: SISAMSatPM1-R3 H: Characterisation	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Sat Oct, 26 2019 / Room: Dr. Christian Bernard
Session Chairs: A. Lindsay Greer; Session Monitor: TBA

14:00: [SISAMSatPM105]
Correlative Characterization from Atoms to Magnetic Fields in Tb-Doped Nd-Fe-B Magnets
Kristina Zagar Soderznik¹ ; Saso Sturm² ; Andras Kovacs³ ; Aleksei Savenko⁴ ; Marko Soderžnik⁵ ; Rafal Dunin Borkowski⁶ ; Joachim Mayer⁷ ; Spomenka Kobe⁸ ; ¹Jozef Stefan Institute, Ljubljana, Slovenia; ²Head of Department for Nanostructured Materials, Ljubljana, Slovenia; ³Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Juelich, Germany; ⁴Thermo Fisher Scientific, Erlangen, Germany; ⁵Jožef Stefan Institute, Ljubljana, Slovenia; ⁶Forschungszentrum Jülich, Jülich, Germany; ⁷Ernst Ruska-Centre for Microscopy and Spectroscopy with Electrons, Jülich, Germany; ⁸Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 347 [Abstract]

High coercivity Nd-Fe-B permanent magnets play an important role in the rapidly-growing renewable energy sector. To retain the coercivity at high operating temperatures, heavy-rare-earth elements (HRE), such as Dy and Tb, are added using the grain-boundary diffusion (GBD) process. The addition of HRE results in a significant improvement of the coercivity due to the increase of the intrinsic resistance to demagnetization. [1] In the present study, we report on the correlation between magnetic properties and the distribution of Tb₄O₇ in the Nd₂Fe₁₄B magnet. The Nd₂Fe₁₄B magnet was coated with Tb₄O₇ powder and annealed. During the annealing process, Tb diffused along grain boundaries (GB) into the outer parts of Nd-Fe-B grains, thus forming core-shell grains with the Tb-rich shell and Nd-Fe-B core. Magnetometry measurements were performed to observe the Tb concentration gradient from the surface of the magnet into its central part. It was found that the coercivity gradually decreases towards the central part where it is still around 30% higher when compared with the untreated magnet. [2,3] Although magnetic measurements clearly indicate the presence of Tb, it is not clear what the actual amount of Tb is in central regions of magnets or how they are distributed in the microstructure and if it is possible to distinguish the magnetisation flux between soft magnetic shells and hard magnetic cores. For that purpose, we applied the Cs-corrected STEM: FEI Titan 80-200 equipped with SuperX electron dispersive X-ray (EDX) spectrometer and electron energy-loss (EEL) spectrometer and FEI Titan 80-300 equipped with electron biprism to perform electron holography. As a complementary method, atom probe tomography (APT) was used using 3D atom probe LEAP 4000x HR. In order to analyse the core-shell region, a lamella was prepared from the representative core-shell grains and the interface between the shell and the core was examined using EELS and APT. Detailed line-scans and spectrum image maps were performed at this interface. The estimated width of the transition area between the shell and the core was 20 nm. Further studies focused on the electron holography of core-shell grains. The magnetic fluxes were within the core and the shell was determined. The thickness and the composition of the shell were determined as a function of the specimen position within the magnet.

References:
[1] P. J. McGuiness, et al., JOM 67 (2015) 1306-1317.
[2] M. Soderžnik, et al., Intermetallics 23 (2012) 158-162.
[3] M.Soderznik, et al., Acta Materialia 115 (2016) 278-284

14:25: [SISAMSatPM106] Invited
Consolidation and Characterization of Ferrite-Based Hybrid Magnets: Towards Rare-Earth-Free Magnets for Energy Storage
Petra Jenus¹ ; Andraz Kocjan² ; Claudio Sangregorio³ ; Michele Petrecca⁴ ; César De Julian Fernandez⁵ ; Blaž Belec⁵ ; Spomenka Kobe⁶ ; ¹Jožef Stefan Institute, Ljubljana, Slovenia; ²Jozef Stefan Institute, Ljubljana, Slovenia; ³ICCOM-CNR, Sesto Fiorentino, Italy; ⁴Dept. of Chemistry, University of Florence and ICCOM - CNR and INSTM, Sesto Fiorentino, Italy; ⁵IMEM-CNR, Parma, Italy; ⁶Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 97 [Abstract]

In the last years, much effort has again been devoted to the research of ferrite-based permanent magnets due to the so-called rare-earth crisis.[1],[2] In particular, a quest to enhance ferrites' BHmax, is still underway.[3] Large BHmax values are found in magnets combining substantial magnetisation at remanence (Mr) with high coercivity. Both parameters are influenced by materials properties, such as crystalline and shape anisotropy and particle' size.<br />Here, the influence of composition, particle size, sintering conditions, and exposure to the external magnetic field before compaction on microstructure and consequently, magnetic properties of strontium ferrite (SFO)-based hybrid composites will be presented. <br />Powders' mixtures consisted of commercial SFO powder consisting of micron-sized, isotropic particles, or hydrothermally (HT) synthesised SFO with hexagonally-shaped platelets with a diameter of 1 micron and thickness up to 90 nm, and a soft magnetic phase in various ratios. Powders were sintered with spark plasma sintering (SPS) furnace. Starting powders and hybrid magnets were examined by means of phase composition (XRD) and microstructure (TEM, SEM). Their magnetic properties were evaluated with vibrating sample magnetometer (VSM), permeameter and by single-point-detection (SPD) measurements. <br />Depending on the concentration and composition of the soft phase, the MR of the composite can be altered. Application of the external magnetic field before the consolidation induces the anisotropy in commercial, and HT synthesised SFO, leading to the increase in the Mr of hybrid magnets [4]. Moreover, sintering with SPS promotes the alignment of HT synthesised SFO particles in the direction of the applied pressure, which is also the direction of SFOs' easy axis. Thus the enhancement in MR is perceived leading to the Mr/Ms higher than 0.8. Besides, after SPS, almost no grain growth was observed, which is beneficial for exploiting advantages of nanosized-induced phenomena also in bulk sintered samples. <br />This work received financial support from the European Commission through the project AMPHIBIAN (H2020-NMBP-2016-720853).

References:
[1] J. M. D. Coey, Permanent magnets: Plugging the gap, Scr. Mater., vol. 67, no. 6, pp. 524-529, 2012.\n[2] M. Stingaciu, M. Topole, P. McGuiness, and M. Christensen, Magnetic properties of ball-milled SrFe12O19 particles consolidated by Spark-Plasma Sintering, Sci. Rep., vol. 5, p. 14112, 2015.\n[3] R. Skomski and J. M. D. Coey, Magnetic anisotropy: How much is enough for a permanent magnet? Scr. Mater., vol. 112, pp. 3-8, 2016.\n[4] P. Jenuš et al., Ferrite-Based Exchange-Coupled Hard-Soft Magnets Fabricated by Spark Plasma Sintering, J. Am. Ceram. Soc., vol. 8, no. 37805, p. n/a-n/a, 2016

14:50: [SISAMSatPM107]
Surface patterning by thermoplastic forming of Ni-free Ti-based bulk metallic glasses
Mariana Calin¹ ; Supriya Bera¹ ; Baran Sarac² ; Juergen Eckert² ; ¹IFW Dresden, Dresden, Germany; ²Erich Schmid Institute of Materials Science, Leoben, Austria;
Paper Id: 285 [Abstract]

Bulk metallic glasses (BMGs) exhibit a unique temperature-dependent mechanical behavior, which enables the processing of polymers at temperatures higher than the critical BMG-specific glass transition temperature [1]. In this work, we report on the thermoplastic behavior of two Ni-free Ti-based bulk metallic glasses by utilizing the dramatic softening of the amorphous structure in the supercooled liquid region. Ti₄₀Zr₁₀Cu₃₄Pd₁₄M₂ (M = Ga, Sn) bulk glassy alloys were produced by copper mold casting. Ga and Sn micro-alloying (2 at.%) improve the glass-forming ability and mechanical properties of Ti₄₀Zr₁₀Cu₃₆Pd₁₄ alloy effectively [2, 3]. The cast rods were thermo-mechanically characterized to determine the most suitable processing temperature, time, and the load that has to be applied for thermoplastic net-shaping of the BMGs into anisotropically etched cavities of silicon chips. Periodic features with high surface smoothness and uniform height were created on the surface of the BMGs. The surface patterning with controllable roughness of Ti-based BMGs can be useful in biomedical studies by mediating material - cell interactions. Financial support through the EC (FP7 VitriMetTech-ITN) and ERC-Advanced Grant "INTELHIB" is gratefully acknowledged.

References:
[1] J. Schroers, Acta Mater. 56 (3) (2008) 471-478.
[2] M. Calin, A. Gebert, A.C. Ghinea, P.F. Gostin, S. Abdi, C. Mickel, J. Eckert, Mat. Sci. Eng. C, 33 (2) (2013) 875-883.
[3] B. Sarac, S. Bera, S. Balakin, M. Stoica, M. Calin, J. Eckert, Mater. Sci. Eng. C, 73 (2017) 398-405.

15:15: [SISAMSatPM108]
Bulk metallic glasses studied by fast calorimetry combined with time resolved X-ray diffraction
Florian Spieckermann¹ ; Innozeznz Steffny² ; Xilei Bian² ; Sergey Ketov² ; Mihai Stoica³ ; Martin Rosenthal⁴ ; Juergen Eckert⁵ ; ¹University of Leoben, Leoben, Austria; ²Erich Schmid Institute, Austrian Academy of Sciences, Leoben, Austria; ³ETH Zuerich, Zuerich, Switzerland; ⁴ESRF, Grenoble, France; ⁵Erich Schmid Institute of Materials Science, Leoben, Austria;
Paper Id: 103 [Abstract]

Novel processing technologies for metals such as 3D printing require the application of high heating and cooling rates and ideally the use of isotropic materials. The glass-forming alloys are good candidates for such applications. We directly determine the thermodynamic fragility index of two metallic glasses (Mg₆₅Cu₂₅Gd₁₀ and Au₄₉Cu_26.9Si_16.3Ag_5.5Pd_2.3) from fictive temperature shifts induced by a variation of the quenching rate using fast differential scanning calorimetry (FDSC). Recent chip calorimeters are able to achieve the cooling rates necessary to perform such an evaluation. For the Mg₆₅Cu₂₅Gd₁₀ and Au₄₉Cu_26.9Si_16.3Ag_5.5Pd_2.3 metallic glasses studied, we find very good agreement of the kinetic fragility index with literature data obtained by conventional calorimetry and rheology. We also applied ultra-fast chip calorimetry in combination with time-resolved micro-diffraction directly recorded with fast pixel array detectors. This way we can investigate the structural modifications of bulk metallic glasses (BMGs), in-situ, on ultra-fast temperature changes. Combining the very high time resolution of structural and calorimetric data acquisition, we investigated the mechanisms and the kinetics of the metastable phase transformations of this group of materials at ultra-high rates of temperature change. The understanding of the kinetic transition paths of- to date still unknown- metastable material states is the foundation for the development of tailored thermomechanical treatment routes towards novel applications of BMGs.

References:
Spieckermann, F.; Steffny, I.; Bian, X.; Ketov, S.; Stoica, M. & Eckert, J.\nFast and direct determination of fragility in metallic glasses using chip calorimetry \nHeliyon, 5 , e01334

SESSION: SISAMSatPM2-R3 H: Characterization cont.	Kobe International Symposium on Science of Innovative and Sustainable Alloys and Magnets (5th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Sat Oct, 26 2019 / Room: Dr. Christian Bernard
Session Chairs: Petra Jenus; Session Monitor: TBA

15:55: [SISAMSatPM209]
Amorphous Al-Ce-Cu-Fe alloys: Glass formation and properties
Luka Kelhar¹ ; Spomenka Kobe² ; Jean-marie Dubois³ ; ¹JSI - K7 Dpt, Ljubljana, Slovenia; ²Josef Stefan Institute, Ljubljana, Slovenia; ³JSI - K7 Dpt for Nanostructured Materials, Ljubljana, Slovenia;
Paper Id: 275 [Abstract]

The Al-Cu-Fe system is well known, for it contains a quasicrystal, the ultimate degree of lattice complexity in an ordered solid. Susbtitution of Ce for Al atoms cancels the formation of the quasicrystals, but favours amorphisation upon rapid solidification from the liquid state. We have accordingly studied the solubility range of Ce in this alloy when replacing Al atoms. We have varied the Cu/Fe ratio at constant Al,Ce concentration as well. We found evidence that the local order in the glass is predominantly icosahedral, which matches the evidence of a very low glass transition temperature in the vicinity of the eutectic concentration known in the binary Al-Ce system. This interesting result can be exploited to prepare bulk specimens by spark plasma sintering, a technique that we used to produce centime-wide specimens. The magnetic properties were studied in a wide composition range and will be reported in the talk.

16:20: [SISAMSatPM210] Keynote
From efficiency to effectiveness: Where technology innovation meets sustainability
Peter Fantke¹ ; ¹Technical University of Denmark (DTU), Kgs. Lyngby, Denmark;
Paper Id: 79 [Abstract]

Ever-growing population and consumption has put continuously increasing pressure on our planet's health including humans, ecosystems, and natural resources [1]. At the same time, efficiency in production and techno-economic performance are the drivers of today's economy. These unsustainable global trends push our industrial civilization toward crossing our planet's boundaries for a resilient climate, functional geochemical cycles, and healthy environments [2]. To ensure that future technologies move away from contributing to an unsustainable future, we need a radical paradigm shift. New designs and developments need to be fundamentally aligned with sustainability constraints. Considering such constraints comes with several key requirements. We need to determine the physical limits of ecosystems, human health, and environmental assets for resources extraction, environmental pollution and global exposure. We also need to understand the complexity of environmental pressure of the thousands of new chemicals, materials and products entering the global market every year along their entire life cycle. Finally, we need to benchmark all new designs against the physical limits of our planet. Physics, material science, and sustainability assessment are all crucial elements to meet these requirements. This will ultimately lead to sustainability-driven innovation in technology design and development of absolutely sustainable products and supply chains [3].

References:
[1] Steffen W, Broadgate W, Deutsch L, Gaffney O, Ludwig C. Anthrop. Rev. 2 (2015) 81-98.
[2] Steffen W, Richardson K, Rockström J, Cornell SE, Fetzer I, Bennett EM, et al. Science 347 (2015) 736-46.
[3] Fantke P, Illner N. Curr. Opin. Green Sustain. Chem. 15 (2019) 91-7.

16:45: [SISAMSatPM211]
Metal-Bonded Magnets Based on YCo5-Type Nanocrystals
Marko Soderžnik¹ ; Matic Korent² ; Kristina Zagar Soderznik³ ; Jean-marie Dubois⁴ ; Pelin Tozman⁵ ; M. Venkatesan⁶ ; Michael Coey⁷ ; Spomenka Kobe⁸ ; ¹Jožef Stefan Institute, Ljubljana, Slovenia; ²Jozzef Stefan Institute, LJUBLJANA, Slovenia; ³Jozef Stefan Institute, Ljubljana, Slovenia; ⁴JSI - K7 Dpt for Nanostructured Materials, Ljubljana, Slovenia; ⁵NIMS, Tsukuba, Japan; ⁶School of Physics and CRANN, Trinity College, Dublin, Ireland; ⁷School of Physics, Dublin, Ireland; ⁸Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 342 [Abstract]

Metal-bonded magnets based on YCo₅-type nanocrystals [i] were produced by hot-compaction using a spark plasma-sintering device. Zn and Zn/Al metallic binders with a melting temperature of ̴ 420°C were employed to fabricate dense cylindrical magnets. Two different pressures were used for compaction. The pressure of 400 MPa provided a metal-bonded magnet with Vickers hardness (HV10) of 460 ± 20 Vickers. The temperature coefficients for remanence (α) and coercivity (β) were derived from magnetization vs. magnetic field measurements in the temperature range of 20°C – 150°C. Temperature coefficients α and β for the Zn/Al-bonded magnet pressed with 400 MPa were -0.055 %/°C and -0.201 %/°C, respectively. The field emission gun scanning electron microscope revealed a ‘core-shell’-type microstructure. The pure YCo_4.8Fe_0.2 phase was detected in the core region whereas the shell was enriched with non-ferromagnetic Zn or Zn/Al phases. The high-resolution transmission electron microscope revealed the presence of clusters with ̴ 20 nm YCo_4.8Fe_0.2 grains. In the Zn/Al-bonded magnet, fabricated at 400 MPa, the coercivity <i>µ₀H_ci</i>, remanent magnetization σ and energy product (BH)_max were 0.87 T, 39.3 Am²/kg and 23.4 kJ/m³, respectively.[ii]

References:
[i] P. Tozman, M. Venkatesan, J. M. D. Coey, Optimization of the magnetic properties of nanostructured Y-Co-Fe alloys for permanent magnets, AIP Adv. 6 (2016) 056016.\n[ii] M. Soderžnik, M. Korent, K. Žagar Soderžnik, J.-M. Dubois, P. Tozman, M. Venkatesan, J. M. D. Coey, S. Kobe, Hot-compaction of YCo4.8Fe0.2 nanocrystals for metal-bonded magnets, J. Mag. and Magn. Mat. 460 (2018) 401-408.

SESSION: MagnesiumThuAM-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Adonis
Session Chairs: TBA Session Monitor: TBA

11:20: [MagnesiumThuAM01] Keynote
Development of Next-Generation Nonflammable High-Strength Magnesium Alloys
Yoshihito Kawamura¹ ; ¹Magnesium Research Center (MRC) Kumamoto University, Kumamoto, Kumamoto, Japan;
Paper Id: 421 [Abstract]

Mg alloys are attractive for use in aircraft components primarily because of their low density and high specific strength. But current commercial Mg alloys, e.g., AZ31, have low yield strength and unacceptably low ignition temperature. Moreover, several years ago America’s FAA (Federal Aviation Administration) has lifted the ban on the use of some Mg alloy forms in the payload area and has set up a standardized testing method of flammability for Mg alloys [1].
We have developed two kinds of high-strength Mg alloys with a high ignition temperature: 1) Mg-Zn-Y alloys consisted of alpha Mg phase and a long period stacking ordered (LPSO) phase [2,3,4], and Mg-Al-Ca alloys consisted of alpha Mg phase and a C36-type intermetallic compound [5].
The LPSO-type Mg₉₆.₇₅Zn₁Y₂Al₀.₂₅ alloy, which was produced by hot extrusion of cast ingot, exhibited very high, symmetrical yield strength in both tension and compression, high heat resistance, and great flame resistance. Its corrosion resistance is the same as AZ31. The LPSO phase, which has a periodical stacking structure of the 4 atomic layers consisting of in-plane ordering of L1₂ Zn₆Y₈ clusters and the 1-4 atomic layer(s) of 2H Mg, is strengthened by kinking, which was formed during the hot extrusion. This kink strengthening is a brand-new concept for strengthening mechanism of materials. On the other hand, the C36-type Mg₈₄.₉₇Al₁₀Ca₅Mn₀.₀₃ alloy, which was also produced by hot extrusion of cast ingot, exhibited high, symmetrical yield strength, high corrosion resistance, and nonflammability; the ignition temperature is higher than the boiling temperature of pure magnesium. These advanced Mg alloys have passed the FAA flammability test for Mg alloys.
The development of more sustainable and more affordable manufacturing technology for these next-generation Mg alloys has been conducted via an integrated and comprehensive collaboration between academia and industry. Moreover, the applications and commercialization of these advanced Mg alloys have been under serious investigation and study for automobile, aircraft, and biomedical industries.

References:
[1] T.R. Marker, DOT/FAA/AR-11/3.\n[2] Y. Kawamura, K. Hayashi, A. Inoue and T. Masumoto, Mater. Trans. 42 (2001) 1172-1176.\n[3] Y. Kawamura and S. Yoshimoto, Magnesium Technology 2005 (TMS, 2005, pp499-502). \n[4] E. Abe, Y. Kawamura, K. Hayashi and A. Inoue, Acta Materialia 50 (2002) 3845-3857.\n[5] Y. Kawamura and A. Inoue, Materials Science Forum 419-422 (2003) 709-714.

11:45: [MagnesiumThuAM02] Keynote
Development of Next-Generation Nonflammable High-Strength Magnesium Alloys
Yoshihito Kawamura¹ ; ¹Magnesium Research Center (MRC) Kumamoto University, Kumamoto, Kumamoto, Japan;
Paper Id: 484 [Abstract]

Mg alloys are attractive for use in aircraft components primarily because of their low density and high specific strength. But current commercial Mg alloys, e.g., AZ31, have low yield strength and unacceptably low ignition temperature. Moreover, several years ago America’s FAA (Federal Aviation Administration) has lifted the ban on the use of some Mg alloy forms in the payload area and has set up a standardized testing method of flammability for Mg alloys [1].
We have developed two kinds of high-strength Mg alloys with a high ignition temperature: 1) Mg-Zn-Y alloys consisted of alpha Mg phase and a long period stacking ordered (LPSO) phase [2,3,4], and Mg-Al-Ca alloys consisted of alpha Mg phase and a C36-type intermetallic compound [5].
The LPSO-type Mg₉₆.₇₅Zn₁Y₂Al₀.₂₅ alloy, which was produced by hot extrusion of cast ingot, exhibited very high, symmetrical yield strength in both tension and compression, high heat resistance, and great flame resistance. Its corrosion resistance is the same as AZ31. The LPSO phase, which has a periodical stacking structure of the 4 atomic layers consisting of in-plane ordering of L1₂ Zn₆Y₈ clusters and the 1-4 atomic layer(s) of 2H Mg, is strengthened by kinking, which was formed during the hot extrusion. This kink strengthening is a brand-new concept for strengthening mechanism of materials. On the other hand, the C36-type Mg₈₄.₉₇Al₁₀Ca₅Mn₀.₀₃alloy, which was also produced by hot extrusion of cast ingot, exhibited high, symmetrical yield strength, high corrosion resistance, and nonflammability; the ignition temperature is higher than the boiling temperature of pure magnesium. These advanced Mg alloys have passed the FAA flammability test for Mg alloys.
The development of more sustainable and more affordable manufacturing technology for these next-generation Mg alloys has been conducted via an integrated and comprehensive collaboration between academia and industry. Moreover, the applications and commercialization of these advanced Mg alloys have been under serious investigation and study for automobile, aircraft, and biomedical industries.

References:
[1] T.R. Marker, DOT/FAA/AR-11/3.\n[2] Y. Kawamura, K. Hayashi, A. Inoue and T. Masumoto, Mater. Trans. 42 (2001) 1172-1176.\n[3] Y. Kawamura and S. Yoshimoto, Magnesium Technology 2005 (TMS, 2005, pp499-502). \n[4] E. Abe, Y. Kawamura, K. Hayashi and A. Inoue, Acta Materialia 50 (2002) 3845-3857.\n[5] Y. Kawamura and A. Inoue, Materials Science Forum 419-422 (2003) 709-714.

12:10: [MagnesiumThuAM03] Invited
Strengthening using the Deformation Kink Band in Mg-Based LPSO-Phase Alloys
Koji Hagihara¹ ; Takayoshi Nakano¹ ; Michiaki Yamasaki² ; Yoshihito .kawamura³ ; ¹Osaka university, Suita, Japan; ²Kumamoto university, Kumamoto, Japan; ³Kumamoto University, Kumamoto, Japan;
Paper Id: 300 [Abstract]

The long-period stacking ordered phase, the so-called LPSO phase, is strongly focused as a suitable strengthening phase of Mg alloys[1-4]. One of the hot topics found in Mg-alloys containing a large amount of LPSO phase is the unusual increase in strength by the extrusion [5]. Concerning this, we recently clarified the mechanisms which induce the drastic strengthening of the LPSO-phase alloys by extrusion, on the basis of the quantitative analysis [6]. This is one of the main purposes in this presentation and the details of this are discussed. In order to achieve this, the temperature and loading orientation dependence of the deformation behavior of the Mg₈₈Zn₄Y₇ extruded alloy, which contains a ~86 vol.% of LPSO-phase, were examined. Using several extruded alloys with different extrusion ratios, the influence of the extrusion ratio to the microstructure formation and the following mechanical properties were examined by compression tests. The tests were conducted in a temperature range between room temperature and 400 °C in a vacuum. Two loading orientations were selected for the compression test; one orientation is parallel to the extrusion direction (0° orientation) and the other is inclined at an angle of 45° from the extrusion direction (45° orientation) which clarifies the anisotropic mechanical properties of the extruded alloys. As a result, the yield stress of the LPSO phase alloy was found to exhibit a strong orientation dependence varied with the extrusion ratio. Especially, the yield stress of the extruded alloy with the reduction ratio of 10 showed an extremely high value of ~460 MPa when loaded at 0° orientation while it was largely reduced when loading at 45° orientation. This strong anisotropy of the plastic deformation behavior was considered to be derived from the variation in the deformation mechanisms depending on the loading orientation because of the development of strong {10-10} fiber texture along the extrusion direction. The basal slip was found to govern the deformation behavior at 45° orientation while the predominate deformation mechanism varied from the basal slip to the formation of deformation of the kink band at 0° orientation as the extrusion ratio increased. In addition, it was found that the introduction the deformation kink band boundary during the extrusion process effectively acts as a strong obstacle against the motion of the basal slip. That is, "the kink band strengthening" was first quantitatively elucidated, which contributes to the drastic increase in the yield stress of the extruded LPSO-phase alloys in the wide temperature range below 400 ºC.

References:
1) Y. Kawamura, K. Hayashi, A. Inoue, T. Masumoto, Mater. Trans. 42, 1172-1176 (2001).
2) K. Hagihara, A. Kinoshita, Y. Sugino, M. Yamasaki, Y. Kawamura, H.Y. Yasuda, Y. Umakoshi, Acta Mater. 58, 6282-6293 (2010).
3) M. Yamasaki, K. Hashimoto, K. Hagihara, Y. Kawamura, Acta Mater. 59, 3646-3658 (2011).
4) K. Hagihara, A. Kinoshita, Y. Fukusumi, M. Yamasaki, Y. Kawamura, Mater. Sci. Eng. A 560, 71-79 (2013).
5) K. Hagihara, A. Kinoshita, Y. Sugino, M. Yamasaki, Y. Kawamura, H. Y. Yasuda, Y. Umakoshi, Intermetallics 18, 1079-1085 (2010).
6) K. Hagihara, Z. Li, M. Yamasaki, Y. Kawamura, T. Nakano, Acta Materialia, 15, 226-239 (2019).

12:35: [MagnesiumThuAM04]
Influence of Cold Severe Plastic Deformation on Structure and Texture of Pure Magnesium
Daria Komkova¹ ; Olga Antonova¹ ; Vlada Petrova¹ ; Alexey Volkov¹ ; ¹M.N. Mikheev Institute of Metal Physics of the Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russian Federation;
Paper Id: 309 [Abstract]

Magnesium and its alloys are one of the lightest metals. The plasticity and formability of magnesium at room and lower temperatures, however, are poor because of its closely packed hexagonal crystal structure. Therefore, the deformation of magnesium by SPD methods is carried out at temperatures above 150 °C [1-3]. On the other hand, cold severe plastic deformation (SPD) of magnesium could lead to significant grain refinement and improvement of mechanical properties. At room and lower temperatures, however, the deformation of magnesium takes place mainly due to basal slip that causes formation of a sharp basal texture (0001) and prevents successful processing of magnesium at a high deformation strain. In this work, an attempt was made to deform magnesium at room and lower (cryogenic) temperatures. Our SPD method included lateral extrusion (LE) and cold rolling (CR). At first, cylindrical Mg-workpieces without basal texture (0001) were subjected by LE at room temperature (deformation strain is ε~3.9). As a result, 1-mm plates were obtained. It was found that the initial grain size was significantly reduced from 7 mm to 1-3 μm and weak basal texture was formed after LE [4]. Plates demonstrated high plasticity and were rolled to foils of 150-µm (ε~6) and 50 µm (ε~7) at room and cryogenic temperatures. CR did lead to nanostructure formation and the average grain size of thin foils deformed at low temperatures was about 5 – 7 µm. The main feature of the foils after CR was that their microstructure had a large number of new recrystallized grains and had areas of fine-grained and cellular substructures. New grains had non-equilibrium grain boundaries. After cryogenic deformation, a higher dislocation density in grains was seen in foils in comparison with room-temperature rolled foils. As for texture, basal texture (0001) became stronger after CR. The results of the work are of particular interest and they can be useful for practical application to create magnesium membranes for biotechnology and improve the mechanical properties of magnesium alloys. This work was carried out with support of the Russian Foundation for Basic Research (the RFBR project no. 18-33-00474) and within the framework of the State task (theme: Pressure No. АААА-А18-118020190104-3).

References:
1. S. Biswas, S.S. Dhinwal, S. Suwas, Acta Materialia. 58 (2010) 3247-3261.
2. J. Swiostek, J. Goken, D. Letzig, K.U. Kainer, Materials Science and Engineering: A. 424 (2006) 223–229.
3. N.B. Tork, N. Pardis, R. Ebrahimi, Materials Science and Engineering: A. 560 (2013) 34–39.
4. O.V. Antonova, A.Yu. Volkov, D.A. Komkova, B.D. Antonov, Materials Science and Engineering: A. 706 (2017) 319-329.

SESSION: MagnesiumThuPM1-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Adonis
Session Chairs: Elias Aifantis; Session Monitor: TBA

14:00: [MagnesiumThuPM105] Invited
Kink Strengthening of LPSO and Mille-Feuille Structures in Mg Alloys
Eiji Abe¹ ; ¹The University of Tokyo, Bunkyo-ku, Japan;
Paper Id: 346 [Abstract]

Dilute Mg alloys containing a few atomic percent of transition-metals and rare-earth elements have attracted increasing attention because of their excellent mechanical properties. The remarkable microstructural feature common for all of these Mg alloys is formation of a novel type of long-period stacking/order (LPSO) structures, which reveal a remarkable strength through the warm-extrusion process. During the process, the LPSO crystals are deformed not by simple dislocation migrations, but by kink-type, that is, the direct relevance to realize excellent properties of the alloys. From the extensive studies of the LPSO-structured Mg alloys for more than a decade, it has become apparent that the kink regions indeed play a critical role for effective strain storage of the alloys, but its detailed mechanism is not fully understood yet. In order to deepen our understanding of the veiled work-hardening mechanism related to kink, we have just launched the new project aiming the establishment of the “Kink strengthening phenomenon” as a universal strengthen principle. In the meantime, the LPSO structure can be generally viewed as a “Mille-feuille structure (MFS)”, in the sense that they are constructed by alternate stacking of microscopic hard-layers and soft-layers. Our preliminary studies have confirmed that the MFS Mg alloys indeed reveal the kink strengthening, whose effect seems to be more prominent than LPSO Mg alloys. Therefore, solving the critical condition and universality on the kink-strengthening phenomenon will certainly lead to a further development of lightweight structural materials, including novel Al and Ti alloys, and even polymer materials in the future.

14:25: [MagnesiumThuPM106]
In Situ Neutron Diffraction during Compression or Tension of Extruded Mg97Zn1Y2
Stefanus Harjo¹ ; Kazuya Aizawa² ; Wu Gong³ ; Takuro Kawasaki² ; ¹Japan Atomic Energy Agency, Naka-gun, Japan; ²Japan Atomic Energy Agency, Tokai-mura, Japan; ³Kyoto University, Tokai-mura, Japan;
Paper Id: 239 [Abstract]

Mg₉₇Zn₁Y₂ alloy is a magnesium alloy with a duplex microstructure consisting of a long period stacking ordered (LPSO) phase and an alpha-Mg phase [1]. Kink deformation was observed in an as-cast Mg₉₇Zn₁Y₂ alloy subjected to hot compression. The refinement of LPSO via kinking was found to be the reason for strengthening of the material from microscopy analyses [2]. Direct evidence, however, has shown that increase in strength via kinking has not been observed so far. In this work, in situ neutron diffraction was used to investigate the anisotropic deformation behavior of LPSO and alpha-Mg phases during uniaxial compression or tension in an as-cast Mg₉₇Zn₁Y₂ alloy and an extruded Mg₉₇Zn₁Y₂ alloy. The evolutions of phase stresses in both the LPSO and alpha-Mg phases were evaluated and discussed with the occurrences of twinning and kinking during compression or tension. The as-cast Mg₉₇Zn₁Y₂ alloy was prepared by high frequency induction melting in a carbon crucible. The extruded Mg₉₇Zn₁Y₂ alloy was prepared by hot extrusion at 623 K of a round bar of an as-cast Mg₉₇Zn₁Y₂ alloy at an extrusion ratio of 10 and a ram speed of 2.5 mm/s in the air. The in-situ neutron diffraction experiment during compression was carried out using TAKUMI of J-PARC and a cylindrical test piece having a length of 16 mm and a diameter of 8 mm. The peak positions and integrated peak intensities were evaluated from the obtained diffraction patterns and the evolutions of lattice strains. The texture was then estimated and the phase stresses were subsequently evaluated. The response of phase stress to the applied stress of alpha-Mg deviated from the linearity which describes a smaller value at the applied stress that is lower than the macroscopic yield stress for the as-cast alloy. The response obtained pretended to keep the linearity up to the macroscopic yield stress for the extruded alloy. The details will be presented.

References:
[1] Y. Kawamura et al., Material Transactions 42 (2001) 1172-1176.\n[2] X.H. Shao, Z.Q. Yang, X.L. Ma, Acta Mater. 58 (2010) 4760-4771.

14:50: [MagnesiumThuPM107]
Kink Microstructures and Solute Segregations in LPSO/MFS-Structured Mg Alloys
Daisuke Egusa¹ ; Eiji Abe¹ ; ¹The University of Tokyo, Bunkyo-ku, Japan;
Paper Id: 291 [Abstract]

Magnesium (Mg) alloys containing long-period stacking/ordered (LPSO) phases have been gathering increasing attention owing to their superior strength and unique deformation mode: "kink" [1]. Kink is a type of plastic deformation that introduces rotation of crystal which has been reported as a deformation mode that is activated in highly anisotropic materials [2]. Since high strength of the LPSO type Mg alloys are realized after high temperature processing, i.e., introducing kink deformed microstructure, kink deformation is believed to play an important role in mechanical properties [3]. In the present study, we investigated microstructures of kinks while especially focusing on solute segregations around boundaries which are known to significantly affect mechanical properties of Mg alloys [4]. Atomic structure and solute segregations at the kink boundaries were directly observed by scanning transmission electron microscopy (STEM). STEM observations clearly show that kink boundaries consist of arrays of basal dislocations extended into Shockley-type partial dislocations. In addition, solute elements segregated within stacking faults were introduced by the extended basal dislocations. The solute segregations around kink boundaries, which can be understood as Suzuki effect, would improve thermodynamic stability of kink microstructure.

References:
[1] Y. Kawamura et al., Mater Trans. 48 (2007) 2986-2992.\n[2] E. Orowan, Nature, 149 (1942) 643-644. \n[3] K. Hagihara et al., Intermetallics, 18 (2010) 1079-1085.\n[4] M. Bugnet et al., Acta Mater., 79 (2014) 66-73.

15:15: [MagnesiumThuPM108]
Deformation Behavior of Novel Magnesium Alloys Prepared by Spark Plasma Sintering Studied by the Acoustic Emission Technique
Michal Knapek¹ ; Peter Minárik² ; ¹Nuclear Physics Institute of the CAS, Řež, Czech Republic; ²Charles University, Department of Physics of Materials, Prague, Czech Republic;
Paper Id: 333 [Abstract]

The spark plasma sintering (SPS) technique was used to prepare a bulk WN43 magnesium alloy from the gas atomized powder. Compression tests were performed to investigate the effect of different sintering regimes on the resulting mechanical properties of the material. It was shown that by increasing the sintering temperature, the ultimate compressive strength and ductility can be significantly improved. Moreover, complementary in-situ acoustic emission (AE) recording was employed to provide insights into microstructural changes during the deformation. Recent advances in the AE signal analysis in the frequency domain, together with microstructure observations, allowed us to reveal the evolution of different deformation mechanisms. It was shown that pronounced twin nucleation takes place around the yield point whereas twin growth and dislocation slip are the dominant deformation mechanisms in the later stages of deformation in this material.

SESSION: MagnesiumThuPM2-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Adonis
Session Chairs: TBA Session Monitor: TBA

15:55: [MagnesiumThuPM209] Invited
Gradient Theory and Mg-Alloys
Elias Aifantis¹ ; ¹Aristotle University of Thessaloniki, Thessaloniki, Greece;
Paper Id: 448 [Abstract]

After a brief introduction of the current status of gradient theory and its implications to elasticity, plasticity and diffusion, a discussion on applications to Mg alloys is provided. An effort is made to focus on the novel Mg alloy discovered by Professor Kawamura and the projects LPSO & FRAMED.

References:
[1] E.C. Aifantis, Internal length gradient (ILG) material mechanics across scales and disciplines, Adv. Appl. Mech. 49, pp. 1-110, 2016.

[2] E.C. Aifantis, Weak nonlocal extension of classical material models, Frontiers in Physics, 2019 (in press).

16:20: [MagnesiumThuPM210]
Dislocation-Based Modeling and Numerical Analysis on the Formation of Kink Band
Ryuichi Tarumi¹ ; Shunsuke Kobayashi² ; Sho Yamada³ ;⁰ ; Masao Ogino⁴ ; ¹Osaka University, Toyonaka, Japan; ², Minoh city, Japan; ³, Osaka, Japan; ⁴Daido University, Nagoya, Japan;
Paper Id: 313 [Abstract]

Long period stacking-ordered (LPSO) magnesium and related alloys frequently show kink deformation under compressive loading. Recent experimental studies revealed that the kink microstructure improves the strength of Mg-based alloys [1]. The mechanism of the kink formation as well as the resulting strengthening, however, is still unclear and further investigation is required. In the present study, we conduct dislocation-based modeling and numerical analysis on the formation of kink bands using extended isogeometric analysis (XIGA). Our modeling is based on the growth of dislocation loops in the basal planes of hexagonal type elastic mediums. Dislocation loops or plastic displacements are introduced into the medium using the Peierls-Nabarro model, and the resulting elastic stress field is solved numerically using IGA. Here, the compressive loading is applied parallel to the Burgers vector of the dislocation loops. Present numerical analysis revealed that, under the uniform growth condition, screw components of the dislocation loop spread-out from the elastic medium since the side surfaces are traction-free. On the other hand, the edge components remained in the medium due to the compressive external loading. The edge dislocations form a polygonization microstructure that stabilizes the elastic strain energy. Although the edge dislocations form localized stress fields around the core of dislocations, the resulting macroscopic displacement induces the kink band.

References:
[1] K. Hagihara, Z.Li, M. Yamasaki, Y. Kawamura, T. Nakano, Acta Materialia, 163 (2019) 226-239.

16:45: [MagnesiumThuPM211]
First-Principles Study on The Origin of Structural Stability of Mg-M-Y (M = Ni, Cu, Co, and Zn) Alloys with Long-Period Stacking Ordered Structure
Takao Tsumuraya¹ ; Tamio Oguchi² ; ¹Kumamoto University, Kumamoto, Japan; ²Osaka University, Ibaraki, Japan;
Paper Id: 301 [Abstract]

A class of dilute magnesium alloys in which solute atoms (Zn, Y) are enriched in a periodic stacking fault to the (0001) plane of the hcp structure show high-strength and ductility [1]. Much attention has been paid to the studies of materials that are expected to be involved in the strengthening of mechanisms. For the class of Mg - transition-metal (M) - rare-earth (RE) metal alloys, transmission electron microscopy (TEM) found various polytype structures such as 12R, 24R, 10H, 18R, and 14H, which have different numbers of Mg layers between solute atoms (M and RE) concentrated layers [2]. Such a unique atomic structure is referred to as a long-period stacking ordered (LPSO) structure. Furthermore, recent structural analysis using TEM and first-principles calculations reveal that solute elements form M₆RE8 (L1₂ type) cluster in the concentrated layer of the LPSO phase [3]. It is experimentally found that the degree of regularity of solute atoms depends on the choice of M and the difference in the amount (composition) of solute atoms, which is correlated to the observed type of LPSO structure [4]. The origin of the phase stabilities and formation mechanisms of the LPSO structure, however, has not been clarified yet. In this study, to understand the microscopic origin of the phase stabilities of the structural polymorphs with different compositions of solute elements, we performed first-principle density-functional theory (DFT) calculations for Mg –M - Y alloys (M = Co, Ni, Cu, Zn) with 12R, 18R and 10H structures. We found that the structural distortion of the L1₂ cluster is uniquely determined by the choice of M atom. We explain how the geometries of the L1₂ solute cluster affects the electronic state near the Fermi level that crucially determines the stabilities of the LPSO phases.

References:
[1] Y. Kawamura, K. Hayashi, A. Inoue, and T. Masumoto, Mater. Trans. 42, 1172 (2001).\n[2] E. Abe, Y. Kawamura, K. Hayashi, and A. Inoue, Acta Metall. 50, 3845 (2002).\n[3] D. Egusa and E. Abe, Acta Mater. 60, 166 (2012). J. Saal and C. Wolverton, Acta Mater. 68, 325 (2014). \n[4] H. Kimizuka, S. Kurokawa, A. Yamaguchi, A. Sakai, S. Ogata, Sci. Rep. 4 7318 (2014).

17:10: [MagnesiumThuPM212]
Kinematical Modeling of Kink Microstructure
Tomonari Inamura¹ ; ¹Tokyo Institute of Technology, Yokohama, Japan;
Paper Id: 213 [Abstract]

A kinematical model of kink microstructure in a material which causes slip deformation on a specific plane is proposed based on the continuity of deformation at interfaces [1]. A kink band was regarded as a domain with a homogeneous shear, being rank-1 connected to the matrix. Ridge and ortho kink were modeled as rank-1 connections between the kink bands. Owing to the simple geometry of the kinks, the kink plane and the crystallographic rotation of the kink band were obtained in analytic forms as functions of the magnitude of the shears inside kinks. It was found that positive and negative partial wedge disclinations are inevitably formed in any kink band connection when the junction plane of the kink bands does not reach the surface of the body. In addition, it is possible for disclinations to annihilate by connection of suitable kink bands to a microstructure with zero elastic energy. A universal mechanism of kink strengthening in the LPSO Mg alloy is discussed.

References:
[1]T. Inamura, Acta Materialia, in press

SESSION: MagnesiumFriAM-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Adonis
Session Chairs: Eiji Abe; Session Monitor: TBA

11:20: [MagnesiumFriAM01] Keynote
Thermodynamics and Kinetics in Magnesium Alloy Design(Part 1)
Michele Manuel¹ ; ¹University of Florida, Gainesville, United States;
Paper Id: 435 [Abstract]

Designing materials that contain complex microstructures and high performance is challenging using a reductionist approach to materials development. A powerful utility in this endeavor is the use of computational thermodynamic and kinetic tools. The integration of these tools into a systems-based materials design methodology that couples experimental research with theory and mechanistic modeling has been established to accelerate materials development. Microstructural properties can be expressed as thermodynamic parameters that are predictable by computational thermodynamic tools, while kinetic simulations can assist in elucidating processing-structure relationships to quantify microstructural evolution. This talk focuses on the high temperature magnesium alloy development as a model system and a new low-cost alloy is demonstrated with improved attributes to commercial high temperature magnesium alloys systems.

11:45: [MagnesiumFriAM02] Keynote
Thermodynamics and Kinetics in Magnesium Alloy Design(Part 2)
Michele Manuel¹ ; ¹University of Florida, Gainesville, United States;
Paper Id: 486 [Abstract]

Designing materials that contain complex microstructures and high performance is challenging using a reductionist approach to materials development. A powerful utility in this endeavor is the use of computational thermodynamic and kinetic tools. The integration of these tools into a systems-based materials design methodology that couples experimental research with theory and mechanistic modeling has been established to accelerate materials development. Microstructural properties can be expressed as thermodynamic parameters that are predictable by computational thermodynamic tools, while kinetic simulations can assist in elucidating processing-structure relationships to quantify microstructural evolution. This talk focuses on the high temperature magnesium alloy development as a model system and a new low-cost alloy is demonstrated with improved attributes to commercial high temperature magnesium alloys systems.

12:10: [MagnesiumFriAM03] Invited
Prediction of Fatigue Crack Initiation in Magnesium Alloys
Manabu Enoki¹ ; Fabien Briffod¹ ; Takayuki Shiraiwa¹ ; ¹The University of Tokyo, Bunkyo-ku, Japan;
Paper Id: 294 [Abstract]

Magnesium (Mg) and its alloys have received particular interest, especially in the automotive industry, for potential lightweight structural applications due to their low density and high specific strength. Most Mg alloys, however, suffer from poor mechanical properties at ambient and elevated temperatures. They also lack strong plastic anisotropy due to the low-symmetry of the hexagonal crystal structure. The strength of heterogeneity of the different deformation mechanisms and the thermo-mechanical processes often lead to strong crystallographic textures. Synthetic microstructures generated from statistical data obtained from EBSD measurements was generated based on a developed approach, and numerical simulations based on the Crystal Plasticity Finite Element Method (CPFEM) were also proposed [1, 2]. Crystal plasticity which takes into account the dislocation slip and twinning is considered and fitted against experimental cyclic stress-strain hysteresis curves. Fatigue simulations are conducted with different loading conditions to quantify and correlate the local plastic strain with the crack initiation sites observed experimentally in various Mg alloys, including LPSO-Mg.

References:
[1] F. Briffod, T. Shiraiwa, M. Enoki, Materials Science and Engineering A, 695 (2017), 165-177.
[2] Briffod, T. Shiraiwa, M. Enoki, Materials Science and Engineering A, 753 (2019), 79-90.

12:35: [MagnesiumFriAM04]
Development of Incombustible Mg-Zn-Y Alloys
Shin-ichi Inoue¹ ; Michiaki Yamasaki² ; Yoshihito .kawamura³ ; ¹Kumamto University, Kumamoto, Japan; ²Kumamoto university, Kumamoto, Japan; ³Kumamoto University, Kumamoto, Japan;
Paper Id: 348 [Abstract]

Mg alloys have been attracting keen attention as promising lightweight materials for aerospace, automobile, and railway applications. On the other hand, it is often pointed out that Mg alloys have poor oxidation resistance and burn easily. The flammability of Mg alloys is a problem to be solved when we consider using Mg alloys as structural materials of mass transportation vessels. In fact, the Federal Aviation Administration (FAA) in the USA has banned the use of Mg alloys for aircraft cabins. From the point of view of reducing aircraft weight, however, the FAA decided to lift the ban on using the Mg alloy in an aircraft cabin and set up a flammability test for Mg alloys. As a part of the development of non-flammable Mg alloys, some metal elements have been added into Mg. It has long been known that the addition of rare earth elements can improve incombustibility of the surface of the oxide film on Mg alloys [1-6]. Among the RE-containing Mg alloys, Mg-Zn-Y with a long period stacking order (LPSO) phase has excellent mechanical properties and is expected to be used in aircraft components. Mg-Zn-Y alloys produced by rapid solidification powder metallurgy have extremely high yield strengths of ~600 MPa. Mg-Zn-Y alloys produced by ingot metallurgy and extrusion have a multimodal microstructure and high yield strengths of ~340 MPa [7, 8]. The Mg₉₇Zn₁Y₂ alloy, however, exhibits an ignition temperature of ~1150 K. This ignition temperature is lower than the flame temperature (~1200 K) of the oil burner of the FAA flammability test. Therefore, to use this alloy safely in an aircraft cabin, it is necessary to increase the ignition temperature of the Mg-Zn-Y alloy. In this study, to increase the ignition temperature, a fourth element was added in the Mg-Zn-Y alloy. Mg-Zn-Y alloys were prepared using high-frequency induction melting in Ar atmosphere. Specimens were heated at 973 K in a muffle furnace in the air. For investigating the structure of oxide films, XRD measurement, SEM, and TEM observations were conducted on the cross section of the film formed on the Mg-Zn-Y alloys. XRD measurement and SEM observation revealed that the surface film of the Mg-Zn-Y alloy was mainly composed of Y₂O₃. An inhomogeneous and thick Y₂O₃ layer was formed by internal oxidation of Y. Cracks were often observed in the inhomogeneous Y₂O₃. Furthermore, the metallic Mg was observed in gaps between the coarse Y₂O₃ crystal gains. Therefore, suppression of internal oxidation of Y will help to form a uniform and thin Y₂O₃ film on the surface of the Mg-Zn-Y alloy and prevent crack formation in the Y₂O₃ layer. On the other hand, Mg-Zn-Y alloys with fourth elements exhibit an ignition temperature of ~1320 K. Furthermore, the thin and homogeneous Y₂O₃ film is formed on the surface of Mg-Zn-Y alloys with the fourth element.

References:
[1] B. S. You et al., Scr Mater. 42 (2000) 1089-1094.\n[2] M. Sakamoto et al., J. Mater Sci. Lett. 16 (1997) 1048-1050.\n[3] B. H. Choi et al., Met Mater. Int. 9 (2003) 395-398.\n[4] D.B. Lee, Mater. Sci. Forum 419-422.\n[5] X. Zenget al., Mater. Sci. Eng. A 301 (2001) 154-644.\n[6] Q. Tan et al., Scr. Mater. 115 (2016) 38-41.\n[7] Y. Kawamura et al., Mater.Trans. 42 (2001) 1172-1176.\n[8] Y. Kawamura et al., Mater. Trans. 48 (2007) 2986-2992

SESSION: MagnesiumFriPM1-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Adonis
Session Chairs: Takao Tsumuraya; Session Monitor: TBA

14:00: [MagnesiumFriPM105] Invited
Texture Evolution of Ca-Containing Mg-Zn Alloys during Annealing
Nack Kim¹ ; ¹POSTECH, Pohang, Republic of South Korea;
Paper Id: 297 [Abstract]

Mg alloys have the lowest density among commercially available structural alloys which can provide significant weight savings in automobiles. For the widespread application of Mg alloys, however, Mg alloys should overcome a critical shortcoming: poor formability at room temperature mainly originating from strong basal texture developed during thermomechanical processing. Although several Mg alloys show random/weak texture and accordingly good room temperature formability, most of such alloys rely on the usage of expensive rare earth elements. It has been recently reported that the addition of Ca to Mg-Zn alloys weakens and randomizes the texture, similar to the effect of RE addition on modification of the texture. The texture of these Ca-containing Mg-Zn alloys can be described as the broadened angular distribution of basal poles along the transverse direction (TD) and split of basal poles along the rolling direction (RD) in as-rolled condition. A significant change in texture, however, occurs after the annealing process, splitting of basal poles toward the TD from the original RD in particular. Despite the weak texture intensity, their texture is less than ideal since one directional orthotropic texture developed during annealing would result in non-uniform deformation during stretch forming. The detailed mechanism of such texture evolution, however, has not been clearly revealed yet. In the present work, an attempt has been made for having a better understanding of the texture evolution during the annealing process of Ca containing Mg-Zn alloys. The details of their texture evolution have been analyzed by quasi-in-situ EBSD after various stages of annealing with particular emphasis on recrystallization and growth behavior.

14:25: [MagnesiumFriPM106]
Influence of Texture on Energy Absorption Capability in Porous Magnesium with Oriented Pores
Tsuyoshi Mayama¹ ; Masakazu Tane² ; Yuichi Tadano³ ; ¹Kumamoto University, Kumamoto, Japan; ²Osaka University, Osaka, Japan; ³Saga University, Saga, Japan;
Paper Id: 290 [Abstract]

Porous metals are used in a wide range of applications because of the several advantages they have over non-porous metals which include low density, high energy absorption capability, and so on [1]. Among the porous metals, porous magnesium (Mg) with parallel cylindrical pores exhibits a higher energy absorption capability compared to porous light metals with isotropic pores [2, 3]. The microstructure of this porous Mg shows several distinctive features: elongated pores in the solidification direction, elongated coarse grains in the solidification direction, and a peculiar crystallographic texture where one of the normal directions of the {10-13} planes is closely oriented to the solidification direction. In the previous research [2], crystal plasticity analysis estimated that the different deformation modes were activated depending on loading direction which led to anisotropic deformation behavior. Furthermore, more detailed numerical investigations were performed to clarify the underlying mechanism for high energy absorption capability of this porous Mg [3]. This suggested significant contribution of texture development triggered by intra-granular misorientations. Based on the understanding of the deformation mechanism from the viewpoint of crystal plasticity, a possible strategy for further improvement of energy absorption properties by pre-loading was also proposed [3]. In this study, the influence of the initial texture on energy absorption capability in porous Mg with oriented pores is summarized based on a series of crystal plasticity finite element calculations. Implemented deformation modes in the present numerical method are the basal slip, prismatic slip, first order pyramidal <<b>a</b>> slip, second order pyramidal <<b>c</b>+<b>a</b>> slip, and {10-12} tensile twinning systems. The analysis models, which reproduce elongated pore structure, grain morphology, and initial texture, were constructed based on microstructural observations [2, 3]. The results of numerical calculations showed significant dependence of initial texture on energy absorption capability.

References:
[1] L.-P. Lefebvre, J. Banhart, D. C. Dunand, Porous metals and metallic foams: Current status and recent developments. Adv. Eng. Mater. 10 (2008) 775-787.\n[2] M. Tane, T. Mayama, A. Oda, H. Nakajima, Effect of crystallographic texture on mechanical properties in porous magnesium with oriented cylindrical pores. Acta Mater. 84 (2015) 80-94.\n[3] T. Mayama, M. Tane, Y. Tadano, Superior energy absorption in porous magnesium: Contribution of texture development triggered by intra-granular misorientations. Acta Mater. 165 (2019) 62-72.

14:50: [MagnesiumFriPM107]
Dynamics of Kink Formation Behavior under Compressive Stress via Hybrid Measurement of In Situ Neutron Diffraction and Acoustic Emission
Kazuya Aizawa¹ ; Wu Gong² ; Stefanus Harjo³ ; Takuro Kawasaki¹ ; ¹Japan Atomic Energy Agency, Tokai-mura, Japan; ²Kyoto University, Tokai-mura, Japan; ³Japan Atomic Energy Agency, Naka-gun, Japan;
Paper Id: 237 [Abstract]

Dynamics of kink formation behavior under compressive stress on the 18R Mg-based LPSO alloy, prepared by the one-directional solidification technique, will be presented. This technique uses materials of high strength dual phase Mg-based LPSO alloys [1]. This is observed at room temperature via a hybrid measurement of in situ neutron diffraction and acoustic emission (AE). By in situ neutron diffraction, we revealed the relationship between the basal plane strains and kink formation. On the other hand, by AE measurement, we obtained statistics about kink formation size by analysis of AE absolute energy which consists of flat behavior in low energy regions and power law behavior in higher energy regions. This is basic knowledge for introducing kink structure efficiently. In the AE data plot, we can clearly observe the emergence of an amoeba which is defined by the image of the logarithm of the absolute complex coordinates of the plane complex algebraic curve in the mathematics context. This excludes the scale factor. Specifically, a plot of the energy-difference between (n+1) and n events versus energy-difference between n and (n-1) events indicates an amoeba whose Newton polygon consists of the coordinates (0,0), (1,0) and (0,1). This characteristic has deep meaning regarding the dynamics of kink formation. This reveals that the statistical sequence of kink formation is governed by a simple complex algebraic curve.

References:
[1] Y. Kawamura et al., Material Transactions 42 (2001) 1172-1176.

15:15: [MagnesiumFriPM108]
Deformation Behavior of Directionally Solidified Mg/LPSO Alloy with Respect to its Lamellar Structure
Daria Drozdenko¹ ; Kristián Máthis² ; Michiaki Yamasaki³ ; Stefanus Harjo⁴ ; Wu Gong⁵ ; Kazuya Aizawa⁶ ; Yoshihito .kawamura⁷ ; ¹Magnesium Research Center, Kumamoto University, Kumamoto, Japan; ²Department of Physics of Materials, Charles University, Prague, Czech Republic; ³Kumamoto university, Kumamoto, Japan; ⁴Japan Atomic Energy Agency, Naka-gun, Japan; ⁵Kyoto University, Tokai-mura, Japan; ⁶Japan Atomic Energy Agency, Tokai-mura, Japan; ⁷Kumamoto University, Kumamoto, Japan;
Paper Id: 308 [Abstract]

Recently, a new generation of Mg alloys with an LPSO phase have received considerable attention due to their enhanced mechanical and promising high-temperature properties compared to the conventional Mg alloys. Nevertheless, those alloys still suffer from anisotropy of mechanical properties. It is generally agreed that besides the dislocation slip, deformation kinking and twinning contribute to the plastic deformation of those alloys. The materials’ parameters (shape and orientation of LPSO phase, grain size, texture) as well as the experimental conditions (loading direction, temperature etc.) are factors on which deformation kinking depends for it to be considered common for Mg/LPSO alloys. The conditions for kink formation in Mg-LPSO alloys and their dependence on temperature, however, are still under consideration. In this present work, a directionally solidified Mg -24 wt.% Y- 12wt.% Zn alloy having a lamellar structure elongated along the solidification direction was investigated. In order to reveal the effect of orientation on deformation behavior, uniaxial compression tests were performed parallel and perpendicular to the LSPO lamellae. Active deformation mechanisms were revealed by combination of two advanced in-situ techniques: acoustic emission and neutron diffraction. Detailed microscopy observations by optical and scanning electron microscopy (including EBSD, BSD imaging and IGMA) were performed for getting information about microstructure changes (e.g. twin and kink formation) with respect to a lamellar structure and crystallographic orientation. Kinking was found to be a dominant deformation mechanism during compression along the lamellar structure, resulting in high yield strength. In the case of loading perpendicular to lamellae, kinking was limited to well oriented lamellae and rather higher activity of the <c+a> dislocation slip was observed. IGMA analysis has shown that all observed kinks in both orientations were found to be of <1-100>-and <1-210>-rotation types.

References:
[1] Kawamura et al. Mater Trans 42(7) 2001 1172-1176
[2] Hagihara et al. Intermetallics 18 (2010) 267-276
[3] Yamasaki et al. Acta Mater, 61 (2013) 2065-2076
[4] Garces et al. Int. J. Plast. 106 (2018) 107-128
[5] W.Gong et al. Int J Plast 111 (2018) 288-306

SESSION: MagnesiumFriPM2-R4	Intl Symp. on Next Generation Magnesium Alloys and Their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Adonis
Session Chairs: TBA Session Monitor: TBA

15:55: [MagnesiumFriPM209] Invited
Activities of Non-basal Slips in Mg-Y and Mg-LI alloy Single and Poly Crystals
Shinji Ando¹ ; Keisuke Takemoto¹ ; Hiromoto Kitahara¹ ; ¹Kumamoto University, Kumamoto, Japan;
Paper Id: 296 [Abstract]

It is well known that the principle slip system of magnesium is a basal slip. Activation of non-basal slip systems, however, is necessary to show good ductility. Recently, the effect of yttrium on ductility of magnesium and discussion for activity of (c+a) pyramidal slips has been reported [1]. In this study, to investigate the effects of yttrium and lithium for non-basal slips, pure magnesium and magnesium alloy single crystals were stretched parallel to the basal plane in various temperatures, and polycrystalline magnesium alloys were also tested to estimate contribution of non-basal slips to their tensile deformation behavior. In pure magnesium and Mg - (7-14)at%Li single crystals, second order pyramidal (c+a) slips (SPCSs) were observed at 77-298K as CRSS of the SPCS was decreased. Above room temperature, the first order pyramidal (c+a) slip (FPCS) was active in pure magnesium. In the Mg-(0.6-0.9) at%Y alloy single crystals, FPCS was observed at 77K to 298K while yield stress of the Mg-Y alloy single crystals was higher than that of pure magnesium [2]. In tensile tests of polycrystalline pure magnesium, Mg-(0.5-1.2)at%Y and Mg-(6-12)at%Li, slip lines of non-basal slip systems such as the SPCS, FPCS and prismatic slip were observed even at yielding in addition to basal slip lines. Among the non-basal slips, activities of FPCS and prismatic slips were increased with increasing strain in magnesium - yttrium and magnesium- lithium alloys. Our study suggested that the active non-basal slip system in tension parallel to the basal plane is a (c+a) pyramidal slip and enhanced ductility of magnesium alloys would be caused from increased activity of FPCS by alloying.

References:
[1] S. Sandlobes, M. Friak, S. Zaefferer, A. Dick, S. Yi, D. Letzig, Z. Pei, L. -F. Zhu, J. Neugebauer, D. Raabe, Acta Materialia, 60(2012), 3011-3021\n[2] Hiroaki Rikihisa1, Takashi Mori, Masayuki Tsushida, Hiromoto Kitahara and Shinji Ando, Materials Transactions, 58(2017) 1656-1663.

16:20: [MagnesiumFriPM210]
Acoustic Emission Study of Active Deformation Mechanisms in Mg Alloys
Patrik Dobron¹ ; Daria Drozdenko² ; Klaudia Horvath¹ ; Juraj Olejnak¹ ; Jan Bohlen³ ; ¹Charles University, Prague, Prague, Czech Republic; ²Magnesium Research Center, Kumamoto University, Kumamoto, Japan; ³Helmholtz-Zentrum Geesthacht, Geesthacht, Germany;
Paper Id: 319 [Abstract]

The activity of individual deformation mechanisms during deformation tests of wrought Mg alloys was investigated using the acoustic emission (AE) technique. The investigated alloys exhibited a typical basal texture with basal planes oriented nearly parallel to the extrusion or rolling direction. Deformation tests were performed at room temperature and the obtained results are supported by microstructure evolution analysis provided by electron backscattered diffraction (EBSD). The AE signal analysis correlates the microstructure and the stress-strain curves to the active deformation mechanisms quite well. To determine the dominant deformation mechanism in a given time period, the adaptive sequential k-means (ASK) clustering was applied. X-ray diffraction was used to characterize the deformation texture before and after the test in order to obtain comprehensive data for texture characterization.

16:45: [MagnesiumFriPM211]
Local Deformation Behavior of Mg Alloy Single Crystals using Ball Indenter
Hiromoto Kitahara¹ ; Momoka Watanabe¹ ; Shinji Ando¹ ; ¹Kumamoto University, Kumamoto, Japan;
Paper Id: 295 [Abstract]

A steel ball indenter was impressed on low index planes in Mg alloy single crystals with different CRSSs: Mg-Al, Mg-Zn, and Mg-Y alloy single crystals. Effects of alloying elements on indentation behavior and roles of slip and twins on indentation size were investigated. Pure Zn single crystals, whose loading direction causing {10-12} twins is opposite to pure Mg, were also prepared. Indentations showed a circular shape on (0001) in the Mg alloys and pure Zn single crystals. Also, slip lines and twins were hardly observed around (0001) indentations. On the other hand, (10-10) and (1-210) indentations showed an elliptical morphology which elongated to [0001]. Basal slip lines and {10-12} twins were observed around (0001) indentations in Mg-Al and Mg-Zn alloys. Twins, however, were hardly observed in Mg-Y alloy single crystals. Indentation sizes of (0001) of the Mg alloys were smaller than that of pure Mg. Also, indentation sizes of pure Mg and Zn were nearly the same. Indentation sizes decreased with increasing CRSS for the basal slip. Therefore, the size would be determined by CRSS for the basal slip. CRSSs for the basal slip of pure Mg and Zn were nearly the same. Therefore, the size gap would be caused by the presence of {10-12} twins. In Mg alloys, indentation sizes decreased as alloy elements were added. The size differences between pure Mg and the Mg alloys would be determined by ratios of basal slip and twinning activities.

SESSION: RecyclingSatAM-R4	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Adonis
Session Chairs: Florian Kongoli; Dominik Hofer; Session Monitor: TBA

11:20: [RecyclingSatAM01]
Non-ferrous and Ferrous Dust Processing by Waelz Process
Pavel Kozlov¹ ; Leontyev Leopold Igoryevich² ; Dyubanov Valeriy Grigorievich³ ; ¹UMMC-Holding, Moscow, Russian Federation; ²Russian Academy of Sciences, Moscow, Russian Federation; ³Baykov Metallurgy & Materials Institute, Moscow, Russian Federation;
Paper Id: 134 [Abstract]

Gas cleaning dusts, forming in ferrous and non-ferrous metallurgy, have a high content of zinc, lead, copper and other components. These metals may be extracted from steel electrosmelting dust and copper smelting dust for matte into the intermediate products for their production. In the Russian Federation (RF), steel electrosmelting dusts, containing 30% or more of zinc [1], began to be recycled only in recent years [2]. Millions of such dusts disposal tonnes have been accumulated. Copper smelting dust for matte contains 10-25% of zinc and 10-30% of lead that makes it perspective for non-ferrous metals recovery [3]. The technological flowsheets of metallurgical dusts processing of steel and copper production are given in this work at the conditions of Chelyabinsk Zinc Plant, PJSC. The main flowsheet with intermediate products obtaining for zinc, lead and iron production, as well as an auxiliary flowsheet with zinc powder and lead fumes production are presented for steel electrosmelting dust. Both flowsheets are presented for coper smelting dust: a functional flowsheet with two pyrometallurgical stages with intermediate products obtaining for zinc, lead, tin and copper production and a developed flowsheet with one pyrometallurgical stage. The valuable components extraction from wastes of steel and copper production contributes to increase the economic and ecological efficiency of production in the nonferrous-metals industry by means of raw materials economy and implication in recycling of resulting and non-utilizable wastes.

References:
[1] Yakornov S.A., Panshin A.M., Kozlov P.A., Ivakin D.A. Current state of electrical arc furnace dusts processing in Russia and abroad // Tsvetnye Metally. - 2017. - No. 4.-P. 23-29.
[2] Stefanova A., Aromaa J. Stefanova A., Aromaa J. Alkaline leaching of iron and steelmaking dust. Helsinki: Aalto University, School of Chemical Technology, 2012. 72 p.
[3] Grudinsky P. I., Kozlov P.A., Dyubanov V.G. Copper smelter dust as promising material for recovery of non-ferrous metals by the Waelz process // Perspektivnye materialy. 2018. No 12. P. 74-81. (In Russian)

11:45: [RecyclingSatAM02] Keynote
Control and Optimization of Steel Dust Rotary Kiln Operations through FLOGEN CONTOP System
Florian Kongoli¹ ; Marcos De Souza² ; ¹FLOGEN Technologies Inc., Mont-Royal, Canada; ²FLOGEN Technologies Inc, Sao Paulo, Brazil;
Paper Id: 483 [Abstract]

FLOGEN Decision Making, Control, and Optimization system has been applied in Waltz Rotary Kiln that produces Zn from steel dust. This resulted in simultaneously reducing the specific coke/coal consumption, maximizing Zn yield, decreasing Zn losses in the slag, minimizing accretions and balls inside the furnace, increasing the operational time without stoppages and enabled greater flexibility in using multiple raw materials. This paper presents some of the above results along with the most recent developments of application in other processes

12:10: [RecyclingSatAM03]
Optimization of a Leaching Process for Pulverized Metal-Containing Residues
Eva Gerold¹ ; Stefan Luidold² ; ¹Montanuniversitaet Leoben, Chair of Nonferrous Metallurgy, Leoben, Austria; ²Montanuniversitaet Leoben, Leoben, Austria;
Paper Id: 234 [Abstract]

The selective recovery of valuable metals from metal-containing residues not only conserves the primary resources, but also improves the availability of raw materials. First and foremost, the focus must be kept on previously unrecycled wastes as these have been removed from the circular resource flow. The recycling of used batteries effects not only the treatment of hazardous waste, but also the recovery of valuable elements used in this field. On the commonly used pyrometallurgical route, mostly only the main metals are recovered. The application of hydrometallurgy remedies this problem and is mentioned in various research papers [1]. This process route gives the possibility of recycling for materials such as rare earths, cobalt and nickel which are often slagged in the pyrometallurgical process [2]. The recycling of metal-containing residues from the battery sector by hydrometallurgical means offers a wide range of possibilities. It is assumed that many different residues, as well as nickel-cadmium or nickel-metal hydride batteries and lithium-ion batteries can be recycled. Recycling processes for these metal-containing residues are divided in chemical processes (leaching, selective precipitation, solvent extraction) and mechanical and/or thermal processes [2,3]. The optimization of leaching parameters in the field of recycling of metal-containing residues represents a complex topic in the literature. In addition to the selection of an appropriate leaching medium, the variation of different leaching parameters such as temperature, time, solid-liquid ratio and concentration of the leaching medium have to be investigated in order to obtain the best possible result. Efficient leaching can only occur if there is an optimized process window with upper and lower limits for the respective parameters [4]. For experimental design and evaluation, a statistical software for design of experiments based on a fully factorial model serves for the interpretation of the process area [5].

References:
[1] Ordonez, J., Gago, E. J., Girard, A. (2016). Processes and technologies for the recycling and recovery of spent lithium-ion batteries. Renewable and Sustainable Energy Reviews 60, 195-205.\n[2] Kaindl, M., Luidold, S., Poscher, A. (2012). Recycling von Seltene Erden aus Nickel-Metallhydrid-Akkumulatoren unter besonderer Beruecksichtigung von Saeurerueckgewinnung. Berg Huettenmaenn Monatsh 157/1, 20-26.\n[3] Xu, J., Thomas, H. R., Francis, R. W., Lum, K. R., Wang, J., Liang, B. (2008). A review of processes and technologies for the recycling of lithium-ion secondary batteries. Journal of Power Sources 177/2, 512-527.\n[4] Takacova, Z., Dzuro, V., Havlik, T. (2017). Cobalt precipitation from Leachate Originated from Leaching of Spent Li-ion Batteries Active Mass-Characterization of Inputs, Intermediates and Outputs. World of Metallurgy - ERZMETALL 70/6, 336-343.\n[5] Mantuano, D. P., Dorella, G., Elias, R. C. A., Mansur, M. B. (2006). Analysis of a hydrometallurgical route to recover base metals from spent rechargeable batteries by liquida-liquid extraction with Cyanex 272. Journal of Power Sources 159/2, 1510-1518.

12:35: [RecyclingSatAM04]
Selective Vaporization of Indium and Silver from an Iron Precipitation Sludge via a Reductive Chlorination Process
Stefan Steinlechner¹ ; ¹Chair of Nonferrous Metallurgy, Leoben, Austria;
Paper Id: 187 [Abstract]

Technologies are getting more complex each day and with that the metals and alloys utilized are getting more specialized and unique in their composition. This in turn leads to an increase in the importance of the so-called high-tech metals [1]. Many such valuable elements are only produced as a by-product of another carrier metal in the absence of the specific minerals mined for their primary production. These minor, rare, valuable or special metals, however those technologically important hitchhikers are labelled, gained their importance in the last few decades [2]. As a result, they recently caught the attention of the recycling industry and as a consequence, industrial residues were landfilled for decades and by-products, as well as intermediate process streams, are still generated today without extracting these elements. A striking example of this is the iron precipitation "jarosite residue" from the hydrometallurgical zinc industry, which is the investigated material described in this paper. As a result of low zinc and lead contents, a targeted economic recycling of this material also has to take into account the present minor elements, such as indium and silver. In this context, a pyrometallurgical process is investigated which recovers zinc, indium and silver simultaneously as a dust product and the iron, as an alloy. The technology investigated is a reductive vaporization step, exploiting the selective formation of volatile compounds especially of Indium and Silver by the addition of a chlorine carrier [3]. Therefore, the paper summarizes the fundamentals, such as morphology of jarosite and required pre-treatment of the material, to allow the formation of volatile indium- and silver-compounds.

References:
[1] Paschen P.: Heavy nonferrous metals in world economy over the last 50 years. World of Metallurgy - ERZMETALL, 60 (2007), 263-272.
[2] Reuter M.: Metal recycling. United Nations Environment Programme, Nairobi, Kenya (2013).
[3] Steinlechner S. and Antrekowitsch J.: Thermodynamic considerations for a pyrometallurgical extraction of indium and silver from a jarosite residue. Metals, 8 (2018) online Proceedings.

SESSION: RecyclingSatPM1-R4	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Adonis
Session Chairs: Tsuyoshi Hoshino; Alexandra-Georgiana Vatui; Session Monitor: TBA

14:00: [RecyclingSatPM105]
Slag Basicity Variation at Block Smelting for the Recycling of Tantalum
Dominik Hofer¹ ; Stefan Luidold¹ ; Tobias Beckmann² ; ¹Montanuniversitaet Leoben, Leoben, Austria; ²H.C.Starck Tantalum & Niobium GmbH, Laufenburg, Germany;
Paper Id: 228 [Abstract]

Tantalum rich ores containing oxidic minerals like tantalite or columbite are primarily mined by artisanal and small scale practices. [1] Major sources located in countries around the African Great Lakes like Congo and Rwanda control global output with a 60 % share. [2] Direct treatment of concentrates with a Ta₂O₅ content higher than 25 % takes place via leaching followed by liquid-liquid extraction. Recycling, chlorination and processing of low grade residues, slags, sludges or dusts represent aspiring alternatives accounting for approximately 30 % of the tantalum world production. [3] The pyrometallurgical manufacturing of synthetic tantalum concentrate (syncon) in a multi-stage process constitutes an established procedure for various input materials. [4] Within this study, the first step (smelting and reduction) is recreated in a small scale induction furnace as well as a DC-EAF. Huge amounts of high melting slag comprising mostly Al₂O₃, CaO, MgO, SiO₂, TiO₂ and ZrO₂ arise whilst Nb and Ta concentrate in the metal phase. Previous flow behaviour investigations [5] and viscosity calculations reveal low viscous slag to be crucial for good metal/slag separation at elevated CaO content. Therefore, a variation of slag basicity is tested for further process optimization and to attain technical standard regarding treatment time, tapping procedure and slag composition of < 0.2 % Ta₂O₅. Accumulation of value components was successfully realized and validated by SEM/EDX. Thus, yield, energy saving potential and other process adjustments for the syncon production can be investigated at the laboratory scale before upscaling to industrial quantity.

References:
[1] Killiches F. et al.: Sorgfaltspflichten in den Lieferketten von Zinn, Tantal, Wolfram und Gold. DERA Deutsche Rohstoffagentur Commodity TopNews 46, 2014.
[2] Reichl C., M. Schatz and G. Zsak: World Mining Data. Minerals Production, 2017.
[3] Andersson K., K. Reichert and R. Wolf: Tantalum and Tantalum Compounds: Ullmann's Encyclopedia of Industrial Chemistry (2000), 1-15.
[4] Schulenburg F., H. Rossel and U. Bartmann: Tantalrecycling: Thiel, Thome-Kozmiensky et al. (Hg) 2017 - Recycling und Rohstoffe, 137-154.
[5] Hofer D. et al.: Influence of CaO/SiO₂/Al₂O₃ Ratio on the Melting Behaviour of SynCon Slags. In: Minerals, Metals and Materials Society, TMS Annual Meeting & Exhibition (Hg.): TMS 2019 148th Annual Meeting & Exhibition supplemental proceedings. Cham: Springer, 1139-1148.

14:25: [RecyclingSatPM106] Keynote
Lithium Recycling from Used Li-ion Batteries using Innovative Dialysis with Lithium Ionic Conductor Membrane
Tsuyoshi Hoshino¹ ; ¹National Institutes for Quantum and Radiological Science and Technology (QST), Rokkasho-mura, Kamikita-gun, Japan;
Paper Id: 165 [Abstract]

As a means of addressing global warming, the world is increasingly turning to the use of Li-ion batteries in electric vehicles and as storage batteries in the home. Therefore, there is a growing need for Li. I propose a method for recovering Li from used Li-ion batteries by using innovative dialysis, wherein Li only permeates from the positive electrode side to the negative electrode side through a Li ionic conductor functioning as a Li separation membrane (LISM). Measurements of the Li ion concentration at the negative electrode side, as a function of dialysis duration, showed that the Li recovery ratio increased to approximately 8.6% after 72 h with 5V applied electric voltage. Moreover, other ions in a solution of used Li-ion batteries did not permeate the LISM. Figure 1 shows the proposed Li recovery method. This innovative method involves the use of an LISM whereby only Li ions in a solution of used Li-ion batteries permeate from the positive electrode side to the negative electrode side during electrodialysis; the other ions, including Co, Al, and F, do not permeate the membrane. Li_0.29La_0.57TiO₃ was selected as the LISM. The positive side of the dialysis cell was filled with used Li-ion battery solution. Then the negative side was filled with distilled water. The applied dialysis voltage was 5 V, and electrode area was 16 cm². The Li recovery ratio increased with electrodialysis time. Then, Co, Al, and F were not permeated. After electrodialysis, CO₂ gas was bubbled in the Li recovery water to produce lithium carbonate (Li₂CO₃) as a raw material for Li-ion batteries. The Li₂CO₃ deposition was easily generated by the reaction of CO₂ gas and the Li recovery solution as a lithium hydroxide (LiOH) solution (Fig. 2).

References:
T. Hoshino, Desalination, 2015, 359, 59-63

14:50: [RecyclingSatPM107] Keynote
Valuable Products from Natural Polymer Waste
Karel Kolomaznik¹ ; Michaela Barinova² ; Jiri Pecha¹ ; Milan Adamek¹ ; ¹Tomas Bata University in Zlin, Faculty of Applied Informatics, Zlin, Czech Republic; ²Tomas Bata University in Zlin, Czech Republic, Zlin, Czech Republic;
Paper Id: 413 [Abstract]

Natural polymers as products of animal and plant organisms play an irreplaceable role in the life of human society. The main natural polymer raw materials are cellulose, starch, chitin and proteins, which are mainly processed by the food, textile, leather, wood-processing and paper industries. Industrial processing of natural polymers, besides valuable final products, also generates large quantities of by-products, i.e. waste of different composition and quality. Our contribution deals particularly with protein waste (predominantly collagen and keratin) generated by the leather, textile and meat industries. Leather industry is one of major producers of solid protein waste, which often contains also potentially hazardous chemicals. In spite of numerous technological solutions described in the literature for collagen-based wastes, huge amounts of this waste are still left unutilized [1] and its sustainable valorization remains challenging not only from the technological point of view, but also from the viewpoint of commercial application of the products. Common utilization of the products as animal feed or fertilizers may not satisfy the increasing market demand for advanced products, or can be limited due to hygienic regulations related to certain animal by-products; therefore, it is necessary to shift research efforts in protein waste processing towards protein-based products with higher utility value [2] and potential applications in other industries. This also applies to waste keratin (wool, hair, feather...), the unique structure of which makes it difficult to process and to find a feasible and efficient technology of its treatment [3].
We present several successful technological procedures for the processing of protein-based waste generated mainly by the leather, textile and meat industries, from laboratory experiments to scale-up from the laboratory to pilot scale and industrial production using mathematical-physical models verified by laboratory measurements. The procedures specifically include: 1) Processing of potentially hazardous chrome shavings from tanneries; 2) Technology of complete processing of green fleshings, another problematic primary waste from tanneries, into biodiesel and protein hydrolysate; 3) Hybrid technology applied to manipulation waste from footwear production; 4) Processing of protein waste generated during production of collagen casings for the meat industry; 5) Innovative method for the treatment of resistant keratin-based waste from textile and food industries.
The processing technologies are based on hydrolysis of the feedstock carried out in an acidic or alkaline environment. Reactions in an alkaline environment are usually catalyzed by proteolytic enzymes. We also present most recent progress in selected technologies, applications of hydrolysis products in agriculture including eco-farming, and discuss their potential as auxiliary agents in the construction, plastic and rubber industries.

References:
[1] Umme Habiba Bodrun Naher, MD. Rashidul Islam, MD. Abu Sayid Mia, MD. Farhad Ali, IJSETR 7 (2018) 837-841.\n[2] M.B.A. Kumar, Y. Gao, W. Shen et al., Front. Chem. Sci. Eng. 9 (2015), 295-307.\n[3] C.R. Holkar, S.S. Jain, A.J. Jadhav, D.V. Pinjari, Process. Saf. Environ. 115 (2018) 85-98.

15:15: [RecyclingSatPM108]
Simultaneous Synthesis And Characterization of Anhydrite and LimeGyp From Nonmetallic LD Slag Fines By a Zero Discharge Hydro-metallurgical Process
Shrenivas Ashrit¹ ; Ravikrishna Chatti¹ ; Supriya Sarkar¹ ; ¹Tata Steel Limited, Jamshedpur, Jamshedpur, India;
Paper Id: 37 [Abstract]

The present study describes a zero discharge hydrometallurgical process for value addition of non-metallic LD Slag fines to multiple products of industrial importance. The process involves the quantitative separation and conversion of calcium along with some key nutrient elements which are part of LD Slag fines. This includes magnesium, iron, phosphorus, and manganese, which are used to form a new chemical compound viz Limegyp (Registered trade mark product) which finds application in the field of agriculture as a multi-nutrient soil conditioner. At the same time, the authors have also converted calcium into an insoluble anhydrite containing silica. The significance of the process lies in producing two types of products at the same time. One of the advantages of the process is that there is no generation of any type of gas or liquid pollutants. Hence it is strictly a zero discharge process which has enormous significance in the current global scenario. Another advantage of the process is that it reduces the recycling of LD Slag fines into iron making, thus limiting the entry of elements like phosphorus, alumina etc., in the steel making process. This innovative process is applied for patent vide Indian patent application No: P||1077||4||2019[1]. The present study further describes chemical and mineralogical characterization by different techniques such as ICP-OES Analysis, XRD, FTIR and Raman study.

References:
[1] World Steel Association report, World Steel in Figures, 2017 (Available from:
https://www.worldsteel.org/media-centre/press-releases/2017/world-steel-in-figures-
2017.html)
[2] National Steel Policy report, 2017 published in The Gazette of India: Extraordinary,
Notification released on 8th May, 2017
[3] Gahan, C., Cunha, M., Sandstrom, A., 2009. Comparative study on different steel slags as
neutralizing agent in bioleaching.In: Hydrometallurgy. Volume 95, 190–197.
[4] Gomes, J., Pinto, C., 2006. Leaching of heavy metals from steelmaking slags. In: Revista De
Metalurgia Madrid.Volume 42, 409–416.
[5] Proctor, D., 2000. Physical and chemical characteristics of blast furnace, basic oxygen furnace,
and electric arc furnace steel industry slags. In: Environmental Science & Technology. Volume
34, 1576–1582.
[6] Vestola, E., Kuusenaho, M., Närhi, H., Tuovinen, O., Puhakka, J., Plumb, J., Kaksonen, A.,
2010. Acid bioleaching of solid waste materials from copper, steel and recycling industries.
In: Hydrometallurgy.Volume 103, 74–79.
[7] Ashrit S., *, Banerjee P.K., Ghosh T.K., Venugopal R and Udayabhanu G. Nair, 2015.
Characterization of Waste Recycling Plant (WRP) reject fines by X-ray Diffraction. In:
Metallurgical Research & Technology, Volume: 112, 1-9.
[8] Waligora J., Bulteel D., Degrugilliers P., Damidot D., Potdevin J.L., Measson M., 2010,
Chemical and mineralogical characterizations of LD converter steel slags: A multi-analytical
techniques approach. In: Material Characterisation, Volume 61, 39 – 48.
[9] Yi H., Xu G., Cheng H., Wang J., Wan Y. and Chen H.,2012. An overview of utilization of
steel slag. In: Procedia Environmental Sciences. Volume 16, 791 – 801
[10] Chang E.E., Pan S.Y., Chen Y.H., Chu H.W., Wang C.F., Chiang P.C.,2011. CO2
sequestration by carbonation of steelmaking slags in an autoclave reactor. In: Journal of
Hazardous Materials.Volume 195, 107-114.
[11] Ashrit S., Banerjee P.K., Chatti R.V., Venugopal R and Udayabhanu G. Nair, 2015.
Characterization of Gypsum Synthesized from LD Slag fines generated at Waste Recycling
Plant of a Steel Plant. In: New Journal of Chemistry. Volume 39, 4128-4134
[12] Ashrit S., Banerjee P.K., Chatti R.V., Venugopal R and Udayabhanu G. Nair, 2015.
Characterization of Yellow Gypsum Synthesized from LD Slag fines generated at Waste
Recycling Plant of a Steel Plant. In: Current Science. Volume 109, 727-732
[13] ASTM D 1193-06 (2011), Standard specification for reagent water
[14] Hardie, L.A. 1967. The gypsum-anhydrite equilibrium at one atmosphere pressure. In:
American Mineralogist. Volume 52, 171 – 200.
[15] Deer, W. A., Zussman, J., Howie, R. A. An introduction to the rock-forming minerals
(2nd ed). Longman Scientific & Technical ; New York, NY : Wiley, Harlow, England, 1992.
Page 528
[16] Conley,R.F. and Bundey,W.M.1958.Mechanism of gypsification. In: Geochimica et
Cosmochimica Acta. Volume 15, 57 – 72.
[17] Billo, S.M.1987. Petrology and kinetics of gypsum – anhydrite transitions. In: Journal of
petroleum Geology. Volume 10, 73 – 85.
[18] ASTM C471M – 01(2012): Standard Test Methods for Chemical Analysis of Gypsum
and Gypsum Products
[19] Degen T., Sadki M., Bron E., König U., Nénert G. 2014. The HighScore suite. In: Powder
Diffraction Volume 29, S13-S18
[20] Liu, Y., Wang, A. and Freeman, J.J., Raman. 2009. MIR, NIR Spectroscopy study of
calcium sufates: Gypsum, Bassanite, & Anhydride, 40th Lunar and Planetary Science
Conference, Saint Louis.
[21] Prasad P.S.R., Pradhan A., and Gowd T.N. 2001. In-situ micro Raman Investigation of
dehydration mechanism in natural gypsum. In: Current Science. Volume 80, 1203 – 1207.
[22] Konečný, P., Plevová, E., Vaculíková, L., Kožušníková, A., Peterková, J. and
Hundáková, M.2011. Composition of gypsum from the Kobeřice quarry (Czech Republic).
In: Acta Geodyn. Geomater. Volume 8, 145–156.
[23] Lucia Fernández-Carrasco, D. Torrens-Martín, L.M. Morales and Sagrario MartínezRamírez
(2012). Infrared Spectroscopy in the Analysis of Building and Construction Materials,
Infrared Spectroscopy – Materials Science, Engineering and Technology, Prof. Theophanides
Theophile (Ed.), ISBN: 978-953-51-0537-4, InTech, Available from:
http://www.intechopen.com/books/infrared-spectroscopy-materials-scienceengineeringand-technology/infrared-spectroscopy-of-cementitious-materials
[24] Black, L., Breen C., Yarwood J., Deng C.-S.,Phipps J. and Maitland G. 2006. Hydration of
tricalcium aluminate (C3A) in the presence and absence of gypsum—studied by Raman
spectroscopy and X-ray diffraction. In: Journal of Materials Chemistry, Volume 16, 1263.

SESSION: RecyclingSatPM2-R4	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Adonis
Session Chairs: Stefan Steinlechner; Eva Gerold; Session Monitor: TBA

15:55: [RecyclingSatPM209]
Comparison of Two Dross Press Systems in the Aluminum Recycling Industry
Stefan Wibner¹ ; Helmut Antrekowitsch² ; ¹, Leoben, Austria; ²Montanuniversitaet Leoben, Leoben, Austria;
Paper Id: 240 [Abstract]

Aluminum dross consists of a heterogeneous mixture of large lumps, fine oxides and metal pieces. Consequently, sampling requires considerable experience and effort. Additionally, the skimming procedure of the melt, the alloy composition, the type of fluxing agent, and the cooling method of the scum all control the amount of free-metal present in the dross [1]. In industrial practice, the formed dross in the Al-smelter is regularly removed and a part of the liquid metal can be squeezed out. Subsequently, the tilting drum furnace recovers most of the aluminum from the scum with the assistance of a crumbly salt slag [2]. Of significant interest is the recovery of the largest possible amount of metallic Al from the dross during the production process by using a dross press. The aim of this work is to compare the press system currently available at an Austrian Al-smelter with a rented dross press. First, an optimized time-distance diagram for the hired press is determined. Thereafter, the masses of recovered metallic Al are recorded for a period of one week. A part of the resulting hot scum of every charge is processed with the existing press, the other part is processed with the rented. As a result, the proportion of recovered Al based on the total amount of dross is determined for both press systems. Furthermore, a comparison in terms of geometry of the press head, economy and appearance of the dross compacts is carried out. The results are of great importance to the Al-processing company as the optimization of the recycling process depends on a higher aluminum output [3, 4].

References:
[1] Manfredi O., Wuth W. and I. Bohlinger: Characterizing the Physical and Chemical Properties of Aluminum Dross. JOM (1997), 48-51.
[2] Krone K.: Aluminiumrecycling: Vom Vorstoff bis zur fertigen Legierung, Aluminium-Verlag, Duesseldorf (2000).
[3] Roth D. J.: History and future of dross processing. Light Metals (2015), 1005-1009.
[4] Perry O. H.: The development of the modern dross press. Light Metals (2000), 675-678.

16:20: [RecyclingSatPM210] Keynote
Rotary Kiln Dust As A Raw Material For Production Of The Magnesium Sulphate In MIM - GOLESHI
Shefik Imeri¹ ; Florian Kongoli² ; ¹MIM-GOLESH, Prishtina, Kosovo; ²FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 167 [Abstract]

The rotary kiln process that produces magnesite sinter creates a considerable amount of dust that contains up to 96% MgO [1]. Usually the quantity of the produced dust is 16% of the quantity of the magnesite concentrate charged in the Rotary Kiln. Up to now, about 90% of the dust is recycled with the feed of the Rotary Kiln, while about 10% of this quantity is lost with the gas. The quantity of the dust recycled creates various problems in the Rotary Kiln such as process disturbances, creation of accretions that decrease the active volume, and decreases in the productivity of magnesite sinter. Another alternative is to stop dust recycling in the Rotary Kiln and use it as a raw material to produce magnesium sulphate in a separate unit after the dedusting chamber. Eliminating dust recycling in the Rotary Kiln will improve the stability and efficiency of the process, increase the production rate since new magnesite concentrate will be charged in the feed instead of the dust, and significantly decrease the production cost of the magnesite sinter. The magnesium sulphate produced in this way will also constitute a new marketable product that will increase the profit of the company. In this paper, the production of magnesium sulphate using the magnesite sinter Rotary Kiln dust as a raw material will be studied and evaluated and the best production technology will be suggested while, in a subsequent publication, a description of the project on building and commissioning of magnesium sulphate production unit and its process will be described.

References:
[ 1 ]. Upustvo za rukovanje postrojenjem za pecenje magnezita sa kapacitetom od 150t/dan. Magnohrom, rudnik nmagnezita Goles, I sveska sa prilozima, Budimpesta, maja 1972, M4 - 02012,

16:45: [RecyclingSatPM211]
EFFICIENT USE OF ZINC-CONTAINING BLAST FUNACE DUST IS POSSIBLE WHEN IT IS PROCESSED TOGETHER WITH ZINC ORE IN ROTATING TUBE FURNACES
Madali Naimanbayev¹ ; ¹Center of Earth Sciences, Metallurgy and Ore Benefication, Almaty, Kazakhstan;
Paper Id: 176 [Abstract]

One of the resources in the production of non-ferrous metals is use of waste iron and the steel industry, in which the content of non-ferrous metals are kept up to industrial conditions. Thus, in dusts of gas purification of some plants of ferrous metallurgy, the zinc content is as high as 15%. The results of the study of the binder agent effect during the briquetting of charge include the type of the carbonaceous reducing agent, the consumption of reducing agent, and the fineness of charge components on the process of carbothermal reduction of zinc from oxidized zinc ore with the addition of stale dust of gas cleaning of blast furnace smelting. Bentonite, hydrated lime, and treacle were tested as a binding agent during briquetting of charge. It is established that the optimum binding agent is treacle in an amount of 4.5-5.0% by the weight of the ore. It is shown that the residual zinc content in a product of the reduction roasting, when using the special coke received from coal of Shubarkol, deposit is 1.9 times less than when using anthracite. It is also 3.3 times less than when using metallurgical coke, i.e. special coke is the most fissile reducing agent. The carbon consumption during carbothermal reduction of zinc from oxide ore with the addition of dust is 22-24% lower than in case of zinc recovery from ore. It was found that crushing of charge to class + 0.071-0.04 microns reduces the degree of zinc sublimation. If the size of the charge is 1.0 microns, then the residual zinc content is increased in the cinder. High recovery efficiency is achieved with the following composition of charge, wt. %: oxidized zinc ore is 53.8; dust of gas purification of blast furnace smelting is 26.9; special coke is 21.0; treacle is 5.3.

References:
1. Zaitsev V.Ia., Margulis E.V. Metallurgiia svintsa i tsinka ( Lead and zinc metallurgy). Moscow: Metallurgy, 1985. 263 (in Russ.)

2. Kozlov P.A. Razrabotka ekologichnoi tekhnologii pererabotki tsinkovykh kontsentratov s povyshennym soderzhaniem kremnezema i kompleksnym izvlecheniem tsennykh komponentov (The development of environmentally friendly technologies for processing of zinc concentrates with high silica content and complex extraction of valuable components): avtoreferat dis. ...doct. tekh nauk (Abstracts of thesis for Dr. Tech. Sci. 05.16.03. Institute Gidrotsvetmet, Moscow.1998. 42 (in Russ.)

3. Naimanbaev M.A., Lokhova N.G., Baltabekova Zh.A., Abisheva A.E. Analiz sushchestvuiushchikh sposobov pererabotki okislennykh tsinkovykh rud i tsinksoderzhashchikh pylei domennoi plavki (The analysis of processing of oxidized zinc ores and zinc containing dust blast furnace). Vestnik KazNAEN = Herald of KazNANS. 2016. 1. 55-60.

4. Meyer, Ganter, Karl-Heinrich Vopel und Willi Janssen. Untersuchungen zur Verwertung von Stauben und Schlammer aus den Abgasreinigungen von Hochofen- und Blasstahlwerken im Drehrohrofen. Stahl und Eisen . 1976. Bd. 96, 24. 1228-1238. (in German)

5. Kotenev V.I., Barsukova E.Iu. Brikety iz melkodispersnykh otkhodov metallurgicheskogo i koksokhimicheskogo proizvodstva - ekonomicheski vygodnaia zamena traditsionnoi shikhty metallurgicheskikh peredelov ( Briquettes made of fine waste of metallurgical and coke production-cost- effective replacement of traditional batch metallurgical processes). Metallurg = Metallurgist. 2002. 10. 42-45. (in Russ.)

6. Bystrov V.A., Novikov N.I. Innovatsii put' povysheniia konkurentosposobnosti metallurgicheskikh predpriiatii. (Innovations way to increase the competitiveness of the metallurgical enterprises) Vestnik Kemerovskogo gosudarstvennogo universitet = Herald of Kemerovo State University. 2010. 1. 47-53. (in Russ.)

7. Letimin V.N., Nasyrov T.M., Makarova I.V. Otsenka pirometallurgicheskikh sposobov obestsinkovaniia pyli i shlamov staleplavil'nykh tsekhov (Evaluation pyrometallurgical methods dezincification pfil and sludge steelwork). Teoriya i praktika metallurgicheskogo proizvodstva = Theory and practice of metallurgical industry. 2013. 1(13). 67-70. (in Russ.)

8. Babanin V.I., Eremin A.Ia., Bezdezhskii G.N. Razrabotka i vnedrenie novoi tekhnologii briketirovaniia melkofraktsionnykh materialov s zhidkim steklom (Development and implementation of new technology briquetting small fraction of materials with liquid glass). Metallurg = Metallurgist. 2007. 1. 68-71.

9. Kobelev V.A., Polotskii L.I., Smirnov L.A. Issledovanie kinetiki vysokotemperaturnogo karbotermicheskogo vosstanovleniia il'menitovykh i titanomagnetitovykh kontsentratov (Kinetics of high temperature carbotermic reduction of ilmenite and titanomagnetite concentrates) Stal' = Steel. 2015. 11. 6-9. (in Russ.)

10. Bersenev I.S., Evstiugin S.N., Gorbachev V.A., Usol'tsev D.Iu., Vinnichuk B.G. Sravnitel'nyi analiz effektivnosti ispol'zovaniia sviazuiushchikh razlichnogo tipa pri aglomeratsii (Comparative analysis of the efficiency of the use of binders with different types of agglomeration). Stal' = Steel. 2015. 8. 2-4.

11. Kim V.A., Torgovets A.K., Dzhundibaev M.K., Kudarinov S.K., Bogoiavlenskaia O.A., Nurmukhanbetov Zh.U. Poluchenie nizkofosforistogo spetskoksa dlya elektrotermicheskogo proizvodstva iz nespekaiushchikhsia uglei Shubarkol'skogo mestorozhdeniia (Getting lowphosphorous special coke for electroproduction of non-coking coal deposit Shubarkol). Povyсhenie tekhnicheskogo urovnya gorno-metallurgicheskikh predpriyatij na osnove innovatsionnykh tekhnologij: Mater. VII mezhdunar. Konf. (Rising technical level of mining-metallurgical enterprises on the basis of innovation technologies: proceedings of VII internation. conf.) Ust'-Kamenogorsk, Kazakhstan. 2013. 296-298. (in Russ.)

12. Ravich B. M. Briketirovanie v tsvetnoi i chernoi metallurgii (Briquetting in color and ferrous metallurgy). Moscow: Metallurgy, 1975. 232.

13. Ozerov S.S., Portov A.B., Tsemekhman L.Sh. Briketirovanie melkozernistykh materialov (Briquetting fine materials). Tsvetnye metally = Non- ferrous metals. 2014. 7. 26-30.

17:10: [RecyclingSatPM212]
An Investigation on the Pyrometallurgical Recovery of Gold from Jewellery Workshop Wastes Using a Mixture of Fluxes
Pouria Zakeri Ketabi¹ ; Hossein Astaraki¹ ; Manadana Adeli² ; ¹Iran Unicersity of Science & Technology, Tehran, Iran; ²School of Metallurgy and Materials Engineering, Iran University of Science and Technology, Tehran, Iran;
Paper Id: 277 [Abstract]

Precious metals such as gold and silver are a priority in recycling processes due to their economic values. In particular, jewellery workshop wastes which contain free gold and silver particles are considered a very valuable waste. These metals are usually extracted from jewellery wastes via the cupellation method using metallic lead. In this study, a pyrometallurgical method using a mixture of fluxes has been considered to recover gold from floor wastes of jewellery workshops. The process yields a relatively high efficiency in recovery, as well as savings in time and energy with the use of non-contaminating chemicals. The effect of type and flux-to-waste weight ratio on the properties of slag and recovery of gold has been studied. XRD, XRF, and DTA analyses have been used to characterize the wastes and the formed slag and to investigate the effect of slag properties on the recovery. A maximum value of 63.26wt.% was obtained for the recovery of gold without using dangerous chemical such as lead or contaminating processes such as cyanide leaching.

References:
1. C. W. Corti, "Recovery and Refining of Gold Jewellery Scraps and Wastes," no. May, pp. 1-22, 2002
2. S. Syed, "Recovery of gold from secondary sources-A review," Hydrometallurgy, vol. 115-116, pp. 30-51, 2012
3. M. Delfini, A. Manni, and P. Massacci, "Gold recovery from jewellery waste," Miner. Eng., vol. 13, no. 6, pp. 663-666, 2000

SESSION: RecyclingSatPM3-R4	Kozlov International Symposium on Sustainable Materials Recycling Processes and Products (7th Intl. Symp. on Sustainable Materials Recycling Processes and Products)
Sat Oct, 26 2019 / Room: Adonis
Session Chairs: Stefan Wibner; Ionut Macarescu; Session Monitor: TBA

17:50: [RecyclingSatPM313]
Initial stages of nitride spent nuclear fuel (SNF) processing Thermodynamic modeling and experimental results
Alexei Potapov¹ ; Kirill Karimov¹ ; Vladimir Shishkin¹ ; Mikhail Mazannikov¹ ; Yurii Zaikov¹ ; ¹Institute of High Temperature Electrochemistry, Ekaterinburg, Russian Federation;
Paper Id: 292 [Abstract]

Currently, a number of countries are developing new nitride (UN-PuN) fuel for fast-neutron nuclear reactors [1]. At the same time, methods for nitride SNF processing are developed. These methods are proposed to abandon water technologies in favor of pyrochemical methods, which use molten salts [2, 3]. As nitrides are electronically conductive, an initial opening of nitride SNF was suggested to be performed by electrochemical dissolution with the transfer of SNF components into the molten LiCl-KCl eutectic. It turned out, however, that the reaction UN - 3e = U³⁺ + 0.5N₂↑ is accompanied by the UNCl formation reaction. UNCl is an insulator, it covers the anode and dissolution stops. Currently, the research is suspended. Another method is “soft” chlorination (i.e. without chlorine gas). In the (LiCl-KCl) _eut. melt, the following reactions are possible: UN + 1.5CdCl₂ = UCl₃ + 1.5Cd + 0.5N₂ ΔG = -60.6 kJ/mol at 500°C (1) PuN + 1.5CdCl₂ = PuCl₃ + 1.5Cd + 0.5N₂ ΔG = -149 kJ/mol at 500°C (2) Experimental verification, however, revealed that at 500 0C the reactions of formation of a number of other stoichiometric and non-stoichiometric nitrides - UN_1.5, UN_1.55, UN_1.5, UN_1.55, UN_1.69, UN_{_1.74}, UN₂ and UNCl proceed along with reaction (1). The UN → UCl₃ conversion degree is ~ 30%. The rest of the uranium was found as a black precipitate that consisted of a mixture of UNCl and various nitrides. Using thermodynamic modeling, it was determined that, at a temperature of 750°C and above all nitrides, including UNCl, dissolve in an excess of CdCl₂ to form UCl₃. The experiment confirmed the calculation results completely. It was also found that the CdCl₂ substitution by PbCl₂ allows reduction of the process temperature to 650°C, but in this case, a UCl₃ + UCl₄ mixture forms. Another likely the first stage of the nitride SNF processing can be voloxidation, i.e. conversion of all nitrides to oxides by heating in air. For example, the uranium oxidation chain is as follows: UN → (U₂N₃+UO₂) → UO₂ → U₃O₇ → U₃O₈ → U₂O₆ (gas) (slowly) An important advantage of this approach is that we obtain a universal process suitable for processing both nitride and oxide SNF.

References:
[1] R. Thetford, M. Mignanelli, J.Nucl. Materials 320 (2003) 44-53.\n[2] Yu.P Zaykov, Yu.S. Mochalov, V.A. Khokhlov, V.Yu. Shishkin, A.M. Potapov, V.A. Kovrov, M.N. Gerasimenko, A.S. Zhidkov, S.G. Terentev, Pyrochemical recycling of the nitride SNF of fast neutron reactors in molten salts as a part of the short-circuited nuclear fuel cycle, in: Int. conf. on Fast Reactors and Related Fuel Cycles: (FR17), 26-29 June 2017, Ekaterinburg, Russia, (CD) IAEA-CN245, Rep.259. \n[3] V.Yu. Shishkin, A.M. Potapov, V. Kovrov, Yu.P. Zaikov, The peculiarities of pyrochemical reprocessing of spent nuclear fuel, in: Int. nuclear fuel cycle conf. Nuclear energy innovation to the carbon-free world (GLOBAL 2017), September 24-29, 2017, Seoul (Korea). Proceedings. Paper EA-104-PD3.

18:15: [RecyclingSatPM314]
Structure Study of Polymeric Materials During Recycling and Additive Influence in their Characteristics
Indrit Vozga¹ ; Jorgaq Kacani² ; ¹, Tirana, Albania; ²Universiteti Politeknik Tirane, Tirane, Albania;
Paper Id: 457 [Abstract]

The purpose of our work was the application of instrumental and analytical methods for studying of changes that happen to plastic materials during the recycling process and the way they are affected by the additives. The research covered the studying of plastic materials microstructure, the specification of additives and the change of principal physical and mechanical properties during the recycling process. The plastic materials analyzed were polyethylene PE, polypropylene PP and polystyrene PS. As recycling process we used extrusion in industrial scale. For the studying of microstructure were used infrared FT-IR and Raman spectroscopy methods and scanning electronic microscopy SEM, equipped with energy distribution system EDS for the qualitative analysis of chemical elements. Moreover we used X-ray diffractometry method to study the crystalline structure and the ability to determine the additives when they contained more than 5% of the total mass. Among the physical properties determined were specific gravity, density, melt flow index MFI, viscosity and average molecular mass. Mechanical properties were determined on polymeric rods with different diameters using the tensile test in one direction. The results obtained show the structural changes and the physico-mechanical properties during the recycling process and the influence of additive on them.

SESSION: OxidativeThuAM-R5	Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings
Thu Oct, 24 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Christian Amatore; HARUHIKO INUFUSA; Session Monitor: TBA

11:20: [OxidativeThuAM01]
The Effect of Ginseng on Human Antioxidant Capacity
Hiroshi Ichikawa¹ ; Yuta Noguchi² ; Maryam Shafei² ; Chiharu Myo² ; Keiko Kobayashi³ ; Yukiko Minamiyama⁴ ; Haruhiko .inufusa⁵ ; Toshikazu Yoshikawa⁶ ; ¹Doshisha University, Kyotanabe City, Japan; ²Major of Medical Life Systems, Graduate School of Life and Medical Sciences, Doshisha University, Kyotanabe City, Japan; ³Kyoto Prefectural University, Kyoto, Japan; ⁴Kyoto Prefectural University, KYoto, Japan; ⁵CEO, TIMA/Gifu University, Osaka, Japan; ⁶Louis Pasteur Center for Med. Res., Tohoku, Japan;
Paper Id: 219 [Abstract]

Ginseng has been reported about for its immunostimulation and its effects on various diseases such as obesity, diabetes and cancer. In this study, from the viewpoint of antioxidant and oxidative stress, the influence of ginseng on humans was examined. By using the MULTIple free-radical Scavenging (MULTIS method), we measured the scavenging activity of the reactive oxygen species: hydroxyl radical (・OH), superoxide radical (O₂^・-), alkyloxy radical (RO・), alkyl peroxy radical (ROO・), methyl radical (・CH₃), and singlet oxygen (¹O₂). We also evaluated the antioxidant capacity multifaceted. On the first day, subjects’ samples (plasma and saliva) were taken before ingesting ginseng tablets (n=5). After that, the samples were taken again, 4 hours after the administration of 18 tablets. They continued taking 18 tablets per day from the second day to the sixth day. On the seventh day, the samples were collected. The antioxidant capacity of the samples was examined using the MULTIS method. By ingestion of ginseng tablets, the ・OH scavenging activity of samples increased after 1 week. Also, plasma ・CH₃, and saliva O₂^・- scavenging activity increased. It was suggested that ginseng improved the antioxidant capacity of human.

References:
1. Chasing great paths of Helmut Sies "Oxidative Stress".
Majima HJ, Indo HP, Nakanishi I, Suenaga S, Matsumoto K, Matsui H, Minamiyama Y, Ichikawa H, Yen HC, Hawkins CL, Davies MJ, Ozawa T, St Clair DK
Archives of biochemistry and biophysics 595 54-60 2016
2. A mitochondrial superoxide theory for oxidative stress diseases and aging
Indo Hiroko P., Yen Hsiu-Chuan, Nakanishi Ikuo, Matsumoto Ken-ichiro, Tamura Masato, Nagano Yumiko, Matsui Hirofumi, Gusev Oleg, Cornette Richard, Okuda Takashi, Minamiyama Yukiko, Ichikawa Hiroshi, Suenaga Shigeaki, Oki Misato, Sato Tsuyoshi, Ozawa Toshihiko, St Clair Daret K., Majima Hideyuki J.
JOURNAL OF CLINICAL BIOCHEMISTRY AND NUTRITION 56(1) 1-7 2015

11:45: [OxidativeThuAM02]
Exposome-Induced Oxidative Stress and Protective Effects of Antioxidants in Rats
Yukiko Minamiyama¹ ; Keiko Kobayashi² ; Ririko Kawatani³ ; Hiroshi Ichikawa⁴ ; Shigekazu Takemura⁵ ; Fuhua (fukka) Yang (you)⁶ ; Haruhiko Inufusa⁷ ; Toshikazu Yoshikawa⁸ ; ¹Kyoto Prefectural University, KYoto, Japan; ²Kyoto Prefectural University, Kyoto, Japan; ³Graduate School of Life and Medical Sciences Doshisha University, Kyotanabe, Japan; ⁴Doshisha University, Kyotanabe City, Japan; ⁵Graduate School of Medicine, Osaka City University, Osaka, Japan; ⁶Gifu University Division of Anaerobe Research, Gifu, Japan; ⁷TIMA Japan Corporation, Gifu, Japan; ⁸Louis Pasteur Center for Med. Res., Tohoku, Japan;
Paper Id: 196 [Abstract]

The exposome can be defined as the totality of exposures (diet, lifestyle, occupational, and environmental factors) received by an individual throughout the entire lifetime. It is unclear how these exposures are related to health. There is an increasing trend to intake food additives due to food mileage extension and maintenance of a healthy lifestyle. Therefore, we investigated the effect of aspartame (APM), an artificial sweetener, and ortho-phenyl phenol (OPP), a broad-spectrum fungicide and antibacterial agent, on oxidative stress in rats. APM (250 mg/kg/day; 1/16 NOAEL) or OPP (1 &#u181;g/kg/day; 1/10⁵ NOAEL) were administered to rats for &#~8776;eight weeks, through their mixed diet and drinking water, respectively. Administration of both exposomes for two weeks led to a significant reduction in reactive oxygen specie (ROS)-scavenging ability for hydroxyl radicals in plasma. In epididymis and hippocampus, both exposome treatments increased the 4-hydroxy-2-nonenal (HNE) levels, an index of lipid peroxidation. APM treatment for two weeks increased ROS generation in sperms without motility changes. Moreover, APM treatment for eight weeks slightly decreased sperm motility. Furthermore, amyloid beta (Abeta) levels were significantly increased in both epididymis and hippocampus after two weeks of OPP administration, that may be related to male infertility and dementia. Pretreatment with the antioxidant Twendee X (20 mg/kg/day; TIMA Japan) inhibited the Abeta level increase in both tissues. In conclusion, our data indicate that some exposomes systemically induce oxidative stress and increase Abeta levels in both epididymis and hippocampus. These results suggested that effective antioxidants such as Twendee X can inhibit exposome-induced oxidative stress in male infertility and neurodegenerative diseases.

References:
1. Takemura S, Ichikawa H, Naito Y, Takagi T, Yoshikawa T, Minamiyama Y. S-allyl cysteine ameliorates the quality of sperm and provides protection from age-related sperm dysfunction and oxidative stress in rats.\nJ Clin Biochem Nutr. 2014 Nov;55(3):155-61.\n2. Minamiyama Y, Ichikawa H, Takemura S, Kusunoki H, Naito Y, Yoshikawa T. Generation of reactive oxygen species in sperms of rats as an earlier marker for evaluating the toxicity of endocrine-disrupting chemicals.\nFree Radic Res. 2010 Dec;44(12):1398-406.

12:10: [OxidativeThuAM03]
Understanding Oxidative Stress in Brain with Ultramicroelectrodes: Implications for a Possible Mechanism of Alzheimer Disease
Christian Amatore¹ ; ¹CNRS & PSL, French Acad. of Sci. and Xiamen University, Paris, France;
Paper Id: 323 [Abstract]

Oxidative stress is an essential metabolic outcome in aerobic organisms due to the activity of the mitochondria in providing the basic energy of cells or during the operation of several enzymatic pools. It also serves to regulate the size and shape of organs or restructure them during foetal development by apoptosis. Oxidative stress is also indispensable to the immune system by allowing macrophages to eliminate virus, bacteria and impaired or dead cells through phagocytosis [1]. In fact, no aerobic organism could live without oxidative stress: a fact that explains why evolution maintained such unsafe mechanisms in aerobic organisms. They are, however, associated to highly negative issues. Indeed, oxidative stress mechanisms provide a variety of life-harmful radicals and species called generically Reactive Oxygen Species (ROS) and Reactive Nitrogen Species (RNS) whose fluxes need to be finely controlled to avoid the destruction of most organic molecules (e.g., lipids in cell membranes, enzymes, etc.) and biological molecules (DNA, proteins, etc.) in cells. Thus, under normal conditions, a panoply of antioxidants and enzymatic systems ensures a fine homeostatic balance. Rupture of this delicate balance, however, is frequent and may provoke severe damages leading to human pathologies (aging, cancers, AIDS, hearth and brain strokes, Parkinson and Alzheimer’ diseases, etc.). Using platinized carbon fiber ultramicroelectrodes, we could establish the composition of primary oxidative stress in macrophages [1, 2] and characterize the nature of functional hyperemia in the brain [3]. This led us to formulate an alternative hypothesis about the onset of Alzheimer disease when Amyloid-β and ascorbate molecules are present [4, 5].

References:
1. K. Hu, Y. Li, S.A. Rotenberg, C. Amatore, M.V. Mirkin. J. Am. Chem. Soc., 141, 2019, 4564-4568.
2. C Amatore, S. Arbault, M. Guille, F. Lemaître. Chem. Rev., 108, 2008, 2585–2621.
3. C. Amatore, S. Arbault, C. Bouton, K. Coffi, J.-C. Drapier, H. Ghandour, Y. Tong. ChemBioChem, 7, 2006, 653-661.
4. R. Giacovazzi, I. Ciofini, L. Rao, C. Adamo, C. Amatore, Phys. Chem. Phys. Chem. (PCCP), 16, 2014, 10169-10174.
5. L. Lai, C. Zhao, M. Su, X. Li, X. Liu, H. Jiang, C. Amatore, X.M. Wang. Biomater. Sc., 4, 2016, 1085-1091.

12:35: [OxidativeThuAM04]
Oxidative Stress: Cancer and Oxidative Stress
Naomi Okada¹ ; Fuhua (fukka) Yang (you)² ; Haruhiko Inufusa³ ; ¹Gifu University, Gifu, Japan; ²Gifu University Division of Anaerobe Research, Gifu, Japan; ³TIMA Japan Corporation, Gifu, Japan;
Paper Id: 230 [Abstract]

Molecular targeting drugs were referred to as a paradigm shift in cancer treatment; it could not be beyond cytotoxic chemotherapy in terms of side effects and drug resistance. Only three treatments, namely surgery, chemotherapy and radiation have been the treatments for cancer for a long time. Because removal of cancer is the essence of these treatments, patients have been forced to carry a heavy burden. Various immunotherapies have been developed based on the theory, but almost all have failed. Immune checkpoint inhibitors (ICIs), however, which were the subjects of the Nobel Prize in Medicine and Physiology in 2018, have changed that aspect. Nivolumab, an immune checkpoint inhibitor, has dramatically improved the prognosis of melanoma which is one of the most refractory and poor-prone tumors. Melanoma is now followed by lung cancer, renal cancer, gastric cancer, and so on. ICIs make immune therapy the 4th cancer treatment. The most important thing is that immune therapy with ICIs is essentially different from the conventional three cancer treatments. ICIs work by adjusting the host side environment whereas the latter are is "artificially" eliminating cancer. ICIs only elicit the ability given by God to eliminate the cancer. As antioxidants also have effects on the environment of the host’s side. These effects have been used in combination with chemotherapy and radiotherapy. Antioxidants have two main effects. One is the prevention from adverse effects of chemotherapy and radiotherapy. Another is the anti-tumor effects. As for the former, the preventing effects from mucinous inflammation and neuropathy caused by chemotherapy and radiotherapy have been reported. The control of these symptoms is important because these adverse effects are the main reason for the discontinuation of the treatments. Many studies have shown that antioxidants have the effects of suppressing the activation of NF-kappaB which leads to cancer growth and apoptosis suppression. According to some reports of chemotherapy, radiotherapy and molecular targeted therapies may have more host-mediated pro-tumorigenic and pro-metastatic effects than anti-tumor effects. Such therapy induced host effects are said to have angiogenesis, metastasis, and tumor-cell repopulation properties which are resistant to therapy. Preliminary in vivo mouse experiments with anti-oxidant composition showed elimination of the pro-metastatic effects of chemotherapy. Tumor growth was observed with short term exposure of 5-FU. Although anti-oxidant composition alone had no anti-tumor effect, tumor growth with 5-FU was completely reversed by anti-oxidant composition. The modulation of host side factors may have the same effects as the treatment itself and antioxidants are considered to be able to become a main player of cancer treatments.

References:
1. Balancing efficacy of and host immune responses to cancer therapy: the yin and yang effects. Shbaked Y, Nat Rev Clin Oncol. 2016 Oct;13(10):611-26.\n2.Systematic Review: Generating Evidence-Based Guidelines on the Concurrent Use of Dietary Antioxidants and Chemotherapy or Radiotherapy. Akiko Nakayama, Karen P, Obianuju Lgbokwe, and Leffrey D. white. Cancer Invest.2011 Dec :29(10 ):655-667.

SESSION: OxidativeThuPM1-R5	Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings
Thu Oct, 24 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Toshikazu Yoshikawa; Shigeru Hirano; Session Monitor: TBA

14:00: [OxidativeThuPM105]
Oxidative Stress Disease (Free Radical Disease) and its Prevention - Appearance of the Effective Antioxidant Material
Toshikazu Yoshikawa¹ ; ¹Louis Pasteur Center for Med. Res., Tohoku, Japan;
Paper Id: 478 [Abstract]

It is widely known that oxidative stress causes many diseases. Free radical species triggering these results from transition metals, ischemia/reperfusion, drugs, inflammation, and environmental factors such as iron, and it causes the pathologies. Materials and mechanisms that are essential to the survival of many organisms including cells, protein and DNA is ruined by a free radical, causing many diseases, and these diseases were proposed that we called these oxidation stress diseases (free radical diseases) as a general term. A lot of specialized international journals about these are proud of the impact factor which is high in each. Although the disorder developmental mechanics and protective efficacy are studied in vitro and in animal experiments in detail, there is yet few antioxidative prevention or drugs to treat for those diseases in clinical studies using human. Drug RADICUT (cut a free radical according to the name. Generic name “Edaravone”) used for brain stroke treatment widely or vitamin E effective in non-alcoholic lipid hepatitis (NASH) are the representative examples. These and other antioxidants cannot be an effective means for treatment and prevention of many other oxidative stress diseases probably because of the characteristics of the drugs. Appearance of a versatile antioxidant material which expresses an effect of prevention and treatment for many oxidation stress diseases without showing any side effects has been waited for. A supplement named Twendee X which was the vitamins and amino acids complex showing strong antioxidant effect finally came up recently. Ingredients and composition ratio of Twendee X was developed to maximize its antioxidant effects. The randomized, double-blind placebo control study of dementia prevention using Twendee X for human with mild cognitive impairment (MCI) was conducted by Professor Koji Abe of the Okayama University, Department of Neurology. Surprisingly, the result showed its preventive effect of MCI progression with a significant difference [1], and, as for this antioxidant material, it has been suggested to be effective in the prevention and treatment of many oxidative stress diseases, and more results are expected in the future. Here, based on these results, I will discuss about possibility of prevention and treatment by antioxidant materials.

References:
[1] J Alzheimers Dis. 2019 Aug 24. doi: 10.3233/JAD-190644

14:25: [OxidativeThuPM106]
Role of Anti-oxidant Twendee X for Maintenance of Voice and Swallow
Shigeru Hirano¹ ; Haruhiko Inufusa² ; Toshikazu Yoshikawa³ ; ¹Kyoto Prefectural University of Medicine, Kyoto, Japan; ²TIMA Japan Corporation, Gifu, Japan; ³Louis Pasteur Center for Med. Res., Tohoku, Japan;
Paper Id: 266 [Abstract]

The larynx and pharynx have important roles in maintaining voice and swallowing functions. Age-related deterioration of vocal and swallowing functions has become a significant problem for the elderly which can lead to aspiration pneumonia in the worst cases. Age-related histological and functional deficit of the pharyngolaryngeal system is the main issue. The vocal fold, the producer of the voice, becomes atrophied and weak which causes glottic insufficiency with reduced mucosal vibration. The voice becomes harsh and weak. Glottic insufficiency also causes mis-swallowing. Laryngeal elevation and pharyngeal constriction are weakened with age which can lead to aspiration. We have confirmed that oxidative stress increases with age in the vocal fold mucosa and muscle, as well as the pharyngeal muscles. Reactive oxygen species (ROS) damage the tissue and hamper function. In the case of singers or other professional voice users, overuse of the vocal fold also causes damage to the function of the vocal fold via ROS. Anti-oxidants are the promising material that can maintain or improve the voice and the swallowing ability. We have revealed that anti-oxidants can maintain the vocal fold during excessive vocal loading tasks, avoiding inflammation or exhaustion of the vocal fold. Twendee X (TWX) has proven the strongest anti-oxidant, and our preliminary study demonstrated that an opera singer's voice was well maintained with the 1-month use of TWX. Another aspect of TWX is its capability to reduce allergic inflammation in the upper airway which is also important for protection of the pharyngolarynx. Anti-oxidants should be effective, useful, and promising for maintaining the pharyngolarynx which secures voicing and swallowing functions.

References:
[1]Inufusa H. Characterization of cell protection effects of Twendee X by oxidative stress. J World Mitochondria Soc 2016;2:42.
[2]Kaneko M, Kishimoto Y, Suzuki R, et al. Protective Effect of Astaxanthin on Vocal Fold Injury and Inflammation Due to Vocal Loading: A Clinical Trial. J Voice. 2017;31(3):352-358.

14:50: [OxidativeThuPM107]
Oxidative Stress: Does Continuous Oxidative Stress Reduction Prevent and Ameliorate Diseases through Species Diversity of Intestinal Bacteria?
Fuhua (fukka) Yang (you)¹ ; Kaori Tanaka² ; Haruhiko Inufusa³ ; ¹Gifu University Division of Anaerobe Research, Gifu, Japan; ²1) Division of Anaerobe Research, Life Science Research Center, Gifu University, Gifu, Japan; ³TIMA Japan Corporation, Gifu, Japan;
Paper Id: 226 [Abstract]

Intestines are said to be involved in 60% of human immunity. More than 100 species, or 100 trillions of bacteria (intestinal bacteria) inhabit in the intestines and those bacteria can be divided into bad bacteria that trigger diseases, good bacteria that are considered to benefit health, and opportunistic bacteria. Regarding 20% of good, 10% of bad, and 70% of opportunistic bacteria as an ideal balance of gut bacteria, this balance can be disturbed by diarrhea, constipation and various diseases. In other words, oxidative stress can reduce diversity of gut bacteria. In that case, how does reducing oxidative stress alter gut microflora, and how does reducing oxidative stress affect daily defecation? Although administering antiseptic agent OPP to rats for 2 weeks increased their blood oxidative stress by 5%, there were no significant changes of bacterial gut diversity. Rats, however, were given a strong antioxidant composition, Twendee X(TWX), from 1 week before OPP decreased their oxidative stress by 13.3% against control, and increased bacterial diversity by 1.5 times. Also, observation of the defecating condition and gut microflora of 57 healthy persons showed increased diversity index and improvement of the defecating condition after TWX administration. These results suggest that, even if exposed to toxic substances which results in oxidative stress, daily effort of decreasing oxidative stress can improve/prevent their host's diseases by increasing gut bacterial diversity.

References:
1. Novel compositions and uses thereof WO 2008071790 A3\n2. Antioxidant composition and its use in diabetes EP 1932542 A1\n3. Composition for accelerating alcohol metabolism and for reducing the risk of alcohol induced diseases WO 2012095509 A8\n4. Composition for moderating triglyceride and cholesterol levels WO 2009062910 A1

15:15: [OxidativeThuPM108]
Brain Disease and Oxidative Stress: Ischemia and Dementia
Haruhiko Inufusa¹ ; Koji Abe² ; Isao Tadokoro² ; Fuhua (fukka) Yang (you)³ ; Toshikazu Yoshikawa⁴ ; ¹TIMA Japan Corporation, Gifu, Japan; ²Department of Neurology, Graduate School of Medicine, Dentistry and Pharmaceutical Sciences, Okayama University, Okayama, Japan; ³Gifu University Division of Anaerobe Research, Gifu, Japan; ⁴Louis Pasteur Center for Med. Res., Tohoku, Japan;
Paper Id: 229 [Abstract]

Reactive Oxygen Species (ROS) are closely related to various diseases of the brain. Twendee X (TWX) is an antioxidant composition consisting of Vitamin C, L-Glutamine, L-Cystine or L-Cysteine, Riboflavin, Succinic acid, Fumaric acid, Coenzyme Q10, and Niacin. TWX was invented from the basic experiments of alcohol, glucose, and fat metabolisms (1-4). TWX strongly reduces ROS (Patent: WIPO WO2013/072441 A1, COMPOSITION FOR PROTECTION AGAINST CELL-DAMAGING EFFECTS). Lysozyme radiation experiments showed that the antioxidant effects of TWX are 6-7 times higher than Vitamin C (Data from Dr. Helmut Durschschlarg, Regensburg Univ. Germany). Oxidative stress and mitochondrial expert ICDD (France) experiments using hepatic cancer cell line HepG2 showed TWX decrease of 63% of mitochondrial ROS and an increase of 147% mitochondrial SOD. ICDD confirmed that TWX is safe and has most strong anti-ROS and protection effects from ROS. TWX increase Neogenesis nerves cell numbers of the hippocampal dentate gyrus of the 56 weeks mouse. The same occurs within 6 weeks by TWX administration. The mitochondrial metabolism of the mouse’s hippocampal dentate gyrus was activated by TWX administration by the metabolome analysis. The model of the brain of the mouse for ischemia and Alzheimer's disease were used to evaluate the effects of TWX. The double blind clinical trial of the Japanese Association for Prevention of Dementia from autumn 2017 to March 2019 for mild cognitive impairment was performed to analyze TWX prevention effects on Alzheimer's disease. TWX decreased volume of brain ischemia to 2/3, and inflammation and oxidative stress in the brain was also reduced in the mouse ischemia model. TWX inhibited deposition of amyloid beta. Inflammation and oxidative stress in the brain was also reduced in the mouse model of Alzheimer. Double blind clinical research resulted in the TWX group significantly increasing the score of the Mini Mental State Examination compared to the placebo group at 6 months after the start of TWX administration. Thus, TWX is effective to prevent Alzheimer's disease and vascular dementia.

References:
1. Novel compositions and uses thereof WO 2008071790 A3\n2. Antioxidant composition and its use in diabetes EP 1932542 A1\n3. Pretreatment Twendee X reduced acute ischemic brain damage. Kusaki M, Inufusa H, Abe K, JSCVD 2017; 26: 1191-1196\n4. Clinical and Pathological Benefit of Twendee X in Alzheimer's Disease Transgenic Mice with Chronic Cerebral Hypoperfusion. XiaLiu, Abe K https://doi.org/10.1016/j.jstrokecerebrovasdis.2019.03.029

SESSION: OxidativeThuPM2-R5	Intl. Symp. on Oxidative Stress for Sustainable Development of Human Beings
Thu Oct, 24 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Alexander Oleinick; Harry van Goor; Session Monitor: TBA

15:55: [OxidativeThuPM209]
Redox Status in Health and Disease
Harry Van Goor¹ ; Arno Bourgonje² ; Amel Eman Abdulle² ; Sanne Gordijn² ; Udo Mulder² ; Gerard Dijkstra² ; Andreas Pasch³ ; ¹UMCG, Groningen, Netherlands; ²University Medical Center Groningen and University of Groningen, Groninge, Netherlands; ³Johannes Kepler University Linz, Linz 4040, Austria;
Paper Id: 430 [Abstract]

Oxidative stress is characterized by an excessive production of reactive oxygen species (ROS) and decreased antioxidant availability. It is considered as a major effector mechanism responsible for extensive cellular and molecular damage, perpetuating chronic inflammation and increased tissue destruction. Serum free thiols (R-SH, sulfhydryl groups) are considered as a robust and powerful read-out of the systemic in vivo reduction-oxidation (redox) status. Systemic oxidative stress is associated with decreased levels of reduced free thiols, since thiols are rapidly oxidized by circulating reactive species. Blood proteins, mainly albumin, harbor the largest amount of redox-active thiol groups (approximately 75% of the total thiol pool). Typically, high extracellular concentrations of reduced free thiols are representative of a healthy redox status. We have examined systemic free thiol levels in a variety of (inflammatory) disease conditions, including pregnancy related, cardiovascular, renal, metabolic and rheumatological diseases. All these studies show a positive association between free thiol levels and favorable disease outcomes. Inversely, decreased free thiols have been linked to cardiovascular risk factors, such as ageing, obesity and alcohol consumption. In patient with Crohn’s disease in clinical remission systemic free thiols were still markedly reduced levels indicating the sensitivity of the Redox system as biomarker for (latent) disease. We evaluated free thiols in patients with inflammatory bowel disease and found them to be a strongly discriminating biomarker for endoscopic disease activity in IBD, even superiorly to classical fecal calprotectin levels. In a prospective clinical study that evaluated effects of dietary intake of the anti-oxidant riboflavin (vitamin B2) in Crohn’s disease, we observed significant improvement of systemic redox status after 3 weeks of riboflavin supplementation. This study highlights the potential significance of free thiols as therapeutic target of the redox signaling network in disease conditions. Finally, In a large population-based cohort (n=6000), the redox status was inversely associated with the risk of cardiovascular events and all-cause mortality (10 year follow up). All these data highlight the potential significance and clinical relevance of the Redox status as modifiable biomarker in both health and disease.

16:20: [OxidativeThuPM210]
Theoretical Aspects of Reactive Oxygen/Nitrogen Species Homeostasis inside Macrophages during Phagocytosis Monitored at Nanoelectrodes
Alexander Oleinick¹ ; Xin-wei Zhang² ; Irina Svir³ ; Christian Amatore⁴ ; Wei-hua Huang⁵ ; ¹CNRS-ENS-SU UMR 8640 PASTEUR, CNRS, Paris, France; ²Key Laboratory of Analytical Chemistry for Biology and Medicine, College of Chemistry and Molecular Sciences, Wuhan, China; ³Ecole Normale Superieure, Department Chemistry, PARIS, France; ⁴CNRS & PSL, French Acad. of Sci. and Xiamen University, Paris, France; ⁵Wuhan University, Wuhan, China;
Paper Id: 322 [Abstract]

Traffic of the lipid-enclosed compartments (vesicles, endosomes, phagosomes etc.) within the cell is extremely important for sustaining cell life and allowing the cell to perform its function. These lipid bilayer bound organelles deliver their cargo through bilayer fusion with the other organelles or with the plasma membrane. In the case when the release of the cargo molecule is controlled only by diffusion, we have shown earlier for the case of vesicular exocytosis that emptying of such organelles occurs exponentially and the rate of the exponential decay is controlled by the size of the fusion pore [1]. The generality of the assumptions made for model derivation, as well as for laws underlying this model, suggest that the assumptions can be applied to a vast variety of cases. This can be done independently if organelles fuse with another part like the cellular membrane or electrode (like in vesicle impact electrochemical cytometry), etc. Moreover, being able to describe mass transport of the cargo molecules inside or out of the organelle allow one to characterize various physicochemical processes occurring within the organelle [2]. In particular, relevantly adapted models were applied to the case of the detection with the platinized carbon nanoelectrode of the reactive oxygen/nitrogen species (ROS/RNS) produced by macrophages inside their phagolysosomes (more on the experiment will be presented in Prof. Wei-Hua Huang's talk) [3]. Modelling the oxidation and mass transport of the ROS/RNS towards the nanoelectrode and comparison with experimental data evidenced <u>for the first time</u> that the consumption of ROS/RNS by their oxidation at the nanoelectrode surface stimulates the production of significant ROS/RNS amounts inside phagolysosomes, i.e., proved the very existence of a ROS/RNS homeostasis during phagocytosis. The homeostatic production rates of ROS/RNS inside individual phagolysosomes were quantified by employing the developed theory [3]. These results allowed measuring the long-time postulated ROS/RNS homeostasis within the phagolysosome, its kinetics and its efficiency. ROS/RNS concentrations may then be maintained at sufficiently high levels to sustain proper pathogen digestion rates without endangering the macrophage internal structures [3].

References:
1. A. Oleinick, I. Svir, C. Amatore. Proc. R. Soc. A, 473, 2017, 20160684.\n2. A. Oleinick, I. Svir, W.-H. Huang, C. Amatore, in preparation.\n3. X.-W. Zhang, A. Oleinick, H. Jiang, Q.-L. Liao, Q.-F. Qiu, I. Svir, Y.-L. Liu, C. Amatore, W.-H. Huang. Angew. Chem. Ind. Ed., 58, 2019, 7753-7756.

16:45: [OxidativeThuPM211]
Electrochemical Monitoring of ROS/RNS Homeostasis Within Individual Phagolysosomes Inside Single Macrophages
Wei-hua Huang¹ ; ¹Wuhan University, Wuhan, China;
Paper Id: 321 [Abstract]

Reactive Oxygen/Nitrogen Species (ROS/RNS) produced by macrophages inside their phagolysosomes are closely related to immunity and inflammation by being involved in the removal of pathogens, altered cells, etc. The existence of a homeostatic mechanism regulating the ROS/RNS amounts inside phagolyso¬somes has been invoked to account for the efficiency of this crucial process, but this could never be unambiguously documented. Here, intracellular electrochemical analysis with platinized nanowires electrodes (Pt-NWEs) allowed monitoring of ROS/RNS effluxes with sub-millisecond resolution from individual phagolysosomes. These randomly impacted onto the electrode and were inserted inside a living macrophage. This evidenced for the first time that the consumption of ROS/RNS by their oxidation at the nanoelectrode surface stimulates the production of significant ROS/RNS amounts inside phagolysosomes. These results established the existence of the long-time postulated ROS/RNS homeostasis and allowed to quantify its kinetics and efficiency. ROS/RNS concentrations may then be maintained at sufficiently high levels for sustaining proper pathogen digestion rates without endangering the macrophage internal structures.

References:
[1] X. W. Zhang, Q. F. Qiu, H. Jiang, F. L. Zhang, Y. L. Liu, C. Amatore, W. H. Huang, Angew. Chem. Int. Ed. 56 (2017) 12997-13000.
[2] X. W. Zhang, A. Oleinick, H. Jiang, Q. L. Liao, Q. F. Qiu, I. Svir, Y. L. Liu, C. Amatore, W. H. Huang, Angew. Chem. Int. Ed. 58 (2019) 7753-7756.

SESSION: Ferro-alloysFriAM-R5	Flink International Symposium on Sustainable Production of Ferro-alloys (6th Intl. Symp. on Sustainable Production of Ferro-alloys)
Fri Oct, 25 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Alp Malazgirt; Johan Svensson; Session Monitor: TBA

11:20: [Ferro-alloysFriAM01] Plenary
A century of alloy production
Bo Flink¹ ; ¹Vargon Alloys AB, Vargön, Sweden;
Paper Id: 476 [Abstract]

In 1907 the large Göta river waterfalls in Trollhättan started to be developed to produce electric energy, more or less, simultaneously negotiations were ongoing with Wargön Bruk AB to acquire the fall rights at Wargön Bruk AB’s property in the same Göta river about 7 km upstream from Trollhättan. A contract was signed where Trollhättan’s Vattenfall acquired the fall rights but Wargöns Bruk AB had to accept a 40-year long contract to pay for 4000 hp consumed or not. Everybody was happy until the first invoice arrived, and no plans were done on how to consume 4000 hp. After a quick survey in the paper mill, a possible consumption of 1000 hp were found where to consume the rest The following was found and discussed; One of the major owners of the company had a manganese mine in his possession Tests to produce SiMn had been performed in Norway with good results. Char coal if needed was available, within the company to be used as reducing assets Good quality quartzite was available at 100 km north of the company and could be shipped by a vessel over the lake Vänern Second-hand equipment could be purchased in Trollhättan The electric power was available In December 1911 it was decided to build a ferroalloy plant close to the paper and pulp plant, and just at 100 m from the river. In January 1913 a board meeting tells that the alloy plant produced about 600 tonnes of SiMn and FeSi during 1912. A century later the alloy plant still exists on the same spot. The paper and pulp mill is closed for some years. That mill was sold already in 1969 and the alloy plant lived by itself. The alloy plant has today 4 units and is producing HC FeCr of various grades. It is procured with raw materials (Chrome ore) from the group’s own mines in Turkey and Kazakhstan. As initially, the company operated as an integrated plant producing various Manganese products using company Manganese ore resources it is today back as an integrated producer. Now for various Cr-products with based on internal Chrome ore resources.

11:45: [Ferro-alloysFriAM02]
The First Application of Underground Fully Mechanized Mining Method on Turkey Chrome Mining Industry
Hasan Giray¹ ; ¹Eti Krom, Merkez, Turkey;
Paper Id: 398 [Abstract]

Fully mechanized underground mining is a valuable method to achieve sustainable development in the mining industry because it achieves simultaneously (1) economic growth and profitability by increasing efficiency and decreasing cost (2) protects the environment by decreasing the specific use of energy and as a result decreasing CO2 emissions and (3) develops the society by reducing and eliminating the life and accidental risks of the miners and improving their quality of life since a part of the increased additional profit of the company is distributed to them also to their community. This paper the experience and results of applying for the first time in the chrome industry of Turkey of an underground fully mechanized method along with its multiple advantages.

12:10: [Ferro-alloysFriAM03] Plenary
Control and Optimization of FeSiMn Alloy Production through FLOGEN CONTOP System
Thamara Rodrigues Silva¹ ; Igor Tiago Santos¹ ; Josenilson Braga Maia¹ ; Rodrigo Junqueira Dos Santos Santos¹ ; Marcos De Souza² ; Florian Kongoli³ ; ¹Maringa, Sao Paulo, Brazil; ²FLOGEN Technologies Inc, Sao Paulo, Brazil; ³FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 487 [Abstract]

FLOGEN Decision Making, Control and Optimization system has been applied to the production of FeSiMn alloy production in an electric furnace. This resulted in simultaneously reducing the specific energy consumption, decreasing Mn losses in the slag, better control of allow specifications and greater flexibility in using multiple raw materials. This paper will present the general features and control system as well as the main results

12:35: [Ferro-alloysFriAM04] Keynote
Falconbridge Dominicana (Falcondo) a Sustainable Producer of FeNi
Panagiotis Kouzoupis¹ ; Ioannis Moutafis² ; ¹Falconbridge, BONAO, Dominican Republic; ²Falconbridge Domenicana S.A., BONAO, Dominican Republic;
Paper Id: 482 [Abstract]

Falconbridge Dominicana (Falcondo) has a long operating history since 1955 and in August 2015 Americano Nickel Ltd acquired the company from Swiss miner Glencore. After two interruptions to operations in the periods 2008-2011 and 2013-2016, the company resumed production in April 2016 under new management. With a total installed Ni capacity of 32000 t annually, it makes Falcondo one of the 10 biggest producers worldwide. The main difficulties that were required to confront were: market conditions, loss of customers after the period of care and maintenance, and an atmosphere of uncertainty and mistrust within the country. Falcondo managed to overcome the difficulties taking initiatives to increase profitability, through the introduction of new and more effective methodologies and technologies, both in the mining operation and in the operation of the plant, reducing also the environmental impact. Falcondo won the price of the biggest exporter in the Dominican Republic for 2019 and in that way the country takes a position between the biggest exporters of Ferronickel together with China, Finland, the United States, Italy, Netherlands, Switzerland, Spain, South Africa, Sweden, and India. In this paper, factors that made Falcondo a successful sustainable producer of Fe-Ni in terms of economic growth, environmental protection and social development along with the description of the process and technological improvements

SESSION: Ferro-alloysFriPM1-R5	Flink International Symposium on Sustainable Production of Ferro-alloys (6th Intl. Symp. on Sustainable Production of Ferro-alloys)
Fri Oct, 25 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Florian Kongoli; Gregor Borg; Session Monitor: TBA

14:00: [Ferro-alloysFriPM105]
Development Of Technology Of Manganese Alloys Production From Poor Dust And Carbonate Ores In Unit SER
Valentin Tsymbal¹ ; Inna Rybenko¹ ; Eugene Protopopov¹ ; Pavel Sechenov¹ ; Florian Kongoli² ; ¹Siberian State Industrial University, Novokuznetzk, Russian Federation; ²FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 394 [Abstract]

Self-organizing jet emulsion reactor (SER), during generation of which some principles of theory of self-organization and a number of interesting physical effects were used, is of certain degree of universality. Pilot installation has demonstrated possibility of implementing several low-energy and even waste-free technologies on it, including: direct reduction of dust-type ores and waste without agglomeration, production of manganese alloys from poor dust-type concentrates, waste-free separation of titanium-magnetite concentrates into metal and conditioned titanium slag, etc. Presented report focuses on technology of direct reduction of manganese in JESI from dust-type ores and concentrates, including oxidized and carbonate ones. Specifics of technology is generation of full cycle of combustion products recycling, which allow for preliminary recovery or roasting of manganese ores in fluosolid unit connected to the output of the main unit, and reduction of energy costs for production of manganese alloys.

14:25: [Ferro-alloysFriPM106]
Bear Metallurgical - a Sustainable Company in Ferro-alloys Production
David Carey¹ ; ¹Bear Metallurgical Company, Butler, United States;
Paper Id: 399 [Abstract]

Founded in 1990, Bear Metallurgical Company (“Bear”) is the sole independent toll converter of ferrovanadium and the largest producer of ferromolybdenum in the United States. The core business of the Company is the toll conversion of vanadium oxide to ferrovanadium and the conversion of molybdenum oxide to ferromolybdenum. Since its founding, the company has developed and adopted various advanced production and managing practices to achieve a sustainable development of the company as a leader in ferro-alloys production. This paper gives an overview of the company history, its industrial processes and its products and then focuses on measures undertaken to achieve a sustainable development that simultaneously achieve (1) economic growth by adopting lean production principles that increase the quality and efficiency and reduce cost (2) protection of the environment by adopting high recyclability and waste treatment schemes and (3) development of the society by increasing the quality of the working conditions, assuring accident free production for record lengths of time and helping communities in the area.

14:50: [Ferro-alloysFriPM107]
ORIEN Technology - An Innovative Solution in Ferro-Alloy Production
Genrikh Dorofeev¹ ; Nikolai Ashpin² ; Florian Kongoli³ ; ¹Ferro-Technology, Moscow, Tula, Russian Federation; ²Ferro-Technology, Tula, Russian Federation; ³FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 485 [Abstract]

The main method of production of the most common ferroalloys such as ferromanganese, ferrosilicon, ferrochromium is the electric furnace. The energy of this furnace is based on the combined use of electrical energy to create the necessary heat that is released in the area of ​​the electrodes as well as in the charge when an electric current passes through it. The advantages and disadvantages of this method of supplying energy are well known. One of the disadvantages is increased energy consumption and reduced productivity. ORIEN Technology is a new method for producing of ferroalloys, which differs from the existing methods of using electric arc heating as a heat source, which is typical for electric arc steel furnaces operating with high electric voltage. The most characteristic feature of this innovative solution is the combination of raw material supply and carbothermic reductions by preliminary agglomeration ore (as raw materials) with carbon (as a reducing agent) and continuous supply of agglomerated materials into the combustion zone of the electric arc. This method is a further development of steel production technology - that bear the same name: ORIEN process. This new technology reduces energy consumption, increases productivity, expands the range of ferroalloys and improves their quality. This process can use natural ore as raw materials as well as poor ores with low content of alloy elements.

15:15: [Ferro-alloysFriPM108] Plenary
A game-changing technology in mineral processing by high-velocity impact comminution with the VeRo Liberator®
Gregor Borg¹ ; Oscar Scharfe² ; ¹VeRo Liberator, Hamburg, Halle, Germany; ²VeRo Liberator, Hamburg, Hamburg, Germany;
Paper Id: 387 [Abstract]

As the highly respectable Mining Journal (issue 20. May 2019) recently stated: “Mining may have pedigree, with its roots in the Bronze Age, but with direction and momentum established over some 5,000 years it also has the turning circle of the QEII and, as such, has long been regarded as an innovation and technology laggard among industries.” This reputation is currently changing fast with major international mining companies and the World Bank Group jointly promoting “The growing role of Minerals and Metals for a Low Carbon Future” [1]. Traditional comminution systems for ores such as ball and SAG mills are trusted for their robustness but also known for their inefficiency, particularly in energy consumption and general rock breakage [2]. With more than 50 % of energy being consumed in a typical mining operation for crushing and milling and – even worse – only 1 % of the energy consumed by a conventional ball mill used for breakage and the rest wasted as heat, there is huge potential for radical improvement. The VeRo Liberator^® was invented some 6 years ago and achieves high-velocity, high-frequency impact comminution through a vertical four-fold axle-in-axle system with hammer tools, rotating clockwise and anticlockwise [3]. The impacts produce highly turbulent particle flow and trigger fracture nucleation and propagation at and along phase boundaries. With energy consumption being reduced by over 70 % and particle liberation far superior to conventional systems, this new technology offers huge operational and economic advantages. The VeRo Liberator^® operates dry and thus produces waste that does not require dewatering and allows for safer direct dry stacking. The VeRo Liberator^® achieves its drastically energy-efficient particle size reduction and particle liberation by high-velocity impacts that achieve an efficient momentum transfer into the ore particles. This leads to the disintegration or quasi “explosion” of the ore particles, predominantly without actual contact with the impact tools. Consequently, the VeRo Liberator^® uses less energy, shows surprisingly little wear, and operates at very low noise levels. Market entry of the VeRo Liberator^® technique was achieved in 2017 and several units are now performing in industrial-scale operations or are on their way to installation for Anglo American. It is now up to the wider mining industry to test and embrace the new technology and develop it to its full potential.

References:
[1] The World Bank (2017) The growing role of Minerals and Metals for a Low Carbon Future, Washington, DC, USA, 92 p.
[2] Napier‐Munn T (2014) Is progress in energy‐efficient comminution doomed? Minerals Engineering, Vol. 73, 1–6.
[3] Borg G, Scharfe F, Scharfe O, Lempp Ch (2018) Mechanical high‐velocity comminution by VeRo
Liberator® technique for efficient particle liberation and size reduction. AT Mineral Processing,
Vol. 59, 04, 66‐80.

SESSION: Ferro-alloysFriPM2-R5	Flink International Symposium on Sustainable Production of Ferro-alloys (6th Intl. Symp. on Sustainable Production of Ferro-alloys)
Fri Oct, 25 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Danica Fazekašová; Oscar Scharfe; Session Monitor: TBA

15:55: [Ferro-alloysFriPM209]
FerroMolybdenum Production at Bear Metallurgical Company
Michael Hart¹ ; ¹Bear Metallurgical Company, Butler, United States;
Paper Id: 407 [Abstract]

The production of ferromolybdenum at Bear Metallurgical is carried out by reducing the Molybdenum Trioxide (MoO3), contained in primary or recycled materials using FeSi (and sometimes aluminum) as a main reductant, iron or iron oxide as alloy formation agents and lime as slag conditioner in a so-called silicothermic reaction which provides the necessary heat for the process and avoids the need for extra sources of energy. In this paper, the production flowsheet from the receipt of the primary materials, to batching, blending, smelting and then crashing, sampling, product specifications and quality testing are described along with the characteristics of this special silicothermic process related to molybdenum reaction, its speed energy and temperature, furnace separation, process control, efficiency as well as and its special reactor furnace

16:20: [Ferro-alloysFriPM210]
FerroVanadium Production at Bear Metallurgical Company
Michael Hart¹ ; ¹Bear Metallurgical Company, Butler, United States;
Paper Id: 403 [Abstract]

The production of ferrovanadium at Bear Metallurgical is carried out by reducing the Vanadium Pentoxide (V2O5) contained in ores or in recycled materials using aluminum as a reductant and iron as alloy formation agent in a so called violent Aluminothermic reaction which is properly controlled during the process. Although the process is straightforward, the nuances in the production make it a complex one. In this paper the production flowsheet from the feed preparation to blending, from smelting to product specifications and quality testing are described along with the characteristics of this special aluminothermic process related to its speed and temperature, its control and efficiency as well as and its special reactor furnace.

16:45: [Ferro-alloysFriPM211]
Behavior of the Major, Trace and Rare Earth Elements Into Lateritic Weathering on Gentio do Ouro Golden District, State of Bahia, Brazil
Francisco Souza¹ ; Nathane Souza² ; ¹IFPB, Campina Grande, Brazil; ²UFRN, Natal, Brazil;
Paper Id: 412 [Abstract]

The Gentio do Ouro Golden District is located on the western edge of the Chapada Diamantina, the central region of the State of Bahia, Brazil. The principal ore-related geological caracteristics of the study are include the presence of Proterozoic gabbroic sills in the lower portion of the Espinhaço Supergroup [1]. The mafic sills were subsequently affected by hydrothermal (metasomatic) alteration that is associated with the emplacement of a first phase of gold mineralization along the contacts between the sills and the wall rocks [2]. Quaternary surface weathering [3] led to the development of thick zones of supergene alteration predominantly developed along topographic highs and which include saprolit, latossol, duricrust and pisolite. Protolithe composition was established geochemically and more particularly through the sydtemstic use of the Fe2O3 (T)/MgO ratio that is considered to be representative of the initial composition of the rocks. The formation of supergene-altered layers through weathering under lateritic conditions, evolved from the parental rocks towards saprolit-latossol-duricrust-pisolite, predominantly in response to partial dessilicification and coprecipitation of trace elements with iron oxides/hydroxides. The dissolution of primary gold occurred in the presence of chemical complexes such as sulphates and sulphites, were produced by the oxidation hydrothermal auriferous sulphides in the presence of carbonates [4]. Mobilized gold was transported under oxidizing conditions as colloidal gold and subsequently precipitated in an array of ferraneous fractures, or filling micro-cavities [5]. The lateritic weathering processes responsible for the mobilization of gold and its secondary precipitation are responsible for its local enrichment, an increase of purity (all other associated trace metals being separated from gold), and, ultimately in the development of nuggets in lateritic materials. Samples of the parent rock and its lateritic products were search for geochemistry with the purpose to study the mobilization and concentration of major, trace and rare earth elements on profile of chemical weathering of gabbroic rocks. The geochemical analysis for major and trace elements was measured by atomic absorption spectrophotometry and ICP – inductively coupled plasma. The results for lanthanides was normalized to chondrites [6].

References:
[1] F.F.M. Almeida. Rev Bras Geociências 7(4) (1977) 349-364.
[2] F.A. Souza. UFBA (1992) 140P.
[3] I.G. Carvalho. UFBA (1985) 59p.
[4] I.G. Carvalho, S.S.P. Mestrinho, V.M.S. Fontes, O.P. Goel, F.A. Souza. Jour. Geochem. Exploration 40 (1991) 385-411.
[5] F.A. Souza, N.V.L. Souza, J.S.I. Santos. Gacmac-Quebec (2019) 175.
[6] N.M. Evensen, P.J. Hamilton, R.K. O’Nions. Geochim Cosmichim Acta 42 (1978) 4792-4805.

SESSION: MiningSatAM-R5	Parameswaran International Symposium on Sustainable Mining and Smelting Operations (6th Intl. Symp. on Sustainable Mining Operations)
Sat Oct, 26 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Lang Liu; Wenchen Li; Session Monitor: TBA

11:20: [MiningSatAM01] Plenary
From Silk Purses and Lead Baloons to Mining and Sustainable Development: A Wonderful Journey
Krishna Parameswaran¹ ; ¹tfgMM Strategic Consulting, Scottsdale, United States;
Paper Id: 469 [Abstract]

My career as a metallurgist with a U.S. copper mining company ASARCO LLC (Asarco) has been bookended with stints of consulting with Arthur D. Little, Inc (A.D. Little) before my tenure at Asarco and with tfgMM Strategic Consulting, a firm I founded after retiring from Asarco in 2015. This paper discusses how my consulting experience prepared me for my sustainability journey. Dr. Arthur Dehon Little, a Massachusetts Institute of Technology chemist who co-founded the company believed that science and technology can be used to solve societal problems and is illustrated by two examples—making a silk purse from a sow’s ear and flying a lead balloon. My sustainability journey began with the presentation in Bhubaneswar, India of a paper co-authored with Asarco’s Vice President of Governmental Affairs in 1998. That paper examined the trends facing the mining industry, one of which was the application of sustainable development principles to mining. The last 15 years of my tenure at Asarco provided an in-depth opportunity to research and be involved in projects that promoted sustainable development. Based on the classic Brundtland Commission definition of sustainable development as “development that meets the needs of the present without compromising the ability of future generations to meet their own needs,” this paper describes how metal mining can be compatible with sustainable development and how sustainability considerations have been applied in the primary copper industry, using selected examples of sustainable mining past and current practices from Asarco operations. The metals mining, smelting and refining industry has been and will continue to be an essential contributor to the economic and social development for generations to come. The demand for minerals and metals will grow to satisfy the needs of a growing world population which is anticipated to grow from 7.7 billion to 9.6 billion by 2050. In order to meet the challenge of declining ore grades, industry will have to focus on increasing productivity through automation, big data analytics and technological and business innovation. It will face challenges related to regulation, geopolitical risks and demands for increasing transparency from increased scrutiny from shareholders, investment community and the public. There will be pressures to transition to a low-carbon economy. Companies in order to succeed in this environment will have to skillfully navigate these challenges and seize on the opportunities. The papers to be presented in this Symposium address the technical, environmental and socio-political aspects of sustainable development as applied to mining. Finally, this paper discusses how these considerations might be used in the future by discussing the need for developing a sustainable development strategy and how this strategy can be aligned with the United Nations Sustainable Development Goals.

11:45: [MiningSatAM02] Keynote
Sulphate Effect on Strength and Self-desication Development of Cemented and Slag-Cemented Paste Backfill
Wenchen Li¹ ; Lijie Guo¹ ; ¹Beijing General Research Institute of Mining and Metallurgy, Beijing, China;
Paper Id: 425 [Abstract]

This paper presents an experimental study on the strength and suction evolution of cemented paste backfill (CPB) and CPB that contains blast furnace Slag (Slag-CPB) with different content of sulphate at early ages. CPB and Slag-CPB with 0, 5,000, 15,000 and 25,000 ppm sulphate content were prepared and cured at room temperature (20°C) for 1, 3, 7 and 28 days. Mechanical, hydraulic conductivity test and microstructural analyses were performed on the studied samples, suction and electrical conductivity of the samples were monitored. The results show that sulphate has a significant negatively effect on the early age strength and suction evolution of CPB and can lead to a positive or negative effect on Slag-CPB i.e., cause an increase or decrease in strength and acceleration or reduction in the amount and rate of self-desiccation. Inhibition of cement hydration and pozzolanic reaction, ettringite induced coarseness of pore structure and sulphate absorption by C-S-H are found as main reasons that affect CPB strength and suction evolution. This study has demonstrated that the effect of sulphate on the early strength and self-desiccation of CPB is an important factor for consideration in the designing of cost-effective, safe and durable CPB structures as well as using slag for reducing the mining cycle time in sulphide mines.

References:
[1] Kesimal A, Ercikdi B, Yilmaz E. The effect of desliming by sedimentation on paste backfill performance. Minerals Engineering. 2003;16(10):1009-11.
[2] Grice AG. Recent minefill developments in Australia. Minefill 2001: 7 th International Symposium on Mining with Backfill2001. p. 351-7.
[3] Yilmaz E, Kesimal A, Ercikdi B. Strength development of paste backfill samples at long term using two different binders. Proceedings of the 8th symposium on mining with backfill2004. p. 281-5.
[4] Fall M, Pokharel M. Coupled effects of sulphate and temperature on the strength development of cemented tailings backfills: Portland cement-paste backfill. Cement and Concrete Composites. 2010;32(10):819-28.
[5] Pokharel M, Fall M. Combined influence of sulphate and temperature on the saturated hydraulic conductivity of hardened cemented paste backfill. Cement and Concrete Composites. 2013;38:21-8.
[6] Fall M, Benzaazoua M, Saa E. Mix proportioning of underground cemented tailings backfill. Tunnelling and Underground space technology. 2008;23(1):80-90.
[7] Abo‐El‐enein S, Ata A, Hassanien A. Kinetics and mechanism of slag cement hydration. Journal of Chemical Technology and Biotechnology. 1982;32(7‐12):939-45.
[8] Ramlochan T, Zacarias P, Thomas M, Hooton R. The effect of pozzolans and slag on the expansion of mortars cured at elevated temperature: Part I: Expansive behaviour. Cement and Concrete Research. 2003;33(6):807-14.
[9] Hou W-M, Chang P-K, Hwang C-L. A study on anticorrosion effect in high-performance concrete by the pozzolanic reaction of slag. Cement and Concrete Research. 2004;34(4):615-22.
[10] Osborne G. Durability of Portland blast-furnace slag cement concrete. Cement and Concrete Composites. 1999;21(1):11-21.
[11] Idorn GM, Roy DM. Factors affecting the durability of concrete and the benefits of using blast-furnace slag cement. Cement, concrete and aggregates. 1984;6(1):3-10.
[12] Pal S, Mukherjee A, Pathak S. Investigation of hydraulic activity of ground granulated blast furnace slag in concrete. Cement and Concrete Research. 2003;33(9):1481-6.
[13] Pokharel M, Fall M. Coupled Thermochemical Effects on the Strength Development of Slag-Paste Backfill Materials. Journal of Materials in Civil Engineering. 2011;23(5):511-25.
[14] Grice T. Underground mining with backfill. Proceedings of the 2nd Annual Summit-Mine Tailings Disposal Systems. 1998:234-9.
[15] Bloss M. Below ground disposal (mine backfill). Paste and Thichened Tailings: a guide, ed Jewell, Fourie and Lord, University of Western Australia. 2002:103-26.
[16] Belem T, Benzaazoua M, Bussière B. Utilisation du remblai en pâte comme support de terrain. Partie I: De sa fabrication à sa mise en place sous terre. Après-mines 2003. 2003:5-7.
[17] Sherwood P. Effect of sulfates on cement-and lime-stabilized soils. Highway Research Board Bulletin. 1962(353).
[18] Fall M, Benzaazoua M. Modeling the effect of sulphate on strength development of paste backfill and binder mixture optimization. Cement and Concrete Research. 2005;35(2):301-14.
[19] Ghirian A, Fall M. Coupled Behavior of Cemented Paste Backfill at Early Ages. Geotechnical and Geological Engineering. 2015:1-26.
[20] Ghirian A, Fall M. Coupled thermo-hydro-mechanical–chemical behaviour of cemented paste backfill in column experiments. Part I: Physical, hydraulic and thermal processes and characteristics. Engineering Geology. 2013;164:195-207.

12:10: [MiningSatAM03]
Functional Backfill and Its Future in Mining
Lang Liu¹ ; ¹XI'AN University of Science and Technology, Xi'an, China;
Paper Id: 422 [Abstract]

Backfill technology is regarded as an important technological carrier to realize safe, green and efficient deep mining [1]. According to the coupled problems of high-stress, high-temperature and multitudinous-goaf, etc., in deep mines, as well as high-cost of backfill mining, an academic ideal of Functional Backfill (FB) was put forward. The proposed FB can not only realize the function of traditional backfill, but can also achieve the expanded functions, i.e., cold-loading, heat-saving, energy-storage, seepage-proofing, etc. Firstly, the concepts of Functional Backfill Materials (FBM) and Functional Backfill Technology (FBT) were scientifically defined, and the conceptual model of the FBM was established. Secondly, from the functional point of backfill materials, the evolution process of backfill technology can be divided into three stages, e.g., volumetric backfill, structural backfill and functional backfill. Finally, on the basis of backfill material functions, the functional backfill were classified as Cold Load /Storage-Functional Backfill (CLS-FB) [2-3], Heat Storage & Release-Functional Backfill (HSR-FB) and Cavity-building -Functional Backfill (CB-FB). Correspondingly, the concepts, functions and basal principles of the mentioned three functional backfill were presented in detail. The application and exploration of functional backfill materials & technologies will further improve the backfill technologies in mines, which have an important and far-reaching impact on the deep mine geothermal co-exploitation, underground goaf reuse and strategic energy reserves, etc.

References:
[1] H.J. Lu, C.C. Qi, Q.S. Chen, D.Q. Gan, Z.L. Xue, Y.J. Hu. J. Clean Prod. 188 (2018) 601-612.
[2] M. Wang, L. Liu, X.Y. Zhang, L. Chen, S.Q. Wang, Y.H. Jia. Appl. Therm. Eng.150 (2019) 121-131.
[3] L. Liu, Z.Y. Fang, C.C. Qi, B. Zhang, L.J. Guo, K.I.-I.L. Song. Powder Technol. 343(2019), 454-464.

12:35: [MiningSatAM04]
Required strength evaluation model and its application for vertically exposed backfill: inspired by Mitchell’s physical model tests
Guangsheng Liu¹ ; Lijie .guo² ; Xiaocong Yang¹ ; ¹BGRIMM Technology Group, Beijing, China; ²Beijing General Research Institute of Mining & Metallurgy, Beijing, China;
Paper Id: 418 [Abstract]

Cemented paste backfill is an increasingly popular technique to improve ground stability in underground mines[1]. This technique is used in several mining methods that require strength evaluation for the vertically exposed cemented backfill following the excavation of an adjacent stope on one side. The critical strength is generally evaluated with an analytical solution proposed by Mitchell et al. [2]. Despite its wide acceptance in academia and application in the mining industry, the Mitchell solution has received only a few updates in the literature, including some new developments given by the authors and colleagues[3]. The original Mitchell solution and its variants were mainly validated against the physical model test results obtained by Mitchell et al. [2]. Even though the Mitchell model debatably assumed a zero backfill friction angle, the required strengths predicted by the Mitchell solution corresponded quite well to those obtained by physical model tests[4]. This study reanalysed the Mitchell solution and its physical model. The testing conditions and procedures for measuring the shear strength parameters are investigated. The stability of the cemented backfill upon removal of a confining wall is analysed with FLAC3D. The comparisons between the numerical modellings, experimental results and analytical solutions are presented, and the applicable range of the classical Mitchell solution is discussed. A new analytical solution is proposed to evaluate the minimum required strength of the cemented backfill confined by two sidewalls exposed on one side and subject to pressure from uncemented backfill on the opposite side. The proposed analytical solution is validated by numerical simulations with FLAC3D. The proposed analytical solution is used to determine the theoretical strength requirement of cemented backfill in primary stopes of an iron mine that employs stage stoping with subsequent backfill mining. The floating Factor of Safety (FS) characterising the current backfilling quality control level of this mine was statistically evaluated with a large amount of uniaxial compressive strength (UCS) data after testing vast drilled samples from field stopes. The engineered strength requirement of the cemented backfill in primary stopes had been finalised by combining the analytical results and floating FS of the mine.

References:
[1] B.D. Thompson, W.F. Bawden, M.W. Grabinsky, Canadian Geotech. J. 49 (2012) 755–772.
[2] R.J. Mitchell, R.S. Olsen, J,D. Smith., Canadian Geotech. J. 19 (1982) 14–28.
[3] L. Li, M. Aubertin, Int. J. Mining Sci. Tech. 24 (2014) 549–558.
[4] G.S. Liu, L. Li, X.C. Yang, L.J. Guo, Int. J. Mining Sci. Tech. 24 (2016) 549–558.

SESSION: MiningSatPM1-R5	Parameswaran International Symposium on Sustainable Mining and Smelting Operations (6th Intl. Symp. on Sustainable Mining Operations)
Sat Oct, 26 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Danai Tsakiri; Guangsheng Liu; Session Monitor: TBA

14:00: [MiningSatPM105] Keynote
A game-changing technology in mineral processing by high-velocity impact comminution with the VeRo Liberator® pt.2
Gregor Borg¹ ; Oscar Scharfe² ; ¹VeRo Liberator, Hamburg, Halle, Germany; ²VeRo Liberator, Hamburg, Hamburg, Germany;
Paper Id: 503 [Abstract]

As the highly respectable Mining Journal (issue 20. May 2019) recently stated: “Mining may have pedigree, with its roots in the Bronze Age, but with direction and momentum established over some 5,000 years it also has the turning circle of the QEII and, as such, has long been regarded as an innovation and technology laggard among industries.” This reputation is currently changing fast with major international mining companies and the World Bank Group jointly promoting “The growing role of Minerals and Metals for a Low Carbon Future” [1]. Traditional comminution systems for ores such as ball and SAG mills are trusted for their robustness but also known for their inefficiency, particularly in energy consumption and general rock breakage [2]. With more than 50 % of energy being consumed in a typical mining operation for crushing and milling and – even worse – only 1 % of the energy consumed by a conventional ball mill used for breakage and the rest wasted as heat, there is huge potential for radical improvement. The VeRo Liberator^® was invented some 6 years ago and achieves high-velocity, high-frequency impact comminution through a vertical four-fold axle-in-axle system with hammer tools, rotating clockwise and anticlockwise [3]. The impacts produce highly turbulent particle flow and trigger fracture nucleation and propagation at and along phase boundaries. With energy consumption being reduced by over 70 % and particle liberation far superior to conventional systems, this new technology offers huge operational and economic advantages. The VeRo Liberator^® operates dry and thus produces waste that does not require dewatering and allows for safer direct dry stacking. The VeRo Liberator^® achieves its drastically energy-efficient particle size reduction and particle liberation by high-velocity impacts that achieve an efficient momentum transfer into the ore particles. This leads to the disintegration or quasi “explosion” of the ore particles, predominantly without actual contact with the impact tools. Consequently, the VeRo Liberator^® uses less energy, shows surprisingly little wear, and operates at very low noise levels. Market entry of the VeRo Liberator^® technique was achieved in 2017 and several units are now performing in industrial-scale operations or are on their way to installation for Anglo American. It is now up to the wider mining industry to test and embrace the new technology and develop it to its full potential.

References:
[1] The World Bank (2017) The growing role of Minerals and Metals for a Low Carbon Future, Washington, DC, USA, 92 p.
[2] Napier‐Munn T (2014) Is progress in energy‐efficient comminution doomed? Minerals Engineering, Vol. 73, 1–6.
[3] Borg G, Scharfe F, Scharfe O, Lempp Ch (2018) Mechanical high‐velocity comminution by VeRo
Liberator® technique for efficient particle liberation and size reduction. AT Mineral Processing,
Vol. 59, 04, 66‐80.

14:25: [MiningSatPM106]
A Comparative Study Between Surface and Physicochemical Properties of Materials Produced by Oxalic and Sulphuric Acid Activation on Different Smectite Samples
Danai Tsakiri¹ ; Iliana Douni¹ ; Maria Taxiarchou¹ ; ¹National Technical University of Athens, Athens, Greece;
Paper Id: 245 [Abstract]

Acid activation of clays is a process in which sulphuric acid is usually used in order to obtain a material with enhanced surface properties. Several researchers have studied acid activation of aluminosilicates by using mineral acids. An alternative method to sufficiently producing acid activated minerals with eliminated environmental cost, however, could be achieved by using oxalic acid. Oxalate is a polyfunctional organic acid that forms strong complexes with aluminum and ferrous ions and enhances the dissolution rate of the minerals. It also has high acidity and preserves the clay structure during activation. Moreover, effluents resulting from oxalic acid activation are considered more environmentally friendly than those resulting from activation by inorganic acids. The main advantage of using oxalic acid is the formation, during activation, of soluble complexes which can be decomposed both microbiologically and under the action of daylight. The target of this work was to compare the surface and structural properties of the materials produced by oxalic acid activation of different smectite samples with the conventional inorganic acid activation. The physicochemical characteristics of raw materials and products were evaluated by various methods: X-Ray Fluorescence (XRF), Thermogravimetric analysis (TGA), X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), and BET (Brunauer-Emmett-Teller) and BJH methods for specific surface area measurement and definition of pore size distribution of the samples. Results showed that acid activation led to new materials with higher specific surface areas and diverse porosity, compared to the raw materials. The organic and inorganic acid activation products presented structural differences which effluent their appropriateness to adsorb undesirable organic molecules.

References:
1. Taxiarchou, M. & Douni, I. The effect of oxalic acid activation on the bleaching properties of a bentonite from Milos Island, Greece. Clay Miner. 49, 541-549 (2014).
2. Wang, X., Li, Q., Hu, H., Zhang, T. & Zhou, Y. Dissolution of kaolinite induced by citric, oxalic, and malic acids. J. Colloid Interface Sci. 290, 481-488 (2005).
3. Tarasova, I.I., Dudeney, A.W.L. and Pilurzu, S. Glass sand processing by oxalic acid leaching and photocatalytic effluent treatment, Minerals Engineering 14, 639-646 (2001).

14:50: [MiningSatPM107]
The Application of Green Chemistry SuperLig® Molecular Recognition Technology and Other Sustainable Processes at Copper Electrorefineries
Luis Navarro¹ ; Roberto Navarro Tovar² ; Ronald Bruening¹ ; Reed Izatt¹ ; ¹IBC Advanced Technologies, American Fork, United States; ²Instituto Tecnologico de Celaya, Celaya, Mexico;
Paper Id: 450 [Abstract]

Copper prices are determined by world supply and demand. The increasing demand for a higher quality refined copper product from ores containing as little as 0.5% copper; varying levels of valuable constituents such as gold, silver, platinum group metals, nickel, selenium and tellurium; and potentially destructive impurities such as arsenic, antimony, lead and bismuth provide the impetus for researching, developing and implementing innovative process technologies in several areas within the copper electrorefining operation.

Recent technological innovations have allowed companies to reduce inefficiencies (e.g., energy consumption, waste generation) and unit costs while meeting increasingly stringent environmental, safety, and health regulations. One promising approach is the adoption of processes incorporating green chemistry, which is defined as “the design of chemical products and processes to reduce or eliminate the generation of hazardous substances.” It has become evident that incorporation of green chemistry principles into innovative process development has helped support investment decisions for these new processes.
This paper presents several examples of green chemistry technologies which have been implemented at copper electrorefineries, including (1) use of SuperLig® Molecular Recognition Technology (MRT), a highly selective technology capable of achieving loading to elution ratios of more than 40 bed volumes (BV) and flowrates above 0.2 BV/minute, in controlling antimony and bismuth concentration levels in copper electrolyte and for the separation of platinum group and other metals in electrorefining; (2) the recovery of sulfuric acid and arsenic in electrolyte purification using acid purification technology via an acid purification unit (APU®) in comparison to the conventional liberator cell (electrowinning) process; (3) recovery of tellurium from copper anode slimes initially through a cementation process followed by alkaline leaching, and (4) recovery of metals such as lead and nickel in electrolyte purification using a selective two-step alkaline precipitation.

References:
[1] Anastas, P., Eghbali, N., Chemical Society Reviews, 39, (2010) 301-312.\n[2] Artzer, A., Moats, M.. Bender, The Journal of the Minerals, Metals & Materials Society 70, (2018) 2033-2040.\n[3] Izatt, R. M., Izatt, S. R., Izatt, N. E., Krakowiak, K. E., Bruening, R. L., Navarro, L., Green Chemistry 17, (2015) 2236-2245.\n[4] Navarro, L., Morris, T., Read, W, Parameswaran, K., in Metal Sustainability: Global Challenges, Consequences and Perspectives, R.M. Izatt (ed.), John Wiley & Sons, Chichester, U.K., (2016) 397-423.\n[5] Parameswaran, K. in the Proceedings of the 58th Annual Conference of Metallurgists (COM) hosting the 10th International Copper Conference 2019, MetSoc, Vancouver, August 18-21, 2019.\n[6] Wang, S., Izatt, N. E., Bruening, R. L., Navarro, L., Izatt, R. M., Izatt, S. R., in the Proceedings of the 58th Annual Conference of Metallurgists (COM) hosting the 10th International Copper Conference 2019, MetSoc, Vancouver, August 18-21, 2019.

15:15: [MiningSatPM108]
Sustainability of mined materials: an assessment of U.S. copper in a life cycle framework
Miranda Gorman¹ ; David Dzombak² ; ¹Carnegie Mellon University, Pittsburgh, United States; ²Carnegie Mellon University(CMU), Pittsburgh, United States;
Paper Id: 251 [Abstract]

As extraction rates of finite mineral resources, and the relative environmental impacts of these activities grow globally (Kesler, 2007; Parameswaran, 2016), initiatives to improve the sustainability of mining have been undertaken (Parameswaran, 2017). A framework for the assessment of sustainability of mining is needed. A review of existing thoughts at the intersection of sustainability and mining has been performed to identify existing frameworks. A common sustainable mining framework is focused on reducing environmental impacts of mining through measuring, monitoring, and working to improve various environmental performance metrics. A more comprehensive framework is emerging, however, that takes into account the complete life cycle of the mineral and includes circularity metrics and a systems view of mineral use in society. This transition from the emphasis on the environmental footprint of mining operations to responsible management of non-fuel mineral resources throughout their entire life cycle, including use phase and end of life, has benefits including reducing the quantity of mined material and preserving reserves for future generations (Gorman and Dzombak, 2018). In this work, through the collection of primary stocks and flows data for the complete copper life cycle from 1970 to 2015, life cycle and circularity analyses were applied to assess sustainability of copper mining, use and recovery in the United States. This is followed by dynamic modeling and assessment of the data. The circularity, and therefore sustainability, of copper is found to be limited by end of life collection. This is mostly from building and construction and electric utility sectors, as well as exports of scrap which limit availability of recyclable copper material in the U.S. and requires raw material imports and continued extraction of virgin materials.

References:
Gorman, M. R., and Dzombak, D. A. (2018). A review of sustainable mining and resource management: Transitioning from the life cycle of the mine to the life cycle of the mineral. Resources, Conservation and Recycling, 137. http://doi.org/10.1016/j.resconrec.2018.06.001
Kesler, S. (2007). Mineral supply and demand into the 21st century. Proceedings, Workshop on Deposit Modeling, Mineral Resource Assessment, and Sustainable Development, 55-62. Retrieved from http://pubs.usgs.gov/circ/2007/1294/reports/paper9.pdf
Parameswaran, K. (2016). Sustainability Considerations in Innovative Process Development. In Innovative Process Development in Metallurgical Industry. Springer International Publishing, Switzerland (pp. 257-280).
Parameswaran, K. (2017). Energy use, conservation, and eco-efficiency considerations in the primary copper industry. Proceedings, COM2017, The Conference of Metallurgists. 1-21. ISBN: 1-926872-36-0

SESSION: MiningSatPM2-R5	Parameswaran International Symposium on Sustainable Mining and Smelting Operations (6th Intl. Symp. on Sustainable Mining Operations)
Sat Oct, 26 2019 / Room: Zeus (55/Mezz. F)
Session Chairs: Greg Baiden; Vaikuntam Lakshmanan; Session Monitor: TBA

15:55: [MiningSatPM209]
Dynamic Solidification of Multiphase Alloys Within Ultrasonic Field
Wei Zhai¹ ; Bingbo Wei² ; ¹Northwestern Polytechnical University, China, Xi'an, China; ²Northwestern Polytechnical University, China, Xi\'an, China;
Paper Id: 389 [Abstract]

Applying power ultrasound during solidification has proven to be an effective way to improve the microstructure and enhance the mechanical properties of metallic alloys. However, most previous investigations focus on the dendritically solidified Al or Mg based single phase alloys, the effect of power ultrasound on the multiphase alloys, including eutectic, pertiectic and monotectic alloys are still remains unclear. In present work, the solidification mechanism of these three kinds of metallic alloys is summarized on the basis of the authors’ work. For binary Sn-Pb eutectic alloy, differing from the regular lamellar eutectic formed during static solidification, there are two typical kinds of spherical eutectic cells formed within the ultrasonic field. Theortectical analysis shows that the local high undercooling induced by cavitation takes responsibility to the formation of anomalous eutectic, while the radial symmetry of both the concentration and temperature fields induced by acoustic streaming ensures that the solid-liquid interface is symmetric in three dimensions. As for binary Cu-Sn peritectic alloy, the ultrasonic field brings about a striking size refinement effect to the primary intermetallic compound by more than one order of magnitude. Meanwhile, it facilitates or even completes the usual peritectic transformation which occurs only to a very limited extent during static solidification. These lead to the remarkable improvement of mechanical properties for such Cu–Sn alloy, whose compressive strength and microhardness are both remarkably increased. Power ultrasound is also introduced to the liquid phase separation and dynamic solidification of ternary Cu-Sn-Bi monotectic alloy. It is found that as compared with the layered structure formed under static condition, the macrosegregation resulted from liquid phase separation is remarkably reduced with the increase of ultrasonic amplitude. This is mainly ascribed to the ultrasonically induced cavitation and acoustic streaming, which promotes the nucleation, the fragmentation, and the dispersion of secondary droplets. The finally solidified immiscible alloy exhibits obvious improvements in electrochemical corrosion resistance, microhardness and wear-resistance.

References:
[1]O. V.Abramov, Ultrasonics, 25(1987) 73-82
[2]W. Zhai, Z.Y.Hong, W.J.Xie, B. Wei, Chin.Sci. Bull. 56(2011)89-96
[3]W.Zhai, Z.Y.Hong, Z.Y. Hong, X.L.Wen, B. Wei. Mater. Design. 72(2015) 43-50
[4]J.M.Liu, W.H.Wu, W.Zhai, B.Wei, Ultrason.Sonochem. 54(2019) 281-289
[5]I. Tzanakis, G.S.B. Lebon, D.G. Eskin, K. Pericleous, Mater. Des. 90 (2016) 979–983.

16:20: [MiningSatPM210]
Lunar Mining - Stretching Human Knowledge in Mining, Telecommunications, Energy, and Robotics
Greg Baiden¹ ; ¹Penguin Automated Systems Inc., Naughton, Canada;
Paper Id: 172 [Abstract]

In 2009, NASA launched the LCROSS mission to the South Pole of the moon to perform a spectral analysis of the contents of the crater material remotely. The results of the mission were positive with strong indications of H₂O and other materials from the analysed plume of material. This began worldwide speculation on returning to the moon with countries setting up programs to consider lunar prospecting and exploration to be followed by creating initial mining plans. Finding H₂O engaged the world in plans for emerging opportunities for new space based industries. Cheap abundant water allows consideration of potentially cheap fuel which is very available. Inexpensive off-earth propellant could be used for future satellite refueling, science missions within the solar system and beyond, and enables commercial missions for mining, hotels and industry. The military in the USA created the first lunar mining plan in 1959. Since that time, many have been created with varying levels of credibility. In 2006, the Canadian Space Agency requested Dr. Baiden to devise a plan for lunar mining. This question resulted from the mining robotics research at his labs in Sudbury Ontario Canada. The plan was created over a two year timeframe and was presented to the AAIA in 2010. It was subsequently refined through work with Shackleton Energy and is now being further refined by a new start-up called MoonRise. Lunar prospecting and exploration will require teleoperated control of exploration robots from earth. There is much work in the literature, showing successful teleoperation with time delays of 2-3 seconds. This type of lunar surface operation has already been performed by NASA and Russia. The data on the size and quality of the H₂O will soon be validated by lunar surface missions in order to consider mining feasibility. Mining plans that have been performed from an aerospace perspective have little real mining work being considered by miners with industry experience. From a miner's perspective there are four major issues that need to be dealt with if lunar mining is to become a reality. These are: gravity, temperature, radiation and the lack of atmosphere. In all terrestrial applications, miners use gravity to their advantage. In thinking about lunar gravity, one sixth gravity is a major consideration. On one side, gravity requires less work, but in actual fact, the same work for mining needs to be done as on Earth. In terms of temperature, H₂O is located in the cold traps of these polar craters. If we mine in warmer areas, the H₂O immediately vaporizes, so we must mine in the cold traps at -250°C or 25 kelvin. Current mining experience limits are digging tools in the oil sand at -70°C. Finding and creating robots and mining tools to work in these temperature environments is another major consideration. As a mining facility, operations can be teleoperated or made autonomous, however, maintenance is a different story. Replacement parts will need changes, so a minimum amount of personnel will be necessary on site. This ground truth means a local habitat will need to be created for operations to occur. And finally, solar radiation is the main constraint for personnel on site as it has a large potential to be the literal fatal flaw. The numbers show extreme danger for personnel without proper protection. Adaptation of terrestrial tunneling technology, however, could provide a simple solution to this dilemma by enabling underground access to get to a sufficient level of protection. This paper presents current thinking from a miner's perspective. This mining plan has been presented and augmented by input from CSA, NASA, Shackleton Energy Co., and now MoonRise Inc.. It identifies the main "show stoppers" or risks for mining H₂O from the moon. The next steps include a recent statement by a major US launch company (United Launch Alliance) of willingness to buy lunar propellant in space. Note this substantially reduces customer or business risk. NASA has also expressed interest in purchasing locally manufactured lunar propellant.

16:45: [MiningSatPM211]
Mineral Certified Reference Material: The Best Tool to Achieve Reliable Analytical Data
Maria Alice Goes¹ ; ¹Center for Mineral Technology - CETEM, Rio de Janeiro, Brazil;
Paper Id: 111 [Abstract]

Nearly every decision-making process in mineral research or the mineral industry depends on analytical data. It is not sufficient, however, to merely data. The data must be traceable and comparable. Precise results are not good enough to warrant reliable data. The lack of accuracy can cause seriously biased results and erroneous decisions. Certified reference materials (CRMs) play an important role in assuring analytical results of high quality. A CRM is a material that is sufficiently stable and homogeneous with respect to one or more specified properties which establish the CRM to be fit for its intended use in a measurement process. This is characterized by a metrologically valid procedure, accompanied by a certificate that provides the value of the specified property, its associated uncertainty, and a statement of metrological traceability [1]. Its uses may include the calibration of a measurement system, assessment of a measurement procedure, assigning values to other materials, and quality control [2]. CRMs are also used in interlaboratory comparisons for method validation and for assessing laboratory proficiency. The demonstration of the scientific and technical competence of reference material producers (RMPs) is a basic requirement for ensuring the quality of CRMs. It is not only necessary for RMPs to provide information about their materials in the form of CRM documents, but also to demonstrate their competence in producing CRMs of appropriate quality [3]. The Center for Mineral Technology (CETEM), a R&D Institute under the Brazilian Ministry of Science, Technology, Innovations and Communications, has been accredited as an ore and mineral certified reference material producer in accordance with ISO 17034 since June 2011. The production concerns all necessary activities leading to a reference material supplied to customers, including production planning, production control, material handling and storage, material processing, assessment of homogeneity and stability, characterization, assignment of property values and their uncertainties, issue of certificates and post-distribution service. The Certified Reference Material Program (PMRC) was established to coordinate all management and technical aspects of the production of certified reference materials at CETEM. It has a fully equipped laboratory for handling large amounts of material, preventing contamination among samples, as well as from outside sources, and a qualified technical team that is committed to ensuring the quality of the reference materials produced. Currently, the majority of CETEM’s certified reference materials are bauxite ores originating from various regions in Brazil. There is a continuing effort for the development of other natural matrix reference materials, driven by the needs of analytical laboratories associated with mining, metallurgy and the environment. CETEM also provides custom-made CRMs from client-supplied materials in order to meet a specific or special application need. This paper describes the production of CETEM’s certified reference materials.

References:
[1] ISO Guide 30:2015, Reference materials -- Selected terms and definitions.
[2] SO Guide 33: 2015, Reference materials -- Good practice in using reference materials
[3] ISO 17034:2016, General requirements for the competence of reference material producers.

17:10: [MiningSatPM212]
The Role Of Clean Technologies For Sustainable Development
Aghil Ojaghi¹ ; Vaikuntam Lakshmanan¹ ; ¹Process Research ORTECH Inc, Mississauga, Canada;
Paper Id: 438 [Abstract]

Sustainable development is a development that achieves the present needs while making sure that the needs of future generations are taken into account as well. Today, clean and smart technologies play an important role in sustainable development; including economic efficiency, environmental and social aspects. Mining industries elevate the lives of millions of people around the world, mainly in rural areas. Therefore, sustainable development in the mining industry focusing on innovative and clean technologies is much needed. Mining agriculture, tourism, clean process technologies, and wastewater treatment are the examples which secure future jobs and protect the environment creating smart communities. Existing and developed digital and clean technologies will assist the industry to be sustainable. Process Research Ortech (PRO) is helping and focusing on developing innovative clean technologies for mining industries for many years. The paper will include innovative technologies that are developed at PRO for Gold, Nickel, Titanium and water treatment.

SESSION: LawsThuAM-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Keith Oliver; Malcolm McNeil; Session Monitor: TBA

11:20: [LawsThuAM01]
International Trade and Tariffs: It’s Business!
Malcolm Mcneil¹ ; ¹Arent Fox, Los Angeles, United States;
Paper Id: 443 [Abstract]

International trade tariffs (read taxes) are in the news globally and are by their nature politically charged. Consequently, a full understanding is necessary, of both pluses and minuses, to critically evaluate their efficacy . Non tariff barriers to trade (NTBs) will also be examined to see how they are used to manipulate the trade channels. NTB’s, sometimes called "Non-Tariff Measures (NTMs)" are any trade barrier that restricts imports or exports of goods or services through mechanisms other than the simple imposition of tariffs. These include import licensing, rules for valuation of goods at customs, pre-shipment inspections, rules of origin ('made in'), and trade prepared investment measures.[2] This segment will focus on the key drivers, politically, economically and socially, to create a framework for analysis that is free of bias or local “fake news” spin. The goal will be to communicate indicators that effectively guide the participants to a reasoned understanding and appropriate analysis of policy choices, and their impact on cross-border transactions.

11:45: [LawsThuAM02]
From Facial Recognition to Fraud: The Rise of the Lex Technologica and its impact on Financial Crime
Keith Oliver¹ ; ¹Peters & Peters, London, United Kingdom;
Paper Id: 388 [Abstract]

The law is dangerously lagging behind today’s ever more digitalized world. Technologies such as Facial Recognition and Biometric Data Stores are on the rise, used in an effort to trace criminals. However, in light of the recent reports of defunct or inaccurate software, incorrect matches, and innocent arrests, has the law harnessed this power properly? Or should we revert to lip-reading as per HAL 9000 in the Kubrick masterpiece 2001: A Space Odyssey? This paper will explore emerging technologies and the peaks and pitfalls of their use in the context of fighting Financial Crime. Is Blockchain the way of the future in terms of asset recovery and tracing? Is Facial Recognition software akin to electronic tagging? In our bid to fight fraud, have we sacrificed our privacy? These are just some of the questions in store for this discussion.

12:10: [LawsThuAM03]
Criminal Investigations and Covert Investigations
Simon John Davison¹ ; ¹Another Day, London, United Kingdom;
Paper Id: 470 [Abstract]

Simon Davison is a Director of Investigations at AnotherDay; a risk, security and investigations consultancy based in London and the Middle East. AnotherDay work with clients around the world to protect their firms from a variety of risks; from terrorism, war, crime to state sponsored spying. As co-founder of the investigations team, Simon conducts numerous criminal investigations and private prosecutions, assisting victims of crime in pursuing justice. AnotherDay also supports international law firms in a variety of ways, such as civil litigation support, asset tracing and intelligence work in challenging jurisdictions around the world. Before AnotherDay, Simon was a detective in the Flying Squad in the Metropolitan Police in London, investigating armed robbery and serious and organised crime. In this presentation, Simon will be providing an overview of private criminal prosecutions in the UK, and explain the process of seeking justice without state assistance. Simon will also be discussing the benefits of covert investigation (such as surveillance), their applications and use in a variety of litigation.

SESSION: LawsThuPM1-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Amalia Neenan; Simon John Davison; Session Monitor: TBA

14:00: [LawsThuPM105]
The Good, The Bad and The Bitcoin: Crypto-assets as a phenomenon
Amalia Neenan¹ ; ¹Peters & Peters, London, United Kingdom;
Paper Id: 468 [Abstract]

Ponzi scheme? Tulip Mania 2.0? Fad? Future? Each word a label that at one point or another has been associated with cryptocurrencies and other crypto-assets since their inception in 2008. But have we been too hasty to paint these unique and revolutionary products with the broad brush of mistrust? This session will address why cryptocurrencies and other associated technologies have gained notoriety in recent years by examining both the media frenzy surrounding them, as well as the inherent design characteristics that can create confusion. It will then be suggested that despite their supposedly ‘bad reputation’ there are legal safety-nets already in place to help harness the unique opportunities that they present and utilize the wide-reaching and groundbreaking benefits that crypto-assets hold for future transactional abilities.

14:50: [LawsThuPM107]
Blockchain & Distributed Ledger Technology: Sustainable Business Revolutions Through Trustless Transactions
William S. Wenzel, Esq.¹ ; ¹Red Road Legal, PC, Denver, United States;
Paper Id: 431 [Abstract]

The purpose of Blockchain is to use technology to supplant the need for (and expense of) intermediaries in inter-party transactions. Global business entails interactions between scores of “arms-length” parties. This necessitates third-party intermediaries to verify the voracity and performance of each participant. Whether confirming ownership, determining that delivery occurred – on time and conforming with expectations, or ensuring that upstream suppliers and downstream purchasers maintain product quality standards, these business models require significant overhead in monitoring and authentication. Blockchain and other Distributed Ledger Technologies remove intermediaries from business transactions. It allows “strangers” to transact with each other in a streamlined, trustless manner. Opportunities abound for businesses to capitalize on this technology as providers and users. We will discuss best practices of implementation and use, challenges like GDPR, and monetization strategies for Blockchain and DLT. We will also examine sustainable system options that ensure Blockchain and DLT will best use a business’ available resources.

SESSION: LawsThuPM2-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Maria Cronin; Dennis Lee; Session Monitor: TBA

15:55: [LawsThuPM209]
Brexit: Sustaining the future? (Part 1)
Keith Oliver¹ ; ¹Peters & Peters, London, United Kingdom;
Paper Id: 474 [Abstract]

<i>‘Be ye never so high, the law is above you’</i>. September 2019 saw the handing down of a tumultuous judgment by the UK Supreme Court, declaring that the Prime Minster, Boris Johnson had acted unlawfully when he advised the Queen to prorogue parliament for five weeks during the key and final stages of debates in the run up to the proposed Brexit Day on 31st October. The Brexit crisis has split the nation, and the constitutional significance of this ruling has been equally as divisive. The overwhelming question amidst all of the turmoil is: ‘What happens now?’ From this, we are greeted by a plethora of trickle-down queries. Can Brexit be done? Will it? On what terms? On who’s terms? And what will be the lasting impact on the UK and the UK’s position globally in the future? This session addresses all of these questions and more, looking at the sustainability of Brexit and what changes this will herald in both the legal sector and commerce in general.

16:45: [LawsThuPM211]
Brexit: Sustaining the future? (Part 2)
Malcolm Mcneil¹ ; ¹Arent Fox, Los Angeles, United States;
Paper Id: 475 [Abstract]

In 1946, Winston Churchill coined the now well-known phrase <i>‘The Special Relationship’ </i>to denote the political, economic, and historical relations between the United States of America and the United Kingdom. Over the years, leaders from both sides of the Atlantic have shared in this set up. However, in light of the Brexit debacle that is ongoing in the UK, how will this impact our symbiotic relationship going forward? The <i>‘New’</i> Special Relationship between the current British Prime Minister, Boris Johnson and the current President of the United States, Donald Trump may be touted as being based on mutual respect for one another, but will this respect translate into a solidified trade agreement when, and if, the UK leaves the European Union? The recent UK Supreme Court judgment regarding the illegality of the parliamentary prorogation sheds a glaring spotlight on the current state of affairs, and this session addresses whether the Special Relationship will be sustained post-exit day. Whenever that may be….

SESSION: LawsThuPM3-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: William S. Wenzel, Esq.; Session Monitor: TBA

17:50: [LawsThuPM313]
“Who is watching Who”: Cybersecurity, Privacy & Legal Professional Privilege
Diana Rhayem¹ ; ¹Diana Rhayem Law Office, Beirut, Lebanon;
Paper Id: 449 [Abstract]

As per the goals defined by the UN, sustainable growth can be achieved through innovation and sharing information being the main components of SDG 9 (develop industry, innovation, and infrastructure) and SDG 17 (revitalize the global partnership for sustainable development . Since commerce, trade and all industries are increasingly becoming cyber-dependent, it would be compulsory for every state to set and implement a cybersecurity strategy for a safer cyberspace and enable sharing of information when possible and when it does not infringe certain privileges. In a symposium centered on the sustainable industrial development, it would be essential to analyze how Cybersecurity and Legal Professional Privilege can essentially and positively contribute to achieving related goals of sustainable development and industrial growth or at least in safeguarding their main objectives.

SESSION: LawsFriAM-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Yoshihisa Hayakawa; Andreas Erotocritou; Session Monitor: TBA

11:20: [LawsFriAM01]
"The AI Seat on the Governing Board – How Influential Should it be in the Decision-Making Process ?"
Malcolm Mcneil¹ ; ¹Arent Fox, Los Angeles, United States;
Paper Id: 442 [Abstract]

Business owners, companies, decision-makers cannot ignore the impact of AI "Artificial Intelligence" in providing efficiencies, statistical analysis, and speed in the decision-making analytical context. However in today's ever-changing global environment, the role should AI process play in the decision-making process ? Are there decisions that can be delegated to AI predictive conclusions ? Does AI provide an answer to both human errors ? This session will examine the proper role of AI in charting a course for the future. Decision-makers clearly understand they utilized AI for effectiveness and at the same time assess its limitations. Session will further explore where AI and human judgment coalesce and diverge. The participants will be encouraged to actively participate with examples within their own working environments.

12:10: [LawsFriAM03]
UK International Cooperation with Foreign Enforcement Agencies in Financial Crime
Maria Cronin¹ ; ¹Peters & Peters, London, United Kingdom;
Paper Id: 354 [Abstract]

Maria Cronin, Partner at Peters & Peters Solicitors LLP, will consider UK international cooperation with foreign enforcement agencies in financial crime. In the last 18 months, the UK has introduced a number of measures aimed at strengthening and streamlining cooperation between international financial crime enforcement agencies. In January 2018, UK law enforcement was given ground-breaking new powers to freeze and recover alleged proceeds of crime with the introduction of Unexplained Wealth Orders (UWOs) and Account Freezing Orders (AFOs). There have now been two UWOs in the UK and a far greater number of AFOs. UWOs essentially create a reverse burden on Politically Exposed Persons (and / or their associates) to demonstrate the legitimacy of income used to acquire property in the UK. AFOs, like UWOs, are a powerful tool allowing law enforcement to freeze funds held in any UK bank or building society in circumstances where there are ‘reasonable grounds’ for suspecting that the money was obtained as result of, or intended for use in, unlawful conduct. It is possible for law enforcement to forfeit frozen funds administratively, without any recourse to the courts. In November 2018, the UK extended these draconian powers to foreign enforcement bodies which can now request UWOs and AFOs through Mutual Legal Assistance. We have yet to see whether this will result in their increase; certainly the extension of these new powers to foreign states is likely to have a significant impact on international cooperation in financial crime.

SESSION: LawsFriPM1-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Dennis Lee; Andreas Erotocritou; Session Monitor: TBA

14:00: [LawsFriPM105]
The Dos and Don’ts & Potential U.S. Tax Issues For International Corporations On Setting Up Their Inbound Investment/Businesses in the U.S.
Dennis Lee¹ ; ¹Dennis M. Lee and Associates, Irvine, United States;
Paper Id: 408 [Abstract]

United States, the largest economy in the world, is a consumer-driven market, with over 300 million people and growing, the U.S. offers an abundance of opportunities for businesses of all sizes to grow and prosper, and the U.S. remains a major key trading partner and market for international companies around the world. Recent developments in the United States has resulted in significant changes in U.S. tax and trade policy, as always, big change presents big opportunities for risk as well as reward, despite of the changes in tax and trade policy the U.S. remains an attractive jurisdiction for foreign inbound investment, and is the largest recipient of foreign direct investment (FDI) in the world. One size doesn’t fit all, not all foreign commercial and industrial enterprises are the same, and the commercial and industrial differences will translate into structuring differences when the foreign inbound investor enters and approaches the U.S. market. “Insufficient facts always invite danger”, our paper/presentation will define the spectrum of U.S. taxation and provide the road map and guidelines on the choice of U.S. business entities and income tax implications and filings in structuring a U.S. inbound investment/business for the foreign enterprises.

14:50: [LawsFriPM107]
Conducting International Business – a Litigation Perspective
Andreas Erotocritou¹ ; ¹, Limassol, Cyprus;
Paper Id: 473 [Abstract]

There are many factors that may cause a business to expand internationally – searching for new markets, attracting capital and acquiring key resources may be some of the them. In conducting business on an international level, it is vital to take into account the correct legal considerations, in order to ensure its long-term survival. The presentation will explore key matters that need to be evaluated by entrepreneurs and investors in safeguarding their rights when conducting business internationally. In this context, factors, such as choosing the right jurisdiction for structuring the business, setting the right structure between the various stakeholders, and avoiding obvious pitfalls will be explored, by analysing how these may affect the successful enforcement of one’s rights in litigation. Ensuring that the chosen jurisdiction offers adequate legal protection, anticipating the ability to recognise and enforce judgments cross-borders, and applying for injunctions when need arises will be some of the topics to be examined. The presentation will consider the example of Cyprus and will explore the practical considerations for structuring business and resolving disputes in Cyprus.

SESSION: LawsFriPM2-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Florian Kongoli; Yoshihisa Hayakawa; Session Monitor: TBA

15:55: [LawsFriPM209]
AI & the future of the legal profession in the context of advising businesses internationally
Angela Diaz Bastien¹ ; ¹ERNESTO DIAZ-BASTIEN & ASOCIADOS, SLP, Madrid, Spain;
Paper Id: 467 [Abstract]

"The application of AI to the legal sector requires a combination of experience in the field, in annotated content and technical expertise: you cannot simply throw AI into legal data and expect good results." For this reason, I believe that "the more lawyers know how AI effectively works, the more comfortable they will feel about it. It is important to understand how artificial intelligence algorithms use data and what its consequences may be on the performance of an artificial intelligence system. People are afraid of what they don't understand, so it's important that they take the time to get to know the big picture of AI and how it applies to the legal." For an AI model to behave in a way that is useful to lawyers, we must train it with data that makes sense and is valuable to lawyers. We need to tell the model what part of the data is important to the behavior we're trying to mimic: it takes experience and mastery of the subject matter to understand which parts of the data should be trusted and which parts should be ignored to make a decision."

16:20: [LawsFriPM210]
Lawyers are being Challenged Now
Yoshihisa Hayakawa¹ ; ¹Rikkyo University, Tokyo, Japan;
Paper Id: 383 [Abstract]

In the legal field, various tasks, which were traditionally provided by practicing lawyers, are being replaced by Information Technology (IT) and Artificial Intelligence (AI). In the area of drafting or reviewing a legal contract for the clients, many types of software have been developed and are being used by the law firms or directly by the clients. A brand-new concept of “Smart Contract” was invented and a structure based on the concept is being used without any assistance by the lawyers. In the area of finance, Initial Coin Offering (ICO) is being used as a powerful fundraising method instead of the traditional method of Initial Public Offering (IPO). The new method enables a business corporation to efficiently fundraise without or with less assistance of the securities companies as well as the finance lawyers In the area of M&A, a due diligence process can be carried out now by many types of software for this function. The software can automatically review digital documents which was collectively gathered in the “Digital Virtual Room”. Demand for the young associate lawyers for this kind of tasks are decreasing due to the introduction of the software. In the area of litigation, especially in the process of “Discovery” in the US, many types of software for this function have been developed and being used in the actual litigation process. Demand for the young associates for this kind of tasks are decreasing as well. One of the most remarkable phenomena is the drastic development of Online Dispute Resolution (ODR) has been drastically developed. In the US, powered by a number of private ODR vendors, ODR is now widely used in the private sectors as well as in the governmental and judicial sectors. The number of filing cases in the ODR for an e-commerce platform vendor in the US has become more than sixty million, which number is bigger than the number of all the filing cases in the State Courts and the Federal Courts in the US. In Europe, the use of ODR has been encouraged in the EU by the ODR Regulation and the ADR Directive in 2013 and ODR is being gradually used now. A trial for the world-wide capacity-building was aimed by the United Nations Commission on International Trade Law (UNCITRAL) and is now aimed by Asia Pacific Economic Cooperation (APEC). The speed of development of ODR is being accelerated now by the actual demands and by the legal instruments above described. It is changing the traditional features of the dispute resolution systems including the National Courts. Moreover, with the use of AI as a provider of settlement plans in the mediation process or as a decision-maker in the arbitration process, ODR will become much more powerful tools in the dispute resolution. In other words, human beings may be replaced by AI even in this field. What is a role of lawyers in the future?

16:45: [LawsFriPM211]
Role of Science and Technology on Legal and Political Framework
Florian Kongoli¹ ; ¹FLOGEN Star OUTREACH, Montreal, Canada;
Paper Id: 368 [Abstract]

Science and technology have a profound effect not only in society as a whole but in the legislative process of creating new laws and applying them in the practice. Science and technology are always 10 steps ahead of the legislative process and have a distinct influence on the way the law are applied or enforced. In this paper, numerous example on the role of science and technology are given and an analysis is done to reflect their importance.

17:10: [LawsFriPM212]
The Unitary Patent and the Unified Patent Court
Márcia Martinho Da Rosa¹ ; ¹ANJAP`S Comission for Intellectual Property and New Technologies, LISBON, Portugal;
Paper Id: 330 [Abstract]

Currently, the only way of obtaining protection in Europe is though the Convention of the European Patent, an international, unified way of obtaining national patents. The protection of inventions through a system of patents is, as we know, an important factor of technical, scientific and economic development and it is a stimulus to innovation and competitiveness. By the craving of a common, the European Union has developed a competitive and balanced market in all its areas and places: regional and national (hence all the member-states). The European Union has an urgent need for a unified way of treating this matter, so it can offer a unitary system of patent protection to inventors and traders. This system would be unique in its procedures and its effects will be uniform, similarly to what has already happened with the very successful brand and model of the Community. Since 1975, this unique title is being created through a process that has undergone several steps which, until now, have hindered the realization of such an aim. The overall effects of patent production on all member-States of the former European Community has been observed by keeping the scope on the creation of a single patent. The Green Book suggested an innovative solution by proposing the creation of such a legal instrument through regulation (proper European Union legal instrument) and not through conventions or agreements between member states. This proposal consolidates itself into a means of integration for the effective implementation of a common market. Following the Green Book, some Member States have advanced towards enhanced patent cooperation, which is still awaiting implementation and ratification by some member states Subsequently, our analysis will focus on the material regime, limiting the analysis to the three main points currently under discussion to create a system of patent protection at the European Union's level: i. European patent creation with unitary effect through a reinforced cooperation; ii. The linguistic regime; iii. The creation of a Unified Patent's Court of Law The European Union is in a financial and market crisis, torn between trying to drive by an informal directory between great countries and their own domestic institution's claims. In addition to the cries of some of the other smaller member states, some of them are struggling to manage their own sovereign debt. The Union as a whole lacks the urgent economic vitality to survive as a power in a global, competitive market full of new harsh players. Such economic vitality is also supported by maintaining and increasing research and innovation capability and by betting on new technologies and objectives that would be fully achieved with a unitary patent. The remaining difficulties of the implementation of the patent system, particularly in terms of the unavoidable language regime and the determined opposition from two medium-sized countries of the Union, there is still an unknown factor in this proposal. This is because we do not know whether these are the right proposals that will lead to a successful conclusion of the much desired, but just as difficult to achieve, unitary patent in the European Union. The process for the implementation of the European Patent System through the new unitary effect and the establishment of the Unified Patent Court is still ongoing. We do not have a date for the execution of this patent system. The European Union needs to close this process and set the date of the application of the UPC Agreement.

SESSION: LawsFriPM3-R6	McNeil International Symposium on Laws and their Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Amalia Neenan; Session Monitor: TBA

17:50: [LawsFriPM313]
Employment Issues for Start-Ups: Sustainable solutions
Malcolm Mcneil¹ ; ¹Arent Fox, Los Angeles, United States;
Paper Id: 477 [Abstract]

Start-Ups. Symbols of innovation and commerce. Yet, many new businesses can find the process of <i>‘starting- up’ </i>mired in a whole host of employment law related issues. In order to successfully wade through these murky waters, a clear understanding of the underpinning (and sometimes competing) legal frameworks is essential. This session offers an insight into some of the most common pitfalls that impact these business models, and how to avoid them to maximize the longevity of these new ventures. We will explore key issues such as how to establish workable renumeration models, attract and retain talent as well as how to protect the business itself, pairing them with practical and sustainable solutions for both now and in the future.

SESSION: MathematicsSatAM-R6	4th Intl. Symp. on Sustainable Mathematics Applications
Sat Oct, 26 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Peter Rowlands; Avraam Konstantinidis; Session Monitor: TBA

11:20: [MathematicsSatAM01]
Nature's algebra
Peter Rowlands¹ ; ¹University of Liverpool, Liverpool, United Kingdom;
Paper Id: 395 [Abstract]

Though a wide variety of mathematical techniques are used in physics and its applications, much of this stems from complexity rather than the underlying fundamental theories. At the most fundamental level, Nature appears to use mathematics in a strikingly minimal way, basing itself on only a few simple principles. Nature, in its most basic aspect, does not appear to require sophisticated mathematics, which seemingly arises only from the entanglement of multiple simple systems. Mathematics at the most fundamental level is almost an accidental result of a very few basic symmetries (principally, duality and anticommutativity, based on the numbers 2 and 3) and a requirement to maintain totality zero. These generate a particular double space algebra which can be seen as the basis of quantum mechanics, classical mechanics, particle physics and even aspects of chemistry and biology, in particular the genetic code.

11:45: [MathematicsSatAM02]
Nanoindentation: A New Modeling Approach to an Old Measuring Technique
Avraam Konstantinidis¹ ; ¹Aristotle University of Thessaloniki, Thessaloniki, Greece;
Paper Id: 86 [Abstract]

Although nanoindentation has been used for more than 40 years for calculating elastic constants (modulus and hardness) of materials at the nanoscale, the test still lacks a concrete theoretical framework. The main problems of the current conceptual framework pertaining nanoindentation include: the one-dimensional consideration of a three-dimensional problem, the calculation of elastic constants after strong local plasticity, and the dependence of the calculated elastic properties on the maximum penetration depth or maximum load. Another problem is that within the current theoretical framework, the measurements acquired through the use of instruments of increasing accuracy are theoretically interpreted by semi-empirical methods, involving many assumptions. The proposed framework in which nanoindentation is considered to be an <i>inhomogeneous compression</i> is due to the tip pyramidal geometry (Berkovich, Vickers) which tries to provide solutions to the aforementioned problems. In the proposed framework, the effect of the tip geometry is modeled in a way to be deducted from the calculation of the modulus of elasticity and hardness. Preliminary results in this direction indicate that the use of gradient theory can actually eliminate the effect of tip geometry by providing values for both the elastic modulus [1] and hardness [2]. These are independent of the maximum indentation depth or load, i.e. proving that the so-called indentation size effect (ISE) is just an artifact of the specific tip geometry.

References:
[1] Konstantinidis A.A., Frantziskonis G., Askes H. and Aifantis E.C., The use of nanoindentation for determining internal lengths and the constitutive response of monument materials: Models and experiments, <i>J. Mechan. Behav. Mater.</i> <b>25</b>, 57-60, 2016.\n[2] Kampouris A.K. and Konstantinidis, A., On the interpretation of the indentation size effect (ISE) through gradient theory for Vickers and Berkovich indenters, <i>J. Mechan. Behav. Mater.</i> <b>25</b>, 161-164, 2016.

12:10: [MathematicsSatAM03]
Modelling and Simulating Various Scenarios of Electricity Demand to Optimize the Cascade Production
Eralda Gjika¹ ; Aurora Ferrja¹ ; Lule Basha¹ ; Arbesa Kamberi² ; ¹University of Tirana, Tirana, Albania; ²Albanian Power Corporation, Tirana, Albania;
Paper Id: 357 [Abstract]

Forecasting energy production by hydropower plants (HPP) is a challenge because of their correlation with many exogenous variables such as precipitations, water inflow, temperature, the minimum and maximum level of the HPP, etc. Albania has a favorite geographical position which makes the electrical energy the main source of energy produced in the country. In our work, we try to analyze hourly and daily data of energy produced in the main cascade of the country which produces the main amount of energy consumption. Our focus is on analyzing the situation of energy demand on a 24 hour period and also on a weekly /monthly period. We analyze the seasonality patterns of the energy demand and try to fit different models to predict the upcoming season (hours or days). Several modeling strategies among hierarchical forecasting, neural network, multistage forecasting, econometric forecasting models were tested and the best was selected looking at the performance obtained on the testing period. Our goal is to use the proposed models to obtain the forecast for electric energy demand in the country which will help the Albanian Power Corporation (KESH) to build various scenarios on optimizing the country demand and production capacities on HPP cascade.

References:
[1] J. Campillo, F. Wallin , D. Torstensson , I. Vassileva Energy demand model design for forecasting electricity Consumption and simulating demand response scenario in Sweden, International Conference on Applied Energy ICAE 2012, Jul 5-8, 2012, Suzhou, China Paper ID: ICAE2012- A10599

[2] J. Huang, Y. Tang, Sh. Chen Energy Demand Forecasting: Combining Cointegration Analysis and Artificial Intelligence Algorithm, Mathematical Problems in Engineering, Volume 2018, Article ID 5194810, 13 pages. https://doi.org/10.1155/2018/5194810
[3] Makridakis, S., et al., The M4 Competition: Results, findings, conclusion and way forward. International Journal of Forecasting (2018), https://doi.org/10.1016/j.ijforecast.2018.06.001.

12:35: [MathematicsSatAM04]
On The Convergence Of An Evolutionary Algorithm, Particle Swarm Optimization (PSO) And Its Application
Besiana Cobani¹ ; Aurora Ferrja¹ ; ¹University of Tirana, Tirana, Albania;
Paper Id: 451 [Abstract]

The evolutionary methods are optimization methods that converge to the global solution. There are many optimization techniques nowadays used and the one we are working is the evolutionary method PSO. Many authors have proposed various modifications of the basic PSO parameters with the goal to obtain a variant of PSO with best performance algorithm complexity. In our case, first, we present a modified PSO algorithm. Then we analyze the convergence of the proposed algorithm using differential equations. More precisely we relate a difference equation with a differential equation, and study the behavior of its solution. The solution brings results for the parameters of PSO, specifically for the coefficients of acceleration. Since the PSO results depend on its parameters, we propose new parametersthem based on the convergence study. We give an application in the energetic field in Albanian case, in the main three hydropower cascades of the country, which consist of three hydro power plants.

SESSION: MathematicsSatPM1-R6	4th Intl. Symp. on Sustainable Mathematics Applications
Sat Oct, 26 2019 / Room: Hermes (64/Mezz. F)
Session Chairs: Aurora Ferrja; Besiana Cobani; Session Monitor: TBA

14:00: [MathematicsSatPM105]
A Combination Of The Finite Element Method With GMRES To Obtain An Efficient Algorithm To Solve An Eigenvalue Problem
Aurora Ferrja¹ ; Besiana Cobani¹ ; ¹University of Tirana, Tirana, Albania;
Paper Id: 452 [Abstract]

To find an analytically solution of a problem involving a system of partial differential equation is a challenging tusk. So, we use iterative methods to obtain an approximate solution. In inverse scattering the transmission eigenvalue problem is important do determine data for the scatterer. From the complexity of the domain (scatterer) we use the finite element method because we can obtain the best approximation of the required zone. The problem we solve is nonlinear and non-selfadjoint. Using variational method and Fredholm alternative we transform it in order to be discretize. Colton and Cakoni give inferior and superior of the refractive index. This information is used in an inequality given by Colton and Haddar to determine a boundary for the eigenvalues involving the first Dirichlet eigenvalue as well. We use an algorithm to find the first eigenvalue. We have the refractive index n also The algorithm used is a combination of finite element method with GMRES algorithm.

SESSION: GeomechanicsThuAM-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Dariusz Gawin; Ugo Galvanetto; Session Monitor: TBA

11:20: [GeomechanicsThuAM01] Plenary
In Favour of Complexity in Modelling
Bernhard Schrefler¹ ; ¹Institute for Advanced Study –TUM,, Munich, Germany;
Paper Id: 377 [Abstract]

Natural phenomena have mostly multiphysics and multiscale character. The same is true for many manmade materials. Multiphysics and multiscale models, if based on sound physical principles and satisfying the numerical requirements such a consistency and stability, can give much more insight in the phenomena under investigation than simpler models and can even allow for discoveries. I shall address a few of these cases where complex models made the difference. The use of an appropriate u-p model allowed to find that cavitation is needed for the onset of localization in dilatant porous media [1]. It also allowed to identify internal length scales governing the phenomenon. A three-fluids model for concrete, which considers a chemo-thermo-hydro-mechanical analysis taking into account of dry air, capillary and adsorbed water and water vapour in the pores allowed for a unified treatment of concrete under very high temperatures with particular regard to thermal spalling, tunnel fires and reactor vessels, concrete at early ages and beyond, leaching, Alkali-Aggregate reactions, freezing and thawing [2,3]. A model for fracturing in saturated porous media based on Biot’s theory, standard Galerkin Finite Elements, cohesive fracture and remeshing enabled to discover at least for the mechanics community that fracturing in saturated porous media is not continuous but stepwise with ensuing pressure oscillations [4,5]. This has important implications both in hydraulic fracturing operations and in geophysics, among others to reproduce the en echelon structure observed in nature. In material mechanics a truly multiscale model allowed to predict correctly the residual strains after cool down of Nb3 Sn superconducting strands [6]. Finally a multiphase model based on an transport oncophysics framework enabled to identify for instance a way to obtain less dense tumors which are desirable for drug delivery [7]. Other examples will be shown in the presentation.

References:
1. “A multiphase media model for simulation of localisation and post localisation behaviour in geomaterials” (with L. Sanavia and C.E. Majorana), Mechanics of Cohesive -Frictional Materials and Structures, 1, 1 (1996), 95-114.
2. “Thermo-hygro-mechanical analysis of concrete” (with P. Baggio and C.E. Majorana), Num. Meth. in Fluids, 20 (1995), 573-595.
3. “Modeling evolution of frost damage in fully saturated porous materials” (with M. Koniorczyk and D. Gawin), Comput. Methods Appl. Mech. Engrg., 292 (2015), 38-61.
4. “Mesh adaptation and transfer schemes for discrete fracture propagation in porous materials” (with S. Secchi and L. Simoni), Int. J. Numer. Anal. Meth. Geomech., (2007), 31:331-345

11:45: [GeomechanicsThuAM02] Plenary
GEOMECHANICS FOR HYDROCARBON PRODUCTION: ON THE IMPLEMENTATION OF PULSED ARC ELECTRICAL DISCHARGES FOR STIMULATION PURPOSES
Christian La Borderie¹ ; Youssef Fawaz¹ ; Pascale Senechal² ; Antoine Jacques³ ; Gilles Pijaudier Cabot¹ ; ¹E2S UPPA, Université de Pau et des Pays de l'Adour, Anglet, France; ²E2S UPPA, Université de Pau et des Pays de l'Adour, Pau, France; ³Total E&P, Pau, France;
Paper Id: 263 [Abstract]

Shock waves generated in water by Pulsed Arc Electrohydraulic Discharges (PAED) have, over the past years, offered new perspectives for the stimulation of hydrocarbon reservoirs, aimed at increasing their production. This contribution addresses the implementation of PAED techniques with two objectives: first, the development of an alternative to classical hydraulic fracturing, and second, the stimulation of existing fractures, aimed at removing debris and particles that may clog drains and decrease the production of oil or gas.<br />With regard to the development of an alternative to hydraulic fracturing that would be more effective for tight formations and potentially less dangerous for the environment, the principle is to induce a shock wave in rock masses generated by PAED. The dynamic load generates distributed damage instead of a localized fracture whose propagation may be difficult to control. In the context of tight rock masses with gas contained in the occluded porosity, it is expected that distributed cracking will be more efficient at connecting these pores, although the volume of rock affected remains confined nearby the well. Experiments reproducing PAED fracturing in reservoir conditions are described. The influences of the amplitude of the shock wave and of the number of shocks applied to laboratory specimens on damage and on the intrinsic permeability of the material are illustrated. Then, a computational model that simulates the entire process is discussed. We focus on the constitutive model for rock masses, based on orthotropic damage with crack closure effects, coupled to an orthotropic description of the evolution of permeability under loads. Rate effects on the damage growth are also included. Finally, numerical simulations of laboratory experiments and PAED fracturing under in situ conditions are discussed.<br />As far as the stimulation of existing fractures is concerned, the issue is to flush out the various particles that may be packed within the propped fracture and may induce a decrease of permeability of the fracture viewed as a drain for hydrocarbon. Applications go beyond unconventional gas production and cover conventional oil and gas production as well, thus making hydrocarbon production more effective. The shock wave generated inside the borehole by PAED is converted into surface waves travelling on the fracture surface. These waves induce fast variations of pressure that may potentially destabilize flocculates and put in suspension particles that have clogged the drain. In order to check this basic principle, an experimental set up has been developed in which a small portion of fracture is clogged and then unclogged by applying a dynamic load. Experiments illustrate the clogging-unclogging effects as a function of the opening of the propped fracture and of the density of fine that are introduced in order to promote clogging. These results should further help at understanding the basic parameters that govern the clogging-unclogging processes and therefore understanding what could be the best conditions of applicability of the method.

References:
Pijaudier-Cabot, G., La Borderie, C. Reess, T., Chen, W., Maurel, O., Rey-Bethbeder, F., de Ferron, A., Electrohydraulic fracturing of rocks, ISTE-Wiley, 2016.\nCandela, T., Brodsky, E.E., Marone, C., Elsworth, D., laboratory evidence for particle mobilization as a mechanism for permeability enhancement via dynamic stressing, Earth Planet. Sci. Lett., vol. 392, pp. 279-291, Apr. 2014.

12:10: [GeomechanicsThuAM03] Plenary
Advanced Approaches for Porous Media – Contributions for Sustainable Development beyond Geomaterials
Wolfgang A. Wall¹ ; ¹Technical University of Munich, Garching, Germany;
Paper Id: 481 [Abstract]

The mechanics of porous media, or briefly poromechanics, sometimes is directly equated with Geomechanics. And this is probably also no surprise as many problems relevant for Geomaterials can be described with theories of poromechanics and also many of the involved interesting effects can be present and relevant for these applications, like large deformations of the solid skeleton, transport of different substances, interface effects on different scales etc. But it is important to note that more or less the same theory, if formulated in a sound and consistent way, can also be used – and actually is often THE appropriate theory – for many other interesting and important applications that also are essential for sustainable development. With his strong and unique background and expertise in the Mechanics of Porous Media and Geomechanics, Bernhard Schrefler also was a pioneer in transferring this expertise to other interesting areas in different fields of Engineering and the Applied Sciences. This serves as an motivation for me to cover advanced computational models and approaches for porous media for interesting problems beyond Geomaterials. In this talk we will present some of our recent work on advanced modeling and development of novel computational approaches in important applications, all of which also play an important role in sustainable development, namely energy storage systems as well as highly relevant biomedical and biophysical applications.

References:
Fang R., Kronbichler M., Wurzer M., Wall W.A.: Parallel, physics-oriented, monolithic solvers for three-dimensional, coupled finite element models of lithium-ion cells. Computer Methods in Applied Mechanics and Engineering, 350 (2019), 803-835

Kremheller J., Vuong A.-T., Schrefler B.A., Wall W.A.: An approach for vascular tumor growth based on a hybrid embedded/homogenized treatment of the vasculature within a multiphase porous medium model. International Journal for Numerical Methods in Biomedical Engineering, accepted 2019

Roth C.J., Becher T., Frerichs I., Weiler N., Wall W.A.: Coupling of EIT with computational lung modelling for predicting patient-specific ventilatory responses. Journal of Applied Physiology, 122 (2017), 855-867

12:35: [GeomechanicsThuAM04] Keynote
Phase-field modelling of desiccation cracks in variably saturated porous media
Lorenzo Sanavia¹ ; Tuanny Cajuhi² ; Claudio Gavagnin² ; Laura De Lorenzis² ; ¹University of Padova, Padova, Italy; ²Technische Universität Braunschweig, Braunschweig, Germany;
Paper Id: 376 [Abstract]

Porous media such as soil, rocks and concrete are of great importance in the context of civil engineering and environmental geomechanics. They consist of a solid skeleton and pores filled with fluids, e.g. air and water. Complex mechanisms of flow and transport take place within the pore network and can lead to deformation of the solid skeleton and eventually to fracture phenomena [1]. Phase-field modeling of fracture has recently emerged as an alternative to conventional approaches such as remeshing, extended finite element methods or cohesive zone modeling. The phase-field framework can be considered a special type of gradient damage modeling approach, where a diffusive approximation of the crack is taken into account and the continuous phase-field parameter is used to describe the material integrity. The essential advantages are the possibility to describe arbitrarily complicated fracture patterns such as nucleation, branching and merging, without ad-hoc criteria on a fixed mesh, through the solution of partial differential equations derived from variational principles [2-5]. Phase-field modeling of fracture in porous media has been addressed in some recent publications [6-7], which however have only focused on the fully saturated case. Objective of this contribution is to describe fracture in partially saturated porous media using a phase-field approach [8]. In this study the air phase is assumed at constant atmospheric pressure with negligible density (passive air phase assumption) and the solid skeleton is described by its linear-elastic properties. Quasi-statics processes are studied. The equilibrium equations of the porous media, the mass balance equation of the liquid water and the phase-field evolution equation constitute a nonlinear coupled and time-dependent system of equations, which needs to be discretized and linearized. We formulate the coupled non-linear system of partial differential equations governing the problem with displacements, capillary pressure and crack phase-field as unknowns. The spatial discretization is carried out with finite elements of appropriate order for the different unknowns. We discuss its solution and present some relevant examples on desiccation tests [8]. The previous model has recently been extended taking into account the contribution of the air phase and the dynamics (u-p approach). The first preliminary numerical results will be shown and discussed.

References:
[1] L. Simoni, B.A. Schrefler, Multi field simulation of fracture. Advances in Applied Mechanics, 2014.
[2] B. Bourdin, G.A. Francfort, J-J. Marigo, Numerical experiments in revisited brittle fracture. Journal of the Mechanics and Physics of Solids, 48, 797-826, 2000.
[3] C. Miehe , F. Welschinger, M. Hofacker, Thermodynamically consistent phase-field models of fracture: variational principles and multi-field FE implementations. Int. J. Num. Meth in Eng, 83, 1273-1311, 2010.
[4] C. Kuhn, R. Muller, A continuum phase field model for fracture. Eng. Fracture Mech. 3625-3634, 2010.
[5] M. Ambati, T. Gerasimov, L. De Lorenzis, A review on phase-field models of brittle fracture and a new fast hybrid formulation. Computational Mechanics 55, 383-405, 2014.
[6] A. Mikelić, M.F. Wheeler, T. Wick, A phase-field method for propagating fluid-filled fractures coupled to a surrounding porous medium. SIAM Multiscale Modeling and Simulation 13(1), 367-398, 2014.
[7] A. Mikelić, M.F. Wheeler, T. Wick, Phase-field modeling of a fluid-driven fracture in a poroelastic medium. Computational Geosciences.1-25, 2015.
[8] Cajuhi T., Sanavia L., De Lorenzis L. (2018) Phase-field modeling of fracture in variably saturated porous media, Computational Mechanics. https://doi.org/10.1007/s00466-017-1459-3

SESSION: GeomechanicsThuPM1-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Gilles Pijaudier-Cabot; Wolfgang A. Wall; Session Monitor: TBA

14:00: [GeomechanicsThuPM105] Plenary
Mechanics and Loss of Hyperelasticity of Geosynthetics Subjected to Chemical Exposure
Patrick Selvadurai¹ ; ¹McGill University, Montreal, Canada;
Paper Id: 181 [Abstract]

Polyvinyl chloride (PVC) membranes are used in geoenvironmental endeavours to prevent groundwater contamination due to leakage of leachates from landfill and other hazardous waste sites. PVC membranes constitute an important component of multi-barrier containment systems that also include layers of impermeable clay and PVC leachate collection systems. Geosynthetic membranes used as landfill liners can be exposed to adverse environments, including heat, exposure to ultra-violet light during construction, bacteria, and chemicals [1]. Despite their widespread use, their long-term effectiveness under exposure to chemicals, such as ultra-violet light, radiation, etc., are poorly understood. A primary requirement of a geosynthetic membrane relates to its ability to undergo large deformations and maintain its integrity, thereby impeding the migration of hazardous chemicals and contaminants to the environment. Experiments conducted in connection with this research indicate that the interaction of the geosynthetics with chemicals such as acetone and ethanol leads to loss of plasticizers that are necessary to maintain the hyperelasticity of geosynthetics [2, 3]. The longevity of the containment provided by PVC geosynthetics can be influenced by these factors, specifically in situations involving the thermal desiccation of clay. Desiccation cracking can be caused by moisture depletion in the clay barrier following exothermic processes associated with the decay of organic matter in a landfill. A cracked clay barrier provides a pathway for contaminants to come into direct contact with a geosynthetic barrier. In contrast to rubber-like elastic materials [4-7], glassy polymeric materials exhibit appreciable irreversible effects, including development of permanent strains during loading-unloading cycles and strain-rate effects. This paper presents constitutive models that first describe the hyperelastic behaviour of a geosynthetic material in its untreated condition. The modelling accounts for both reversible and irreversible components of hyperelastic behaviour and incorporates strain-rate dependency in the constitutive response. The constitutive modelling is then extended to include the long-term loss of hyperelasticity because of exposure to pure ethanol. The constitutive parameters were determined from uniaxial tests and constrained tests conducted at different strain rates. The constitutive models were implemented in a general-purpose finite element code to examine the mechanics of a membrane fixed along a circular boundary and loaded by a hemi-spherical indenter. The comparison between the experimental results and the computational estimates were used for the purposes of validating the modelling approach.

References:
[1] Yu Q, Selvadurai APS, 2005, Polym Degr Stability, 89 (2005) 109-124.
[2] Pita VJRR., Sampaio EEM, Monteiro EEC, Polym Test, 21(2002) 545-550.
[3] Pezzin G, et al. J Appl Polym Sci, 16 (1972)1839-1849.
[4] Treloar LRG, Trans Faraday Soc, 39 (1943) 59-70.
[5] Rivlin RS, 1948,. Phil Trans Roy Soc, A 241, (1948) 379-397.
[6] Green AE, Adkins JE, Large Elastic Deformations, OUP, (1970) London.
[7] Spencer AJM, J Inst Math Applics, 6(1970)164-200.

14:25: [GeomechanicsThuPM106] Keynote
Coupling phenomena in soil mechanics: Beyond failure of slopes
Manuel Pastor¹ ; Diego Manzanal² ; Miguel Martin Stickle³ ; Ángel Yagüe³ ; Saeed S.m. Tayyebi⁴ ; Miguel Molinos³ ; Jose Antonio Fernandez Merodo⁵ ; Pablo Mira⁶ ; Pedro Navas³ ; ¹Universidad Politécnica de Madrid, Madrid, Spain; ²ETS Camnos UPM, madrid, Spain; ³ETS Caminos UPM, Madrid, Spain; ⁴ETS Ingenieros de Caminos UPM, Madrid, Spain; ⁵IGME, Madrid, Spain; ⁶CEDEX, Centro de Estudios y Experimentacion de Obras Publicas, Madrid, Spain;
Paper Id: 179 [Abstract]

Geotechnical engineers have been concerned for many years to determine the conditions under which a geostructure would fail. In order to determine the failure load and the mechanism type, mathematical, constitutive and numerical models have been used. As an example, we can consider the case of a slope subjected to seismic loading. Here, the mathematical model has to describe the coupling between the solid skeleton and the pore fluids. The contributions of Olek Zienkiewicz and Bernardo Schrefler have been of paramount importance for both saturated and unsaturated soils. To describe soil behaviour, constitutive relations are used. We will consider here Generalized Plasticity models for both saturated and unsaturated soils where we have included a state parameter. Regarding numerical models, most of practical cases have been modelled using coupled finite elements. Special techniques have been proposed in the past years to improve the accuracy of the models. Once failure has been triggered, large deformations and displacements can occur. New mathematical models enlarging the domain of application of the classical pre-failure models have been derived, taking into account large relative displacements between phases. Regarding the rheological behaviour of fluidized soil, the progress has been much slower, and much work lies ahead of the concerned researchers. During last years, we have explored the similarity between rheological models and viscoplastic constitutive equations of Perzyna's type, which seem to provide a suitable bridge between solid and fluidized geomaterials behaviour. Regarding numerical modelling, lagrangian meshless techniques such as SPH provide a suitable framework. In cases of landslides propagating distances much larger than their initial length, thin layer approximations provide suitable compromises between accuracy and cost of computation.

References:
Haddad, B; Pastor, M; Palacios & D; Munoz-Salinas, E A depth-integrated, coupled SPH model for flow-like landslides and related phenomena Engng.Geology 114 (3-4), 312-339, 2010

Hutter, K., Siegel, M., Savage, S. B. & Nohguchi, Y. 1993 Two dimensional spreading of a granular avalanche down an inclined plane. Part 1. Theory. Acta Mech. 100, 37-68

Hutter, K., Wang, Y. & Pudasaini, S. P. (2005) The Savage-Hutter avalanche model: how far can itbe pushed?. Phil. Trans. R. Soc. A 363.

Laigle, D. & Coussot, P. (1997): Numerical modelling of mudflows. Journal of Hydraulic Engineering, ASCE, 123 (7): 617-623.
McDougall, S. & Hungr,O. (2004). "A model for the analysis of rapid landslide motion across three-dimensional terrain." Canadian Geotechnical Journal 41.6 (2004): 1084-1097

Pastor, M., Quecedo, M., Fernández Merodo, J.A., Herreros, M.I., Gonzalez, E. & Mira, P.: Modelling tailings dams and mine waste dumps failures. Geotechnique. 52, 579-591 (2002).

Pastor, M., Haddad, B., Sorbino, G., Cuomo, S., Drempetic, V.: A depth-integrated, coupled SPH model for flow-like landslides and related phenomena. Int. J. Numer. Anal. Methods Geomech. 33, 143-172 (2009).

Pastor, M., Quecedo, M., Gonzalez, E., Herreros, I., Fernandez Merodo, J.A. & Mira, P., "Simple Approximation to Bottom Friction for Bingham Fluid Depth Integrated Models," J. Hydraul. Eng., vol. 130, no. 2, pp. 149-155, Feb. 2004.
M. Pastor, M. Martin Stickle, P. Dutto, P. Mira, J. A. Fernández Merodo, T. Blanc, S. Sancho& A. S. Benítez, "A viscoplastic approach to the behaviour of fluidized geomaterials with application to fast landslides," Contin. Mech. Thermodyn., Nov. 2013.M. Pastor, T. Blanc, B. Haddad, S. Petrone, M.
Sanchez Morles, V. Drempetic, D. Issler, G.B. Crosta, L. Cascini, G. Sorbino & S. Cuomo (2014), Application of a SPH depth-integrated model to landslide run-out analysis Landslides (DOI) 10 http://dx.doi.org/10.1007/s10346-014-0484-y

Pastor, M., Blanc, T., Haddad, B., Drempetic, V., Morles, M. S., Dutto, P., & Merodo, J. F. (2015b). Depth Averaged Models for Fast Landslide Propagation: Mathematical, Rheological and Numerical Aspects. Archives of Computational Methods in Engineering, 22(1), 67-104.

Pastor, M., Yague,A., Martin Stickle, M, Manzanal,D. & Mira, P. "A two-phase SPH model for debris flow propagation", Int J Numer Anal Methods Geomech. 2018 DOI: 10.1002/nag.2748
Pitman EB & Le L. A two-fluid model for avalanche and debris flows. Philos Trans A Math Phys Eng Sci. 2005; 363: 1573-601.

Pudasaini SP. A general two-phase debris flow model. Journal of Geophysical Research. 2012; 117, F03010

Pudasaini, S. P. & K. Hutter (2007), Avalanche Dynamics: Dynamics of Rapid Flows of Dense Granular Avalanches, 602 pp., Springer, New York.

Zienkiewicz, O.C. & Shiomi, T. (1984). Dynamic behaviour of saturated porous media: The generalised Biot formulation and its numerical solution. International Journal of Numerical and Analythical Methods in Geomechanics,8, pp. 71-96

14:50: [GeomechanicsThuPM107]
Multiscale Materials Modeling of Metals from AToms to Components
Siegfried Schmauder¹ ; ¹University of Stuttgart, Lenningen, Germany;
Paper Id: 374 [Abstract]

Multiscale Modeling of Metals from Atoms to Components Prof. Dr. Dr. h. c. Siegfried Schmauder Institute for Materials Testing, Materials Science and Strength of Materials (IMWF), University of Stuttgart, Pfaffenwaldring 32, D-70569 Stuttgart, Germany siegfried.schmauder@imwf.uni-stuttgart.de In this overview the first successful examples of real multiscaling from atoms to macroscale for different applications of metals will be presented. In this context, multiscale simulation comprises all length scales from atomistics via microme¬cha-nical contributions to macroscopic materials behavior and further up to applications for compo-nents, nowadays called multiscale materials modelling (MMM). A main focus of the presentation will be put on new developments with special emphasis on MD-simulations and other methods involved and how they interact within the present approach. It will be shown that each method is superior on the respective length scale. Furthermore, the parameters which transport the relevant information from one length scale to the next one are decisive for performing physically based multiscale simulations [1]. While in the past, different methods were tried to be combined into one simulation, it is nowadays obvious in many fields of research that the only way to succeed in understanding the mechanical behavior of materials is to apply scale bridging techniques in sequential multiscale simulations to achieve phy¬sically based practically relevant material solutions without adjustment to any experiment. This has opened the door to real virtual material design strategies. In a final step it will be shown that the approach is not limited to metals but can be extended to other material classes and can be also applied for composites [2] as well as to many aspects of material problems in modern technical applications where the different disciplines meet, from physics to materials science and further on to en¬gineering applications. In the second part of the presentation, emphasis will be put on the problem of fatigue of metals where multiscale materials modeling can answer a number of questions such as the influence of the lattice type or the relevance of mate¬ri¬als properties.

References:
References
[1] S. Schmauder, I. Schäfer (Eds.) 2016, Multiscale Materials Modelling – Approaches to Full Multiscaling, Walter de Gruyter GmbH, Berlin/Boston, 326 p.
[2] S. Schmauder, L. Mishnaevsky (Eds.) 2008, Micromechanics and Nanosimulation of Metals and Composites – Advanced Methods and Theoretical Concepts, Springer, Berlin/Heidelberg, 420 p.

15:15: [GeomechanicsThuPM108] Invited
Multiscale Simulations For The Development Of Advanced Composite Structures
Aleksandr Nemov¹ ; Alexey Borovkov² ; ¹Peter the Great St. Petersburg Polytechnic University, Saint-Petersburg, Russian Federation; ²Peter the Great St. Petersburg Polytechnic University, St. Petersburg, Russian Federation;
Paper Id: 256 [Abstract]

The introduction of composite materials in industry forced the development of a specific branch of computational science known as mechanics of composite materials. Homogenization, a basic technique of this theory, has been known for about a hundred years, counting from the pioneering work of Voigt [1] and Reuss [2]. The development of advanced composite structures, however, is still pushing the analysis tools and techniques for multiscale simulations, e.g. [3-6] forward. The paper is aimed to review challenges in the design of complex composite structures and ways to overcome them. The following problems are considered as examples for application of the multiscale simulations: prediction of micro-strains in ITER superconducting cables, design of novel composite materials for 3D printing, and design of a new carbon fiber high-speed catamaran. Application of both conventional and novel techniques for homogenization and heterogenization (unsmearing) in multiscale analysis is discussed and pros and cons of various approaches are highlighted.

References:
[1] Voigt, W. Theoretische Studien Uber die Elasticitatsverhaltnisse der Krystalle // Abh.Kgl.Ges.Wiss.Gottingen, Math.Kl. 1887; 34. pp. 3-51.\n[2] Reuss, A. Berechnung der Fliessgrenze von Mischkristallen auf Grund der Plastizitatsbedingung fur Einkristalle // Journal of Applied Mathematics and Mechanics, 1929; 9. pp. 49-58.\n[3] Schrefler, B.A., Boso, D.P., Lefik, M. Numerical multiscale modelling of elasto-plastic behavior of superconducting strand // Solid Mechanics and its Applications, 2006, 135, pp. 151-158.\n[4] Kanoute, P., Boso, D.P., Chaboche, J.L., Schrefler, B.A. Multiscale methods for composites: A review // Archives of Computational Methods in Engineering, 2009, 16 (1), pp. 31-75. \n[5] Li, X., Liang, Y., Du, Y., Schrefler, B. Advances in multiscale modeling of granular materials // Springer Tracts in Mechanical Engineering, 2016, 18, pp. 63-73. \n[6] Zobacheva, A.U., Nemov, A.S., Borovkov, A.I. Multiscale simulations of novel additive manufactured continuous fiber-reinforced three-component composite material // Materials Physics and Mechanics, 2017, 32 (1), pp. 74-82.

SESSION: GeomechanicsThuPM2-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Lorenzo Sanavia; Patrick Selvadurai; Session Monitor: TBA

15:55: [GeomechanicsThuPM209] Plenary
Is coupling PD with FEM the way forward to solve in an efficient way crack propagation problems?
Tao Ni¹ ; Greta Ongaro² ; Pablo Seleson³ ; Mirco Zaccariotto⁴ ; Ugo Galvanetto² ; ¹Hohai University, Nanjing, China; ²University of Padova, Padova, Italy; ³Oak Ridge National Laboratory, Oak Ridge, United States; ⁴University of Padua, Padova, Italy;
Paper Id: 217 [Abstract]

Environmental, economic and safety concerns require more and more precise capabilities to perform the life cycle assessment of engineering structures. Therefore, structural engineers should be capable of describing all stages of the structural life even that involving the propagation of cracks and branching under complex loading conditions. The description of the propagation of cracks in structural materials, however, is still an open problem. The unavoidable presence of discontinuities prevents a direct application of the methods based on Classical Continuum Mechanics (CCM). Recently, Peridynamics (PD) has been proposed [1, 2] as a theory in which cracks are not part of the problem but part of the solution; PD is based on integral equations that do not make strong assumptions on the continuity of the displacement field. The integrals of the peridynamic theory are computed on a neighborhood of each material point, which is affected, in a nonlocal way, even by points that are not in direct contact with it. As a consequence of such a nonlocality, computational methods based on PD are usually more computationally expensive than those based on CCM. Several researchers are trying to couple computational methods based on CCM with those based on PD to obtain a computational tool able to simulate crack propagation in an efficient way [3-5]. Coupling two different continuum theories is not straightforward. In our presentation, coupling is realized at the discrete level between the standard displacement version of the Finite Element Method and a meshless version of the Ordinary State based PD. The domain is divided in two portions, one discretized with FEM and the other with OSBPD. If a perfect bonding between the displacements of the two portions is imposed, some out of balance forces are generated. The paper evaluates the magnitude of the out of balance forces and discusses some ways to reduce them.

References:
1) S.A. Silling, Reformulation of elasticity theory for discontinuities and long-range forces, J. Mech. Phys. Solids, 48 Issue: 1, 175-209, (2000).
2) S. A. Silling, M. Epton, O. Weckner, J. Xu, E. Askari, Peridynamic states and constitutive modeling, J. Elasticity 88 (2007): 151-184.
3) G. Lubineau,Y. Azdoud, F. Han, et al., A morphing strategy to couple non-local to local continuum mechanics, J. Mech. Phys. Solids, 60 Issue: 6, 1088-1102, (2012).
4) U. Galvanetto, T. Mudric, A. Shojaei, M. Zaccariotto, An effective way to couple FEM meshes and Peridynamics grids for the solution of static equilibrium problems, Mechanics Research Communications 76, 41-47, (2016).
5) M. Zaccariotto, T. Mudric, D.Tomasi, A. Shojaei, U. Galvanetto, Coupling of FEM meshes with Peridynamic grids, Comp. Meth. Appl. Mech. Eng., Volume: 330, Pages: 471-497, (2018).

16:20: [GeomechanicsThuPM210] Keynote
On Established Dynamic Front Propagation Regimes in Structured and Continuous Media.
Gennady Mishuris¹ ; Leonid Slepyan² ; ¹Aberystwyth University, Aberystwyth, United Kingdom; ²Tel-Aviv University, Ramat Aviv, Israel;
Paper Id: 247 [Abstract]

Recently, non-continuous (step-wise) crack propagation has been observed in the numerical and experimental analysis concerning hydraulic fracture propagation in porous rock. It has been shown that the phenomenon is of a fundamental nature in the HF process [1,2]. Simultaneously, various regular crack propagation regimes (e.g. crack speed oscillation) have been discovered in the dynamic processes: in discrete elastic structures (splitting chain strips, crack propagation in lattices with different links [3-5]), and in continuous media (delamination of a flexural elastic beam rested on the Winkler foundation [6]). The latter case has much in common with the phenomenon discussed in [1,2]. Among others, it was shown in [6] that, under the action of an incident sinusoidal wave, the steady-state mode exists only in a bounded domain of the wave amplitude. For higher amplitudes, local separation segments periodically emerge at a distance ahead of the main transition front. The analytical solution obtained allows analysis of this effect in detail and allows identification of a boundary between the steady-state and forerunning modes into the parametric space. In a structured material (even of a simplest regular structure), depending on the applied load and the material properties, the following basic established (regular) dynamic fault / fracture propagation regimes can be identified [3-5]: fully open (classic) crack, bridge crack, and cluster-type propagation and forerunning. For more complex materials, all of those modes can appear together as a specific combination organized into rather complex, but still regular, regimes. We do not include the so-called branching crack propagation regime into this classification. This regime may also be very regular but it is not supported in one-dimensional front propagation as the previous modes.

References:
[1] Cao T, Hussain F, Schrefler B. J. Mech. Phys. Solid. (2018); 111:113-133.
[2] Peruzzo C, Cao D, Milanese E, Favia P, Pesavento F, Hussain F, Schrefler B. Eur. J. Mech. A Solids (2019), 74:471-484.
[3] Slepyan, L., Movchan, A., Mishuris, G., Int J Fract, (2009) 162, 91-106.
[4] Ayzenberg-Stepanenko, M., Mishuris, G., Slepyan, L., Proc. R. Soc. A (2014), 470, 20140121.
[5] Nieves, M., Mishuris, G., Slepyan, L., Int. J. Solids Struct, (2016), 97-98, 699-713.
[6] Slepyan, L., Ayzenberg-Stepanenko, M., Mishuris, G., Forerunning mode transition in a continuous waveguide. (2015) J. Mech. Phys. Solids 78, 32-45.

16:45: [GeomechanicsThuPM211] Keynote
Influence of Plastic Deformation and Inherent Anisotropy of Rocks on Hydraulic Fracturing Process
Qingdong Zhen¹ ; Jianfu Shao² ; ¹China University of Petroleum (East China), Qingdao, China; ²University of Lille, Villeneuve Ascq, France;
Paper Id: 267 [Abstract]

In this study, we shall investigate the effect of plastic deformation and inherent anisotropy of rocks on the hydraulic fracturing process. For this purpose, we propose an efficient numerical solution by combining the extended finite element method (XFEM) and the embedded discrete fracture model (EDFM) for studying hydraulic fracturing under coupled thermal-hydraulic conditions in an elastic-plastic porous medium. We consider both the fluid flow (and heat transfer) through the porous medium and the exchange between the medium and fracture. An efficient iterative scheme is developed to deal with the interaction between rock deformation, fracture propagation, fluid flow and heat transfer. The proposed method is assessed through comparisons with analytical solutions for a number of well-established problems. A series of numerical calculations are performed in order to investigate the effect of plastic deformation and inherent anisotropy of rocks on the process of hydraulic fracture propagation. Particular attention will be paid to the analysis of the process zone ahead of fracture in the context of anisotropic and plastic rocks.

References:
Zeng, Q., Yao, J., 2016. Numerical simulation of fracture network generation in naturally fractured reservoirs. Journal of Natural Gas Science and Engineering 30, 430-443.
Zeng, Q.D., Yao, J., Shao, J., 2018. Numerical study of hydraulic fracture propagation accounting for rock anisotropy. Journal of Petroleum Science and Engineering 160, 422-432.
Zeng, Q.D., Yao, J., Shao, J., 2019. Study of hydraulic fracturing in an anisotropic poroelastic medium via a hybrid EDFM-XFEM approach. Computers and Geotechnics 105, 51-68.

17:10: [GeomechanicsThuPM212] Keynote
Flow-like landslide mechanisms and modelling: filling the gap between hydraulic and geotechnical engineering
Sabatino Cuomo¹ ; ¹University of Salerno, Fisciano, Italy;
Paper Id: 459 [Abstract]

Landslides of the flow-type are dangerous and also challenging to study [1]. A wide literature has been investigating the principal mechanisms governing each stage in which these phenomena can be ideally subdivided: namely, triggering [2], post-failure [3] and propagation [4]. However, holistic contributions and general overviews are very rare. In addition, a number of numerical methods have been issued and validated so that new chances exist to efficiently model those threats. One main limitation has been represented by the tremendous gap among those contributions based on the effective stress principle in soil mechanics and other studies conceived in fluid mechanics. The former ones have been applied to slope stability while the latter to landslide evolution, including propagation, deposition and even impact/interaction with structures and protective measurements. As emblematic cases, two classes of rainfall-induced landslides of the flow-type namely debris flows and debris avalanches could be mentioned. The principal numerical methods are reviewed for modeling the landslide initiation and propagation and are later used for analyzing a series of benchmark slopes and real case histories which are successfully simulated.

References:
[1] Pastor, M., Blanc, T., Haddad, B., Petrone, S., Morles, M. S., Drempetic, V., Issler D., Crosta G.B., Cascini L., Sorbino G., Cuomo, S. (2014). Landslides, 11(5), 793-812.\n[2] Cascini, L., Cuomo, S., Pastor, M., Sorbino, G. (2009). Journal of Geotechnical and Geoenvironmental Engineering, 136(1), 85-98.\n[3] Cascini, L., Cuomo, S., Pastor, M., Sacco, C. (2013). Canadian Geotechnical Journal, 50(9), 924-934.\n[4] Cuomo, S., Pastor, M., Cascini, L., Castorino, G. C. (2014). Canadian Geotechnical Journal, 51(11), 1318-1330.

SESSION: GeomechanicsThuPM3-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Thu Oct, 24 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Andrew Chan; Herbert MANG; Session Monitor: TBA

17:50: [GeomechanicsThuPM313] Invited
Convergence in Dynamic Hydraulic Fracturing Modeling: Step-Wise Crack Advancement and Pressure Oscillations in Saturated Porous Media
Mohammadreza Hirmand¹ ; Mohammad Vahab² ; Katerina D. Papoulia³ ; Nasser Khalili² ; ¹University of Waterloo, Waterloo, Canada; ²UNSW, Sydney, Australia; ³Applied Mathematics, University of Waterloo, Waterloo, Canada;
Paper Id: 328 [Abstract]

Crack propagation is most frequently implemented on the basis of so-called extrinsic models in which discontinuity surfaces (cracks) are introduced upon satisfaction of an external stress criterion. Often, an implicit time marching scheme is employed in which the crack is kept fixed within the computations of the iterative solver. The crack is advanced to a pre-determined length on the basis of a pre-determined propagation law at the end of the load step. This approach has been shown to lack mathematical soundness and is especially problematic in the context of hydraulic fracturing. The sequential solution of the displacement and crack surface in unknown fields leads to crack propagation velocities that do not converge with time step and mesh size refinement. A consequence of this issue is that the hydraulic fracturing model cannot properly capture the step-wise crack advancement and pressure oscillations in saturated porous media. This is not a coincidence but a manifestation of robustness issues with extrinsic crack propagation algorithms. We propose a hydraulic fracturing model with non-differentiable energy minimization for cohesive fracture in which formation and propagation of cracks are direct outcomes of the computations within the time step. The method allows advancement for any length of crack within a time step given the applied loads without need to introduce crack nucleation and crack increment length criteria. Numerical results show step-wise behavior which also exhibit convergence with time step and mesh size refinement.

References:
[1] K. D. Papoulia, C.-H. Sam, S. A. Vavasis, Time continuity in cohesive finite element modeling, International Journal for Numerical Methods in Engineering 58 (2003) 679-701.
[2] K. D. Papoulia, Non-differentiable energy minimization for cohesive fracture, International Journal of Fracture 204 (2017) 593 143-158.
[3] M. R. Hirmand, K. D. Papoulia, A continuation method for rigid-cohesive fracture in a discontinuous Galerkin finite element setting, International Journal for Numerical Methods in Engineering 115 (2018) 627-650.
[4] M. R. Hirmand, K. D. Papoulia, Block coordinate descent energy minimization for dynamic cohesive fracture, Computer Methods in Applied Mechanics and Engineering (2019). https://doi.org/10.1016/j.cma.2019.05.051.
[5] C. Peruzzo, T. D. Cao, E. Milanese, P. Favia, F. Pesavento, F. Hussain, B. A. Schrefler, Dynamics of fracturing saturated porous media and self-organization of rupture, Journal of the Mechanics and Physics of Solids 111 (2018) 113-133.
[6] A. Khoei, M. Vahab, M. Hirmand, An enriched FEM technique for numerical simulation of interacting discontinuities in naturally fractured porous media, Computer Methods in Applied Mechanics and Engineering 331 (2018) 197-231.

18:15: [GeomechanicsThuPM314] Keynote
Robust Simulation of Dynamic Hydraulic Fracturing in Naturally Fractured Formations
Mohammad Vahab¹ ; Mohammadreza Hirmand² ; Katerina D. Papoulia³ ; Nasser Khalili¹ ; ¹UNSW, Sydney, Australia; ²University of Waterloo, Waterloo, Canada; ³Applied Mathematics, University of Waterloo, Waterloo, Canada;
Paper Id: 7 [Abstract]

In this study, an energy based hydro-mechanical model and computational algorithm for the problem of hydraulically driven fracture networks developing in naturally fractured impermeable media is developed. The model is based on non-differentiable energy minimization for the dynamic deformation and fracture of the body coupled with mass balance of fluid flow within the hydro-fractures. Time-discontinuity induces spurious crack-opening velocity fields which lead to nonphysical solutions for the coupled fluid pressure field defined locally along the crack faces. The use of a time-continuous fracture model, such as the present non-differentiable energy minimization approach, is crucial for the numerical soundness and stability of the hydraulic fracture propagation algorithm. A discontinuous Galerkin finite element formulation is implemented, in which every element edge in the mesh is a potential site of hydro-fracture initiation and propagation. The presence of pre-existing natural fractures, as a common challenge in nearly all geological formations, are modelled with desirable edibility by simply assigning different fracture properties to the element edges defining the natural fractures. Using the graph theory principals, a search algorithm is proposed to identify, among all, the sub-set of cracked interfaces that form the interconnected hydraulically loaded fracture network. Robustness of the proposed computational algorithm and its versatility in the study of hydraulic fracturing is shown through several numerical simulations.

References:
[1] M.R. Hirmand, K. D. Papoulia, Int. J. Numer. Meth. Eng. 115 (2018) 627-650.
[2] M. Vahab, N. Khalili, Rock. Mech. Rock. Eng. 51(2018) 3219-3239
[3] A.R. Khoei, M. Vahab, E. Haghighat, S. Moallemi, Int. J. Fract. 188 (2014) 79-108.

SESSION: GeomechanicsFriAM-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Nasser Khalili; Bernd Markert; Session Monitor: TBA

11:20: [GeomechanicsFriAM01] Plenary
Working at the Geo/Bio Interface: Elastoplasticity of the Hierarchical Material System Bone
Christian Hellmich¹ ; Valentina Wittner¹ ; Viktoria Vass¹ ; Claire Morin² ; ¹Vienna University of Technology, Vienna, Austria; ²Ecole des Mines de Saint-Etienne, Saint-Etienne, France;
Paper Id: 317 [Abstract]

Many biological systems integrate inorganic, mineral components which are also used by nature in a geological context. This provides a fascinating avenue for interdisciplinary work at the “bio/geo-interface”. The present lecture will cover 20 years of research concerning works that translate and adopt concepts from poro-micromechanics, a theory having originally arisen in geoengineering, to move towards the deciphering of the mechanics of complex biological systems. In this context, particular emphasis will be laid on the use of the Mohr-Coulomb failure criterion, one of the most fundamental theoretical concepts in geomechanics. This criterion is within the framework of multiscale continuum micromechanics, so it allows prediction of the strength of bone from elastic and strength properties of the material’s elementary components: hydroxyapatite crytals, type I collagen, and water with non-collageneous organics. In this context, the following theoretical steps, all carefully implemented numerically and tested by very many biomechanical, biophysical, and biochemical experiments, are the following: the hierarchical sequencing of traditional homogenization schemes such as the two-phase Mori-Tanaka and self-consistent scheme [1,2,3], the extension from two-phase to multi-phase systems [4,5], and the consideration of eigenstrains and their upscaling characteristics [6], which paved the way towards a unified vision of bone multiscale biomechanics, encompassing poro-elasticity, poro-plasticity [7,8], and creep [9].

References:
[1] A. Fritsch, Ch. Hellmich, J Theor Biol 244, 597-620, 2007.
[2] Ch. Hellmich, J.-F. Barthélémy, L. Dormieux, Eur J Mech 23A, 783—810, 2004.
[3] V. Vass, C. Morin, S. Scheiner, Ch. Hellmich, CISM Vol. 578, 175-229, 2018.
[4] Ch. Hellmich, J. Celundova, F.-J. Ulm, J Eng Mech 135, 382-394, 2009.
[5] C. Morin, Ch. Hellmich, Ultrasonics 54, 1251-1269, 2014.
[6] B. Pichler, Ch. Hellmich, J Eng Mech 136, 1043-1053, 2010.
[7] A. Fritsch, Ch. Hellmich, L. Dormieux, J Theor Biol 260, 230-252, 2009.
[8] C. Morin, V. Vass, Ch. Hellmich, Int J Plast 91, 238-267, 2017.
[9] L. Eberhardsteiner, Ch. Hellmich, S. Scheiner, Comp Meth Biomech Biomed Eng 17, 48-63, 2014.

11:45: [GeomechanicsFriAM02] Invited
Numerical Modelling of the effect of blasting and rock cutting in resources mining
Hongyuan Liu¹ ; Andrew Chan¹ ; ¹University of Tasmania, Hobart, Australia;
Paper Id: 386 [Abstract]

Mining is essential to economy of the nations as well as technological development and human industry. Until we can stop using some of the material mined or replace the process with a more environmental friendly one, reduction of environmental impact of existing processes would be the best way forward. Monitoring and laboratory experiments have provided very good data concerning mining activities but it is usually expensive and time-consuming to perform field studies or laboratory experiments. Numerical modelling is one way to assess the process and to extract useful information from field observations and experimental data. Numerical modelling can also provide predictions for future operations or new mining process. In this paper, the finite discrete element method [1] will first be introduced and the development of the method to model blasting and rock cutting [2] will be explained. With a better understanding of the method involved, its environmental impact can be minimised.

References:
1. Munjiza AA, Knight EE, Rougier E (2011) Computational mechanics of discontinua. John Wiley & Sons
2. Liu HY, Kang YM, Lin P (2015) Hybrid finite–discrete element modeling of geomaterials fracture and fragment muck-piling International Journal of Geotechnical Engineering 9:115-131 doi:10.1179/1939787913Y.0000000035

12:10: [GeomechanicsFriAM03] Keynote
Second Gradient Poromechanics: Constitutive Modeling and Numerical Implementation in IGA-FEM
Carlos Plua¹ ; Pierre Besuelle¹ ; Claudio Tamagnini² ; ¹Laboratoire 3SR Universite Grenoble Alpes, INP, CNRS, Grenoble, France; ²University of Perugia, Perugia, Italy;
Paper Id: 409 [Abstract]

In this work, a fully coupled hydromechanical formulation for unsaturated 2nd gradient elastoplastic porous media is presented and applied to the numerical modeling of some geomechanics IBVP characterized by strain localization into shear bands. The introduction of internal length scales associated to the weakly non-local character of the constitutive equations effectively regularizes the numerical solutions. The 2nd gradient elastoplastic model adopted is based on two independent plastic mechanisms. The first one is provided by a three-invariant isotropic--hardening elastoplastic model similar to the one presented by Nova et al. [1], extended to unsaturated soils. In lack of sufficient experimental evidence, the second-gradient mechanism is based on a simple elastic-perfectly plastic formulation. Foe the numerical solution of the governing system of non-linear PDEs, the Isogeometric (IGA) Finite Element Method [2] has been adopted. When applied to constrained micromorphic media such as second-gradient materials, IGA offers the advantage of providing higher-order continuity of the approximating functions across element boundaries, which allows a more efficient and straightforward implementation of the discrete equilibrium problem, as compared to existing mixed FE formulations based on conventional polynomial shape functions, see [3]. This feature is also very important in coupled hydromechanical problems. In fact, the smoothness of the approximated displacements and pore pressure fields can mitigate significantly the requirements for minimum time steps. The simulation of some relevant consolidation problems demonstrates the good performance of the IGA implementation, and shows its effectiveness in regularizing the FE solutions when localization patterns occur in the strain field.

References:
[1]. Nova, R., Castellanza, R., & Tamagnini, C. (2003). A constitutive model for bonded geomaterials subject to mechanical and/or chemical degradation. International Journal for Numerical and Analytical Methods in Geomechanics, 27(9), 705-732.

[2]. Hughes, T. J., Cottrell, J. A., & Bazilevs, Y. (2005). Isogeometric analysis: CAD, finite elements, NURBS, exact geometry and mesh refinement. Computer methods in applied mechanics and engineering, 194(39), 4135-4195.

[3]. Collin, F., Chambon, R., & Charlier, R. (2006). A finite element method for poro mechanical modelling of geotechnical problems using local second gradient models. International journal for numerical methods in engineering, 65(11), 1749-1772.

12:35: [GeomechanicsFriAM04] Invited
Predictive Geosciences for Georesources Exploration and Management, Underground Exploitation, and Environmental Issues
Mohamed Azaroual¹ ; ¹ISTO (Earth Science Institute of Orleans), Orléans, France;
Paper Id: 272 [Abstract]

Constant growth in world population and intense industrial development inevitably cause degradation of the environment and induce scarcity, sometimes also causing conflicts and tension regarding georesources. Predictive geosciences gather knowledge from fields such as mathematics, physics, and material sciences in order to develop geo-technologies based on Big Data assessment and predictive/inverse numerical simulations. Also necessary is the development of theoretical concepts and continuously improving methods of application derived from recent advancements in scientific and technological innovation in related domains. Land surfaces and subsurfaces are increasingly solicited for different uses including exploitation of water resources for farming, agriculture, and other uses. In addition, exploration and exploitation of energy resources, useful substances, and storage of undesirable substances in the underground require knowledge of the dynamics of multiphase hydrosystems, from the surface to depths of several kilometers. The fundamental issue is transfer of mass and heat between phases (water - rock - gas - "microorganisms") on different scales of time and space, from soil to groundwater and deep aquifers. Such knowledge and application demands multidisciplinary competencies and complementary methods to enrich and extend both theoretical approaches and databases to build advanced concepts as well as interpretive and predictive numerical models [1]. These models must be continuously fed, updated, improved, tested, and validated on potentially similar and analogous systems on large scales. The advanced concepts are based on field observations highlighting the expression and footprints of several complex and coupled physico-chemical and biological processes, such as those for reactive facies, redox zone, pH-buffering zone, capillary fringe, and mixing zone, that can be nested in generic and generalizable patterns (i.e., Critical Zone, etc.). These concepts can be used as guides to explore and manage geosystems to exploit resources (water, oil, gas, heat, recyclable materials, etc.) as well as to store some resources temporarily (water, heat, gas, etc.) and store undesirable substances permanently (CO₂, industrial water, acid gases, radioactive waste, etc.) [2]. Several platforms for the environment, artificial recharge of aquifers, mineral extraction, and recycling materials, were constructed at different scales to sustain these scientific developments [3]. Biodegradation processes based on the triggering of biogeochemical reactions result in the installation of active redox zones with relatively variable spatial extension and lifespan [4]. It is clear that future industrial and socio-economic developments must be rethought and improved by moving closer to an ideal of "zero rejection" and optimal and efficient use of natural resources. A comprehensive review of the state of knowledge, success stories, challenges, and innovation potentials will be presented. In addition, the areas of development in geosciences at BRGM (French Geological Survey) and ISTO (Earth Sciences Institutes of Orléans), institutes that share observation sites, research infrastructures, and pilot sites for developing environmental monitoring tools, and validation models supports will be presented.

References:
[1] Azaroual M., Pettenati M., Besnard K., Casanova J., Rampnoux N. (2011). In: Water Security in the Mediterranean Region. NATO Science for Peace and Security Series - C: Environmental Security. Springer Science, Chap. 9; pp. 111-128.
[2] André L., Azaroual M., Bernstone Ch., Witteck A. (2015). Transport in Porous Media. Vol. 108; 185-205.
[3] Ollivier P., N. Surdyk N., Azaroual M., Besnard K., Casanova J., Rampnoux N. (2013). Chemical Geology, Vol. 356; 109-125.
[4] Viggi C, Matturro B, Frascadore E, Insogna S, Mezzi A, Kaciulis S, Sherry A, Mejeha OK, Head IM, Vaiopoulou E, Rabaey K, Rossetti S, Aulenta F. (2017) Water Res. Vol. 15; 11-21.

SESSION: GeomechanicsFriPM1-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Elias Aifantis; Carlo Pellegrino; Session Monitor: TBA

14:00: [GeomechanicsFriPM105] Plenary
Thermo-hydro-mechanical Modeling of Soil Freezing Using a Coupled Phase-field–porous Media Approach
Bernd Markert¹ ; Abdel Hassan Sweidan² ; Baharin Ali² ; ¹Institute for General Mechanics, RWTH Aachen University, Aachen, Germany; ²Institute of General Mechanics (IAM), RWTH Aachen University, Aachen, Germany;
Paper Id: 378 [Abstract]

Studying the freezing process in water-saturated soils is of great interest in many engineering fields. During the freezing of fine-grained soils, volume expansion known as frost heave is usually observed. Such phenomenon can cause detrimental deformation and damage to highways, building foundations and pipelines in cold regions subjected to seasonal freezing or during mining and tunneling where artificial freezing is adopted. The frost heave is attributed to the formation and growth of ice lenses associated with water migration to the freezing front. Based on several experimental works and previous studies, it is found that the ice lens formation is related to cracking of the soil in the frozen fringe [1]. Therefore, according to the stress criterion, the soil skeleton separates and a new ice lens forms when the pore pressure exceeds the sum of the overburden stress and the separation strength of the freezing soil. Moreover, suction occurs when the pore water solidifies into ice, facilitating water migration from the unfrozen zone to feed the growth of the ice lens [2]. Here we propose a thermo-hydro-mechanical model consisting of a porous solid matrix and a pore-fluid phase representing solid ice and liquid water based on a coupled phase-field-porous media approach. The model accounts for the phase change, water migration, ice lens formation and soil deformation due to the freezing process. We use the macroscopic theory of porous media (TPM) for the description of the deformable, heterogeneous porous solid [3] with the phase changing fluid constituent described by a unified formulation employing a phase-field model (PFM) [4]. The diffusive interface treatment of the freezing front can be easily implemented numerically as no explicit front tracking and application boundary conditions at the interface is required. The ice lens formation is modeled based on the rigid ice model adopting the stress criterion. In this context, a fracture related PFM is used to describe the crack formation preceding the ice lens initiation [5]. Additionally, the Clapeyron equation is employed to calculate the suction pressure at the water–ice interface. Finally, numerical examples are presented to demonstrate the ability of the proposed model in describing the freezing process in fluid-saturated porous media.

References:
[1] T.F. Azmatch, D. C. Sego, L. U. Arenson, K. W. Biggar, Cold Reg. Sci. Technol. 82 (2012) 8-13.
[2] F. Ming, Y. Zhang, D.q. Li, Geosci. J. 20 (2016) 667–679.
[3] B. Markert, Arch. Comput. Methods Eng. 15 (2008) 371–446.
[4] A.H Sweidan, Y. Heider, B. Markert, Contin. Mech. Thermodyn. (2019) 1-22.
[5] Y. Heider, S. Reiche, S., P. Siebert, B. Markert, Eng. Fract. Mech. 202 (2018) 116–134.

14:25: [GeomechanicsFriPM106] Plenary
Scale-dependent Continuum Descriptions for Materials with Microstructure: Old Ideas and New Formulations
Patrizia Trovalusci¹ ; ¹Sapienza - University of Rome, Rome, Italy;
Paper Id: 279 [Abstract]

The mechanical behaviour of complex materials, characterized by complex non-linear behavior and complex internal sub-structure (micro), strongly depends on their microstructural features. In particular, in the modelling of these materials, such as particle composites that are polycrystals with interfaces or with thin or thick interfaces, as well as rock or masonry-like materials, the discrete and heterogeneous nature of the matter must be taken into account. This is because interfaces and/or material internal phases dominate the gross behaviour. This is definitely ascertained. What is not completely recognized instead is the possibility of preserving the memory of the microstructure, and of the presence of material length scales, without resorting to the discrete modelling which can often be cumbersome in terms of non-local continuum descriptions. In the possibility of accounting for non-symmetries in strains and stresses, the classical Cauchy continuum (Grade1) does not always seem appropriate for describing the macroscopic behaviour while taking into account the size, the orientation and the disposition of the micro-heterogeneities. This occurs in the case of materials made of particles of prominent size and/or strong anisotropy anisotropic media which lack in-material internal scale parameters. This calls for the need of non-classical continuum descriptions [1, 2], that can be obtained through multiscale approaches, aimed at deducing properties and relations by bridging information at proper underlying sub-levels via energy equivalence criteria. In the framework of such a multiscale modelling, the non-local character of the description is then crucial for avoiding physical inadequacies and theoretical computational problems. In particular, there are problems in which a characteristic internal (material) length, l, is comparable to the macroscopic (structural) length, L [3]. Among non-local theories, it is useful to distinguish between 'explicit' or 'strong' and 'implicit' or 'weak' non-locality [4]. Implicit non-locality concerns generalize continua with extra degrees of freedom, such as micromorphic continua [1] or continua with configurational forces [2]. This talk wants firstly to focus on the origins of multiscale modelling, related to the corpuscular(molecular)-continuous models developed in the 19th century and to give explanations 'per causas' of elasticity (Cauchy, Voigt, Poincare). This is in order to find conceptual guidelines for deriving discrete-to scale-dependent continua that are essentially non-local models with internal length and dispersive properties [4, 5]. Then, a discrete-to-scale dependent continuous formulation, developed for particle composite materials, based on a generalized version of Voigt's molecular/continuum approach is proposed [6]. Finally, with the aid of some numerical simulations concerning ceramic matrix composites (CMC), and microcracked media and masonry assemblies, the focus will be on the advantages of micropolar modelling with respect to other generalized continuum formulations [7-9].

References:
[1] Eringen, A.C. (1999), Microcontinuum Field Theories, Springer-Verlag, New York
[2] Gurtin, M. E. (2000), Configurational Forces as Basis Concept of Continuum Physics, Springer-Verlag, Berlin.
[3] Trovalusci P., Ed. (2016), Materials with Internal Structure. Multiscale and Multifield Modeling and Simulation, P. Trovalusci (Ed.), Springer Tracts in Mechanical Engineering, Vol.18:109-131, Springer.
[4] Trovalusci, P. (2014), Molecular approaches for multifield continua: origins and current developments. CISM (Int. Centre for Mechanical Sciences) Series, 556: 211-278, Springer.
[5] Trovalusci, P., Capecchi, D., Ruta, G. (2009), Genesis of the multiscale approach for materials with microstructure, Archive of Applied Mechanics, 79(11): 981-997.
[6] Trovalusci, P., Varano, V., Rega, G. (2010), A generalized continuum formulation for composite materials and wave propagation in a microcracked bar, Journal of Applied Mechanics, 77(6):061002/1-11.
[7] Trovalusci, P., Pau, A. (2014), Derivation of microstructured continua from lattice systems via principle of virtual
works. The case of masonry-like materials as micropolar, second gradient and classical continua. Acta Mechanica,
225(1):157-177
[8] Fantuzzi, N., Trovalusci P., Dharasura S. (2019), Mechanical behaviour of anisotropic composite materials as micropolar continua, Frontiers, 59 (6):1-11 (https://doi.org/10.3389/fmats.2019.00059).
[9] Settimi, V., Trovalusci, P., Rega, G. (2019), Dynamical properties of a composite microcracked bar based on a generalized continuum formulation, Continuum Mechanics and Thermodynamics, 1-18. (DOI: 10.1007/s00<span class="fon_main_wrapper"><span phone-source="161-019-00761" class="fon-phone-wrap fon-hightlighted active-call" id="fon-phone-oSFtbooasj">161-019-00761</span><a phone-source="161-019-00761" href="#" class="fonCallLinkButton active-call"><img src="data:image/png;base64,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" alt="F"/></a></span>-7)

14:50: [GeomechanicsFriPM107] Plenary
How Far can we Stretch the Application of Modelling Techniques of Geomechanics to Biological Tissues and to Medical Issues?
Jacques Marie Huyghe¹ ; Eanna Fennell² ; Philip Poillot² ; ¹University of Limerick, Limerick, Ireland; ²Bernal Institute, University of Limerick, Limerick, Ireland;
Paper Id: 363 [Abstract]

Geomaterials and biological tissues have numerous properties in common. Both are naturally evolving porous media, the fluid of both is water, both exhibit large specimen-to-specimen variability of material properties, both are anisotropic, both have microstructure evolving from an intricate communication between environmental conditions and internal physics, both have ionisation along fluid-solid interfaces, and both have numerous ionic species dissolved in the fluid. It is no wonder that myriads of applications on geomechanical models have been found in biology. Many applications include herniation of the intervertebral disc [1,2], tissue differentiation driven by ion-exchange [3-4], swelling at extremely large deformation [5], osteoporosis, osteoarthritis [6], coronary vascular disease as a multiporosity problem [7], mechanotransduction in gel-like tissues [8-9], diffusiophoresis-driven propulsion [10-11]. These applications have led to novel numerical techniques, novel design of prostheses and better understanding of tissue engineering constructs [9].

References:
1. Barthelemy V.M.P., van Rijsbergen M.M., Wilson W., Huyghe J.M., van Rietbergen B., Ito K., A computational spinal motion segment model incorporating a matrix composition-based model of the intervertebral disc. J. Mech. Behav. Biomed. Mat. 54: 194–204 (2016)\n2. Wilke H.-J., van Rijsbergen M., Ito K., Huyghe J.M., Brayda-Bruno M., Galbusera F. Ageing and degenerative changes of the intervertebral disc and their impact on spinal flexibility. Eur. Spine J. 23 (S3) : S324-S332 (2014) .\n3. Florea D., Musa S., Huyghe J.M., Wyss H.M. Long–range repulsion of colloids driven by ion–exchange and diffusiophoresis. Proc Nat. Acad. Sci. USA,111(18): 6554-6559 (2014).\n4. Musa S., Florea D. , Wyss H.M. and Huyghe J.M., Convection associated with exclusion zone formation in colloidal suspensions, Soft Matter DOI: 10.1039/C5SM01502B (2015).\n5. Yu C.,_Malakpoor K. and Huyghe J.M.. A three-dimensional transient mixed hybrid finite element model for swelling hydrogels with strain dependent permeability. Soft Matter14(19): 3834-3848 (2018)\n6. Wilson W., Huyghe J.M., van Donkelaar C.C, Depth-dependent compressive equilibrium properties of articular cartilage explained by its composition. Biomech. Mod. Mechanobiol. 6(1-2), 43-53, (2007).\n7. J.M. Huyghe. Finite deformation poromechanics, with application to heart muscle and blood perfusion. ALERT Doctoral School 2015. Coupled and Multiphysics phenomena. Ed. By B.A. Schrefler, L. Sanavia, F. Collin, 68-115 (2015)\n8. Roos, R.W., Petterson, R., Huyghe, J.M. Confined compression and torsion experiments on a pHEMA gel in various bath concentrations Biomech Mod. Mechobiol. 12: 617-626 (2013).\n9. P. Poillot, J.W. Snuggs, C.L. Le Maitre, J. Huyghe. Voltage-Gated Ion Channels in the Intervertebral Disc, abstract presented at the Society for Back Pain Research meeting, September 2019, Sheffield, England, UK. \n10. J.M. Huyghe, On the physics underlying longitudinal capillary recruitment, Advances in Experimental Medicine and Biology 1097: 191-200 (2018)\n11. J.M. Huyghe, On the physics underlying longitudinal capillary recruitment. In “Molecular, Cellular and Tissue Engineering of the Vascular System”, ed. By B.Fu, N. Wright, Springer Verlag, Berlin (2018).

15:15: [GeomechanicsFriPM108] Invited
Constitutive laws for concrete at different scales
Carmelo Maiorana¹ ; Gianluca Mazzucco² ; Xotta Giovanna² ; Beatrice Pomaro² ; Nico De Marchi² ; Valentina Salomoni³ ; ¹, Padova, Italy; ²University of Padova, Padova, Italy; ³University of Padova, Vicenza, Italy;
Paper Id: 428 [Abstract]

Robust models are required in geomechanics to make reliable predictions of engineering applications close to collapse both in the field of cementitious materials and soils. The lecture is aimed at giving some highlights on possible strategies to the numerical modelling of concrete materials, in particular proving the soundness of FEM numerical models for the correct simulation of its mechanical behaviour, when close to failure. The suggested approach is an elasto-plastic-damaged formulation in function of two invariants of the deviatoric stress tensor and in line with non-associated plasticity, i.e. the hardening, non-associated model by Menétrey and Willam [1], enriched with the potential function proposed by Grassl et al. [2] with a reformulation of what proposed in [3] for the damage effects; in this case a non-local integral type regularization technique is included [4] to avoid mesh-dependency in the results. In addition to this, to overcome the limitations in the iterative return-mapping scheme of the elasto-plastic model for the cement paste under tensile regime, due to the presence of singularities, or apex points in the adopted non-smooth yield surface, an improved return-mapping procedure is numerically implemented, able to catch locally the optimal return point on the active yield surface [5]. When dealing with concrete, ITZ can be modelled or not, and so characterized mechanically or not, depending if it is expected to have an important role in the failure mechanism; this may happen when maybe the collapse is interface-driven. In case ITZ is mechanically characterized, a possible cohesive formulation is illustrated, accounting for its lower stiffness and different degree of compactness than the surrounding cement paste. On the other hand, the predictive simulation of damage triggering and evolution in concrete under generic 3D stress states requires the definition of the continuum at a meso-scale level, i.e. as a heterogeneous material, where coarse aggregates are explicitly modeled together with the cement paste, while the finer aggregates are included in the latter component, which is treated as homogeneous. At this purpose, special procedures to conduct meso-scale FE analyses on ordinary concrete made with calcareous aggregates, as well as sustainable concrete made with recycled aggregates from Electric-Arc Furnace (EAF) steel slag, is proposed, based on 3D X-ray computed tomography (X-ray CT) for the digitalization of the outer geometry of the aggregates and for the definition of their orientation in the matrix.

References:
[1] P. Menétrey, K.J. Willam, Triaxial failure criterion for concrete and its generalization. ACI Structural Journal, 92(3), 311-318, (1995).
[2] P. Grassl, L. Karin, G. Kent, Concrete in compression: a plasticity theory with a novel hardening law, International Journals of Solids and Structures, 39(20), 5205-5223, (2002).
[3] J. Mazars, F. Hamon, S. Grange, A new 3D damage model for concrete under monotonic, cyclic and dynamic loadings, Materials and Structures, 48(11), 3779-3793, (2015).
[4] G. Mazzucco, G. Xotta, V.A. Salomoni, C.E. Majorana, Integral-type regularization of non-associated softening plasticity for quasi brittle materials', submitted for publication in International Journal, (2019).
[5] G. Mazzucco, B. Pomaro, V.A. Salomoni, C.E. Majorana, Apex control within an elasto-plastic constitutive model for confined concretes. Mathematics and Computers in Simulation, 162, 221-232, (2019).

SESSION: GeomechanicsFriPM2-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Patrizia Trovalusci; Christian Hellmich; Session Monitor: TBA

15:55: [GeomechanicsFriPM209] Plenary
Bridging the Gap between the Microstructure of Concrete and Traffic Infrastructure
Hui Wang¹ ; Eva Binder² ; Jiao-long Zhang¹ ; Thomas Schlappal² ; Yong Yuan¹ ; Bernhard Pichler² ; Herbert Mang³ ; ¹Tongji University, Shanghai, China; ²Technische Universität Wien, Wien, Austria; ³Technische Universitaet Wien, Vienna, Austria;
Paper Id: 242 [Abstract]

The title of this work refers to a fundamental scientific research about bridging the gap between the microstructure of concrete and the studied traffic infrastructure. It has been carried out in the framework of a joint research project of the Institute for Mechanics of Materials and Structures of Vienna University of Technology and the Department of Geotechnical Engineering of Tongji University, Shanghai. It reads as: bridging the gap by means of multiscale structural analysis. Four different topics are treated in the framework of the general subject of this report. The first two topics deal with the analysis of traffic infrastructure, subjected to exceptional load cases. The first topic is on multiscale analysis of thermal stresses in concrete pavements due to sudden temperature changes and the second one is on microstructural analysis of the impact and blast loading in tunnel linings. The last two topics deal with reinforced concrete hinges in different types of traffic infrastructure. One of them is on multiscale structural analysis of segmented tunnel rings used in mechanized tunneling and the other one on experiments and Finite Element modeling of reinforced concrete hinges used in integral bridge construction.

16:20: [GeomechanicsFriPM210] Keynote
A Non-equilibrium Approach to Modeling Chemical Deterioration Processes in Concrete Structures Exposed to Variable Hygrothermal Conditions
Dariusz Gawin¹ ; Francesco Pesavento² ; Marcin Koniorczyk¹ ; ¹Lodz University of Technology, Lodz, Poland; ²University of Padova, Padova, Italy;
Paper Id: 223 [Abstract]

Concrete structures are widely used in civil, environmental, and nuclear engineering. During their lifetime, the structures are often exposed to severe environmental conditions, causing various deterioration processes, which might significantly reduce their durability. The aim of this contribution is to present a general approach [1] to modelling various chemical deterioration processes in concrete, due to combined action of variable hygro-thermal, chemical and mechanical loads. For this purpose, mechanics of multiphase porous media and delayed damage theory are applied. The mass, energy, and momentum balances, as well as the evolution equations describing the progress of chemical reactions and the constitutive and physical relations are briefly summarized. The kinetics of physicochemical deterioration processes like calcium leaching [2], Alkali Silica Reaction (ASR) [3], and salt crystallization-dissolution [4, 5], are described by means of evolution equations based on linear thermodynamics of chemical reactions. The mutual couplings between the chemical, hygral, thermal and mechanical processes are presented and discussed, both from the viewpoint of physicochemical mechanisms and mathematical modelling. Numerical methods used for solution of the model governing equations are presented. For this purpose, the finite element method is applied for space discretization and the finite difference method for integration in the time domain. Some examples of the model application for analysis of transient chemo-hygro-thermo-mechanical processes in porous construction materials are presented and discussed. The first example deals with calcium leaching from a concrete wall due to chemical attack of pure water exposed to gradients of temperature and pressure. The second one describes cracking of a concrete element, caused by development of expanding products of ASR. The third example concerns salt crystallization during the drying of a wall made of concrete and ceramic brick, causing degradation of the surface layer due to development of crystallization pressure.

References:
[1] D. Gawin, M. Koniorczyk and F. Pesavento, Modelling of hydro-thermo-chemo-mechanical phenomena in building materials, Bulletin of The Polish Academy of Sciences: Technical Sciences 61(1) (2013) 51-63.
[2] D. Gawin, F. Pesavento and B.A. Schrefler, Modeling deterioration of cementitious materials exposed to calcium leaching in non-isothermal conditions, Computer Methods in Applied Mechanics and Engineering 198 (37-40) (2009) 3051-3083.
[3] F. Pesavento, D. Gawin, M. Wyrzykowski, B.A. Schrefler, L. Simoni, Modeling alkali-silica reaction in non-isothermal, partially saturated cement based materials, Computer Methods in Applied Mechanics and Engineering 225-228 (2012) 95-115.
[4] M. Koniorczyk, D. Gawin, Modelling of salt crystallization in building materials with micro-structure - poromechanical approach, Construction and Building Materials 36 (2012) 860-873.
[5] M. Koniorczyk, D. Gawin, B.A. Schrefler, Multiphysics model for spalling prediction of brick due to in-pore salt crystallization, Computers and Structures 196 (2018) 233-245.

16:45: [GeomechanicsFriPM211] Keynote
A General Framework for the Numerical Modeling of Concrete Structures Behavior
Francesco Pesavento¹ ; Dariusz Gawin² ; Giuseppe Sciumè³ ; Marcin Koniorczyk² ; ¹University of Padova, Padova, Italy; ²Lodz University of Technology, Lodz, Poland; ³Université de Bordeaux, Bordeaux, France;
Paper Id: 222 [Abstract]

The prediction of the behavior of cementitious materials and concrete structures under severe conditions and/or for long time spans is of paramount importance in civil, environmental and nuclear engineering. Often, commercial tools do not provide a sufficiently accurate response, so it is necessary to use more sophisticated approaches. In this work, a general framework for the simulation of the non-linear behavior of concrete is shown and described. It is based on the mechanics of multiphase porous media. The mathematical model is developed by writing the relevant balance equations for the constituents at the pore scale, i.e. the local form of governing equations formulated at micro-scale, and by upscaling these equations to the macroscopic scale, taking into account thermodynamic constraints according to the so-called TCAT (Thermodynamics Constrained Averaging Theory) which assures that all the thermodynamics are properly up scaled from the micro to the macro level. Thanks to this approach, all the relevant quantities involved are thermodynamically correct, no unwanted dissipations are generated, and both the bulk phases and interfaces are taken into account. This procedure does not exclude, however, the use of a numerical multiscale approach in the formulation of the material properties. The numerical solution is obtained directly at the macro level by discretizing the governing equations in their final form. The resulting model can be usefully applied to several practical cases: evaluation of the concrete's performance at early stages of maturing massive structures [1-3], structural repair works [2,3], exposure of concrete to high temperatures, e.g. during fire [4,5], cementitious materials subject to freezing/thawing cycles [6], etc. In this work, the general model focuses on the specific situations described above and several examples are shown.

References:
[1] D. Gawin, F. Pesavento, B.A. Schrefler, Modelling creep and shrinkage of concrete by means of effective stress, Materials & Structures 40 (2007) 579-591.
[2] G. Sciume, F. Benboudjema, C. De Sa, F. Pesavento, Y. Berthaud, B.A. Schrefler, A multiphysics model for concrete at early age applied to repairs problems, Engineering structures 57 (2013) 374-387.
[3] F. Pesavento, B.A. Schrefler, G. Sciumè, Multiphase Flow in Deforming Porous Media: A Review. Archives of Computational Methods in Engineering 24 (2017) 423-448.
[4] D. Gawin. F. Pesavento, B.A. Schrefler , Modelling of hygro-thermal behaviour of concrete at high temperature with thermo-chemical and mechanical material degradation, Comput. Methods Appl. Mech. Engrg. 192(13-14) (2003) 1731-1771.
[5] D. Gawin, F. Pesavento, B.A. Schrefler, Towards prediction of the thermal spalling risk through a multi-phase porous media model of concrete, Computer Methods in Applied Mechanics and Engineering 195 (2006) 5707-5729.
[6] D. Gawin, F. Pesavento, M. Koniorczykc, B.A. Schrefler, Non-equilibrium modeling hysteresis of water freezing - ice thawing in partially saturated porous building materials, Int. Journal of Building Physics, in print.

17:10: [GeomechanicsFriPM212] Invited
Green Concretes: An Efficient Route to Promote Sustainability in the Construction Industry
Carlo Pellegrino¹ ; ¹University of Padova, Padova, Italy;
Paper Id: 316 [Abstract]

Recent years have shown the growth of a great number of recycled building materials, among which green concretes, made with recycled aggregates coming from construction and demolition waste (C&DW), metallurgical slags, plastic and other man-made materials, are being increasingly studied and used in several real-scale applications. Such a scenario aims to achieve challenging goals in terms of reduction of carbon emissions, reuse of waste materials promoting a circular economy, and avoidance of the use of bulk natural resources. This work shows the recent research carried out at the University of Padova on this topic. Experimental work, aimed at proving the suitability of using recycled aggregates and mainly slag from the Electric Arc Furnace in structural concrete, is shown. Particularly, results both about small-scale specimens for the analysis of mechanical and durability properties, and also about large-scale applications are presented. These latter applications allow the study of the structural performance of reinforced concrete elements under gravity and seismic-like actions. Lastly, some real construction projects are discussed, highlighting how environmental impacts can be effectively mitigated through the use of such materials.

SESSION: GeomechanicsFriPM3-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Fri Oct, 25 2019 / Room: Athena (105/Mezz. F)
Session Chairs: David Smeulders; Claudio Tamagnini; Session Monitor: TBA

17:50: [GeomechanicsFriPM313] Invited
Macro-simulation of fluid flow and the interaction with the excavation process of the Brenner Base Tunnel
Konrad Bergmeistser¹ ; Tassilo Weifner² ; ¹, Vienna, Austria; ²Brenner Base Tunnel BBT SE, Innsbruck, Austria;
Paper Id: 465 [Abstract]

The tunnel track of the Brenner Base Tunnel crosses the base of the Brenner Massif passing through an important aquifer in the Hochstegen zone, which shows an essential influence on the water balance on the ground surface. In order to investigate the hydrological situation before and after the tunnel construction, two-dimensional models of the groundwater flow system with the finite difference code MODFLOW were produced. The scope of these models was on one hand to obtain information about the effects of the drawdown of the groundwater table by the draining effect during the tunnel excavation. On the other hand, an intention of the model was to investigate whether the drawdown of the groundwater table could be kept to a small and acceptable extent through suitable grouting measures and thus keep the influence on the groundwater balance in the model area low. The calculations show that the drawdown of the groundwater table in the zone of the aquifer of the Hochstegen Zone can be reduced to a small, acceptable extent. A drilling campaign with pumping tests was in execution and gave already additional input data. The paper deals with the model, the hydraulic parameters, the data from grouting measures obtained in other deep tunnel projects and from the drilling campaign and their effects on the modelling parameters and describes in detail the knowledge gained.

References:
Weifner, T.; Bergmeister, K.; Ziegler H.: Wide-area hydrogeological modelling for the Brenner Base Tunnel. Geomechanics and Tunneling. Ernst & Sohn, 1014-4, pag. 163-77

18:15: [GeomechanicsFriPM314] Keynote
Learning from complexity - geomechanical back analysis of complex rock failures of the Brenner Base Tunnel
Konrad Bergmeistser¹ ; ¹, Vienna, Austria;
Paper Id: 464 [Abstract]

With a total length of 64km, the Brenner Base Tunnel will be the world's longest tunnel. The northernmost construction lot, Tulfes-Pfons, comprises 41.5 km of tunnel. Conventional tunnelling methods were used for 26.5 km of this length, and an open gripper tunnel boring machine for the remaining 15 km. The area extends from the Innsbruck Quartz Phyllite zone to the Penninic Bündnerschiefer group. An open tunnel boring machine made it possible to investigate the rock mass in greater detail. Several fault zones and 10 large overbreaks in the different shapes and geotechnical rock mass behaviours were encountered in the first 13 km. One of them is presented more in detail in this contribution: the overbreak “San Francisco”, which was investigated with two-dimensional finite element back analyses which were including also the interaction effects with the ongoing advance of the main tunnels. The determination of the material parameters for the material laws for the rock mass and sprayed concrete is described and the finite element model including the concrete shells is explained. The calculations show that advanced material models are appropriate and loading/unloading effects can be successfully simulated. Purpose-built heavy steel segments, injected infill concrete and a cement/water suspension for binding the collapsed rock made it possible to bridge these cavities. Bergmeister, K.; Reinhold, C. (2017): Learning and optimization from the exploratory tunnel - Lernen und Optimieren vom Erkundungsstollen – Brenner Basistunnel. In: Geomechanics and Tunneling. Berlin, 05/2017 Österreichische Gesellschaft für Geomechanik, Ernst&Sohn, Berlin Bergmeister, K. (2011): Brenner Basistunnel – Der Tunnel kommt. Tappeinerverlag – Lana Bergmeister, K. (2012): Life Cycle Design for the world longest tunnel project. In: IAALCE (Editors: Strauss, Frangopol, Bergmeister), Vienna

References:
Bergmeister, K.; Reinhold, C. (2017): Learning and optimization from the exploratory tunnel - Lernen und Optimieren vom Erkundungsstollen – Brenner Basistunnel. In: Geomechanics and Tunneling. Berlin, 05/2017 Österreichische Gesellschaft für Geomechanik, Ernst&Sohn, Berlin
Bergmeister, K. (2011): Brenner Basistunnel – Der Tunnel kommt. Tappeinerverlag – Lana
Bergmeister, K. (2012): Life Cycle Design for the world longest tunnel project. In: IAALCE (Editors: Strauss, Frangopol, Bergmeister), Vienna

SESSION: GeomechanicsSatAM-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Sat Oct, 26 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Marek Lefik; Francesco Pesavento; Session Monitor: TBA

11:20: [GeomechanicsSatAM01] Keynote
Coupled Problems in Fracture Propagation in Fluid-Saturated Porous Media
Joris Remmers¹ ; Elisa Bergkamp¹ ; Clemens Verhoosel¹ ; David Smeulders² ; ¹TUE, Eindhoven, Netherlands; ²Eindhoven University of Technology, Eindhoven, Netherlands;
Paper Id: 303 [Abstract]

For the extraction of heat from deep geothermal layers, the creation of fracture networks in these layers is needed. Water is injected under high pressure and fracture initiation and growth is induced. For modeling fracture growth, the Extended Finite Element Model (XFEM) has proven to be a powerful numerical tool. For hydraulic fracturing in low permeable rocks the so-called Enhanced Local Pressure (ELP) model was recently introduced. In this approach, the fluid pressure within the fracture is included as an additional degree of freedom with respect to the original XFEM displacement field, which greatly increases the applicability of the model. The fluid pressures in the fracture and the surrounding porous material, however, are still only coupled by means of a simplified, analytical Terzaghi relation. In order to further improve the model, the interaction of the fracture fluid flow and the deformable porous medium is studied. We developed a coupled model in which the free flow is described by the Stokes equations and the fluid-saturated porous medium by Biot’s equations. We solve the coupled problem using a staggered FEA approach. The numerical model is shown to fully couple the free flow and the fluid flow in the saturated poro-elastic medium, taking into account the slippage effect and surface flow impedance. We now combine the coupled free flow model and the ELP method to better predict fracture propagation in fluid-saturated poro-elastic materials and corresponding fracture leak-off rates.

References:
Remij, E.W., J.J.C. Remmers, J.M. Huyghe, and D.M.J. Smeulders (2015). The enhanced local pressure model for the accurate analysis of fluid pressure driven fracture in porous materials. Computer Methods in Applied Mechanics and Engineering, 286:293-312

11:45: [GeomechanicsSatAM02] Invited
Numerical Investigation of Fault Activation in Underground Gas Storage Reservoirs
Massimiliano Ferronato¹ ; Andrea Franceschini² ; Matteo Frigo¹ ; Pietro Teatini¹ ; Claudia Zoccarato¹ ; ¹University of Padova, Padova, Italy; ²Stanford University, Stanford, United States;
Paper Id: 233 [Abstract]

Underground gas storage (UGS) is a practice that is becoming widely implemented to cope with seasonal peaks of gas consumption. When the target reservoir is located in a faulted basin, a major safety issue is the re-activation of pre-existing faults, possibly inducing (micro-) seismicity. Faults are reactivated when the shear stress exceeds the limiting acceptable strength. It has been observed that this occurrence can happen unexpectedly during the life of a UGS reservoir, i.e. when the actual stress regime is not expected to reach the failure condition. A numerical analysis has been carried out to cast light in this respect, by investigating the mechanisms and the critical factors that can be responsible for fault activation during the various UGS stages. The reservoir’s geomechanical behavior is simulated by an original elasto-plastic 3D Finite Element (FE) approach where the fault strength is taken into account by means of Lagrange multipliers [1]. The fault geometry is reproduced using special zero-thickness Interface Elements (IE), and the possible activation is controlled by the Mohr-Coulomb failure criterion. The simulations are carried out on a 3D regional-size geological setting, which requires the use of advanced numerical techniques for the solution of the resulting discrete problem [2]. The model is applied in a physical context representative of the typical UGS reservoirs located in the Netherlands, in terms of reservoir properties, fault geometry and pressure history. The Norg and Bergermeer UGS fields represent the reference for this modelling application. The analysis addresses the role of: (i) the space and time pore pressure gradients in the UGS formation, within the faults bounding/compartmentalizing the reservoir; (b) the poroelastic stress changes with respect to the natural stress regime; (c) the specific geological settings, such as the geometric configuration and the hydro-geomechanical properties of the faults and reservoir. The numerical results show that "unexpected" fault re-activations are likely to occur during UGS when micro-seismicity had been already experienced in the primary reservoir exploitation, even if the pore pressure does not exceed the initial undisturbed conditions.

References:
[1] A. Franceschini, M. Ferronato, C. Janna, P. Teatini. A novel Lagrangian approach for the stable numerical simulation of fault and fracture mechanics. Journal of Computational Physics, 314, pp. 503-521, 2016.

[2] A. Franceschini, N. Castelletto, M. Ferronato. Block preconditioning for fault/fracture mechanics saddle-point problems. Computer Methods in Applied Mechanics and Engineering, 344, pp. 376-401, 2019.

12:10: [GeomechanicsSatAM03] Keynote
Examples of inverse problem in geotechnics: comparative analysis of various strategies of solutions involving artificial neural networks
Marek Lefik¹ ; Marek Wojciechowski² ; ¹Lodz University of Technology, Kalonka, Poland; ²Lodz University of Technology, Lodz, Poland;
Paper Id: 216 [Abstract]

In geotechnics we rarely directly measure the parameters of the soils we need for engineering computations. Thus, the inverse problem that allows the needed values from directly measured data is frequently solved. Although the four presented strategies can be used to elaborate results of many geotechnical tests (such as CPTU or Marchetti dilatometer), in this summary we focus on one example only, namely the Falling Weight Deflectometer (FWD). This test is used to evaluate mechanical parameters of layered structures of road and pavements. Deflections due to an impulse load from the falling weight are measured in several points using geophones aligned on a rigid support. Determination of the mechanical parameters of the pavement layers is done by minimization of a mean square difference between the measured and a theoretical deflection. In the kernel of minimization procedures, there are costly computations of the theoretical deflections and their gradients (see [1]). The simplest use of Artificial Neural Network (ANN) in this context is the application of the well trained ANN as a surrogate of costly FEM computations in the minimization process. Once trained with limited number of results of the direct FE solutions the ANN gives the deflections for trial set of searched parameters. We use the ANN that approximates also the gradients with respect to its input. Such an ANN used it in frame of Truncated Newton method assures acceleration of the procedure. As a second strategy, we approximate directly the inverse relation between the set of parameters of the FE model of the layered structure and the deflection of its surface (see [2]). The input of the ANN is valued with the deflections and the output with the corresponding set of the model parameters. The ANN acts here as a universal approximate of an unknown functional relationship among the observed deflections and the searched parameters. Using various qualitative FE models, we can also train the ANN to discover qualitative properties of the structure which seems to be novel in the field of the inverse problem. Another possibility is the use of the ANN to directly approximate the inverse relation trained with the laboratory data collected from numerous real tests. We show that the necessary number of the laboratory test to train the ANN is reasonably small. The ANN trained with direct laboratory data acts here a special model-less form of phenomenological representation of constitutive relationships, based on observations (as in [3]).

References:
[1] P. Ruta, B. Krawczyk, A. Szydło, Identification of pavement elastic moduli by means of impact test, Engineering Structures, 100 (2015) 201-211
[2] M. Lefik and D.P. Boso, Inverse problem : soft solution, In Bytes and Science, Zavarise G. and Boso D.P. (eds.), CIMNE, Barcelona, Spain 2012.
[3] R.W. Meier. Backcalculation of Flexible Pavement Moduli from Falling Weight Deflectometer Data Using Artificial Neural Networks. Report prepared for U.S. Army, report GL-95-3, Washington DC, 1995.

12:35: [GeomechanicsSatAM04]
Quasi-Zero-Thickness Interface Elements for the Simulation of Fracture Processes in Geomechanics
Ignasi De Pouplana Sarda¹ ; Eugenio Oñate¹ ; ¹CIMNE - Centre Internacional de Metodes Numerics en Enginyeria, Barcelona, Spain;
Paper Id: 332 [Abstract]

The present work models problems in which the initiation and propagation of cracks in porous materials represents a key issue and is strongly influenced by the interaction between the solid matrix and the fluid in pores. The methodology is based on a work by the authors already published [1]. In this case, discontinuities are modelled by means of quasi-zero-thickness interface elements using an FEM-based approach. These special elements, which can be used to define either pre-existing or propagating cracks, act as joints that allow representation of the jump in the displacement field and the directional preferences in the fluid flow. To ensure that the direction of the crack growth is not heavily influenced by the mesh, a non-local damage model is used to predict the degradation pattern of the domain and the interface elements are then inserted, followed by a remeshing. FIC-stabilized elements of equal order interpolation in the displacement and the pore pressure have been successfully used under complex conditions near the undrained-incompressible limit [2]. A bilinear cohesive fracture model describes the mechanical behaviour of the joints. A formulation derived from the cubic law models the fluid flow through the crack. Examples in 2-D and 3-D, using 3-noded triangles and 4-noded tetrahedra respectively, are presented to illustrate the features of the proposed methodology in hydraulic fracture processes. Other examples solved by the authors using joint elements in dam engineering [3] will be shown to introduce some of their alternative applications.

References:
[1] De-Pouplana, I. and Oñate, E., Finite element modelling of fracture propagation in saturated media using quasi-zero-thickness interface elements, Computers and Geotechnics (2017), http://dx.doi.org/10.1016/j.compgeo.2017.10.016 .
[2] I. de Pouplana and E. Oñate. A FIC-based stabilized finite element method with equal order interpolation for solid-pore fluid interaction problems. International Journal for Numerical and Analytical Methods in Geomechanics, vol. 41, pp. 110-134, 2016. DOI: 10.1002/nag.2550
[3] I. de Pouplana, L. Gracia, F. Salazar and E. Oñate. Cracking of a concrete arch dam due to seasonal temperature variations. Proceedings of the 14th International Benchmark Workshop on Numerical Analysis of Dams, pp. 147-156, 2017. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-223593

SESSION: GeomechanicsSatPM1-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Sat Oct, 26 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Manuel Pastor; Konrad Bergmeistser; Session Monitor: TBA

14:00: [GeomechanicsSatPM105] Keynote
The New Paradigm of Thunderstorm Downbursts for Safe and Sustainable Development
Giovanni Solari¹ ; ¹University of Genoa, Genova, Italy;
Paper Id: 64 [Abstract]

The wind climate of Europe and of many other countries in the world is dominated by synoptic extra-tropical cyclones and by mesoscale thunderstorm downbursts. Thunderstorms are frequent phenomena that cause wind speeds and wind-induced damage often greater than those due to synoptic cyclones. This new paradigm of wind engineering has given rise to a recent burst of research despite which there is not yet a model of thunderstorms and their loading of structures like that developed for cyclones in the early 1960s which is still in use in engineering practice (1). This shortcoming leads to unsafe and expensive structures. The insufficient safety of low- and medium-rise structures is testified by frequent damage and collapse in thunderstorm days. The excessive cost of tall buildings is apparent due to the absence of critical situations due to the wind. Both these aspects are derived from the fact that thunderstorm outflows intensify close to the terrain and reduce their speed while increasing the height, whereas traditional wind speeds and loading increases with height. THUNDERR (www.thunderr.eu) is a project funded by the European Research Council aiming to pursue three objectives: 1) to formulate a novel, interdisciplinary and unitary model of thunderstorm outflows (2, 3); 2) to assess a wind loading model of structures due to thunderstorm outflows (4, 5) and to encapsulate this and the classical method for cyclones into a novel wind loading format easily transferable to engineering and codification; 3) to spread the results throughout the international community, to strengthen a renewed culture on wind actions on structures. This paper provides the general framework of the THUNDERR project, illustrates the results obtained in this phase of the research, describes the perspectives of the studies currently undertaken under the scientific and technical viewpoints, and discusses their potential impact on civil and structural engineering, as well as their consequences on building safety and sustainability

References:
(1) A.G. Davenport, Proc. Inst. Civ. Eng. 19 (1961) 449-472.
(2) P. De Gaetano, M.P. Repetto, T. Repetto, G. Solari, J. Wind Eng. Ind. Aerod. 126 (2014) 132-143.
(3) M. Burlando, D. Romanic, G. Solari, H. Hangan, S. Zhang, Mon. Weather Rev. 145 (2017) 3507-3527.
(4) G. Solari, Eng. Struct. 108 (2016) 28-46.
(5) G. Solari, P. De Gaetano, Eng. Struct. 176 (2018) 188-207.

14:25: [GeomechanicsSatPM106] Keynote
A Multiphysics Approach for High Temperature Superconducting Tapes
Daniela P. Boso¹ ; ¹University of Padova, Padova, Italy;
Paper Id: 369 [Abstract]

Superconductivity is currently exploited in several technological applications, from small-scale electronic devices to large-scale particle accelerators and fusion reactors. High field magnet technologies are still based on the use of low temperature superconducting (LTS) materials, either NbTi or Nb₃Sn. Nb₃Sn cables are brittle and strain sensitive [1]-[3], but they perform better than NbTi ones. Actual challenges given by nuclear fusion and high-energy physics require more and more performing materials, capable to transport high current densities at high temperature and at very high magnetic fields [4]. High Temperature Superconducting (HTS) materials are nowadays considered as possible candidates for such demanding conditions. These materials are thus named because they exhibit superconducting behavior at much higher temperatures than NbTi and Nb₃Sn. Among the various HTS concepts, the coated conductors, also referred to as rare-earth-barium-copper-oxide (Rare-Earth1Ba2Cu3O7-x) or REBCO tapes, are promising competitors. The coated conductor tapes have exhibited high current carrying capability under high magnetic field and good mechanical properties that meet the specific requirements in the superconducting motors and coils [5] – [7]. HTS magnets, however, are a new technology. If the LTS technology is well established, a robust R&D is needed to explore the possible use of high-temperature superconductors in high field magnets, as the superconductors performances are not only influenced by the magnetic field and the operating temperature, but also by the mechanical strain [8]–[9]. As a consequence, the development of these new generations of conductors requires extensive investigation about the impact of the main characteristics of the cable architecture on the electrical performances of a single superconducting tape. In particular, for a proper conductor design, it is important to fully characterize the single tape in its working conditions. In this work, a coupled thermo-electro-mechanical model is developed, suitable to analyze the behavior of HTS tapes and predict their performances inside the coil. The drop of electrical performances at the yield strength of the tapes under different loading conditions is evaluated. The multiphysics model is going to be validated against experimental measurements of the critical current now being performed on REBCO tapes by SuNAM Co., immersed in liquid nitrogen.

References:
[1] D.P. Boso, A simple and effective approach for thermo-mechanical modelling of composite superconducting wires, Supercond. Sci. Technol., 26, 2013\n[2] A.S. Nemov, D.P. Boso, I.B. Voynov, A.I. Borovkov, B.A. Schrefler, Generalized stiffness coefficients for ITER superconducting cables, direct FE modeling and initial configuration. Cryogenics, 50, 2010\n[3] D.P. Boso, M. Lefik, A thermo-mechanical model for Nb3Sn filaments and wires: strain field for different strand layouts, Supercond. Sci. Technol., 22, 2009\n[4] S.R. Foltyn, l. Civale, J.l. Macmanus-Driscoll, Q. X. Jia, B. Maiorov, H. Wang, M. Maley, Materials science challenges for high-temperature superconducting wire, Nature materials, 6, 2007\n[5] T. Qu et al., Test of an 8.66-T REBCO insert coil with overbanding radial build for a 1.3-GHz LTS/HTS NMR magnet, IEEE Trans. Appl. Supercond., 27, 2017\n[6] Y. H. Choi, S. Hahn, J. B. Song, D. G. Yang, and H. G. Lee, Partial insulation of GdBCO single pancake coils for protection-free HTS power applications, Supercond. Sci. Technol., 24, 2011\n[7] [3] M.Kawamura, J. Jones, Superconducting supermotor and generator, IEEE Trans. Appl. Supercond., 27, 2017.\n[8] C. Zhou, K. A. Yagotintsev, P. Gao, T. J. Haugan, D. C. van der Laan, and A. Nijhuis, Critical Current of Various REBCO Tapes Under Uniaxial Strain, IEEE Transactions on Applied Superconductivity, 26, 2016\n[9] N. Bykovsky, D. Uglietti, R. Wesche, P. Bruzzone, Strain Management in HTS High Current Cables, IEEE Transactions on Applied Superconductivity, 25, 2015

14:50: [GeomechanicsSatPM107]
Computational Simulations of Catastrophic Plate Tectonics in our Earth’s History
Mark F. Horstemeyer¹ ; ¹Liberty University, Virgina, United States;
Paper Id: 446 [Abstract]

Simulations using a history-dependent and physically-motivated Internal State Variable (ISV) constitutive model implemented into a spherical Finite Element code, TERRA3D, for the entire Earth’s mantle is used to illustrate the catastrophic plate tectonics event in our Earth’s history. We investigate the kinetics of dynamic recrystallization, grain size, and their influences on the mantle dynamics during its convection. The unique aspect of this study was that an explicit recrystallization variable was introduced and connected with the grain size kinetics, thus unifying static (grain size increases) and dynamic recrystallization (grain size decreases). We found that significant dynamic recrystallization (grain size reduction) occurred in the descending slabs and adjacent mantle, thus weakening its strength. Due to the rheological weakening, frequent episodic overturns and mantle avalanches were observed. Furthermore, strongly heterogeneous microstructures and associated viscosities were predicted in the entire mantle, because of the competition between the dynamic recrystallization, grain refinement, and grain growth under the geological setting. The grain size tended to be larger (~106 µm) in the upper mantle (below the lithospheric mantle) as the grain growth rate overtook the grain size reduction rate, while relatively small grain sizes (102 ~ 103 µm) were observed in the lower mantle as dynamically recrystallized downwelling slabs continuously flowed. In particular, exceptional heterogeneity of microstructure and rheology was observed nearby the core-mantle boundary depending on the kinetics of the dynamic recrystallization and grain size. Amazingly, this high rate event appears to align with worldwide flood stories as documented in the bible as well as other ancient manuscripts such as the Epic of Gilgamesh.

15:15: [GeomechanicsSatPM108] Plenary
Fighting Singularities in Solids and Fluids
Elias Aifantis¹ ; ¹Aristotle University of Thessaloniki, Thessaloniki, Greece;
Paper Id: 447 [Abstract]

One of the still persisting problems in both solid and fluids mechanics is to deal with singularities in the stress/strain fields or the flow field. An associated problem is the mesh-size dependence and non-convergence in finite element calculations in the material softening regime. A simple regularization method can be used to overcome both difficulties. This is shown for both elastic and plastic solids, as well as for both Newtonian and complex fluids.

References:
[1] E.C. Aifantis, Internal length gradient (ILG) material mechanics across scales and disciplines, Adv. Appl. Mech. 49, pp. 1-110, 2016.

[2] E.C. Aifantis, Weak nonlocal extension of classical material models, Frontiers in Physics, 2019 (in press).

SESSION: GeomechanicsSatPM2-R7	Schrefler International Symposium on Geomechanics and Applications for Sustainable Development
Sat Oct, 26 2019 / Room: Athena (105/Mezz. F)
Session Chairs: Gennady Mishuris; Daniela P. Boso; Session Monitor: TBA

15:55: [GeomechanicsSatPM209] Invited
From Civil Engineering to Oncophysics: Successful and Present Challenging Applications of Multiphase Porous Media Mechanics
Giuseppe Sciumè¹ ; Stefano Dal Pont² ; ¹Université de Bordeaux, Bordeaux, France; ²Laboratoire Sols, Solides, Structures, Risques (3SR), Grenoble, France;
Paper Id: 310 [Abstract]

The mechanics of porous media is among the most fascinating and interesting branches of continuum mechanics since it can be applied to extremely broad fields of science. From the beginning of the XX century, when Karl von Terzaghi postulated the effective stress principle in soils mechanics, the theory of porous media advanced substantially, particularly thanks to the contribution of Maurice Anthony Biot. He introduced the general concept of the poroelastic medium and developed the theory of dynamic poroelasticity (now known as Biot’s theory) which is the basis of porous media mechanics. More recent developments consider averaging procedures which also include interface mechanics [1]. Porous media mechanics is ordinarily used for geomechanical problems at large, but nowadays it is also applied to model biomechanical ones. Teeth and bone decalcification, herniation of intervertebral discs and glaucoma and tumor growth are examples of clinical pathologies which can be modeled using mathematical approaches based on porous media mechanics. Two very different applications are briefly presented to highlight the flexibility of this theory. The first one is a thermo-hygro-chemo-mechanical (THCM) model for concrete. The presented approach is inspired by the theoretical framework of Gawin, Pesavento and Schrefler [2]; the reference model has been further improved for structural application by accounting for shrinkage, as well as creep and mechanical damage in a fully coupled fashion. The second one is a multiphase model of tumor growth. The tumor is modeled as a four-phase system which consists of a solid phase, an extracellular matrix, and three fluid phases. The fluid phases are the interstitial fluid, tumor cells and healthy cells, with the latter two phases modeled as adhesive fluids. Since tumor growth is strongly influenced by nutrient availability, the diffusion of oxygen coming from the nearby existing vessels is also considered. Examples of biological interest will be presented.

References:
[1] Gray, W.G. and Miller C.T., "Thermodynamically constrained averaging theory approach for modeling flow and transport phenomena in porous medium systems: 1. Motivation and overview" Advances in Water Resources 28 161–180 (2005).
[2] Gawin, D., Pesavento, F. and Schrefler B.A. "Hygro-thermo-chemo-mechanical modelling of concrete at early ages and beyond. Part I: Hydration and hygro-thermal phenomena", International Journal for Numerical Method in Engineering, 67(3), 299-331 (2006).

16:20: [GeomechanicsSatPM210] Plenary
Hybrid Twins: the new data-driven and physics-based alliance
Francisco Chinesta¹ ; ¹Arts et Metiers, ParisTech, Paris, France;
Paper Id: 180 [Abstract]

In the previous industrial revolution, virtual twins (emulating a physical system) were major protagonists. Usually, numerical models (virtual twins), however, are static, that is, they are used in the design of complex systems and their components, but they are not expected to accommodate or assimilate data. The reason is that the characteristic time of standard simulation strategies is not compatible with the real-time constraints which are mandatory for control purposes. Model Order Reduction techniques opened new possibilities for more efficient simulations. The next generation of twins, the so-called digital twins, allowed for assimilating data collected from sensors with the main aim of identifying parameters involved in the model as well as their time evolution in real time, anticipating actions using their predictive capabilities. Thus, simulation-based control was envisaged and successfully accomplished in many applications. Despite an initial euphoric and jubilant period, unexpected difficulties appeared immediately. Namely, in practice, significant deviations between the predicted and observed responses were noticed, limiting or abandoning their use in many applications. In that framework of multi-uncertainty evolving environments, Hybrid Twins we proposed, consisting of three main ingredients: (i) a simulation core able to solve complex mathematical problems representing physical models under real-time constraints, (ii) advanced strategies able to proceed with data-assimilation, data-curation, data-driven modelling and finally data-fusion when using compatible descriptions for the physical and data-based models, and (iii) a mechanism to adapt the model online to evolving environments (control).

References:
Virtual, Digital and Hybrid Twins. A new paradigm in data-based engineering and engineered data. F. Chinesta, E. Cueto, E. Abisset, J.L. Duval, F. El Khaldi. Archives of Computational Methods in Engineering, https:\\doi.org\10.1007\s11<span class="fon_main_wrapper"><span phone-source="831-018-9301" class="fon-phone-wrap fon-hightlighted active-call" id="fon-phone-qZ5RMVJAUQ">831-018-9301</span><a phone-source="831-018-9301" href="#" class="fonCallLinkButton active-call"><img src="data:image/png;base64,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" alt="F"/></a></span>-4, 2018.

16:45: [GeomechanicsSatPM211] Keynote
On Surface Elasticity Models and Their Applications to Description of Material Behavior at the Nano- and Micro-Scales
Victor Eremeyev¹ ; Leonid Igumnov² ; Svetlana Litvinchuk² ; Ivan Volkov² ; ¹Gdansk University of Technology, Gdansk, Poland; ²National Research Lobachevsky State University of Nizhny Novgorod, Nizhny Novgorod, Russian Federation;
Paper Id: 262 [Abstract]

The aim of this lecture is to discuss the applications of surface elasticity determination for effective properties of materials, and for some related phenomena as surface wave propagation. Here, in addition to the constitutive relations in the bulk, constitutive relations at the surface are independently introduced. Nowadays the most popular models of surface elasticity relates to the models by Gurtin and Murdoch [1, 2] and by Steigmann and Ogden [3, 4]. Some other models are also known in the literature, which can describe surface/interface related phenomena, see e.g. [5-7]. First, we discuss some useful surface elasticity models. From a physical point of view, surface elasticity models correspond to an elastic solid with an elastic membrane or shell or another 2D continuum attached to its boundary. The corresponding boundary dynamic boundary conditions are derived at the smooth parts of the boundary as well as its edges and corner points. Let us underline that these conditions also include dynamic terms. As a result, we have here a dynamic generalization of the Laplace-Young equation as known from the theory of capillarity. Second, we discuss the influence of the surface stresses at the effective stiffness parameters of layered plates and shallow shells. For small deformations, we derived the exact formulae for modified tangent and bending stiffness parameters of the plates and shells. The influence of residual surface stresses is also discussed. Unlike the previous case, where surface stresses are slightly changing the material properties, there is another example of the essential influence of surface properties. This example relates to the propagation of anti-plane surface waves. We discuss some peculiarities of the wave propagation.

References:
[1]. Gurtin ME, Murdoch AI. 1975 A continuum theory of elastic material surfaces. Arch. Ration. Mech. Analysis. 57, 291-323.
[2]. Gurtin ME, Murdoch AI. 1978 Surface stress in solids. Int. J. Solids Struct. 14, 431-440.
[3]. Steigmann DJ, Ogden RW. 1997 Plane deformations of elastic solids with intrinsic boundary. Proc. Roy. Soc. A. 453, 853-877.
[4]. Steigmann DJ, Ogden RW. 1999 Elastic surface-substrate interactions. Proc. Roy. Soc. A. 455, 437-474.
[5]. Duan HL, Wang J, Karihaloo BL. 2008 Theory of elasticity at the nanoscale. Adv. Appl. Mech. 42, pp. 1-68. Elsevier.
[6]. Wang J, Huang Z, Duan H, Yu S, Feng X, Wang G, Zhang W, Wang T. 2011 Surface stress effect in mechanics of nanostructured materials. Acta Mech. Solida Sin. 24, 52-82.
[7]. Eremeyev VA. 2016 On effective properties of materials at the nano- and microscales considering surface effects. Acta Mechanica 227, 29-42.

17:10: [GeomechanicsSatPM212] Plenary
Modelling and Computation of Interfaces in Multiphase Flows
Alfredo Soldati¹ ; ¹Tu Wien, Wien, Austria;
Paper Id: 327 [Abstract]

Drop size distribution of aerosols controls the efficiency of crucially important environmental processes, e.g. transfer fluxes greenhouse gases at air-sea interface, and industrial processes, e.g. the energetic and environmental efficiency of energy production from liquid fuels. In these processes, all the relevant momentum, heat and mass transfer fluxes occur across the tiny interfaces, separating the drops by the carrier fluid. Interfaces are an inherently hard to define non-place! The accurate determination of interface position, shape and interaction with the fluid turbulence, however, is crucial to predict the overall behavior of the involved macroscopic physical phenomena. Although considerable observational and theoretical attention is being focused on this topic, a clear and comprehensive picture on formation and properties of the dispersed phases is not currently available yet. Our effort is to provide a general theoretical framework to describe the evolution of dispersed multiphase systems in turbulent flows. To this aim, Direct Numerical Simulation (DNS) of turbulence and accurate tracking of the interface are required, but the range of scales involved for most of practical environmental and industrial applications is so wide that performing this task is a formidable challenge for present day computers. These challenges include the grid resolution for DNS of turbulence which is of the order of the Kolmogorov scale, but of course, physical interfaces have a much smaller scale (order of few molecules) making the direct resolution unfeasible. In this talk, we will briefly review the historical pioneering studies and current experimental findings and computational methodologies used to describe interfaces and then, we will focus on the phase-field approach in turbulent flows. In this Eulerian approach, the phase distribution is described by the order parameter ϕ. We will examine several flow instances and phenomena ranging from turbulent stratified flows to turbulent dispersion of drops and bubbles to reveal potentials and limitations of the phase-field method. Interface interactions with turbulence, coalescence and breakup phenomena for different important physical phenomena involving changes of fluids density and viscosity and presence of surfactants (Marangoni effects) will be discussed in connection with the characteristics of turbulence. Finally, potentials to upscale current results and comparison with current theoretical and experimental findings will be presented.

References:
Deane, G.B. & Stokes, M.D. 2002 Scale dependence of bubble creation mechanisms in breaking waves. Nature 418 (6900), 839.
Garrett, C., Li, M. & Farmer, D. 2000 The connection between bubble size spectra and energy dissipation rates in the upper ocean. J. Phys. Oceanogr. 30 (9), 2163-2171.
Soligo, G., Roccon, A. & Soldati, A. 2019a Coalescence of surfactant-laden drops by Phase Field Method. J. Comput. Phys. 376, 1292-1311.
Soligo, G., Roccon, A. & Soldati, A. 2019b Breakage, coalescence and size distribution of surfactant laden droplets in turbulent flow. J. Fluid Mech.

SESSION: IronThuAM-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Thu Oct, 24 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Akinori Murao; Lauri Holappa; Session Monitor: TBA

11:20: [IronThuAM01] Plenary
A General Vision for Reduction of Energy Consumption and CO2 Emissions from the Steel Industry
Lauri Holappa¹ ; ¹Professor emeritus, Espoo, Finland;
Paper Id: 480 [Abstract]

The 2018 IPCC report defined the goal to limit the global warming to 1.5°C by 2050. Accordingly, that would require “rapid and far-reaching transitions in land, energy, industry, buildings, transport, and cities”. The challenges fall on all sectors, but on energy and industry sectors they are most essential and explicitly measurable also. Iron and steel making is an energy-intensive industrial branch. It is playing a significant role in the global energy consumption, as it is largely based on fossil fuel and generates about 7% of overall carbon dioxide emissions. In order to conduct its own share in cutting CO2 emissions, great advancements must be achieved. This contribution will highlight the present situation of steel industry and show plausible scenarios for the future. Potential methods to decrease CO2 emissions in current processes via improved energy efficiency, increasing recycling and alternative energy sources are surveyed. The role of recycled steel will considerably grow over the next few decades. These factors influence, that the specific energy consumption per ton steel and respective CO2 emissions will strongly decrease. The growth of emissions will be stopped and, in spite of the predicted growth of the steel production from the current 1.8 BT up to 2.5 BT/year, the total emissions from the steel sector can be significantly cut. However, these advancements are not sufficient for the final aim of carbon neutrality. That demands more radical changes in energy sources and systems as well as in iron & steel production technologies. Still today, energy systems are largely based on fossil fuel, but extensive transfer to renewable energy is coming true soon. Corresponding developments are taking place also in steel industry. Several on-going programs and initiatives for low-carbon and carbon-free ironmaking utilizing hydrogen are in progress. These projects as well as trends of future energy systems are surveyed. Finally, a simplified holistic model is shown demonstrating the steel´s contribution in solving the global CO2 emissions problem.

References:
[1] V. Masson-Delmotte et al (19 editors)]. Global Warming of 1.5 °C. IPCC report, 2018: Summary for Policymakers. In: https://report.ipcc.ch/sr15/pdf/sr15_spm_final.pdf , 32 pp.
[2] https://www.worldsteel.org/steel-by-topic/statistics.html. https://www.worldsteel.org/publications/fact-sheets.html
[3] J-P. L. Birat, Environmental Metallurgy: Continuity or New Discipline? steel research int. 85 (2014) No. 8, 1240-56. [4] M. Åhman et al (9 authors). Hydrogen steelmaking for a low-carbon economy. A joint LU-SEI working paper for the HYBRIT project. EESS report no 109, SEI working paper WP 2018-07, Sept. 2018, 28 pp. In: https://www.sei.org/wp-content/uploads/2018/09/hydrogen-steelmaking-for-a-low-carbon-economy.pdf [5] S. Tonomura, Outline of COURSE 50. Energy Procedia Dec.2013, 37:7160-67

11:45: [IronThuAM02] Plenary
CO2 ultimate reduction in steelmaking process (COURSE50 project)
Natsuo Ishiwata¹ ; Akinori Murao² ; ¹JFE Steel Corporation, Chiyoda-ku, Japan; ²JFE Steel Corporation, Fukuyama, Japan;
Paper Id: 424 [Abstract]

Tile: CO2 ultimate reduction in steelmaking process (COURSE50 project)<br />Author:Natsuo Ishiwata #1, Kazukuni Hase #1, Masaru Ujisawa#2, Kyouichi Araki#2 <br />#1: Technology Planning Dept. JFE Steel Corporation,<br />2-3, Uchisaiwai-cho 2-chome, Chiyoda-ku, Tokyo 100-0011 Japan<br />#2:Ironmaking Technology Div., NIPPON STEEL CORPORATION,6-1, Marunouchi 2-chome, Chiyoda-ku, Tokyo 100-8071 Japan<br />Abstract:<br />Four blast furnace steel makers and one engineering company in Japan have been engaged in the “CO2 Ultimate Reduction in Steelmaking Process by Innovative Technology for Cool Earth 50 (COURSE50) Project”, since FY2008. This project is a National Projects commissioned by New Energy and Industrial Technology Development Organization (NEDO).<br />The target of COURSE50 is a reduction of approximately 30% in CO2 emissions in the steel manufacturing process. Two technologies, which are a) Reduction of iron ore by using hydrogen-amplified coke oven gas to curb CO2 emissions from blast furnaces, and b) separation and recovery of CO2 from blast furnace gas by effective utilization of unused waste heat in the steel works are investigated.

12:10: [IronThuAM03] Keynote
Hydrogen and Natural Gas: The new alternatives for Siderurgy
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 334 [Abstract]

The use of Hydrogen and natural gas promise a revolution in Syderurgy. At the present time, the cost of wind and solar energy are decreasing [1] and also, new sources of natural gas have been discovered [2,3]. As a consequence, cheap electric energy can be available in a near future, as well as natural gas. This opens new possibilities for the energy use in Steelmaking [4]. Electric energy can be used for generating hydrogen, for use in reduction processes. In this talk, the many possibilities for application of hydrogen and natural gas in Syderurgy are discussed. Direct reduction processes based on shaft furnaces can open new possibilities for mini mill facilities. A detailed model for the direct reduction of iron oxides in the shaft furnace was developed [5]. This model can be used to simulate the steady state condition of a commercial shaft furnace for pellets and lump ore reductions. The model is able to predict the productivity and efficiency of the gas shaft furnace.

References:
[1] Chestney, Nina. “Solar, Onshore Wind Costs Set to Fall below New Fossil Fuel Energy: Report.” <i>Business Insider</i>, Reuters, 29 May 2019, www.businessinsider.com/solar-onshore-wind-costs-set-to-fall-below-new-fossil-fuel-energy-report-2019-5. Accessed June 18, 2019.

[2] Petrobras. “Petrobras Clarifies on Natural Gas Discovery in the Sergipe Basin.” <i>Petrobras</i>, 17 June 2019, www.investidorpetrobras.com.br/enu/15008/c-15008-enu.html. Accessed June 18, 2019.
[3] World Oil. “Petrobrás Makes Biggest Gas Discovery in the Sergipe Basin since 2006.” <i>World Oil - Upstream News</i>, 17 June 2019, www.worldoil.com/news/2019/6/17/petrobr%C3%A1s-makes-biggest-gas-discovery-in-the-sergipe-basin-since-2006. Accessed June 18, 2019.
[4] World Steel Association. “Energy Use in the Steel Industry.” <i>World Steel</i>, Apr. 2019, www.worldsteel.org/en/dam/jcr:f07b864c-908e-4229-9f92-669f1c3abf4c/fact_energy_2019.pdf. Accessed June 18, 2019.

[5] Castro, José Adilson de, Rocha, Elisa Pinto, Oliveira, Elizabeth Mendes de, Campos, Marcos Flavio, & Francisco, Alexandre Santos. (2018). Mathematical modeling of the shaft furnace process for producing DRI based on the multiphase theory. REM - International Engineering Journal, 71(1), 81-87. http://www.scielo.br/pdf/remi/v71n1/2448-167X-remi-71-01-0081.pdf. Accessed June 18, 2019.

12:35: [IronThuAM04]
A Combined Thermochemical and Biotechnological Route to Produce Hydrogen Using Cassava Residues: Preliminary Results and Materials Characterization
Cintia De Faria Ferreira Carraro¹ ; Carla Cristina De Almeida Loures¹ ; Jose Adilson De Castro² ; ¹CEFET-Angra dos Reis, Angra dos Reis, Brazil; ²UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 227 [Abstract]

The industry of cassava represents an important source of residues commonly released in the environment. Special concerns are raised about the cassava bagasse and the waste water residue produced during the processing steps. In this study, we propose a sustainable route, which involves two steps of gas production. A first step uses the cassava bagasse in a thermal reactor to produce rich hydrogen gas suitable for use in the direct reduction processes. Then the waste water is treated in a biotechnological reactor using algae to produce hydrogen. To characterize the thermochemical processing step of the cassava bagasse decomposition, thermogravimetric analyses (TGA) and simultaneous differential scanning calorimetry (DSC) were carried out in a broader range of temperature and gas flow rates. This was done using the design of experiment techniques (DOE) to draw generalized correlations. In the second step of the waste water processing treatment, the concentrations and the culture conditions of the Chlorella minutissima microalgae were investigated. This was done to design feasible controllable parameters to maximize hydrogen production under the laboratory batch. Results indicated that gasification of the cassava bagasse presented high conversion rates in the temperature range of 600-700°C. Additionally, the microalgae conversion is proved possible in near environment temperatures under a controlled environment.

References:
[1] SOCCOL, C.R. Biotechnological products from cassava roots by solid state fermentation. Journal of Scientific and insdutrial research, v.55p. 358-364, 1996.
[2] NAJAFI, G.; GHOBADIAN, B.; YUSAF, T. F. Algae as a sustainable energy source for biofuel production in Iran: a case study. Renew Sustain Energy, v. 15, p. 3870-3876, 2011.

SESSION: IronThuPM1-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Thu Oct, 24 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Jose Adilson de Castro; Basant Kumar Singh; Session Monitor: TBA

14:00: [IronThuPM105] Keynote
Hydrogen Shaft Furnace Process Using Bio-Self-Reducing Agglomerates
Jose Adilson De Castro¹ ; Giulio Antunes De Medeiros² ; Jonni Guiller Ferreira Madeira³ ; Elizabeth Oliveira⁴ ; Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil; ²UFF-Programa de Pos Graduação em Engenharia Metalurgica, Volta Redonda, Brazil; ³CEFET-Angra dos Reis, Angra dos Reis, Brazil; ⁴Center for Technological Education Celso Suckow da Fonseca, Valenca, Brazil;
Paper Id: 206 [Abstract]

The reduction of pellets and lump ores in the shaft furnace process is widely used to produce direct reduced iron (DRI). The traditional process of DRI production uses a gas reforming system based on catalytic reactions and demands high amount of fossil source energy from natural gas. A new hydrogen-based process has been proposed. In this study, we propose to combine self-reducing characteristics with hydrogen technology with self-catalytic reactions to avoid the natural gas-based reforming step. We analyzed this new technology using an in-house computational code. The computational analysis is a numerical model based on transport equations of momentum, energy and chemical species for gas and solid phases to reproduce the inner phenomena in the direct reduction of the shaft furnace process for producing DRI. The model is used to investigate promising scenarios of hydrogen-based technology. Four cases were considered using partial replacement of the burden by bio-self-reducing agglomerates combining with hydrogen and oxygen injections on the bustle level. The inner temperature, pressure and phase composition distributions are discussed for the selected scenarios. The simulation results indicated that the efficiency of the process can be improved with the adequate choice of operational parameters and raw materials burden.

References:
[1] Castro, JA, Takano, C., Yagi, J. A theoretical study using the multiphase numerical simulation technique for effective use of H2 as blast furnaces fuel. Journal of Materials Research and Technology, v.6(3), p.258-270, 2017.

14:25: [IronThuPM106] Invited
Using agribusiness residues as energy supply for blast furnaces
Alex Campos¹ ; Paulo Assis² ; Tateo Usui³ ; ¹Federal University of Ouro Preto, Ouro Branco, Brazil; ²Federal University of Ouro Preto, Ouro Preto, Brazil; ³Osaka University, Ibaraki, Japan;
Paper Id: 393 [Abstract]

Biomass is generated in agro industry and it was proved by some authors that the generation of residues is high and relevant to be used in the iron and steel making processes. In this sector there is interest to reduce the Green House Gas and biomasses appear as a new idea on renewable source of energy, replacing a part of the material injected on blast furnaces. Brazil has a huge production of biomass, for example, last year was produced around 300 Million ton of grains making it a major agricultural producers, while rich in natural resources. Brazil has an important role in the steel industry, these two activities now represent the largest contributors to greenhouse gases responsible for the greenhouse effect. Looking at this point, the purpose of this paper is analyze the technical, economic and environmental aspects of replacing part of the coal, commonly used in blast furnace, for some agribusiness waste as sugarcane bagasse, moringa oleifera husk and maize cob and straw. Some researches appointed that is possible to replace around 40% of the coal without change the process and bring some economics and environmental gains.

References:
Assis, C.F.C., Tenório, J.A.S., Assis, P.S., Nath, N.K., 2014a. Experimental simulation and analysis of agricultural waste injection as an alternative fuel for blast furnace. ACS Energy&Fuels, v.28, p. 7268-7273.\nCampos, A.M.A, Novack, K.M., Assis, P.S. Uses Of The Husk From Moringa Oleifera Seed For Blast Furnace Injection, ABMWeek 2018, São Paulo-SP, Brazil.\nFAO, Food and Agriculture Organization of the United Nations, 2018. Production of crops. Available at: http://www.fao.org/faostat/en/#data.\nMachado, L.A.; Habib, M. Perspectivas e impactos da cultura de cana-de-açúcar no Brasil. 2009. Available at: <http://www.infobibos.com/Artigos/2009_2/Cana/index.htm>. \nOrth, A., Anastasijevic, N., Eichberger, H., Low CO2 emission technologies for iron and steelmaking as well as titania slag production, Minerals Engineering, 2007, volume 20, issued 9, pp. 854-861.\nPrundergraund. The 2015 Global Moringa Meet updates Moringa Export Market Trend, Upward Integration & Opportunities, 2015. Available at: <http://www.prunderground.com/the-2015-global-moringa-meet-updates-moringa-export-market-trend-upward-integration-opportunities/0064082/>\nRAMOS e PAULA, L. E. , de et al . Characterization of Residues from Plant Biomass for Use in energy Generation. Cerne, Lavras , v. 17, n. 2, p. 237-246, abr./jun. 2011. \nRethink the Rust Belt, 2013. Available at: http://siliconrustbelt.com/rethink-the-rust-belt/\nSuopajärvi, H., Pongrácz, E., Fabritius, T., 2013. The potential of using biomass-based reducing agentes in blast furnace: A review of Thermochemical conversion Technologies and assenssments related to sustainability. Renewable and Sustainable Energy Reviews 25, 511-528p.\nSuopajärvi, H., Kemppainen, A., Haapakangas, J., Fabritius, T., 2017. Extensive review of the opportunities to use biomass-based fuels in iron and steelmaking processes. Journal of Cleaner Production, v.148, p.709-734.\nWang, C., Mellin,P., Lövgren,J., Nilsson,L., Yang,W., Salman,H., Hultgren,A., Larsson,M.,2015. Biomass as blast furnace injectant-Considering availability, pretreatment and deployment in the Swedish steel industry. Energy Conversion and Management, v.102, p.217-226.

14:50: [IronThuPM107]
THE BAKING ACID TECHNIQUE ALTERNATIVE TO DECREASE THE PHOSPHORUS CONTENT OF THE IRON ORE
Jose Adilson De Castro¹ ; Leonardo Martins Da Silva² ; Marcos De Campos¹ ; Elizabeth Oliveira³ ; Rayla De Souza Caldas⁴ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil; ²Universidade Federal Fluminense, Volta Redonda, Brazil; ³Center for Technological Education Celso Suckow da Fonseca, Valenca, Brazil; ⁴UFF-Programa de Pos Graduação em Engenharia Metalurgica, Volta Redonda, Brazil;
Paper Id: 201 [Abstract]

Unlike the available mineral resources, the steel-making processes require raw material with lower phosphorous content in order to decrease the costs, energy use and the residue generated within the steel plant. One alternative is to develop pre-treatment of the iron ore concentrates, achieving raw materials with lower phosphorous. Depending on the mineral structure, a heat treatment combined with leaching can be an efficient way to achieve concentrates with low phosphorous (less than 0.01%). A fast and efficient way of applying energy to iron ore particles is the use of microwave energy to heat the particles. Thus, we propose a treatment using microwave heating while admixing low concentration sulfuric acid, followed by quenching during leaching with water as a feasible route for phosphorus removal from iron ore particles. We performed a design of experiment (DOE) to investigate the optimal conditions of heating and leaching which maximize the rate of phosphorous removal. The structure of the iron ore particles after their treatment with microwave energy was observed using scanning electron microscopy (SEM). Disclosing results must be presented here: the optimal conditions for heating and leaching, how the structure of the iron ore particles is affected and which is the mechanism to which it corresponds, as well as the equations and the controlling mechanism. We demonstrated that, under the most favorable combination of heating and leaching conditions proposed in this study, the reduction of the phosphorus content in the iron ore sample could reach 100%.

References:
1) Yong SJ, Jiang T, Yang YB, Li Q, Li GH, Guo YF. Removal of phosphorus from iron ores by chemical leaching. School of Minerals Processing and Bioengineering, Central South University, Changsha. 2006; 410083.

15:15: [IronThuPM108] Keynote
Reduction of Material and Utilities Consumption by optimization of the usage at I- Blast Furnace
Padma Pal¹ ; Basant Kumar Singh¹ ; Bhaskar Ramdasu¹ ; Dhiren Patnaik² ; Vishwakarma Raj Kumar³ ; G.s.r. Murthy .³ ; Singh Anil Kumar⁴ ; ¹Tata Steel, Jamshedpur, India; ²Tata Steel Ltd., JAMSHEDPUR, India; ³Tata Steel Ltd., Jamshedpur, India; ⁴Tata Steel Ltd, Jamshedpur, India;
Paper Id: 221 [Abstract]

The rapid increase in world steel output during the last three decades has been accompanied by a growing geographical distribution of production, especially among developing countries. There have been tendencies towards both larger and more efficient units for achieving high production and less environmental impact. Currently, about 40% of steel is manufactured from recycled scrap, which uses only 15-20% of the energy needed to make steel from virgin ore. The cut throat competition from the electric furnaces and environmental norms is getting more stringent. The very sustenance of Blast Furnace is chiefly dependent on the level of optimized usage of available raw material. Apart from the regular raw materials, like coke, coal, iron bearing materials and fluxes, the blast furnaces also consume many utilities such as nitrogen, steam, water and consumables for safe and efficient operation. This paper elaborates the actions taken to reduce the raw materials, utilities and consumables, thereby saving over USD 30 M.

References:
1. Elsayed A. MOUSA, Alexander BABICH and Dieter SENK: ISIJ International, Vol. 51 (2011)\n2. Maarten Geerdes Hisko Toxopeus Cor van der Vliet; Modern Blast Furnace Ironmaking-an introduction; second edition 2009

SESSION: IronThuPM2-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Thu Oct, 24 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Moritoshi Mizutani; Shunsuke Hori; Session Monitor: TBA

15:55: [IronThuPM209]
Heat Loss Control in Stave Cooled Blast Furnace by Optimizing Gas Flow Pattern through Burden Distribution
Basant Kumar Singh¹ ; Bhaskar Ramdasu¹ ; Padma Pal¹ ; Dhiren Patnaik² ; G.s.r. Murthy .³ ; Vishwakarma Raj Kumar³ ; Kumar Lal Santosh³ ; Jaya Krishna P.³ ; ¹Tata Steel, Jamshedpur, India; ²Tata Steel Ltd., JAMSHEDPUR, India; ³Tata Steel Ltd., Jamshedpur, India;
Paper Id: 220 [Abstract]

The productivity of Blast Furnaces is largely impacted by fuel efficiency. Control of heat loss is one of the enabling parameters for achieving lower fuel rate. I-Blast Furnace is the latest and largest Blast Furnace of Tata Steel Jamshedpur with a working volume of 3230m³ and with rated capacity of 3.055 million tons per annum. Optimizing heat losses in Belly and Bosh zones remains a major challenge for blast furnace operators. The I-Blast furnace has installed Cast Iron & Copper Staves cooling members where copper staves are installed in Belly, Bosh & Lower Stack, whereas cast iron staves are installed in the upper stack area. Stave cooled Blast Furnaces are prone to higher heat losses in the Belly and Bosh regions with increase in coal injection rate as Bosh gas volume increases. Under these conditions, managing gas flow patterns through proper burden distribution, casting techniques, and maintenance of desired raw material qualities are of upmost importance for sustaining high injection rates. This study details the burden distribution control by the Ore & Coke ratio adjustment at the wall and center of the Blast Furnace as the coal injection rates increase from 140 kg/thm to 220 kg/thm. Control of blowing parameters, casting philosophy, specification for raw materials, and division of operational practices for controlling heat losses is also elaborated with the model that is used to visualize heat loss patterns in different zones of the Blast Furnace.

References:
1. Principles of blast furnace ironmaking: Theory and practice: A. K Biswas\n2. An Introduction to Modern Iron Making" by R. H. Tupkary and V. R. Tupkary

16:20: [IronThuPM210] Invited
In-Situ Evaluation for Crack Generation and Propagation Behavior of Iron Ore Burden during Low Temperature Reduction by Applying Acoustic Emission Method
Moritoshi Mizutani¹ ; Tsunehisa Nishimura² ; Takashi Orimoto¹ ; Kenichi Higuchi¹ ; Seiji Nomura¹ ; Koji Saito³ ; Eiki Kasai⁴ ; ¹Nippon Steel Corp., Futtsu, Japan; ²Nippon Steel Corpo., Futtsu, Japan; ³Nippon Steel & Sumitomo Metals Corp., Futtsu City, Japan; ⁴Graduate School of Environmental Studies, Tohoku University, Sendai, Japan;
Paper Id: 21 [Abstract]

Volumetric expansion during low temperature reduction of hematite to magnetite causes disintegration of iron ore burden in the upper part of blast furnace (1). The extent of such a property is generally evaluated by ISO11258/JISM8720 as a Reduction Disintegration Index (RDI) at low temperatures, where test samples are reduced with the constant gas composition at a constant temperature followed by the strength test after cooling. It is difficult, however, to observe detailed behaviors of crack formation during the test operation. Therefore, we have applied an acoustic emission (AE) method for an RDI test equipment (2). AE is an <i>in-situ</i> non-destructive technique that enables detection of the incidences of the generation and propagation of the crack (3)-(6). In a single particle reduction, the sinter emitted a large number of AEs during cooling, and the AE energy of the sinter was higher than that of the pellet. Furthermore, lump ores containing high combined water emitted a large number of AEs during heating. The latter result implies that this method is useful for the evaluation the decrepitation of iron ore lumps. In the packed bed tests, the effective AE signals were obtained against noise probably caused by frictions between the sample and the wave guide. The guide represents the average properties of the iron ore burden. The measurements revealed that thermal energy stress during cooling was higher than during reduction at 823 K for 30 min. The results show that the value of the standard RDI is affected by the cooling operation, which is different from blast furnace conditions. The AE method will be applied as a unique measure to observe real disintegration behaviors of iron ore burden during reduction.

References:
1) T. Inazumi, K. Shinada and M. Kawabe: Tetsu-to-Hagana, 68(1982), 2207.\n2) M. Mizutani, T. Nishimura, T. Orimoto, K. Higuchi, S. Nomura, K. Saito and E. Kasai: ISIJ Int., 58(2018), 1413.\n3) M. Enoki, S. Fujikawa and T. Kishi: Journal of the Japan Institue of Metals, 58(1994), 418.\n4) M. Ohtsu: Research in Nondestructive Evaluation, 6(1995), 169.\n5) K. Ito, H. Kuriki, M. Watanabe, S. Kuroda and M. Enoki: Materials Transactions, 53(2012), 671.\n6) H. Nakamura: Journal of The Japanese Society for Non-Destructive Inspection, 62(2013), 267.

16:45: [IronThuPM211] Invited
Effect of Ore Contraction Behavior on Permeability of Coke Slit Layer in Cohesive Zone
Kazuhira Ichikawa¹ ; Toshiyuki Hirosawa² ; Takeshi Sato³ ; Taihei Nouchi³ ; Kiyoshi Fukada² ; ¹, Chiba, Japan; ²JFE Steel Corporation, Fukuyama, Japan; ³JFE Steel Corporation, Chiba, Japan;
Paper Id: 87 [Abstract]

Recently, due to increases in the price of ironmaking coal, low coke rate operations in the blast furnaces have been necessary. Because coke works as a spacer in the blast furnace, however, low coke ratio operation causes deterioration of furnace permeability [1]. This is remarkable in the cohesive zone. The results of measurements of the shape of the cohesive zone in dissected blast furnaces revealed that the ore layer and coke slit layer were alternately layered [2]. Therefore, in the cohesive zone, gas is expected to flow horizontally along the coke slit layer. Thus, the permeability of the coke slit layer in cohesive zone is important. The authors developed a new simulator called the Cohesive Zone Simulator for quantifying the effect of the coke slit layer thickness on permeability. The authors revealed that this is because of the decrease in void fraction of the coke slit layer, caused by the increasing thickness of the penetration layer of melting the ore layer [3]. On the other hand, the effect of ore melting behavior on the permeability of the coke slit layer was not studied enough. Ore properties, i.e. reduction ratio and effect on the melting behavior, however, are known [4]. Based on the background outlined above, the effects of the contraction ratio of the melting ore layer to permeability were studied by using the cohesive zone simulator.

References:
[1] M.Ichida, S.Matsuzaki, T.Tanaka and F.Koizumi: Tetsu-to-Hagane, 87(2001), 342.\n[2] Y.Togino, M.Sugata, I.Abe and M.Nakamura: Tetsu-to-Hagane, 65(1979), 1526.\n[3] K.Ichikawa, Y.Kashihara, N.Oyama, T.Hirosawa, J.Ishii, M.Sato and H.Matsuno: Tetsu-to-Hagane, 102(2016), 1.\n[4] T.Nishimura, K.Higuchi, K.Ohno and K.Kunitomo: Tetsu-to-Hagane, 102(2016), 61.

17:10: [IronThuPM212] Invited
Gas Permeability Improvement at the Lower Part of Blast Furnace by Converter Slag Injection from Tuyere
Shunsuke Hori¹ ; Akito Kasai¹ ; Rikizo Tadai¹ ; Kentaro Nozawa¹ ; ¹KOBE STEEL, LTD., Kakogawa, Japan;
Paper Id: 420 [Abstract]

One significant operational problem in increasing pulverized coal rate and decreasing coke rate must be the increased pressure drop or the worsened gas permeability at the lower part of the blast furnace. In order to improve gas permeability around the blast furnace bird’s nest region during high pulverized coal injection rate operation, flux injection technology from the tuyere is surveyed with the purpose of decreasing slag hold-up. In this study, converter slag is focused on as the flux material. The advantages of converter slag are its low melting point due to high FeO content and its smaller endothermic quantity as a pre-melt slag. Results obtained by experiments and actual blast furnace tests are as follows: (1) Converter slag was expected almost completely to be smelted during flight within the raceway and showed an excellent assimilation property with bird’s nest slag. (2) A scheme is newly established which estimates the improvement degree of gas permeability using the operational conditions for the blast furnace and the converter slag injection conditions. (3) A decrease in pressure drop at the lower part of the blast furnace was demonstrated by converter slag injection tests at Kobe No.3 blast furnace. The operational results showed fairly good agreement with those estimated by the scheme of the present study.

SESSION: IronThuPM3-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Thu Oct, 24 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Marcos de Campos; Sergey Komarov; Session Monitor: TBA

17:50: [IronThuPM313] Keynote
Control of Interfacial Phenomena in Pyrometallurgical Processes through the Use of Acoustic Oscillations
Sergey Komarov¹ ; Takuya Yamamoto¹ ; ¹Tohoku University, Sendai, Japan;
Paper Id: 331 [Abstract]

This work provides results of the author's activity in the field of application of sound and ultrasound waves for controlling interfacial phenomena in steelmaking and aluminum making processes. The corresponding investigations have been carried out using laboratory and industrial scale equipment. The physical basis for controlling interfacial phenomena is the fact that gaseous, liquid and solid phases differ greatly in acoustic impedance. Therefore, when a sound wave is incident on an interface between two phases, the major part of the wave’s energy is reflected from and/or absorbed by the interface, resulting in a number of effects beneficial for pyrometallurgical processes. In steelmaking processes, airborne sound/ultrasound waves provide the possibility to influence the interface mass transfer and thus, to control the rates of steelmaking reactions. Particularly, application of sound waves to the interphase between oxidizing atmosphere and molten Fe-C alloy causes enhanced oxidation of iron and influences thus the decarburization rate. Other examples of sound application effects are control of foaming phenomena and dust formation in steelmaking converters or electric arc furnaces.
In aluminum production, as the melting point of aluminum is much lower than iron, the ultrasonic vibrations can be introduced directly in the molten aluminum alloys using refractory metal or ceramics sonotrodes. This makes it possible to transmit the ultrasound energy directly to the liquid-solid interface and thus, to break and disperse various particulates in the melt before or during its solidification. Examples include, but are not limited to, dispersion of refiner particles and fragmentation of growing dendrites. This offers an attractive way to control macrostructure and microstructure of aluminum alloys in casting processes. Besides, this technique is applicable to the development of new aluminum alloys and composite materials.

18:15: [IronThuPM314] Invited
From Tatara furnace to Tamahagane Steel and the Japanese Sword
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 205 [Abstract]

The Tatara furnace was the traditional method for steel production in ancient Japan. Tamahagane steel ("precious metal" in Japanese) obtained from the Tatara furnace was used for the manufacturing of Japanese swords. These Japanese swords were produced with two types of steel: one with high carbon (kawagane) and another with low carbon (shingane). The high carbon steel was used for the blade region. The ductile low carbon steel was used for the interior part of the sword. Japanese swords have a curvature, which is produced in the moment of the quenching. One of the interesting aspects of the Japanese sword is that the processing occurs in such a way that compression of residual stress is introduced on the side of the blade [1]. Thus, if a crack appears, it does not open. The Western swords with blades on both sides were much less reliable in combat. As for Western swords, existence of tensile residual stress on the surface of the swords makes them much easier to break. Other details of the physical metallurgy of the steel employed in Japanese swords are also discussed.

References:
[1] Tatsuo Inoue. Tatara and the Japanese sword: the science and technology. Acta Mech 214, 17-30 (2010)

SESSION: IronFriAM-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Fri Oct, 25 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Masaaki Naito; Oleg Ostrovski; Session Monitor: TBA

11:20: [IronFriAM01] Plenary
Gaseous Reduction of Iron Ore Agglomerates --- Reaction Behavior and Reaction Models
Tateo Usui¹ ; Masaaki Naito² ; Hirotoshi Kawabata³ ; Hideki Ono⁴ ; Hirokazu Konishi³ ; Paulo Assis⁵ ; ¹Osaka University, Ibaraki, Japan; ²Nippon Steel Technology Corporation, Futtsu, Japan; ³Osaka University, Suita, Japan; ⁴University of Toyama, Toyama, Japan; ⁵UFOP, Ouro Preto, Brazil;
Paper Id: 437 [Abstract]

Gaseous reduction behavior of iron oxide pellets and iron ore sinter with CO and H₂ were studied experimentally. In reaction models for gaseous reduction of iron ore agglomerates, the formations of both unreacted-core shrinking (UCS) model for one interface and UCS model for three interfaces and the developments of multi-stage zone-reaction models without and with considering solid-state diffusion are summarized; these models were used mainly for pellets but sometimes used for sinter. UCS model for six interfaces in consideration of quaternary calcium ferrite reduction process was newly developed for sinter. Comparisons of these reaction models for pellets and sinter were carried out by using experimental data on gaseous reduction of these iron ore agglomerates.

References:
1 T. Usui, M. Naito, T. Murayama and Z. Morita: Kinetic Analysis on Gaseous Reduction of Agglomerates, Part 1, Reaction Models for Gaseous Reduction of Agglomerates (in Japanese), Tetsu-to-Hagané, 80 (1994), 431-439.

2 T. Usui, M. Ohmi, M. Naito, H. Kamiya, Y. Oshima and Z. Morita: Kinetic Analyses on the Rate of Gaseous Reduction of Single Particles and Packed Beds of Iron Ore Agglomerates, Proceedings of The Julian Szekely Memorial Symposium on Materials Processing, ed. by H. Y. Sohn, J. W. Evans and D. Apelian, (October, 1997, Boston, Massachusetts, U.S.A.), 67-80, TMS.

3 M. Ohmi, T. Usui, M. Naito and Y. Minamide: Experimental Study of the Resistance Due to the Rate of Gas Flow on the Hydrogen Reduction of an Iron Oxide Pellet, Tetsu-to-Hagané (in Japanese), 67 (1981), 1943-1951; Trans. ISIJ (Transactions of the Iron and Steel Institute of Japan), 23 (1983), 81-89

4 M. Ohmi and T. Usui: Study on the Rate of Reduction of Single Iron Oxide Pellet with Hydrogen (in Japanese), Tetsu-to-Hagané, 59 (1973), 1888-1901; On the Unreacted-core Shrinking Model for Reduction of a Single Hematite Pellet with Hydrogen, Trans. ISIJ, 16 (1976), 77-84.

5 M. Ohmi, M. Naito and T. Usui: Applicability of Three Interface Model to the Analysis of Reduction Rate of Iron Oxide Pellets with Hydrogen, Technology Reports of the Osaka University, 34 (1984), No.1743, 19-27.

6 T. Usui, M. Ohmi and E. Yamamura: Analysis of Rate of Hydrogen Reduction of Porous Wustite Pellets Basing on Zone-reaction Models, Tetsu-to-Hagané (in Japanese), 72 (1986), 1263-1270; ISIJ International, 30 (1990), 347-355.

7 M. Ohmi, M. Naito and T. Usui: Multi-stage Zone-reaction Model for the Gaseous Reduction of Porous Hematite Pellets (in Japanese), Tetsu-to-Hagané, 68 (1982), 592- 601.

8 M. Ohmi and T. Usui: Improved Theory on the Rate of Reduction of Single Particles and Fixed Beds of Iron Oxide Pellets with Hydrogen, Trans. ISIJ, 22 (1982), 66-74.

9 M. Ohmi, M. Naito and T. Usui: Kinetic Analysis of Hydrogen Reduction of Various Hematite Pellets on the Basis of the Multi-stage Zone-reaction Models (in Japanese), Tetsu-to-Hagané, 69 (1983), 546-555.

10 M. Ohmi, M. Naito and T. Usui: Effects of Various Factors on the Reduction Rate of Hematite Pellets with Hydrogen (in Japanese), Tetsu-to-Hagané, 68 (1982), 1503-1512.

11 M. Ohmi, M. Naito and T. Usui: Multi-stage Zone-reaction Model with Solid-state Diffusion for the Hydrogen Reduction of Porous Hematite Pellets (in Japanese), Tetsu-to-Hagané, 69 (1983), 363-370.

12 T. Usui, M. Ohmi, S. Hirashima and N. Kitagawa: Kinetic Analysis on the Rate of Stepwise Reduction of a Single Sinter with CO-CO2-N2 Gas Mixture (in Japanese), Tetsu-to-Hagané, 73 (1987), 1956-1963.

13 T. Usui, M. Ohmi, S. Kaneda, M. Ohmasa and Z. Morita: Re-examination of Method of Kinetic Analysis on the Rate of Stepwise Reduction of a Single Sinter Particle with CO-CO₂-N₂ Gas Mixture, ISIJ International, 31 (1991), 425-433.

14 T. Usui, M. Ohmi, N. Kitagawa, S. Kaneda, H. Kawabata and Z. Morita: Change of Sinter Minerals and Final Fractional Reduction in the Reduction Stage from Hematite to Magnetite with CO-CO₂-N₂ Gas Mixture (in Japanese), Tetsu-to-Hagané, 77 (1991), 1251-1258.

15 T. Usui, H. Kawabata, T. Fujimori, I. Fukuda and Z. Morita: Influence of CO Ratio and Reduction Temperature upon the Reducibility of Calcium Ferrite in Sinter in the Initial Stage of Reduction with CO-CO₂-N₂ Gas Mixture (in Japanese), Tetsu-to-Hagané, 78 (1992), 982-989.

16 H. Ono-Nakazato, Y. Tsubone, Y. Takaki and T. Usui: Measurement of Hydrogen Reduction Rates of FeO in 2FeO.SiO₂ and CaO.FeO.SiO₂ (in Japanese), Tetsu-to-Hagané, 87 (2001), 320-326.

17 T. Usui, Y. Nakamuro, M. Nishi, M. Naito, H. Ono and Paulo S. Assis: Gaseous Reduction Model for Sinter in Consideration of Calcium Ferrite Reaction Process (Unreacted-core Shrinking Model for Six Interfaces), Tetsu-to-Hagané (in Japanese), 100 (2014), 294-301; ISIJ International, 55 (2015), 1617-1624.

18 T. Murayama, T. Usui, M. Naito and Y. Ono: Kinetic Analysis on Gaseous Reduction of Agglomerates, Part 2, Rate Parameters Included in the Mathematical Model for Gaseous Reduction of Agglomerates (in Japanese), Tetsu-to-Hagané, 80 (1994), 493-500.

19 M. Naito, T. Murayama and T. Usui: Kinetic Analysis on Gaseous Reduction of Agglomerates, Part 3, Application of Gaseous Reduction Models for Agglomerates to Blast Furnace Analysis (in Japanese), Tetsu-to-Hagané, 80 (1994), 581-586.

20 T. Usui, H. Konishi, K. Ichikawa, H. Ono, H. Kawabata, Francisco B. Pena, Matheus H. Souza, Alexandre A. Xavier and Paulo S. Assis: Evaluation of Carbonisation Gas from Coal and Woody Biomass and Reduction Rate of Carbon Composite Pellets, Advances in Materials Science and Engineering, Special Issue on Biomass Materials for Metallurgical Applications, Vol. 2018, Article ID 3807609, (2018), pp.1 – 14.

11:45: [IronFriAM02] Keynote
Application of Multi-stage Zone Reaction Model for Agglomerates to Blast Furnace Analysis
Masaaki Naito¹ ; ¹Nippon Steel Technology Co., Ltd., Futtsu, Japan;
Paper Id: 429 [Abstract]

It is important to evaluate the reduction behavior of agglomerates as well as permeability for Blast Furnace analysis. Generally, rate-parameters of an agglomerate is used for several BF analysis. But, sinter has a different porosity in a different particle size. In radius direction of a blast furnace top, sinter particle size is different by burden distribution control. And also, sinter particle size changes by reduction degradation in a low temperature region of BF. In the high temperature region over 1100○C, porosity of sinter decreases by melt formation inside of sinter. It is needed to consider the change of particle size and porosity by above phenomena in the BF analysis <br />Here, Multi-Stage Zone Reaction model (MSZR) is used for analyzing the reduction of agglomerates. How to evaluate the rate-parameters is considered and the influence of agglomerate quality is analyzed.

References:
M.Naito,T.Murayama and T.Usui: Tetsu-to Hagane,「Kinetic Analysis on Gaseous Reduction of Agglomerates,Part3, Application of Gaseous Reduction Models for Agglomerates to Blast Furnace Analysis」,80(1994)8, p581

12:10: [IronFriAM03] Invited
Influence of Basicity on Reduction Rate of Iron Oxide
Hirokazu Konishi¹ ; Tateo Usui² ; Hideki Ono³ ; ¹Osaka University, Suita, Japan; ²Osaka University, Ibaraki, Japan; ³University of Toyama, Toyama, Japan;
Paper Id: 273 [Abstract]

Since reducibility of iron oxide in iron ore directly affects the amount of CO₂ from BF, the enhancement of reducibility of iron oxide is important to reduce CO₂ emissions. The iron ore grade, however, becomes lower year by year. Gangue in iron ore is increasing especially in Al₂O₃. It is observed that the reducibility of sintered iron oxide pellets decreases with the increase of Al₂O₃ content in softening and melting zones over 1373 K in BF. Besides, it is reported that the initial melt formation temperature drops and the amount of melt increases with the increase of Al₂O₃ content [1]. Since molten oxide formed inside sintered iron oxide pellets causes pore occlusion [2], melt formation can affect reducibility in the softening and melting zones. Therefore, it is required to determine the effect of melt on reduction behavior to enhance reducibility of sintered iron oxide pellets. We focused on the reduction behavior and rate of sintered iron oxide pellets on the initial melt formation stage and investigated the effect of melt on the reducibility of iron oxide. The sample was prepared by sintering a mixture of Fe₂O₃, CaO, SiO₂, and Al₂O₃ regent powder. Reduction experiments were carried out to clarify the reduction behavior of a sample from 1273 K to 1473 K and to determine the effect of melt on reduction rate of a sample at 1473 K. The microstructure of a sample was observed by a scanning electron microscope (SEM) and porosity was estimated by an image analysis technique.

References:
[1] H. Konishi, H. Kawabata, H. Ono and E. Takeuchi, Advanced Experimental Mechanics, 1(2016), 251.\n[2] H. Kawabata, Y. Iwaki, H. Konishi, H. Ono, T. Usui, E. Takeuchi, M. Naito, T. Nishimura and K. Higuchi: Journal of JSEM, 16(2016), 20.

12:35: [IronFriAM04] Keynote
Knowns and Unknowns in the Solid State Reduction of Metal Oxides
Oleg Ostrovski¹ ; ¹The University of New South Wales Sydney, Sydney, Australia;
Paper Id: 358 [Abstract]

The paper discusses (1) gaseous reduction of iron oxides and ores, (2) reduction of manganese, chromium and titanium oxides using methane-containing gas, (3) constraints in the reduction of manganese, chromium ores, ilmenite and quartz, and (4) the effect of the gas atmosphere in the carbothermal reduction of stable metal oxides. Reduction of metal oxides was studied using a fixed-bed reactor. Reduction of iron oxides and ores was also examined using high-temperature XRD. Under standard conditions, methane is thermodynamically unstable above 550°C and decomposes to solid carbon and hydrogen. At appropriate CH₄/H₂ ratio and temperature, carbon activity in the methane-containing gas phase can be well above unity relative to graphite, which provides favorable thermodynamic conditions for reduction. To maintain these conditions, the rate of reduction/carburisation should be higher than the rate of solid carbon deposition. This condition is difficult to maintain in the reduction of stable oxides and ores. Carbothermal reduction of stable oxides in hydrogen is a promising avenue for processing of manganese ores and ilmenites.

SESSION: IronFriPM1-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Fri Oct, 25 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Henrik Saxen; Hiroshi Nogami; Session Monitor: TBA

14:00: [IronFriPM105] Keynote
Modeling and Analysis of Reactions in Blast Furnace
Hiroshi Nogami¹ ; Shungo Natsui¹ ; ¹Tohoku University, Sendai, Japan;
Paper Id: 390 [Abstract]

In recent years, many approaches have been made to reduce the environmental impact of iron and steelmaking industries. Replacement of reducing agents and reaction control of blast furnace are expected to decrease the greenhouse gas emission. Under such operation, internal states of the blast furnace changes drastically, thus the operation conditions should be carefully adjusted. Kinetic-based mathematical simulation is one of the useful tools for design and optimization of blast furnace operation. This paper first summarizes the outline of the blast furnace model and the reaction sub-models for reduction of iron ore and gasification of coke. Then the characteristics and utilizing methods of these models are introduced. Namely effect of coke substrate reactivity on intra-particle reaction progress of coke, and the effect of reducing gas on the form of reaction of iron oxide reduction. Finally, the recent approaches to the iron ore reduction under the scales of particle and burden layer are introduced.

14:25: [IronFriPM106] Keynote
Mathematical model of burden distribution in the blast furnace
Henrik Saxen¹ ; Mikko Helle² ; Haifeng Li³ ; ¹Abo Akademi University, 20500 Abo, Finland; ²Abo Akademi University, Abo, Finland; ³Northeastern University, Shenyang, China;
Paper Id: 271 [Abstract]

The distribution of the burden plays a key role for the operation of the blast furnace [1], as it affects the thermal and chemical phenomena in the lumpy zone. Through these, the efficiency of heat and mass transfer and chemical reactions in the shaft are also affected. It also influences the level and shape of the cohesive zone, which has considerable impact on process stability and fuel rate. Therefore, many mathematical models (e.g., [2]) have been developed to gain understanding of the complex burden layer-formation process. A mathematical model of the distribution of burden in a blast furnace with bell-less charging has been developed. Special attention was paid to the computation efficiency to make the model fast enough to allow for real-time simulation and interactive planning of charging programs. The model, which describes the formation of burden layers and their descent in the shaft of the furnace, has been verified by charging experiments at a small scale [3] and has been applied for automatic generation of charging programs satisfying certain criteria concerning the radial distribution of the burden [4]. The present paper presents some results where the model is applied to study new charging programs and the resulting distribution of coke and ore in the furnace shaft. Furthermore, the model's predictions of the distribution of burden layers are validated by comparison with measurements from a 3D top scanner in an operating furnace, through which the radial distribution of the layers can be measured. The model has been proven as a valuable tool in the design of charging programs and in the simulation of the distribution and descent of the burden layers in the throat and shaft regions of the blast furnace.

References:
[1] J.I. Park, H.J. Jung, M.K. Jo, H.S. Oh and J.W. Han, Met. Mater. Int. 17 (2011) 485-496.
[2] V.R. Radhakrishnan, K.M. Ram, J. Proc. Control 11 (2001) 565-586.
[3] T. Mitra, H. Saxen, Metall. Mater. Trans. B 45B (2014) 2382-2394.
[4] T. Mitra, H. Saxen, Mater. Manuf. Proces. 30 (2015) 474-487.

14:50: [IronFriPM107] Keynote
FLOGEN Contop Design, Decision-Making, Control, Optimization and Automation System Applied at Blast Furnaces
Paulo Afonso Gomes¹ ; Marcos De Souza² ; Florian Kongoli³ ; ¹FLOGEN Technologies Inc., Belo Horizonte, Brazil; ²FLOGEN Technologies Inc, Sao Paulo, Brazil; ³FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 479 [Abstract]

FLOGEN Technologies Inc. has implemented and commissioned FLOGEN CONTOP, a Design/Decision-Making/Control/Optimization/Automation System at various blast furnaces of pig iron producers in Brazil. The system instantaneously makes a complete optimization of all raw materials, including limestone, silica, air and oxygen volumes, in order to achieve specific targets according to the needs of the company. The main achievements of the implementation of the FLOGEN CONTOP system were the increase of the pig iron production by about 14% and the decrease of total consumption of charcoal (breeze and fines) by about 4%. Additionally, fines injected through the tuyeres were decreased, temperature and composition of slag and pig iron (including Si and P) were better controlled and silica addition as a flux was minimized. An overall instantaneous mass and energy balance helped fix various mechanical and procedural problems in the plant. CONTOP system was also successfully used to determine the annual procurement strategies by predicting various raw material cost-based scenarios related to productivity and fuel consumption in short- and long-term future. CONTOP increased productivity and reduced cost up to the highest designed limit of the technology. CONTOP also changed the way of operating from a reactive wait-the-lab-results-approach to a proactive forecast-and-act approach.

15:15: [IronFriPM108] Invited
Mathematical Modeling of the Shaft Furnace Process for Producing DRI Using Self-Reducing Pellets
Jose Adilson De Castro¹ ; Marcos De Campos¹ ; Elizabeth Oliveira² ; Giulio Antunes De Medeiros³ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil; ²Center for Technological Education Celso Suckow da Fonseca, Valenca, Brazil; ³UFF-Programa de Pos Graduação em Engenharia Metalurgica, Volta Redonda, Brazil;
Paper Id: 200 [Abstract]

The shaft furnace process is widely used to produce DRI from pellets and lump ore. One of the largest shortcomings of the process is the need for a reforming gas station for producing reducing gas. This study proposes the enhancement of the efficiency of the process using self-reducing burden with poor reducing gas. A numerical model based on transport equations of momentum, energy and chemical species for gas and solid phases is proposed to simulate the inner phenomena in the direct reduction of the shaft furnace process for producing direct reducing iron (DRI). The model is verified using industrial data of productivity, raw materials and final composition of the DRI product. The model is used to evaluate operational practices using new raw materials and composition of reducing gas in the process. Five cases were considered which correspond to available raw materials and operational conditions on the process. The effects on the gas and solid inner temperature, pressure and phase compositions distributions are quantified. The simulation results indicated that good agreement for overall parameters of the process could be achieved. Afterwards, detailed features of the inner conditions of the process are predicted.

References:
[1] CASTRO JA, NOGAMI H, YAGI J. Numerical analysis of multiple injection of pulverized coal, prereduced iron ore and flux with oxygen enrichment to the blast furnace. ISIJ International, v. 41, n. 1, p. 18-24, 2001.

[2] CASTRO JA, SILVA A.J, SAZAKI Y, YAGI J. A six-phases 3-D model to study simultaneous injection of high rates of pulverized coal and charcoal into the blast furnace with oxygen enrichment. ISIJ International, v. 51, n.7, p. 748-758, 2011.

SESSION: IronFriPM2-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Fri Oct, 25 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Taichi Murakami; Cyro Takano; Session Monitor: TBA

15:55: [IronFriPM209] Plenary
Evaluation of Ferro-coke Reaction Behavior in Blast Furnace
Yuki Iwai¹ ; Hideki Fujimoto² ; Takashi Anyashiki² ; Takeshi Sato³ ; Michitaka Sato² ; ¹JFE Steel Corporation, Fukuyama, Japan; ²JFE Steel, Fukuyama, Japan; ³JFE Steel Corporation, Chiba, Japan;
Paper Id: 419 [Abstract]

In recent years, development of innovative energy saving technologies for preventing global warming becomes more important for the steel industry. Ferro-coke is an innovative ironmaking process for energy saving in terms of realizing the low reducing agent ratio (RAR) operation in the blast furnace. In the Ferro-coke process, coal and iron ore were mixed and formed by a briquetting machine, and carbonized in a vertical type carbonization furnace. Ferro-coke causes lower thermal reserve zone temperature in a blast furnace because of its high gasification reactivity by Fe catalytic effect. In this study, the reactivity of ferro-coke was measured under the condition simulated a blast furnace. As a result, it was found that ferro-coke has remarkably higher reactivity and lower reaction starting temperature than normal coke and in the case of mixing sinter, the reduction of sinter was enhanced. In the former NEDO project, 2000 ton of ferro-coke was produced by the pilot plant with a capacity of 30 ton/day and the effect on RAR was confirmed in the actual blast furnace. For the next step, NEDO began the project “Environmentally Harmonized Steelmaking Process Technology Development (Ironmaking Process Technology Using Ferro-coke)” with a 6 year schedule from FY 2017. In this project, a ferro-coke production technology is to be established through a medium-scale plant producing 300 ton/day of ferro-coke with the aim of a 10% reduction in energy consumption in the ironmaking process by around the year 2022.

16:20: [IronFriPM210] Plenary
Binders for Cold Agglomerations with Perspective for Strengthening at High Processing Temperatures
Cyro Takano¹ ; Tiago Ribeiro² ; Marcelo Mourao¹ ; ¹University of Sao Paulo, Sao Paulo, Brazil; ²Institute for Technological Research, Sao Paulo, Brazil;
Paper Id: 372 [Abstract]

There are many articles and some reviews on inorganic [1] and organic binders [2] for agglomeration of ores. Most of them are related with obtaining enough strengths at green and dried stages (avoiding degradation during transport and processing) and after sintering (firing). For iron ore pellets, using 0.7% sodium bentonite as binder, the firing temperatures is around 1300oC and energy consumption represents highest cost of the pelletizing process. The cold agglomeration presents benefits for saving energy with consequences for environment. The cold agglomeration process using cement as binder is well known but presents two negative constraints: i) needs high (around 7%) content of the binder, resulting in slag increment; and ii) since the strength is given during curing by hydration, mainly of tri-calcium silicate, it starts the decompose at high temperatures and the strength of the pellets go down, reaching the minimum around at 950oC (increasing degradation). The objective of this paper is to analyze how may compose the organic and inorganic binders, in a synergetic effect, such that during reduction (temperature above 600oC) the agglomerates keeps its strength without much degradation. For carbon-ore composite agglomerates (self-reducing) the consolidated process is to use the properties of high fluidity coal and treat it thermally to serve as reducer and binder. The preliminary results, using bentonite and boric acid, are indicating hot strength of the pellets better than those obtained with the use of cement.

References:
[1] Eisele TC, Kawatra SK. A review of binders in iron ore pelletization. Mineral Processing & Extractive Metall. Rev., 24 (2003) 1-90.
[2]Halt JA, Kawatra SK. Review of organic binders for iron ore concentrate agglomeration. Minerals & Metallurgical Processing v.31 no. 2 (May 2014) 73-94.

16:45: [IronFriPM211] Keynote
Method for measuring charcoal bulk compression strength
Solon Tagusagawa¹ ; Martim H.n. Kurauchi² ; Cyro Takano³ ; Tiago Ribeiro⁴ ; Marcelo Mourao³ ; Cesar Yuji Narita⁵ ; ¹USP - Universidade De Sao Paulo, Sao Paulo, Brazil; ²University of Sao Paulo Polytechnic School, Sao Paulo, Brazil; ³University of Sao Paulo, Sao Paulo, Brazil; ⁴Institute for Technological Research, Sao Paulo, Brazil; ⁵Polytechnic School of the University of Sao Paulo, Sao Paulo, Brazil;
Paper Id: 385 [Abstract]

Charcoal is an existing alternative to the use of coal and coke in the metallurgical industry, but it has inherently low mechanical strength. The existing methods to evaluate charcoal compression strength rely on preparing test specimens free of defects and compress it in the direction of the fibres. Since charcoal is anisotropic, these tests may not reveal the behaviour of charcoal, as a whole, when suffering compressive loads. As a consequence, such approach may not relate to industrial conditions, where the load on charcoal is not only on the direction of the fibres. This paper proposes a new method to quantify the effects of applying a compressing load on randomly distributed bulk charcoal, simulating what would be expected in industrial conditions, such as in a blast furnace, rather than the analysis of individual pieces of charcoal. It is shown that the results are normally distributed when analysed by means of the friability index proposed by ASTM D440.

References:
(1) The Art, Science, and Technology of Charcoal Production. Antal Jr., Michael Jerry e Gronli, Morten. 42, s.l. : Ind. Eng. Chem. Res., 2003.
(2) Análise do processo de produção de carvão vegetal para siderurgia. Ribeiro, Tiago R., et al., et al. Vila Velha : Associação Brasileira de Metalurgia, Materiais e Mineração, 2011. ISSN: 2176-3135.
(3) Mechanical properties of acacia and eucalyptus wood chars. Kumar, M, Verma, B. B. e Gupta, R. C. 21, s.l. : Energy Sources, 1999. ISSN: 0090-8312.
(4) Bulk compression characteristics of straw and hay. Nona, Kenny D., et al., et al. 118, s.l. : Biosystems Engineering, 2014. ISSN: 1537-5110.

17:10: [IronFriPM212] Invited
Effect of Iron Ore-Carbon Composite Structure on Phosphorus Content in Reduced Molten Iron and Slag
Taichi Murakami¹ ; Daisuke Maruoka² ; Eiki Kasai¹ ; ¹Graduate School of Environmental Studies, Tohoku University, Sendai, Japan; ²Tohoku University, Sendai, Japan;
Paper Id: 76 [Abstract]

Demand for utilizing iron ore with high phosphorus content is increasing because of the depletion of the resource for high-grade iron ore. Utilization of oolitic hematite with very high phosphorus content [1] and development of the dephosphorization method by reduction and melting of iron ore-carbon composite are the main focus of this paper. It is known that most of phosphorus exists as calcium phosphate in oolitic hematite. It is known that calcium phosphate can reduce to phosphorus gas and moves into metallic iron in iron ore-carbon composites. In this study, the effect of the iron ore layout in composite on dephosphorization behavior is evaluated. Four thin composite samples, using hematite reagent, coke and three compacts of oolitic hematite, were prepared. These samples (thickness=2mm) were then set in the alumina crucible, which is named as the layer sample. The mixing ratio of total carbon to oxygen in iron oxide was 0.8 in molar [2]. For comparison, a uniform mixing composite sample was prepared using oolitic reagent, hematite powders (Ore: Reagent = 2:1) and coke. The sample was heated up to different target temperatures at a heating rate of 0.167°C/s. Phosphorus content in oolitic hematite, reduced iron, and slag was measured by ICP-AES. Phosphorus content in oolitic hematite was 0.78%. After heating up to 1300°C, melted iron and slag were obtained, and phosphorus content in melted iron of the layer sample was estimated at approximately 0.04% while that of the uniform mixing composite was approximately 0.4%.

References:
[1] M.Omran, T.Fabritius, R.Mattila, Powder Technology, 269(2015), 7-14.\n[2] T.Murakami, T.Nishimura, E.Kasai, ISIJ International, 49(2009), 1686-1693.

SESSION: IronFriPM3-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Fri Oct, 25 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Tateo Usui; Masashi Nakamoto; Session Monitor: TBA

17:50: [IronFriPM313] Plenary
Assessment guidelines for industrial by-products
Juergen Antrekowitsch¹ ; ¹Chair of Nonferrous Metallurgy, Leoben, Austria;
Paper Id: 286 [Abstract]

The development of the raw materials supply is characterized by decreasing metal grades and still relatively low recycling rates. While the recycling of metallic scrap is nowadays state of the art, metal-containing by-products from the metallurgical industry represent a new potential secondary resource. Due to the genesis of the primary polymetallic ores, it is especially the metallurgical processes used in the copper, lead and zinc industries that offer a high potential in their by-products. Besides the base metals, also many minor metals declared as critical by the European Union regarding their supply will be recoverable. To allow a better assessment of these materials, a certification system similar to the ones already existing for primary resources needs to be established. Through special characterization of selected residues and the evaluation of possible recycling processes, a generally valid assessment scheme is to be developed. The optimized use of by-products as secondary raw materials helps to preserve valuable primary resources and to minimize landfilling of potentially hazardous wastes. An evaluation system followed by a certification step is beneficial for both continuously produced metallurgical by-products, and landfilled materials from the past. These resources will be opened to recycling step by step, offering new potentials that enlarge the present metal resource base. A case study for zinc containing residues gives an insight on the ongoing research and development.

11:45: [IronSatAM02] Keynote
HIGHLY EFFICIENT USE TECHNOLOGY OF THE BY-PRODUCT GAS IN IRON AND STEEL MAKING PROCESS
Hanlin Song¹ ; Xiangxin Xue¹ ; ¹Northeastern University, Shenyang, China;
Paper Id: 375 [Abstract]

China, a country with a total industrial energy consumption ranking in the forefront of the world. China's steel industry has a large energy consumption and low energy recycling rate, which is one of the reasons for the limited development of Green & Low-Carbon metallurgy. BOF gas, with an annual output of more than 100 billion standard cubic meters, is one of the main by-product energy resources in the steelmaking process. However, the up to 34.7% abandoned rate of BOF gas has caused a lot of carbon emissions and energy resources waste. The abandoned BOF gas, with a high temperature of 1773~1873K and 20~40%(vol.%) CO and 20~30%(vol.%) CO₂, has a huge physical sensible heat and chemical latent heat. It means there is a predictable recyclable value and comprehensive utilization prospects to achieve the ultra-low carbon emissions, reduction of energy consumption, resources recovery and energy conversion in iron and steel making process. The paper has carried out detailed calculation and analysis of the energy value of abandoned BOF gas, and the feasibility analysis and program design of the overall resource recycling and energy utilization in iron and steel making process that include blast furnace (BF) smelting of vanadia-titania magnetite (VTM), Combined blowing in BOF and vanadium-extracting converter, Co-production of steel-chemicals industry.

References:
[1] Wenying C, Xiang Y, Ding M. 2014. A bottom-up analysis of China’s iron and steel industrial energy consumption and CO₂ emissions. In: Applied Energy. Volume 136. Beijing (China): Tsinghua University. p. 1174-1183.\n[2] HU L, Hongguang J, Lin G, Na Z. 2014. A polygeneration system for methanol and power production based on coke oven gas and coal gas with CO₂ recovery. In: Energy. Volume 74. Beijing (China): Chinese Academy of Sciences. p. 174-180.\n[3] Kun H, Li W. 2017. A review of energy use and energy-efficient technologies for the iron and steel industry. In: Renewable and Sustainable Energy Reviews. Volume 70. Beijing (China): University of Science and Technology Beijing. p. 1022-1039.\n[4] Yihui T, Qinghua Z, Yong G. 2013. An analysis of energy-related greenhouse gas emissions in the Chinese iron and steel industry. In: Energy Policy. Volume 56. Dalian (China): Dalian University of Technology. p. 352-361.\n[5] Qianqian C, Yu G, Zhiyong T, Wei W, Yuhan S. 2018. Assessment of low-carbon iron and steel production with CO₂ recycling and utilization technologies: A case study in China. In: Applied Energy. Volume 220. Shanghai (China): Chinese Academy of Sciences. p. 192-207.\n[6] Qi Z, Yu L, Jin X, Guoyu J. 2018. Carbon element flow analysis and CO₂ emission reduction in iron and steel works. In: Journal of Cleaner Production. Volume 172. Shenyang (China): Northeastern University. p. 709-723.\n[7] Dolf G, Yuichi M. 2002. CO₂ in the iron and steel industry: an analysis of Japanese emission reduction potentials. In: Energy Policy. Volume 30. Ibaraki (Japan): National Institute for Environmental Studies. p. 849-863.\n[8] Xuecheng W, Liang Z, Yongxin Z, Lingjie Z, Chenghang Z, Xiang G, Kefa C. 2016. Cost and potential of energy conservation and collaborative pollutant reduction in the iron and steel industry in China. In: Applied Energy. Volume 184. Hangzhou (China): Zhejiang University. p. 171-183.\n[9] Yuan L, Lei Z. 2016. Cost of energy saving and CO₂ emissions reduction in China’s iron and steel sector. In: Applied Energy. Volume 130. Beijing (China): Chinese Academy of Sciences. p. 603-616.\n[10] Z.C. G, Z.X. F. 2010. Current situation of energy consumption and measures taken for energy saving in the iron and steel industry in China. In: Energy. Volume 35. Beijing (China): University of Science and Technology Beijing. p. 4356-4360.\n[11] H. S, Y. M, T. H. 2013. Development of PSA System for the Recovery of Carbon Dioxide and Carbon Monoxide from Blast Furnace Gas in Steel Works. In: Energy Procedia. Volume 35. Hiroshima (Japan): JFE Steel Corp. p. 7152-7159.\n[12] Chao F, JianBai H, Miao W, Yi S. 2018. Energy efficiency in China's iron and steel industry: Evidence and policy implications. In: Journal of Cleaner Production. Volume 177. Changsha (China): Central South University. p. 837-845.\n[13] Boqiang L, Ya W, Li Z. 2011. Estimates of the potential for energy conservation in the Chinese steel industry. In: Energy Policy. Volume 39. Fuzhou (China): Minjiang University. p. 3680-3689.\n[14] Xun W Tianjiao W. 2012. Hydrogen amplification from coke oven gas using a CO₂ adsorption enhanced hydrogen amplification reactor. In: Hydrogen energy. Volume 37. Beijing (China): Chinese Academy of Sciences. p. 4974-4986.\n[15] Bing Y, Xiao L, Yuanbo Q, Lei S. 2015. Low-carbon transition of iron and steel industry in China: Carbon intensity, economic growth and policy intervention. In: Journal of Environmental Science. Volume 28. Beijing (China): Tsinghua University. p. 137-147.\n[16] Nicolás P, José Antonio M. 2013. Prospective scenarios on energy efficiency and CO₂ emissions in the European Iron & Steel industry. In: Energy. Volume 54. Petten (Netherlands): Institute for Energy and Transport. p. 113-128.\n[17] Fang Z, Keman H. 2017. The role of government in industrial energy conservation in China: Lessons from the iron and steel industry. In: Energy for Sustainable Development. Volume 39. Medford (USA): Tufts University. p. 101-114.\n[18] Haijuan W, Rong Z, Xueliang W, Zhizheng L. 2017. Utilization of CO₂ in metallurgical processes in China. In: Mineral Processing and Extractive Metallurgy. Volume 126. Beijing (China): University of Science and Technology Beijing. p. 47-53.\n[19] Sari S, Mari T, Pekka A. 2017. Variables affecting energy efficiency and CO₂ emissions in the steel industry. In: Energy Policy. Volume 38. Aalto (Finland): Aalto University. p. 2477-2485.

12:10: [IronSatAM03]
Methods to Remove Tramp Elements in Steel for Recycling Ferrous Scraps
Hideki Ono¹ ; Kenji Taguchi² ; Katsuhiro Yamaguchi³ ; Tateo Usui⁴ ; ¹University of Toyama, Toyama, Japan; ²Nippon Stool Corporation, Tokai City, Japan; ³Kobe Steel, Ltd., Kobe City, Japan; ⁴Osaka University, Ibaraki, Japan;
Paper Id: 416 [Abstract]

For preserving the environment and preventing the resource depletion, it is important to extend the allowance of recycling low grade ferrous scraps in iron- and steel-making. It is well known that the recycling also contributes to the reduction of carbon dioxide emissions from iron- and steel-making processes. However, lower grade ferrous scraps generally contain more tramp elements, such as copper and tin. It is difficult to remove such tramp elements from molten iron in iron- and steel-making processes. Highly-concentrated tramp elements negatively affect the quality of steel. For example, it is well known that copper in steel causes hot shortness by concentrated melting of copper onto the surface in hot-rolling process. In this work, the possibilities of removing impurities from molten iron by oxidation and evaporation, which are usual methods in metal refining, are firstly investigated. Of all the elements which are dissolved in molten iron, Cu, Sn Ni, Co, Mo and W are found to be difficult to be removed by such usual methods as oxidation and evaporation [1]. Subsequently, the prospective methods to remove such tramp elements are discussed. Copper, which is one of the most important tramp elements in iron, can be removed by evaporation [2] or by sulfurization [3]. As the other methods, the possibilities to remove copper in molten iron by oxidation [4] and by reduction are considered, and the lowering limits by these methods have been investigated.

References:
[1] H. Ono: CAMP-ISIJ, 31(2018), 40.
[2] H. Ono, K. Taguchi, Y. Seike and T. Usui: ISIJ Inter., 43(2003), 1691.
[3] T. Imai and N.Sano: Tetsu-to-Hagané, 74(1988), 640.
[4] K. Yamaguchi, H. Ono and T. Usui: Tetsu-to-Hagané, 96(2010), 531.

12:35: [IronSatAM04] Invited
Antifouling activity of natural products of marine macroalgae against the Limnoperna fortunei - Golden Mussel. A review.
Camila Freitas De Araújo¹ ; Alex Campos² ; Adriano Batista³ ; Bernardo Da Gama⁴ ; Renato Crespo Pereira⁵ ; Rodrigo Pinheiro De Almeida Santos⁶ ; Bruna Helena Malovini Loiola⁷ ; Paulo Assis⁸ ; Tateo Usui⁹ ; ¹Federal University of Ouro Preto - UFOP/REDEMAT, Ouro Preto, Brazil; ²Federal University of Ouro Preto, Ouro Branco, Brazil; ³IFMG, Ouro Preto, Brazil; ⁴UFF, Niterói, Brazil; ⁵Instituto de Pesquisas Jardim Botânico do Rio de Janeiro, Rio de Janeiro, Brazil; ⁶Departamento de Biologia Marinha - Fluminense Federal University, Niterói, Brazil; ⁷Federal University of Ouro Preto - REDEMAT, Ouro Preto, Brazil; ⁸University of Ouro Preto / REDEMAT, Ouro Preto, Brazil; ⁹Osaka University, Ibaraki, Japan;
Paper Id: 365 [Abstract]

AUTHORS and AFFILIATION:
Camila Freitas de Araújo – Civil Engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (camilafr.eng@gmail.com).
Alex Milton Albergaria Campos – MSc Metallurgical Engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (alexcampos88@yahoo.com.br).
Adriano Corrêa Batista – Professor, DSc Instituto Federal de Minas Gerais, Ouro Preto, Brazil (adrianocorrea77@gmail.com).
Bernardo Antônio Perez da Gama – Professor, PhD UFF, Niterói, Brazil (bapgama@gmail.com).
Renato Crespo Pereira – Professor, DSc UFF, Niterói, Brazil (rcrespo@id.uff.br).
Rodrigo Pinheiro de Almeida Santos – Doctoral Student at UFF, Niterói, Brazil (pinheiro153@gmail.com).
Bruna Helena Malovini Loiola – Metallurgical Engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (malovinibruna@gmail.com).
Paulo Santos Assis –Professor, PhD REDEMAT/UFOP, Ouro Preto, Brazil (assis@ufop.edu.br).
Tateo Usui – Professor emeritus, DSc Osaka University, Suita, Japan (usui@mat.eng.osaka-u.ac.jp).

Abstract
The golden mussel (Limnoperna fortunei) is a species of bivalve mollusc introduced in Brazil via ballast water in the 1990s. Given the biological and ecological characteristics of the species, as well as the favorable environment in the country for its proliferation, the golden mussel has become an exotic invasive species that has caused several problems in the aquatic environment because of its ability to form colonies in structures. The species adheres on the surfaces by protein filaments, causing serious environmental, social and economic damages, provoking structural and functional alterations in the ecosystems and damages to the human activities.
The challenge presented consists of biological fouling combat through treating underwater surfaces with freshwater natural products, in particular those from red algae. Fouling control tends to arouse the interest of shipbuilders, marine vessel operators, fish farming in tanks and hydroelectric power plants. In Brazil, the chemical treatment against the incrustation of the golden mussel, for example, made only in three hydroelectric power plants in Minas Gerais, has annual cost of R$ 1,494,000.00 [1].
With the worldwide ban of TBT-based antifouling paints since 2008, alternative, environmentally safe treatments gain more appeal, considering the risk associated with the alternative products currently in use. Natural marine products have since been recognized as a promising alternative for the replacement of commercially used antifouling until the moment [2].
A selection of natural seaweed products with antifouling activity may provide effective results with little or no environmental impact compared to currently used products [3], while contributing to the understanding of ecological functions and mechanisms of metabolic production secondary. At least 18 different regulatory biocides are currently being used as an alternative to tributyltin free antifouling paints, but these also pose some threat to the aquatic environment. In fact, even biocide-free antifouling paints are toxic to marine organisms over a broad spectrum [4]. For this reason there is still an urgent demand for new low-impact anti-fouling products.
This article aims to disseminate this broad line of research and consolidate information about the potential of marine organisms as producers of secondary metabolites (natural products) with antifouling activity, in the light of scientific production.

Key words: Golden Mussel; red algae; anti-fouling products; secondary metabolites; tributyltin.

References:
REFERENCES:\n[1] CEMIG. Companhia Energética de Minas Gerais. O mexilhão Dourado, uma ameaça às águas e hidrelétricas brasileiras. Ed. CEMIG, Belo Horizonte, p. 24, 2014.\n\n[2] Bhadury, P.& Wright, P.C. (2004). Exploitation of marine algae: biogenic compounds for potential antifouling applications. Planta, v. 219, p. 561–578.\n\n[3] DA GAMA, B. A. P. et al. The Effects of Seaweed Secondary Metabolites on Biofouling. Biofouling, v. 18, n. 1, p. 13-20, 2002.\n\n[4] Löschau, M.&Krätke, R. (2005). Efficacy and toxicity of self-polishing biocide-free antifouling paints. Environmental Pollution, v. 138, p. 260–267.

SESSION: IronSatPM1-R8	Usui International Symposium on Advanced Sustainable Iron and Steel Making (7th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Sat Oct, 26 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Cyro Takano; Mery-Cecilia Gomez-Marroquin; Session Monitor: TBA

14:00: [IronSatPM105] Invited
Estimation of thermodynamic parameters in liquid metal based on predictive model for surface tension of liquid alloys
Masashi Nakamoto¹ ; ¹Osaka University, Suita, Japan;
Paper Id: 423 [Abstract]

In high temperature material processes like iron & steelmaking, the thermodynamic parameters in liquid metals are the crucial guidelines for optimizing and improving the processes. Therefore, the thermodynamic data have been aggressively collected by a variety of sophisticated experimental techniques so far[1,2]. In addition, several researchers[3,4] have developed the estimation model for thermodynamic parameters in parallel with experimental researches because of the limitation of experimental data caused by difficulty of experiment at high temperature. In the present work, the estimation method for the activity coefficient of element in liquid mental is proposed based on a predictive model for surface tension of liquid alloys with Butler’s equation[5] in order to realize the enlargement of thermodynamic data. The equation for calculating an activity coefficient of solute in infinite dilute liquid metal from the values of surface tension for liquid alloy is derived by focusing on infinite dilute liquid metal solution and modifying Butler’s equation. The estimation results in this work give a reasonable reproducibility in comparison with the literature values.

References:
[1] The 19th Committee on Steelmaking, The Japan Society for the Promotion of Science, Steelmaking Data Source Book, Gordon and Breach Science Publishers, New York (1998).
[2] Ed. by M. Hino and K. Ito, Thermodynamic data for steelmaking, Tohoku Univ., Sendai (2010).
[3] T. Tanaka, N. A. Gokcen, Z. Morita and T. Iida, Z. Metallkd, 84 (1993), 192-200.
[4] F. Wang, X. Li, Q. Han and Z. Zhang, Metall. Mater. Trans. B, 28B (1997), 109-113.
[5] J.A.V. Butler, Proc. Roy. Soc., A135 (1932), 348-375.

14:25: [IronSatPM106] Keynote
Leaching Behavior and Chemical Structure of Boron in Steelmaking Slag with Different Basicity
Yohsuke Masaki¹ ; Takafumi Takahashi² ; Koji Kanehashi² ; ¹Nippon Steel Corporation, Ibaraki, Japan; ²Nippon Steel Corporation, Chiba, Japan;
Paper Id: 350 [Abstract]

Although boron (B) is well known as one of the effective elements to prevent slag dusting [1], there is the possibility that B concentration and its leaching amount of steelmaking slag exceed the limit of environmental standards [2]. Therefore, it is important to understand the leaching behavior of B in slag. There are, however, few reports on the behavior and mechanism of B leaching from slag. The leaching behavior of steelmaking slag, modified by B-containing flux, has been reported [3]. Although the effect of the particle size was investigated in the publication, the effect of the component condition of the slag on the leaching behavior of B has not been understood. In this study, the leaching test has been performed using the steelmaking slag with a different basicity. In addition, the chemical structure of B in slag before leaching has been analyzed by solid-state ¹¹B NMR and FIB-TOF-SIMS. The leaching amount of B decreased with increasing slag basicity and calcium (Ca) concentration in water. The effect of slag basicity should be related to the leaching amount of Ca because the slag with higher basicity increases free-CaO and Ca concentration in water. From NMR and FIB-TOF-SIMS results, B is found to coexist primarily with Ca in the slag. Consequently, it is considered that B leaches with Ca. The slag with higher basicity decreases the leaching amount of B due to the common-ion effect by calcium.

References:
[1] A. Seki, Y. Aso, M. Okubo, F. Sudo and K. Ishigaki : Kawasaki Steel Giho, 18(1986), pp. 20-24.
[2] T. Sasaki : Nippon Steel & Sumitomo Metal Technical Report, 109(2015), pp. 189-194.
[3] K. Kakimoto, F. Noguchi, N. Sakamoto, S. Sato and S. Kawada : CAMP-ISIJ, 18(2005), p.285.

14:50: [IronSatPM107] Invited
Hierarchizing BOF Slopping Variables from Big Data Analysis
Bruna Helena Malovini Loiola¹ ; Carlos Antônio Silva¹ ; Henrique Silva Furtado² ; Camila Freitas De Araújo³ ; Paulo Assis⁴ ; Tateo Usui⁵ ; Alex Campos⁶ ; ¹Federal University of Ouro Preto - REDEMAT, Ouro Preto, Brazil; ²+55 27 33483601, Vitoria, Brazil; ³Federal University of Ouro Preto - UFOP/REDEMAT, Ouro Preto, Brazil; ⁴University of Ouro Preto / REDEMAT, Ouro Preto, Brazil; ⁵Osaka University, Ibaraki, Japan; ⁶Federal University of Ouro Preto, Ouro Branco, Brazil;
Paper Id: 371 [Abstract]

AUTHORS and AFFILIATION:
Bruna Helena Malovini Loiola – Metallurgical Engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (malovinibruna@gmail.com);
Carlos Antônio da Silva – Professor, PhD REDEMAT/UFOP, Ouro Preto, Brazil (casilva@ufop.edu.br);
Henrique Silva Furtado – DSc. Eng. ArcelorMittal Global R&D South America, Vitória, Brazil (henrique.furtado@arcelormittal.com.br);
Camila Freitas de Araújo – Civil engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (camilafr.eng@gmail.com). Alex Milton Albergaria Campos – MSc. Metallurgical Engineer, Graduate Student at REDEMAT/UFOP, Ouro Preto, Brazil (alexcampos88@yahoo.com.br)

Paulo Santos Assis – Professor, PhD REDEMAT/UFOP, Ouro Preto, Brazil (assis@ufop.edu.br);
Tateo Usui – Professor emeritus, DSc Osaka University, Suita, Japan (usui@mat.eng.osaka-u.ac.jp).
ABSTRACT

Slopping is a phenomenon which is observed when the volume the emulsion inside of BOF (Basic Oxygen Furnace) is excessive and a fraction of slag and metal is then expelled. This phenomenon concerns steelmakers since it leads to material losses, health hazards, reduction of refining efficiency and, mainly, environmental issues. Big Data files from a steelmaking shop in Brazil have been analysed in order to identify the central causes of the slopping. Statistical techniques including Multivariate Analyzes have been employed in order to identify the main variables that affect slopping. Statistica, Genes and Rbio software were used to do so; also principal components, path analysis, and correlation network were chosen as tools. It was possible to identify and hierarchize the variables most affecting slopping in good agreement with literature. The resulting variables can be used to a model to generate anticipate slopping..


Key-words: Slopping; Emulsion; BOF; Multivariate Analyzes.

References:
[1] Rizzo, E. M. D. S. Processos de refino primário dos aços nos convertedores a oxigênio. São Paulo: ABM, 2006.
[2] Fruehan, R. et al. The Making, Shaping and Treating of Steel. 10. ed. Pittsburgh: AISE Steel Foundation, 1998.
[3] Bramming M. 2010. Avoiding Slopping in Top-Blown BOS Vessels [thesis]. Lulea: Lulea.
University of Technology.
[4] Walker, D. I.; Kemeny, F. L.; Jones, J. A. T. Vessel Slopping Detection. AISTech 2005 Proceedings - Volume I. Pittisburgo: AIST. 2005. p. 711-720.
[5] Evestedt, M. et al. Slopping Warning System for the LD Converter Processe - An Extended Evaluation Study. Lulea University of Technology, Lulea, 2007.

15:15: [IronSatPM108] Keynote
EFFECT OF BENTONITE ON THE STABILIZATION AND MECHANICAL STRENGTH OF BRICKS MADE OF PERUVIAN ELECTRIC ARC FURNACE DUSTS
Mery-cecilia Gomez Marroquin¹ ; Jose Carlos D Abreu² ; ¹National University of Engineering, Lima, Peru; ²PUC-Rio, Rio de Janeiro, Brazil;
Paper Id: 326 [Abstract]

One of the most important problems of the steelmaking industry is the recycling of galvanized steel scrap and the benefit or disposal of the powders produced in the Electric Arc Furnaces (EAFD) and LD / BOF converters. This issue is well-known worldwide. Transportation costs, disposal in appropriate places and increasing environmental demands are making many steel companies in the world look for ways to avoid, minimize and / or treat their powders and particulates correctly. The methodology of the project consists of collecting, sampling, selecting and molding the raw materials involved: powders from electric steelworksor Electric Arc Furnace Dust-EAFD, bentonite-Ben., refractory clay-AR and construction cements. Following that, these materials were characterized partially. Afterwards, heating tests were carried out on mixtures of EAFD and bentonitein, in the form of cylindrical briquettes, using electric ovens to evaluate how preset factors favorably influence the porosity response variable. This experience also provided the proportion in optimal weight of the mixtures. These proportions were used to form test bricks with all the aforementioned raw materials in order to evaluate the effect of their new factors on another variable responses to the resistance towards compression. All these tests were carried out according to experimental planning with the simple factorial method 23 that evaluated the effect of the factors using the COLMEIA software. It can be concluded that: A> B> AB, where the individual synergy of (A) EAFD / Ben. is more influential than the one of (B) Heating temperature. This in turn is more influential than the double synergy (A) EAFD / Ben. and (B) Heating temperature or AB in the porosity of the cylindrical briquettes formed of EAFD and bentonite. During the second run the result of A> AC explains that the individual synergy of (A) EAFD / Ben. is more influential than the dual synergy of (A) EAFD / Ben. and (C) Setting time or AC in the compressive strength of the set of test bricks. This compressive strength was based on electric steel, bentonite, refractory clay and construction cement powders. Finally, it is concluded that in both experiences, the proportion PAE / Ben. = 7/3 is the optimal mixture and therefore, the factor most influential in the porosity-stabilization and resistance to compression or mechanical strength of the specimens was tested.

References:
[1] Autelitano Federico, Giuliani Felice (2016). Electric arc furnace slags in cement-treated materials for road construction: Mechanical and durability properties. Construction and Building Materials 113 (2016) 280–289.

[2] Alanyalı, H., Çöl, M., Yılmaz, M., & Karagöz, Ş. (2006). Application of magnetic separation to steelmaking slags for reclamation. Waste Management, 26(10), 1133-1139.

[3] Barrenechea Camila, Fernández A. Inés, Niubóa Maria, Chimenos José M., Espiell Ferran, Segarraa Mercè, Solé Cristian, Cabeza Luisa F. (2013). Development and characterization of new shape-stabilized phase change material (PCM)-Polymer including electrical arc furnace dust (EAFD), for acoustic and thermal comfort in buildings. Energy and Buildings 61 (2013) 210–214.

[4] Colorado. Henry A., García Edwin, Buchely M. F., (2016). White Ordinary Portland Cement blended with superfine steel dust with high zinc oxide contents. Construction and Building Materials 112 (2016) 616-824.

[5] Da Luz Adao Benvindo; Fernando Antonio Freitas Lins (2005). Rochas & Minerais Industriais. Usos e Especificaçoes 5ta. Edición. Editorial CENTRO DE TECNOLOGIA MINERAL. MINISTERIO DA CIENCIA E TECNOLOGIA-CETEM pp. 217-230.

[6] Da Luz Adao Benvindo; De Almeida Salvador Luiz M. (2012). Manual de agregados para la construcción civil. 2da. Edición. Editorial CENTRO DE TECNOLOGIA MINERAL. MINISTERIO DA CIENCIA E TECNOLOGIA-CETEM pp. 217 – 218, 22-223,

[7] Drobíková, K., Plachá, D., Motyka, O., Gabor, R., Kutláková, K. M., Vallová, S., & Seidlerová, J. (2016). Recycling of blast furnace sludge by briquetting with starch binder: Waste gas from thermal treatment utilizable as a fuel. Waste Management, 48, 471-477.

[8] Etxeberria, M., Pacheco, C., Meneses, J. M., & Berridi, I. (2010). Properties of concrete using metallurgical industrial by-products as aggregates. Construction and Building Materials, 24(9), 1594-1600.

[9] Gómez Marroquín, Mery Cecilia (2008). “CARACTERIZAÇÃO E CINÉTICA DA REDUÇÃO DE FERRITA DE ZINCO PRESENTE EM POEIRAS DE ACIARIA, POR MISTURAS CO-CO2”.Tesis de Doctorado presentada al

[10] Departamento de Ciencia de los Materiales y Metalurgia - DCMM de la Pontificia Universidad Católica de Rio de Janeiro. BRASIL.

[11] Karayannis, V. G. (2016). Development of extruded and fired bricks with steel industry byproduct towards circular economy. Journal of Building Engineering, 7, 382-387.

[12] Lian, F., Ma, L., & Chou, K. (2017). Industrial research on the high-temperature modification of Basic Oxygen Furnace slag with solid waste compound. Journal of Cleaner Production, 143, 549-556.

[13] Loayza Alexandra, Cifuentes Sergio, Colorado. Henry A. (2017). Asphalt modified with superfine electric arc furnace Steel dust (EAF dust) with hih zinc oxide content. Construction and Building Materials 145 (2017) 538-547.
[14] Madias Jorge, 2014. Innovaciones Tecnológicas. Reciclado del Polvo del Horno Eléctrico. Disponible en el sitio web: https://www.researchgate.net/publication/261365779_Reciclado_de_polvo_de_horno_electrico

[15] Mohammad A.T. Alsheyaba, Taisir S. Khedaywi (2013). Effect of electric arc furnace dust (EAFD) on properties of asphalt cement mixture. Resources, Conservation and Recycling 70 (2013) 38–43.

[16] Monteiro, S. N., & Vieira, C. M. F. (2014). On the production of fired clay bricks from waste materials: A critical update. Construction and Building Materials, 68, 599-610.

[17] Pickles, C.A. (2010). Thermodynamic modelling of the formation of zinc–manganese ferrite spinel in electric arc furnace dust. Journal of Hazardous Materials 179 (2010) 309–317.

[18] Quijorna N., de Pedro M., Romero M., Andrés A. (2014). Characterisation of the sintering behaviour of Waelz slag from electric arc furnace (EAF) dust recycling for use in the clay ceramics industry. Journal of Environmental Management 132 (2014) 278-286.

[19] Pelino, M., Karamanov, A., Pisciella, P., Crisucci, S., & Zonetti, D. (2002). Vitrification of electric arc furnace dusts. Waste Management, 22(8), 945-949.

SESSION: NanomaterialsSatPM2-R8	6th Intl. Symp. on Synthesis and Properties of Nanomaterials for Future Energy Demands
Sat Oct, 26 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Chun Li; Damian Onwudiwe; Session Monitor: TBA

15:55: [NanomaterialsSatPM209]
Copper Tin Sulphide Nanocrystals For Photovoltaics
Damian Onwudiwe¹ ; ¹North-West University, South Africa, Mmabatho, South Africa;
Paper Id: 434 [Abstract]

ABSTRACT:<br />The high demand for energy due to global population boost and industrialization is currently satisfied by coal, natural gas and fossil fuels. This results in their high prices and also impacts negatively on the environment [1]. Photovoltaic technologies is believed to hold the solution to the challenge of pollution and global warming. Compound semiconductor nanomaterials have emerged as new building blocks for the construction of light energy harvesting assemblies, and have opened up new ways to utilize renewable energy resources. Earth-abundant ternary nanomaterials have attracted considerable attention for eco-friendly and low-cost solar cells [2]. <br />This study reports the synthesis of Cu2SnS3, a ternary metal sulphides nanoparticles, with light absorbing properties, from earth abundant elements. The compound, classified as I-II-VI semiconductor, possesses interesting optoelectronic properties such as p-type conductivity, high chemical stability, high absorption coefficient of about 105 cm-1 and band gap of 1.1-1.7eV [3]. The method devised for the synthesis of these ternary nanoparticles was the solvothermal decomposition of dual single source precursors in oleylamine, using cheap, readily obtainable and easy to handle dithiocarbamate complexes [4]. This route afforded monodispersed nanopartcles of different sizes and morphologies. The optical characterization and electrochemical studies showed that the synthesized Cu2SnS3 are capable of converting solar radiation to electrical energy.

References:
REFERENCES:\n[1] B. Pejjai, V.R.M. Reddy, S. Gedi, C. Park, Int. J. Hydrogen Energy 42 (2017) 2790-2831.\n[2] V. R. M.Reddy , H. Cho, S.Gedi, K.T. R. Reddy, W. K. Kim, C. Park, J. Alloys Compd. 806 (2019) 410 – 417.\n[3] M. Kumar, C.Persson, Energy Procedia, 44 (2014) 176-183.\n[4] A. Roffey, N. Hollingsworth, G. Hogarth, Nanoscale Adv. 1 (2019) 3056-3066.

16:20: [NanomaterialsSatPM210] Invited
Calcium Phosphate-based Composites for Medical Applications: Physicochemical, Mechanical and Surface Properties
Hassan Noukrati¹ ; Christele Combes² ; Hicham Ben Youcef³ ; Hassane Oudadesse⁴ ; Christian Rey² ; Allal Barroug⁵ ; ¹University Cadi Ayyad - Marrakech, MARRAKECH, Morocco; ²University of Toulouse, CIRIMAT, ENSIACET, Toulouse, France; ³Mohammed VI Polytechnic University, Benguerir, Morocco; ⁴University of rennes 1, Rennes, France; ⁵Ballal00111957&, Marrakech, Morocco;
Paper Id: 287 [Abstract]

Calcium phosphate (CaP) materials have received major attention in the biomedical field during the last decades, mainly for their compositional resemblance with the mineral phase of bone and their biological properties [1]. Nevertheless, the drawbacks associated with the low mechanical properties, injectability, and biodegradability of these materials have paved the way to design biocomposites for advanced applications [2]. Another challenge in the conception of CaP biomaterials is their use as a bone substitute or drug delivery system for the local treatment of bone diseases [3]. Furthermore, the interaction mechanisms at the interface between CaP and the surrounding biological environments are still far from being fully understood. The present work focuses on (i) the precipitation of biological CaP materials under various synthesis conditions and (ii) the formulation of biocomposites based on a biomimetic calcium phosphate cement (CPC), loaded with a polysaccharide (PS) and a broad antibacterial spectrum antibiotic. The effects of PS and drug incorporation on the CPC physicochemical and rheological characteristics, as well on the in vitro drug release, were assessed. The binding/release experiments performed with various biomolecules and precipitated apatite crystals indicated that adsorption from dilute solutions could be described as an ion-exchange process, involving the functional groups of the molecules and the ionic groups at the apatite surface. The interaction appears to be reactive for concentrated solutions, leading to a dissolution-re-precipitation phenomenon. A correlation between the physicochemical and surface properties of the specimens and their loading/release capacity was established. The combination of the polymer and the drug with the reference cement did not affect its structure and composition. Increases of the compressive strength, as well as improvement of cohesion and injectability, however, were noticed. The release tests performed in the sodium chloride medium showed prolonged release profiles over several weeks; the release rate was dependent on cement composition. The understanding of the interfacial phenomena of apatite materials and the control of the physicochemical and mechanical properties of bio-composites based calcium phosphate cements promote them as attractive candidates for biomedical applications.

References:
[1] W. Habraken, P. Habibovic, M. Epple, and M. Bohner, Materials Today, 19 (2016.) 69-87.
[2] M.P. Ginebra, C. Canal, M. Espanol, D. Pastorino, E.B. Montufar, Adv. Drug Deliv. Rev., 64 (2012) 1090-1111.
[3] A. Bigi and E. Boanini, J. Funct. Biomater., 9 (2018), 6-18.

16:45: [NanomaterialsSatPM211]
Influence of Adhesive Layer on Ballistic Performance of Ceramic-based Armour Systems
Chun Li¹ ; Saleema Noormohammed Noormohammed² ; Yadienka Martinez Rubi¹ ; Geneviève Toussaint³ ; Behnam Ashrafi⁴ ; Michael Jakubinek¹ ; ¹National Research Council Canada, Ottawa, Canada; ²National Research Council Canada, Saguenay, Canada; ³Defence Research and Development Canada, Valcartier, Canada; ⁴National Research Council Canada, Montreal, Canada;
Paper Id: 28 [Abstract]

In addition to ballistic penetration performance and blast survivability, weight has been one of the key drivers for modern armour system design [1-5]. Excessive weight of traditional metallic armour not only affects armour vehicles’ fuel efficiency, but also affects their deployability and mobility. Hybrid armour systems, made of ceramic strike face with metallic or composite backing, deliver an efficient solution by combining the light weight, high ballistic resistance of ceramics with ductility of the backing. This confines the ceramic fragment and absorbs the kinetic energy of the projectile. The primary approach to combine the ceramic strike face and backing is the use of adhesives. Knowledge of the influence of the adhesive properties on target damage, deformation and the ballistic resistance is of importance for composite armor design [1]. Optimization of adhesive selection and design could potentially increase survivability and reduce weight of ceramic-based armour systems. This study investigated the effect of adhesive layers on the ballistic performance of ceramic based armour, which was adhesively bonded onto a Kevlar composite backing. The influence of two classes of commonly used adhesive systems, a polyurethane and an epoxy-based adhesive, as well as that of a nanomaterial-modified polyurethane adhesive were investigated. Polyurethane based adhesive systems are more ductile than epoxy, but they often exhibit lower stiffness and strengths. Epoxy systems, on the other hand, are less ductile, but the usage of epoxy could lead to much improved acoustic impendence matching with ceramics. This allows increased energy transmission from the ceramic to the adhesive; hence the ceramic is less likely to fail [2-4]. The newly developed nanomaterial-modified polyurethane adhesive allowed for enhancement of stiffness, strength and acoustic impedance without significantly sacrificing other properties such as toughness and ductility of the base adhesive [5]. This study demonstrated that adhesive properties, in particular ductility and acoustic impedance, had a significant impact on ballistic performance. In spite of the advantages of the studied epoxy system of better stiffness, strength and acoustic impedance matching over polyurethane, the ceramic armour bonded with the epoxy was prone to disbonding at ceramic/Kevlar interface. Ballistic performance is also reduced as a result of low toughness and ductility. The effect of adhesive thickness was also found to be important for ballistic performance in past studies [6-8]. Thus, with regards to performance under ballistic impact, it was also investigated that increased elongation, along with the increase of adhesive thickness did not enhance multi-hit ballistic performance for the studied configuration. The usage of the nanomaterial-modified adhesive, with increased stiffness, strength, and adequate toughness, was promising to enhance the ballistic performance of ceramic-based armour.

References:
[1] W. Seifert, E. Strassburger, S. Grefen, S. Schaare, Experimental study about the influence of adhesive stiffness to the bonding strengths of adhesives for ceramic/metal targets, Defence Technology 12 (2016) 188-200
[2] R. Zaera, S. Sanchez-Saez, JL. Perez-Castellanos, C. Navarro, Modelling of adhesive layer in mixed ceramic/metal armours subjects to impact. Composites A Appl Sci Manuf 2000;31:823-33.
[3] A.J. Harris, B. Vaughan, J.A. Yeomans, P.A. Smith and S.T. Burnage, Journal of the European Ceramic Society 33 (2013) 2925.
[4] W. Seifert, E. Strassburger, S. Grefen, S. Schaare, Experimental study about the influence of adhesive stiffness to the bonding strengths of adhesives for ceramic/metal targets, Defence Technology 12 (2016) 188-200.
[5] Rubi, Yadienka Martinez; Ashrafi, Behnam; Jakubinek, Michael B.; Zou, Shan; Laqua, Kurtis; Barnes, Michael; Simard, Benoit, Fabrication of high content carbon nanotube-polyurethane sheets with tailorable properties, ACS Appl. Mater. Interfaces (2017) 9, 36, 30840-30849.
[6] S. Noormohammed, C. Li, S. Nikumb, Adhesive bonding of ceramic-based armor system, NATO STO AVT-266 Specialists- Meeting-Use of Bonded Joints in Military Applications, Torino, Italy, April 16-17, 2018
[7] J. Lopez-Puente, A. Arias, C. Zaera, C. Navarro, The effect of the thickness of the adhesive layer on the ballistic limit of ceramic/metal armours. An experimental and numerical study. Int J Impact Eng 2005;32:321-36.
[8] A. Prakash, J. Rajasankar, N. Anandavalli, M. Verma, NR. Iyer, Influence of adhesive thickness on high velocity impact perfomance of ceramic/metal

17:10: [NanomaterialsSatPM212]
Formation of New Architecture of Boron Based Composite Powders under Effect of Concentrated Light
Lina Sartinska¹ ; Izabella Timofeeva¹ ; Tarik Eren² ; Anatoly Efimov³ ; Olena Fecenko⁴ ; ¹Frantsevich Institute for Problems of Materials Science, NAS of Ukraine, Kyiv, Ukraine; ²Yildiz Technical University, Istanbul, Turkey, Istanbul, Turkey; ³Los Alamos National Laboratory, Los Alamos, USA, Los Alamos, United States; ⁴Institute of Physics, NASU, Kyiv, Ukraine, Kyiv, Ukraine;
Paper Id: 261 [Abstract]

Nanocomposites are materials of the twenty-first century [1]. Because nanocomposites offer the possibility of combining many desired properties, they are expanding their potentials in aerospace applications and in future space missions. Due to its mechanical, thermal, electrical, chemical and biodegradable properties, and low weight requirements, boron nitride based nanocomposites are the most prospective for use in aerospace applications. Therefore, boron based composite powders of new architecture will increase the spectrum of properties of nano-enabled composites. The composite powders of new architecture are produced under effect of concentrated light in an optical furnace for aerospace applications. Concentrated light heating of an optical furnace has a number of advantages such as high heating and cooling rates, versatility, ability to adjust temperature profile along each axis, and adaptability to maximum operating temperatures and environments. Moreover, the high-flux optical furnace presents one of cleanest energy sources available for nanotechnology and this technique is appropriate for both conducting and non-conducting materials [1]. Transformation of boron nitride and boron powders with 25 wt. % indium, aluminum, coper, iron or nickel added in flow of nitrogen was considered. This demonstrated the effect of temperature distribution and temperature gradients within an experimental camera on architecture, phase composition and other properties of obtained powdered materials. The presence of a catalyst in boron nitride powder during transformation under effect of concentrated light promotes formation of nanostructures. Formation of a new architecture of nanostructures can be explained in framework of “gaseous model” which was based on the evolution of the bubble during heating in an optical furnace [2]. The bursting of these bubbles results in the formation of graphene-like structures and nano-petal structures. The stepwise transformation of bubbles of appropriate chemical composition leads to nanotube formation because of their upwards pulling by heated gases. Fullerene-like particles can also have complicated “fish-eye” (“core shell”) structure as a result of the segregation of the transparent BN shell with the H₃BO₃ layer on the surface around crystalline InN. Nanopowders prepared in an optical furnace under concentrated light heating have complicated gradient or layered structures. According Raman, AES and FTIR studies, the surface of all powders is composed of BN. XRD disclosed pure amorphous boron inside the particles. Gradient transformation of pure boron to BN in the framework of one particle, as well as a layered nanostructure, was observed by the TEM study.

References:
1. Frolov, A. A., Sartinska, L. L., Kovala A, Y. & Danilenko, N. A. Application of the optical furnace for nanosized boron nitride production. Nanomaterials 2, 4 (2008).
2. Sartinska, L. L. Catalyst-free synthesis of nanotubes and whiskers in an optical furnace and a gaseous model for their formation and growth. Acta Mater. 59, 4395-4403 (2011).

SESSION: NanomaterialsSatPM3-R8	6th Intl. Symp. on Synthesis and Properties of Nanomaterials for Future Energy Demands
Sat Oct, 26 2019 / Room: Ambrosia B (77/RF)
Session Chairs: Elizabeth Oliveira; Ayesha Alkhoori; Session Monitor: TBA

17:50: [NanomaterialsSatPM313]
Hydrogen Production via the Glycerol Steam Reforming using Ce-La-xCu Catalysts
Ayesha Alkhoori¹ ; Kyriaki Polychronopoulou¹ ; ¹Khalifa University, Abu Dhabi, United Arab Emirates;
Paper Id: 231 [Abstract]

An unintended consequence of the drive towards replacing petro-based sources in the transport sector and the subsequent growth of the biodiesel industry is the co-production of large amounts of crude glycerol (C₃H₈O₃) which constitutes the main by-product of the transesterification process [1-3]. A promising solution is its steam reforming since every mol of C₃H₈O₃ can theoretically produce 7 mol of H₂. Thus, research efforts are directed towards the discovery of cheap (i.e., transition metal based), highly active and stable catalysts. In the work presented herein, a series of Ce-La-xCu, (x=3, 5, 7, 10, 20 at.%) catalysts were evaluated for the glycerol steam reforming reaction in the 400-750^oC temperature range. Stability tests were conducted at 650^oC for 12h. The catalysts were prepared by coupling microwave radiation with the sol-gel method and BET, XRD, Raman, NH₃-TPD, CO₂-TPD, H₂-TPR, SEM, HAADF-STEM and XPS. These were used in order to derive information regarding their textural, morphological and physic-chemical properties to elucidate their effect on catalytic performance. The results obtained show that C₃H₈O₃ conversion of over 85% can be achieved with values for H₂ selectivity and approaches the yield of the thermodynamically predicted ones. The liquid effluents produced contained differing amounts of acetol, acetone, acetic acid, acrolein, allyl alcohol and acetaldehyde depending on the reaction temperature. Time-on-stream results, which were undertaken at more severe conditions, showed that all catalysts maintain quite a stable performance.

References:
[1] Papageridis, K.N.; Charisiou, N.D.; Siakavelas, G.; Avraam, D.G.; Tzounis, L.; Kousi, K.; Goula, M.A. Comparative study of Ni, Co, Cu supported on gamma-alumina catalysts for hydrogen production via the glycerol steam reforming reaction. Fuel Process. Technol. 2016, 152, 156-175.\n[2] Bepari, S.; Pradhan, N.C.; Dalai, A.K. Selective production of hydrogen by steam reforming of glycerol over Ni/Fly ash catalyst. Catal. Today 2017, 291, 36-46.\n[3] Goula, M.A.; Charisiou, N.D.; Pandis, P.K.; Stathopoulos, V.N. Ni/apatite-type lanthanum silicate supported catalyst for the glycerol steam reforming reaction. RSC Adv. 2016, 6, 78954-78958.

18:15: [NanomaterialsSatPM314]
Analysis of the Efficiency of the Soil Particles of Landfill Layers as Collector of Harzadous Nanoparticles in the Environment
Elizabeth Oliveira¹ ; Jose Adilson De Castro² ; Ivaldo Leão Ferreira³ ; Mara Do Carmo Paresque⁴ ; ¹Center for Technological Education Celso Suckow da Fonseca, Valenca, Brazil; ²UFF - Federal Fluminense University, Volta Redonda, Brazil; ³UFPA, Belem, Brazil; ⁴UFF-Programa de Pos Graduação em Engenharia Metalurgica, Volta Redonda, Brazil;
Paper Id: 202 [Abstract]

The technological applications for newly developed nanoparticles are continuously increasing. Nevertheless, their reduced size, forming colloidal suspensions, may facilitate the transport and bioaccumulation in the environment. The particular properties of each nanoparticle and their interactions with the dissolved organic matter (DOM) and the living organisms are important issues in this scenario. The landfill waste disposal method is still dominant worldwide. In the landfill, the nanoparticles can undergo phenomena such as leaching, agglomeration, flocculation, complexation, adsorption, dissolution and neoformations. Among the concerns, it is recognized that the nanoparticles behave as carriers for the contaminants in the environment which strongly impacts the water resources. This research is focused on the development of a mathematical model able to predict the transport of TiO₂, SiO₂, ZnO, and CuO nanoparticles and their mutual interaction within soils commonly used as protective layers of controlled landfill for municipal waste disposal. A combined methodology based on numerical procedures using inverse method principles and controlled column experiments were carried out. Firstly, the model parameters were determined and secondly, the model was validated by confronting numerical and experimental data. The model formulated new ways to address the interactions phenomena of colloidal suspensions of nanoparticles percolating through landfill soils protective layers. It has been found that SiO₂ nanoparticles presented the strongest deleterious effect on the efficiency of the soil protective layers while ZnO plays a positive role, promoting flocculation and complexation with soil particles and enhances their effectiveness.

References:
[1] Oliveira EM, Castro J A, Leão I., 2016. Study of the Interaction of Copper Nanoparticles with Titanium in Landfill Soils Layers. Materials Science Forum 869:778-783.
[2] Oliveira EM, Nogueira DA, Lopes LCR, Feiteira J F S and Castro JA., 2016. Analysis of Percolation of the Stabilized Suspensions of TiO2 and SiO2 Nanoparticles in Soil Columns Simulating Landfill Layers. Journal of Mechanics Engineering and Automation 6:47-52.
[3] Oliveira EM, Valadão ICRP, Araújo ASF and Castro José., 2014. Application of Nanoparticle Tracking Analysis (NTA) in Aqueous Solutions of TiO2. Materials Science Forum 802:624-629.
[4] Oliveira, E. M., Rojas, E. E. G., Valadão, I. C. R. P., Araújo, A. S. F., Castro, J. A., 2017 . Effects of the silica nanoparticles (NPSiO2) on the stabilization and transport of hazardous nanoparticle suspensions into landfill soil columns. Rev. Esc. Minas. 70, 317-323.

SESSION: ChemistryThuAM-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Thu Oct, 24 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Alain Tressaud; Matthew Jonathan Rosseinsky; Session Monitor: TBA

11:20: [ChemistryThuAM01] Plenary
Faceted rare earth and alkaline earth oxide perovskite nanoparticles as catalyst supports
Kenneth Poeppelmeier¹ ; ¹Northwestern University, Evanston, United States;
Paper Id: 39 [Abstract]

The focus of this talk will be on the question: how does the metal/oxide interface modify the activity and selectivity of supported noble metal catalysts? Specifically, we utilize the variable strength of interaction between different perovskite oxide supports and noble metal catalysts. The lattice parameters of LnScO₃ match well with several noble metals, which allows for a systematic study of how certain support properties can affect the catalytic performance of these metals. Lanthanide scandates were produced through a low-temperature heat treatment of a stoichiometric hydroxide gel (sol-gel) in a humid environment. (1) Water vapor was necessary to preserve the higher diffusivity of the gel, but an excess of water vapor led to the formation of secondary phases. The temperature of the reaction was used to tune the Gibbs free energy of reaction and kinetics of particle growth to produce faceted nanoparticles. Hydrothermal synthesis of SrTiO₃, for example, may produce materials that are controllably terminated with SrO-rich {100}, TiO₂-rich {100}, or TiO₂-rich {110} surfaces. Supported Pt nanoparticles, which have a close lattice match to SrTiO₃, showed a higher selectivity in acrolein hydrogenation towards allyl alcohol on SrTiO3 than BaTiO₃ when the Winterbottom shape on SrTiO₃ had a higher ratio of facets to edges or corners. Exploiting the Strong Metal-Support Interaction further improves the selectivity. (2,3)

References:
1) "Synthesis of Gadolinium Scandate from a Hydroxide Hydrogel", R. J. Paull, Z. R. Mansley, T. Ly, L. D. Marks, and K. R. Poeppelmeier, Inorg. Chem., 57(7), 4104-4108 (2018).

2) "Replications of SMSI via ALD: TiO2 Overcoats Increase Pt-Catalyzed Acrolein Hydrogenation Selectivity", R. M. Kennedy, L. A. Crosby, K. Ding, C. P. Canlas, A. Gulec, L. D. Marks, J. W. Elam, C. L. Marshall, K. R. Poeppelmeier, and P. C. Stair, Cataly. Lett., 148(8), 2223-2232 (2018).

3) "Morphology and CO Oxidation Activity of Pd Nanoparticles on SrTiO3 Nanopolyhedra", B.-R. Chen, L. A. Crosby, C. George, R. M. Kennedy, N. M. Schweitzer, J. Wen, R. P. Van Duyne, P. C. Stair, K. R. Poeppelmeier, L. D. Marks, and M. J. Bedzyk, ACS Catal., 8, 4751-4760 (2018).

11:45: [ChemistryThuAM02] Keynote
Innovative Materials for oxygen electrodes of Solid Oxide Cells
Jean-claude Grenier¹ ; ¹CNRS, University of Bordeaux, ICMCB, PESSAC Cedex, France;
Paper Id: 95 [Abstract]

The architecture of Solid Oxide fuel Cells/Solid Oxide Electrolysis Cells (SOFC/SOEC) has changed with time, mainly with regard to the operating temperature. Decreasing this temperature from 950°C down to 600°C required not only to decrease the ohmic drop of the electrolyte, but also to enhance the electrode performances. If the classical hydrogen electrode remains the efficient Ni/electrolyte cermet, the oxygen electrode has to be significantly improved with the aim to reduce the overpotential. Early oxygen electrodes in ESC (Electrolyte Supported Cell operating at T > 900°C) were made of a screen printed YSZ (Yttria Stabilized Zirconia) - LSM (Lanthanum Strontium Manganite) composite. Later on, these composite electrodes were replaced in ASC (Anode Supported Cells operating at about 750°C) by appropriate unique oxides showing mixed ionic and electronic conduction, such as the Lanthanum Strontium Ferro-Cobaltite (LSFC) [1]. More recently, we have shown that lanthanide nickelates Ln₂NiO_4+δ (Ln = La, Pr or Nd) exhibit very good ionic diffusivity of oxides ions as well as oxygen exchange properties leading to outstanding electrochemical properties as oxygen electrode materials [1-2]. Improvement of the cell performance was also achieved thanks to the addition of a thin interlayer ( = 2-3 µm) in between the electrolyte and the oxygen electrode; it mainly plays the role of a barrier against cation diffusion due to the reactivity of these materials with each other [3]. In the last generation of cells, the so called MSC (Metal Supported Cell operating at 600-700°C), has to allow imagination of new ways to make the oxygen electrodes. This has to be done with regard to the presence of metal which can be oxidized at temperatures higher than 900°C during the fabrication process. The infiltration technique has proven to be a promising route to make highly efficient electrodes [4]. The electrocatalyst is infiltrated in a porous skeleton (Gadolinia doped Ceria, GDC) sintered on the YSZ electrolyte, then fired at low temperatures (T = 600-800°C), leading to the formation of nanoparticles showing high electrocatalytic properties [5]. A review of all these issues is presented.

References:
[1] J.-C. Grenier, J.-M. Bassat, F. Mauvy, Functional materials for sustainable energy applications, eds. J. A. Kilner, S. J. Skinner, S. J. C. Irvine and P. P. Edwards, Woodhead Publishing 402-444 (2012)
[2] Ogier T., Mauvy F., Bassat J. M., Laurencin J., Mougin J. and Grenier J.-C. Int. J. Hydrogen Energy, 40(46) 2015, 15885-15892.
|3] A. Flura, C. Nicollet, B. Zeimetz, V. Vibhu, A. Rougier, J.-M. Bassat, J.-C. Grenier, Int. J. Electrochemical Soc. 163(6) (2016) F523-F532.
[4] J. Vohs, R. Gorte, Adv. Mater., 21, 943-956 (2009).
[5] C. Nicollet, A. Flura, V. Vibhu, A. Rougier, J.-M. Bassat, J.-C. Grenier, Intern. J. Hydrogen Energy, 41(34), 15538-15544 (2016).

12:10: [ChemistryThuAM03]
Fluorooxoborates: Novel Candidates for Deep-UV Nonlinear Optical Materials
Shilie Pan¹ ; ¹Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi, China;
Paper Id: 5 [Abstract]

The ever-growing application of deep-ultraviolet (deep-UV, I� < 200 nm) nonlinear optical (NLO) materials in various fields requires searching for candidates to generate the deep-UV lasers through direct second-harmonic generation (SHG) method. Among them, fluorooxoborates, benefiting from the large optical band gap, high anisotropy and ever-greater possibility to form non-centrosymmetric structures activated by the large polarization of the functionalized [BO_xF_4-x]^(x+1)- (x =1, 2 and 3) building blocks, have been considered as the new fertile fields for searching the deep-UV NLO materials.^1,2 Two series of fluorooxoborates AB₄O₆F (A = NH₄, Na, Rb, Cs, K/Cs and Rb/Cs)^3-6 and MB₅O₇F₃ (M = Ca and Sr)^7,8 were rationally designed and synthesized, which not only inherit the favorable structural characteristics of KBBF, but also possess superior optical properties. Property characterizations reveal that these two series possess the optical properties (deep-UV cutoff edges, large SHG responses, improved growth habit and also large birefringence to ensure the phase matching behavior in the deep-UV spectral region, etc.) required for the deep-UV NLO applications, which make them potential candidates to produce the deep-UV coherent light by the direct SHG process.

References:
References
(1) Mutailipu, M and Pan, S. L.* etc. Acc. Chem. Res. 2019, DOI: 10.1021/acs.accounts.8b00649
(2) Zhang, B. B and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2017, 56, 3916.
(3) Shi, G. Q.; Pan, S. L* and Poeppelmeier, K. R.* etc. J. Am. Chem. Soc. 2017, 139, 10645.
(4) Wang, X. F and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2017, 56, 14119.
(5) Wang, Y and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 2150.
(6) Zhang, Z. Z and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 6577.
(7) Mutailipu, M and Pan, S. L.* etc. Angew. Chem. Int. Ed. 2018, 57, 6095.
(8) Zhang, Z. Z and Pan, S. L.* etc. Inorg. Chem. 2018, 57, 4820.

12:35: [ChemistryThuAM04] Keynote
Electronic Structure and Energy Applications of Layered Materials
Tekalign Terfa Debela¹ ; Hafiz Ghulam Abbas² ; Hong Seok Kang³ ; ¹Jeonju University, Jeonju, South Korea; ²Chonbuk National University, Jeonju, South Korea; ³Jeonju University, Chonju, South Korea;
Paper Id: 396 [Abstract]

Based on a combination of various first-principles methods, we propose various kinds of layered materials. One is tetragonal GeP2, which has optimal band offset for photocatalyzed CO2 decomposition in wide pH range.[1] The second one TeSe2, which exhibits phase polymorphism, phase transition on charge doping, ferroelectricity, and interesting spin texture.[2,3] I also describe a series of my recent collaborations with an experimental group. First, combined experimental and theoretical effort is described for an efficient photoelectrochemical (PEC) water splitting of p-GeAs/n-Si heterojunction based on the band alignment, buildup of space charge in the junction, and the band bending of the n-Si at the electrolyte interface.[4] Second, our extensive DFT calculation complemented by analysis of charge transfer, band structure analysis, and reaction path for Volmer-Heyrovsky reactions give a deep insight into our experimental results, which has shown that the 1T'-phase guest-intercalated MoS2/WS2 nanosheets synthesized by one-step hydrothermal reaction exhibit excellent stability as well as higher catalytic activity toward the hydrogen evolution reaction at specific guest concentrations.[5-7] Finally, our extensive ab initio molecular dynamics simulations not only reproduce collaborative experimental voltage-charge capacity curves for WS2@graphite and WS2@nitrogen-doped graphite composites in lithium ion battery but also gives us a detailed picture on the structural evolution in the charge-discharge process.[8]

References:
[1] F. Shojaei, J. R. Hahn, H. S. Kang, J. Mater. Chem. A 5 (2017), 22146. (Selected as cover article)\n[2] T. T. Debela, H. S. Kang, J. Mater. Chem. C 6 (2018), 10109. (Selected as the Cover Article)\n[3] T. T. Debela, S. Liu, J.-H. Choi, H. S. Kang, in submission.\n[4] C. S. Jung et al. J. Mater. Chem. A. 6 (2018), 6, 9089.\n[5] I. H. Kwak et al, J. Mater. Chem. A, 6 (2018) 5613.\n[6] I. H. Kwak et al, J. Mater. Chem. A, 7 (2019) 2334.\n[7] I. H. Kwak et al, J. Mater. Chem. A, Advanced Article.\n[8] T. T. Debela et al. ACS Appl. Mater. Interfaces 10 (2018), 37928.

SESSION: ChemistryThuPM1-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Thu Oct, 24 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Kenneth Poeppelmeier; Jean-Claude GRENIER; Session Monitor: TBA

14:00: [ChemistryThuPM105] Plenary
Oxygen Incorporation and Release Behaviors in Perovskite-Structure Oxides
Yuichi Shimakawa¹ ; ¹Kyoto University, Uji, Japan;
Paper Id: 157 [Abstract]

Oxygen ions are incorporated in and released from transition-metal oxides when the valence states of the transition-metal ions change [1]. In topotactic changes of perovskite-structure oxides like SrFe²⁺O₂ - SrFe³⁺O_2.5 - SrFe⁴⁺O₃, we found that the oxygen incorporation and release behaviors are strongly influenced by the structural factors. The A-site disordered perovskite (La_1/3Ca_2/3)FeO₃ with unusually high valance Fe^3.67+ releases oxygen gradually above 500°C, whereas the A-site-layer-ordered perovskite LaCa₂Fe₃O₉ with the identical chemical composition of (La_1/3Ca_2/3)FeO₃ readily releases oxygen around 400°C [2,3]. From the B-site-layer-ordered double perovskite Ca₂FeMnO₆ with Mn⁴⁺ and unusual high valence Fe⁴⁺, oxygen is released only form the two-dimensional Fe-O layers according to the successive changes of Ca₂Fe⁴⁺Mn⁴⁺O₆ - Ca₂Fe^3.5+Mn⁴⁺O_5.75 - Ca₂Fe³⁺Mn⁴⁺O_5.5. The B-site-disordered Ca₂(FeMn)O₆, on the other hand, oxygen appears to be released at about 390°C by a single change of Ca₂(Fe⁴⁺Mn⁴⁺)O₆ - Ca₂(Fe³⁺Mn⁴⁺)O_5.5 [4,5]. Thus, the oxygen release behaviors differ depending on both A-site and B-site cation order. An important point for the behaviors of oxides with unusually high valence cations like Fe⁴⁺ is that the incorporation and the release of oxygen can occur at much lower temperatures than those with typical valence transition-metal ions. We will discuss the details of such behaviors from temperature-dependent structure analysis.

References:
[1] Y. Shimakawa, <i>Bull. Chem. Soc. Jpn.</i> <b>86</b>, 299-311 (2013).\n[2] H. Guo, Y. Hosaka, H. Seki, T. Saito, N. Ichikawa, and Y. Shimakawa, <i>J. Solid State Chem.</i> <b>246</b>, 199-202 (2017).\n[3] H. Guo, Y. Hosaka, F. D. Romero, T. Saito, N. Ichikawa, and Y. Shimakawa, <i>Inorg. Chem.</i> <b>56</b>, 3695-3701 (2017).\n[4] Y. Hosaka, N. Ichikawa, T. Saito, P. Manuel, D. Khalyavin, J. Paul Attfield, and Y. Shimakawa, <i>J. Am. Chem. Soc.</i> <b>137</b>, 7468-7473 (2015).\n[5] H. Hosaka, N. Ichikawa, T. Saito, J. P. Attfield, and Y. Shimakawa, <i>Phys. Rev. B</i> <b>94</b>, 104429 (2016).

14:25: [ChemistryThuPM106] Keynote
Fe2+/Fe3+: Couple, an Ideal Redox for Topochemical Reactions
Olivier Mentre¹ ; ¹UCCS, Villeneuve d'Ascq, France;
Paper Id: 315 [Abstract]

The possibility to modify inorganic oxides at moderate temperatures, under kinetic rather than thermodynamic control leads to metastable structural rearrangements with novel electronic partitions and original properties. In most cases, the abundant literature reports modifications of the anionic sub-array dealing with anionic vacancies, interstitials or anionic exchanges. However, intercalation or morerare exsolution cases show exotic cationic modifications towards original intercalated/depleted phases. The Fe²⁺/Fe³⁺ redox properties stand ideally for easy in-lab reactions. For instance, the controlled oxidation of the 2D-ising ferromagnetic BaFe²⁺₂(PO₄)₂ into Fe-depleted BaFe₂/3+2-x(PO₄)₂ (x<0.66) leads to a series of intermediate phases with full vacancy/Fe ordering and to nanometric Fe₂)O₃) [1]. On the opposite, playing redox chemistry in 2D-oxides such as the multiferroic, YbFe_2.5+2O₄ and Yb₂Fe_2.66+3O₇, the metal content is maintained but re-organized during reduction/oxidation very similarly to the hexagonal YMn³⁺O₃ system [2,3]. Generally, all transformed compounds require complex crystal-chemistry features with occurrence of supercells, modulated structures, and/or disordered intergrowths. The possibility to tune, in a controlled way, various pristine frameworks opens a wide field of investigation for tailor-made crystallographic architectures within the field of giant anion/cation-labile systems.

References:
[1] I.Blazquez Alcover. et al., Crystal Growth and Design, 15(2015) 4237-4247.
[2] S. Nicoud et al., JACS, 139 (2017),17031-17043.
[3] H. Kabbour et al., Inorg. Chem, 56(2017), 8547-8553.

14:50: [ChemistryThuPM107] Invited
Color Tuning for Electrochromic Displays
Aline Rougier¹ ; Issam Mjejri² ; Romain Futsch³ ; ¹Institu de Chimie de la Matière Condensée de Bordeaux, Pessac, France; ²ICMCB, Pessac, France; ³ICMCB, LUQUET DURANTON, Pessac, France;
Paper Id: 400 [Abstract]

Smart materials are the salient feature of our modern e-connected society. Among them, optical materials are continuously evolving and finding more areas of application, such as the electrochromic windows in the Boeing 787 Dreamliner and Gentex Corporation’s antiglare mirrors. Electrochromic smart windows can be used in cars or buildings to adjust brightness or in spacecraft to moderate the intense thermal fluctuations by switching between light/infrared transmission and reflection. Electrochromic materials and devices change their optical properties in a reversible and persistent way under an applied voltage¹. The most frequently used electrochromic compounds include transition metal oxides, such as WO₃, MoO₃, TiO₂, IrO₂, V₂O₅, NiO, Prussian blue (iron ferrocyanide) analogues and organic polymers, such as polyaniline, polypyrrole, and polythiophen. Inorganic electrochromic materials are stable and WO₃ is central to most applications, however their range of available colors and brightness are limited. On the contrary, organic polymers show high color efficiency and a huge range of colors but suffer from limited stability-particularly when exposed to the ambient environment. Aiming at improving EC properties for displays applications, our approach combines hybrid materials and novel design for ambient air and room temperature fabrication. In this presentation, focusing in particular on enlarging the palette of color, the advantage of mixing oxides and polymers will be demonstrated. As an example, the addition of iron oxide on poly(3,4-ethylenedioxythiophen), allows to switch not only from light to deep blue but also from blue to red². An additional step towards multichromism can be achieved by using vanadium oxides based devices reaching color modulation from orange to green and blue³. Acknowledments : This activity included in the SUPERSMART project has received funding from the European Institute of Innovation and Technology (EIT). This body of the European Union receives support from the European Union’s Horizon 2020 research and innovation program.

References:
[1] C. G. Granqvist, Handbook of Inorganic Materials, 1995.
[2] D. Levasseur, I. Mjejri, T. Rolland, A. Rougier, Polymers 11(1) (2019) 179.
[3] I. Mjejri, M. Gaudon, G. Song, C. Labrugère, A . Rougier ACS Applied Energy Materials, 1(6) (2018) 2721-2729.

15:15: [ChemistryThuPM108]
Towards a New Generation of Gold-Based Pigments
David Sallagoity¹ ; Lydia Roudier¹ ; Jerome Majimel¹ ; ¹UGIEL / CNRS, Univ. Bordeaux, Bordeaux INP, ICMCB, UMR 5026, F-33600 Pessac, France, PESSAC, France;
Paper Id: 276 [Abstract]

Pigments can be classified into two families: the organic ones, related to carbon chemistry and the inorganic ones; both of them have advantages and drawbacks. The variety of colours available in organic pigments is greater and these colours are more resistant to exposure to sunlight or chemicals. Organic pigments, however, are easier to stabilize and disperse and they exhibit brighter colours. In order to combine the advantages of both organic and inorganic types, UGIEL - a spin-out company from the ICMCB/CNRS laboratory - developed and patented green chemistry routes to graft and texture gold onto a wide range of support with nanometric precision. This results in a new generation of fully inorganic or hybrid organic-inorganic pigments with a wide range of colourful appearances and functionalities, relying on the inalterability and the biocompatibility of gold. First, a brief historical overview of nanosized gold and silver pigments will be given [1]. Then, microstructural features of UGIEL pigments will be described and related to their colourful appearances and applications.

References:
[1] P. Colomban, Photoniques HS1 (2015) 37-41

SESSION: ChemistryThuPM2-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Thu Oct, 24 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Teofilo Rojo; Aline ROUGIER; Session Monitor: TBA

15:55: [ChemistryThuPM209]
Computationally-Enabled Routes to New Inorganic Materials
Matthew Jonathan Rosseinsky¹ ; ¹University of Liverpool, Liverpool, United Kingdom;
Paper Id: 361 [Abstract]

The knowledge we have developed through the synthesis and experimental study of extended solids allows us to efficiently identify new materials. In many cases, this knowledge includes scientifically interesting or technically important changes in properties. An example is the chemical control of the transparent conducting behaviour of correlated metals (1), evaluated as epitaxial films through optical and transport data. The selection of d0 cations to stabilise oxygen-oxygen bond formation upon deep oxidation of lithium ion cathodes is another example (2). Here, computation provides underpinning guidance in the selection of experimental targets. The large potential range of accessible compositions and structures, however, challenges our present capabilities. As part of the current interest in exploring computationally-enabled routes to new materials, we are developing computational tools for the identification of stable new compositions. We have recently (3) been able to predict ab initio the regions of composition space that afford new materials. We then subsequently isolate those materials experimentally, using the computation of the energies of probe structures identified by new crystal structure prediction methods (4) to explore the space. The presentation will discuss the potential offered by informatics approaches often referred to as machine learning in such work.

References:
(1) J.L. Stoner et al., Advanced Functional Materials 29, 1808609, 2019
(2) Z. Taylor et al., J. Am. Chem. Soc. 141, 7333, 2019
(3) C. Collins et al., Nature 546, 280-284, 2017
(4) C. Collins et al., Faraday Discussions 211, 117, 2018

16:20: [ChemistryThuPM210] Invited
Optical Properties and Applications of Non-Oxide Glasses
Jean-luc Adam¹ ; ¹Université de Rennes 1 - CNRS, Rennes, France;
Paper Id: 16 [Abstract]

Vitreous materials based on fluorides or on chalcogen elements (S, Se, Te) show large transparency windows in the infrared. Indeed, fluoride glasses are transparent from the UV to 7 micrometers in the infrared, while chalcogenides can be transparent from the visible up to 12-15 micrometers, depending on their compositions [1]. This is due to the lower phonon energies of non-oxide glasses, which are also responsible for enhanced luminescence of rare-earth ions embedded in such matrices, as compared to oxides. Thus, these glasses allow light emission at wavelengths not accessible with silica. In addition, chalcogenide glasses contain large polarisable atoms and external lone electron pairs that induce exceptional non-linear properties. The non-linear properties of chalcogenides can be 100 to 1000 times as high as the non-linearity of silica.<br />As far as shaping is concerned, specific fluoride and chalcogenide glasses can be obtained in the form of optical fibers. Applications are directly related to the combination of unique optical properties and shaping abilities. <br />The presentation deals with an overview of the synthesis and properties of non-oxide glasses, completed by the latest results, in terms of applications, in two fields of technological or societal importance. The first one is the generation of supercontinuum of infrared light by using fluoride and/or chalcogenide optical fibers [2-4]. The second one is the detection of green-house-effect gases like CO₂ by using optical sensors based on rare-earth-doped chalcogenide fibers [5].

References:
[1] J. Sanghera and D. Gibson, Optical Properties of Chalcogenide Glasses and Fibers, in Chalcogenide Glasses, eds., J.L. Adam and X.H. Zhang (Woodhead Publishing, Cambridge, UK), pp. 113-138 (2014).\n[2] R.A. Martinez, G. Plant, K. Guo, B. Janiszewsji, M.J. Freeman, D.L. Maynard, M.N. Islam, et al., Opt. Lett. 43 (2018) 296-299\n[3] U. Moller, Y. Yu, I. Kubat, C. R. Petersen, X. Gai, L. Brilland, D. Mechin, C. Caillaud, J. Troles, B. Luther-Davies, and O. Bang, Optics Exp. 23 (2015) 3282-3291\n[4] C. Caillaud, C. Gilles, L. Provino, L. Brilland, T. Jouan, S. Ferre, M. Carras, M. Brun, D. Mechin, J.-L. Adam, and J. Troles, Optics Exp. 24 (2016) 7977-7986\n[5] A.L. Pele, A. Braud, J.L. Doualan, R. Chahal, V. Nazabal, C. Boussard-Pledel, B. Bureau, R. Moncorge, and P. Camy, Optics Express 23 (2015) 4163

16:45: [ChemistryThuPM211]
Aspects of MOF Chemistry Related to the Nuclear Energy Field: Chemistry of Actinides Carboxylates and Use of MOFs for the Capture Radioactive Elements.
Thierry Loiseau¹ ; ¹University of Lille, Villeneuve d'Ascq, France;
Paper Id: 210 [Abstract]

Coordination polymers are built up from the association of metallic centers with organic (e.g. O- or N-donor) ligands. For the last two decades, this assembling concept has been applied for the generation of the so-called Metal-Organic Frameworks (MOFs), which have been investigated for many potential applications in various domains like catalysis, gas storage, optics or medicine. Recently, the strategy has been successfully used with the particular case of actinides (An) [1]. Most of the studies have mainly reported the synthesis of such solid open-framework networks bearing U(VI) or Th(IV), while trans-uranium elements have been much less studied due to their high radiotoxicity and limited amount of source material. Among the possible oxidation states of An, the tetravalent state has been investigated less actively and large polyoxo clusters have been isolated for U or Pu. In contrast, there is not much data concerning Np(IV) compounds. In the present talk, we firstly present the formation of several series of uranyl-organic frameworks associated to poly-carboxylate linkers, by following the pH variation parameter of the reaction medium, related to the hydrolysis rate. This strategy was then applied to actinides(IV), which are known to exhibit a strong affinity for the hydrolysis reaction in order to form inorganic entities with high nuclearities. In this approach, the control of water content in reaction media containing organic solvent will be investigated in different chemical systems with Th(IV) and U(IV) [2] in the presence of dicarboxylic acids molecules (typically terephthalic acid), and was then extended to Np(IV) for some cases [3]. The structural descriptions of the different coordination polymers will point out the nuclear variation of the inorganic bricks from mononuclear [AnO ₉] up to hexanuclear entities [An ₆O ₈]. The latter is observed in the well-known series of UIO-66(Zr) MOF compounds. The second strategy was to use prototypical MOFs (MIL-n, UiO-66, ZIF-8) for the capture of radioactive molecules generated during a nuclear accident like iodine derivatives (I ₂, CH ₃I) or actinides (U, Th) [4]. In each case, the MOF compounds exhibit very high sorption capacities, modulated by the size of the pores and the functionalization of the framework. The resistance of MOF compounds under irradiative conditions (gamma ray irradiation) will be also discussed [5].

References:
[1] T. Loiseau, I. Mihalcea, N. Henry, C. Volkringer, Coord. Chem. Rev. 266-267 (2014) 69-72.
[2] C. Falaise, A. Assen, I. Mihalcea, C. Volkringer, A. Mesbah, N. Dacheux, T. Loiseau, Dalton Trans. 44 (2015) 2639.
[3] N.P. Martin, J. Marz, H. Feuchter, S. Duval, P. Roussel, N. Henry, A. Ikeda-Ohno, T. Loiseau, C. Volkringer, Chem. Commun. 54 (2018) 6979-82.
[4] M. Chebbi, B. Azambre, C. Volkringer, T. Loiseau, Mic. Mes. Mater. 259 (2018) 244-54.
[5] C. Volkringer, C. Falaise, P. Devaux, R. Giovine, V. Stenvenson, F. Pourpoint, O. Lafon, M. Osmond, C. Jeanjacques, B. Marcillaud, J.C. Sabroux, T. Loiseau, Chem. Commun. 52 (2016) 12502-505.

17:10: [ChemistryThuPM212]
Preparation, characterization and application of the hydrotalcite nanoparticles derived catalysts in dry reforming of methane
Zoulikha Abdelsadek¹ ; Patrick J. Masset² ; ¹Laboratory of Chemistry and Natural Gas, Faculty of Chemistry, USTHB, Institute of Electrical and Electronics Engineering, University of M’hamed Bougara, ALgiers, Algeria; ²Technallium Engineering & Consulting, Steinberg am See, Germany;
Paper Id: 197 [Abstract]

Hydrotalcite-based nanomaterials have gained considerable interest by academic and industrial researchers due to their properties in several industrial domains such as in medicine, the pharmaceutical industry, catalysis, electrochemistry, and in polymerization reactions [1, 3]. Catalytic properties can especially be tuned due their double lamellar sheet structure charged positively where divalent M²⁺ and trivalent M³⁺metals are located. In the present work, hydrotalcite-derived samples based on Ni and Co (NiMgAl, CoMgAl and NiCoMgAl) were prepared by low saturation coprecipitation at constant basic pH (pH = 11). The precursors were calcined at 450°C (4°C/min) for 6 hours. After that, the temperature was reduced to 700°C (4°C/min) during 1 hour. All obtained solids (none calcined, calcined and reduced) were characterized by several physico-chemical analysis methods (DRX, SAA, FTIR, SEM, MET, RTP, ATG/ATD and BET).The catalysts obtained were tested in dry reforming of methane (DRM), considered as promising for the production of syngas (H₂ + CO) in order to reduce the footprint of greenhouses gas (CH₄, CO₂), which is one of the keys of the climate transition. Catalytic testing of DRM for the series of the catalysts (NiMgAl-HTc-R, CoMgAl-HTc-R and NiCoMgAl-HTc-R) was carried out at 700°C (4°C/min) for 20 hours. The catalytic performances of examined solids showed the following sequence:<br />NiMgAl-HTc-R >NiCoMgAl-HTc-R >>>>CoMgAl-HTc-R.<br />NiMgAl-HTc-R was found to exhibit the best catalytic activity, selectivity with the highest resistance to the carbon poisoning and was ascribed to the good textural and structural features presented by NiMgAl-HTc-R such as high surface area, strong basic character and well dispersion of the active phase.

References:
[1] F. Cavani, F. Trifirb, A. Vaccari., Catal. Today, 11 (1991) 173.
[2] A. Vaccari., Catal. Today, 41 (1998) 53.
[3] C. Forano, T. Hibino, F. Leroux,Taviot-Guiho, Handbook of Clay Science, 1 (2006) 1021.
[4] L.A. Rodrigues, A. Figueiras, F.Veiga, R. M. Freitas, Colloids and Surfaces Biointerfaces, 103 (2013) 642.

SESSION: ChemistryFriAM-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Fri Oct, 25 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Igor Flerov; Session Monitor: TBA

11:20: [ChemistryFriAM01] Plenary
Fluoride Materials for Advanced Technologies, Energy, and Sustainability Issues
Alain Tressaud¹ ; ¹ICMCB-CNRS, University Bordeaux, Pessac, France;
Paper Id: 174 [Abstract]

Inorganic fluoride materials constitute an important part of solid-state chemistry since they are present today as components in many advanced technologies, for instance in energy storage devices, such as Li-ion batteries, F- ion-based all-solid-state batteries, or fuel cells. Beside this type of applications, fluoride materials are also decisive components in microphotonics, fluorescent chemical sensors, solid-state lasers, nonlinear optics, bio- and medicinal technologies, etc [1]. Most of these outstanding properties can be correlated to the exceptional electronic properties of the element "Fluorine" [2]. The strategic importance of inorganic fluoride materials will be illustrated by some examples: - In energy storage and conversion fields, fluorinated carbon nano-particles (F-CNPs) have been tested as active materials in electrodes of primary lithium batteries, whereas in secondary Li batteries, 3d-transition metal fluorides and oxyfluorides are proposed as active electrodes. - Among the huge variety of solid-state d-transition metals, fluorides derived from the perovskite, layered BaCuF₄ and iron fluorides (TTB- K₃Fe₅F₁₅), are noticeable multiferroics, in which magnetism and ferroelectricity coexist. - Functionalization processes and surface modifications using various fluorination treatments yield nano-sized materials with very high surface areas. In the case of fluorinated nano-carbons, the physical properties that can be drastically modified may concern: electrical conductivity, varying from insulating to metallic behavior, switchable hydrophobic/hydrophilic surfaces of substrates treated with fluorinated rf plasmas, high mobility in FET systems involving fluoro-graphene, and new kinds of fluorinated nano-carbons providing higher potential and energy density values, and thus improving the electrochemical performances of primary Li-battery. Concerning environmental and sustainable issues, new alternatives are proposed to substitute CFCs, HFCs and PFCs by molecules much favorable for our troposphere because of their lower GWP. In many fields such as the ceramics industry or aluminum production, new technologies allow to considerably lower the level of fluorine and fluoride emission or wastes. Finally, in areas of the world where the level of fluorine in water is dangerously high, various de-fluoridation processes improve the quality of drinking water, lower the risks of fluorosis, and bringing most promising development for these populations [3].

References:
[1] <i> "Progress in Fluorine Science"</i>, A. Tressaud Series Editor, Elsevier, USA Vol. 1 - <i>"Photonic & Electronic Properties of Fluoride Materials"</i>, A.Tressaud & K. Poeppelmeier Eds. (2016) ; Vol. 2 - <i>"New Forms of Fluorinated Carbons"</i>, O. Boltalina & T. Nakajima, Eds. (2016); Vol. 3 " <i>"Modern Synthesis Processes and Reactivity of Fluorinated Compounds"</i>, H. Groult, F. Leroux & A. Tressaud, Eds. (2017); Vol. 4 - <i>"Fluorine & Health: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals"</i>, G. Haufe, & F. Leroux Eds. (2018).
[2] <i>Fluorine Chemistry, a thematic issue</i>, Chemical Reviews, V. Gouverneur, K. Seppelt, Eds., Chem. Rev. 115 (2<span class="fon_main_wrapper"><span phone-source="015) 563-1306" class="fon-phone-wrap fon-hightlighted active-call" id="fon-phone-8VRbwKOSQr">015) 563-1306</span><a phone-source="015) 563-1306" href="#" class="fonCallLinkButton active-call"><img src="data:image/png;base64,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" alt="F"/></a></span>.
[3] <i>"Fluorine and the Environment"</i>, Vol.1: F-emissions and atmospheric chemistry. Vol.2: Green Chemistry, Water, Agriculture, and Analytical aspects, Advances in Fluorine Science Series, A. Tressaud, Ed. Elsevier (2006)

11:45: [ChemistryFriAM02] Keynote
The Role of Advanced Fluorine Materiais in our Daily Life.
Dayal Meshri¹ ; Navin C. Mathur¹ ; Sanjay Meshri¹ ; Robert Adams¹ ; Devender Pinnapareddy¹ ; Sudhir Bhagat¹ ; Harpreet Bhinhar¹ ; ¹Advance Research Chemicals, CATOOSA, United States;
Paper Id: 163 [Abstract]

Fluorinated materials have unique and extraordinary properties and that lead to their development and usage in all manufacturing and service sectors. The use of fluorine is no longer confined to traditional glass, metal, nuclear, fluoropolymer, pharmaceutical or agrochemical industries. New and challenging requirements next generation technologies of energy conversion, optoelectronics, semiconductors and electrical vehicle manufacturing industries have driven technological development of more advanced fluorinated materials. Fluorine is everywhere in our daily lives from our comfortable air-conditioned rooms, offices, and kitchens to cars and hospitals. The exponential growth in all manufacturing sectors and fluorochemical industries and increased consumption of fluorinated products have resulted in depletion occurring naturally, but this limits the main resource, fluorspar. This has provided opportunities to researchers to think and work on conservation and recycling and focus on the sustainable development of the fluorochemical industry in general. ln this paper, the important role of fluorine materials in our daily lives shall be summarized. Help from Contributions of Advance Research Chemicals, lnc. , including production of inorganic fluorides for the semiconductor industry and energy conversion will be briefly described. Actions taken by the scientific community and industry on sustainable development will also be presented.

12:10: [ChemistryFriAM03] Invited
New Iron-Based Fluorides as Positive Electrode for Lithium Secondary Batteries
Vincent Maisonneuve¹ ; ¹Institut des Molecules et Materiaux du Mans (IMM, UMR CNRS 6283), LE MANS, France;
Paper Id: 60 [Abstract]

Fluoride materials attract much interest as cathode materials for secondary batteries because of the high electronegativity of the fluorine atom, affording higher potentials than oxide analogues.[1] In this context, iron trifluoride FeF₃ has been intensively used due to its straightforward elaboration in relatively mild synthesis conditions; iron is considered as environmentally friendly. In the case of an intercalation mechanism, the theoretical capacity for FeF₃ (1Li⁺ per Fe) reaches 237 mAh.g^-1, a value higher than that obtained for the LiFePO₄ commercial material (170 mAh.g^-1). With the conversion reaction, this capacity can even reach 712 mAh.g^-1, implying a reduction of the trivalent iron. Despite good electrochemical performances in capacity and redox potential, the high ionicity of M-F bonds induces a large band-gap resulting in poor electronic conductivity. A recent study shows that the dehydration of HTB-FeF_2.2(OH)_0.8.0.33H₂O (Hexagonal Tungsten Bronze) leads to a lacunar oxyfluoride with anionic vacancies, thus having a positive effect on electrochemical performances (cyclability and capacity).[3] In this work, mixed fluorides M^IIM^III₂F₈(H₂O)₂, M^IIM^IIIF₅(H₂O)₂ weberites, and their corresponding dehydrated intermediate phases were considered for their electrochemical activity (M = V, Mn, Fe, Co, Ni, Cu).[4] The hydrated phases were synthesized by a solvothermal route, eventually assisted by microwave heating and characterized by X-ray diffraction (XRD) and ⁵⁷Fe Mössbauer spectrometry. The formulations and structural features of the intermediates stabilized after heating treatments under different atmospheres were determined by combining thermal analysis, powder XRD, MET, pair distribution function, IRTF and Mössbauer spectrometry. Finally, the electrochemical performances of all-synthesized fluoride materials demonstrate that several dehydrated phases could be a good alternative as positive electrode materials with capacities at the first discharge up to 306 mAh.g^-1.[4]

References:
[1] C.X. Zu, H. Li, "Thermodynamic analysis on energy densities of batteries". Energy & Environmental Science, 2011, 4(8), 2614.
[2] D.E. Conte, N. Pinna "A review on the application of iron(III) fluorides as positive electrodes for secondary cells". Mater. Renew. Sustain. Energy, 2014, 3:37.
[3] M. Duttine, D. Dambournet, N. Penin, D. Carlier, L. Bourgeois, A. Wattiaux, K.W. Chapman, P. J. Chupas, H. Groult, E. Durand, A. Demourgues. "Tailoring the Composition of a Mixed Anion Iron-Based Fluoride Compound: Evidence for Anionic Vacancy and Electrochemical Performance in Lithium Cells". Chem. Mater., 2014, 26, 4190.
[4] K. Lemoine, L. Zhang, D. Dambournet, J.-M. Greneche, A. H&ouml;mon-Ribaud, M. Leblanc, O. Borkiewicz, J.-M. Tarascon, V. Maisonneuve, J. Lhoste."Pyrochlore and HTB type Iron Hydroxyfluorides: from Synthesis to Li Insertion Properties". Chem. Mater., 2019, DOI: 10.1021/acs.chemmater.9b01252.

12:35: [ChemistryFriAM04] Invited
Fluoride and Oxide Fluoride Compounds during Fluoride Processing of Titanium-Containing Raw Materials
Natalia Laptash¹ ; Irina Maslennikova¹ ; ¹Institute of Chemistry, Far Eastern Branch of RAS, Vladivostok, Russian Federation;
Paper Id: 53 [Abstract]

Titanium dioxide (TiO₂) is one of the most attractive materials during the last decades because of its variety of practical applications such as photocatalysis, amphiphilic coatings, and dye-sensitized solar cells. So far, numerous TiO₂ nanostructures have been prepared such as spheres, films, nanowires, nanofibers, and nanotubes. In addition to the trend of nanostructural fabrication, the microarchitecture of TiO₂ has become a new paradigm in recent materials, chemistry, and nanotechnology [1]. Ammonium oxofluorotitanate (NH₄TiOF₃) crystals have been intensively studied and used as precursors for the synthesis of highly ordered and morphologically controlled TiO₂ [2]. It has been found that co-doping of nonmetal (especially with N and F) and metal (Fe) elements is capable of extending the light absorption edge of TiO₂ to the visible light region and improving photocatalytic activity due to the synergistic effect [3, 4]. For the large-scale applications of such materials, their mass quantity is required. In this case, the fluoride processing of the most abundant natural mineral ilmenite (FeTiO₃) with solid NH₄HF₂ (m. p. 126 ^oC) can be used. We have carefully studied this process [5]. Fluorination reactions of raw materials with NH₄HF₂ are thermodynamically possible and proceed exothermally (even at room temperature). Fluorination products are mainly nonstoichiometric phases of high symmetry: tetragonal double salts of silicon and titanium (NH₄)₃[Si(Ti)F₆]F, cubic fluoroelpasolites and fluoroperovskites, which were isolated in a single crystal form and their crystal structures were determined (or refined). Their phase transitions at temperature decreasing, thermal and hydrolytic properties were studied. The compounds were investigated by X-ray diffraction, differential thermal analysis (DTA), differential scanning microcalorimetry (DSM) and adiabatic calorimetry, NMR, infrared, Raman, XPS, and Mössbauer spectroscopies. The tensimetry method was also used for establishment of incongruent sublimation of (NH₄)₂SiF₆. Comparative analysis of fluoride processing methods of titanium-containing raw materials indicates the preference of NH₄HF₂ use.

References:
[1] H.K. Lee, S.W. Lee, Chem. Lett. 44 (2015) 604-606.
[2] H.K. Lee, T. Fujiwara, T. Okada, T. Fukushima, S. W. Lee, Chem. Lett. 47 (2018) 628-631.
[3] P. Zhang, M. Fujitsuka, T. Majima, Appl. Catalysis B, 185 (2016) 181-188.
[4] Y.F. Zhang, H.Y. Shen, Y.H. Liu, Res. Chem. Intermed. 42 (2016) 6265-6287.
[5] N.M. Laptash, I.G. Maslennikova, Adv. Mater. Phys. Chem. 2 (2012) 21-24.

14:25: [ChemistryFriPM106] Invited
Complex Fluorides and Oxyfluorides: Successive Ferroelastic Phase Transitions and Barocaloric Effect
Igor Flerov¹ ; Mikhail Gorev¹ ; Evgeniy Bogdanov¹ ; ¹Kirensky Institute of Physics, Krasnoyarsk, Russian Federation;
Paper Id: 27 [Abstract]

In recent years, caloric effects near phase transitions in solids have attracted growing interest from investigators. First, this is due to the possibility of obtaining information about a direct relationship between fundamental values such as entropy, temperature, order parameter, structural disorder and sensitivity to external fields (electric, magnetic, mechanical stress and hydrostatic pressure). [1,2] The second reason is associated with the actual problem of searching for high-performance solid refrigerants and for designing alternative refrigeration cycles which are competitive compared to the traditional vapor-compression cycles. [3,4] Barocaloric effect (BCE) associated with the reversible change in the entropy/temperature, ΔS_BCE / ΔT_AD, under pressure variation under the isothermal/adiabatic conditions is a common caloric characteristic for substances of different physical nature. We performed the analysis of the extensive and intensive BCE in some complex fluorides and oxyfluorides which are very sensitive to a change of the chemical pressure and very often undergo successive order-disorder phase transitions of a ferroelastic nature. Different types of the T - p phase diagrams, including the triple points, are considered in connection with the complicated dependences of T(p) observed experimentally. Analyzed diagrams do not cover all possible variants of the phase transition temperature behavior under pressure. They show, however, which parameters of the phase transitions and phase diagrams should be taken in consideration when analyzing BCE. A very important point is that rather low hydrostatic pressure practically does not affect the entropy of the ferroelastic transformations. Therefore, the behavior of extensive and intensive BCE is not changed with increase in pressure. In the case of close temperatures of the successive phase transitions, there is a possibility to realize extensive BCE as the sum of entropies of two transformations. Due to the large magnitude of the extensive and intensive BCE, complex fluorides and oxyfluorides can be considered as new competitive solid refrigerants.

References:
[1] A.M. Tishin and Y.I. Spichkin, The Magnetocaloric Effect and its Applications (Bristol: Institute of Physics Publishing) 2003.
[2] I.N. Flerov, M.V. Gorev, A. Tressaud, N.M. Laptash, Cryst. Rep. 56 (2011) 9-17.
[3] L. Manosa, A. Planes, M. Acet, J. Mater. Chem. A 1 (2013) 4925-4936.
[4] M. Ožbolt, A. Kitanovski, J. Tušek, A. Poredoš, Int. J. Refrig. 40 (2014) 174-88.

14:50: [ChemistryFriPM107] Keynote
Polyanionic Structures and Competitive Bonds around Fluorine : Tuning the Band Gap for New Applications in Solid State Chemistry
Alain Demourgues¹ ; ¹ICMCB-CNRS-University of Bordeaux, Pessac, France;
Paper Id: 36 [Abstract]

Around various transition metals (Ti and Fe), p-block elements (In) or rare-earths (Ce) associated to at least two different anions (F, O, S), original networks can be designed associated to specific optical and electronic properties and various elemental rules can be established. First, the Ti-based oxy-hydroxy-fluorides with the HTB network were prepared by the solvothermal route and the original structure has been determined. The optical band gap can be tuned in UV range as a function of the O/F atomic ratio, leading to the design of UV-absorbers with low refractive index. V or Mo partial substitution contributes to shift the band gap in the visible range. The heat-treatment of Fe fluoride trihydrate up to T=350°C under Ar leads to stability for the first time where Fe oxy-fluoride has anionic vacancies in the HTB network. The formation of structural units containing 5-fold coordinated Fe atoms in this HTB network leads to a strong reduction of the optical band gap from 4.05 eV in FeF₃, 3H₂O to 2.05 eV in the Fe oxyfluoride thanks to the occurrence of 2p-oxygen states on the top of the valence band. The reaction between anhydrous In fluoride and water at 400°C under Ar (InF₃ + H₂O → InOF + 2HF) leads to In oxyfluoride which adopt a derived fluorite-type structure with O/F ordering. InOF can be considered as a transparent conductive oxyfluoride with band gap energy of 3.7 eV. It can also be considered as a smaller work function compared to In2O₃ due to the destabilization of conduction band thanks to the structural features of InOF. With these unusual optical and electronic properties, numerous In-based oxyfluorides can be designed. The reduction under H₂ at 700°C of Ce fluoro-carbonate CeFCO₃ leads to the preparation of pure CeOF with O/F ordering which exhibits a blue-grey coloration. The H₂S treatment at T=700°C-800°C of CeIII fluoride, oxyfluoride or fluorocarbonate, allows obtainment of Ce fluoro-sulfide CeSF which adopts a 2D network like CeOF, derived from the fluorite-type structure. The band gap strongly varies from UV in CeOF to visible range in CeSF with around 2eV associated to a red coloration. The key features of mixed anion systems will be highlighted from the analysis of reactivity, structure and local environments to tune the band gap.

References:
[1] A. Demourgues, N. Penin, F. Weill, D. Dambournet, N. Viadere and A. Tressaud. Chem. Mater. 21, (2009) 1275-1283
[2] M. Duttine, D. Dambournet, N. Penin, D. Carlier, L. Bourgeois, A. Wattiaux, K. W. Chapman, P.J. Chupas, H. Groult, E. Durand, A. Demourgues. Chem. Mater, 25(14) (2014) 4190-4199
[3] M. Burbano, M. Duttine, B.J. Morgan, O.J. Borkiewicz, K. W. Chapman, A. Wattiaux, A. Demourgues, H. Groult, M. Salanne and D. Dambournet.
J. Phys. Chem. Lett, (2019), 10, 107-112
[4] D. Pauwels, A. Demourgues, H. Laronze, P. Gravereau, F. Guillen, O. Isnard and A Tressaud. Solid State Sciences, 4 (2002) 1471-1479

15:15: [ChemistryFriPM108] Invited
Heteroanionic titanium oxide-fluoride compounds: from anionic ordering to defects
Damien Dambournet¹ ; ¹Sorbonne University, Paris, France;
Paper Id: 91 [Abstract]

The crystal chemistry of inorganic compounds featuring mixed anionic framework provides a broad richness from the standpoint of the structure and properties.(1-2) The solid-state chemistry of titanium-based oxide-fluoride compounds is a school case to exemplify how anions can arrange in different structural arrangements. In this presentation, we shall exemplify the structural arrangements through two examples showing how anions, particularly fluoride, can be ordered. In a first example, we will describe the structure of a cubic phase TiOF₂ from the average to the local order standpoints. Thereafter, we will describe how monovalent anions such as fluoride and hydroxide can be stabilized in an oxide framework, leading to the stabilization of cationic vacancies (3). Finally, we will present how these defects can unlock the electrochemical activity toward multivalent ions opening new avenues to develop new electrochemical devices (4).

References:
(1) Kageyama, H.; Hayashi, K.; Maeda, K.; Attfield, J. P.; Hiroi, Z.; Rondinelli, J. M.; Poeppelmeier, K. R. Expanding Frontiers in Materials Chemistry and Physics with Multiple Anions. Nat. Commun. 2018, 9 (1), 772. https://doi.org/10.1038/s41467-018-02838F-4.
(2) Harada, J. K.; Charles, N.; Poeppelmeier, K. R.; Rondinelli, J. M. Heteroanionic Materials by Design: Progress Toward Targeted Properties. Adv. Mater. 0 (0), 1805295. https://doi.org/10.1002/adma.201805295.
(3) Li, W.; Corradini, D.; Body, M.; Legein, C.; Salanne, M.; Ma, J.; Chapman, K. W.; Chupas, P. J.; Rollet, A.-L.; Julien, C.; et al. High Substitution Rate in TiO2 Anatase Nanoparticles with Cationic Vacancies for Fast Lithium Storage. Chem. Mater. 2015, 27 (14), 5014-5019. https://doi.org/10.1021/acs.chemmater.5b01407.
(4) Koketsu, T.; Ma, J.; Morgan, B. J.; Body, M.; Legein, C.; Dachraoui, W.; Giannini, M.; Demortire, A.; Salanne, M.; Dardoize, F.; et al. Reversible Magnesium and Aluminium Ions Insertion in Cation-Deficient Anatase TiO2. Nat. Mater. 2017, 16 (11), 1142. https://doi.org/10.1038/nmat4976.

SESSION: ChemistryFriPM2-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Fri Oct, 25 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Jean-Luc ADAM; Thierry Loiseau; Session Monitor: TBA

15:55: [ChemistryFriPM209] Keynote
Sodium manganese-rich layered oxides (NaTMO2): a rational approach to cathode material development
Nicholas Drewett¹ ; Elena Gonzalo¹ ; Juan Miguel Lopez Del Amo¹ ; Nagore Ortiz Vitoriano¹ ; Begona Acebedo¹ ; Laura Acebo¹ ; Galceran Montserrat¹ ; Teofilo Rojo¹ ; ¹CIC energiGUNE, Vitoria-Gasteiz, Spain;
Paper Id: 169 [Abstract]

Sodium ion Batteries (SIBs) offer a strong alternative to existing battery technologies, particularly in the field of stationary storage due to their potentially low cost, and natural abundant precursors.[1,2] One key component of an SIB is the cathode, the nature of which is critical to its performance. Sodium layered oxides (SLOs), with the stoichiometry NaT_MO₂ (T_M = one or more transition metals, e.g. Mn, Fe, Co, Ni, etc.), are a promising family of cathode materials due to their excellent electrochemical properties, structural simplicity, and tuneable stoichiometries.[3] SLOs, consisting of repeating sheets of T_MO₆ layers with Na ions located between, are classified by a letter and number (e.g. O3-, P2-, etc.) where the letter indicates the Na is located (O: octahedral, P: prismatic) and the number indicates the number of interlayers that are surrounding.[4] Performance of these materials is frequently governed by their structure, and in this work we will highlight the importance of taking this into consideration. For example, while Manganese-rich layered oxides are particularly attractive due to their combination of low cost and low toxicity, their performances are often hindered by the effect of Jahn-Teller distortion (resulting from the presence of Mn³⁺).[5] We will not only discuss this in detail, but also highlight mitigation strategies, such as doping with electrochemically active (e.g. Fe) and inactive (e.g. Mg, Ti) elements, or synergetic P2/O3 combination effects.[5-8] We will also examine the importance of Na-ion conductivity, determined through the use of combined electrochemical techniques and solid-state NMR spectroscopy, and show how the mobility of Na ions is related to the different local environments of Na ions (i.e. O- or P- phase) and diffusion pathways.[9] This way, we will not only show a thorough knowledge where SLO structure is key to understanding their behaviour, but also how to link this to the key descriptors for the cathode material's electrochemical performance.

References:
[1] V. Palomares, P. Serras, I. Villaluenga, K.B. Hueso, J. Carretero-Gonzalez, T. Rojo, Energy Environ. Sci. 5 (2012) 5884-5901.
[2] V. Palomares, M. Casas-Cabanas, E. Castillo-Martínez, M.H. Han, T. Rojo, Energy Environ. Sci. 6 (2013) 2312-2337.
[3] M.H. Han, E. Gonzalo, G. Singh, T. Rojo, Energy Environ. Sci. 8 (2015) 81-102.
[4] C. Delmas, C. Fouassier, P. Hagenmuller, Phys. B+C. 99 (1980) 81-85.
[5] N. Ortiz-Vitoriano, N.E. Drewett, E. Gonzalo, T. Rojo, Energy Environ. Sci. 10 (2017) 1051-1074.
[6] J. Billaud, G. Singh, A.R. Armstrong, E. Gonzalo, V. Roddatis, M. Armand, T. Rojo, P.G. Bruce, Energy Environ. Sci. 7 (2014) 1387-1391.
[7] E. Gonzalo, N. Ortiz-Vitoriano, N.E. Drewett, B. Acebedo, J.M. Lopez del Amo, F.J. Bonilla, T. Rojo, J. Power Sources. 401 (2018) 117-125.
[8] M. Bianchini, E. Gonzalo, N.E. Drewett, N. Ortiz-Vitoriano, J.M. Lopez Del Amo, F.J. Bonilla, B. Acebedo, T. Rojo, J. Mater. Chem. A. 6 (2018).
[9] E. Gonzalo, M.H. Han, J.M. Lopez del Amo, B. Acebedo, M. Casas-Cabanas, T. Rojo, J. Mater. Chem. A. 2 (2014) 18523-18530.

16:20: [ChemistryFriPM210]
Renewable Energy Systems: Current Status and Prospects
Soteris Kalogirou¹ ; ¹Cyprus University of Technology, Limassol, Cyprus;
Paper Id: 177 [Abstract]

This presentation examines the current status of renewables in the world. The presentation starts with some facts about the climate change, global warming and the effects of human activities such as the burning of fossil fuels on the climate problem. It then examines the current status of conventional resources of energy such as oil, coal, natural gas and their reserves based on current consumption, and known resources. This is followed by a general outline of the status of renewables in the world, which includes the shares with respect to conventional fuel use for electricity and power and jobs created. Then the basic forms of renewables are examined in some detail, which include solar and thermal applications, both for low and high temperatures, photovoltaics, hydro power, onshore and offshore wind energy systems and biomass/biofuels. In all these, the basic technology is presented followed by the current status as well as the prospects of the technology and new research findings. Finally, some basic facts about the Renewable Energy Journal in which the speaker is the Editor in Chief are presented.

References:
[1] Renewables 2018 – Global Status Report, REN 21.
[2] Werner Weiss, Monika Spörk-Dür, Solar Heat Worldwide, Global market development and trends, Solar Heating and Cooling Program, IEA, 2018.
[3] Snapshot of Global PV markets 2018. IEA-PVPS – Annual Report 2017.

16:45: [ChemistryFriPM211] Plenary
From Solid State Chemistry to Solid State Electrochemistry: Lithium Metal Polymer Batteries
Christian Julien¹ ; Karim Zaghib² ; Michel Armand³ ; John Goodenough⁴ ; Alain Mauger¹ ; ¹Institut de Minéralogie, de Physique des Matériaux et de Cosmochimie (IMPMC), Paris, France; ²Hydro-Quebec's Center of excellence in transportation electrification and Energy Storage, Varennes, Canada; ³CIC Energigune, Paris, France; ⁴Texas Materials Institute, Austin, United States;
Paper Id: 405 [Abstract]

HQ-CNRS started work on lithium metal with polymer electrolyte in lithium rechargeable batteries in 1979. Since that time, battery research has expanded worldwide. Several new polymers, solid electrolytes and ionic liquids with improved conductivity have resulted from a better understanding of the major parameters controlling ion migration, such as favorable polymer structure, phase diagram between solvating polymer and lithium salt, and the development of new lithium counter-anions. In spite of the progress so far, the quest for a highly conductive dry polymer at room temperature is still continuing and all-lithium polymer battery (LPB) developers presently face the challenge of whether to heat the PEO-based polymer electrolyte to enable high-power performance, as required for electric vehicle and energy storage or develop a polymer electrolytes conductive at RT. LPB developers have explored both the high-temperature and low-temperature options. This presentation provides an overview and progress in developing three battery technologies: 1. Lithium-metal-based batteries made from dry polymer and ionic liquid-polymer electrolytes for rechargeable lithium batteries with olivine (LFP and LMFP). 2. All solid-state batteries using Li°-NMC. 3. High voltage composite polymer- ceramic for all solid state batteries. We compare the performances the energy density, the cost, and safety of li-ion batteries vs. solid state batteries. In this presentation we will explain the process from materials to the system (cell, module and pack).

17:10: [ChemistryFriPM212] Invited
Electronic structure engineering as a new tool in development of Li-ion and Na-ion batteries
Janina Molenda¹ ; ¹AGH University of Science and Technology, Kraków, Kraków, Poland;
Paper Id: 379 [Abstract]

The author of this work basing on her own investigations of Li_xMO₂ cathode materials ( M=Ni, Co, Mn, Cu) has demonstrated that the chemical disorder influenced on electronic structure of these materials plays an important role in the electrochemical intercalation process [1]. The paper reveals correlation between chemical disorder, crystal and electronic structure, transport and electrochemical properties of layered Li_xCoO₂, Li_xNi_1-y-zCo_yCu_zMn_0.1O₂ and Na_xCoO_2-y [2] cathode materials and explains of apparently different character of the discharge/charge curve in those systems. Comprehensive experimental studies of physicochemical properties of Li_xNi_1-y-zCo_yCu_zMn_0.1O₂ and Na_xCoO_2-y cathode materials (XRD, electrical conductivity, thermoelectric power) are supported by electronic structure calculations performed using the Korringa-Kohn-Rostoker method [3] with the coherent potential approximation (KKR-CPA) to account for chemical disorder. It is found that even small O defects (~1%) may significantly modify DOS characteristics via formation of extra broad peaks inside the former gap leading to its substantial reduction. Moreover, these DOS peaks of “defects” strongly evolve with Li and Na contents, actually leading to the overall reducing of the gap and to even the pseudogap. The battery on the base on the developed LiNi_0.9-y-zCo_yMn_0.1Cu_zO₂ cathode materials are characterized by high potential, high capacity and high rate capability guaranteeing high energy and power densities. This work was funded by the National Science Centre Poland (NCN) under the “OPUS 12 programme on the basis of the decision number UMO- 2016/23/B/ST8/00199.

References:
REFERENCES:
[1] J.Molenda, A.Milewska, W. Zajac, M.Rybski, J. Tobola, Phys. Chem. Phys. Chem. 19, (2017)25697.
[2] J. Molenda, D. Baster,M. Molenda, K.Świerczek, J. Tobola, Anomaly in the electronic structure of the NaxCoO2-y cathode as a source of its steplike discharge curve, Physical Chemistry Chemical Physics,16 (2014)14845-14857.
[3] A. Bansil, S. Kaprzyk, P. E. Mijnarends and J. Tobola, Phys., Rev. B: Condens. Matter Mater. Phys., 60 (1999) 13396.

SESSION: ChemistryFriPM3-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Fri Oct, 25 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Khalil Amine; Session Monitor: TBA

17:50: [ChemistryFriPM313] Keynote
Advanced Energy Storage systems for enabling electrification of vehicles Lithium Ion and Beyond
Khalil Amine¹ ; ¹Argonne National Laboratory, Argonne, United States;
Paper Id: 62 [Abstract]

To meet the high-energy requirements that can enable the 40-mile electric drive plug-in hybrid electric vehicle (P-HEVs), long range electric vehicle (EV) and smart grid, it is necessary to develop very high energy and high power cathodes and anodes that, when combined in a battery system, must offer over 5,000 charge-depleting cycles, 15 years of calendar life as well as excellent abuse tolerance. These challenging requirements make it difficult for conventional battery systems to be adopted in P-HEVs and EVs. In this talk, we will first introduce the next generation lithium ion battery that include the Ni rich full gradient cathode [1], a high voltage and nonflammable Fluorinated based electrolyte and Silicon-graphene composite anode including a novel pre-lithiation technology to overcome the irreversible loss of this anode in the first cycle . We will then finish by describing a novel lithium superoxide based on a close battery system that offers at least 3 times the energy density of the state of the art lithium ion battery [2-3] and a SeS system with novel electrolytes that suppress the dissolution of polysulfide species [4].

References:
[1]Sun, Y. K.; Chen, Z. H.; Noh, H. J.; Lee, D. J.; Jung, H. G.; Ren, Y.; Wang, S.; Yoon, C. S.; Myung, S. T.; Amine, K., Nature Material 2012,11 (11), 942-947

[2] Zhu, Z.; Kushima, A.; Yin, Z. Y.; Qi, L.; Amine, K.; Lu, J.; Li, J., Anion-redox nanolithia cathodes for Li-ion batteries. Nature Energy,2016, 1, 16111

[3] Lu, J.; Lee, Y. J.; Luo, X. Y.; Lau, K. C.; Asadi, M.; Wang, H. H.; Brombosz, S.; Wen, J. G.; Zhai, D. Y.; Chen, Z. H.; Miller, D. J.; Jeong, Y. S.; Park, J. B.; Fang, Z. Z.; Kumar, B.; Salehi-Khojin, A.; Sun, Y. K.; Curtiss, L. A.; Amine, K., Nature 2016,529 (7586), 377-+.

18:15: [ChemistryFriPM314]
Revisiting Crystal Structure - Hole Doping - Tc Relations in Overdoped M-1212 Superconducting Cuprates.
Miguel Angel Alario Franco¹ ; Sara Almudena Lopez Paz¹ ; Xabier Martinez De Irujo² ; ¹Inorganic Chemistry DPT.Facultad de Química Universidad Complutense, MADRID, Spain; ²Inorganic Chemistry DPT.Facultad de Química Universidad Complutensi, MADRID, Spain;
Paper Id: 61 [Abstract]

Among the factors controlling the critical temperature (Tc) in the high temperature superconducting cuprates (HTSC), the hole-doping level is one of the most crucial ones. In fact, superconductivity is suggested to be restricted to a “universal” hole doping level 1 psh comprised between ~0.06 and 0.31 holes per copper plane. While the complex charge-spin-lattice interplay in the underdoped regime (i.e. at p<popt) has attracted most of the efforts, the overdoped regime (p>popt) remains less explored and perceived as simpler, Fermi-liquid behaved. Recent results, however, are highlighting the potential of this overdoped region in the understanding of the condensation mechanism. In searching for overdoped systems, the so-called M-1212 phases resulting from partial or total substitution of copper in the Charge Reservoir Layer by other transition metals (TM) are suitable candidates. This is because they allow the total oxygen content to be widely modified with respect to the YSCO parent compound. This is particularly true for high valent TM, as the Mo(V-VI) and Fe(III-IV) cations in the Mo_0.3Cu_0.7Sr₂RECu₂Oy₃ and FeSr₂YCu₂Oy phases, in which the oxygen content can be raised to y > 7, above the YBCO limit. This leads to very highly doped CuO₂ planes, outside the Tc-psh paradigm. To shed light to the superconducting properties of these substantially overdoped (Mo & Fe)-1212 systems, we have varied both the oxidation degree and the RE size, looking at the effect of the crystal structure on Tc. We specifically focus on the connection between the atomic arrangement within the unit cell and the hole distribution. To that end, we have performed a joint structural-electronic characterization by means of NPD, ARM and EELS spectroscopy of ozone4 and high-pressure oxidized phases. We have observed that these materials, which are outside the paradigm, can be superconducting. Due to the Tc increasing with a whole doping level almost double than the above limit. We have also established the upmost importance of order-disorder in both the cation and anion sublattices.

References:
1. Zhang, H. & Sato, H. Universal relationship between Tc and the hole content in p-type cuprate superconductors. Phys. Rev. Lett. 70, 1697-1699 (1993).
2. Božović, I., He, X., Wu, J. & Bollinger, A. T. Dependence of the critical temperature in overdoped copper oxides on superfluid density. Nature 536, 309-311 (2016).
3. Gauzzi, A. et al. Bulk superconductivity at 84 K in the strongly overdoped regime of cuprates. Phys. Rev. B 94, 180509 (2016).
4. Martínez de Irujo-Labalde, X., Urones-Garrote, E., García-Martín, S. & Alario-Franco, M. A. Influence of Structural (Cation and Anion) Order in the Superconducting Properties of Ozone-Oxidized Mo 0.3 Cu 0.7 Sr 2 RECu 2 O y (RE = Yb, Tm, Gd, Nd, and Pr). Inorg. Chem. 57, 12038-12049 (2018).
5. Marik, S., Labrugere, C., Toulemonde, O., Morán, E. & Alario-Franco, M. A. Core-level photoemission spectra of Mo 0.3 Cu 0.7 Sr 2 ErCu 2 O y , a superconducting perovskite derivative. Unconventional structure-property relationships. Dalt. Trans. 44, 10795-10805 (2015).

SESSION: ChemistrySatAM-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Sat Oct, 26 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Janina Molenda; Fernand D. S. Marquis; Session Monitor: TBA

11:20: [ChemistrySatAM01] Keynote
Cellulose based functional materials in flexible electronic devices
Luis Pereira¹ ; ¹CENIMAT/I3N, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal;
Paper Id: 439 [Abstract]

The growing demand of new and sustainable consumer printed electronics led to the increased interest in devices integrating natural materials. Here we present the wok resulting from recent research concerning the application of cellulose based materials in flexible electronic devices. First topic is related to with the development of electrolytic membranes to be used as dielectric in transistors exploring the high capacitance that can be obtained by the formations of electric-double layers. Second topic to be addressed are printable inks based on commercial carbon fibers and zinc oxide nano-particles mixed with some cellulose derivatives that were optimized to create printed active layers at temperatures lower than 150 °C. This allowed the development of fully screen-printed sensors and transistors with mobility above 10 cm²V^-1s^-1 and on/off current ratio higher than to 10⁵ on substrates like paper and cork. Finally, we will show how cellulose nano-crystals can self-assemble in a chiral nematic structures that mimic those existing in nature. These can be then used as dielectric in field effect transistors making possible the detection of circular polarized light in such devices.

11:45: [ChemistrySatAM02]
Homoleptic Fluoride Complexes as Modules for Molecular Spin-Architectures
Kasper Pedersen¹ ; ¹Technical University of Denmark, Lyngby, Denmark;
Paper Id: 397 [Abstract]

Diffuse orbitals and large magnetic anisotropy resulting from strong spin-orbit coupling make complexes with central ions from the 4d and 5d series interesting modules for magnetic materials [1]. The vast majority of molecule-based magnetic materials encompassing those elements utilize cyanide bridging. The common linearity of {M–CN–M} motifs is paralleled in fluoride-bridged systems, which thereby also proffers the desired synthetic handle in the design of new materials. When using simple [MF₆]^n– complexes as building blocks for complex architectures, the main obstacle is their common inherent lability outside hydrofluoric acid solutions, towards, for example, hydrolysis. This tendency is strongly diminished for several 4d and 5d [MF₆]^2– complexes and we herein present the use of [MF₆]^2– (M = Zr, Re, Ir, Os,…) anions, prepared by various fluorination routes, as modules for molecular magnetic systems of various dimensionality [2]. We also discuss the chemistry and potential of related 5f systems such as [UF₆]^2– [3]. The ability of fluoride to mediate significant exchange interactions dwarfs the coupling present in related cyanide-bridged systems. Conclusively, our results reveal structurally simple, robust and strongly anisotropic [MF₆]^2– complexes of the heavier transition elements to be unique and versatile building blocks for novel types of (magnetically interesting) molecular systems.

References:
[1] X.-Y. Wang, C. Avendano, K. R. Dunbar, Chem. Soc. Rev. 2011, 40, 3213.
[2] (a) K. S. Pedersen et al. Angew. Chem. Int. Ed., 2014, 53, 1351; b) K. S. Pedersen et al. Nat. Commun. 2016, 7, 12195; c) K. S. Pedersen et al. Chem. Eur. J. 2017, 23, 11244.
[3] K. S. Pedersen et al. Angew. Chem. Int. Ed. 2019, accepted.

12:10: [ChemistrySatAM03]
The Way to White Light Emitting Diodes by Quantum Chemical Calculations
Werner Urland¹ ; ¹Private Institute of Theoretical Chemical Physics, Muralto, Switzerland;
Paper Id: 26 [Abstract]

Quantum chemical calculations (semi-empirical and non-empirical) are used to design new phosphors with Eu ²⁺ for white Light Emitting Diodes (LEDs) used for artificial lighting. This is of ultimate importance as the quest for optimal white LEDs is still relevant. The model which uses Density Functional Theory is based on an effective Hamiltonian that includes electrostatic, spin-orbit and ligand field contributions. From these calculations, the multiple energy levels arising from the ground 4f7 and excited 4f65d1 electron configurations of Eu²⁺ in their chemical environment are obtained. The results are in good agreement with the experimental investigations, validating the usefulness of theoretical modelling to understand and characterize the luminescence spectra of phosphors with Eu²⁺. [1,2] The luminescence properties of the new phosphor BaSnSi₃O₉:Eu²⁺ have been theoretically predicted and then experimentally verified. [3]

References:
1. A. Garcia-Fuente, F. Cimpoesu, H. Ramanantoanina, B. Herden, C. Daul, M. Suta,\n C. Wickleder, W. Urland, Chem. Phys. Lett. 622, 120 (2015)\n2. H. Ramanantoanina, F. Cimpoesu, C. Göttel, M. Sahnoun, B. Herden, M. Suta,\n C. Wickleder, W. Urland, C. Daul, Inorg. Chem. 54, 8319 (2015).\n3. A. Garcia-Fuente, F. Baur, F. Cimpoesu, A. Vega, T. Jüstel, W. Urland,\n Chem. Eur. J. 24, 16276 (2018).

12:35: [ChemistrySatAM04]
Spinodal Decomposition in the TiO2-VO2 system
Zenji Hiroi¹ ; ¹Institute for Solid State Physics, University of Tokyo, Kashiwa, Japan;
Paper Id: 184 [Abstract]

Spinodal decomposition is a ubiquitous phenomenon leading to phase separation from a uniform solution. We show that spinodal decomposition occurs in a unique combination of two rutile compounds of TiO₂ and VO₂ [1-3], which are chemically and physically distinguished from each other: TiO₂ is a wide-gap insulator with photocatalytic activities, and VO₂ is assumed to be a strongly correlated electron system which exhibits a dramatic metal-insulator transition at 342 K. Spinodal decomposition takes place below 830 K at a critical composition of 34 mol% Ti. It generates a unidirectional composition modulation along the c axis with a wavelength of approximately 6 nm, and finally results in the formation of self-assembled lamella structures made up of Ti-rich and V-rich layers stacked alternately with 30-50 nm wavelengths. A metal-insulator transition is not observed in quenched solid solutions with intermediate compositions, but emerges in the thin V-rich layers as the result of phase separation. Interestingly, the metal-insulator transition remains as sharp as in pure VO₂ even in such thin layers and takes place at significantly reduced temperatures of 310-340 K. This is probably due to a large misfit strain induced by lattice matching at the coherent interface.

References:
[1] Z. Hiroi, H. Hayamizu, T. Yoshida, Y. Muraoka, Y. Okamoto, J. Yamaura, Y. Ueda, Chem. Mater. 25 (2013) 2202-2210.
[2] Z. Hiroi, Prog. Solid State Chem. 43 (2015) 47-69.
[3] Z. Hiroi, T. Yoshida, J. Yamaura, Y. Okamoto, APL Mater. 3 (2015) 062508.

SESSION: ChemistrySatPM1-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Sat Oct, 26 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Yuichi Shimakawa; Alain Demourgues; Session Monitor: TBA

14:00: [ChemistrySatPM105] Plenary
Carbon Nanotubes and Graphene Hybrid Materials Systems for Multifunctional Applications
Fernand D. S. Marquis¹ ; ¹San Diego State University, San Diego, United States;
Paper Id: 335 [Abstract]

Carbon nanotubes and graphene are almost perfect molecules with truly amazing combinations of thermal, electrical and structural properties. In order to achieve their full potential, they need to be fully integrated hybrid materials in all sorts of matrices. Full integration requires their development beyond conventional composites so that the level of the non-nanomaterial is designed to integrate fully with the amount of nanotubes and graphene. Here the nanomaterials are part of the matrix rather than a differing component, as in the case of conventional composites. In order to advance the development of multifunctional materials and to integrate nanotubes and graphene, this research is focused on the simultaneous control of the nano-architecture, structural properties, thermal and electrical conductivity of fully integrated hybrid materials. These hybrid material systems are designed to surpass the limits of the rules of mixtures in conventional composite design. The goals are to implement multifunctional designs to fully mimic the properties of carbon nanotubes and grapheme on larger scales for enhanced thermal and electrical management in addition to the control of other properties such as strength, toughness energy and power. These new approaches involve exfoliation, functionalization, dispersion, stabilization, alignment, polymerization, reaction bonding and coating in order to achieve full integration. Typical examples of structural applications of polymeric and ceramic matrices and applications in energy systems such as capacitors and batteries as well as other material systems are presented and discussed.

References:
1. Marquis, F.D.S. “Carbon Nanotube Nanostructured Hybrid Materials Systems for Renewable Energy Applications” JOM, Vol 63, 1 (2011) 48
2. Marquis, F.D.S. and L.P.F. Chibante “Improving the Heat Transfer of Nanofluids and Nanolubricants with Carbon Nanotubes” JOM, 12 (2005) 32-44.
3. Functional Composites of Carbon Nanotubes & Applications”, Lee, K-P, Gopalan, A.I. and Marquis, F.D.S. Marquis, Research Signpost (2009), ISBN 978-81-7895-413-4.
4. Marquis, F.D.S. “The Nanotechnology of Carbon Nanotube Nanofluids” in “Functional Composites of Carbon Nanotubes and Applications”, Lee, K-P, Gopalan, A.I. and Marquis, F.D.S. Marquis, ISBN 978-81-7895-413-4, (2009).

14:25: [ChemistrySatPM106]
Combined experimental and modelling approaches for assessing and predicting the existence of new phases in the field of Solid State Chemistry
Jean Etourneau¹ ; Samir F. Matar² ; ¹University of Bordeaux, Bordeaux, France; ²Lebanese German University, Jounieh, Lebanon;
Paper Id: 370 [Abstract]

In this presentation it will be shown, through examples chosen in the field of Solid State Chemistry based (i) on light p elements (B,C,N), a proposition of a new ultra-hard carbon nitride C2N1 and (ii) on p and 3d elements (B,Cr), a new di-chromium hexaboride Cr2B6 exhibiting a 2D boron network,. in addition to the phases identified experimentally: Cr2B, Cr5B3, CrB, Cr3B4, Cr2B3 and CrB2. Investigation and concepts first arising from experimental observables are shown to be aided and accelerated via First Principle calculations of energy and energy related quantities and the electron transfer and electron localization between atoms will be illustrated by using the electron localization function (ELF)2,3.

References:
1- High pressure in solid state chemistry: Combined experimental and modelling approaches for assessing and predicting properties, Jean Etourneau, Samir F.Matar, Solid State Sciences 80 (2018) 178-195
2- D.Becke, K.E. Edgecombe; J.Chem.Phys., 92 (1990) 5397
3- .F. Matar, Prog.Solid State Chem., 41, Issue 3, (2013) 55-85

14:50: [ChemistrySatPM107] Keynote
High Energy Primary Lithium Battery using Oxidized Sub-Fluorinated Graphite Fluorides
Marc Dubois¹ ; ¹Clermont Auvergne University, Aubière, France;
Paper Id: 283 [Abstract]

Although primary lithium batteries have shown promising performances as a cathode, only a few works have been devoted to graphite oxyfluorides [1]. For such applications, most of the studies about covalent Graphite Interclation Compounds (GICs) mainly concern graphite oxides (GO) [2] and graphite fluorides (GF) [3-10]. Nevertheless, the rare works on oxyfluorides suggest high potentialities, such as an energy density of 1347 Wh.Kg^-1 for a sample obtained by a two-step synthesis combining fluorination and oxidation and even 2265 Wh.Kg^-1, thus exceeding graphite fluorides [11]. Fluorinated oxides were highly capacitive while oxidized fluorides have highest discharge potential despite having the same graphite precursor. Such data demonstrated that engineering the synthesis enables to modulate the properties. Different graphite oxyfluorides were synthesized via Hummer's oxidation of sub-fluorinated graphites in order to maintain sp² carbon atoms available for the oxidation, C-F bonds being non-reactive. In comparison with the graphite fluoride precursors, significant improvement of the energy density in primary lithium battery is achieved when the graphite oxyfluorides are used as cathode. When Hummer's oxidation was carried out on graphite fluoride with both the CF_0.60 composition and a homogenous dispersion of non-fluorinated regions into fluorinated lattice, oxidation focused on the remaining sp² carbon atoms and decomposed them. Defected graphite fluorides were then synthesized. The highest ever measured energy density in the primary lithium battery with fluorinated carbons as cathode, i.e. 2825 Wh.Kg^-1, was reached with this particular sample. Solid state NMR allowed the functional groups C-F, COC, COH, COOH and sp² C to be quantified in graphite oxyfluorides and fluorides and their role in electrochemical processes to be highlighted.

References:
[1] R.J. Lagow, R.B. Badachhape, J.-L. Wood, J.-L. Margrave, Some new synthetic approaches to graphite-fluorine chemistry. Dalton Trans. 12 (1974) 1268-1273.
[2] H.F. Hunger, G.J. Heymach, Cathodic Discharge of Graphite Intercalation Compounds in Organic Electrolytes. J Electrochem Soc. 120(9) (1973) 1161-1168.
[3] T. Nakajima, Fluorine-carbon and fluoride-carbon materials: chemistry, physics, and applications. New York: Marcel Dekker, 1995. p337.
[4] Y. Kita, N. Watanabe, Y. Fujii, Chemical composition and crystal structure of graphite fluoride. J Am Chem Soc. 101(14) (1979) 3832-3841.
[5] W. Radorff, Radorff G. Zur Konstitution des Kohlenstoff-Monofluorids. Z Far Anorg Chem. 253(5-6) (1947) 281-296.
[6] K. Braeuer, Feasability study of the lithium/CxF primary cell. R&D Technical Report ECOM-3322. 1970.
[7] R.J. Lagow, R.B. Badachhape, J.L. Wood, J.L.Margrave, Some new synthetic approaches to graphite-fluorine chemistry. J Chem Soc Dalton Trans. 12 (1974) 1268-1273.
[8] M.A. Reddy, B. Breitung, M. Fichtner, Improving the Energy Density and Power Density of CFx by Mechanical Milling: A Primary Lithium Battery Electrode, ACS Appl. Mater. Interfaces 5 (2013) 11207-11211.
[9] T. Nakajima, Fluorine-carbon and fluoride-carbon materials: chemistry, physics, and applications. New York: Marcel Dekker, 1995. p337.
[10] I. Al-Saleh, Oxyde, fluorure et oxyfluorure de graphite: synthèse-Étude structurale-propriétés electrochimiques, Clemont-Ferrand University France, PhD thesis, 1992.

15:15: [ChemistrySatPM108]
The Fascinating World of Fluoropolymers: From the Synthesis to Applications
Bruno Ameduri¹ ; Mohammad Wehbi² ; ¹Institute Charles Gerhardt Montpellier, Montpellier, France; ²ICGM, Montpellier, France;
Paper Id: 38 [Abstract]

Fluoropolymers are valuable materials endowed with outstanding properties that allow them to be involved in many High-Tech applications [1]. This presentation aims at reporting how the design of functional fluoropolymers may influence the properties and applications. Actually, 2-trifluoromethacrylic acid (MAF) is a versatile building block for the synthesis of new functional monomers. [2] It can be homopolymerized by anionic initiation [2-3] but fails in the presence of any radical systems. However, its radical copolymerization with vinylidene fluoride (VDF) has been successful. This presentation reports overall strategies to synthesize novel functional 2-trifluoromethacrylate monomers and macromonomers, as well as their radical copolymerization with VDF, leading to various materials such as higher thermal stable thermoplastics,[4] polymer gel electrolytes for Lithium ion batteries,[5-7] and anticorrosion [8] and adhesive hybrid coatings [9] (Figure 1). Figure 1 shows the overall strategies to synthesize novel functional 2-trifluoromethyl monomers from 2-trifluoromethacrylic acid (MAF) and their radical copolymerization with VDF (left). The figure also shows steel plates coated with poly(VDF-co-MAF Phosphonate) copolymer at the beginning of the experiment (A), after 1 h (B), and after 18 h (C). (D): uncoated steel plate used as reference sample after 1 h (right). Tosoh FineChem Corporation (Shunan, Japan) is acknowledged for suppling MAF monomers.

References:
[1] B. Ameduri, and H. Sawada; Fluoropolymers: Applications; vol. 2, RSC, Oxford, 2016.
[2] Y. Patil and B. Ameduri, Progr. Polym. Sci., 38 (2013), 703-739.
[3] T. Narita, a) Makromol. Chem. Rapid. 6 (1985) 301-304; b) J. Fluorine Chem. 131 (2010), 812.
[4] M. Wadekar, Y. Patil, B. Ameduri, Macromolecules, 47 (2014) 47, 13-25.
[5] A. Alaeddine, J. Vergnaud, D. Vlad, J.F. Gohy, B. Ameduri, Polym. Chem. 6 (2015) 6021-6032.
[6] M. Wehbi, J. F. Gohy et al. J. Mat Chem. A, 6 (2018) 8514-8526.
[7] M. Wehbi, J. Brassine, et al., Macromolecules, 52 (2019) DOI: 10.1021/acs.macromol.9b00355.
[8] S. Banerjee, M. Wehbi et al., ACS Appl. Mater. Interface, 9 (2017) 6433-6443.
[9] M. Wehbi, S. Banerjee, et al., Macromolecules, 50 (2017) 50, 9329-9339.

SESSION: ChemistrySatPM2-R9	Tressaud International Symposium on Solid State Chemistry for Applications and Sustainable Development
Sat Oct, 26 2019 / Room: Aphrodite A (100/Gr. F)
Session Chairs: Werner Urland; Zenji Hiroi; Session Monitor: TBA

15:55: [ChemistrySatPM209] Plenary
Future of Electron Correlated Materials: from Multiferroics to Nanomagnets and to Thermoelectrics
Bernard Raveau¹ ; ¹University of Caen, Normandy, France;
Paper Id: 171 [Abstract]

Numerous studies have been performed these last three decades on perovskites and derivatives showing the possibility to create and to tailor exciting physical properties. This has been previously exemplified by the high Tc superconducting cuprates, the colossal magnetoresistance manganates and the thermoelectric cobaltates. Herein we describe several new classes of materials that appear most promising for the generation of attractive physical/ chemical properties and applications. <i>Multiferroic materials</i>, involving the coexistence of ferroelectricity and ferromagnetism, have been the object of numerous investigations due to their potential application for memory devices. In this respect, oxides with a triangular sub-lattice present a rich potential which to date has not been fully investigated. The mixed valent "114" tetrahedral cobaltates open the route to attractive multiferroic properties as exemplified by the magneto-electric ferrimagnet CaBaCo₄O₇ which exhibits gigantic magnetic field induced polarization and high magneto-electric coupling. Beside oxides, Hybrid organic-inorganic frameworks (HOIF) represent an important source for the realization of multiferroic properties which has been, to date, insufficiently explored. In particular, transition metal phosphonates with a layered structure offer a potential for the realization of magneto-electric properties by coupling spins of the inorganic layers with electric dipoles of the organic layers. This is illustrated by the non-centro symmetric layered metal-phosphonate, MnO₃PC₆H₄Br.H₂O, whose structure consists of perovskite layers stacked with organic bromo-phenyl layers. This compound has been designed from the layered phosphonate MnO₃PC₆H₅.H₂O; It exhibits complex magnetic features which are exactly captured in T and H-dependent dielectric constants, ɛ'(T) and ɛ'(H). This demonstrates direct ME coupling in this designed hybrid and yields a new path to design a magnetoelectric hybrid. Low dimensional magnets, especially single molecule magnets (SMM) and single chain magnets (SCM) have been thoroughly investigated in metal organic frameworks in view of applications in quantum computing, spintronics and memory devices. In contrast, similar features were only recently reported for spin chain oxides built up of face-sharing MnO₆ octahedra and CoO₆ trigonal prisms. We describe the huge potential of one dimensional A_1x+(Mn_2-xCo_x)O_3+δ oxides with A=Ca, Sr, Ba whose aperiodic structures can be designed by considering a mechanism of extra oxygen incorporation (EOI). We show that these oxides exhibit a crossover from a single chain magnet (SCM) to a long range order (LRO), or more exactly, to a partially disordered antiferromagnetic (PDA) behavior. Thermoelectric (TE) materials, which allow the conversion of waste heat into clean electricity, have been the object of extensive investigations in last fifteen years. Quite a limited number of sulfides have been investigated to date in spite of the rich crystal chemistry of these materials that offers a promising route for the discovery of new physical properties. This is exemplified by the copper rich sulfides with a 3D tetrahedral conductive "Cu-S" framework. The presence of large amounts of univalent copper in these materials makes them remarkable p-type thermoelectrics. Various frameworks can be realized by mimicking the natural minerals such as stannite, bornite, colusite, germanite and stannoidite. The very recent discovery of the thermoelectric colusites Cu₂₆T₂Ge₆S₃₂with T=Mo, W, Cr which exhibit outstanding power factors and high ZT figures of merit, illustrates the great potential of these materials.

16:20: [ChemistrySatPM210]
Impact Of Trepca Mine On Drinking Water In Some Villages And Its Impact On Health
Florent Dobroshi¹ ; ¹Universiteti i Mitrovices "Isa Boletini", Mitrovica, Kosovo;
Paper Id: 72 [Abstract]

The main purpose of this study was to identify some physical and chemical characteristics of drinking water in some villages in the vicinity of the "Trepca" mine. A part of Kosovo’s economic development has primarily been oriented towards the development of the mining sector for the sake of large natural and underground resources. Exploitation technologies as well as processing technology were not at the level as they are nowadays. Consequently, many problems have also been inherited in the field of the environment. Here, first of all, the environmental impact of industrial wastes, industrial plants, mining landfills, chemical landfills and the agriculture sector should be highlighted. The study consists of physical-chemical bacteriological analysis and determination of heavy metals in underground waters in some villages around the "Trepeca” mine. Based on these analyzes, the possibility of using sources of this water as drinking water was tested. Water is a substance with a number of unique attributes that acknowledge the existence of the living world in general, as well as the existence of the industry. Drinking water acidity is emphasized in these villages, due to the strong impact of the "Trepca" Mines, and of course there is no branch of the industry that does not use this water. Physico-chemical and bacteriological analyzes were carried out at the National Institute of Public Health in Mitrovica, whereas the determination of heavy metals was done at the Mining Laboratory with Flotation in the "Trepeca" in Mitrovica. Qualitative assessment consisted in analyzing key indicators as well as comparing them with drinking water standards according to the Standards of Direc. 98/83 EC, WHOs. The main purpose was to search through physical-chemical parameters to determine the quality of drinking water in these villages and highlight the determination of acidity. I think this will serve the first point of the local population living in the vicinity of the source. I also believe that the results will be used by state institutions as a basis for further research.

References:
mining sector, water resources, physic-chemical, bacteriological, metals and health indicators

16:45: [ChemistrySatPM211] Invited
Modified Fluoride ZBLAN Glasses
Maria Brekhovskikh¹ ; Liudmila Moiseeva² ; ¹Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russian Federation; ²Prokhorov General Physics Institute of the Russian Academy of Sciences, Moscow, Russian Federation;
Paper Id: 57 [Abstract]

Fluoride glasses have been an attractive material for thirty years in shorter optical devices with applications lying in the visible and mid IR spectral range due to their low phonon energy (~500-600 cm-1). In this review, the information on glass-forming fluoride systems is presented, and the main methods for synthesizing glasses on the basis of fluorides of the metals of Groups IIV, their physicochemical properties, techniques for producing fibers, areas of application, and the techniques for purifying them from undesired impurities are discussed. Modern materials science studies in the area of fluoride glasses are aimed at searching for glasses activated with rare-earth elements (REEs) or transition elements with a broad IR transmission range and high optical homogeneity. This is in the purpose of creating efficient active optical media in a wide spectral range [1-3], as well as creating converters of IR radiation into the visible range for enhancing the efficiency of solar cells[4]. At present, the fluoride phosphors activated by Mn⁴⁺ ions, which emit a narrow-band spectrum in the red region and absorb strong optical radiation in the blue spectral region, are considered to be the most promising light converters. The modified fluorozirconate glasses (ZBLAN) doped with BaCl₂, BaBr₂ MnO₂ were synthesized and their luminescence and EPR spectra were measured. As a result, we synthesized a new phosphor based on fluorozirconate glass doped with manganese ions, in which a long-wavelength shift of the manganese green luminescence band into the red region (610 nm) has been found.

References:
[1] J.-L. Adam, Non-oxide glasses and their applications in optics, J. Non-Cryst. Solids 287 (2001) 401-404.\n[2] J. Lucas, F. Smektala, J.-L. Adam, Fluorine in optics, J. Fluor. Chem. 114 (2002) 113-118.\n[3] B. Boulard, Fluoride glasses and planar optical waveguides, in: A. Tressaud (Ed.), Functionalized Inorganic Fluorides, Jonn Wiley & Sons. Ltd., UK, (2010) p. 538.\n[4] S. Schweizer, B. Henke, P.T. Miclea, B. Ahrens, J.A. Johnson, Multi-functionality of fluorescent nanocrystals in glass ceramics, Radiat. Meas. 45 (2010) 485-489.\n[5] M. N.Brekhovskikh, S. Kh.Batygov, L. V.Moiseeva, S. P.Solodovnikov, I. A.Zhidkova, G. L. Denisov, and V. A. Fedorov , Optical Properties and Electron Paramagnetic Resonance of MnO2-Doped Fluorozirconate Glasses, Inorganic Materials, 54, (2018), 1157-1161.

: [Ferro-alloysAM]
Test
Sara Deybali¹ ; ¹, Roxboro, Canada;
Paper Id: 364 [Abstract]

Since 1973 the European Industry has been dealing with a growing regulatory pressure that obliged to generate additional cash flow to be invested in environmental protection -process and equipment- resulting in the correspondent increase of the operating costs without any or negligible financial compensation. Nevertheless those policies have greatly contributed not only to the reduction of the pollutants and to the improvement of the quality of life but also they have been a driver for an unparalleled industrial sustainable development across the states members of the EU. This presentation will review the regulatory steps and the contribution of the Copper industry to the above joint endeavor.

: [Ferro-alloysAM]
rkgvsegw
Perla Basho¹ ; ¹Flogen, Mont Royal, Canada;
Paper Id: 366 [Abstract]

Since 1973 the European Industry has been dealing with a growing regulatory pressure that obliged to generate additional cash flow to be invested in environmental protection -process and equipment- resulting in the correspondent increase of the operating costs without any or negligible financial compensation. Nevertheless those policies have greatly contributed not only to the reduction of the pollutants and to the improvement of the quality of life but also they have been a driver for an unparalleled industrial sustainable development across the states members of the EU. This presentation will review the regulatory steps and the contribution of the Copper industry to the above joint endeavor.

: [Ferro-alloysAM]
Test 1001 MySQL
Claude Tetom¹ ; ¹Flogen&Technologies, Mont-Royal, Canada;
Paper Id: 341 [Abstract]

It's very useful to see your query in order to detect problems with syntax. Most often, the output message from MySQL doesn't let you see enough of the query in the error message to let you see where your query went bad- it a missing quote, comma, or ( or ) could have occured well before the error was detected. I do -not- recomend using this procedure, however, for queries which execute on your site that are not user-specific as it has the potential to leak sensative data. Recomended use is just for debugging/building a script, and for general user-specific queries which would at the worst, leak the users own information to themself.