ORALS

SESSION: IronMonAM-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Mon Nov, 5 2018 / Room: Mar Azul (50/1st)
Session Chairs: Florian Kongoli; Fausto Varela Cançado; Session Monitor: TBA

11:20: [IronMonAM01] Plenary
The Rise and Fall of the Northern Brazilian Pig Iron Production
Paulo Afonso Gomes¹ ; ¹Consultant, Belo Horizonte, Brazil;
Paper Id: 370 [Abstract]

In July of 1967, an unexpected landing of a Vale's helicopter was the cause of the discovery of the minerals in the province of Carajas. The mines of Carajas, located in the Para State, are today among the biggest iron ore deposits in the world, that contain also manganese, copper and gold minerals. In 1985, Vale made its first transportation of iron ore through the railroad of Estrada de Ferro Carajas and exported it by shipping it out from the port of Ponta da Madeira. Aided by the incentives given by the Brazilian Government and Vale to develop this region of Brazil, many companies from Minas Gerais state came to Para and Maranhao states and started producing pig iron using mini Blast Furnaces, Vale granulated iron ore, and charcoal made out of the sawmill wood residues that were previously exported. These factors created perfect conditions for pig iron production. As a result, the installed capacity reached more than 5 million tons of pig iron per year, and the production reached its peak between 2006-2008. Today, less than 30 years later, only one company is producing pig iron for export, while only two others are producing pig iron to use solely in their own steel plants without selling it in the market. The questions of what happened with this boom and bust, and what should be done to remedy this situation remains unanswered. Did the pig iron production using Mini Blast Furnaces that was dominant in this area became unfeasible with high Capex and Opex? Can the production of pig iron resume in a feasible way? Can this be done through a new, more feasible technology that might able to replace the mini blast furnaces with lower Capex and Opex? In the latter case, what should be done with existing Eucalyptus forests planted by the pig iron producers to produce charcoal for mini blast furnaces? And in general: what does the future look like for this region of Brazil? This paper responds to these questions and proposes some solutions which are submitted for a wider discussion.

11:45: [IronMonAM02] Plenary
Sustainable Production of Pig Iron in Brazil
Fausto Varela Cançado¹ ; ¹SINDIFER, Belo Horizonte, Brazil;
Paper Id: 376 [Abstract]

Brazil produces important volumes of pig iron from domestic ores using various extraction technologies, and also has important current and potential capacities to produce pig iron in a sustainable way. In this paper, a detailed overview of the pig iron production in Brazil is carried out from the point of view of plant locations, their capacity and characteristics, the type of products and their specifications as well as the thermo-reduction agent used. Special attention is given to Minas Gerais and Espirito Santo states, which are the most important for pig iron production in the Brazilian Federation. A distinct part of the paper is an analysis of the use of charcoal as a thermo-reduction agent in the extraction technologies that produce pig iron, and its advantages compared to the use of metallurgical coke in terms of sustainability. The sustainability programs are specifically discussed, along with the current stimulus and barriers for the pig iron industry.

12:10: [IronMonAM03] Plenary
Viena Siderurgica: A Successful Story of Sustainable Pig Iron Production
Rodrigo Valladares¹ ; ¹Viena Siderúrgica S/A, Açailândia, Brazil;
Paper Id: 387 [Abstract]

Viena Siderurgica, which is celebrating its 30th anniversary of operations in November 2018, is the largest pig iron producer and exporter in Brazil, with an achieved production of 401,917 MT in 2017 and an expected production over 500,000 MT in 2018. The key factor of the company's success is the continuous investment in three sustainable directions: (a) biomass production, forestation, and reforestation, and its equal consumption of the forest for charcoal production in order to achieve a zero CO₂ balance ; (b) sinter plants that use the fines of iron ores and coke in order to minimise waste and increase productivity; and (c) power plants in order to effectively use the heat produced in the blast furnaces to produce electric energy that inputs in the public electric grid. The story of the company proves that investing in sustainability is also a key to survival and market success.

12:35: [IronMonAM04] Plenary
FLOGEN CONTOP Design, Decision-Making, Control, Optimization and Automation System Applied at Brazilian Blast Furnaces
Paulo Afonso Gomes¹ ; Marcos De Souza² ; Florian Kongoli³ ; ¹Consultant, Belo Horizonte, Brazil; ²FLOGEN Technologies, Sao Paulo, Brazil; ³FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 417 [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 makes instantaneously 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 10%, the decrease of total consumption of charcoal (breeze and fines) by about 5%, the increase of fines injected through the tuyeres, a better control of pig iron and slag temperatures, minimization of silica addition (less charcoal consumption), a better control of pig iron composition (mainly Si and P), and complete mass and energy balance. The CONTOP system was also used to determine the annual procurement strategies and different scenarios and to determine raw material cost-based scenarios regarding productivity, fuel consumption and to develop specific useful scenarios for this purpose. 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.

SESSION: IronMonPM1-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Mon Nov, 5 2018 / Room: Mar Azul (50/1st)
Session Chairs: Tateo Usui; Jose Carlos D Abreu; Session Monitor: TBA

14:00: [IronMonPM105] Plenary
Characterization of Fine and Coarse Sludges of LD Peruvian Steelworks
Mery-cecilia Gomez Marroquin¹ ; Kenny Salazar¹ ; Jose Carlos D Abreu² ; ¹National University of Engineering, Lima, Peru; ²PUC-Rio, Rio de Janeiro, Brazil;
Paper Id: 134 [Abstract]

Nowadays, one of the most important global issues in the steelmaking industry is the benefits of recycling or provision of the particulate wastes generated by blast furnaces, LD / BOF converters, and electric arc furnaces. Transportation costs, disposal in appropriate places, and increasing environmental constraints are demanding steel companies for ways to avoid, minimize, and / or properly treat their residues. Several solid residues in the form of slags, powders, and sludges emerge from reactor steel plants, such as blast furnaces, electric arc furnaces, converters, and Basic Oxygen /Linz Donawitz - LD. The chemical composition of these residues depends on the load fed to these reactors. This waste may contain: Fe, C, Ca, Zn, Pb and others hazardous elements, which can be reused in a sustainable manner [1]. The LD Oxygen Converter is the most common process for the production of steel in the world. Institutions, such as United States Geological Survey (USGS) and World Steel Association, noted that the Basic Oxygen Furnace LD/BOF produced 40% of the total steel from the USA (USGS, 2014) and 70% of the total steel produced in the world (World Steel Association, 2014) [2]. However, the production of steel through LD converters also generates a large amount of gaseous discharge of emissions which are collected through gas cleaning systems. This waste can be of two types: powders (dry material - BOF OG) and sludges (wet material - BOFS). The production of BOF OG can vary between 0.75 and 24 kg/tLS based on European Commission (Remus et al., 2013). The generation of BOF OG on average is 18 kg/tlS (American Iron and Steel Institute, 2001). In 2015, world steel production reached 78.8 thousand tons in the USA and 1620 million tons in the world (World Steel Association, 2016). According to information from the World Steel Association, in 2013, 626 thousand tons of BOF OG were generated only in USA and around 20 million tons worldwide[3]. In Brazil, about 80% of crude steel production comes from LD converters. In addition, this country had the great advantage of owing ore deposits with high iron contents and low contents of contaminants. In terms of environmental performance, LD steelmaking gas is very rich in CO, and is more suitable for the process of self-power generation. It is also necessary to develop other more noble ways of using LD steel slag, as well as the treatment of sludges and emissions containing powders [4]. In Peru, previous studies on characterization of sludges in LD steelworks have not been reported or published specifically in continuous form, as it had been with the characterization and treatment of electric arc furnace dusts (EAFD). This fact makes it novel and relevant, and through this complete characterization of both fine and coarse sludge samples of LD steelwork, this project will attempt to predetermine a sequence of carbothermic self-reduction treatments that may or may not add up to coal fines collected from other sources, in order to obtain high grades of iron metallization and controlled extraction/separation mainly in the form of vapor from metals such as zinc and lead [5, 6]. Therefore, the sludges of LD steelworks are important for their significant iron contents as well as its low phosphorus content, which can be reinserted into the production system for reuse [7]. Therefore, this waste accumulated by the Peruvian steel industry (especially the old sediments of LD converter) will tend to be reused in the steel plant itself, to give an added value to this material that until now is constituted as an environmental liability of considerable economic value. The experimental methodology in this work comprised the characterization of materials from a sludge site, mainly the coarse and fine sludges generated at a primary wet LD dedusting system. It is for this purpose, that the following were utilized: chemical analysis, Atomic Absorption, X-Ray Diffraction, Optical Microscopy-OM and Scanning Electron Microscopy-SEM, Scanning Thermal Analysis-STA, Differential Scanning Calorimeter-DSC, Thermogravimetric Analysis-TGA, Diferential Thermogravimetric Analysis-DTG, and physical properties such as specific gravity and average particle size. From these characterizations, the following technological routes were suggested: a) the production of coarse/fine residues composite briquettes, to be used as burden in ironmaking reactors; b) the production of coarse/fine self-reducing briquettes, complemented by a carbon resource in their composition, to be used as an alternative cooling material for the liquid steel temperature control and as burden in reactors demanding fast iron metallization.

References:
[1] Das B, Prakash S, Reddy PSR, Misra VN. An overview of utilization of slag and sludge from steel industries. Resources, Conservation and Recycling. 2007; 50: 40-57
[2] El Acero. Fabricacion y los procesos de transformacion en caliente. Available in: https://www.scribd.com/doc/98463629/Convertidor-Ld
[3] Naiyang Ma. Recycling of basic oxygen furnace steelmaking dust by in-process separation of zinc from the dust. Journal of Cleaner Production. 2016; 112: 4497-4504.
[4] Centro de Gestao e Estudos Estratagicos Siderurgia no Brasil 2010-2025. Serie de Documentos Tecnicos Novembro 2010. NA. 09 p. 53-54.
[5] Gomez-Marroquin, Mery C.; D'Abreu, J. C. Comparative Study of Zinc Ferrite and EAF Dust Reduction by CO-CO2 Mixture. SIPS 2016-Sustainable Industrial Processing Summit & Exhibition, Sanya-China 2016.
[6] Gomez-Marroquin, Mery C.; D'Abreu, J. C. Characterization of Peruvian Linz Donawitz-LD Steel Sludges. SIPS 2017-Sustainable Industrial Processing Summit & Exhibition, Cancun-Mexico 2017.
[7] D'Abreu, J. C.; Falero E.E.T, Kohler, H. M; Bentes, M. A. G.; Oliveira, L. F. R. Briquetes Autorredutores de Residuos da Siderurgia Integrada: Reducoes em Fase Salida e Liquida. In: 45 Seminario de Reduceo de Minerio de Ferro e Materias Primas. Abmweek-2015. Sao Paulo-Brasil, 2015.

14:25: [IronMonPM106] Plenary
Reduction behavior of composite manganese ore-carbon: an analysis
Cyro Takano¹ ; Jose Dabreu² ; Ricardo Braga¹ ; Ferry S Belisario Benique³ ; Flavio Beneduce⁴ ; ¹University of Sao Paulo, Sao Paulo, Brazil; ²PUC-Rio University, Rio de Janeiro, Brazil; ³Catholic University of Rio de Janeiro, Rio de Janeiro, Brazil; ⁴USP, Sao Paulo, Brazil;
Paper Id: 401 [Abstract]

There is a great diversity of minerals containing manganese. The important ones are psilomelane (Ba,H₂O)₂Mn₅O₁₀) pyrolusite (MnO₂), criptomelane (K(Mn⁺⁺⁺⁺,Mn⁺⁺)₈O₁₆), rhodochrosite (MnCO₃) and some ore with high content of iron oxides. For ferro-manganese production, the accepted reduction steps are gas/solid reaction to reduce higher oxides to lower ones (MnO₂> MnO and Fe₂O3>FeO) and at temperatures higher than around 1000°C gas/solid, solid/solid, liquid/solid and liquid/liquid reactions. The liquid/liquid and metal/slag reactions are the predominant ones at conventional Smelting Electric Furnace, for effective reduction of MnO>Mn at temperatures (~>1300°C) and it involves slag formation, dissolution of MnO in the slag, reduction of Mn++ in slag by carbon embebeded by slag or by slag/metal reaction by carbon dissolved in liquid Fe-Mn(MnxCy). The result is low production rate due to slow reactions. This paper analyzes some important effects from the characteristics of the manganese ores for ferromanganese production, such as: gangue and mineral compositions regarding the components that may form liquid phase during high temperature processing, impairing the rate of reduction of manganese ore-carbon composite. It may conclude that ores with high manganese content and low content of silica, iron oxide, (and others which may form liquid phase-slag at temperatures around 1350/1400°C) are prone to having better reduction behavior and consequently higher productivity and lower energy consumption.

References:
1 Braga, R.S., Takano, C., Mourao, M.B. Prereduction of self-reducing pellets of manganese ore. Ironmaking & Steelmaking. London. The Institute of Materials, Minerals and Mining. 2007, v.34, no. 4, pp. 279-284. ISSN: 0301-9233.\n2 Benique, F.B., DAbreu, J.C., Kohler, H.M., Rodrigues, R.N. Auto-reducao carbotermica de aglomerados de oxidos de manganes. Proc. 7th Japan-Brazil Symposium on Dust Processing-Energy-Environment in Metallurgical Industries. ABM-Sao Paulo- Brazil Sept 2008. pp 1-10

14:50: [IronMonPM107] Plenary
Rate Enhancement of Composite Iron Oxide Pellets by Using Semi-char and Semi-charcoal
Tateo Usui¹ ; Hirokazu Konishi² ; Kazuhira Ichikawa³ ; Hideki Ono² ; Hirotoshi Kawabata² ; Francisco Pena⁴ ; Matheus Souza⁴ ; Alexandre Xavier⁴ ; Paulo Assis⁴ ; ¹Osaka University, Ibaraki, Japan; ²Osaka University, Suita, Japan; ³JFE Steel Corporation, Fukuyama, Japan; ⁴UFOP (Federal University of Ouro Preto), Ouro Preto, Brazil;
Paper Id: 114 [Abstract]

The exhaustion of natural resources (quantity and quality) and CO₂ emission controls are becoming increasingly important in the steel industry. Several steel engineers studied various means to decrease the reducing agent at blast furnace for reduction of CO₂ emissions [1]. For example, the injection of waste plastics [2] and carbon neutral materials, such as biomass, into the blast furnace is a better alternative [3, 4]. In particular, biomass has the novel advantage of producing no CO₂ emissions, due to being carbon neutral. Production of carbon composite iron ore agglomerates that have good reducibility and strength is becoming one of the most important subjects [5]. Carbon composite iron oxide pellets using semi-char or semi-charcoal were produced from the measured results of the carbonization gas release behavior. The carbonization was done under a rising temperature condition, until arriving at a maximum carbonization temperature Tc,max to release some volatile matter (V.M.). Starting point of reduction of carbon composite pellet using semi-charcoal produced at Tc,max = 823 K under the rising temperature condition was observed at the reduction temperature TR = 833 K, only a little higher than Tc,max, which was the aimed phenomena for semi-charcoal composite pellet. As Tc,max increases, the emitted carbonization gas volume increases, the residual V.M. decreases and, as a whole, the total heat value of the carbonization gas tends to increase monotonically. The effect of the particle size of the semi-charcoal on the reduction rate was studied. When TR is higher than Tc,max, the reduction rate increases, as the particle size decreases. When TR is equal to Tc,max, there is no effect. With decreasing Tc,max, the activation energy E a of semi-charcoal decreases. The maximum carbonization temperature Tc,max may be optimized for reactivity (1/E a) of semi-charcoal and the total carbonization gas volume or the heat value.

References:
[1] T. Ariyama and M. Sato, ISIJ International, 46 (2006), 1736-1744.
[2] M. Asanuma, T. Ariyama, M. Sato, R. Murai, T. Nonaka, I. Okochi, H. Tsukiji and K. Nemoto, ISIJ International, 40 (2000), 244-251.
[3] T. Ariyama, R. Murai, J. Ishii and M. Sato, ISIJ International, 45 (2005), 1371-1378.
[4] T. Matsumura, M. Ichida, T. Nagasaka and K. Kato, ISIJ International, 48 (2008), 572-577.
[5] M. Nakano, M. Naito, K. Higuchi and K. Morimoto, ISIJ International, 44 (2004), 2079-2085.

15:15: [IronMonPM108]
Theoretical and Experimental Studies on Agglomeration of Fine Particles and Dispersion of Agglomerated Particles in Liquid
Yoshiei Kato¹ ; Md. Azhar Uddin¹ ; ¹Okayama University, Okayama, Japan;
Paper Id: 110 [Abstract]

For obtaining clean steel, it is important to remove nonmetallic inclusions from molten steel by agglomeration or dispersion of particles. Cold model experiments were carried out by using polymethymethacrylate (PMMA) particles of 2.8m in mean diameter and 3.0 mol/L KCl solution as solid and liquid phases, respectively, and compared with the calculated results of newly developed mathematical models. Three kinds of mixing practices were examined: mechanical stirring by an impeller, gas blowing, and ultrasonic irradiation. The PMMA agglomeration rate of impeller mixing explained by a turbulence agglomeration model was larger than that of gas blowing at the same energy input rate. By introducing a breakup model where the adhered particles on the bubbles were divided on the free liquid surface, the calculated results agreed well with the experiment. The ultrasonic irradiation promoted the dispersion of agglomerated particles, and the dispersion rate increased with the decreasing ultrasonic irradiation frequency and increasing electric power. However, as for impeller mixing, the dispersion proceeded at higher rotation speed and agglomeration occurred at lower speed. Based on the experimental results, mathematical models for ultrasonic irradiation and impeller mixing were developed, and the calculation of the temporal change in total number of particles agreed well with the experiment.

References:
[1] S. Sumitomo, K. Yoshitomi, M.A. Uddin, Y. Kato: ISIJ Int., 58(2018), 1-9
[2] T. Nakaoka: Kobe Steel Eng. Rep.,56(2006), 40-43
[3] S. Sumitomo, H. Koizumi, M.A. Uddin, Y. Kato: Ultrasonics-Sonochemistry, 40(2018), 822-831

SESSION: IronMonPM2-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Mon Nov, 5 2018 / Room: Mar Azul (50/1st)
Session Chairs: Juergen Antrekowitsch; Session Monitor: TBA

15:55: [IronMonPM209] Plenary
Steel Mill Dust - Only a Zinc Resource or a Potential Material for Multi Metal Recycling?
Juergen Antrekowitsch¹ ; Gustav Hanke¹ ; ¹University of Leoben, Leoben, Austria;
Paper Id: 448 [Abstract]

Steel mill dust nowadays is a well-known secondary resource for zinc. Most of the companies treating this dust operate the established waelz process. However, even though it is known as best available technology, it finally only recovers zinc and does not create any value out of the other metals contained in the dust such as lead, iron etc. Moreover, the waelz process generates huge amounts of new residues which become more and more difficult to landfill. The often promoted concept of circular economy also requires a more efficient use of different resources to avoid the loss of raw materials. With this even the waelz kiln operators have started to think about utilization of the resulting slags and an optimized use of the produced zinc concentrate which also includes lead. Beside this, new developments try to offer better solutions especially regarding the realization of zero waste strategies. This paper discusses different options for a multi-metal recovery out of steel mill dust from the technical as well as economical point of view. Special emphasis is put on a development done at the University of Leoben. This so called 2sDR-process (two-step-dust-recycling) tries to combine two general aims, the recovery of different metals and the generation of a high quality zinc product and is currently undergoing the upscaling process to a pilot plant size.

References:
[1] R�tten, J. (2011). Various Concepts for the Recycling of EAFD and Dust from Integrated Steel Mills, 3rd Seminar, Networking between Steel and Zinc, GDMB, Leoben.

[2] Antrekowitsch J, R�sler G, Steinacker S. State of the Art in Steel Mill Dust Recycling. Chemie-Ingenieur-Technik. 2015 ;87 (11):1498-1503

[3] Steinlechner, St. (2013). Amelioration and market strategies for zinc oxide with focus on secondary sources, Dissertation, Leoben.

[4] R�sler G., C. Pichler, J. Antrekowitsch und S. Wegscheider: �2sDR�: Process Development of a Sustainable Way to Recycle Steel Mill Dusts in the 21st Century. JOM 66 (2014) 9, S. 1721�1729

SESSION: IronMonPM2-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Mon Nov, 5 2018 / Room: Mar Azul (50/1st)
Session Chairs: Juergen Antrekowitsch; Session Monitor: TBA

15:55: [IronMonPM209]
The Renewability of Metal Resources, Recycling Opportunities and Limits
Juergen Antrekowitsch¹ ; Gustav Hanke¹ ; ¹University of Leoben, Leoben, Austria;
Paper Id: 358 [Abstract]

Primary resources nowadays show decreasing qualities regarding metal content and impurities. The alternative, to go for secondary raw materials like scraps and follow circular economy strategies, suffers from the often low availability of relevant scraps. In parallel the question, how limited Europe is in allowing new technologies to utilize possible metal resources, becomes important. In this context, a relatively new metal resource, by-products from metallurgical industry, have to be considered. Due to the long history of Europe in metal industry, huge amounts of such materials are available. Nevertheless, also in this case the question emerges, if Europe is able to cope with its limits to use this potential metal source in an appropriate way. The University of Leoben tries to realize an optimized use of various by-products combined with the development of a certification system, similar to procedures used in primary metallurgy to allow a better evaluation of by-products.

16:20: [IronMonPM210] Plenary
Energy, Environment and Economic Aspects of Orien Technology
Genrikh Dorofeev¹ ; Florian Kongoli² ; ¹Ferro-Technology, Moscow, Tula, Russian Federation; ²FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 375 [Abstract]

In a previous publication at FLOGEN SIPS 2016, ORIEN Technology was introduced as a new technology that is compact, energy intensive and self-sufficient. It is also environmentally friendly with numerous advantages compared to the classical iron and steel production technologies. In a subsequent paper at FLOGEN SIPS 2017, the basic physicochemical principles of this process were described. This included its special characteristics of direct liquid-state reduction of unique iron-ore cold-pressed briquettes which simultaneously achieve the reduction of iron ore out of the briquettes and convert it into steel. This process is performed in a single electric furnace unit and produces a unique iron melt of a special type in which the carbon exists in a non-equilibrium colloidal form that can be controlled to vary widely from 0.04% to 30%. This paper describes various unique characteristics and advantages of this process in terms of energy saving, environmental protection, economy and steel quality.

References:
[1] Dorofeev G and Kongoli F. Orien Technology, A Sustainable Paradigm Shift In Iron And Steel Industry. In: Kongoli F, Akiyama T, Nogami H, Saito K, Fujibayashi A, editors. Sustainable Industrial Processing Summit SIPS 2016 Volume 6: Yagi Intl. Symp. / Metals & Alloys Processing. Volume 6. Montreal (Canada): FLOGEN Star Outreach; 2016. p. 386-393.

[2] Dorofeev G and Kongoli F. Basic Physicochemical Principles of ORIEN Process - A Direct Iron Ore to Steel Technology. In: Kongoli F, Conejo A, Gomez-Marroquin MC, editors. Sustainable Industrial Processing Summit SIPS 2017 Volume 9: Iron and Steel, Metals and Alloys. Volume 9. Montreal (Canada): FLOGEN Star Outreach; 2017. p. 116-126

[3] G.A. Dorofeev, P.R. Yantovskiy, K.G. Smirnov, Ya.M.Stepanov. ORIEN Process for Smelting High-Quality Steels from Ore and Energy Raw Materials on the Principle of Energy-Self-Supplying. In: Ferrous metals. Volume 5. 2017. p.17-22.

[4] G.A. Dorofeev and etc. The Method of Liquid-Phase Production of Iron of Direct Reduction. Patent of the Russian Federation No. 2511419.

[5] G.A. Dorofeev and etc. The method for Steel Smelting in Electric Arc Furnace and Electric Arc Furnace. Patent of the Russian Federation No. 2539890.

[6] Patent of the Russian Federation No.2610975. The method for steel smelting in electric arc furnace. G.A. Dorofeev and etc.


[7] A.G. Shalimov, A.E. Semin, M.P. Galkin, K.L. Kosyrev. Innovative Development of Electric Steel Smelting: Monograph. Metallurgizdat; 2014. p.306

[8] L.A. Schulz - M. Elements of Non-Waste Technology in Metallurgy: A Textbook for Universities. In: Metallurgy; 1991. p.174.

[9] Yu.S. Yusfin, A.A. Gimmelfarb, N.F. Pashkov–M. New Metal Production Processes (Iron Metallurgy): Textbook for Universities. In: Metallurgy; 1994. p.320.

16:45: [IronMonPM211] Plenary
Improvements on Industrial Physical Processes Using Simulation
Nehemias Lacerda¹ ; ¹FEMTO Applied Sciences, Sao Jose dos Campos, Brazil;
Paper Id: 397 [Abstract]

There are three different main opportunities on process improvement in industry, to obtain more profitable and sustainable results: the conceptual design phase of a new project, the optimization of an existing equipment and the troubleshooting on non-conformities. The manufactured products and industrial processes exhibit a great number of physical phenomena. Many of those phenomena closely relates to Physics of Fluids and associated solutions. That engineering technique pays attention to the correction on the cause of non-conformities due to physical phenomena but never on its effects, reaching the intimacy of such processes, avoiding tedious and expensive trials and errors procedures. The methodology employed consists on studying the physical phenomena, that govern all the fluid flow which occurs in a physical process, that operate in a market product or industrial process, regarding to one of the three opportunities of improvements. An extensive review of up-to-date data basis publications, on similar phenomena and associated mathematical model, present in advanced technologies such as Aeronautics, Space and Defense, as well as basic principles books [1 to 5] provide the scientific basis for the search on a suitable solution. The final solution takes advantage on the understanding and correction of details present in fluid flow during CFD computer simulation of the physical processes, which involves its geometric characteristics and operational condition. The following industrial sectors are using solutions provided by FEMTO: aeronautics, space, defense, appliances, energy, aluminum, oil and gas, pulp and paper, sugar and alcohol, food, petrochemical, plastics, personal products, health and glass, among many others. The present work will explore several solution examples that improved both market products and industrial processes indicating the qualitative or quantitative gain obtained using mathematical modeling and high performance CFD simulation.

References:
1 - ANDERSON, J.D. (1995) Computational Fluid Dynamics. New York, NY: McGraw-Hill.
2 - ÇENGEL, Y.A. & CIMBALA, J.M. (2018) Fluid Mechanics: Fundamentals and Applications. New York, NY: McGraw-Hill.
3 - LIEPMANN, H.W. & ROSHKO, A. (2001) Elements of Gasdynamics. New York, NY: Dover.
4 - REYNOLDS, W.C. (1979) Thermodynamic Properties in SI: Graphs, Tables and Computational Equations for Forty Substances. Palo Alto, CA: Stanford Publishing.
5 - SHAPIRO, A.H. (1953) The Dynamics and Thermodynamics of Compressible Fluid Flow. New York, NY: John Wiley & Sons.

17:10: [IronMonPM212] Plenary
Feasibility of Iron Production by Electrowinning
Jose Adilson De Castro¹ ; Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 335 [Abstract]

Some metals, for example aluminium, and many rare-earths such as lanthanum and neodymium, are produced by electrowinning. Nowadays, the blast furnace is the typical process for iron and steel. However, through this process coal is needed, which generates pollution. It is possible to produce iron by igneous electrolysis, but there are also many problems. One of them is the high temperature of fusing iron, 1538°C. Thus, the process for iron is much more complicated than for aluminium, which melts at 660°C. Nevertheless, if electricity can be produced by renewable sources, such as solar and wind energy, iron production by molten oxide electrolysis can be economically feasible some moment in the future. Thus, the feasiblity of iron production by electrolysyis is directly related to the price of renewable energy. Solar and wind are intermittent sources, and energy storage is a big problem. But excess of energy produced on a windy day can be, for example, stored as a reduced metal, aluminium, or even steel. Excess solar energy produced during noon can also be stored as a reduced metal.

References:
[1] Umair Irfan. May 9, 2013. Cleaner, Cheaper Way to Make Steel Uses Electricity. Available at:
https://www.scientificamerican.com/article/cleaner-cheaper-way-to-make-steel-uses-electricity/

SESSION: IronMonPM3-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Mon Nov, 5 2018 / Room: Mar Azul (50/1st)
Session Chairs: TBA Session Monitor: TBA

17:40: [IronMonPM313] Plenary
Metallization and Carburization Kinetic in DR Shaft Furnaces
Edelink Efrain Tinoco Falero¹ ; Mauricio Otaviano² ; Jose Carlos D Abreu¹ ; ¹PUC-Rio, Rio de Janeiro, Brazil; ²Samarco Mining Company, Ubu, Brazil;
Paper Id: 135 [Abstract]

Presently, the production and consumption of DRI are continuously increasing, as a consequence of a specific condition of the NG market, generated for the economic impact assigned to the shale gas extraction technology. Considering this context, DRI can thus effectively improve the BF, EAF and LD converters' productivity and, consequently their competitiveness. In this work, the results of a cooperative research between PUC-Rio University and a Brazilian mining company are presented. Laboratory-scale simulation tests, using RD commercial pellets and typical industrial operational parameters of a bench market RD shaft furnace, were conducted and planned using statistical and factorial analysis. In the simulated experiments, the following three regions of the DR shaft furnace were considered: Reduction, Transition, and Cooling zones. Basically, three stages were considered in the research development: step one, which analyzed the reactions and equations concerning pellet metallization and carbon precipitation; step two, where the experiments focused essentially on the definition of the carburization kinetic equations occurring in the Transition and Cooling zones; and finally step three, which aimed to develop the "METCARB" computational program, conceived to mathematically simulate the metallization and carbon reactions along the height of the furnace. At last, an industrial case was presented in order to compare to the "METCARB" outputs.

References:
[1] Mamani Paco L.J. "Cinética da redução de pelotas de minério de ferro em condições simuladas de um reator Midrex"(MSc. Abstract, Pontifícia Universidade Católica; October 2010), 62-65.
[2] D'Abreu J.C., Kohler H.M., Rodrigues de Araujo D. "DRI Carburization in the Reduction Zone of a Shaft Furnace". (Samarco's Technical Seminar III: The Global Experience, Vitoria, Brazil 2008), 5.
[3] D'Abreu J.C., Vera, J. C., Kohler, H.M., Araujo, Contribution on DRI carburization Kinetics in the Reduction Zone of a Shaft Furnace Midrex Type. In: 15th Conferencia de Acería - Conferencia de Reducción, San Nicolás, Argentina. 5th Ironmaking Conference. San Nicolás: Argentine Institute of Metallurgy, 2005. v1. P.39-46.
[4] Belisario F, D'Abreu J.C., Otaviano M.M., Kohler H.M. "Simulação experimental da carburização de DRI em reator de cuba tipo Midrex". (40th Seminar of Iron ore and Raw Material Reduction 11th Brazilian Symposium on Iron Ore, Belo Horizonte-MG, September 2010).
[5] Turkdogan E.T, Vinters J.V. Catalytic effect of iron on decomposition of carbon monoxide. Part I. Metallurgical Transactions B, (vol 5, Jan 1974), 11-19.
[6] Towhidi N, Szekely J. The influence of carbon deposition on the reduction kinetics of commercial grade hematite pellets with CO, H2 and N2. Metallurgical Transactions B, (Vol. 14B, September 1983), 359-367.
[7] Szekely J., Tawil E.L. The reduction of hematite pellets with carbon monoxide- hydrogen mixtures. Metallurgical transactions B, (vol 7B, 1976), 490- 492.
[8] Szekely J, Choudhary M, Tawil E.L. On the reaction of solids with mixed gases, metallurgical transaction B, (vol 8B, 1975), 103.
[9] D'Abreu J.C, Kohler H.M, Tinoco Falero E.E. "Simulaceo Experimental e Modelamento Computacional da Metalização e Carburização simultâneas em Reatores RD de Cuba". Tese de Doutorado, Rio de Janeiro, Fevereiro 2016.
[10] D'Abreu J.C, Kolher H.M, Falero E.T, Otaviano M.M. (2015) on the simultaneous Iron Oxide Reduction and Carburization Kinetics, paper presented at the 144th TMS Annual Meeting, Orlando, Florida, 15- 19 March 2015
[11] D'Abreu J.C, Kolher H.M, Falero E.T, Otaviano M.M. (2015) Simultaneous metallization and DRI carburization kinetics in DR shaft furnaces, paper presented at the 7th International Conference on the Science and Technology of Ironmaking, ICSTI 2015, Cleveland Convention Center Cleveland; United States, 4- 7 May 2015

SESSION: IronTueAM-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Tue Nov, 6 2018 / Room: Mar Azul (50/1st)
Session Chairs: Libor Kraus; Michael Potesser; Session Monitor: TBA

11:20: [IronTueAM01] Plenary
Microstructure-related Issues for Miniaturized Tensile Tests
Jan Dzugan¹ ; Libor Kraus¹ ; Miroslava Sindelarova¹ ; Karel Sperlink¹ ; ¹COMTES FHT Inc., Dobrany, Czech Republic;
Paper Id: 106 [Abstract]

Mechanical characterization of construction materials is a fundamental step to enabling reliable design. Globally, many standards in the field of mechanical characterization have been developed. With improving FEM simulations and material models, the local properties and anisotropies become very interesting, as they can be implemented in FEM simulations. However, data on local properties should be provided based on so fan no-standard miniaturized specimens providing information for specific locations/orientation to feed material models. With specimens downsizing there are consequently many issues, such as geometrical similarity between standard and miniaturized specimens and probably the main one, the microstructure. As the miniaturized specimens for engineering applications should still be related to bulk material behavior, some critical number of grains should be within the volume of the specimens gauge section in order to represent polycrystal behavior. This paper deals with the investigation of grain size influence on tensile behavior determined with the use on miniaturized tensile specimens with gauge section thickness of 0.5mm. Tensile tests are a very basic test in the field of mechanical properties characterization, and specimens downsizing can be seen in many papers nowadays, eg. (1-2). It has been proven that the performance of miniaturized tensile tests in comparison to standard ones is very good. In order to set the boundaries up to which it is possible to go regarding the specimens cross section and maintain comparability with standard sized specimens, the grain size influence is investigated here. Two steels with several different grains sizes are investigated here. Various grain sizes were obtained by heat treatment, resulting in a wide range of the grain sizes. Tensile tests of standard specimens and miniaturized ones are carried out on the investigated heats of steels for comparison. The results obtained here point out that very good performance of miniaturized tensile tests in terms of providing information on "bulk" material behavior can be achieved, even with very few grains over the specimen's thickness.

References:
[1] Džugan, J., Prochazka, R., Konopik, P.: Micro-tensile test technique development and application to mechanical property determination, ASTM Special Technical Publication STP 1576, 2015, pp. 12-30.
[2] Gussev, M.N., Busby, J.T., Field, K.G., Sokolov, M.A., Gray, S.E.: Role of scale factor during tensile testing of small specimens, 2015, ASTM Special Technical Publication STP 1576, pp. 31-49.

11:45: [IronTueAM02] Plenary
Optimization Potentials for Steel Production from the Application of Oxygen Combustion
Michael Potesser¹ ; Johannes Rauch¹ ; Davor Spoljaric¹ ; ¹Messer Group GmbH, Gumpoldskirchen, Austria;
Paper Id: 118 [Abstract]

Oxygen combustion technologies are lowering the production costs of many processes, since energy costs are continuously raising. Oxygen is used more and more in combustion systems technologies, like oxygen burners, oxygen lancing, or oxygen enrichment, in order to increase the capacity or conserve energy in particular furnaces, Oxyfuel is used to provide discrete oxygen rich areas in a furnace to allow complete combustion separately from a reducing zone or lower the emission volumes. This article analyzes the possibilities and the advantages of oxygen application in different furnaces used for steel production, based on Messer results and literature review.

References:
[1] Holleis, B., Spoljaric, D., Adendorff, M.: Einsatz von technischen Gasen in Giessereien Sauerstoff bei Schmelzprozessen, Giesserei-Rundschau 52, 2005
[2] Milani et. al.: Flameless Technologies: Industrial Applications and R & D projects in Italy 5th International Symposium in Hight Temperature Air Combustion and Gasification, Tokyo, 2002
[3] Potesser, M., B. Holleis, A. Hengelmolen, H. Antrekowitsch and D. Spoljaric: Highest Efficiency and Economic burner concepts for the metallurgical industry. Proc. Light Metals 2008 (TMS), New Orleans, USA, 2008, 553 - 556
[4] Gross, G. and J.Vetter: Sauerstoff in Schmiedeofen steigert die Leistung und verbessert die Wirtschaftlichkeit, Gas Aktuell, 4, 1979,13-19
[5] Pardo N. et al: Prospective Scenario on Energy Efficiency and CO2 Emissions in the Eu Iron & Steel Industry, JRC Scientific and Policy Reports, 2012

12:10: [IronTueAM03] Plenary
Numerical Simulation of Softening Layer Shape with Variable Size of Blast Furnace
Dongjo Lee¹ ; ¹POSCO, Pohang, Gyeongbuk, South Korea;
Paper Id: 71 [Abstract]

Understanding the behaviour of softening layer is very important to the control and optimization of the blast furnace operation, because the softening layer has a strong influence on the gas flow in the blast furnace. Futhermore, location and shape of softening and melting layer has a heavy relation to the wearness of refractories. For these reasons, prediction of the softening layer is considered to be an important subject for different sizes of blast furnace. In this study, mathematical modelling has been conducted. The first step of the simulation is the prediction of the solid flow, such as large or small sintered ore cokes using VOF (Volume of Fluid) model; the second step is evaluating the permeability of the burden distribution; and finally, the distribution of gas, heat transfer, and reaction between solid and gas phase are simulated using multi-domain coupling. The layered materials were explicitly considered not an averaged value such as Lo/Lc. Basically, different softening layers may relate to different burden distributions at the furnace top. In addition, the profile and productivity of blast furnace are strongly linked to the location and shape of softening layer. To understand and to evaluate the effects of the blast furnace size on softening layer shape and location, simulation approaches have been conducted with #1(1,660m3), #2(2,550m3), #4 (5,600m3) blast furnace in Pohang, South Korea. As the size of the blast furnace increases, the shape of softening layer changes from reverse-V to L or W. With reverse-V shape of softening layer, coke slits are vertically spread and it is able to distribute the reducing gas uniformly. However, the distribution of gas worsens with L and W shape of softening layer, because of thick coke slits at the lower and wall side softening layer.

References:
[1] P. R. Austin, H. Nogami and J. Yagi, ISIJ International, Vol. 37, No. 5, 1997, pp. 458-467
[2] P. R. Austin, H. Nogami and J. Yagi, ISIJ International, Vol. 37, No. 8, 1997, pp. 748-755
[3] P. R. Austin, H. Nogami and J. Yagi, ISIJ International, Vol. 38, No. 3, 1998, pp. 246-255
[4] J. A. Castro, H. Nogami and J. Yagi, ISIJ International, Vol. 39, No. 1, 1999, pp. 15-22

12:35: [IronTueAM04] Plenary
Reduced Environmental Impact and Increased Energy and Material Recovery in the Ferro-alloy Industry Through Staged Combustion of Flue Gas
Torbjørn Pettersen¹ ; Bernd Wittgens² ; Olaf Trygve Berglihn² ; Balram Panjwani² ; Benjamin Ravary³ ; Edin Myrhaug⁴ ; ¹SINTEF Industry, 7034 Trondheim, Norway; ²SINTEF, Trondheim, Norway; ³Eramet Norway, Trondheim, Norway; ⁴ELKEM AS, Trondheim, Norway;
Paper Id: 54 [Abstract]

The Norwegian ferro-alloy industry is a world leader in sustainable production of ferro-silicon, silicon, and manganese alloys. Even if the industry is currently operating with very low specific energy consumption, there is a considerable amount of energy available in the off-gas from the submerged arc furnaces, both in terms latent heat and unconverted chemical energy. For FeMn production, the off-gas also contains mineral rich particles which are contaminated by tar and polycyclic aromatic hydrocarbon (PAH) components. The dust particles are currently removed from the off-gas and deposited as a wet sludge waste stream. Results from recent experimental validation are presented for a new concept for off-gas processing, which enables an increased energy recovery and can facilitate future material recovery through production of tar and PAH free mineral dust. New results from a techno-economic evaluation of the concept will be presented, including ideas for material recovery from the currently unutilized waste stream. The overall objective is a maximized energy recovery and simultaneously prepare for a comprehensive reduction of waste streams.

References:
[1] Y. Ladam, M. Tangstad, and B. Ravary, "Energy mapping of industrial ferroalloy plants", presented at the The thirteenth International Ferroalloys Congress, Almaty, Kazakhstan, 2013, pp. 919-925.
[2] S. Gaal, M. Tangstad, and B. Ravary, "RECYCLING OF WASTE MATERIALS FROM THE PRODUCTION OF FeMn AND SiMn", presented at the The Twelfth International Ferroalloys Congress Sustainable Future, Helsinki, Finland, 2010.
[3] B. Wittgens, B. Panjwani, T. Pettersen, R. Jensen, B. Ravary, and D.-O. Hjertenes,"SCORE: Staged Combustion for Energy Recovery in Ferro-alloy Industries - Experimental Validation", Infacon XV Int. Ferro-Alloys Congr., 2018.

SESSION: IronTuePM1-R1	Afonso International Symposium on Advanced Sustainable Iron and Steel Making(6th Intl. Symp. on Advanced Sustainable Iron and Steel Making)
Tue Nov, 6 2018 / Room: Mar Azul (50/1st)
Session Chairs: Hemant Upadhyay; Shambhu Nath; Session Monitor: TBA

14:00: [IronTuePM105]
Importance of Coke Quality and Optimization for Higher Pulverized Coal Injection Rates in Blast Furnace
Hemant Upadhyay¹ ; Deepesh Chandra¹ ; Arvind Bhagat¹ ; ¹Jindal Steel and Power Ltd, Raigarh, India;
Paper Id: 172 [Abstract]

Coke is a fuel with few impurities and high carbon content. It is the solid carbonaceous material derived from destructive distillation of low-ash, low-sulfur bituminous coal. Coke is the most important factor in blast furnace iron making, which provides heat, reactants, and mechanical support to burden, and accounts for more than 50% of hot metal production cost alone. In modern blast furnace operational practices significant efforts are made to decrease the costly coke consumption mainly by introducing cheaper coals in pulverized form through tuyeres. This alters the in-furnace aerodynamics, reduction conditions, burden distribution and demands on raw material, particularly coke, quality. Therefore coke quality such as its hot and cold strength, reactivity, composition, size fraction and granulometry etc. exerts great influence on the performance of blast furnaces. With increasing productivity & pulverized coal injection, the quality requirement becomes more and more stringent. This is due to the fact that ascending injection rates cause descend in coke unit per charge and the function of coke from being thermal, chemical and mechanical equally shifts to become predominantly mechanical. Hence, in order to maintain stable operation with higher rates of performance, it is important to have lowest possible degradation of coke during its travel from top to bottom of the furnace. This in turn demands proper understanding of the conditions coke has to face in the BF (i.e. effect of alkali, lime, other oxides, char/dust & reactions with surrounding gases) and mechanisms of fines generation & consumption in the blast furnace. In this work, a study on the role of coke and its functions in traditional as well as modern high PCI furnace operations, has been made. The mechanisms inducing and affecting coke degradation have been investigated and correlated with the actual experience from one of the best blast furnaces operating in the world.

14:25: [IronTuePM106]
Development and Application of Mathematical Models to Simulate Liquid Phase Accumulation, Drainage, and Heat Transfer in Blast Furnace Hearth
Hemant Upadhyay¹ ; Deepesh Chandra¹ ; Tarun Kumar Kundu² ; ¹Jindal Steel and Power Ltd, Raigarh, India; ²Department of Metallurgical and Materials Engineering, Kharagpur, India;
Paper Id: 173 [Abstract]

Proper understanding and control of accumulation, drainage, and heat transfer of hot metal and slag in BF (Blast Furnace) hearth is essential for a stable and efficient blast furnace operation. Abnormal drainage behavior may lead to high liquid build up in the hearth. Operation problems are normally encountered if the liquid levels exceed a critical limit when hearth coke and deadman start to float. This not only causes sluggish or irregular descent of burden material, but also results in irregular casting intervals, damage to lining, low blast intake, and furnace pressurization. Similarly, hot metal temperature is an important parameter to be controlled in the BF operation; it should be kept at an optimal level to obtain desired product quality and a stable BF performance. Predicting hot metal temperature variation during the tapping process is extremely useful, since it gives a clear picture to the operator about the tapping operation and prevents any panic. At the same time, it allows the correction of process parameters in case of any major deviation. If the metal temperature is too high or too low, it may directly affect the process and cost efficiency of BF as well as BOF (Basic Oxygen Furnace) plants. Efforts have continuously been made for BF process optimization to improve its productivity, energy efficiency, environment, and product quality. The control of the hot metal / slag accumulation, drainage pattern, and tapping temperature is of great importance for optimizing the BF process and making it productive, energy efficient, and cost competent. Therefore, it is utmost important for furnace operators to understand the mechanisms governing the liquid flow, accumulation, drainage and heat transfer between various phases in BF hearth. As it's extremely difficult to carry out any direct measurement due to the hostile conditions in the hearth with chemically aggressive hot liquids, estimation, and simulation based on rules of physics and mathematical calculations, taking into account available operating parameters is the only viable solution. The objective here is to develop a mathematical model to simulate the variation in hot metal/slag accumulation and temperature during the taping of the furnace, based on: the computed drainage rate; production rate; mass balance; heat transfer between metal and slag, metal, and solids; slag; solids; as well as the various zones of metal and slag itself. [1,3,4]

References:
[1] Hemant Upadhyay and T. K. Kundu, "Drain Rate and Liquid Level Simulation in Blast Furnace Hearth Using Plant Data," ISRN Metallurgy, vol. 2013, Article ID 960210, 7 pages, 2013. doi:10.1155/2013/960210
[2] Johnny Brännbacka and Henrik Saxén, Modelling the Liquid Levels in the Blast Furnace Hearth, ISIJ International, 2001, Vol-41, No.10, Pg No. 1131-1138
[3] W.B.U. Tanzil, P. Zulli, J.M. Burgess, and W.V. Pinczewski, Experimental Model Study of the Physical Mechanisms Governing Blast Furnace Hearth Drainage, Transactions ISIJ, 1984, Vol-24, Pg No. 197-205.
[4] J. Brännbacka, J. Torrkulla, H. Saxén, Ironmaking Steelmaking, 2005, 32, 479-486.
[5] T. Nouchi, M. Sato, K. Takeda, T. Ariyama, ISIJ Int., 2005, 45, 1515-1520.
[6] Koki NISHOKA, Takayuki MAEDA, Masakata SHIMIZU, Effect of various in furnace conditions on Blast Furnace hearth drainage, ISIJ International, 2005, Vol-45, No.10, Pg No. 1496-1505.
[7] W.M. Husslage, M.A. Reuter, R.H. Heerema, T. Bakker, and A.G.S. Steeghs, Flow of Molten Slag and Iron at 1500°C to 1600°C through Packed Coke Beds, Metallurgical and Materials Transactions, 2005, Vol-36B, No.10, Pg No. 765-776.
[8] W.B.U. Tanzil and W.V. Pinczewski, Blast Furnace Hearth Drainage: Physical Mechanisms, Chemical Engineering Science, 1987, Vol-42, NO. 11, Pg No. 2557-2568.

14:50: [IronTuePM107]
A Journey Towards Increasing Pulverized Coal Injection and Reduction in Coke Rate at F Blast Furnace - Tata Steel
Shambhu Nath¹ ; ¹Tata Steel, Jamshedpur, India;
Paper Id: 288 [Abstract]

The scarcity of coke has been long known to all the iron making units. Various attempts have been made to optimize the requirement of coke by developing alternative route for iron making, and alternative methods to meet the thermal requirement of the blast furnace iron making process. Most popular among these developments has been the development of coal injection in the blast furnaces at the tuyere level. In order to sustain Blast furnace route of iron making, cost and productivity need to be improved. Tata Steel has been practicing injection of coal in the blast furnaces at its Jamshedpur works since 1991. This paper describes the enhancement of injection rate at FBF with existing facilities from 150 kg/thm to 195 kg/thm.

References:
[1] K. Ishii, Advanced Pulverized Coal Injection Technology and Blast Furnace Operation, Elsevier Publications, 2000.
[2] A.K. BISWAS, Principles of Blast Furnace Ironmaking, 1st Ed, SBA Publications, 1984.
[3] Subhashis Kundu Et al., High PCI Rate at H Blast Furnace - the Operating Experience, Tata Search, Vol. 1, No. 8, 2011, P. 45.
[4] Uttam Singh et al. , Record coal injection rates at Tata Blast Furnace - H , Steel Tech, Vol. 10, No. 2. January 2016, P. 55

SESSION: ManufacturingTuePM3-R1 Metal Forming / Metal Removal Processing / Non-Conventional Techniques- ΙΙ	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Tue Nov, 6 2018 / Room: Mar Azul (50/1st)
Session Chairs: Paata Kervalishvili; Session Monitor: TBA

17:40: [ManufacturingTuePM313]
Improving the Efficiency of Machining Through Modifying Carbide Cutting Tips by Pulsed Magnetic Field Processing
Viktor Kovalov¹ ; Yana Vasilchenko¹ ; Maxim Shapovalov¹ ; ¹Donbas State Engineering Academy, Kramatorsk, Ukraine;
Paper Id: 419 [Abstract]

This paper solves the problem of increasing the productivity of machining, as well as reducing both the cost of cutting tools and equipment downtime associated with tool failures and its replacement. The task of increasing the strength characteristics of the hard alloy tools necessitates the development of modification methods that affect the entire volume of the material. The requirements that are put forward for these methods are low cost, environmentally friendly, and make its application in the conditions of the machine - building enterprise possible. The method of processing by a pulsed magnetic field satisfies these requirements [1-4]. It is found that the modification of hard alloy metal by pulsed magnetic field processing leads to the increase in its homogeneity, the decrease in the thickness of the crack layer, the stabilization of mechanical characteristics, and the increase in the bending strength. Modification of carbide cutting tips by pulse magnetic field machining is carried out on the equipment, which consists of a pulse generator with a power supply and an inductor. The influence of the pulsed magnetic field on the strength and wear resistance of carbide cutting tips for improving the performance of tooling and reducing the operation and tool costs is investigated. Technological modes of pulsed magnetic field machining by combined technologies (pulsed magnetic field processing + vacuum plasma coating) of samples of tool materials and carbide cutting tips have been worked out. The application of the method of "destructive feeding" for laboratory and production evaluation of structural strength of carbide tips is justified. The method of step-by-step increase of cutting conditions (feeding and cutting speed) allows to implement the principle of extrapolation on loads by gradually increasing loading of strength and wear rate of the tool material. It was found that by roughing of materials with carbide cutting tips hardened by pulsed magnetic field, a multiple tool burnishing with several degrees of slowdown and acceleration of the wear process takes place. This leads to wear resistance increase of carbide cutting tips.

References:
[1] Postnikov, S.N.: Perestrojka defektnyh kompleksov v kristallicheskih tvyordyh telah pod dejstviem magnitnyh polej doporogovyh ehnergij. Prikladnye problemy prochnosti i plastichnosti. Statika i dinamika deformiruemyh system. Vsesoyuznyj mezhvuzovskij sbornik. Gor'kij, 1980, 138 p. (in Russian)
[2] Soroka, O., Rodichev, Y., Kovalov, V., Vasilchenko, Y.: Strengthening of carbide cutting tool for heavy machinery on the base of surface and bulk modification by physical methods. Vіsnik Ternopіl's'kogo Nacіonal'nogo tekhnіchnogo unіversitetu іm. І. Pulyuya. 2013, vol. 71, 3, pp. 133-145. (In Ukrainian)
[3] Y.Rodichev, O. Soroka, V. Kovalov, Y.Vasilchenko, Predicting the fatigue strength of hard alloys, treated with pulsed magnetic field. Proceeding. 13th International conference "Research and Development in Mechanical Industry". RaDMI. Vrnjacka Banja, Serbia, vol. 2, 2013, pp. 254-259. [15] Loshak, M.G. Prochnost' i dolgovechnost' tverdyh splavov. Kiev, Naukova Dumka, 1984, 328 p
[4] Bataineh, O., Klamecki, В., Koepke, B.G.: Effect of pulsed magnetic treatment on drill wear. Journal of Materials Processing Technology. 2003, vol. 134, 2, pp. 190-196.

18:05: [ManufacturingTuePM314]
Improving the Accuracy of Heavy Lathes
Viktor Kovalov¹ ; Yana Antonenko² ; Marina Saenko¹ ; ¹Donbas State Engineering Academy, Kramatorsk, Ukraine; ², Kramatorsk, Ukraine;
Paper Id: 418 [Abstract]

Improving the accuracy of heavy lathes is a complex and critical problem in achieving the quality of new products. At present, from the theoretical and experimental studies of numerous scientists, considerable material on technological quality assurance of processing [2] has been accumulated, which allows the creation of mathematical models for controlling the processing on machines [1-3]. Based on the calculation of limit values of distributed loads which act on the base frame support, deformation strength by method of finite elements were modeled with the tool package CosmosWorks. The simulation was performed for the cases that have the most significant effect on the size of the deformation of the carrier system [4]. To determine the optimal construction of a heavy machine lathe with a carrying capacity of 100 tons, a comparative analysis of the results of computer modeling of the welded frame and field studies of the cast frame of heavy lathes were carried out. As a result of production tests, the coincidence of the results of mathematical modeling with full-scale tests is found to be 6-25%. The design of the frame heavy lathe high accuracy load capacity of 100 tons, with the possibility of machining up to 12.5 m and 2.5 m in diameter with maximum cutting powers of 200 kN are developed. Recommendations on designing of carrier systems of CNC heavy machine tools high accuracy are given. Deformations of the frame of support under extreme workloads are presented in a range from 29 microns to 83 microns. The results are introduced at PJSC KZTS range with the release of heavy CNC lathes of new generation. One of the most promising ways to further improve the accuracy of machine tools is to equip their with adaptive systems [5].

References:
References:
[1] Brgozovsky B.M. The accuracy and reliability of automated precision machine tools.Saratov: SGTU 1992; 124. (In Russian)
[2] Averchenkov V.I., Fedorov V.P., Heyfec M.P. Fundamentals of mathematical modelling of engineering systems. Bryansk: BGTU 2004; 271. (In Russian)
[3] Jung J.H., Choi J.P., Lee S.J. Machining accuracy enhancement by compensating for volumetric errors of a machine tool and on-machine measurement. Journal of Materials Processing Technology 2006, 174 (1-3); 56-66.
[4] Kovalev V., Vasilchenko Y., Gakov S., Kurilenko Y. Trends of adaptive control of accuracy of the technological system on the basis of heavy machine-tools, 2. International Conference "ICQME 2007", Budva, Montenegro, 2007, pp. 263-275.
[5] Kovalev, V.D.; Vasilchenko, Y.V. and DašiA�, P.: Adaptive optimal control of a heavy lathe operation. Journal of Mechanics Engineering and Automation (JMEA), Vol. 4, Issue 4 (April 2014), pp. 269-275.

SESSION: ManufacturingWedAM-R1 High Strain-Rate Phenomena / Treatment under Shock Loading- II	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Mar Azul (50/1st)
Session Chairs: TBA Session Monitor: TBA

11:20: [ManufacturingWedAM01] Invited
Explosion Systems with Inert High Modulus Components: Unexpected Phenomena and Opportunities
Igor Balagansky¹ ; ¹Novosibirsk State Technical University, Movosibirsk, Russian Federation;
Paper Id: 33 [Abstract]

The data received during the experiments on detonation in high explosive charges, which contain inert elements made of materials in which sound velocity is significantly higher than detonation velocity, are systematically reviewed. The shock waves exiting from inert materials due to detonation may outrun the detonation front and compress the explosive material ahead of the front. These lead to changes in the explosive state and related changes in kinetics of the detonation transition. As a result, the stationarity of the process is violated, which lead to unpredictable alterations in the detonation phenomena. The phenomena occurring in such systems are described in detail: desensitization of high explosives, nonstationary detonation processes, energy focusing, and Mach stems formation. The hyper-speed flows of ceramic particles arising due to the explosive collapse of ceramic tubes are described. The possibility of designing protective structures from explosion, based on high modulus ceramic materials, is considered. The structural transformations, caused by energy focusing, or by the impact of hyper-speed ceramic jet in metallic materials, are discussed. These transformations include, but are not limited to adiabatic shear banding, phase transformations, mechanical twinning, melting, boiling, and even evaporation of the impacted substrates. From the practical point of view, this may lead to the decrease or increase in the efficiency of various explosive technologies. The understanding of its origins, time evolution, and the non-stationary phenomena in such explosion systems may provide us a useful instrument to increase the efficiency of explosive technologies and to purposefully control the detonation process.

References:
[1] Balagansky I.A., Razorenov S.V., Utkin A.V. Detonation parameters of condensed high explosive charges with long ceramic elements // Proceedings of the
10th International Detonation Symposium. Boston, USA, 1993. P. 841-845.
[2] Acceleration device based on high explosive charge which contains high modular ceramic tube / I.A. Balagansky, V.A. Agureikin, I.F. Kobilkin, N.I. Nosenko, V.V. Naumov, A.V. Vinogradov, A.I. Balagansky // International Journal of Impact Engineering. 1999. Vol. 22. P. 813-823.
[3] Evolution of shock waves in silicon carbide rods / I.A. Balagansky, A.I. Balagansky, S.V. Razorenov, A.V. Utkin // Proceedings of the 14th APS Topical Conference on Shock Compression of Condensed Matter. Baltimore, USA, 2006. P. 835-838.
[4] Study of energy focusing phenomenon in explosion systems, which include high modulus elastic elements / I.A. Balagansky, K. Hokamoto, P. Manikandan, A.D. Matrosov, I.A. Stadnichenko, H. Miyoshi, I.A. Bataev, A.A. Bataev, A.A. Stepanov // Proceedings of the 14th International Detonation Symposium. Coeur d'Alene, Idaho, 2010. P. 583-590.
[5] Mach stem formation in explosion systems, which include high modulus elastic elements / I.A. Balagansky, K. Hokamoto, P. Manikandan, A.D. Matrosov, I.A. Stadnichenko, H. Miyoshi, I.A. Bataev, A.A. Bataev // Journal of Applied Physics 110, 123516 (2011); doi: 10.1063/1.3671063.
[6] Balagansky I.A., Stepanov A.A. Numerical simulation of Composition B high explosive charge desensitization in gap test assembly after loading by precursor wave // Shock Waves. 2016. Vol. 26. P. 109-115. doi: 10.1007/s00193-015-0584-1.
[7] Balagansky I.A., Vinogradov A.V., Merzhievsky L.A., Matrosov A.D., Stadnichenko I.A. Analysis of Shell Material Influence on Detonation Process in High Explosive Charge, Key Engineering Materials (2016) ISSN: 1662-9795, Vol. 715, pp 27-32.
[8] Balagansky I. A. Modelling of fast jet formation under explosion collision of two-layer alumina/copper tubes / I. A. Balagansky, A. V. Vinogradov, L. A. Merzhievsky // The International Journal of Multiphysics. - 2017. - Vol. 11, 3. - P. 265-375. - DOI: 10.21152/1750-9548.11.3.265.
[9] Generation of Hypervelocity Particle Flows by Explosive Compression of Ceramic Tubes / I. A. Balaganskii, L. A. Merzhievskii, V. Y. Ul'yanitskii, I. A. Bataev, A. A. Bataev, A. D. Matrosov, I. A. Stadnichenko, I. S. Batraev, A. V. Vinogradov // Combustion, Explosion, and Shock Waves. - 2018.- Vol. 54.- No. 1.- pp. 119-124. - DOI: 10.1134/S0010508218010173.

11:45: [ManufacturingWedAM02]
On Ballistics of Damaging Fragmentation Elements
Aram Baghiyan¹ ; ¹Improvis LLC, Armenia, Yerevan, Armenia;
Paper Id: 85 [Abstract]

This paper considers the parameters of motion of the damaging fragmentation elements of an arbitrary shape. The impact velocity of the damaging fragmentation elements is critical for assessing the effectiveness of the ammunition use. The distance from the explosion point at which the fragmentation element still retains damaging properties is also an important factor for estimating the safety of ammunition application as well as effectiveness. The determination of those two factors demands the analysis of the ballistics of damaging fragmentation elements. The core element affecting the velocity and range of flight of fragmentation elements is their drag coefficient. There is an approach [1] that is widely used for the consideration of aerodynamic coefficients related to the Reynolds number. However, for the velocities at which the fragmentation elements have damaging properties, the approach mentioned above can provide less important data than the consideration of aerodynamic coefficients related to the Mach number. In the literature [2-6] there are many papers providing several mathematical descriptions on the relation of drag coefficient of the spherical fragmentation elements to the Mach number, however these functions include physically unexplained gap points. The paper [7] provides the table data on the relation mentioned above, and its precise mathematical description is provided in the paper [8]. Generally, the relation of drag coefficient of fragmentation elements to the Mach number is a stochastic function. This paper provides an analysis of this stochastic function based on the experimental data from [9]. The standard deviation measures of the drag coefficients of fragmentation elements of an arbitrary shape show that for more accurate estimations in future experiments, drag coefficient data collection needs the grouping of fragmentation elements by masses and sizes.

References:
[1] Drela M. Flight Vehicle Aerodynamics. The MIT Press, 2014. - 304 p.
[2] Miropolskiy F.P., Sarkisyan R.S., Vishnyakov O.L., Popov A.M. Aircraft ammunition and their research. Moscow: Zhukovsky Air Force Engineering Academy, 1978 - 528 p.
[3] Balaganskiy I.A., Merzhievskiy L.A. Effects of ammunition and means of destruction. Novosibirsk: Novosibirsk State Technical University, 2004 - 408 p.
[4] Means of Destruction and Ammunition. Ed. Selivanov V.V. Moscow: Bauman Moscow State Technical University, 2008 - 984 p.
[5] Physics of the explosion. Ed. Orlenko L.P. In 2 volumes, Vol. 2. Moscow: Fizmatlit,
2004 - 656 p.
[6] Ammunition. Ed. Selivanov V.V. In 2 volumes, Vol. 1. Moscow: Bauman Moscow State Technical University, 2016 - 512 p.
[7] Krasilshchikov A.R., Podobin V.P. Experimental study of the aerodynamic characteristics of a sphere in free flight with the Mach numbers up to M = 15 // Mechanics of liquid and gas, 1968, No 4, pp. 190-193.
[8] Baghiyan A.H., Skrynnikov A.A., Voronko O.V., Dorofeyev V.A., Pominov V.N. Analitic Representation of Drag Coefficient of Fragmentation Elements // Ammunition, 2007, No. 1, pp. 15-17.
[9] Wentzel E.S. Thesis for the degree of Doctor of Technical Sciences. Several issues of the effectiveness of air firing by remote shells to the airplanes. Moscow: Zhukovsky Air Force Engineering Academy, 1953 - 219 p.

12:10: [ManufacturingWedAM03]
Study of Bonding Plates in a Fine-mesh Objects Manufactured by Selective Laser Melting of a Steel Powder
Anton Zhukov¹ ; Boris Barakhtin¹ ; Pavel Kuznetcov¹ ; ¹NRC "Kurchatov Institute" - CRISM "Prometey", Saint-Petersburg, Russian Federation;
Paper Id: 331 [Abstract]

The possibility of products of complex shape with a fine-mesh structure, manufactured by the method of selective laser melting (SLM) of powders, initiated active scientific and practical investigations in the choice of geometric models, technological modes of melting, and available materials that make it possible to produce strong and lightweight structures [1, 2]. Damping elements manufactured by the SLM from metal powders, in view of their possible application in machine building and the space industry, are of particular interest. It is believed that the integrity of the products is ensured by the geometric parameters of structural support elements whose angular slopes are chosen like oriented bonds in the crystal lattice of diamond [3], and the strength of the material is obtained by the SLM and works in the product under compression conditions [4]. The main objective is to determine the mechanisms of plastic deformation and destruction of the structural support elements in the form of tie plates operating under compression in the dissipative object (a fine-mesh model of the clip). On the EOSINT M270 unit, with a laser power of 200 W and a scanning speed of 800 mm / s, a series of clips was made using the method of selective laser melting of 316L steel powder. The tests revealed a mechanical response of the metal plate, which is characteristic for materials with an auxetic property, in which, due to the anharmonicity of the interatomic bonds, elastic counteraction to the applied deforming load occurs. It was established that the discontinuities in the continuity of the material were accompanied by local reversals of the microvolumes with the formation of oppositely curved lens-like bundles and bridges between the deformation nature. Thus, the orientation and extent of melt volumes, as well as the elastoplastic accommodation of their boundaries, are the determining structural factors for the manifestation of the auxetic effect and the growth of elastic moduli.

References:
[1] E. D. Herderick, JOM 3 v. 68 (2016) 721-723.\n[2] S.Shan, S. H., Kang, J. R. Raney et al., Advanced Materials 29 v. 27 (2015) 4296-4301.\n[3] C. Yan, L. Hao, A. Hussein, D. Raymont, International Journal of Machine Tools & Manufacture 62 (2012) 32-38.\n[4] V. Bobyr, A. Deev, A. Zhukov, P. Kuznetsov, MATEC Web of Conferences 129 (2017) 01053.

12:35: [ManufacturingWedAM04]
Plasmon Spectroscopy of the Transition Metal Films Surface
Sergii Sidorenko¹ ; M.a. Vasylyev² ; S.m. Voloshko¹ ; V.v. Yanchuk¹ ; O.i. Kruglov¹ ; ¹Igor Sikorsky Kyiv Polytechnic Institute, Kyiv, Ukraine; ²G.V. Kurdyumov Institute for Metal Physics, Kyiv, Ukraine;
Paper Id: 177 [Abstract]

Plasmon spectroscopy for the first time was used to analyze the surface of the nanosized transition metal films [1]. Multilayer Ni/Cu/Cr and Ni/Cu/V systems with a thickness of 25 nm layers, obtained by electron-beam deposition in a super-high vacuum of 10-7 Pa, were studied. The samples were irradiated with Ar⁺ ions with a current density of 5 µA/cm² and an energy of 600 eV at doses of 2-1017 and 12-1017 ions/cm² and maintained in an atmosphere of atomic oxygen for 24 hours at 6-10-8 Pa in the electron spectrometry. The averaged values of the energy of the surface (E_s) and bulk (E_b) plasmons, the concentration of the conduction electrons involved in plasma oscillations, as well as the relative changes of the interplanar distances, are calculated [2]. The low-energy ion effects greatly improve the physico-chemical state of the sample's surface, since E_s increases with increasing E_b. At the same time, the conduction electrons concentration is noticeably reduced due to the formation of radiation defects of the vacancy type and the static relaxation of the type of "expansion" of the interplanar distances. Exposure in oxygen after ion bombardment reduces the indicated changes in the concentration of conduction electrons and reduces the manifestation of the effect of surface relaxation by ~6 times. Replacing the "lower" layer of Cr with the layer V in a three-layer system affects the results of quantitative analysis of the plasmon spectra of the "upper" Ni layer. This necessitates the consideration of the long-range effects of the transition metal layers that are applied to the substrate, for example, to improve adhesion (usually Cr or V), when interpreting the results of the plasmon spectroscopy of the nanosized film surfaces. The difference between the experimental data obtained from the theory of free electron gas, which is confirmed for massive samples of transition metals, can be caused by several reasons: the participation of not all valence electrons in collective vibrations; the influence on the energy of the plasmons by interband transitions; as well as the actual physical and chemical state of the film material surface [3].

References:
[1] V.A. Tinkov, M.A. Vasylyev, G.G. Galstyan, Vacuum 85 (2011) 677-686.
[2] Y. Wu, G. Li, J.P. Camden, Chem. Rev. 10 (2017) 124-131.
[3] Y. Fujiyoshi, T. Nemoto, H. Kurata, Ultramicroscopy 175 (2017) 116-120.

SESSION: ManufacturingWedPM1-R1 Non-Ferrous Advanced Materials from Macro- to Nanoscale - II	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Mar Azul (50/1st)
Session Chairs: Tahir Cagin; Session Monitor: TBA

14:00: [ManufacturingWedPM105]
Nanaocomposites Based on Graphene/Polymer for 3D Printers
Natia Jalagonia¹ ; Nino Darakhvelidze² ; Avtandil Sichinava² ; Ekaterine Sanaia² ; Marcello Casa³ ; Leila Kalatozishvili² ; ¹Ilia Vekua Sokhumi Institute of Physics and Technology, Tbilisi, Georgia; ²Ilia Vekua Sukhumi Institute of Physics and Technology, Tbilisi, Georgia; ³, Salerno, Italy;
Paper Id: 342 [Abstract]

Three-dimensional (3D) printing is often considered synonymous with additive manufacturing. Several types of 3D printer are known where polymers are usually used. Stereolithography (SLA) employs a single beam laser to polymerize or crosslink a photopolymer resin. By drawing on the liquid photopolymer resin with a light beam, thin layers of polymer are stacked layer by layer. Elastomer based on polydimethysiloxanes (PDMS) are an important class of materials, because of properties such as chemical inertness, flexibility, and optical transparence. In addition, they have a very low surface tension (20.4 mN/m) and glass transition temperatures (146 K). it is possible to print a support material that holds the PDMS prepolymer in place until it can be cured by UV light using a photoactive cross-linking agent. It is possible to graft photoactive group on PDMS backbone and obtain a new UV curable polymer [1,2]. The aim of the presented work is to obtain photopolymers based on PDMS [3]. For this purpose, we have conducted a hydrosilylation reaction of polymethylhydrosiloxane (PMHS) with allyl acrylate and vinyltriethoxysilane in the presence of Karstedta's catalyst in Toluene. The obtained polymer is liquid, which is well soluble in organic solvents with specific viscosity ηsp = 0.4. The end of reaction was tested by FTIR, where peak at 1260 cm-1 disappears, which belongs to Si-H bonds. After this the polymer is distilled in vacuum, about 1% of a cross-linking agent was added and curried by UV during 1 h.

References:
[1] J. T. Sheridan, Photopolymers Materials (Light Sensitive Organic Materials): Characterization and Application to 3D Optical Fabrication and Data Storage. [Online] Available at: http://www.ucd.ie/t4cms/Photopolymers%20Materials_%20Characterization%20and %20Application%20to%203D%20Optical%20Fabrication%20and%20Data%20Stora ge.pdf. [Accessed: 07.10.2013].
[2] B. Thavornyutikarn, R. Nonthabenjawan, P. Ngamdee, W. Janvikul. Synthesis, Characterization and Crosslinking of Dual-Curable Siloxane Copolymers. Journal of Metals, Materials and Minerals. 18, 2, 213-218, 2008.
[3] N. Jalagonia, I. Esartia, T. Tatrishvili, E. Markarashvili, J. Aneli, O. Mukbaniani. Siloxane matrix with methylpropionate side groups and polymer electrolyter membranes on their basis. Oxid. Commun., 39, 2, 1282-1292, 2016;

14:25: [ManufacturingWedPM106]
Numerical Investigation of a Nonsmooth Rotor-stator System Considering a Shape Memory Alloy Coated Stator
Alberto Paiva¹ ; Rodrigo Veronese Moreira¹ ; Alex Brandão¹ ; ¹Federal Fluminense University (UFF), Volta Redonda, Brazil;
Paper Id: 356 [Abstract]

Rotating systems have been a subject of great relevance since the first industrial revolution, when the first rotating machines started to appear. Since then, several dynamical models have been proposed to describe the behavior of such systems. In the early 19th century, the first rotor models did not consider any interaction with adjacent parts [1] but, as more complete models were developed and solved by numerical methods, nonlinear behavior and chaotic responses were observed as a result from contact and friction between the rotating and stationary parts of the system [2]. The contact phenomenon is still a challenging topic; therefore, recent authors are still interested in its effects considering different approaches [3-5]. Recently, with the increasing Shape Memory Alloy (SMA) exploration [6], a new branch of nonlinear dynamic systems have arisen [7], including nonsmooth systems [8] and rotordynamics applications [9].<br /> This work deals with the numerical simulation of a planar rotor-stator model based on the Jeffcott rotor with four degrees of freedom, namely: two of them related to the rotor, while the other two refer to the surrounding bearing (or stator). The bearing inner surface is subjected to contact and friction and is coated with an SMA layer, whose behavior is described by a first-order phase transition polynomial constitutive model [10].<br /> The SMA layer thermomechanical behavior influences the contact forces between rotor and stator, as its temperature is subjected to two competing phenomena: heating from friction during impact and cooling from convection caused by the interaction with the nearby environment.<br /> The nonlinear system characteristics result from both the intermittent contact possibility and the nonlinear temperature-dependent SMA layer behavior. Such features lead to a vast richness of dynamical behavior, including chaotic responses. The numerical results analyze the dynamical response of the SMA rotor-stator system and investigate the influence of the convective coefficient over the system dynamics.

References:
[1] Jeffcott, H.H. (1919) The Lateral Vibration of Loaded Shafts in the Neighbourhood of a Whirling Speed: The Effect of Want of Balance. Philosophical Magazine 37, p. 304-315.\n[2] Muszynska, A., Goldman, P. (1995) Chaotic Responses of Unbalanced Rotor/Bearing/Stator Systems with Looseness or Rubs. Chaos, Solitons and Fractals 5 (9), p. 1683-1704.\n[3] Edwards, S., Lees, A.W., Friswell, M.I. (1999) The influence of Torsion on Rotor/Stator Contact in Rotating Machinery. Journal of Sound and Vibration 225(4), p. 767-778.\n[4] Popprath, S., Ecker, H. (2007) Nonlinear Dynamics of a Rotor Contacting an Elastically Suspended Stator. Journal of Sound and Vibration 308, p. 767-784.\n[5] Fonseca, C.A.L.L., Aguiar, R.R., Weber, H.I. (2016) On the Non-Linear Behaviour and Orbit Patterns of Rotor/Stator Contact with a Non-Conventional Containment Bearing. International Journal of Mechanical Sciences 105, p. 117-125.\n[6] Cisse, C., Zaki, W., Zineb, T.B. (2016). A Review of Constitutive Models and Modeling Techniques for Shape Memory Alloys. International Journal of Plasticity 76; p. 244-284.\n[7] Savi, M.A. (2015) Nonlinear Dynamics and Chaos in Shape Memory Alloy Systems. International Journal of Non-Linear Mechanics 70, p. 2-19.\n[8] Sitnikova, E., Pavlovskaia, E., Wiercigroch, M., Savi, M.A. (2010) Vibration Reduction of the Impact System by an SMA Restraint: Numerical Analysis. International Journal of Nonlinear Mechanics 45(9), p. 837-849.\n[9] Silva, L.C., Savi, M.A., Paiva, A. (2013) Nonlinear Dynamics of a Rotordynamic Nonsmooth Shape Memory Allow System. Journal of Sound and Vibration 332, p. 608-621.\n[10] Falk, F. (1983) One-Dimensional Model of Shape Memory Alloys. Archives of Mechanics 35, p. 63-84.

14:50: [ManufacturingWedPM107]
The Influence of Aging Treatments on a Ti-Ni 50.7 at. % Mechanical Spring
Hugo De Souza Oliveira¹ ; Henrique Alves Bandeira² ; Aline Souza De Paula¹ ; ¹University of Brasilia, Brasilia, Brazil; ²University of Brasilia, Brasília, Brazil;
Paper Id: 363 [Abstract]

Near equiatomic Ti-Ni shape memory alloys have been attracting much interest for practical applications in many research fields, such as medical, orthodontic, mechanical, and aerospace industries [1], [2]. <br />The remarkable ability in recovering large strains as well as generating high stresses has caused an increase in manufacturing devices made up of these materials[1], [3]-[5].<br />Many studies assert that shape memory characteristics of binary Ti-Ni alloys can be improved through specific thermomechanical treatments, such as annealing following cold working [6]-[8], thermal and/or stress cycling [9], and aging after solution treatment [6], [8], [10]. For Ni rich Ti-Ni alloys, aging treatment is the most effective method for improving the shape memory and mechanical characteristics of the alloys [6], [8], [10].<br />In literature, many studies correlate the effects of aging treatments on the transformation behavior of the Ti-Ni alloys [5], [6], [11]-[15], however few focus on how it can influence the stress-strain hysteresis in mechanical elements [3], such as mechanical springs. This study presents how aging treatments ranging from low to high temperatures (573K to 773K) [16] for different times can affect the cyclic hysteretic behavior of a Ti-Ni 50.7 at. % shape memory spring. The findings enable the choice of appropriate heat treatments where specific energy dissipation rates are required.

References:
[1] D. C. Lagoudas, Shape Memory Alloys: Modeling and Engineering Applications. Springer, 2008.\n[2] J. Mohd Jani, M. Leary, A. Subic, and M. A. Gibson, A review of shape memory alloy research, applications and opportunities, Mater. Des. 1980-2015, vol. 56, pp. 1078-1113, Apr. 2014.\n[3] S. Jiang, Y. Zhao, Y. Zahng, L. Hu, and Y. Liang, Effect of solution treatment and aging on microstructural evolution and mechanical behavior of NiTi shape memory alloy, Trans. Nonferrous Met. Soc. China, vol. 23, no. 12, pp. 3658-3667, 2013.\n[4] Y. Zheng, F. Jiang, L. Li, H. Yang, and Y. Liu, Effect of ageing treatment on the transformation behaviour of Ti 50.9at.% Ni alloy, Acta Mater., vol. 56, no. 4, pp. 736-745, 2008.\n[5] Q. C. Fan et al., Influences of transformation behavior and precipitates on the deformation behavior of Ni-rich NiTi alloys, Mater. Sci. Eng. A, vol. 700, pp. 269-280, Jul. 2017.\n[6] S. Miyazaki, Y. Ohmi, K. Otsuka, and Y. Suzuki, Characteristics of Deformation And Transformation Pseudoelasticity In Ti-Ni Alloys, J. Phys. Colloq., vol. 43, no. C4, pp. C4-255-C4-260, Dec. 1982.\n[7] H. C. Lin and S. K. Wu, The tensile behavior of a cold-rolled and reverse-transformed equiatomic TiNi alloy, Acta Metall. Mater., vol. 42, no. 5, pp. 1623-1630, May 1994.\n[8] J. I. Kim and S. Miyazaki, Effect of nano-scaled precipitates on shape memory behavior of Ti-50.9at.%Ni alloy, Acta Mater., vol. 53, no. 17, pp. 4545-4554, Oct. 2005.\n[9] S. Miyazaki, Y. Igo, and K. Otsuka, Effect of thermal cycling on the transformation temperatures of TiNi alloys, Acta Metall., vol. 34, no. 10, pp. 2045-2051, Oct. 1986.\n[10] S. Miyazaki, T. Imai, Y. Igo, and K. Otsuka, Effect of cyclic deformation on the pseudoelasticity characteristics of Ti-Ni alloys, Metall. Trans. A, vol. 17, no. 1, pp. 115-120, Jan. 1986.\n[11] J. Khalil-Allafi, A. Dlouhy, and G. Eggeler, Ni4Ti3-precipitation during aging of NiTi shape memory alloys and its influence on martensitic phase transformations, Acta Mater., vol. 50, no. 17, pp. 4255-4274, 2002.\n[12] J. Khalil-Allafi, G. Eggeler, A. Dlouhy, W. W. Schmahl, and C. Somsen, On the influence of heterogeneous precipitation on martensitic transformations in a Ni-rich NiTi shape memory alloy, Mater. Sci. Eng. A, vol. 378, no. 1-2, pp. 148-151, Jul. 2004.\n[13] G. Fan, W. Chen, S. Yang, J. Zhu, X. Ren, and K. Otsuka, Origin of abnormal multi-stage martensitic transformation behavior in aged Ni-rich Ti-Ni shape memory alloys, Acta Mater., vol. 52, no. 14, pp. 4351-4362, 2004.\n[14] B. K. Ravari, S. Farjami, and M. Nishida, Effects of Ni concentration and aging conditions on multistage martensitic transformation in aged Ni-rich Ti-Ni alloys, Acta Mater., vol. 69, pp. 17-29, May 2014.\n[15] G. Fan, Y. Zhou, W. Chen, S. Yang, X. Ren, and K. Otsuka, Precipitation kinetics of Ti3Ni4 in polycrystalline Ni-rich TiNi alloys and its relation to abnormal multi-stage transformation behavior, Mater. Sci. Eng. A, vol. 438-440, no. SPEC. ISS., pp. 622-626, Nov. 2006.\n[16] X. Wang, B. Verlinden, and S. Kustov, Multi-stage martensitic transformation in Ni-rich NiTi shape memory alloys, Funct. Mater. Lett., vol. 10, no. 01, p. 1740004, Dec. 2016.

15:15: [ManufacturingWedPM108]
Modelling Shape Memory Effect in Hybrid Composite
Lucas Vignoli¹ ; Marcelo Amorim Savi¹ ; ¹Federal University of Rio de Janeiro, Rio de Janeiro, Brazil;
Paper Id: 360 [Abstract]

Composite materials have been widely used in a large range of industrial applications, mainly because of their lightweight characteristics and high capability to increase strength and stiffness in certain directions, especially in unidirectional laminates. On the other hand, the unique thermomechanical behavior of Shape Memory Alloys (SMAs) has a set of remarkable properties resulting from microscopic phase transformation, allowing the possibility to design new devices that consider pseudoelasticity and shape memory effect (SME) [1,2]. In this study, a unidirectional composite made by SMA fibers embedded in an epoxy matrix is considered. Two different temperature cycles are modelled: first, the curing manufacture process is simulated [3], and then the applied temperature on the SMA fibers to induce the SME. The generalized plane strain state is assumed, and two approaches are used to model the interaction between fibers and matrix. A simplified 1D model, which considers fibers and matrix as springs in parallel, is introduced to evaluate the maximum recovery capability of the composite and a 2D equivalent cell model is used to represent a hexagonal array [4]. The Brinson constitutive model [5] and its modified version with the von Mises equivalent for general stress state [6,7] are applied for the SMA fibers, while the matrix is assumed linearly-elastic with properties defined as functions of the temperature. The maximum recoverable strain range is found to be function not only of the SMA maximum recoverable strain but also of the matrix and interface failures [8]. Results indicate a good correlation between both approaches, however the 2D model has the advantage to be able to computer interface stresses and nonuniform phase transformation. A comparison with the analytical single-fiber model is also carried out [9].

References:
[1] D.D.A. Costa, M.A. Savi, (2017), "Nonlinear dynamics of an SMA-pendulum system", Nonlinear Dynamics, 87, 1617-1627. \n[2] P.B.C., Leal, M.A. Savi, (2018), "Shape Memory Alloy-Based Mechanism for Aeronautical Application: Theory, Optimization and Experiment", Aerospace Science and Technology, 76, 155-163.\n[3] J.B. Berman, S.R. White, (1996), "Theoretical modelling of residual and transformational stresses in SMA composites", 5, 731-743.\n[4] A.B. Morais, (1996), "Modelling Lamina Longitudinal Compression Strength of Carbon Fibre Composite Laminates", Journal of Composite Materials, 30, 1115-1131.\n[5] L.C. Brinson, (1993), "One dimensional constitutive behavior of shape memory alloys: themomechanical derivation with non-constant material functions and redefined martensite internal variable", Journal of Intelligent Material Systems and Structures, 4, 229-242.\n[6] D. Lagoudas, D. Hartl, Y. Chemisky, L. Machado, P. Popov, (2012), "Constitutive model for the numerical analysis of phase transformation in polycrystalline shape memory alloys", International Journal of Plasticity, 32, 155-183.\n[7] S. Enemark, I.F. Santos, M.A. Savi, (2016), "Modelling, characterisation and uncertainties of stabilised pseudoelastic shape memory alloy helical springs", Journal of Intelligent Material Systems and Structures, 27, 2721-2743. \n[8] Y. Huang, L. Xu, S.K. Ha, (2012), "Prediction of three-dimensional composite laminate response using micromechanics of failure", Journal of Composite Materials, 46, 2431-2442. \n[9] Y. Wang, L. Zhou, Z. Wang, H. Huang, L. Ye, (2011), "Analysis of internal stresses induced by strain recovery in a single SMA fiber-matrix composite", Composites: Part B, 42, 1135-1143.

SESSION: ManufacturingWedPM2-R1 Non-Ferrous Advanced Materials from Macro- to Nanoscale - III	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Mar Azul (50/1st)
Session Chairs: Vladimir Kirko; Session Monitor: TBA

15:55: [ManufacturingWedPM209]
Nanostructured Austempered Ductile Cast Iron (ADI)
Susil Putatunda¹ ; Saranya Pannerselvam¹ ; ¹Wayne State University, Detroit, United States;
Paper Id: 315 [Abstract]

Austempered Ductile Cast Iron (ADI) has emerged as an important engineering material in recent years, due to its excellent combination of mechanical properties such as high strength with good ductility, fatigue strength, fracture toughness, and excellent wear resistance. This combination of properties is achieved in ADI by the microstructure consisting of acicular ferrite and high carbon austenite. Refining of the ausferritic microstructure could further enhance the mechanical properties of ADI. An investigation was carried out to develop nanostructured austempered ductile cast iron (ADI) consisting of bainitic ferrite and high carbon austenite. This was achieved by applying a unique process consisting of austenitization and subsequent high temperature plastic deformation at the same austenitizing temperature, followed by single step and two step austempering. The influence of plastic deformation on the microstructure and mechanical properties of nanostructured ADI has been examined. Test results indicates that high temperature plastic deformation together with austempering can result in nanostructured grains in ADI. TEM micrograph was compared with conventional ADI, which provided a detailed insight of the nanostructured ADI.

References:
[1] P.P. Rao and S.K. Putatunda, "Influence of microstructure on fracture toughness of austempered ductile iron" Metallurgical and Materials Transactions A, Vol 28A, pp. 1457-1470, (1997).
[2] P.P. Rao and S.K. Putatunda, "Comparative study of fracture toughness of austempered ductile irons with upper and lower ausferrite microstructures", Material Science and Technology, Vol 14, pp.1257-1265, (1998).
[3] J.L. Doong, F.C. Ju, H.S. Chen and L.W. Chen, "Influence of Austempering on Fracture Toughness in Bainitic Nodular Cast Iron", Journal of Materials Science Letters, pp. 555-558, (1986).
[4] I. Schmidt, Z. Metallkd. Vol.75, pp.747-751, (1984).

16:20: [ManufacturingWedPM210]
Damage Modeling of Shape Memory Alloys
Vanderson Marcio Dornelas¹ ; Sergio Almeida Oliveira² ; Marcelo Amorim Savi¹ ; ¹Federal University of Rio de Janeiro, Rio de Janeiro, Brazil; ²Centro Federal de Educação Tecnológica Celso Suckow da Fonseca (CEFET/RJ), Rio de Janeiro, Brazil;
Paper Id: 361 [Abstract]

Shape memory alloys (SMAs) belong to smart materials being employed in several kinds of applications [1]. Modeling and simulations are essential issues to be considered for proper designs of these systems. In this regard, fatigue phenomenon is a special subject that needs to be investigated. In general, SMAs exhibit two kinds of fatigue: functional fatigue, related to the decrease of the functional properties; and structural fatigue, that is characterized by the nucleation and growth of microcracks which can lead to fracture [2]. This paper discusses a macroscopic three-dimensional constitutive model that describes functional fatigue in shape memory alloys. Comparisons between numerical and experimental uniaxial results are performed for the validation of the proposed model. In addition, general numerical simulations are presented in order to explore the general thermomechical behavior of SMAs.

References:
[1] M.A. Savi, A. Paiva, A.P. Baota-Neves, Journal of Intelligent Material Systems and Structures 13 (2002) 261-273.
[2] G. Eggeler, E. Hornbogen, A. Yawny, M. Wagner, Materials Science and Engineering 378 (2004) 24-33.

16:45: [ManufacturingWedPM211]
Chemical Transformation of Carbon Nanostructures and its Use in Nanocomposites
Guram Bokuchava¹ ; Tinatin Kuchukhidze¹ ; Tamari Archuadze¹ ; Ekaterine Sanaia¹ ; Natia Jalagonia² ; ¹Ilia Vekua Sukhumi Institute of Physics and Technology, Tbilisi, Georgia; ²Ilia Vekua Sokhumi Institute of Physics and Technology, Tbilisi, Georgia;
Paper Id: 341 [Abstract]

The discovery of graphene as an important material transformed nanotechnologies. The great interest in graphene is testified by lots of articles, which are published monthly in scientific literature. It seems though, 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], which is why it is possible to modify carbon nanostructures by different compounds and then obtain organic and inorganic composites based on the aforementioned modified nanoparticles. For example, chemically active metalorganic compounds of I, II and III group metals can react to all functional groups which contains carbon nanostructures. For this purpose, graphene suspension in DMF (obtained modified Hummers' method) has been carried out thermally at 1700°C (for removal of adsorbed water) and then triisobutylaluminum solution in toluene was added. As a result, isobutene was excreted at ambient temperature, meaning that aluminum was connected to carbon nanostructure by oxygen bridges. We have gotten C₈O₂(OH)₂ as the estimated formula of graphene for quantitative calculation. Modified graphene oxide suspension by alumoorganic compunds in DMF was mixed with alumina suspension in toluene, and then the homogenization process was carried out in a nanomill. The concentration of graphene oxide suspension is 1.5%w in composite. The obtained mixture was dried and then consolidated in high temperature vacuum furnace at 14500°C under pressure 478 kg/sm². Microhardness is 15.88 GPa (loading - 200 g) of obtained ceramic materials. Microhardness is 12.025 GPa of ceramic materials obtained from pure alumina in same condition. Testing was carried out using the Oliver-Pharr method according to ISO-14577 standard. We are continuing works to determine the optimal concentration of modified graphene oxide and researching other physical-mechanical properties [2].

References:
[1] Lee, C. et al. Elastic and Frictional Properties of Graphene. Phys. Stat. Solidi. B 246, 2562-2567 (2009);
[2] 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. Unoxidized Graphene/Alumina Nanocomposite: Fracture- and Wear-Resistance Effects of Graphene on Alumina Matrix. DOI: 10.1038/srep05176;

17:10: [ManufacturingWedPM212]
Maxwell-Boltzmann Energetics-enabled Design of Ball Milled Reactive Fractal Materials
Haris Doumanidis¹ ; ¹Nazarbayev University, Astana, Kazakhstan;
Paper Id: 53 [Abstract]

Ignitable reactive bimetallic nanostructured systems, such as Al-Ni multilayers, have been of recent importance for rapid thermal annealing and joining in microelectronics, self-heating materials, and biomedical analysis and drug delivery. Design of their self-propagating exothermic reaction (SPER) properties, such as ignition threshold, front velocity, enthalpic release and adiabatic temperature profile, through design of their fractal (Apollonian pack or Brownian network) structure calls for understanding of their fabrication processing conditions, such as surface impact and bulk deformation in ball milling (BM) of metal powders. However, theoretical and computational analysis of BM in the literature only addresses the kinematics of milling balls by computationally expensive discrete element methods (DEM) and empirical correlations. Recently, a numerical model of the structure-property connection in bimetallic layer SPER capturing the kinetics and dynamics of conduction, diffusion and reaction, as well as a predictive real-time simulation of the process-structure relation in BM multilayers based on Hertzian contact, Coulomb friction and Castiglianoa's deformation theorem of Lagrangian domain primitives has been introduced by the authors' team, offering valuable insights for design. This work elaborates on the theoretical underpinnings of the energetics in BM processing of multi-metallic powders into reactive multilayer material structures, based on statistical mechanics akin to the Brownian kinetics of ideal gases and solutions. Understanding of analogies and differences between kinetic theory and BM fabrication in thermomechanical equilibrium with the container, gravitational field and surface effects from atmosphere and process control agents, and impact coupling in milling ball and particulate interactions is specifically pursued. The theory leads to a Maxwell-Boltzmann probability density function for the collision velocity and energy spectra, along with a uniform distribution of BM impact directionality. This mono-parametric descriptive formulation is calibrated and validated by DEM and experimental data from the bibliography and laboratory tests, and is integrated with the full predictive model of process-structure mechanics above. Simulations of the stochastic multi-layer lamellar structure of bimetallic powders during the BM process are validated against scanning electron microscopy (SEM) sections of Al-Ni particulates in experimental low-energy ball milling, matching the fractal Hausdorff dimensions of the micrographs. This theory-based comprehensive computational tool of the full process-structure-property connection provides new understanding of the reactive materials and enables off-line design approaches for their structure along with real-time process control of BM.

References:
[1] Rebholz, C., Gunduz, I.E., Ando T. and Doumanidis, C.C., "Miniature Thermal Matches: From Nanoheaters to Reactive Fractals", Materials Research Express 2 (2015) 045009 (8 pages)
[2] Doumanidis, C.C., Gunduz, I.E., Rebholz, C. and Doumanidis, C.C., "Real-time Computational Model of Ball-Milled Fractal Structures", ASME J. of Nanotechnology in Eng. & Med. (2015) doi:10.1115/1.4031276 (http://nanoengineeringmedical.asmedigitalcollection.asme.org/article.aspx?articleid=2428190)
[3] Doumanidis, C.C; Al Kaabi, H.A; Alzaabi, A.S.M; Gunduz, I.E; Rebholz, C; Doumanidis, C.C; "Brownian
Kinetics of Ball Milling for Particulate Structural Modeling", Advanced Powder Techn. (submitted 2015)

SESSION: ElectrochemistryMonAM-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Mon Nov, 5 2018 / Room: Copacabana B (150/1st)
Session Chairs: Emmanuel Mousset; Session Monitor: TBA

11:20: [ElectrochemistryMonAM01] Plenary
A Combined SERS-DFT Study Towards Deep Understanding Electrocatalysis
Zhongqun Tian¹ ; Yi-fan Huang² ; Christian Amatore³ ; An Wang² ; De-yin Wu² ; Sandra Rondinini⁴ ; ¹Department of Chemistry, Xiamen Uinversity, Xiamen, China; ²Xiamen University, Xiamen, China; ³CNRS & PSL, French Academy of Sciences, Paris, France; ⁴Universita degli Studi di Milano, Milan, Italy;
Paper Id: 277 [Abstract]

Surface-enhanced Raman spectroscopy (SERS) is one of the few powerful in-situ electrochemical spectroscopies, since it is highly sensitive on the surface species and almost inert on the species in the bulk of electrolyte. However, in order to comprehensively understand electrocatalysis, EC-SERS has to be correctly understand and consistent with the electrochemistry and theory. Here, we present the EC-SERS study on the electrocatalytic reduction of benzyl chloride on Ag by combing experiments and theoretical calculations. To identify the electrode surface species, we performed DFT calculations with Raman spectroscopy on the possible reaction intermediates and products. The results show that the Raman spectrum of the negatively charged benzyl-Ag cluster shows similar spectroscopic characters as experimental spectra, which indicates benzyl anion adsorbed Ag electrode is the key intermediate of the electrocatalytic reduction of benzyl chloride on Ag. By applying the same strategy, we also studied the adsorption of benzyl chloride and the possible products. In light of the reaction pathway roughed out by the consistent EC-SERS observations and DFT simulations on the spectra, the details of the electrocatalysis regarding the binding energy and the activation energy of reactants and intermediates are revealed by electrochemical kinetics calculation combined with DFT calculation. We found that the weakly interaction between distorted benzyl chloride anion and Ag facilitates the dissociation of C-Cl bond and drives the conversion of benzyl chloride. The more detailed discussion will be given. The combined EC-SERS/DFT investigation provides a key entry for understanding the origin of electro-catalytic activity by consistent experimental observations and theoretical calculations.

References:
[1] A. Wang, Y. F. Huang, U. K. Sur, D. Y. Wu, B. Ren, S. Rondinini, C. Amatore, Z. Q. Tian, J. Am. Chem. Soc. 132(2010)9534-9536.
[2] Y. F. Huang, D. Y. Wu, A. Wang, B. Ren, S. Rondinini, Z. Q. Tian, C. Amatore, J. Am. Chem. Soc. 132(2010)17199-17210.

11:45: [ElectrochemistryMonAM02]
Selective Reduction of Carbon Dioxide in Water using Earth Abundant Metal and Nitrogen Doped Carbon Electrocatalysts
Kim Daasbjerg¹ ; Xin-ming Hu¹ ; Jun-jie Shi¹ ; Steen U. Pedersen¹ ; Troels Skrydstrup¹ ; Halvor H. Hval¹ ; ¹Interdisciplinary Nanoscience Center, Aarhus University, Aarhus C, Denmark;
Paper Id: 256 [Abstract]

Earth-abundant transition metal (Fe, Co, or Ni) and nitrogen doped porous carbon electrocatalysts (M-N-C) were synthesized for CO₂ valorization from cheap precursors via silica templated pyrolysis. [1] The effect of the material composition and structure (i.e. porosity, nitrogen doping, metal identity, and oxygen functionalization) on the activity for the electrochemical CO₂ reduction reaction (CO₂RR) in water was investigated. The activity/selectivity order for CO₂-to-CO conversion is Ni > Fe >> Co with respect to the metal in M-N-C. Notably, the Ni doped carbon exhibits a high selectivity with a faradaic efficiency of 93% for CO production. The metal free material exhibits a high selectivity but low activity for the CO₂RR. Tafel analysis shows a change of the rate-determining step as the metal overtakes the role of the nitrogen as the most active site.<br />Recording of X-ray photoelectron spectra and extended X-ray absorption fine structure demonstrates that the metals are atomically dispersed in the carbon matrix, most likely coordinated to four nitrogen atoms and with carbon atoms serving as a second coordination shell. Presumably, the carbon atoms in the second coordination shell affect the CO₂RR activity, considering that the reactivity order for the central metal in carbon supported metal meso-tetraphenylporphyrin complexes is the opposite. From a better understanding of the relationship between the CO₂RR activity and the material structure, it becomes possible to rationally design high-performance porous carbon electrocatalysts for CO₂ valorization. [2]

References:
[1] H. W. Liang, S. Brüller, R. H. Dong, J. Zhang, X. L. Feng, K. Müllen, Nat. Commun. 6 (2015) 7992.\n[2] W. Ju, A. Bagger, G.-P. Hao, A. S. Varela, I. Sinev, V. Bon, B. Roldan Cuenya, S. Kaskel, J. Rossmeisl, P. Strasser, Nat. Commun. 8 (2017) 944.

12:10: [ElectrochemistryMonAM03]
Electrochemical Activation of Carbon Dioxide for the Synthesis of Chemicals
Christian Amatore¹ ; Alessandro Galia² ; Onofrio Scialdone² ; ¹CNRS & PSL, French Academy of Sciences, Paris, France; ²University of Palermo, Palermo, Italy;
Paper Id: 63 [Abstract]

To curb the negative effect of carbon dioxide as a greenhouse gas, an interesting approach is the utilization of Carbon Capture and Conversion (CCC) methodologies. These recycling technologies are focused on the use of CO₂ waste as a feedstock for the production of industrially relevant chemicals. In the past years, increasing attention has been devoted to the electrochemical conversion of CO₂, which would combine the utilization of excess electric energy from intermittent renewable sources with the selective conversion of CO₂ into added value products. Furthermore, it would be possible, in order to reduce the costs, to use the excess of the daily produced electricity, not matching actual demand energy, that is usually lost or not properly used. Researches have shown that several products, including carbon monoxide, formic acid, methane, methanol, ethylene and oxalic acid, can be obtained by this process. Furthermore, it has been shown that carbon dioxide can be introduced in the backbone of other molecules, generating fine chemicals with high economic value, such as anti-inflammatory drugs, by cathodic reduction in aprotic solvents In this work, various routes for the electrochemical conversion of carbon dioxide will be presented and discussed from both a scientific, technical and economic point of view, such as the synthesis of formic acid in water (in conventional and pressurized cells) or the electrocarboxylation of aromatic ketones and benzyl chlorides in organic solvents, in order to illustrate the current scenario.

References:
[1] S. Sabatino, A. Galia, G. Saracco, O. Scialdone, Development of an electrochemical process for the simultaneous treatment of wastewater and the conversion of carbon dioxide to higher value products, ChemElectroChem 4 (1), 150-159, 2017.
[2] O. Scialdone, A. Galia, G.L. Nero, F. Proietto, S. Sabatino, B. Schiavo, Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and other operating parameter, Electrochimica Acta 199, 332-341, 2016

12:35: [ElectrochemistryMonAM04] Invited
New Way of Free Hydroxyl Radical (•OH) Reaction Mode Evidenced by Advanced Electrochemical Process
Emmanuel Mousset¹ ; ¹Reactions and Chemical Engineering Laboratory (LRGP) / CNRS - University of Lorraine (UMR 7274), Nancy, France;
Paper Id: 187 [Abstract]

Hydroxyl radical (•OH) is a very powerful oxidizing agent (E°(•OH/H₂O) = 2.8 V/SHE), second after fluorine. The presence of unpaired electron confers to •OH a very high reactivity towards organic and inorganic compounds, through three action modes established until now: (i) hydrogen abstraction; (ii) electrophilic addition to unsaturated bond; and (iii) electron transfer [1]. Its exceptional oxidation properties have attracted attention in many sectors, and especially in water and wastewater treatment. Thus, hazardous emerging micropollutants such as pesticides, pharmaceuticals, dioxin, etc. are released into the water bodies, being resistant to biodegradation in wastewater treatment plants and in natural waters. Recently, these contaminants have been successfully degraded by •OH involved in the so-called advanced oxidation processes (AOPs). However, •OH has been considered in several studies as unreactive with perhalogenated alkanes (C_xX_y) since they don't have any hydrogen atoms or non-saturated bonds, and they possess a high degree of oxidation due to the electrons of the carbon atoms that are drawn toward the halogen. Interestingly, CCl₄ could be degraded in a Fenton process, while superoxide ion (O2^*-) that is a weak nucleophile and reductant was suggested to be responsible for its degradation; still, the mechanisms of CCl₄ degradation remain unclear. Emerging electrochemical AOPs (EAOPs) offer the advantage to continuously generate •OH in situ in the electrolytic cell according to the electrode materials employed [2]. Excitingly, the implementation of EAOPs highlighted the primary role of •OH radicals for CCl₄ degradation according the ipso-substitution of the radical onto the perhalogenocarbon compound [3]. This new route of •OH oxidation opens up many applications, especially in environmental applications.

References:
[1] E. Brillas, I. Sirés, M.A. Oturan, Chem. Rev. 109 (2009) 6570-6631.
[2] E. Mousset, L. Frunzo, G. Esposito, E.D. van Hullebusch, N. Oturan, M.A. Oturan, Appl. Catal. B Environ. 180 (2016) 189-198.
[3] E. Mousset, N. Oturan, M.A. Oturan, Appl. Catal. B Environ. 226 (2018) 135-146.

SESSION: ElectrochemistryMonPM1-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Mon Nov, 5 2018 / Room: Copacabana B (150/1st)
Session Chairs: Wei-Hua Huang; Session Monitor: TBA

14:00: [ElectrochemistryMonPM105] Plenary
Sustainability of Tissue in the Face of Injury and Disease: Electroanalytical Tools to Promote Life Sustainability
Martyn G Boutelle¹ ; ¹Imperial College London, London, United Kingdom;
Paper Id: 219 [Abstract]

The sustainability of human organs, including the brain, rely on complex networks of connections throughout the body to maintain viability. These networks exchange information using global physical methods— such as temperature, force, blood flow, or point to point electrical signals - such as neuronal impulses, and locally acting chemical signals. Clinicians have traditionally diagnosed disease and treated injury by looking at the overall state of these networks at a point in time— that is, doctors take your temperature, measure your blood pressure, or take a blood sample for analysis. By comparing these individual measurements to the "normal" values of a population, a course of treatment is selected. If required, progress is checked by using a second point measurement. Advances in computerized instrumentation, and in particular, electroanalytical sensors and biosensors, are allowing us to imagine a different "real-time" medicine where the patient information networks are measured directly and continuously. Injury or disease onset, progression, and treatment can be assessed directly through effects on the measured signals. Such an approach has the great advantage that it takes into account the health of the patient as an individual, and hence offers the possibility of a precise and personalized treatment. This presentation will use examples from our work to explore how measurement of tissue chemical signals, using electroanalytical devices, can be combined with other real-time measurements to understand injury processes and hence guide treatment.

References:
[1] Booth MA, Gowers SAN, Leong CL, Rogers ML, Samper IC, Wickham AP, Boutelle MG. 2018. Analytical Chemistry 90: 2-18

[2] Gowers SAN, Hamaoui K, Cunnea P, Anastasova S, Curto VF, Vadgama P, Yang GZ, Papalois V, Drakakis EM, Fotopoulou C, Weber SG, Boutelle MG. 2018. Analyst 143: 715-24

[3] Rogers ML, Leong C, Gowers S, Samper I, Jewell SL, Khan A, McCarthy L, Pahl C, Tolias CM, Walsh DC, Strong AJ, Boutelle MG. 2017. J Cerebral Blood Flow and Metab 37: 1883 - 95

14:25: [ElectrochemistryMonPM106] Invited
Stretchable Electrochemical Sensor for Real-Time Monitoring of Cell and Tissue Mechanotransduction
Wei-hua Huang¹ ; ¹Wuhan University, Wuhan, China;
Paper Id: 230 [Abstract]

Nearly all kinds of cells within organisms are sensitive to mechanical forces and convert into specific biochemical responses. This important and sophisticated process is described as mechanotransduction. To monitor such presumably transient and weak signaling events from very early stages of mechanotransduction, flexible and stretchable biocompatible electrochemical sensors should offer ideal platforms for applying mechanical strains and monitoring electroactive biochemical responses at the same time. However, to date, despite several stimulating progresses in stretchable physical sensors and very few emerging successes in wearable electrochemical devices, very few breakthrough has emerged for inducing mechanotransduction and investigating it in real-time by a single electrochemical device. To address this issue, we reported high-performance stretchable electrodes based on interlacing networks of gold nanotubes (Au NTs) or carbon nanotubes (CNTs) deposited on polydimethylsiloxane (PDMS) thin films. This allowed for the first time, real-time electrochemical monitoring of mechanically sensitive cells on the sensor both in their stretching-free and stretching states, as well as sensing of the inner lining of blood vessels. To detect very weak transient signals triggered from cells by stretching strains only, the mechanical and electrochemical performances of stretchable sensor were further enhanced by implementing a percolating CNTs network onto the Au NTs backbones, which allowed monitoring stretch-induced transient release of vasoactive molecules by endothelial cells cultured on this sensor and submitted to stretching strains. Furthermore, by combination of electrochemical sensing materials and nanophotocatalyst, we developed a stretchable and photocatalytically renewable sensor which endows the sensor with excellent electrochemcial performance and high photocatalytic activity, and thereby providing a versatile and efficient way to promote the biomedical applications of stretchable devices in cell and tissue monitoring.

References:
[1] N. Wang, J. D. Tytell, D. E. Ingber, Nat. Rev. Mol. Cell Biol. 2009, 10, 75-82.
[2] Y. L. Liu, Z. H. Jin, Y. H. Liu, X. B. Hu, Y. Qin, J. Q. Xu, C. F. Fan, W. H. Huang, Angew. Chem. Int. Edit. 2016, 55, 4537-4541.
[3] Z. H Jin, Y. L. Liu, J. J. Chen, S. L. Cai, J. Q. Xu, W. H. Huang, Anal. Chem. 2017, 89, 2032-2038.
[4] Y. L. Liu, Y. Qin, Z. H. Jin, X. B. Hu, M. M. Chen, R. Liu, C. Amatore, W. H. Huang, Angew. Chem. Int. Edit. 2017, 56, 9454-9458.
[5] J. Q. Xu, Y. L. Liu, Q. Wang, H. H. Duo, X. W. Zhang, Y. T. Li, W. H. Huang, Angew. Chem. Int. Edit. 2015, 54, 14402-14406.
[6] Y. W. Wang, Y. L. Liu, J. Q. Xu, Y. Qin, W. H. Huang, Anal. Chem. 2018, DOI: 10.1021/acs.analchem.8b01396.

14:50: [ElectrochemistryMonPM107]
Quantitative Analysis of Fusion Pore Dynamics During Vesicular Exocytosis in Neuroendocrine Cells
Alexander Oleinick¹ ; Irina Svir² ; Christian Amatore³ ; ¹CNRS-ENS-SU UMR 8640 PASTEUR, CNRS, Paris, France; ²Ecole Normale Superieure, Department Chemistry, PARIS, France; ³CNRS & PSL, French Academy of Sciences, Paris, France;
Paper Id: 98 [Abstract]

Vesicular exocytosis is a key biological mechanism through which cells communicate with each other or with their environment. It is involved in many systems in our body (e.g. nervous, endocrine, digestive, etc.), which makes its understanding of paramount importance from both fundamental and practical points of view. Amperometric measurements of vesicular exocytosis with ultramicroelectrode in artificial synapse configuration [1] provide two important advantages: unsurpassed temporal resolution on emitted fluxes of neurotransmitter during single exocytotic events and possibility to obtain massive data. These two advantages allow statistical analysis of exocytotic events and observe trends in different cell types and/or under various physico-chemical conditions (osmotic shocks, effect of drugs etc.). However, generally statistical analysis is restricted to the examination of some shape features of the amperometric spikes (half-peak time width, charge released etc.) representing individual exocytotic events, even though all relevant physico-chemical parameters are intricately convoluted in the monitored current. Extraction of these thought parameters is extremely difficult, due to the fact that each exocytotic event is unique in terms of vesicle size, its internal composition, neurotransmitter load etc. We developed a theoretical framework providing means to extract statistically sound fusion pore sizes during exocytotic event from individual amperometric spikes [2-3], that is the information hardly accessible or not accessible by other approaches. This permits us to analyze and quantify vesicle pore sizes from amperometric data obtained at bovine chromaffin cells [4]. Recently we dramatically simplified the fusion pore size extraction procedure (without sacrificing its accuracy) so that it can be easily implemented by the experimentalists, e.g. in spreadsheet or general purpose mathematical software. This advance allow us to address a larger data set of spikes obtained at chromaffin cells and reveal statistical changes in fusion pores topology under modified conditions (osmotic stress, modification of cell membrane with exogeneous lipids) with respect to control conditions. Of high interest was the finding that in all considered cases the fusion pore radius was never larger than 30 nm, that is much smaller to the average radius of the chromaffin cell vesicle (156 nm). Taking into account significant size of the data set (more than 1000 spikes) this questions the 'inevitable full fusion' paradigm and statistically support a mode of exocytosis where the pore size is significantly smaller the vesicle size [4].

References:
[1] C. Amatore, S. Arbault, M. Guille, F. Lemaitre. Chem. Rev. 108 (2008) 2585-2621.
[2] C. Amatore, A. Oleinick, I. Svir. ChemPhysChem 11 (2010) 149-158; 159-174.
[3] A. Oleinick, F. Lemaitre, M. Guille Collignon, I. Svir, C. Amatore. Faraday Discuss. 164 (2013) 33-55.
[4] A. Oleinick, I. Svir, C. Amatore. Proc. Roy. Soc. A 473 (2017) 20160684.

15:15: [ElectrochemistryMonPM108]
Plasmon Enhanced Spectroscopic and Electrochemical Detection of Biomolecules
Xing-hua Xia¹ ; ¹Nanjing University, Nanjing, China;
Paper Id: 88 [Abstract]

The localized surface plasmon resonance (LSPR) arises from the collective oscillation of conduction electrons of metal nanostructures, which can be used to monitor recognition events of biomolecules at single nanoparticles [1]. The enhanced electric field around the nanostructures due to LSPR will significantly enhance the Raman scattering, fluorescence, and IR spectra, which enable the realization of single molecule detection. In addition, the LSPR will excite high-energy electron-hole pair (referred to as "hot electrons" and "hot holes") emerging on metal surface. The energetic charges will considerably affect the electrochemical reactions occurring at the nanoparticles. When the plasmonic metallic nanostructures are coupled to other substrates, for example, the semiconductor (i.e., TiO₂, MoS₂) and the plasmon-excited hot electron-hole at nanoparticle surface can communicate with the conductance and valence bands of the semiconductors, resulting in variation in electro/photocatalytic activity. In this talk, we will start with the study on the possibility of LSPR for monitoring biomolecules and their recognition events at single nanoparticles. [1] Then, we report the LSPR enhanced IR for biosensing. [2] In the third part, we will show how the LSPR accelerates electrochemical reactions of electroactive biomolecules, such as glucose on gold nanoparticles and hydrogen evolution reaction at molybdenum disulphide nanosheets. [3] Based on the plasmonics accelerated electrochemical reactions (PAER), high sensitive electrochemical biosensors for detection of glucose and other electroactive biomolecules have been constructed.

References:
[1] (a) Y. Zhao, et al. Anal. Chem. 2013, 85: 1053; (b) Y. Zhao, et al. Chem. Commun. 2014, 50: 5480.
[2] (a) J.Y. Xu, B. Jin, Y. Zhao, K. Wang, X.H. Xia, Chem. Commun. 2012, 48: 3052; 187. (b) B. Jin, G. X. Wang, D. Millo, P. Hildebrandt, X. H. Xia, J. Phys. Chem. C 2012, 116: 13038; (c) B. Jin, W. J. Bao, Z. Q. Wu, X. H. Xia, Langmuir 2012, 28: 9460; (d) J. Y. Xu, T. W. Chen, W. J. Bao, K. Wang, X. H. Xia, Langmuir 2012, 28: 17564; (e) W. J. Bao, Z. D. Yan, M. Wang, Y. Zhao, J. Li, K. Wang, X. H. Xia, Z. L. Wang, Chem. Commun. 2014, 50: 7787.
[3] (a) Y. Shi, J. Wang, C. Wang, T.T. Zhai, W.J. Bao, J.J. Xu, X.H. Xia, H.Y. Chen, J. Am. Chem. Soc. 2015, 137: 7365-7370. (b) C. Wang, Y. Shi, Yuan-Yuan Dan, X.G. Nie, Jian Li, X.H. Xia, Chem. Eur. J. 2017, 23: 6717-6723. (c) Y. Shi, Y. Zhou, D.R. Yang, W.X. Xu, C. Wang, F.B. Wang, J.J. Xu, X.H. Xia, H.Y. Chen, J. Am. Chem. Soc. 2017, 139: 15479-15485; (d) C. Wang, Y. Shi, D. R. Yang, X.H. Xia, Curr. Opin. Electrochem. 2018, 7:95-102.

SESSION: ElectrochemistryMonPM2-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Mon Nov, 5 2018 / Room: Copacabana B (150/1st)
Session Chairs: Huangxian Ju; Session Monitor: TBA

15:55: [ElectrochemistryMonPM209] Invited
Photoelectrochemical Bioanalysis
Hong-yuan Chen¹ ; Wei-wei Zhao¹ ; Jing-juan Xu¹ ; ¹Nanjing University, Nanjing, China;
Paper Id: 69 [Abstract]

Photoelectrochemical (PEC) bioanalysis is a newly established analytical approach based on the photo- to-electrical properties of photoactive materials. It possesses many intrinsic advantages such as remarkable sensitivity, simple instrument, and inherent miniaturization. From the combination of photoelectrochemistry and bioanalysis, PEC bioanalysis has advantageously inherited the high sensitivity and specificity. Its general sensing mechanism is that, upon illumination, the photoactive materials could convert the specific biorecognition events into electrical signals, thereby realizing the quantification of various analytes. In past years, the rapid development of PEC bioanalysis has attracted considerable interest, and significant progress has been achieved in its advancement and application. This talk introduces the basic principles, classification, characteristics, as well as the recent progress of PEC bioanalysis in our group.

References:
[1] W. W. Zhao, J. J. Xu, H. Y. Chen, Anal. Chem. 90 (2018) 615-627.
[2] G. Wang, F. Yuan, T. Gu, Y. Dong, Q. Wang, W. W. Zhao, Anal. Chem. 90 (2018) 1942-1947.
[3] N. Zhang, Y. Ruan, L. Zhang, W. W. Zhao, J. J. Xu, H. Y. Chen, Anal. Chem. 90 (2018) 2341-2347.[4] L. Mei, X. Jiang, X. Yu, W. W. Zhao, J. J. Xu, H. Y. Chen, Anal. Chem. 90 (2018) 2749-2755.
[5] Q. Wang, Y. Ruan, W. W. Zhao, P. Lin, J. J. Xu, H. Y. Chen, Anal. Chem. 90 (2018) 3759-3765.

16:20: [ElectrochemistryMonPM210]
Electrochemical Catalytic Probes for Amplified Biosensing
Huangxian Ju¹ ; ¹Nanjing University, Nanjing, China;
Paper Id: 103 [Abstract]

Recently, the investigation on electrochemical biosensing has made great progress. The developed biosensors have extensively been used in different fields, particularly, the sensitive and accurate detection of DNA, protein and metal ions. The designs of specific electrochemical catalytic probes are becoming the main topic of electrochemical biosensing research. This presentation will introduce new electrochemical catalytic probes designed in our group for development of amplified biosensing strategies in last two years. For example, we prepared two electrochemical catalytic probes to design two molecular switches for electrochemical DNA sensing by coupling with porphyrin-encapsulated metal-organic frameworks. Several new signal amplification strategies based on nanotechnology and molecular biology have been presented for DNA detection and immunoassay. By the recognition of nucleic acids to metal ions, some label-free methods have been developed for specific and sensitive detection of heavy metal ions. Some new electrochemiluminescent emitters have been synthesized and used for design of new ECL biosensing mechanisms. A wavelength-resolved ratiometric photoelectrochemical technique has also been developed for sensing applications. These works led to a series of amplified methods for sensitive detection of DNA, microRNA and proteins.

References:
[1] H.X. Ju, et al., Biosens. Bioelectron. 79 (2016) 861; 77 (2016) 733; 77 (2016) 557; 85 (2016) 698; 92 (2017) 171; 96 (2017) 8; 100 (2018) 28.
[2] H.X. Ju, et al., Anal. Chem. 88 (2016) 845; 88 (2016) 8339; 88 (2016) 9856; 88 (2016) 10680; 89 (2017) 7659; 89 (2017) 13480; 90 (2018) 1202; 90 (2018) 1202; 90 (2018) 3703.
[3] H.X. Ju, et al., Chem. Sci. 7 (2016) 774; Chem. Commun. 52 (2016) 1226; ACS Applied Mater. Interf. 8 (2016) 341; 9 (2017) 27185.

17:10: [ElectrochemistryMonPM212] Invited
Some Electrochemical Behavior of Self-assembled DNA-metal Nanoparticle Lattice Films
Lauro Tatsuo Kubota¹ ; Sergio Kogikoski Junior¹ ; ¹Instituto de Quimica - University of Campinas, Campinas, Brazil;
Paper Id: 267 [Abstract]

Many electrochemical processes involving self-assembled nanoparticles are subjects of intense research [1]. Most studies use drop casting of nanoparticles on an insulating barrier, however this method has an enormous drawback, since it does not offer control over the deposition process [2]. Here, we used a strategy based on the self-assembly of programmable atom equivalents consisting of AuNps with complementary DNA strands [3] to prepare the self-assembled lattice film on the electrode surface. The investigations of the properties of the films by EIS and CV will be shown. The results reveal how the 3D structure influences the electrical conduction, as well as how the impedance shows that conduction is dependent on the organization and thickness of the superlattice film. The results demonstrating the formation of a hybrid electroactive device with a well-organized structure composed of different nanoscopic entities working together are combined. In this way, we intend to show that our results pave the way for the future development of electrochemically active nanomachines based on DNA nanostructures.

References:
[1] G.P. Kissling, D.O. Miles, D.J. Fermin, Phys. Chem. Chem. Phys., 13 (2011) 21175-21185.
[2] S.L. Young, J.E. Kellon, J.E. Hutchison, J. Am. Chem. Soc., 138 (2016) 13975-13984.
[3] A.J. Senesi, D.J. Eichelsdoerfer, R.J. Macfarlane, M.R. Jones, E. Auyeung, B. Lee, C.A. Mirkin, Angew. Chem. Int. Ed., 52 (2013) 6624-6628.

SESSION: ElectrochemistryTueAM-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Tue Nov, 6 2018 / Room: Copacabana B (150/1st)
Session Chairs: Tsuyoshi Hoshino; Session Monitor: TBA

11:20: [ElectrochemistryTueAM01] Invited
Electrochemistry for Sustainable Solar Photovoltaics
Meng Tao¹ ; ¹Arizona State University, Tempe, United States;
Paper Id: 171 [Abstract]

Commercial solar photovoltaic technologies such as Si and CdTe are traditionally considered to be in a separate domain from electrochemistry. Their device operation is governed by semiconductor physics and their production involves non-electrochemical processes such as diffusion, screen printing, fractional distillation, etc. However, electrochemistry will likely play an indispensable role in sustaining the commercial solar technologies. This talk will discuss three roadblocks to sustainable solar photovoltaics and how electrochemistry can remove these roadblocks: 1) storage of intermittent solar electricity, 2) scarce Ag used in today's Si solar cells, and 3) high energy input in producing solar Si wafers. An off-grid route is proposed for solar electricity storage based on a closed loop of Zn-ZnO [1], in which Zn rods are produced in a solar electrolyzer from ZnO. The Zn rods are shipped to homes, offices, factories, and electric vehicles to be inserted into mechanically-recharged Zn/air batteries, for electricity on demand. The spent Zn anodes are collected for regeneration of Zn in the solar electrolyzer. This Zn-ZnO loop is advantageous over the H₂-H₂O loop in terms of theoretical performance and technical readiness. Electroplated Al on Si is proposed to replace the screen-printed Ag electrode in Si solar cells [2]. 18% efficiency has been demonstrated in a Si solar cell with an electroplated Al front electrode and a screen-printed Al back electrode, i.e., an Ag-free all-Al Si solar cell. To overcome the high resistivity of the solar Si wafer, direct Al plating on Si without any seed layer is developed through light-induced Al plating. Direct Al plating on Si drastically simplifies the metallization process for Al, resulting in a significantly-lower cost than competing technologies. Finally, electrochemical refining of metallurgical-grade Si for solar-grade Si has been unsuccessful. While metals up to 99.99% purity are readily produced by electrochemistry, solar-grade Si requires a purity of at least 99.9999%. This is coupled with non-electrochemical difficulties in Si purification such as oxidation of the Si anode and crystallinity of the Si cathode. An analysis will be presented on the foundation for ultrapure materials by electrochemistry [3]. The reason for unsuccessful Si electrochemical refining will be discussed through an analogy between electrochemical refining and fractional distillation.

References:
[1] M. Tao, A Zn-ZnO loop for terawatt-scale storage of solar electricity, 43rd IEEE Photovoltaic Specialist Conference (Portland, OR, 2016), p. 2011
[2] W.-C. Sun, X. Han, and M. Tao, Electroplating of aluminum on silicon in an ionic liquid, ECS Electrochemistry Letters, 4, D5 (2015)
[3] M. Tao, Impurity segregation in electrochemical processes and its application to electrorefining of ultrapure silicon, Electrochimica Acta, 89, 688 (2013)

11:45: [ElectrochemistryTueAM02]
Nanoscale Electrochemical Imaging for Functional Energy Materials
Akichika Kumatani¹ ; Yasufumi Takahashi² ; Tomokazu Matsue³ ; ¹Tohoku University, Sendai, Japan; ²Kanazawa University, Kanazawa, Japan; ³Tohoku University, Sendai, Japan;
Paper Id: 405 [Abstract]

Emergence of energy harvesting and storage applications is an essential in next generation with electrochemical reactions including ion transport for secondary batteries and electrocatalytic reactions for hydrogen evolution and oxygen reduction. For introducing their high functionality, active materials can be synthesized in micro-/nano-meter scale. Indeed, their exotic phenomena are induced by nanoscale effects in the comparison with the materials in bulk scale. Therefore, one of key issues is to standardize a quantitative technique for nanoscale electrochemical analysis and imaging [1]. Scanning probe microscopies are good candidates for this purpose in resolution. For example, scanning tunneling microscopy and conductive atomic force microscopy can analyze materials at atomic scale precisely. On the other hand, their information is mainly limited to electronic properties which would be indirect information related to their electrochemical properties. In recent years, scanning electrochemical microscopy (SECM) has become popular as a spatially resolved electrochemical analysis. As the challenge for SECM, it is still remained to satisfy the distance control between the sample and probe, sensitivity, spatial and temporal resolution. In this talk, as a family of SECM techniques, we will introduce our scanning electrochemical cell microscopy (SECCM) system with a single barrel nanopipette [2]. The SECCM uses a meniscus as a nanoscale electrochemical cell simulator which created between the sample and nanopipette. Further, our recent progress of nanoscale electrochemical imaging will be presented on battery electrodes and two dimensional materials for electrocatalyst [3-4].

References:
[1] Y. Takahashi et al., Anal.Chem., 2017, 89, 342.
[2] Y. Takahashi et al., Nature Commun., 2014, 5, 6450.
[3] A. Kumatani et al., Surf. Interface Anal. in press.
[4] A. Kumatani et al., submitted.

12:10: [ElectrochemistryTueAM03]
Vitamin Based Redox Active Organic Molecules for Energy Storage
Sherman Lauw¹ ; Raymond Shi¹ ; Bao Yun Foo¹ ; Richard Webster¹ ; ¹Nanyang Technological University, Singapore, Singapore;
Paper Id: 220 [Abstract]

Conventional batteries function by storing the electrical energy inside solid electrodes, while redox flow batteries (RFBs) are able to store their electrical energy within molecules in solution. RFBs have a number of proposed advantages over conventional batteries; including, (i) the huge number of molecular systems that can potentially be utilized, (ii) the ability to tune the voltage over a wide range, (iii) simple electrode designs that do not change morphologies during charging and discharging, and, (iv) cost-effectiveness for large-scale energy storage. Nevertheless, RFBs suffer several drawbacks in their implementation compared to conventional solid-state batteries, such as their relatively low energy densities due to low molecular solubility, and the increased reactivity of the redox active species. In this study, two fully organic molecular systems were identified that were able to function as the anolyte and catholyte in solution phase batteries. The systems studied were based on modified forms of the naturally occurring vitamin E [1,2] and vitamin K₁ [3]. The systems were chosen because of their suitable reduction (vitamin K₁) and oxidation (vitamin E) potentials measured by cyclic voltammetry, because the compounds had long-lifetimes in their reduced/oxidized states, and because the compounds were highly soluble in acetonitrile containing acid/water. Furthermore, the molecules were found to be able to be utilized in a "mixed-reactant" system were the solutions had exactly the same composition in both compartments (anolyte and catholyte). The lifetime of the reduced forms of vitamin K₁ were affected by the acidity of the solution, which allowed the pH of the solution to be adjusted to allow for the optimal stabilities of the reduced/oxidized quinonoids. Repeated electrolysis experiments in acidified solutions indicated that the systems were fully chemically reversible and so suitable for long-term energy storage applications.

References:
[1] L. L. Williams, R. D. Webster. J. Am. Chem. Soc. 126 (2004) 12441-12450.\n[2] H. M. Peng, B. F. Choules, W. W. Yao, Z. Zhang, R. D. Webster, P. M. W. Gill, J. Phys. Chem. B 112 (2008) 10367-10374.\n[3] Y. Hui, E. L. K. Chng, C. Y. L. Chng, H. L. Poh, R. D. Webster, J. Am. Chem. Soc. 131 (2009) 1523-1534.

12:35: [ElectrochemistryTueAM04] Invited
Lithium Recycling from Used Li-ion Batteries using Innovative Electrodialysis with Lithium Ionic conductor
Tsuyoshi Hoshino¹ ; ¹Rokkasho Fusion Energy Research Centre, Rokkasho-mura, Kamikita-gun, Japan;
Paper Id: 100 [Abstract]

In recent years, the industrial importance of lithium (Li) has increased due to its use in Li-ion batteries. Previously, the author had developed a method for the recovery of Li from seawater using a Li ionic superconductor functioning as a Li-ion separation membrane (LISM). In this method, only Li ions were successfully recovered from seawater through the LISM. Consequently, the author then developed a new innovative method for recycling Li from used Li-ion batteries using the LISM. 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. Subsequently, 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. This new method for recycling Li-ion batteries shows good energy efficiency and is easily scalable. Thus, this electrodialysis method is suitable for the recovery of Li from used Li-ion batteries.

References:
[1] T. Hoshino, Desalination, 359, 59-63 (2015).

SESSION: ElectrochemistryTuePM1-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Tue Nov, 6 2018 / Room: Copacabana B (150/1st)
Session Chairs: Guobao Xu; Session Monitor: TBA

14:00: [ElectrochemistryTuePM105]
ECl Color Devices Based on Bipolar Electrode
Jing-juan Xu¹ ; Hong-yuan Chen¹ ; ¹Nanjing University, Nanjing, China;
Paper Id: 73 [Abstract]

ECL is a powerful tool for the study of electron transfer pathways and development of luminescent devices. Ru(II) and Ir(III) luminophores are the most commonly used concomitant electrochemiluminophores, owing to their high ECL efficiencies with TPrA as the co-reactant. Although the selective excitation of electrochemiluminophores was highly expected to open new avenues for multianalyte detection, over the years its application in this area was still limited. The major drawback is the weak solubility of Ir complexes in water, which limits the biological application of multi-color ECL. We adopted closed bipolar electrode (BPE), which solved the challenge by separating organic ECL emitters from the analyte. Selective excitation of the electrochemiluminophores (Ru(II) and Ir(III) luminophores) could be achieved by tuning the interfacial potential at the poles of BPE. Along with the increasing potential, the ECL intensities of the two emitters varied, and the emission color changed, which enabled us to detect biomarkers on a BPE array with different strategies. With a single DC power supply, prostate-specific antigen (PSA), circulating microRNA-141 (mRNA-141) and small molecular marker, sarcosine were simultaneously detected by the array.

References:
[1] Wang YZ, Ji SY, Xu HY, Zhao W, Xu JJ, Chen HY. Anal. Chem. 10.1021/acs.analchem.8b00014.
[2] Wang YZ, Xu CH, Zhao W, Guan QY, Chen HY, Xu JJ. Anal. Chem. 2017, 89 (15), 8050

14:25: [ElectrochemistryTuePM106]
New Materials for Electrochemiluminescent Analysis
Guobao Xu¹ ; ¹State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, China;
Paper Id: 252 [Abstract]

Electrochemiluminescence (ECL), or electrogenerated chemiluminescence, is an electrochemically triggered light-emitting phenomenon. It has been extensively studied in immunoassays, DNA probe assays, aptasensors, enzymatic biosensors, coreactant detection, light-emitting devices, drug screening, and so on. It is one of the most successful electrochemical in vitro diagnostic techniques. Luminophores, coreactants, electrodes, electrocatalysts, quenchers, and microbeads are often used in ECL. These materials have critical effects on ECL performance. Herein, we reported some new materials with excellent features, such as luminophor ([Ru(bpy)₂dppz]²⁺), coreactant (2-(dibutylamino)ethanol), electrodes (stainless steel electrode and bismuth electrode), noble metal nanocrystal electrocatalyst with high-index facets, single-walled carbon nanohorn ECL quencher, and microbead [1-5].

References:
[1] Liu X, Shi L, Niu W, Li H, Xu G. Angew. Chem. Int. Ed., 2007, 46: 421-424.
[2] Hu L, Bian Z, Li H, Han S, Yuan Y, Gao L, Xu G. Anal. Chem., 2009, 81: 9807-9811.
[3] Kitte S, Gao W, Zholudov Y, Qi L, Nsabimana A, Liu Z, Xu G. Anal. Chem., 2017, 89: 9864-9869.
[4] Zhang L, Niu W, Gao W, Qi L, Lai J, Zhao J, Xu G. ACS Nano., 2014, 8: 5953-5958.
[5] Zhao J, Niu W, Zhang L, Cai H, Han M, Yuan Y, Majeed S, Anjum, S and Xu G. Macromolecules, 2013, 46: 140-145.

14:50: [ElectrochemistryTuePM107]
Nanospectroscopy for Electrochemistry-Electrochemical Tip-enhanced Raman Spectroscopy
Bin Ren¹ ; ¹Xiamen University, Xiamen, China;
Paper Id: 152 [Abstract]

Surfaces and interfaces play a key role in heterogeneous reactions. The electronic and geometric structure of the surface may significantly influence surface reactions. It is important for developing a method to probe the surface structure and the interaction of reactants or products with the active sites at the nanometer scale. In this regard, tip-enhanced Raman spectroscopy (TERS) appears to be an ideal tool. We demonstrated that TERS can chemically and spatially resolve the site-specific electronic and catalytic properties bimetallic model catalysts of Pd or Pt on Au(111) with a spatial resolution of about 3 nm, using the vibrational fingerprints of phenyl isocyanide (PIC) adsorbed and reacted on the surface. The distinct chemical (electronic) and physical (plasmonic) properties of Pd or Pt steps compared with terraces have been directly visualized. We further extend TERS to electrochemical systems for studying electrochemical surface and interfacial processes with the unique potential control over the sample. With the designed spectroelectrochemical cell, we were able to synergistically control the reaction by both electrode potential and laser power and characterize the reaction at the nanometer spatial resolution. The plasmon-induced reaction can lead to a reaction region of 30 nm in radius, which equals the mean free path of electron in Au. We further used TERS to characterize the defects of MoS2 with a spatial resolution better than 10 nm and combined electrochemistry to reveal the evolution of the active sites during electrocatalytic processes.

References:
[1] J. H. Zhong, X. Jin, L. Meng, X. Wang, H. S. Su, Z. L. Yang, C. T. Williams, B. Ren, Nat. Nanotech. 2017, 12, 132.
[2] Z. C. Zeng, S. C. Huang, D. Y. Wu, L. Y. Meng, M. H. Li, T. X. Huang, J. H. Zhong, X. Wang, Z. L. Yang, B. Ren, J. Am. Chem. Soc. 2015, 137, 11928.

15:15: [ElectrochemistryTuePM108]
Highly Sensitive Electrochemical Bioanalysis of Unicellular Samples based on Au@Pt Nanaostructures Modified Diamond Microelectrode Arrays
Xuemei Wang¹ ; Hui Jiang¹ ; Alberto Pasquarelli² ; Chunmei Li¹ ; Hang Zhang¹ ; Jun Ruan¹ ; ¹Southeast University, Nanjing, China; ²Ulm University, Ulm, Germany;
Paper Id: 229 [Abstract]

In this work, aiming at the construction of a sensitive, disposable system for the bioanalysis of unicellular samples, we report a single cell detection electrochemical (SCDE) platform based on Au@Pt nanostructures modified boron-doped nanocrystalline diamond microelectrode arrays (BNCD-MEAs) with 16 channels. The SCDE platform could be readily adapted for a highly sensitive detection of H₂O₂ released from stimulated single cell by ascorbic acid (AA), which could be utilized to distinguish cancer unicellular and normal unicellular ones. The Au@Pt nanostructures have good electrocatalytic activity for the H₂O₂ detection and were modified in the BNCD-MEAs by Pt NPs which were electrodeposited onto the BNCD-MEAs through an electrodeposition approach. As a result, this SCDE platform exhibited a wide linear range with a low detection for H₂O₂ determination. Furthermore, it also displayed satisfactory selectivity, excellent stability, and good reproducibility. The developed method opens a new pathway to clinical bioassay.

References:
[1] Du, T.; ; Zhao, C.; ur Rehman, F.; Lai, L.; Li, X.; Sun, Y.; Luo, S.; Jiang, H.; Gu, N.; Selke, M.; Wang, X., In Situ Multimodality Imaging of Cancerous Cells Based on a Selective Performance of Fe2+-Adsorbed Zeolitic Imidazolate Framework-8. Advanced Functional Materials 2017, 27 (5), 1603926;
[2] Nascimento, R. A.; Ozel, R. E.; Mak, W. H.; Mulato, M.; Singaram, B.; Pourmand, N., Single Cell "Glucose Nanosensor" Verifies Elevated Glucose Levels in Individual Cancer Cells. Nano letters 2016, 16 (2), 1194-200.
[3] Lai, L.; Jiang, X.; Han, S.; Zhao, C.; Du, T.; Rehman, F. U.; Zheng, Y.; Li, X.; Liu, X.; Jiang, H.; Wang, X., In Vivo Biosynthesized Zinc and Iron Oxide Nanoclusters for High Spatiotemporal Dual-Modality Bioimaging of Alzheimer's Disease. Langmuir : the ACS journal of surfaces and colloids 2017, 33 (36), 9018-9024.
[4] Actis, P.; Maalouf, M. M.; Kim, H. J.; Lohith, A.; Vilozny, B.; Seger, R. A.; Pourmand, N., Compartmental genomics in living cells revealed by single-cell nanobiopsy. ACS nano 2014, 8 (1), 546-53.
[5] Adam Seger, R.; Actis, P.; Penfold, C.; Maalouf, M.; Vilozny, B.; Pourmand, N., Voltage controlled nano-injection system for single-cell surgery. Nanoscale 2012, 4 (19), 5843-6.
[6] Zhang, X.; Ding, S. N., Graphite paper-based bipolar electrode electrochemiluminescence sensing platform. Biosensors & bioelectronics 2017, 94, 47-55.
[7] Shen, R.; Liu, P.; Zhang, Y.; Yu, Z.; Chen, X.; Zhou, L.; Nie, B.; Zaczek, A.; Chen, J.; Liu, J., Sensitive Detection of Single-Cell Secreted H2O2 by Integrating a Microfluidic Droplet Sensor and Au Nanoclusters. Analytical chemistry 2018, 90 (7), 4478-4484.
[8] Kniss-James, A. S.; Rivet, C. A.; Chingozha, L.; Lu, H.; Kemp, M. L., Single-cell resolution of intracellular T cell Ca(2+) dynamics in [9] Gao, Y.; Xu, W.; Mason, B.; Oakes, K. D.; Zhang, X., Anion-exchange membrane-separated electrochemical cells enable the use of sacrificial anodes for hydrogen peroxide detection with enhanced dynamic ranges. Electrochimica Acta 2017, 246, 707-711.
[10] Ruan, J.; Zhang, W.; Zhang, H.; Chen, Y.; Rehman, F. U.; Jiang, H.; Strehle, S.; Pasquarelli, A.; Wang, X., Highly sensitive electrochemical detection of living cells based on diamond microelectrode arrays. Chinese Chemical Letters 2017.

SESSION: ElectrochemistryTuePM2-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Tue Nov, 6 2018 / Room: Copacabana B (150/1st)
Session Chairs: Lauro Tatsuo Kubota; Session Monitor: TBA

15:55: [ElectrochemistryTuePM209] Invited
Oxidative Stress: Can We Reduce Oxidative Stress in Various Diseases?
Haruhiko Inufasa¹ ; ¹Gifu University, Osaka, Japan;
Paper Id: 399 [Abstract]

Reactive Oxygen Species (ROS) are closely related to various diseases or symptoms. 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 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 decreases 63% mitochondrial ROS and increases 147% mitochondrial SOD. ICDD confirmed that TWX is safe and has the strongest anti-ROS and protection effects from ROS. TWX was also shown to increase the Neogenesis nerve cell number of the hippocampal dentate gyrus in the 56 week-old mouse, which was increased to the same as the 6 week-old mouse. Mitochondrial metabolism of the mouse hippocampal dentate gyrus was activated by TWX administration according to metabolome analysis. The Japanese Association for Prevention Dementia started a double blind clinical trial from autumn 2017 for 400 patients with Mild Cognitive Impairment and stroke, to prove TWX prevention effects on Alzheimer's disease and Vascular dementia. TWX effects were monitored in various disease and symptoms. Monitoring questionnaires was conducted by I’s Corporation (Tokyo), who holds over 100,000 of internet monitoring members in Japan. TWX (13-15 mg/kg/day) was administered to those that suffered from the following disease or symptoms: chronic sinusitis (80 patients), atopic dermatitis (68 patients), asthma (44 patients), pollinosis (107 patients), fatigue (107 patients), etc. All data collected by the website was analyzed by I’s Corporation. A small clinical trial was also conducted for sleep apnea, hepatic disease, hyperthyroidism, diabetes, and stroke. All reports from I’s Corporation are listed on I’s Corporation home page (https://www.eyez.jp/case_reports). The effectiveness and partial effectiveness of TWX in these diseases' symptoms are as follows: chronic sinusitis 78%, atopic dermatitis 80%, asthma 95%, pollinosis 85%, fatigue 80%. Asthma attack numbers were significantly reduced from before TWX administration. All other diseases also showed positive effects. Diabetic peripheral neuropathy patients reported that symptoms disappeared within 8 weeks after start administration of TWX. TWX has strong potential to treat various disease and symptoms, and its ability to decrease asthma attacks without side effects has presented itself as a major benefit for asthma patients.

16:20: [ElectrochemistryTuePM210]
Simultaneous Electrochemical Detection of Primary Reactive Oxygen and Nitrogen Species Released by Cell Populations in Integrated Microdevices
Yun Li¹ ; Catherine Sella¹ ; Frederic Lemaitre¹ ; Manon Guille Collignon¹ ; Christian Amatore² ; Laurent Thouin¹ ; ¹Ecole normale superieure - CNRS, Paris, France; ²CNRS & PSL, French Academy of Sciences, Paris, France;
Paper Id: 383 [Abstract]

Innovative microdevices were designed to monitor electrochemically primary reactive oxygen (ROS) and reactive nitrogen species (RNS) released by populations of aerobic cells. Taking advantage of the space confinement and microelectrodes performances, only few experiments were sufficient to provide significant statistical data relative to the average behavior of cells during oxidative stress bursts.<br />Platinum-black coated platinum (Pt/Pt-black) electrodes were microfabricated and optimized to achieve optimal performance during the electrochemical detection of four primary species H₂O₂, NO, ONOO^- and NO₂^-.^1,2 The results demonstrated that relative ROS/RNS contents in synthetic mixtures can be easily assessed at selected detection potentials. Under given experimental conditions, the Pt/Pt-black electrodes allow detection limits down to 10 nM with high sensitivities and long-term stability of the electrodes responses.<br />The electrochemical detection of ROS/RNS released by cell populations was then implemented in a multi-chambers microsystem³ and in a microfluidics device.⁴ As an important cell type, RAW 264.7 macrophages secretion triggered by a calcium ionophore was chosen for assessing the performance, sensitivity and specificity of the detection in both cases. In comparison to some previous evaluations obtained from single-cell measurements, reproducible and relevant determinations could be achieved. However, separating emitting cells from the detection area in the microfluidic device seems to be a better approach to avoid any perturbations of cell behaviors by electrode operations. Furthermore, any biological effects during oxidative stress of living cells can be easily investigated. As a proof of concept, we reported the analysis of the influence of a NO synthase inhibitor during the perfusion culture.

References:
(1) Li, Y.; Sella, C.; Lemaitre, F.; Guille-Collignon, M.; Thouin, L.; Amatore, C. Electroanalysis 2013, 25, 895-902. DOI 10.1002/elan.201200456.\n(2) Li, Y.; Sella, C.; Lemaitre, F.; Guille-Collignon, M.; Thouin, L.; Amatore, C. Electrochim. Acta 2014, 144, 111-118. DOI 10.1016/j.electacta.2014.08.046.\n(3) Li, Y.; Meunier, A.; Fulcrand, R.; Sella, C.; Amatore, C.; Thouin, L.; Lemaitre, F.; Guille-Collignon, M. Electroanalysis 2016, 28, 1865-1872. DOI 10.1002/elan.201501157.\n(4) Li, Y.; Sella, C.; Lemaitre, F.; Collignon, M. G.; Amatore, C.; Thouin, L. Anal. Chem. 2018. DOI 10.1021/acs.analchem.8b02039.

16:45: [ElectrochemistryTuePM211]
The Development of Dendrimer-gold Nanocomposite Electrochemical Sensor for the Detection of Lead (II) ion in Water
Kgaogelo Jalda¹ ; Nonhlangabezo Mabuba² ; Omotayo Arotiba² ; ¹University of Johannesburg, Polokwane, South Africa; ²University of Johannesburg, Johannesburg, South Africa;
Paper Id: 355 [Abstract]

In South Africa, industrial development and mining sustains the country's economy. Unfortunately, the effluents from these industries introduce heavy metal pollutants such as lead into the environmental water. Lead(II) is widely recognized as a highly toxic and non-biodegradable metal [1,2,3]. This study addresses a method of monitoring lead(II) by modifying glassy carbon electrode (GCE) with gold nanoparticles (AuNPs) and generation 2 (G2) poly(propyleneimine) dendrimer (PPI), to provide a highly sensitive electrochemical sensor for the determination of lead(II) ions in water using square wave anodic stripping voltammetry (SWASV). The co-deposition of PPI and AuNPs on the surface of GCE was confirmed by field emission scanning microscopy (FESEM). Voltammetric probing showed that the GCE/PPI-AuNP platform exhibited reversible electrochemistry and conductivity in [Fe(CN)6]^3-/4- redox probe. The electroactive surface area of the modified electrodes were also calculated in order to illustrate that the prepared PPI+AuNP nanocomposite could improve the surface area and conductivity of the GCE and was found to be 8.17 mm², GCE-AuNP, 10.84 mm², GCE-PPI, 11.03 mm², while 11.13 mm² was found for GCE-PPI+AuNP. The electroactive surface area of GCE-PPI+AuNP modified electrode increased to approximately 36.23% as compared to bare GCE, which provided an effective evidence for the superior conductivity of PPI+AuNP as expected. The effect of different electrochemical parameters on the sensitivity of the sensor for the Pb2+ detection were also scrutinized, including supporting electrolyte (HNO₃), pH (1), deposition potential (-0.8 V) and deposition time (150s). The sensor was applied in the detection of lead(II) in real water sample and it was exhibited good stability and the results were validated by ICPOES.

References:
[1] [1] Pizent, A., Tariba, B. and Živković, T., 2012. Reproductive toxicity of metals in men. Archives of Industrial Hygiene and Toxicology, 63(Supplement 1), pp.35-46.
[2] Aragay, G., Pons, J. and Merkoçi, A., 2011. Recent trends in macro-, micro-, and nanomaterial-based tools and strategies for heavy-metal detection. Chemical reviews, 111(5), pp.3433-3458.
[3] Navas-Acien, A., Guallar, E., Silbergeld, E.K. and Rothenberg, S.J., 2007. Lead exposure and cardiovascular disease: a systematic review. Environmental health perspectives, 115(3), p.472.

17:10: [ElectrochemistryTuePM212] Invited
Innovative Electrochemical Processes and Reactors for the Treatment of Wastewater
Onofrio Scialdone¹ ; Christian Amatore² ; ¹University of Palermo, Palermo, Italy; ²CNRS & PSL, French Academy of Sciences, Paris, France;
Paper Id: 62 [Abstract]

The electrochemical treatment of wastewater contaminated by organic and inorganic pollutants resistant to conventional processes is considered a very promising and appealing approach. The most interesting processes are the electrochemical direct oxidation, the indirect oxidation by electro-generated active chlorine, and the electro-Fenton. However, various problems limit the potential application of such methodologies [1], such as the cost of electric energy necessary to drive the process; the costs due to the addition of electrolyte for wastewater with low conductivity; the low current efficiencies due to the low mass transfer for low concentrations of pollutants. In this work, various innovative approaches to solve or minimize such problems will be presented and discussed, such as the utilization of microfluidic cells (for both direct anodic oxidation and electro-Fenton) [2,3], pressurized reactors (for electro-Fenton) [4], microbial fuel cells [5] and reverse electrodialysis [6]. It will be shown that the utilization of such processes can drastically improve the performances of various electrochemical processes for the treatment of wastewater. In particular, the activation of various molecules able to oxidize organic pollutants will be discussed.

References:
[1] C.A. Martinez-Huitle, M.A. Rodrigo, I. Sires, O. Scialdone, Single and coupled electrochemical processes and reactors for the abatement of organic water pollutants: a critical review. Chemical reviews 115, 13362-13407, 2015.
[2] O. Scialdone, A. Galia, S. Sabatino, Electro-generation of H2O2 and abatement of organic pollutant in water by an electro-Fenton process in a microfluidic reactor, Electrochemistry communications 26, 45-47; O Scialdone, A. Galia, S. Sabatino, Abatement of Acid Orange 7 in macro and micro reactors. Effect of the electrocatalytic route. Applied Catalysis B: Environmental 148, 473-48, 2015.
[3] O. Scialdone, C. Guarisco, A. Galia, G. Filardo, G. Silvestri, C, Amatore, Anodic abatement of organic pollutants in water in micro reactors, Journal of Electroanalytical Chemistry 638 (2), 293-296.
[4] O. Scialdone, A. Galia, C Gattuso, S Sabatino, B Schiavo, Effect of air pressure on the electro-generation of H 2 O 2 and the abatement of organic pollutants in water by electro-Fenton process, Electrochimica Acta 182, 775-780
[5] G Riccobono, G Pastorella, F Vicari, A D'Angelo, A Galia, P Quatrini, Abatement of AO7 in a divided microbial fuel cells by sequential cathodic and anodic treatment powered by different microorganisms, Journal of Electroanalytical Chemistry
[6] O. Scialdone, A. D'Angelo, E. De Lume, A. Galia, Cathodic reduction of hexavalent chromium coupled with electricity generation achieved by reverse-electrodialysis processes using salinity gradients, Electrochimica Acta 137, 258-265, 2014; A. D'Angelo, M. Tedesco, A. Cipollina, A. Galia, G. Micale, O. Scialdone, Reverse electrodialysis performed at pilot plant scale: Evaluation of redox processes and simultaneous generation of electric energy and treatment of wastewater, Water research 125, 123-131, 2017.

SESSION: ElectrochemistryWedAM-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Wed Nov, 7 2018 / Room: Copacabana B (150/1st)
Session Chairs: Meng Tao; Session Monitor: TBA

11:20: [ElectrochemistryWedAM01]
Cyclic Voltammetry on Nanoelectrode and Nanostructured Electrode
Dongping Zhan¹ ; Zhongqun Tian² ; ¹Department of Chemistry, Xiamen University, Xiamen, China; ²Department of Chemistry, Xiamen Uinversity, Xiamen, China;
Paper Id: 160 [Abstract]

Prof. Christian Amatore is one of the pioneering and most authoritative scientists on ultramicroelectrodes, in both its fundamentals and methodologies. In his honorary symposium, we would like to give a mini-review of our work on nanoelectrodes at Xiamen University, to which many helpful discussions were contributed by our respected old friend, Prof. Amatore. First, we will present a method based on Fick's second law, to further prove the surface diffusion of adsorbates and quantitative measurements of surface diffusion coefficient of Faraday adsorbates on Au or Pt nanoelectrodes. Second, we will present the single molecular enzyme catalysis on the nanoelectrode, including a statistical method to obtain the turnover number of single molecular enzymes. Third, we will present the plasmon-induced voltammetric behavior on the nanostructured Au electrode. The mobility of adsorptive atoms and molecules on catalyst surfaces is one of the most fundamental issues in solid surface science. It plays a pivotal role in various physiochemical processes, especially in thin-film deposition and heterogeneous catalysis. Quantifying the surface mobility will aid in a more in-depth understanding of the mechanism underlying these processes. Therefore, numerous spectroscopic methods have been developed for measuring surface diffusion coefficients, and many systematic investigations have been performed on solid surfaces in vacuum or atmospheric environment. However, studying surface mobility on solid surface in liquid environment, especially in electrochemical systems, still faces challenges both in experiment and theory. The reason mainly stems from the fact that most of the techniques adopted for surface diffusion traditionally don't work at solid/liquid interfaces. Moreover, the co-adsorption of the water molecules or electrolyte ions, and the presence of strong electric fields make it extremely complicated at the electrochemical interface. Nevertheless, information on the transport and interaction of atoms or molecules on electrode surfaces is badly needed for gaining insights into many electrochemical interface processes, such as electrodeposition and electrocatalysis. These processes are directly related to electrochemical energy conversion, metal electrode processes, as well as other electrocatalytic domains.

References:
[1] W. Wang, J. Zhang, F. Wang, B.-W. Mao, D. Zhan, Z.-Q. Tian, Mobility and Reactivity of Oxygen Adspecies on Platinum Surface, J. Am. Chem. Soc. 2016, 138, 9057-9060.
[2] D. Zhan, J.Velmurugan, M. V. Mirkin, Adsorption/Desorption of Hydrogen on Pt Nanoelectrodes: Evidence of Surface Diffusion and Spillover. J Am Chem Soc 2009, 131 (41), 14756-14760.
[3] L. Han, W. Wang, J. Nsabimana, J.-W. Yan, B. Ren, Dongping Zhan, Single molecular catalysis of a redox enzyme on nanoelectrodes, Faraday Discuss., 2016, 193, 133-139.
[4] D. Huang, Q. He, J.-J. Shan, M. Sartin, R. Pang, F.-Z. Yang, Y. Zhou, B. Ren, Z.-Q. Tian, D. Zhan, Illuminating nanostructured gold electrode: surface plasmon or electron ejection? Faraday Discuss. 2018, DOI: 10.1039/C8FD00012C

11:45: [ElectrochemistryWedAM02]
Performance of Lyotropic Liquid Crystal-based Photoelectrochemical Capacitors for Solar-to-Electrical Energy Conversion
Jonathan Halls¹ ; Haydn Ward¹ ; Amal A. Althali¹ ; Laetitia Testut¹ ; David Kocsis¹ ; Huda S. Alhassan¹ ; S.m. Kelly¹ ; Nathan Lawrence¹ ; Jay Deep Wadhawan² ; ¹The University of Hull, Hull, United Kingdom; ²The University of Hull, Kingston-upon-Hull, United Kingdom;
Paper Id: 410 [Abstract]

Regenerative photoelectrochemical capacitors adapted from an experimental system previously reported (J. E. Halls, J. D. Wadhawan, Energy Environ. Sci., 2012, 5, 6541) and based on the doping of a lamellar lyotropic liquid crystal with visible light sensitizer tris(2,2'-bipyridyl)ruthenium(II), N-methylphenothiazine, zinc(II) ions and potassium chloride (as electrolyte) are examined in this work. The two dye species, by virtue of similarity in redox potentials and difference in size and lipophilicity, allow for electron transfer cascades to occur under illumination, which can be harnessed in a power-generating device through the use of a sacrificial counter electrode. In operation as a solar cell, a maximum light-to-electrical power conversion efficiency is reported as being 5.0% under green light (530 nm centreband, 30 nm bandwidth, 2.2 mW cm-2 intensity), which extrapolates to the opportunistic value of 1% under one Sun conditions. The electrical characteristics of the devices under illumination afford specific capacitances of ca. 2 F g-1 and have fill factors ~20% which are close to the 25% expected for a perfect photogalvanic cell. The time constants of the reported devices (~1 s) are consistent with the notion of electroporation of the surfactant lamellæ. The advantages of these mid-ranging photoelectrochemical capacitors are suggested as being their low cost and versatility afforded by their flexible liquid framework that is able to realign itself under conditions of open circuit.

References:
J. E. Halls, J. D. Wadhawan, Energy Environ. Sci., 2012, 5, 6541

12:10: [ElectrochemistryWedAM03] Invited
Actual Problems of the Electrochemistry of Metal Complexes - Fundamentals and Applications: Part 1
Arvydas Survila¹ ; ¹Center for Physical Sciences and Technology, Vilnius, Lithuania;
Paper Id: 195 [Abstract]

A systematic quantitative description of the main stages of the electrochemical process involving metal complexes is presented, and methods for taking into account the role of chemical stages are proposed. The generalized model of mass transfer of chemically interacting particles is based on a system of differential equations containing both diffusion and kinetic terms [1]. The total surface concentration of metal-containing species can be determined at any kinetics of chemical steps using the convolution of current transients. Surface distribution of individual species depends on the degree of system liability. It serves as the basis for determining the surface concentrations that are used further in the analysis of the charge transfer kinetics. Based on the congruence of voltammograms and plots of potentiometric titration, the features of the processes occurring in labile systems are revealed. These are: development of cathodic pre-waves, anodic pseudo-limiting currents, double current maxima, etc. Methods for determining the composition of the electrochemically active complex (EAC) are substantiated taking into account the specificity of complex systems. Kinetic equations of direct and consecutive charge transfer are analyzed with their further transformation into Tafel plots normalized with respect to the EAC surface concentration. Prospects for extension of theoretical developments to other systems, in particular, to the processes of hydrogen evolution involving ligands as proton donors, are considered.

References:
[1] A. Survila, Electrochemistry of metal complexes. Applications from electroplating to oxide layer formation. Weinheim: WILEY, 2015. 304 p.

12:35: [ElectrochemistryWedAM04] Invited
Actual Problems of the Electrochemistry of Metal Complexes - Fundamentals and Applications: Part 2
Arvydas Survila¹ ; ¹Center for Physical Sciences and Technology, Vilnius, Lithuania;
Paper Id: 196 [Abstract]

This report presents the main results of investigations of electrochemical processes involving complexes of various metals, such as copper, tin, zinc, cobalt. Particular attention is paid to systems containing ecological ligands: glycolic, malic, tartaric, citric, gluconic and other hydroxy acids.<br />The presence of pre-waves and double maxima on cathodic polarization curves obtained in the ligand-deficient solutions is experimentally confirmed. Kinetic parameters of charge transfer process are determined while taking into account the redistribution of species at the electrode surface [1]. In this case, the transformation of experimental voltammograms into normalized Tafel plots is used, which turn out to be close to linear, even in the case of very complex initial voltammograms. Similar data are given for the deposition of the Cu-Zn, Cu-Sn, Co-Sn, Co-Mo alloys. The characteristics and sequence of partial processes are analyzed, as well as their interaction under the codeposition conditions. The role of surfactants leading to the formation of surface complexes is demonstrated by the example of Cu and Sn codeposition in the presence of polyethers.<br />Brief information is provided on the account of side processes that often attend the reduction of metal complexes. Conditions for spontaneous formation of photosensitive surface Cu₂O layers are established and their photoelectrochemical behavior is investigated. The appearance of current oscillations is demonstrated in the region of voltammogram characterized by negative impedance. The regularities of hydrogen evolution involving ligands as proton donors are discussed.

References:
[1]A. Survila, Electrochemistry of metal complexes. Applications from electroplating to oxide layer formation. Weinheim: WILEY, 2015. 304 p.

SESSION: ElectrochemistryWedPM1-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Wed Nov, 7 2018 / Room: Copacabana B (150/1st)
Session Chairs: Dongping Zhan; Session Monitor: TBA

14:00: [ElectrochemistryWedPM105]
Electrochemical Behavior of Boron-doped Synthetic Diamond Compacts - A New Electrode Material
Yuri Pleskov¹ ; Marina Krotova² ; Eugeniy Ekimov³ ; ¹Frumkin Institute of Physical Chemistry and Electrochemistry, Russian Academy of Sciences, Moscow, Russian Federation; ²1FRUMKIN INSTITUTE OF PHYSICAL CHEMISTRY AND ELECTROCHEMISTRY, Moscow, Russian Federation; ³INSTITUTE FOR HIGH PRESSURE PHYSICS, Moscow, Russian Federation;
Paper Id: 81 [Abstract]

Traditional thin-film synthetic diamond electrodes produced by chemical-vapor deposition (CVD, see [1, 2]) are remarkable for their wide potential window and low background current in supporting electrolytes and good reproducibility. However, they are not free of disadvantages, particularly from the film exfoliation from substrate, thru-holes, etc. In this work we presented a new electrode material, heavily boron-doped diamond compacts whose electrochemical properties are studied for the first time. Cylinder-shaped polycrystalline samples, 3.5-4 mm in diameter and 2.5 mm in height, were prepared by thermobaric processing of graphite-boron carbide mixtures at the pressure of 8-9 GPa and temperature of ~2500 K [3]. Their diamond nature, in particular, the absence of graphite, was confirmed by Raman spectroscopy and XRD technique. Their electrode behavior is studied by using cyclic voltammetry and electrochemical impedance spectroscopy. The compacts are shown to be superior to conventional thin-film CVD-diamond electrodes in their electrode characteristics. In particular, they have wide potential window, low background current in indifferent electrolytes (KCl, K₂SO₄), and good reproducibility. Moreover, their extremely high doping level makes them more electroactive, as can be seen by the current of Cl₂ anodic evolution from KCl solutions (figure), some organics electrooxidation, etc. [4]. Thus, the diamond compacts are well comparable to the CVD-diamond electrodes. At the same time, they are free of some drawbacks inherent in the latter. Moreover, their concentrated form can be advantageous in the designing of electrochemical devices. One might think that they can successfully be used, e.g., as electrodes in electrosynthesis, electroanalysis, water treatment, etc. [5].

References:
[1] Yu.V. Pleskov, A.Ya. Sakharova, M.D. Krotova, L.L. Bouilov, B.V. Spitsyn, J. Electroanal. Chem. 228 (1987) 19-27.
[2] Synthetic Diamond Films: Preparation, Electrochemistry, Characterization and Applications, Brillas, E. and Martinez-Huitle, C.A., Eds., New York: Wiley, 2011.
[3] E.A. Ekimov, V. Ralchenko, A. Popovich, Diamond Related Mater. 50 (2014) 15-19.
[4] Yu.V. Pleskov, M.D. Krotova, V.V. Elkin, E.A. Ekimov, Russ. J. Electrochem. 52 (2016) 3-9.
[5] Yu.V. Pleskov, M.D. Krotova, V.V. Elkin, E.A. Ekimov, Electrochim. Acta 201 (2016) 268-273.

14:25: [ElectrochemistryWedPM106]
3D Printing Electrodes for Electrochemical Energy Storage and Conversion
Marcus Worsley¹ ; ¹Lawrence Livermore National Laboratory, Livermore, United States;
Paper Id: 316 [Abstract]

Two-dimensional (2D) nanomaterials, such as graphene and transition metal dichalcogenides, hold extraordinary promise for applications in a number of electrochemical technologies. Electrochemical energy storage (EES) devices, such as lithium-ion batteries, flow batteries, and supercapacitors, in particular, have seen 2D materials integrated into various components with exciting results. In general, EES devices are emerging as primary power sources for global efforts to shift energy dependence from limited fossil fuels towards sustainable and renewable resources. These EES devices, while renowned for their high energy or power densities, portability, and long cycle life, are still facing significant performance hindrance due to manufacturing limitations. One major obstacle is the ability to engineer macroscopic components that possess designed and highly resolved microstructures with optimal performance, via controllable and scalable manufacturing techniques. 3D printing covers several additive manufacturing methods that enable well-controlled creation of functional materials with 3D architectures, representing a promising approach for fabrication of next-generation EES devices with high performance. Here, we present recent work to a) develop modeling and optimization algorithms that determine the optimal electrochemical cell geometries for various performance objectives (e.g. maximize current, minimize pressure drop, etc.) and b) fabricate 3D functional electrodes utilizing 3D printing-based methodologies. Specifically, the framework of the 3D printing techniques such as projection microstereolithography and direct ink writing are described, as well as the details of respective feedstock development efforts. Finally, characterization of the 3D-printed electrodes and their performance in various EES applications (e.g. supercapacitors and batteries) will be compared with predicted performance and discussed.

References:
[1] C. Zhu, T. Liu, F. Qian, W. Chen, S Chandrasekaran, B. Yao, Y. Song, E.B. Duoss, J.D. Kuntz, C.M. Spadaccini, M.A. Worsley, Y. Li,"3D Printed Functional Nanomaterials for Electrochemical Energy Storage," Nano Today, 15 107 (2017).
[2] S. Chandrasekaran, P.G. Campbell, T.F. Baumann, M.A. Worsley, "Carbon Aerogel Evolution: Allotrope, Graphene-Inspired, and 3D-Printed Aerogels," Journal of Materials Research, 32 4166 (2017).
[3] Y. Song, T. Liu, F. Qian, C. Zhu, B. Yao, E.B. Duoss, C.M. Spadaccini, M.A. Worsley, Y. Li, "Three-dimensional Carbon Architectures for Electrochemical Capacitors," Journal of Colloid and Interface Science, 509 529 (2018).

14:50: [ElectrochemistryWedPM107]
Influence of the Cobalt and Iron Doping on the Platinum-free Carbon-based Electrocatalysts for Oxygen Reduction Reaction Properties
Tatiana Lastovina¹ ; Yulia Pimonova¹ ; Andriy Budnyk¹ ; ¹Southern Federal University, Rostov-on-Don, Russian Federation;
Paper Id: 265 [Abstract]

Air-hydrogen low temperature fuel cells are promising devices for a sustainable energy supply. Carbon-supported platinum-based nanoparticles are the most active and stable cathodic electrocatalysts [1]. Nowadays, attention has been moving towards Pt-free catalysts like metal oxides, carbides/nitrides, and metals-free or metals-doped carbons. In this study, we investigated the influence of the cobalt and iron concentration in carbons on their catalytic activity and stability in the oxygen reduction reaction. Catalytically active carbons were prepared from a bimetallic zeolitic imidazolate framework (ZIF) [2]. The synthetic procedure included three steps: i) preparation of a hybrid Co/Zn-ZIF; ii) impregnation with iron acetate (II) and 1,10-phenanthroline; iii) calcination at 700 °C for 3 h under argon flow [3]. The properties of prepared materials were assessed with the set of techniques, including HR-TEM and SEM, TGA, XRD. High energy resolution fluorescence detection XANES spectra were measured at the ESRF. The electrochemical properties of the prepared electrocatalysts were investigated by cyclic voltammetry and linear sweep voltammetry. The metal content was found influencing both morphology and catalytic activity of the prepared carbons. Increase in relative quantity of cobalt and in the final material stimulated formation of bamboo-like carbon nanotubes.

References:
[1] V.E. Guterman, T.A. Lastovina, S.V. Belenov, N.Y. Tabachkova, V.G. Vlasenko, I.I. Khodos, E.N. Balakshina, J. Solid State Electrochem. 18 (2014) 1307-1317.
[2] T. A. Lastovina, J. A. Pimonova, A. P. Budnyk, J. Phys. Conf. Ser. 829 (2017) 012007.
[3] T. A. Lastovina, A. P. Budnyk, Y. A. Pimonova, A. L. Bugaev, A. G. Fedorenko, V. P. Dmitriev, Electrochem. Commun. 88 (2018) 83-87.

15:15: [ElectrochemistryWedPM108]
Electrochemical Impedance Analysis of Oxygen Reduction Reaction Kinetics in HTPEMFCs
Panagiotis Giotakos¹ ; Stylianos G. Neophytides¹ ; ¹FORTH ICE-HT, University of Patras, Patras, Greece;
Paper Id: 396 [Abstract]

Even though Oxygen Reduction Reaction, (ORR), kinetics have been studied by many authors over several decades, [1-3], the electrochemical mechanism still remains an open subject of debate and research. Elucidating ORR kinetics is of paramount importance in advancing Fuel Cell technology, which in turn will result in faster commercialization and robust applications for a greener future. In this work we propose a microkinetic transition state multistep reaction mechanism for ORR which takes place inside the cathodic electrode of a High Temperature Polymer Electrolyte Fuel Cell, (HTPEMFC). ORR kinetics are analyzed by the means of Electrochemical Impedance Spectroscopy, (EIS), in the kinetic low current density, (lcd), regime of operation where ORR activation power losses are dominant. The corresponding impedance spectra contain a linear high frequency part feature and two arcs depending on the double layer capacitance, (Cdl), value. This high frequency linear part of the spectrum originates from the finite ionic, (H+), resistance in the catalyst layer. The high frequency arc, under which all charge transfer reaction steps appear, is directly related to the Cdl of the electrochemical interface, (EI), while the low frequency arc stems from the relaxation of the adsorbed surface reaction intermediates on the catalyst surface, which is caused by the depletion of OHad on the surface. Our proposed kinetic model provides two Tafel slopes in the low and high current density (hcd) regime equal to 60 (mV/dec) and 180 (mV/dec) respectively.

References:
[1] N.M. Markovic, T.J. Schmidt, V. Stamenkovic, P.N. Ross, Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review, Fuel Cells. 1 (n.d.) 105-116. doi:10.1002/1615-6854(200107)1:2<105::AID-FUCE105>3.0.CO;2-9.
[2] J.X. Wang, F.A. Uribe, T.E. Springer, J. Zhang, R.R. Adzic, Intrinsic kinetic equation for oxygen reduction reaction in acidic media: the double Tafel slope and fuel cell applications, Faraday Discuss. 140 (2008) 347-362; discussion 417-437. doi:10.1039/B802218F.
[3]J.A. Keith, G. Jerkiewicz, T. Jacob, Theoretical Investigations of the Oxygen Reduction Reaction on Pt(111), ChemPhysChem. 11 (2010) 2779-794. doi:10.1002/cphc.201000286

SESSION: ElectrochemistryWedPM2-R2	Amatore International Symposium on Electrochemistry for Sustainable Development
Wed Nov, 7 2018 / Room: Copacabana B (150/1st)
Session Chairs: Yuri Pleskov; Session Monitor: TBA

15:55: [ElectrochemistryWedPM209] Invited
Electroless Metal Deposition Using Multivalent Metal Ions as Reducing Agents
Eugenijus Norkus¹ ; ¹Center of Physical Sciences and Technology, Vilnius, Lithuania;
Paper Id: 136 [Abstract]

The possibility and conditions of using lower oxidation state metal ions as reducing agents for autocatalytic electroless metal deposition are discussed. The theoretical background of these types of reactions is presented from a thermodynamics perspective. Kinetic data on electroless silver, copper, palladium, and platinum deposition, using Co (II)/Co (III) redox systems with different ligands are presented and discussed. Ti (III)/Ti (IV) redox systems with different ligands were also shown to be suitable reducing agents for reducing Pt (IV), Pd (II), Ni (II) and Co (II) to a metallic state and forming a continuous metal layer on the surface to be plated. The morphology of metal layers deposited using above-mentioned reducing agents was characterized by means of Field Emission Scanning Electron Microscopy (FESEM). Kinetics of the metal deposition rate was investigated by means of the gravimetry or Electrochemical Quartz Crystal Microgravimetry (EQCM).

References:
[1]. E. Norkus, I. Stankeviciene, A. Jagminiene, A. Joi, L. Tamašauskaite-Tamašiūnaite, Y. Dordi, Z. Sukackiene. "Electroless deposition of continuous cobalt layer using complexed Ti3+ metal ions as reducing agents". U.S. Pat. 9428836 B2 (2016).
[2]. E. Norkus, A. Jagminiene, A. Žieliene, I. Stankeviciene, L. Tamašauskaite-Tamašiūnaite, A. Joi, Y. Dordi. "Electroless deposition of continuous platinum layer". U.S. Pat. 9469902 B2 (2016).
[3]. E. Norkus, I. Stankeviciene, A. Jagminiene, L. Tamašauskaite-Tamašiūnaite, A. Joi, Y. Dordi. "Electroless deposition of continuous platinum layer using complexed Co2+ metal ion reducing agent". U.S. Pat 9499913 B2 (2016).

16:20: [ElectrochemistryWedPM210]
Highly Regio and Enantioselective Synthesis of Functionalized Dihydropyridines and One-Pot Synthesis of Pyridines Triggered by Heck Coupling of Monocyclopropanated Heterocycles
Julietta Yedoyan¹ ; ¹University of Regensburg, Regensburg, Germany;
Paper Id: 350 [Abstract]

Over the last few years, our group has been intrigued by catalytic cyclopropanations of N-Boc-pyrroles, which provides a stereoselective entry into bicyclic donor-acceptor substituted cyclopropanes that can be manipulated in various ways to natural products and synthetically useful building blocks. [1,2]. Herein we report the palladium catalyzed Heck-Mizoroki cross-coupling reaction between monocyclopropanated N-Boc-pyrroles and hetero/aryl halides leading to substituted 1,2-dihydropyridine preparation in moderate to good yields (40-81%). The arylation occurs selectively from the convex face of monocyclopropanated N-Boc-pyrrole, giving 1,2-dihydropyridine with an excellent transfer of chirality. The developed approach offers an attractive general method for accessing important six-membered nitrogen-containing scaffolds, which are in high demand in the pharmaceutical sciences and beyond. [3]

References:
[1] O. Reiser, Isr. J. Chem. 2016, 56, 531-539
[2] L. Pilsl; T. Ertl, and O. Reiser. Org. Lett. 2017, 19, 2754a-2757.
[3] M. Hilton, R. Dolewski, and A. McNally J. Am. Chem. Soc. 2016, 138, 13806-13809

16:45: [ElectrochemistryWedPM211]
Membrane Electrolysis as a New Method for Lithium Recovery From Brines
Victoria Flexer¹ ; Noelia Palacios¹ ; Cesar Diaz Nieto² ; Korneel Rabaey³ ; ¹Centro de Investigación y Desarrollo en Materiales Avanzados y Almacenamiento de Energía de Jujuy-CIDMEJu, Palpalá, Argentina; ²Centro de Investigacion y Desarrollo en Materiales Avanzados y Almacenamiento de Energia de Jujuy-CIDMEJu, Palpalá, Argentina; ³CMET, Ghent University, Gent, Belgium;
Paper Id: 250 [Abstract]

The electrification of our world, particularly road transportation and power storage, drives a strong increase in demand for lithium. The continued availability of lithium can only rely on a strong increase of mining and ore processing. It would be an inconsistency if the increased production of lithium salts for a more sustainable society would be associated with non-sustainable practices. Currently 2/3 of the world production of lithium is extracted from brines, a practice that evaporates half a million cubic metres of water per ton of lithium carbonate. We will present an integrated membrane electrolysis concept to separate lithium from brines, driven by renewable power and delivering byproducts instead of waste. Our technology is based on a 4 stage process, each based on a water electrolyser with a side crystallizer. The chambers of the electrolysers are separated by anion and/or cation exchange membranes (AEM or CEM). At the anode, water will be oxidized to oxygen, and/or chloride to chlorine gas. In the cathode, water will be reduced to hydrogen, and the pH will increase. The applied potential and the need to maintain electroneutrality will make cations and anions selectively move to the cathodic or anionic compartments. By a careful pH adjustment with current flow, and selectively bubbling CO₂ at interval, it is possible to sequentially precipitate the different brine components, with Li₂CO₃ precipitating last. Our proposed technology is fast, not requiring time consuming evaporation. Because it is much less dependent on solution composition, it could render the exploitation of a large number of currently unexploited resources possible, including salar brines and geothermal waters in Europe. Moreover, this technology will be much easier to adapt to different brines, and pilot scale runs will be performed quickly, as opposed to sluggish optimization in the evaporitic technology.

References:
[1] Vikström, H., et al. Applied Energy, 2013. 110: 252-266
[2] Talens Peiró, L., et al. JOM, 2013. 65(8): 986-996.
[3] Swain, B. Separation and Purification Technology, 2017. 172: 388-403.
[4] Flexer, V. et al., 2018, submitted for publication.

SESSION: MoltenMonAM-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Mon Nov, 5 2018 / Room: Bossa (150/3rd)
Session Chairs: Anders Riisager; Session Monitor: TBA

11:20: [MoltenMonAM01]
My Life in Molten Ionic Media
Rasmus Fehrmann¹ ; ¹DTU Chemistry, Lyngby, Denmark;
Paper Id: 56 [Abstract]

It was almost 50 years ago, during my study of Chemical Engineering (Civil Engineer) at the Technical University of Denmark (DTU), that I was "baptised" in molten alkali chloroaluminates in the group of Prof. Niels Bjerrum. Since then, I have stayed faithful to molten media for nearly the entirety of my scientific career. Firstly, my PhD degree (Licentiatus Technices at that time...) concerned unusual oxidation states of the chalcogenes in molten chloroaluminates. Selected experimental results covering rare oxidation states like +1/2, + 1/4 and +1/8 of pure Sulfur, Selenium, and Tellurium species will be highlighted here. At the end of the 1970's I turned to catalysis in molten salts, with a special focus on the chemistry of the sulfuric acid catalyst, the key material for the production of the most important chemical at the tonnage scale in the world - at that time as well as now. For the following 35 years, more than 60 journal publications and a large number of reports described the efforts of me and my numerous collaborators and students. The most important results will be shown, including the discovery of the complex and compound chemistry Vanadium in molten alkali pyrosulfate melts, and the state-of-the-art reaction mechanism modelling the working sulfuric acid catalyst. In addition, our in-situ and operando investigations of commercial industrial catalysts have been essential to link our ex-situ results to the "real world", and our efforts to achieve the global goal of the catalyst producers - the low temperature sulfuric acid catalyst- allowing more economic and sustainable sulfuric acid production, will also be highlighted. My educational background as a chemical engineer that focused on organic chemistry during my Master's and on inorganic chemistry during the PhD, combined with my Master thesis on "Hydroformylation by Rh-phosphine Catalysis" (modified Shell Process) was probably essential to me joining the early efforts of research and application of ionic liquids from year 2000. Shortly after, our first results on Supported Ionic Liquid Phase (SILP) continuous flow catalysis were published, regarding Rh-phosphine complexes dissolved in ionic liquids and subsequent impregnated in meso porous inorganic supports. This concept – parallel to the sulfuric acid catalyst also being a Supported Liquid Phase (SLP) catalyst during operation- allowed continuous conversion of gas phase olefins with H₂ and CO to gas phase aldehydes, since no evaporation of solvent or catalyst took place. Thus, an attractive design of the otherwise batch operated Oxo process was provided– a concept that whose commercialization is currently being attempted by, among others, our group and an European industrial partner. Subsequently, we have also applied the SILP concept to other important catalytic industrial processes, like carbonylation of methanol to acetic acid (our patent acquired by an European chemical company), in addition to alkoxycarbonylation of alkenes (important for e.g. MMA production), and also in the Water-Gas-Shift (WGS) process through collaboration with FAU (Erlangen, DE) and the European industry . Selected results of our SILP catalyst research and applications will also be shown at this occasion. In addition, we have recently extended the SILP concept to continuous gas separation and encircled appropriate ionic liquids and porous supports for the selective reversible absorption of gasses like CO₂, NO_x, SO₂ and H₂S. Our fundamental results and the possible application of these selective SILP filters to e.g. CO₂ capture, flue gas cleaning, biogas and natural gas sweetening – pursued industrially together with a Nordic partner – will be described as well. In conclusion, the importance of the concept "From Molecular Understanding to Industrial Application" – the motto of our research center at DTU (Centre for Catalysis and Sustainable Chemistry) - should be obvious from our achievements so far and undoubtedly also in the future.

References:
[1] Svovls, Selens og Tellurs Kemi i Chloroaluminatsmelter (The Chemistry of Sulfur, Selenium and Tellurium in Chloroaluminate Melts). Rasmus Fehrmann, Thesis, Chemistry Department A, The Technical University of Denmark, Lyngby 1976.

[2] Lower Oxidation States of Selenium. 2. Potentiometric Study Involving Tetravalent Selenium, Tetraselenium(2+), Octaselenium(2+), and Three Other Low Oxidation States of Selenium in a Chloroaluminate Melt. R. Fehrmann and N.J. Bjerrum, Inorg. Chem. 16, 2089, 1977.

[3] Progress on the mechanistic understanding of SO2 oxidation catalysts. O.B. Lapina, B.S. Bala'zhinimaev, S. Boghosian, K.M. Eriksen, and R. Fehrmann, Catal. Today, 51, 469, 1999.

[4] R. Fehrmann, A. Riisager and M. Haumann (Eds.), Supported Ionic Liquids - Fundamentals and Applications, Wiley-VCH, Weinheim, 2014.Applications, Wiley-VCH, Weinheim, 2014.

11:45: [MoltenMonAM02] Plenary
SILP at SIPS: Combining Pharmaceuticals with Ionic Liquids on Silica-Supports
Robin Rogers¹ ; ¹University of Alabama, Tuscaloosa, United States;
Paper Id: 58 [Abstract]

Ionic Liquids (ILs, salts that melt below 100 °C) loaded on silica have been studied for gas phase reactions, but they have not been used in solution due to the leaching properties of the ILs and the deactivation of the catalyst. One area where the "Supported Ionic Liquid Phase" (SILP) strategy would be a tremendous advantage would be in the loading of ILs that are intended and necessarily leached in order to carry out their functions, as is the case of ILs of Active Pharmaceutical Ingredients (APIs). We have found that IL-APIs are readily loaded and leached from silica, giving to the material a few advantages, including the ability to deliver these liquid salt drugs in solid form as free flowing powders. This presentation will discuss the loading, leaching, and favorable physical and chemical properties exhibited by these IL-APIs in solid form.

References:
[1] Bica, K.; Rodriguez, H.; Gurau, G.; Cojocaru, O. A.; Riisager, A.; Fehrmann, R.; Rogers, R. D. "Pharmaceutically Active Ionic Liquids with Solids Handling, Enhanced Thermal Stability, and Fast Release," Chem. Commun. 2012, 48, 5422-5424. DOI: 10.1039/C2CC30959A

[2] Cojocaru, O. A.; Siriwardana, A.; Gurau, G.; Rogers, R. D. "Pharmaceutically active supported ionic liquid phases," In Supported Ionic Liquids - Fundamentals and Applications, Fehrmann, R., Riisager, A., Haumann, M., Eds.; Wiley-VCH: Weinheim, Germany, 2014; Chapter 19; pp 387-406. ISBN: 978-3-527-32429-3.

12:10: [MoltenMonAM03] Keynote
Spectroscopy and Catalysis: The Operando Methodology and Reaction Monitoring, Tools to Understand Structure-Activity Relationships
Miguel Banares¹ ; Raquel Portela¹ ; Mariví Martinez Huerta¹ ; Pedro Avila¹ ; Susana Pérez Ferreras¹ ; Søren Birk Rasmussen¹ ; Vanesa Calvino Casilda² ; Alba E. Diaz Alvarez¹ ; Ines Reyero¹ ; Katarzyna Stawicka³ ; Maciej Trejda³ ; Maria Ziolek³ ; Olga Guerrero⁴ ; Marco Daturi⁵ ; Philippe Bazin⁵ ; Guillaume Clet⁵ ; Zhenyou Gui⁶ ; Nanette Zahrtmann⁷ ; Shunmugavel Saravana⁶ ; Zhiwen Qi⁸ ; Anders Riisager⁷ ; Eduardo J. García Suárez⁷ ; ¹Institute for Catalysis and Petroleum Chemistry (CSIC), Madrid, Spain; ²ETS de Ingenieros Industriales, UNED, Madrid, Spain; ³Adam Mickiewicz University, Poznan, Poland; ⁴University of Malaga, Malaga, Spain; ⁵LCS University of Caen Normandy, Caen, France; ⁶DTU Chemistry, Lyngby, Denmark; ⁷DTU Chemistry, Kgs. Lyngby, Denmark; ⁸East China University of Science and Technology, Shanghai, China;
Paper Id: 403 [Abstract]

Spectroscopy is an enabling tool to understand structure-reactivity relationships, that can be applied from predicting toxicity of nanomaterials to engineer better catalytic processes. Operando methodology analyzes both, the catalyst structure and its activity/selectivity simultaneously in a cell that is fit for in situ spectroscopy and performs like a catalytic reactor; correlating structure changes with catalytic performance. Some representative works illustrate this. 1-3 We will present a study on the role of additives, support, coverage, hydration and reaction conditions on the states of supported vanadium and its relevance for catalytic reaction and reducibility. This is applied to assess the molecular basis for activation/deactivation and the nature of the catalyst active site for oxide reduction, alkane oxidative dehydrogenation, ammoxidation and for environmental selective catalytic reduction of NOx. We will also illustrate the capacity of real time spectroscopy to understand reaction mechanism for liquid phase reactions,4 like the role of Brønsted Acid Sites (BAS) vs. that of Lewis Acid Sites (LAS) for the acetalization of glycerol into solketal. Mesoporous cellular foams modified to contain exclusively BAS, LAS and combinations thereof illustrate the role of BAS.4 This relevance led us to use novel Brønsted acid ionic liquids (BAILs).5 The transversal nature of the operando approach places it at the junction between fundamental catalytic chemistry and applied chemical engineering. This work is supported by European Commission BIORIMA GA 760928 and Spanish Ministry RIEN2O, CTM2017-82335-R.

References:
[1] Calvino-Casilda, V.; Stawicka, K.; Trejda, M.; Ziolek, M.; Banares, M. A. Real-Time Raman Monitoring and Control of the Catalytic Acetalization of Glycerol with Acetone over Modified Mesoporous Cellular Foams. J. Phys. Chem. C 2014, 118 (20).
[2] Stawicka, K.; Díaz-Álvarez, A. E.; Calvino-Casilda, V.; Trejda, M.; Banares, M. A.; Ziolek, M. The Role of Brønsted and Lewis Acid Sites in Acetalization of Glycerol over Modified Mesoporous Cellular Foams. J. Phys. Chem. C 2016, 120 (30), 16699–16711.
[3] Gui, Z.; Zahrtmann, N.; Saravanamurugan, S.; Reyero, I.; Qi, Z.; Banares, M. A.; Riisager, A.; Garcia-Suarez, E. J. Brønsted Acid Ionic Liquids (BAILs) as Efficient and Recyclable Catalysts in the Conversion of Glycerol to Solketal at Room Temperature. ChemistrySelect 2016, 1 (18).

12:35: [MoltenMonAM04]
Use of Ionic Liquids for the Extraction of Actinides and Lanthanides: Synergistic Effects and Task-specific Extractants
Clotilde Gaillard¹ ; Maria Boltoeva² ; ¹CNRS, Villeurbanne, France; ²CNRS, Strasbourg, France;
Paper Id: 222 [Abstract]

Room-Temperature ionic liquids (IL) have been widely studied over the past several years for metal ion extraction, as their unique physico-chemical properties can be adjusted by selecting their ionic components for a specific need. For the extraction of metal ions like actinides (An) and lanthanides (Ln), IL can be used in several ways: as a solvent in the replacement of conventional molecular solvents [1], as an extracting molecule by using task-specific ionic liquid synthesised from a well-known extracting pattern, or as a synergistic agent in a traditional extractant/molecular solvent system [2]. This presentation will be focused on the extraction of actinides and lanthanides, to illustrate how the use of IL can result in higher efficiency and/or selectivity. With the support of spectroscopic techniques, UV-Vis and EXAFS, to identify the nature of extracted complexes and a modelling of the extraction data, we also demonstrate the mechanisms involved in the ion extraction, and compare them with those occurring in conventional extracting systems using molecular solvents. The advantages and drawbacks of the IL use will be discussed. Typical examples on the use of IL for the An and Ln separation will be presented. First, we will focus on how the extraction of uranium(VI) proceeds in a hydrophobic IL used in replacement of the usual organic solvent. Two extracting systems were investigated, using either TBP or a malonamide extractant. Then, we will present the An(III)/Ln(III) separation using a task-specific ionic liquid based on the CMPO pattern. We show that it allows a sequential separation of U(VI) and Eu(III)/Am(III), just by changing this ligand concentration in the organic phase. Finally, we will show how the extraction of uranium(VI) from nitric acid solutions with TODGA into the molecular solvent dichloroethane can be strongly enhanced by addition of a small amount of the ionic liquid C₄mimTf₂N in the organic phase, by the mean of a synergistic effect [3,4].

References:
[1] C. Gaillard, M. Boltoeva, I. Billard, S. Georg, V. Mazan, A. Ouadi, D. Ternova and C. Hennig, ChemPhysChem, 16 (2015) 16.
[2] G.A. Pribylova, I.V. Smirnov, A.P. Novikov, J. Radioanal. Nucl. Chem., 295 (2013) 83.
[3] A.N. Turanov, V.K. Karandashev, M. Boltoeva, C. Gaillard, V. Mazan, Sep. Purif. Technol. 164 (2016) 97.
[4] M. Boltoeva, C. Gaillard, S. Georg, A. N. Turanov, Sep. Purif. Technol. 203 (2018) 11.

SESSION: MoltenMonPM1-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Mon Nov, 5 2018 / Room: Bossa (150/3rd)
Session Chairs: Peter Wasserscheid; Session Monitor: TBA

14:00: [MoltenMonPM105] Keynote
Anomalous Behaviour of Ionic Liquids in Electric Fields
Mohd Azizi Nawawi¹ ; Ryan Clark¹ ; Aleksandar Ivanov¹ ; Qingshan Liu¹ ; Joshua Edel¹ ; Marina Kuimova¹ ; Alastair Mcintosh¹ ; Tom Welton¹ ; ¹Imperial College London, London, United Kingdom;
Paper Id: 390 [Abstract]

Ionic liquids are liquids composed entirely of ions. These ions are in constant motion. Ionic liquids have found use in a wide range of electrochemical applications, such as batteries, fuel cells and solar cells. In these applications ionic liquids are exposed to electric fields. It is, therefore, surprising that the dynamics of ions in ionic liquids has been hardly studied. This paper reports our results on the diffusion of solutes in ionic liquids using Fluorescence Correlation Spectroscopy. We show that the diffusion of these ions slow on the application of an electric field. Further to this, we show that the relaxation of this motion after discharge of the cell is remarkably slow on the timescale of tens of minutes. We also report a study of the rotation of molecular rotors by Fluorescence Lifetime Spectroscopy, which can be correlated with the viscosity of the solvent in the cybotactic region of the probe rotor. These results show that the slower motion of ions is associated with an increase in this viscosity. We have also been studying these systems with molecular dynamics simulations. These are giving an insight into how the ionic liquid ions behave in electric fields.

14:25: [MoltenMonPM106] Invited
Understanding the Different Partial Charge Representations of Ionic Liquids
Patricia Hunt¹ ; ¹Imperial College London, London, United Kingdom;
Paper Id: 305 [Abstract]

Ionic liquids (ILs) are composed entirely of ions; however, unlike molten salts, the ions are larger and more complex. Typical ILs include organic cations and mineral, inorganic, or biological anions. The large ions experience reduced Coulombic interactions, frustrated crystal packing, and enhanced entropic contributions that also help to lower the melting point— ILs are liquid at or just above room temperature. ILs are promising solvents and electrolytes with a number of appealing physical and chemical properties. ILs are of particular interest as advanced functional materials and engineering fluids (additives, storage media, fuels, and lubricants) and as electrolytes in electrochemical applications (Li-batteries, supercapacitors, fuel/solar-cells, industrial electrochemistry). A key feature and advantage of ionic liquids is the potential ability to tailor physico-chemical properties by varying the constituent ions. However, advances in the development and use of ILs are being hampered by an inability to predict, or even rationalise, IL properties. Computational studies can help by establishing a link between the chemical make-up of constituent ions and the resultant properties of an IL. However, ILs also present some difficult aspects in modeling and simulation. Interactions within ILs are dominated by Coulombic forces; the size and distribution of partial atomic charges is particularly relevant. However, very different charge distributions are generated by different methods. [1] MK and CHelpG charges are based on fitting to the electrostatic potential (ESP); however, the charges produced do not necessarily correlate with the underlying bonding and electronic interactions. NPA and QTAIM charges are based on the electronic density; however, the produced charges generate a poor fit to the ESP. In addition, the quality of the representation provided by each method can be evaluated by comparison to experimentally derived data (NEXAFS, XPS).[2,3] Our goal has been to better understand the dichotomy raised by these apparently opposing "charge" distributions and to establish if there is any common ground between the methods.

References:
[1] P.A. Hunt*, B. Kirchner and T. Welton, Chem. Eur. J, 2006, Vol 12, Iss 26, 6762-6775
[2] R. Fogarty, R. Rowe, R, Matthews, M. Clough, C. Ashworth, A. Brandt, P. Corbett, R. Palgrave, E. Smith, R. Bourne, T. Chamberlain, P. Thompson, P.A. Hunt*, K. Lovelock*, Faraday Discuss., 2018 206, p183-201
[3] R. Fogarty, R, Matthews, C. Ashworth, A. Brandt, P. Corbett, R. Palgrave, E. Smith, R. Bourne, T. Hoogerstraete, P.A. Hunt* and K. Lovelock*, J. Chem. Phys., 2018 148, no. 193817

14:50: [MoltenMonPM107]
Switchable Aqueous Pentaethylenehexamine for CO₂ Capture
Santosh Khokarale¹ ; Jyri-pekka Mikkola² ; ¹Chemistry Department, Umeå University, Umeå, Sweden; ²Abo Akademi University, Turku, Finland;
Paper Id: 180 [Abstract]

Carbon dioxide (CO₂) concentration in the atmosphere surpassed the 400 ppm milestone in 2016 [1], approximately 120 ppm higher compared to the pre-industrial era. Along with the significant increase in the CO₂ level during the past decades, the human race has witnessed unprecedented climate change [2]. Therefore, it is necessary to find an efficient solution for capturing CO₂ from flue gases, in order to cut down anthropogenic CO₂ emissions. There is an increasing interest in polyamines, because they possess multiple reactive sites for high CO₂ uptake capacity, high thermal stability, as well as lower toxicity compared to the today's alternatives. Polyamines have the potential to improve the CO₂ loading, CO₂ absorption rate, and has a lower energy penalty [3, 4]. <br /> A reversible CO₂ uptake study was performed in neat pentaethylenehexamine (PEHA) and its aqueous solutions, and the performance was compared with industrially applied aqueous solution of monoethanolamine (MEA). Simultaneously, the relative amount of CO₂ chemisorbed chemical species, such as carbamates/(bi)-carbonates forming, was studied using NMR analysis and a calculation method introduced by Holmes et al. [5]. Furthermore, the CO₂ capture capacity of the solvents, correlated with their respective Kamlet-Taft polarity parameters, and the system were modelled with Linear Solvation Energy Relationship (LSER) approach. <br />It was observed that CO₂ capture capacity, as well as the nature of chemical species were influenced by water. The LSER calculations represented that amongst the studied Kamlet-Taft parameters, the CO₂ capture capacity merely depends on hydrogen bond acceptor ability (beta) and polarizability (pi). Upon the thermal regeneration study, the pure PEHA was obtained from CO₂ saturated reaction mixture at 120°C. Considering the high CO₂ absorption capacity and very low evaporation rate during regeneration compared to aqueous solution of MEA, PEHA can be used as a sustainable solvent for CO₂ capture in large-scale flue gas cleaning processes.

References:
[1] E. Dlugokencky, P. Tans, NOAA/ESRL (www.esrl.noaa.gov/gmd/ccgg/trends/).
[2] R. A. Kerr, Science 316 (2007), 188-190
[3] Y. E. Kim, S. J. Moon, Y. I. Yoon, S. K. Jeong, K. T. Park, S. T. Bae, S. C. Nam, Separation and Purification Technology 122 (2014) 112-118
[4] P. Muchan, J. Narku-Tetteh, C. Saiwan, R. Idem, T. Supap, Separation and Purification Technology 184 (2017) 128-134
[5] P. E. Holmes II, M. Naaz, B. E. Poling, Ind. Eng. Chem. Res. 37 (1998) 3281-3287

15:15: [MoltenMonPM108]
Ionic Liquids for Controlled Synthesis of Functional Materials for Energy-related Applications
Sheng Dai¹ ; ¹University of Tennessee, Knoxville, United States;
Paper Id: 287 [Abstract]

The conventional synthesis of functional materials relies heavily on water and organic solvents. Alternatively, the synthesis of functional materials using or in the presence of ionic liquids represents a burgeoning direction in materials chemistry [1]. Ionic liquids are a family of non-conventional molten salts that can act as both templates and precursors to functional materials, as well as solvents. They offer many advantages, such as negligible vapor pressures, wide liquidus ranges, good thermal stability, tunable solubility of both organic and inorganic molecules, and much synthesis flexibility. The unique solvation environment of these ionic liquids provides new reaction media for controlling the formation of porous materials and tailoring morphologies of advanced materials. Challenges and opportunities in using ionic liquids for synthesizing functional materials in energy-related applications will be discussed.

References:
[1] Ma, Z.; Yu, J. H.; Dai, S. "Preparation of Inorganic Materials Using Ionic Liquids," Adv. Mater. 2010, 22, 261-285.

SESSION: MoltenMonPM2-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Mon Nov, 5 2018 / Room: Bossa (150/3rd)
Session Chairs: Tom Welton; Session Monitor: TBA

15:55: [MoltenMonPM209] Keynote
Bulk Liquid Phase Processes Using Ionic Liquids — Success Factors and Recent Examples
Peter Wasserscheid¹ ; Jakob Albert² ; ¹Friedrich-Alexander-Universitat, Erlangen, Germany; ²Institute for Chemical Reaction Engineering, Erlangen, Germany;
Paper Id: 289 [Abstract]

This presentation highlights two recent developments of our group using ionic liquids as bulk liquid phase in industrially relevant, new process concepts. The first part of the presentation is dedicated to the role of an IL sorbent during the catalytic hydrogenation of CO₂ to methanol. This reaction is limited under stoichiometric conditions to around 20 % methanol yield by the equilibrium (75 bar total pressure, 250 °C). However, in the presence of an IL that absorbs both methanol and water under reaction conditions, significantly higher overall MeOH yields can be realized. This new application of IL sorbents has been demonstrated on a 5 L reactor scale with a continuous methanol production rate of more than 50 g per hour. The second part of the presentation deals with a novel liquid-phase technology to convert lactic acid from fermentation to bio-acrylic acid. Acrylic acid is a major industrial chemical that is so far exclusively produced by a two-step oxidation process from propene. Selective conversion from biomass via lactic acid promises a strong reduction of the CO2 footprint, but also higher productivity under much milder conditions. The new process applies a bromide ionic liquid reaction medium to realize a nucleophile assisted dehydration process in hitherto unreached selectivity and yield.[2, 3]

References:
[1] J. Albert, M. Baldauf, J. Reichert, K. Stark, A. Tremel, P. Wasserscheid, WO 2017212016 A1 20171214.
[2] M. Kehrer, J. Mehler, N. Taccardi, J. Nagengast, J. Kadar, D. Collias, P. Dziezok, P. Wasserscheid, J. Albert, ChemSusChem 2018, 11(6), 1063-1072.
[3] J. Albert, P. Wasserscheid, N. Taccardi, J. Nagengast, M. Kehrer, J. Kadar, D. I. Collias, WO 2018022826 A1 20180201.

16:20: [MoltenMonPM210] Invited
Are Ionic Liquids Revolutionizing Analytical Chemistry?
Mihkel Koel¹ ; ¹Tallinn University of Technology, Tallinn, Estonia;
Paper Id: 31 [Abstract]

Analytical chemistry is very actively searching for the possibilities of taking into use ionic liquids (ILs), which are completely different from conventional molecular solvents. More and more specific ILs have appeared with the aim to fill the task of a certain application task specific ionic liquids (TSIL) - and this has been a growing trend in analytical applications as well. The design and optimisation of TSILs is becoming a part of good practice in the development of ionic liquids. Ionic liquids in gas-liquid chromatography have already stepped into the commercialization stage, as listed in catalogues [1]. The great potential of ILs for expanding opportunities of almost all of the separation technologies has been clearly expressed in many publications. In case of micro-extraction, the use of ILs increases the performance and speed of a method and makes it greener in terms of reagents consumption [2]. Even in analytical methods like liquid chromatography and electrophoresis, where ILs are used mostly as ordinary salt additives, the structural novelty of these compounds is supplying a wider range of interaction modalities [3]. In liquid chromatography there are examples of the use of pure ILs as eluents, which were considered impossible in the past [4]. With unique elution pattern, they are showing a new potential of ILs application. In this case, the use of ILs increases the performance of a method and makes it greener in terms speed and reagents consumption. Here, the design of functional ILs with suitable physico-chemical properties is also the key issue. A rapidly emerging field in analytical research is the development of sensors and diagnostic devices, where use of ILs as alternatives to molecular solvents and conventional materials are increasing sensitivity, selectivity, and limits of analysis detections [5]. However, there are some areas in analytical chemistry, like mass spectrometry, which have experienced loss of inflated expectations. It means only slowing down the development to look at things from other angles, and working towards a second generation of methods and materials. Several studies on the toxicity and environmental impact of ILs have raised questions about their real "greenness". However, despite that, ILs have a great potential for green chemistry solutions that needs to be realized. Moreover, since relevant physico-chemical and biological properties, including toxicity and biodegradability, can be modified and optimized through a rational design, ILs should represent a continuous stimulus and an endless challenge to chemists.

References:
[1] Sigma-Aldrich: Ionic liquid capillary GC columns. http://www.sigmaaldrich.com/analyticalchromatography/
analytical-products.html?TablePage=101691909. Accessed 16 February 2016.
[2] E.M.Martinis, P.Berton, R.G.Wuilloud,. Ionic liquid-based microextraction techniques for trace element
analysis, Trends Anal. Chem., 60(2014)54-70.
[4] M.C. Garcia-Alvarez-Coque, M.J. Ruiz-Angel, A.Berthod, S.Carda-Broch, On the use of ionic liquids
as mobile phase additives in high-performance liquid chromatography. A review, Anal. Chim. Acta,
883(2015)1-21
[4] K. Kuroda and H.Ohno, High Performance Ionic Liquid Chromatography, in Anal. Appl.Ionic Liquids ed. M.Koel World Sci. 2017
[5] J. Gebicki; Application of electrochemical sensors and sensor matrixes for measurement of odorous chemical compounds, TrAC-Trends Anal. Chem., 77(2016) 1-13

16:45: [MoltenMonPM211] Invited
Removal of NO from Gas Streams Using Nitrate-based Ionic Liquids
Susanne Mossin¹ ; Rasmus Fehrmann¹ ; Peter L. Thomassen¹ ; ¹DTU Chemistry, Lyngby, Denmark;
Paper Id: 130 [Abstract]

The demand for end-of-pipe deNO_x technologies has driven the research for activation and conversion of nitric oxide, NO, at low temperatures compared to the traditional selective catalytic reduction of NO with ammonia. This study describes the progress made in the absorption and catalytic conversion of NO by ionic liquids. Nitrate based ionic liquids such as BMIM (butyl-methyl-imidazolium) nitrate has proven surprisingly efficient for conversion of NO_x to nitric acid using air as the oxidant.[1,2] The nitric acid is absorbed into the ionic liquid. Desorption can occur in a successive separation step forming commercial grade concentrated nitric acid and a fully regenerated absorber. Using the SILP (Supported Ionic Liquid Phase) technology the ionic liquid is impregnated onto a porous support. Alternatively, the SILP material can be extruded as monoliths and loaded into a catalyst bed for continuous NO oxidation at low temperature (< 100°C) and high humidity.[3] The technology facilitates the conversion of NO into a mixture of higher oxygenates (NO₂, HNO₂, and HNO₃) for further downstream processing or absorption. Recently[3], we have discovered that small amounts of alcohols injected into the flue gas upstream the SILP material enhances the low temperature oxidation of NO considerably, increasing the effectiveness of the catalyst. Currently we pursue the invention for gas cleaning application in collaboration with industry.

References:
[1] A. J. Kunov-Kruse, P. L. Thomassen, A. Riisager, S. Mossin, R. Fehrmann Chem. Eur. J. 2016, 22, 11745-11755.
[2] P. K. Kaas-Larsen, P. L. Thomassen, L. Schill, S. Mossin, A. Riisager, R. Fehrmann ECS Trans. 2016, 75, 3-16.
[3] P. W. Jakobsen, S. Mossin, R. Fehrmann In preparation

17:10: [MoltenMonPM212]
Polymer Ionic Liquids Layers for Textile Chemiresistors
Eva Maresova¹ ; David Tomecek¹ ; Premysl Fitl¹ ; Jan Vlcek¹ ; Sarka Havlova¹ ; Martin Vrnata¹ ; ¹University of Chemistry and Technology Prague, Prague, Czech Republic;
Paper Id: 259 [Abstract]

Application of functional elements and nanostructures on flexible substrates is a promising trend in electronics. Textiles represent material with great potential, whose mechanical properties (high strength, large surface area, lightness, flexibility, easy integrability into clothing) make it unique even in comparison with other flexible substrates [1,2]. Polymerized ionic liquids (PILs) was first reported in 1998, and a brief overview of their properties can be found in [3]. Their electrotransport properties are unique (when compared with other organic substances), as they are purely ionic conductors. Moreover, a majority of them can be considered to be single-ion conductors. PILs are characterized by a large capacity to absorb gases (analytes) with small molecules, especially CO₂ and water. On such absorption, the internal volume of the polymer is modified, and hence mobility of ions changes [4]. In the field of sensing, PILs are often employed in electrochemical sensors [5], but much rarely for sorbents in QCM sensors [6]<br />This work deals with textile chemiresistors with sensitive layers based on two types of cationic PILs / poly(tetrabutylphosphonium 3-sulfopropylacrylate) and poly(tributylhexylphosphonium 3-sulfopropyl acrylate). It includes: (i) investigation of sensitive layer - electrode contact phenomena by measuring current voltage characteristics; (ii) general characterization of these PILs by impedance spectroscopy; (iii) overview and analysis of DC- and AC- responses of PILs sensors to 10 ppm of methanol (MeOH), nitrogen dioxide (NO₂), 4-bromoacetophenone (4-BAP), diethylmalonate (DEM) and yperite; and (iv) FTIR spectra of PILs— exposed and unexposed— to analyte vapours [7]. <br />Under these circumstances, the DC- responses (SDC) varied from 0.48 to 1.36, and maximum AC- responses (Spa) from 8 to 26 deg. It was shown that sensor dynamics depend mainly on molecular weight of the analyte. Moreover, the magnitude of AC-responses correlates both qualitatively and quantitatively with the dipole moment of the analysed molecule.

References:
[1] D. Kincal, A. Kumar, A.D. Child, J.R. Reynolds, Conductivity switching in polypyrrole-coated textile fabrics as gas sensors, Synth. Met., 92 (1998), pp. 53-56\n[2] T. Ghosh, A. Dhawan, Electronic textiles and their potential, Indian J. Fibre Text. Res., 31 (2006), pp. 170\n[3] N.Nishimura, H. Ohno, 15th anniversary of polymerised ionic liquids, Plomers 55 (2014) 3289\n[4] J. Yuan, D. Mecerreyes, M. Antonietti, Poly(ionic liquid)s: An update, Prog. Polym. Sci., 38 (2013), pp. 1009\n[5] D. Wei, A. Ivaska, Applications of ionic liquids in electrochemical sensors, Anal. Chim. Acta., 607 (2008), pp. 126\n[6] P. Kubersky, J. Altšmid, A. Hamacek, S. Nešpůrek, O. Zmeškal, An electrochemical NO2 sensor based on ionic liquid: influence of the morphology of the polymer electrolyte on sensor sensitivity, Sensors, 15 (2015), pp. 28421\n[7] E.Maresova et all. Textile chemiresistors with sensitive layers based on polymer ionic liquids: Applicability for detection of toxic gases and chemical warfare agents, Sensors and Actuators B, 266 (2018) 830.

SESSION: MoltenTueAM-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Tue Nov, 6 2018 / Room: Bossa (150/3rd)
Session Chairs: Robin Rogers; Session Monitor: TBA

11:20: [MoltenTueAM01]
Application of Ionic Liquids in Oxidative and Acidic Catalysis
Nina Kuznetsova¹ ; Nikolay Adonin¹ ; Bair Bal'zhinimaev¹ ; ¹Boreskov Institute of Catalysis, Novosibirsk, Russian Federation;
Paper Id: 165 [Abstract]

Ionic liquids (IL) are drawing increasing and considerable attention in the field of catalysis as perfect, non-volatile, thermally stable solvents and media for liquid phase selective reactions [1]. We represent here examples from the catalytic chemistry, where ILs has been successfully used for improving two industrially important reactions. Well-known commercial synthesis of terephthalic acid (TPA) is based on aerobic oxidation of p-xylene in acetic acid solution of the Co/Mn/Br catalyst, that followed by the cost and energy-consuming hydropurification of the crude TPA product from p-carboxybenzaldehyde (4-CBA) [2]. We showed that addition of ILs (dialkylimidazolium acetate and bromide) and ammonium acetate changes properties of the conventional solvent to improve solubility and accelerate oxidation of 4-CBA to TPA. Efficient combinations of the additives and appropriate reaction conditions have been selected to obtain the target product with 4-CBA content below 25 ppm [3]. Positive effect is caused by excellent solvating ability of ILs for TPA and 4-CBA. The designed catalytic systems can be applied to obtain high-quality TPA just after oxidation stage, without the hydropurification. The next example is related to the alkylation of benzene with dodecene-1 for production of linear alkylbenzene catalyzed with binary 1-butyl-3-methylimidazolium chloride-aluminum chloride system. This catalyst showed high performance in the synthetic detergent not only from neat dodecene-1, but from the feedstock containing a mixture of C10-C13 alkanes and C10-C13 alkenes. The best results have been obtained when the mole fraction of [BMIM]Cl ionic liquid is around 40%. Furthermore, the optimal reaction conditions, such as benzene/alkene ratio (1.6-3) and temperature (30-40°C), have been found. In this case, a very high 98-99% yield of detergent is achieved [4].

References:
[1] C. Dai, J. Zhang, C. Huang and Z. Lei, Chem. Rev. 117 (2017) 6929-6983.
[2] C. Park, J. R. Sheehan, In Kirk-Othemer Encyclopedia of Chemical Technology, 4th Ed. V.18, New York, 1996, pp. 478-491.
[3] N. I. Kuznetsova, B. S. Bal'zhinimaev, A. Bhattacharyya, J. T. Walenga, ChemistrySelect, 2 (2017) 11815-11820.
[4] M.G. Riley, A. Bhattacharyya, N.Y. Adonin, M.N. Timofeeva, S.A. Prikhodko, B.S. Bal'zhinimaev, Benzene alkylation using acidic ionic liquids. US Patent 9328037.

11:45: [MoltenTueAM02]
Screening of [DCN] and [TF₂N]-based Promising Ionic Liquids for Carbon Dioxide Capture: Solubility and Thermodynamic Modeling
Amr Henni¹ ; Mohamed Zoubeik¹ ; ¹University of Regina, Regina, Canada;
Paper Id: 364 [Abstract]

Carbon dioxide (CO₂) capture is the key to global warming. Advances in CO₂ capture technology are being sought by industries in an attempt to revolutionize the energy sector and divert some of the CO₂ being released from industrial emissions onto greener paths. Among the endless capture technologies, the use of ionic liquids has gained tremendous popularity as a novel environmentally and energy efficient solution. Three different ionic liquids were investigated for their ability to capture CO₂. With the aid of a gravimetric microbalance, their capacity to absorb carbon dioxide was determined experimentally. The ionic liquids explored in this study were a dicyanamide [DCN]-based solvent, and two bis (trifluoro methylsulfonyl)imide [TF₂N] based solvents. Solubilities were examined at readings of 313.15, 323.15 and 333.15K and over a pressure range up to 20 bar. Experimental densities were also measured, and the Henry's law constants, entropy and the enthalpy values were calculated and reported. Three thermodynamic models were used to correlate the data. The Non-Random Two-Liquid (NRTL) model and the Peng-Robinson and Soave-Redlich-Kwong equations of state correlated the data quite accurately. The best ionic liquid in his study, [TDC][TF₂N], was found to be akin to some popular ionic liquids such as [hmim][TF₂N], which makes it an attractive physical solvent for CO₂ removal processes.

12:10: [MoltenTueAM03]
Ionic Liquid Promoted Synthesis of Aryl Ureas in Pd-catalyzed Oxidative Carbonylation
Anders Riisager¹ ; Nanette Zahrtmann¹ ; Cyril Godard² ; Carmen Claver² ; Eduardo J. García Suárez¹ ; ¹DTU Chemistry, Kgs. Lyngby, Denmark; ²Universitat Rovira i Virgili, Tarragona, Spain;
Paper Id: 245 [Abstract]

Ureas are important compounds found in the structures of a large number of biologically active compounds and widely used as agrochemicals, dyes, antioxidants, and HIV inhibitors, as well as key intermediates in organic synthesis [1]. Ureas can be prepared via the oxidative carbonylation of amines in the presence of a Pd-complex catalyst, usually at high pressure and temperature and under an explosive CO/O₂ gas mixture making the overall system unsafe [2]. Accordingly, it is desirable to develop an active catalytic system applicable for the oxidative carbonylation of amines under milder reaction conditions.<br />Ionic liquids (ILs) can have beneficial effects in many homogeneously catalyzed reactions [3]. Furthermore, the use of ILs in liquid-liquid biphasic reactions makes processes in many cases greener than when using traditional organic solvents, due to associated advantages such as low vapor pressure, as well as good thermal stability, tunable solubility, and coordination properties [4]. In addition, such systems provide good separation of reaction products and catalyst recovery.<br />In this work, we present a new efficient, robust, and versatile Pd-complex/IL catalytic biphasic system for the oxidative carbonylation of aromatic amines under mild reaction conditions [5]. Reaction parameters, including oxidant agent, pressure, temperature, catalyst and IL loading were optimized, resulting in a catalytic system which operates under mild conditions, is fully recyclable, is 100% selective and has activity two orders of magnitude higher than previously reported systems [6].

References:
[1] D. J. Diaz, A. K. Darko, L. McElwee-White, Eur. J. Org. Chem., 27 (2007) 4453.\n[2] S.-Z. Zheng, X.-G. Peng, J.-M. Liu,W. Sun, C.-G. Xia, Chin. J. Chem., 25 (2007) 1065.\n[3] Supported Ionic Liquids: Fundamentals and Applications, R. Fehrmann, A. Riisager, M. Haumann, Wiley-VCH, 2014.\n[4] M. Haumann, A. Riisager, Chem. Rev., 108 (2008) 1474.\n[5] N. Zahrtmann, C. Claver, C. Godard, A. Riisager, E. J. Garcia-Suarez, ChemCatChem, DOI: 10.1002/cctc.201800004.\n[6] B. Chen, S. S. C. Chuang, Green Chem., 5 (2003) 484.

12:35: [MoltenTueAM04]
Topological Forecast of 4D T-x-y-z Diagram Li,Na,Rb,La||F
Vasily Lutsyk¹ ; Anna Zelenaya¹ ; Maria Parfenova² ; ¹Institute of Physical Materials Science SB RAS, Ulan-Ude, Russian Federation; ²Tomsk State University of Control Systems and Radio-electronics, Tomsk, Russian Federation;
Paper Id: 120 [Abstract]

Interest in systems with fluoride metals is due to the fact that they have been considered as a potential component for nuclear reactor fuel in molten salts. Three ternary systems of Li,Na,Rb||F, Li,Rb,La||F and Na,Rb,La||F on the boundary of quaternary system Li,Na,Rb,La||F have been analyzed. Model for the 4th boundary Na,Li,La||F was built earlier [1]. Li,Na,Rb||F has the simplest structure. Its eutectic type is complicated by the compound R=LiRbF₂, decaying in the solid phase, and is characterized by two invariant equilibria: eutectic one and decomposing of R (dot Y). Space model includes 3 liquidus surfaces, 3 - solidus, 10 - solvus, 22 - ruled ones, and 2 horizontal complexes at temperatures of E and Y, and has 4 monophase regions (А, В, С, R), 9 - 2-phase (L+A, L+В, L+С, A+B, A+C, B+C, A+R, B+R, C+R) and 7 - 3-phase ones (L+A+В, L+A+C, L+B+C, A+B+C, A+C+R, A+B+R, B+C+R). System Li,Rb,La||F is complicated by 5 binary compounds: R₁=LiRbF₂ - with the exotermic decaying, and 4 incongruently melting R₂=Rb₃LaF₆, R₃=Rb₂LaF₅, R₄=RbLaF₃, R₅=RbLa₂F₇. Compounds R3, R5 have endothermic decay and exist in the short temperature interval. Space model consists of 7 liquidus surfaces, 31 ruled surfaces, 6 horizontal complexes and includes 10 2-phase regions (L+A, L+B, L+C, L+R2, L+R3, L+R4, L+R5, R1+R2, A+R2, A+R4) and 16 3-phase regions (L+A+B, L+A+C, L+A+R2, L+A+R4, L+B+R2, L+C+R4, L+C+R5, L+R2+R3, L+R2+R4, L+R3+R4, L+R4+R5, A+R1+R2, A+B+R2, A+R2+R4, A+C+R4, B+R1+R2). 2-phase regions R1+R2, A+R2, A+R4 have a degenerated structure in the form of vertical planes. System Li,Rb,La||F has a similar structure, but is sophisticated by the additional liquidus surface of R1=NaLaF₄. As a result, there are 3 invariant equilibria, 8 liquidus surfaces, 35 - rules ones and 6 horizontal complexes on the boundary of 28 phase regions (L+A, L+B, L+C, L+R1, L+R2, L+R3, L+R4, L+R5, A+R2, A+R4, R1+R4, L+A+B, L+A+R1, L+A+R2, L+A+R4, L+B+R2, L+C+R1, L+C+R4, L+C+R5, L+R1+R4, L+R2+R3, L+R2+R4, L+R3+R4, L+R4+R5, A+R1+R2, A+R2+R4, A+R1+R4, R1+R4+C). Concentration fields in the 4 ternary systems with the different trajectories of phases have been analyzed [2-3]. 4 ternary systems are used to forecast a topological structure of T-x-y-z diagram Li,Na,Rb,La||F [4] with 6 binary compounds: R₁=LiRbF₂, R₂=NaLaF₄, R₃=Rb₃LaF₆, R₄=Rb₂LaF₅, R₅=RbLaF₄, R₆=RbLa₂F₇ (R1 decays in solid, R2-R6 - with incongruently melting, and R3, R5 with endothermic decaying). In the ternary systems there are 14 invariant equilibria. For T-x-y-z diagram Li,Na,Rb,La||F it is forecasted 4 invariant 5-phase equilibria with 9 liquidus hypersurfaces.

References:
[1] R.N. Savchuk, N.V. Faidyuk, A.A. Omelchuk, V.I. Lutsyk, A.E. Zelenaya, Journal of Inorganic Chemistry, 59 (2014) 780-785. (In Russian)
[2] V. Lutsyk, A. Zelenaya, Journal of Physics: Conference Series, 790 (2017), 012020.
[3] Y.V. Pogorenko, R.M. Pshenychnyi, V.I. Lutsyk, A.O. Omel'chuk, IOP Conf. Series: Materials Sci. and Eng., 175 (2017), 012039.
[4] V.I. Lutsyk, A.E. Zelenaya, Journal of Physics: Conference Series, 790 (2017), 012020.

SESSION: MoltenTuePM1-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Tue Nov, 6 2018 / Room: Bossa (150/3rd)
Session Chairs: Anja-Verena Mudring; Session Monitor: TBA

14:00: [MoltenTuePM105]
Upgrading of Biogas Using Supported Ionic Liquid Phase (SILP) Materials
Leonard Schill¹ ; Frederik Bork Jansen¹ ; Christian Weibel¹ ; Anders Riisager² ; Rasmus Fehrmann¹ ; ¹DTU Chemistry, Lyngby, Denmark; ²DTU Chemistry, Kgs. Lyngby, Denmark;
Paper Id: 72 [Abstract]

Upgrading of biogas requires the removal of both CO₂ and H₂S. Amino Acid based ionic liquids (AA-ILs) are known to efficiently remove CO2 by binding to the carboxylate group and DFT studies suggest that H₂S can bind to both the carboxylate and the amine group of the amino acid anion. This study has demonstrated that that indeed two moles of H₂S can bind to one mole of [P4444][Pro] even when a highly dilute stream (750 ppm) is used. Adsorption to the stronger sites (amine groups) is possible even in the presence of a vast excess of CO₂. There is reason to believe that H₂S removal levels of > 90 % could be maintained for several days at a space velocity of 100 h-1 with an H₂S inlet concentration of 750 ppm. Potential pressure drop problems were solved by impregnating the ionic liquid onto mesoporous pellets prepared by a simple and scalable technique. H₂S removal under relatively mild conditions (60 °C, 50 mbar) was unsuccessful and raises concerns about the ability to regenerate [P4444][Pro]. This might also mean that pure CO₂ removal using [P4444][Pro] requires gas streams practically free of H₂S.

References:
[1] Angelidaki, I.; Treu, L.; Tsapekos, P.; Luo, G.; Campanaro, S.; Wenzel, H.; Kougias, P. G. Biogas upgrading and utilization: Current status and perspectives. Biotechnology Advances 2018, 36, 452-466, doi:10.1016/j.biotechadv.2018.01.011.
[2] Strauch, S.; Krassowski, J.; Singhal, A. Biomethane Guide for Decision Makers Policy - guide on biogas injection into the natural gas grid. Frauenhaofer UMSICHT, Research group biogas technology 2013. http://www.greengasgrids.eu/fileadmin/greengas/media/Downloads/Documentation_from_the_GreenGasGrids_project/Biomethane_Guide_for_Decision_Makers.pdf
[3] Liu, S.; Zhou, H.; Song, Q.; Ma, Z. Journal of the Taiwan Institute of Chemical Engineers Synthesis of higher alcohols from CO 2 hydrogenation over Mo-Co-K sulfide-based catalysts. 2017, 76, 18-26, doi:10.1016/j.jtice.2017.04.007.
[4] Kaas-Larsen, P. K.; Thomassen, P.; Schill, L.; Mossin, S.; Riisager, A.; Fehrmann, R. Selective Reversible Absorption of the Industrial Off-Gas Components CO 2 and NO. ECS Trans. 2016, 75, 3-16, doi:10.1149/07515.0003ecst.
[5] Jansen, F. B.; Weibel, C. Selective absorption of gases by ionic liquids. Bachelor Thesis, Technical University of Denmark, Kgs. Lyngby, Denmark 2017.

14:25: [MoltenTuePM106]
Synthesis and Catalysis with Ionic Liquids - From Batch to Flow
Katharina Schröder (bica)¹ ; ¹Institute of Applied Synthetic Chemistry, Vienna, Austria;
Paper Id: 352 [Abstract]

Despite remarkable developments in ionic liquid technologies with a diverse range of applications, considerably less progress has been made in their preparation. Until today, most hydrophobic prepared in a two-step batch process involves the initial alkylation of an amine or phosphine followed by subsequent metathesis to exchange the anion, a strategy which has already been described in seminal books and reviews on ionic liquids in synthesis in the late 1990s, and has since then remained almost unaltered [1]. Yet a number of critical aspects limits its utility for the large-scale production of hydrophobic ionic liquids in this classical batch process. In parallel to their classical synthesis, the majority of applications of ionic liquids in catalysis is dedicated to batch processes, despite the clear advantages and benefits of a continuous flow set-up.<br />In here, we present novel strategies for the continuous flow production of ionic liquids, aiming for a fast and halide-free approach that eliminates the need of anion metathesis [2]. Critical aspects of an atom efficient continuous-flow synthesis of ionic liquids, but also of their application in catalysis will be discussed. Eventually, advantages and limitations of continuous flow processes will be highlighted, with a number of processes varying from ionic liquid synthesis to their application as reaction media or catalysts in hydrogen or carboxylation reactions either with bulk or supported ionic liquids [3,4].

References:
[1] T. Welton and P. Wasserscheid, Ionic Liquids in Synthesis, VCH-Wiley, Weinheim, 2002.\n[2] K. Bica, M. Schoen, P. Gaertner and M. D. Mihovilovic, Method for producing ionic liquids containing bis(trifluoromethanesulfonyl)imide anions, PCT Int. Appl. (2017), WO 2017112972 A1 20170706\n[3] J. Bruenig, Z. Csendes, S. Weber, N. Gorgas, R. W. Bittner, A. Limbeck, K. Bica, H. Hoffmann, and Karl Kirchner, ACS Catal. 2018, 8, 1048.\n[4] A. Sainz Martinez, C. Hauzenberger, A. Ranjan Sahoo, Z. Csendes, H. Hoffmann and K. Bica, ACS Sus. Chem. Eng. 2018, submitted.

14:50: [MoltenTuePM107]
Carbon Capture in Molten Salts - Calcium Looping in the Molten State
Espen Olsen¹ ; Nils Rusås Ruud¹ ; Heidi S. Nygård¹ ; ¹Norwegian University of Life Sciences, Ås, Norway;
Paper Id: 325 [Abstract]

Carbon Capture in Molten Salts (CCMS) is a method for extracting CO₂ from a variety of flue gases related to power generation and industrial processes [1-3]. It is based on a well known principle called calcium looping, where CaO reacts with CO₂, forming CaCO₃ in a reactor chamber at temperatures well below 900°C. By moving the formed carbonate to another chamber and raising the temperature above 900°C, CaCO₃ decomposes - driving CO₂ off in a controlled manner reforming CaO. Solid sorbents may be moved between chambers by applying fluidized bed principles. In CCMS, the active chemicals are present as dissolved or partly dissolved in an inorganic molten salt. The salt is frequently based on CaCl₂, with additions such as CaF₂ or NaF to suit specific needs with regards to capture efficiency, handling, and costs. In this paper we report on the most recent developments in CCMS technology as well as the economical aspects of using this method for capturing carbon from industrial flue gases. By dissolving and suspending the CaO and CaCO₃ in a molten salt, very rapid reaction kinetics are experienced due to catalytic properties exhibited by the molten salts. This is evidenced by activity coefficients for CaO and CaCO₃ being substantially above unity. This enables more efficient absorption than in systems based on sorption in the solid state.

References:
[1] E. Olsen and V. Tomkute, Energy Science & Engineering, 2013. 1(3): p. 144-150.

[2] V. Tomkute, A. Solheim, and E. Olsen, Energy & Fuels, 2014. 28(8): p. 5345-5353.

[3] E. Olsen, M. Hansen and H.S. Nygård, AIMS Energy, 5,(6), 2017, p. 873-886.

15:15: [MoltenTuePM108]
A Computational Model for Dimulating Rare Earth Reduction on Electrowinning Cells
Jose Adilson De Castro¹ ; Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 319 [Abstract]

A computational model for simulating the production of metallic rare earth by reduction process of molten salts within an electrowinning cell is discussed. The model was formulated based on the multiphase and multicomponent Navier-Stokes and k-epsilon turbulence transport equations, coupled with Maxwell's relations to account for the magneto hydrodynamic phenomena. The multiphase transport equations are solved using the finite volume formulation. The SIMPLE algorithm is used to couple the momentum and pressure equations, and the algebraic coefficients are calculated using the power law scheme. The set of the discretized algebraic equations are iteratively solved using the line by line procedure based on the tridiagonal matrix. The model equations were implemented in a computational code, and the parametric geometry and operational data used were based on the actual operation of the electrowinning cell specially designed for rare earth production. Results based on the simulation cases were discussed and shown feasibility and accordance with actual operation units. Simulated scenarios indicated that optimal conditions could be achieved with lower emissions and high energy consumption efficiency. The model is useful for predicting optimal parameters of processing, such as cell geometry, current density, gas and particulate emissions, and cell stability.

References:
[1] N. Krishnamurthy, C. K. Gupta. Extractive Metallurgy of Rare Earths, Second Edition. 2015. CRC Press.
[2] D. Rodrigues, J. A. de Castro,. M. F. de Campos. Perspectives for Rare-Earth Magnets in Brazil. Proceedings of 23rd International Workshop on Rare Earth and Future Permanent Magnets and Their Applications REPM 2014, 2014, Annapolis, Maryland, USA. v. 1. p. 12-14.
[3] E. Morrice, T A. Henrie. Electrowinning high-purity neodymium, praseodymium, and didymium metals from their oxides [Washington, D.C.] U.S. Dept. of the Interior, Bureau of Mines, 1967.
[4] K. C.Karki, S. V. Patankar: Numerical Heat Transfer Vol. 14, (1988), pp. 295-307.
[5] M. C. Melaaen: Numerical Heat Transfer Vol 21, part B (1992), pp 1-19.

SESSION: MoltenTuePM2-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Tue Nov, 6 2018 / Room: Bossa (150/3rd)
Session Chairs: Sheng Dai; Session Monitor: TBA

15:55: [MoltenTuePM209] Keynote
Ionic Liquids and their Role in Creating Efficient Emitter Materials for Light Emitting Electrochemical Cells
Anja-verena Mudring¹ ; ¹Stockholm University, Stockholm, Sweden;
Paper Id: 398 [Abstract]

Energy consumption is one of the most challenging issues that humankind is facing. Approximately 20% of the world's energy is used for lighting. It is therefore important to reduce the energy consumption of lighting devices and increase their efficiency. For that reason, the old incandescent lamp which has been used for illumination for over 130 years is being phased out in most countries. The most common replacement are CFLs (compact fluorescent lamps), which have certain drawbacks related to the mercury content. LEDs (light emitting diodes) have become competitive for illumination as energy efficient lighting sources. However, it is now realized that both CFLs and LEDs rely on materials like rare earths, gallium and indium that bear a severe supply risk. Thus, there is a significant driving force to look for alternative lighting sources. The discovery of OLEDs (organic light-emitting diodes) marks a significant progress in this direction. However, one of the major drawbacks of OLEDs for lighting applications is their complex device architecture and air-sensitivity which makes them expensive to manufacture and prone to de-composition. The alternative, LECs (light emitting electrochemical cells) can be as simple as being only composed of a light emitting material sandwiched between two electrodes (one reflective electrode: widely the cathode and a second transparent electrode: usually the anode to allow light to exit the device) and LECs are promising as a low cost large area future lighting technology which allows overcoming the problems of OLEDs. Ionic liquids play a key role to enable this still young technology. One of the key challenges is to develop ionic, ionic liquid-based, efficient emitter materials that have a significant lifetime need to be provided for this technology to enter the market. Ionic Ir(III) complexes are the most promising emitters in light emitting electrochemical cells (LECs), especially in the high energy emission range for which it is difficult to find emitters with sufficient efficiencies and lifetimes. To overcome this challenge, the concept of intramolecular π-π-stacking of an ancillary ligand (6-phenyl-2,2'-bipyridine, pbpy) is introduced in the design of a new green emitting iridium ionic transition metal complex with a fluoro-substituted cyclometallated ligand, 2-(4-fluorophenyl)pyridinato (4Fppy). [Ir(4Fppy)2(pbpy)][PF6] has been synthesized, characterized and its photophysical and electrochemical properties have been studied. The complex emits green light with maxima at 561 and 556 nm under UV excitation from powder and thin film, respectively, and displays a high photoluminescence quantum yield (PLQY) of 78.5%. [Ir(4Fppy)2(pbpy)][PF6] based LECs driven under pulsed current conditions showed under an average current density of 100 A m-2 (at 50% duty cycle) a maximum luminance of 1443 cd m-2, resulting in 14.4 cd A-1 and 7.4 lm W-1 current and power efficiencies, respectively. A remarkable long device lifetime of 214 hours was observed. Reducing the average current density to 18.5 A m-2 (at 75% duty cycle) led to an exceptional device performance of 19.3 cd A-1 and 14.4 lm W-1 for current and power efficiencies, an initial maximum luminance of 352 cd m-2 and a lifetime of 617 hours.

References:
J.E. Namanga, N. Gerlitzki, V. Smetana, A.-V. Mudring, Optimizing green light emitting electrochemical cells: Stability improvement without compromising the efficiency , ACS Appl. Mat. Interf. 2018,. DOI: 10.1021/acsami.7b18159.

M. Di Marcantonio, J. E. Namanga, N. Gerlitzki, F. Vollkommer, A.-V. Mudring, G. Bacher, E. Nannen, Bright and Stable Greenish Hybrid Light Emitting Electrochemical Cells, J. Mat. Chem. C, 2017, 5, 12062-12068. DOI: 10.1039/C7TC02976D

J.E. Namanga, N. Gerlitzki, B. Mallick, A.-V. Mudring, Long term stable deep red light-emitting electrochemical cell based on an emissive, rigid cationic Ir(III) complex, J. Mat. Chem. C 2017, 5, 3049-3055, DOI: 10.1039/C6TC04547B.

J.E. Namanga, N. Gerlitzki, V. Smetana, A.-V. Mudring, Scrutinizing design principles towards efficient, long-term stable green light emitting light emitting electrochemical cells, Adv. Func. Mat. 2017, 27, 1605588 (8 pages) DOI: 10.1002/adfm.201605588.

16:20: [MoltenTuePM210] Invited
X-ray Photoelectron Spectroscopy of Ionic Liquids – From Half-cell Measurements to In-situ Electrochemical XPS
Annette Foelske Schmitz¹ ; ¹TU Wien, 1060 Vienna, Austria;
Paper Id: 6 [Abstract]

X-ray Photoelectron Spectroscopy (XPS) is widely accepted to be a powerful tool to study electrochemically induced changes of the electrode/electrolyte interface as it is very surface sensitive, allows for quantitative analysis and assignment of oxidation states or chemical environment of the detected species. As electrochemical experiments are commonly performed under atmospheric pressure using liquid electrolytes that are not ultrahigh vacuum (UHV) compatible, XPS can usually not be applied directly in the analyser chamber of the spectrometer and one may distinguish three experimental approaches, that are (i) transfer of the electrode into the UHV system via air contact, also referred to ex situ analysis, (ii) transfer of the electrode under inert conditions, also referred to as quasi in situ approach, and (iii) performing electrochemistry directly in the analyser chamber of the spectrometer, also referred to as in situ EC XPS [1]. The in situ approach may be realized using ambient pressure XPS or UHV compatible electrolytes such as ionic liquids (IL). Ionic liquids are also known to provide large electrochemical stability windows making them attractive for electrochemical applications such as electrochemical double layer capacitors (EDLC) [2]. In order to elucidate the electrochemical stability windows of carbon/IL systems in detail, quasi in situ [3] and in situ [4] EC XPS setups were realized. The setups and results as well as recently performed XPS half-cell measurements of IL [5] will be presented and discussed with respect to their opportunities and limits, interfacial processes and interpretation of XPS data.

References:
[1] A. Foelske-Schmitz, X-Ray Photoelectron Spectroscopy in Electrochemistry Research, Reference Module in Chemistry, Molecular Sciences and Chemical Engineering, Elsevier, ISBN: 978-0-12-409547-2, (2017)
[2] D. Weingarth, H. Noh, A. Foelske-Schmitz, A. Wokaun, R. Kötz, Electrochim. Acta 103 119 (2013)
[3] A. Foelske-Schmitz, D. Weingarth, R. Kötz, Electrochim. Acta 56 1032 (2011)
[4] D. Weingarth, A. Foelske-Schmitz, A. Wokaun, R. Kötz, Electrochem. Commun. 13 619 (2011)
[5] A. Foelske-Schmitz, M. Sauer, J. Electron Spectrosc. Relat. Phenom. (2017) in press

16:45: [MoltenTuePM211]
Multi-stabilized Pd-SILCA with Nitrogen-rich Ionic Liquids as a Recyclable Catalyst for Heck Reaction
Nemanja Vucetic¹ ; Jyri-pekka Mikkola¹ ; ¹Abo Akademi University, Turku, Finland;
Paper Id: 232 [Abstract]

The palladium-catalysed reaction between aryl halides or vinyl halides and alkenes in the presence of a base — referred to as the Heck reaction — facilitates the carbon-carbon coupling with preservation of double bond. Next to the common VOC solvents, ionic liquids (ILs) have shown great potential for Heck reaction under homogeneous conditions.[1,2] However, for the recycling of expensive metal heterogenization, this system becomes a necessity. One of the potential methods includes supporting Pd complexes and an ionic liquid in a form of Supported Ionic Liquid Catalyst (SILCA) while avoiding the use of toxic and expensive ligands. In a present study, we designed new silica supported catalyst with the nitrogen-rich ionic liquid layer that can ligate active palladium. Through the multiple anchoring points, leaching of the metal was suppressed, and catalyst activity was preserved. Optimization was done by changing the support, metal sources, and varying anion-cation parts of ILs. Remarkable activity in different Heck reactions was demonstrated. In order to get a full understanding of the catalyst structure and behaviour, it was characterised by means of nitrogen physisorption, TGA, XRD, FT-IR, solid-state NMR, XPS, SEM and ICP-MS.

References:
[1] Li, S., Lin, Y., Xie, H., Zhang, S. & Xu, J. Bronsted Guanidine Acid "Base Ionic Liquids": Novel Reaction Media for the Palladium-Catalyzed Heck Reaction. Tetrahedron 2003-2006 (2006).
[2] Wang, R., Piekarski, M. M. & Shreeve, J. M. Pyrazolyl-functionalized 2-methylimidazolium-based ionic liquids and their palladium(ii) complexes as recyclable catalysts. Org. Biomol. Chem. 4, 1878 (2006).

17:10: [MoltenTuePM212] Invited
Materials for the Nuclear Reactors of Generation IV: Polyhedration of the Chloride-Fluoride Reciprocal Systems
Vasily Lutsyk¹ ; Vera Vorob'eva¹ ; Maria Parfenova² ; Marina Lamueva¹ ; ¹Institute of Physical Materials Science SB RAS, Ulan-Ude, Russian Federation; ²Tomsk State University of Control Systems and Radio-electronics, Tomsk, Russian Federation;
Paper Id: 96 [Abstract]

Fluorides of metals with low neutron capture cross-section are usually considered as a basis for the fuel compositions of the molten salts nuclear reactor of IV generation. The advantages of chloride systems can be attributed to less aggressiveness towards the reactor material and lower melting temperatures. However, the chloride systems, compared to the fluoride systems, have higher vapour pressure and a low thermodynamic stability at high temperatures. Therefore, in order to ensure a more reliable operation of new generation reactors, it is advisable to consider the features of the reciprocal chloride-fluoride systems. Some additional problems exist in the manipulation with the multicomponent reciprocal systems: recalculation of the concentrations and dividing of the polyhedral complexes into the simplexes. Relation between the mass-centric coordinates in multicomponent salt systems have been considered in [1]. Tetrahedration of the quaternary reciprocal systems with the inner diagonals were discussed in [2-3]. Later, an algorithm for topological correction of lists of simplexes of different dimensions for polyhedration of multicomponent systems was formulated [4], and has been used to correct the published data on the quaternary reciprocal systems with the inner diagonals and with some variants of tetrahedration [5]. In this paper, this technique is used to divide the complex Li,Na,U||F,Cl with the 2 congruently melting binary compounds R1=3NaFa*UF₄ and R2=7NaFa*6UF₄ into the simplexes. First variant of tetrahedration with the inner diagonal LiF-UCl₃ and 3 diagonals from the top NaCl produces 5 simplexes: LiF-NaF-NaCl-R1, LiF-UF₄-NaCl-UCl₃, LiF-UF₄-NaCl-R2, LiF-LiCl-NaCl-UCl₃, LiF-NaCl-R1-R2. Second variant with the same inner diagonal and 3 diagonals from the top UCl₃ produces 5 simplexes too: LiF-LiCl-NaCl-UCl₃, LiF-UCl₃-R1-R2, LiF-NaF-NaCl-UCl₃, LiF-NaF-UCl₃-R1, LiF-UF₄-UCl₃-R2. To search the low-temperature solvents parameters, the nonplanar tie-lines method are used [6].

References:
[1] V.I. Lutsyk, V.P. Vorob'eva, Z. Naturforsch., 63a (2008) 513-518.
[2] V. Lutsyk, V. Vorob'eva, M. Parfenova, Advanced Materials Research, 704 (2013) 55-60.
[3] V.I. Lutsyk, V.P. Vorob'eva, O.G. Sumkina, M.V. Lamueva, IFAC-PapersOnline, 15(I) (2013) 288-293.
[4] V.I. Lutsyk, V.P. Vorob'eva, Russian. Journal Inorgan. Chem., 59 (2014) 956-970.
[5] V.I. Lutsyk, V.P. Vorob'eva, Russian Journal Inorgan. Chem., 59 (2014) 1123-1137.
[6] V.I. Lutsyk, A.E. Zelenaya, A.M. Zyryanov, Crystallogr. Reports, 57 (2012), 984-987.

SESSION: MoltenTuePM3-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Tue Nov, 6 2018 / Room: Bossa (150/3rd)
Session Chairs: TBA Session Monitor: TBA

17:40: [MoltenTuePM313] Keynote
Energy and Molten Salts
Marcelle Gaune Escard¹ ; ¹Aix-Marseille Universite/Polytech, CNRS/IUSTI UMR7343, Marseille, France;
Paper Id: 445 [Abstract]

Molten salt technology [1] has very diverse applications. Interest in the use of molten salts in industrial processes is continually increasing, and these media are gradually becoming accepted as a normal field of chemical engineering. Applications include extraction of metals, as well as heat and surface treatment of metals and alloys. In the field of energy, molten salts are commonly used as a medium for high-temperature batteries, fuel cells as well as for nuclear and solar energy systems. They play a crucial role for heat transfer and energy storage in nuclear and solar energy systems. Molten salt reactors might spell a nuclear energy revolution. A molten salt reactor (MSR) is a type of nuclear reactor that uses liquid fuel instead of the solid fuel rods used in conventional nuclear reactors. Using liquid fuel provides many advantages in safety and simplicity of design.MSRs are a huge departure from the conventional reactors most people are familiar with. Key features include: unparalleled safety, a solution to nuclear waste and stockpiles of plutonium, abundant energy cheaper than energy from coal, load following solar and wind power, abundant energy for hundreds of years, replacement of fossil fuels where wind and solar are problematic (CO₂ -free liquid fuels). Molten salts are also excellent materials for thermal energy storage for high-efficiency solar power facilities. Among the different types of thermal energy storage, one can be realized through two different phenomena associated with materials that produce storage. This is known as storage by sensible heat and latent heat storage. Sensible heat of molten salts is also used for storing solar energy at a high temperature. Molten salts can be employed as a thermal energy storage method to retain thermal energy. Presently, this is a commercially used technology to store the heat collected by concentrated solar power (e.g., from a solar tower or solar trough). The heat can later be converted into super-heated steam to power conventional steam turbines and generate electricity in bad weather or at night. Various eutectic mixtures of different salts are used (e.g., sodium nitrate, potassium nitrate and calcium nitrate).

References:
References:

1. Molten Salts Chemistry and Technology, Marcelle Gaune-Escard, Geir Martin Haarberg,
, Eds., John Wiley & Sons, Ltd, 2014

SESSION: MoltenWedAM-R3	Fehrmann International Symposium on Sustainable Molten Salt and Ionic Liquid Processing (6th Intl. Symp. on Sustainable Molten Salt and Ionic Liquid Processing)
Wed Nov, 7 2018 / Room: Bossa (150/3rd)
Session Chairs: Rasmus Fehrmann; Session Monitor: TBA

11:20: [MoltenWedAM01] Invited
Homogeneous Catalysis for Sustainable Chemistry
Martin Nielsen¹ ; ¹Technical University of Denmark, Kgs. Lyngby, Denmark;
Paper Id: 137 [Abstract]

The transformation of biofeedstock into higher value bulk and fine chemicals is of paramount importance to become fully independent of fossil fuels. Using homogeneous catalysis for such valorization processes allows for highly selective transformation to be carried out under mild conditions. Here, we demonstrate the use of homogeneous PNP transition metal complexes for catalyzing a range of biofeedstock valorization processes. In addition, we show how this catalyst type may be used for hydrogen storage in organic compounds. For example (bio)ethanol may be transformed to to sodium acetate, ethyl acetate, or butanol. Likewise, potassium lactate is produced from glycerol and gamma-valerolactone is made from levulinates. Furthermore, we show how methanol, (bio)ethanol, isopropanol, glycerol, sugar alcohols, and carbohydrates all are well tolerated substrates for extruding hydrogen molecules.

References:
[1] R. M. Padilla, M. Nielsen. Unpublished work.

[2] E. Alberico, M. Nielsen. 2015. Towards a methanol economy based on homogeneous catalysis: methanol to H2 and CO2 to methanol Chem. Commun., 51, 6714-6725

[3] M. Nielsen, E. Alberico, W. Baumann, H.-J. Drexler, H. Junge, S. Gladiali, M. Beller
2013, Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide, Nature, 495, 85-89

[4] M. Nielsen, H. Junge, A. Kammer, M. Beller
2012, Towards a Green Process for Bulk-Scale Synthesis of Ethyl Acetate: Efficient Acceptorless Dehydrogenation of Ethanol, Angew. Chem. Int. Ed., 51, 5711-5713

11:45: [MoltenWedAM02]
How to Predict Physico-chemical Properties from MD Simulations
Christian Schröder¹ ; ¹University of Vienna, Vienna, Austria;
Paper Id: 304 [Abstract]

Ionic liquids are complex Coulombic fluids with many interesting physico-chemical properties. However, experimental results are often difficult to interpret in terms of cationic and anionic contributions. In addition, the impact of particular functional groups, of the chain length of the cations or of different compositions of ionic liquid mixtures, is unclear. Consequently, fundamental knowledge on the modes of interaction between the ions is appreciated for the design of more efficient ionic liquid combinations for a particular application [1]. Here, simulations on quantum-mechanical as well as on molecular dynamics level may help to decompose the overall behavior of the ionic liquid mixtures into contributions of interest, e.g. cationic/anionic/co-solvent, translational/rotational/vibrational, permanent and induced dipoles, hydrogen bonded networks, ionic clusters, etc. [2,3]. Furthermore, hypotheses on corresponding mechanisms can be tested individually for their validity [4]. In this talk we will discuss the advantages and limits of several computational methods to predict and interpret various physico-chemical properties with an emphasis on equilibrium and non-equilibrium molecular dynamics simulations [5].

References:
[1] C. Schröder: "General review of ionic liquids and their properties" in "Analytical applications of ionic liquids" (World Scientific) edited by M. Koel (2016)

[2 ] Carlos E. S. Bernardes, Karina Shimizu, Jose Nuno Canongia Lopes, Philipp Marquetand, Esther Heid, Othmar Steinhauser and Christian Schröder, Phys. Chem. Chem. Phys. (2016), 18, 1665

[3] Schröder, C. Top Curr Chem (Z) (2017) 375, 25

[4] V. Zeindlhofer, M. Berger, O. Steinhauser and C. Schröder J. Chem. Phys. (2018), 148, 193819

[5] E. Heid C. Schröder Phys. Chem. Chem. Phys. (2018), 20, 5246

SESSION: ManufacturingWedPM1-R3 Specific Applications to Bioengineering / Energy / Materials	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Bossa (150/3rd)
Session Chairs: TBA Session Monitor: TBA

14:00: [ManufacturingWedPM105]
A Novel Approach to Methods and Tools of Optical Spectroscopy of Viruses
Paata Kervalishvili¹ ; ¹Georgian Technical University, Tbilisi, Georgia;
Paper Id: 93 [Abstract]

Study and detection of viruses using their oscillation optical spectrum is a revolutionary step in the development of novel methods of measurement and treatment for different diseases in modern health care. For strengthening the identification and characterization of viruses, elaboration of new instrumental designs for specific clinical needs and building up extensive databases with probabilistic identification algorithms, optical spectrometry has real potential as reliable characterization and treatment technique of viruses and virus-like particles (VLPs). Advantages of spectrometry methods before traditional methods of diagnostics are: minimized expenditure of materials, speed of response, elimination of long stages of sample preparation, elimination of the need to use of labeled reagents and chromogenic substrates, and possibility of detecting rarely cultivated forms of viruses. Nowadays, due to issues of proliferation of dangerous viruses such as Ebola, flu, and others, it is extremely important to elaborate novel procedures of biological security and relevant optical nanoinstruments (sensors). Work which was done by the international team includes: elaborating firstly in the world the methods for measurement of spectral characteristics of viruses, and VLPs with aim of their later treatment; monitoring oscillation characteristics of viruses with "Improvement the Sum Frequency Generation method"; investigating the possibilities of Pico and Femto second laser and other sources for performing of nonlinear measurements; developing simulation methods of oscillation effects in viruses and VLPs; elaborating the schemes of working high effective spectrometric sensory networks; studying common properties of nano-scale virus-like particles, and elaborating the basic concept of the new method for estimation unique vibration/oscillation properties, which determines the "fingerprints" of pathogenic micro-organisms, especially viruses [1-5].

References:
[1] Paata J. Kervalishvili, Tamar N. Bzhalava, Investigations of Spectroscopic Characteristics of Virus-Like Nanobioparticles, American Journal of Condensed Matter Physics, Vol. 6 No. 1, (2016), pp. 7-16.
[2] P.J. Kervalishvili, T.N. Bzhalava, Modeling of Vibrational/Spectroscopic Properties of Virus-Like Nanoparticles, International Sci. Conference eRA - 11 The SynEnergy Forum, Piraeus Greece, 21- 23 September (2016), http://era.teipir.gr
[3] P.J. Kervalishvili, Optical Spectroscopy Study of Oscillation of Pathogenic Bionanoobjects (keynote), NANOTEK-2017 March 11th-13th, (2017), Hamburg, Germany.
[4] M. Mostafavi, A. Tadjeddine, C. Humbert, P.Kervalishvili, T. Bzhalava, T. Berberashvili, "Nonlinear Optical Spectroscopy of Nano-Bio-Materials", San-Diego State University Conference, September 6-7,(2015).
[5] M. Mostafavi, A. Tadjeddine, C. Humbert, P. Kervalishvili, T.Bzhalava, V. Kvintradze, T. Berberashvili, Optical Spectroscopy of Nanobioobjects for Sensory Applications, "2015 NanoCon (NanoTech) ISTC- Korea Conference", Seoul 2-6 November, (2015).

14:50: [ManufacturingWedPM107]
Nano Thermometry: Origin, Evolution, and Emergence
Pragati Kumar¹ ; Nupur Saxena¹ ; Tania Kalsi¹ ; ¹Central University of Jammu, Jammu, jammu, India;
Paper Id: 247 [Abstract]

The physical entity that has an effect on even the tiniest elements of daily life and is involved in a broad spectrum of human activities is temperature. Accurate and reliable measurement of temperature with high spatial resolution of many special inaccessible objects is a challenging task. The conventional methods of temperature measurements are not companionable with the current nano/bio technologies, as they demand precise thermometry down to the nanoscale regime. Optical temperature sensing using nanomaterials is a promising method to achieve it. This is the only thermometry that works in non-contact mode and has high resolution and sensitivity. A range of versatile materials have been utilized to fabricate luminescence-based optical thermometers to achieve high sensitivity and wide working range. This review article focuses on the gradual advances in luminescence-based optical temperature sensors and highlights the wide range of materials used to fabricate them. The article covers the importance of temperature sensors and their applications, followed by the overview of various types of thermometry and their mode of operations with detailed description of optical thermometry, particularly luminescence based sensors. Later section deals with different detection modes for the analysis of the luminescent sensors. The subsequent section will discuss a number of materials and their structures used for fabrication of luminescence based temperature sensor; viz. (a) Metal Organic Frameworks, (b) Quantum Dots (QDs), (c) Rare Earth Doped Phosphors and (d) Nanocomposites. In all, the article compares different thermometers in the basis of mechanism, constituting materials, and their performance parameters. Among all the device parameters, sensitivity and temperature range are the most concerned issues. To the best of our knowledge, highly luminescent rare earth doped phosphors¹ could achieve the maximum sensitivity as 7% K^-1 and a temperature range of 20-500K. However, our group has reported a relative sensitivity of 8.4 K^-1 and the widest temperature range of 20-560K using CdS:SiO₂ nanocomposite². Further improvement in these parameters by doping of Ag in CdS:SiO₂ nanocomposite system will be discussed in this article. The review features a comprehensive summary on challenges and new direction in designing luminescence based temperature sensor.

References:
[1] S. Huang, X. Wei, Y. Chen and M. Yin, J. Lumin., 2014, 152, 148.
[2] N. Saxena, P. Kumar, and V. Gupta, RSC Advances, 2015, 5, 73545.

15:15: [ManufacturingWedPM108]
Synthesis of Fe-Al Alloys by a Novel Reactive Infiltration Method
Srdjan Milenkovic¹ ; ¹IMDEA Materials Institute, Getafe, Spain;
Paper Id: 244 [Abstract]

FeAl intermetallics are potential candidates to substitute Cr/Ni based (stainless) steel parts used in high volume end consumer products such as in the lock industry, electronics, process industry, and automotive industry, in order to reduce consumption of the critical raw materials [1,2]. Their impact would therefore be much higher if a cost effective industrial process would be available, that allows manufacturing complex 3-D geometries of almost unlimited shapes from small grain size (0.1-5 μm) high ductility material [3,4] In this work, a novel processing method has been investigated. It involves reactive infiltration of liquid Al into the porous Fe preforms, with the aim of obtaining fine grained Fe-Al. The feasibility of using pressureless infiltration process was examined. Initially, preliminary DTA experiments were conducted to analyse the effect of the melt temperature and composition on the thermodynamic effects of reaction between the preform and the melt. It was found that the pure Al melt interacts with Fe porous preform intensively with high exothermic effect, thus causing a great risk of melting of the preform or can lead to formation of rather porous material. In the next step, the feasibility of pressureless reactive infiltration was investigated using two different approaches. The first one is the drop casting of the melt into the preform being contained in a mould. The second one is the immersion method, which is applied by immersing the preform into the melt pool. In both cases, parameters like melt temperature, mould material, and time were investigated, and their influence on the final microstructure, morphology, and phase constitution has been discussed. Comparison and analysis of the outcomes of the DTA, drop casting, and immersion experiments provided useful results to understand main features of the reactive infiltration process and hints on how the process can be further optimized by a suitable heat management.

References:
[1] P. Kratochval, Intermetallics, 16 (2008) 587-591.
[2] D.G. Morris, M.A. Morris-Munoz, Intermetallics, 7 (1999) 1121-1129.
[3] N.S. Stoloff, Mater. Sci. Eng. A, 258 (1998) 1-14.
[4] N.S Stoloff, C.T Liu, S.C Deevi, Intermetallics, 8 (2000) 1313-1320.

SESSION: ManufacturingMonAM-R4 Advanced Manufacturing and Industrial Sustainability	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Mon Nov, 5 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Dimitris C. Lagoudas; Session Monitor: TBA

11:20: [ManufacturingMonAM01] Plenary
Advanced Manufacturing of Advanced Materials from Macro- to Nanoscale: Static to Shock Loading
Athanasios G. Mamalis¹ ; ¹PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 423 [Abstract]

Some recent trends and developments in advanced manufacturing of advanced materials from macro- to nanoscale subjected to impact and shock loading, with industrial applications to net-shape manufacturing, bioengineering, safety, transport, energy and environment, an outcome of the very extensive, over 45 years, work on this field performed by the author and his research international team, are briefly outlined. The benefits of such advanced materials, manufacturing and loading techniques, products and applications in many technological areas are significant, since their impact will make the manufacturing/machine tool sector, communications, transportations, data storage, health treatment, energy conservation, environmental and human-life protection and many other technological applications better, faster, safer, cleaner and cheaper. My items considered the SIPS 2018 Mamalis International Symposium may be listed as: 1. Mechanics (Structural plasticity, Low / High speed impact loading, Hypervelocity impact, Shockwaves loading) 2. Precision / Ultraprecision manufacturing from macro-, micro- to nanoscale (Metal forming, Metal removal processing, Surface engineering / Wear, Non-conventional techniques) 3. Nanotechnology / Nanomaterials manufacturing 4. Ferrous and non-ferrous (Metals, Ceramics, Superhard, Polymers, Composites, Multifunctional), materials from macro- to nanoscale (Nanostructured materials, Nanoparticles, Nanocomposites) 5. Powder production and processing technologies (High strain-rate phenomena and treatment under shock: Explosives, Electromagnetics, High temperature / high pressure techniques) 6. Biomechanics / Biomedical engineering 7. Transport / Crashworthiness of Vehicles: Passive and active safety for passengers and cargo (Surface transport: Automotive, Railway; Aeronautics: Aircraft, Helicopters) 8. Energy (Superconductors, Semiconductors, Electromagnetics, Solar cells, Photovoltaics, Nuclear reactors) 9. Environmental aspects (Impact on climate change: Nanotechnology; Automotive industry; Aeronautics industry) 10. Safety (Detection of explosives and hazardous materials) 11. Defense (Ballistics, Projectiles hitting targets, Shock loading) 12. Industrial sustainability

11:45: [ManufacturingMonAM02] Keynote
The Ethics of Sustainability
Jeremy Ramsden¹ ; Athanasios G. Mamalis² ; Nikolaos T. Athanassoulis³ ; ¹University of Buckingham, Buckingham, United Kingdom; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³Laboratory of Industrial and Energy Economics, NTUA, Athens, Greece;
Paper Id: 95 [Abstract]

As crowding on our planet increases, sustainability has become a major preoccupation at many levels: national and supranational (for example, the European Union is strongly promoting the "circular economy", essentially a waste management strategy), but also local and even individual. A considerable body of academic work has arisen around the "circular economy", mostly of recent origin, even though the roots of the concept go back decades and even centuries. On the whole the field seems to suffer from a dearth of analytical thinking, and much of the literature is little more than polemics between supporters and detractors, along with the loose injection of words like "entropy". On the material plane, at the atomic level everything is recycled, except hydrogen and helium; at higher levels involving sophisticated superatomic structures, an illusion of recycling may depend on inadequate definitions of materials that fail to capture all their essential features (for example, paper cannot be endlessly recycled because the cellulose fibres are progressively shortened). This paper seeks to establish what precisely sustainability and the circular economy mean, what the intentions of their protagonists are, and how they fit in with alternative moral schemata, notably the individual versus the social. The goal of our investigation is to establish whether the circular economy can make any claim on our attention as a worthwhile pursuit.

References:
[1] Ramsden, J.J. The impacts of nanotechnology. Nanotechnol. Perceptions 7 (2011) 28-66.

[2] Ramsden, J.J. The sustainability of "postmodern" university research. In: Philosophy and Synergy of Information: Sustainability and Security (eds P.J. Kervalishvili & S.A. Michailidis), pp. 74-87. Amsterdam: IOS Press (2012).

[3] Ramsden, J.J. and Kiss-Haypál, G. On a possible limit to economic progress. Nanotechnol. Perceptions 9 (2013) 71-81.

[4] Ramsden, J.J. Applied Nanotechnology (3rd edn). Amsterdam: Elsevier (2018).

12:10: [ManufacturingMonAM03] Keynote
Nanotechnology and Sustainability
Jeremy Ramsden¹ ; Alexandra Mamali² ; Athanasios G. Mamalis³ ; Nikolaos T. Athanassoulis⁴ ; ¹University of Buckingham, Buckingham, United Kingdom; ²Maersk Broker Hellas, Athens, Greece; ³PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ⁴Laboratory of Industrial and Energy Economics, NTUA, Athens, Greece;
Paper Id: 94 [Abstract]

The sustainability of our present civilization and, ultimately, of human life itself is challenged on many fronts. The most prominent of the challenges are climate change, extreme food and water shortages, rising chronic diseases, and rampant obesity. They are all of great significance in terms of death and morbidity, and at the same time seemingly intractable. This paper looks at the technical dimension of overcoming these challenges, contrasting the apparent impotence of conventional technologies with the potential of nanotechnology. Particular attention is paid to the scalability of any proposed nanotechnology-based solutions (bearing in mind the vast scale required for meaningful implementation), as well as the related aspect of realizable timescales. Where alternative solutions exist, a criterion of choice based on the life quality index is proposed. The paper concludes by examining the practical problems of implementing solutions projected to be successful.

References:
[1] Ramsden, J.J. What is sustainability? Nanotechnol. Perceptions 6 (2010) 179-195.

[2] Ramsden, J.J. The nanotechnology industry. Nanotechnol. Perceptions 9 (2013) 102-118.

[3] Mamalis, A.G., Ramsden, J.J., Holt, G.C., Vortselas, A.K. and Mamali, A.A. The effect of nanotechnology on mitigation and adaptation strategies in response to climate change. Nanotechnol. Perceptions 7 (2011) 159-179.

[4] Ramsden, J.J. Nanotechnology and Gaia. Nanotechnol. Perceptions 10 (2014) 173-189.

[5] Ramsden, J.J. Doomsday scenarios: an appraisal. Nanotechnol. Perceptions 12 (2016) 35-46.

[6] Ramsden, J.J. Applied Nanotechnology (3rd edn). Amsterdam: Elsevier (2018).

12:35: [ManufacturingMonAM04] Keynote
Simulation of the Seismic Performance of Ceiling-Piping-Partition Nonstructural Systems
Manos Maragakis¹ ; ¹University of Nevada, Reno, Reno, United States;
Paper Id: 280 [Abstract]

Nonstructural components and systems are defined as the elements of a building that are not part of its structural load-bearing system. However, these elements are subjected to the same dynamic environment experienced by the building caused by an earthquake. These systems represent over 75% of the loss exposure of US buildings to earthquakes, as they usually represent the major portion of the total investment in buildings. Furthermore, damage to nonstructural systems occurs at response intensities much lower than those required to produce structural damage. Therefore, it is not surprising that recent earthquakes have demonstrated that poor performance of nonstructural systems and components can result in significant damage. In the US they account for over 78% of the total estimated national annualized earthquake loss. One of the major nonstructural systems in a building is the ceiling-piping-partition nonstructural system, which includes a key set of interconnected subsystems. These include different types of ceiling subsystems; complex floor-to-floor, in-floor, and in-ceiling water distribution piping subsystems with varying geometric configurations; specialized piping such as fire sprinkler subsystems; different types of partition subsystems; components such as pipe fittings, light fixtures, hangers, braces, valves and pumps; and HVAC components that affect the seismic response of ceiling-piping partition systems such as diffusers and ducts. The ceiling-piping-partition system is a very widely used nonstructural system that has been a main contributor to both seismic damage and associated property damage, functional loss, fire spread and hence casualty risks. All of its subsystems (i.e. piping, partitions and ceilings) have suffered significant damage in recent earthquakes. Such damage has resulted in property loss, loss of function, increased fire hazard and loss of life and has compromised the seismic resilience of communities. This presentation summarizes damage of nonstructural systems in recent earthquakes and its impact on all categories of seismic risk and discusses the importance of these elements on the functionality of buildings. Furthermore, it presents major experimental and analytical research studies on the seismic response of these elements that were performed as part of an NSF NEESR Grand Challenge research project on this topic. This Grand Challenge project integrated multidisciplinary system-level studies that developed, for the first time, a simulation capability and implementation process for enhancing the seismic performance of the ceiling-piping-partition nonstructural system. It included a comprehensive experimental program that used the University of Nevada, Reno (UNR) and University at Buffalo (UB) NEES Equipment Sites as well as the E-Defense facility in Japan. A series of component- level experiments were performed initially t UB. Then a series of comprehensive system-level experiments, including several interacting components and sub-systems were performed at UNR. Finally, system level experiments using a full-scale 5-story building were performed at the E-Defense facility in Japan. Integrated with this experimental effort was a comprehensive numerical simulation program that developed experimentally verified analytical models and system and subsystem fragility functions.

SESSION: ManufacturingMonPM1-R4 Advanced Manufacturing / Mechanics / Structural Plasticity	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Mon Nov, 5 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Pengwan Chen; Session Monitor: TBA

14:00: [ManufacturingMonPM105]
Dynamic Pressure Change of a Liquid Sloshing in a Rotating, Laterally Oscillating, Cylindrical Container
Tatsuo Sawada¹ ; Eisaku Yokose¹ ; Yusuke Saito¹ ; ¹Keio University, Yokohama, Japan;
Paper Id: 111 [Abstract]

Sloshing is the largely wave-like motion of the free surface of a liquid caused by the oscillation of a container. Even if the oscillation is small, the changes in the liquid level may increase. Swirling is the rotation of the free surface of a liquid that takes place when sloshing occurs in an axisymmetric container. There are two types of swirling: stable rotations and unstable rotations. Both sloshing and swirling are concerns for oil tanks, membrane-type LNG tankers, liquid-fuel tanks in rockets and missiles, etc. Hutton [1] investigated the motion of fluid in a tank undergoing transverse oscillations, and he predicted the range of frequencies over which swirling occurs. Numerous theoretical, experimental, and numerical studies of these phenomena have been conducted, as summarized by Ibrahim et al. [2-3]. Ohaba et al. [4] experimentally investigated the frequency response of the lateral sloshing and rotation of the (1, 1) mode wave in a cylindrical container undergoing uniform rotation around the vertical axis. They found that the direction of the swirling rotation depends on the excitation conditions and the rotation frequency. They pointed out that the swirling generated in a cylindrical container undergoing lateral oscillations can be stabilized by the energy dissipation caused by the rotational motion. Saito and Sawada [5] considered the qualitative influence of the rotation frequency of the cylindrical container on water sloshing, and they speculated that the rotational motion may stabilize the sloshing fluctuations of the free surface. In the present study, we clarify the dynamic characteristics of swirling in a rotating, laterally oscillating, cylindrical container. We measured the time-dependent dynamic pressure of the liquid on the wall of the container instead of the free-surface displacement of the liquid. The experimental parameters are the lateral forcing frequency, the rotation frequency of the cylindrical container, the liquid depth, and the viscosity of the liquid. We have also carried out a theoretical analysis in order to understand the experimental results.

References:
[1] R. E. Hutton, NASA Tech. Note D-1870 (1963) 1-64.
[2] R. A. Ibrahim, V. N. Pilipchuk, T. Ikeda, Appl. Mech. Rev. 54 (2001) 133-199.
[3] R. A. Ibrahim, Liquid sloshing dynamics, (Cambridge University Press, New York, 2005).
[4] M. Ohaba, T. Sawada, S. Sudo, T. Tanahashi, Proc. JSME Fluids Eng. Conf. (1995) 203-204.
[5] Y. Saito, T. Sawada, Unvrsl. J. Mech. Eng. 5 (2017) 97-101.

14:25: [ManufacturingMonPM106]
Dynamic Compressive Behavior of An E-Glass/Polyester Composite Material Subjected to Repeated Loads
Alper Tasdemirci¹ ; Mesut Bayhan¹ ; Semih Berk Seven¹ ; Ayda Ramyar¹ ; Mustafa Guden¹ ; ¹İzmir Institute of Technology, İzmir, Turkey;
Paper Id: 124 [Abstract]

Composite materials are generally used as spall liner of the vehicle hull in military applications to protect the cabin crew from injuries [1]. In these applications, composite materials may be subjected to single or multiple impact loads. There are several studies on single loading impact events, but very few studies focused on repeated loadings. To determine the multi hit protection capability of materials using Split Hopkinson Pressure Bar (SHPB), Chen and Luo modified the conventional SHPB apparatus to deform ceramic specimen using two consecutive stress pulses [2]. Xia et al. performed an experimental study on OFHC Copper materials using stuffed strikers [3]. Rachel et al. conducted a study on copper and iron using a single striker bar formed two rods of dissimilar materials [4]. Bazle et al. carried out ballistic tests to obtain the multi hit capacity of S-2 glass/SC15 thick section composites [5]. In this study, multi-hit compressive behavior of a composite material was investigated both experimentally and numerically in the through-thickness direction. Repeated loading tests were carried out using the SHPB set-up, and LS-DYNA was used to simulate the tests numerically. To understand the failure mechanisms and damage progression, MAT_162 material model was selected. DYNAIN method was used to model the multiple impacts. This method allows to incorporate the damage attained in the specimen occurred during the first impact in the numerical model of the subsequent loadings. It was observed that delamination was occurred between the layers at regions particularly close to the specimen-incident bar interface. After the second hit, matrix damage propagated along the interfaces and the composite failed catastrophically. Experimental and numerical results showed close agreement in terms of failure mechanisms and damage initiation/progression. The numerical model can successfully predict the amount of strength decrease between the repeated loadings.

References:
[1] R. A. Ash, "9 - Vehicle armor A2 - Bhatnagar, Ashok," in Lightweight Ballistic Composites (Second Edition), ed: Woodhead Publishing, 2016, pp. 285-309.
[2] W. Chen and H. Luo, "Dynamic compressive responses of intact and damaged ceramics from a single split Hopkinson pressure bar experiment," Experimental Mechanics, vol. 44, pp. 295-299, Jun 2004.
[3] K. Xia, R. Chen, S. Huang, and S. N Luo, Controlled multipulse loading with a stuffed striker in classical split Hopkinson pressure bar testing vol. 79, 2008.
[4] R. E. Briggs, D. R. Drodge, D. M. Williamson, and W. G. Proud, "TWO-STEP LOADING IN A SPLIT HOPKINSON PRESSURE BAR," AIP Conference Proceedings, vol. 955, pp. 1173-1176, 2007.
[5] Z. H. Bazle, L. H. Jessica, and John W Gillespie, Jr., "Multi-hit ballistic impact on S-2 glass/SC15 thick-section composites: experiments," The Journal of Strain Analysis for Engineering Design, vol. 47, pp. 480-494, 2012/10/01 2012.

14:50: [ManufacturingMonPM107]
The Investigation of Low-velocity Drop Weight Impact on Concrete Plates
Alper Tasdemirci¹ ; Semih Berk Seven¹ ; Mehmet Alper Cankaya² ; Cetin Uysal³ ; Selcuk Saatci³ ; Mustafa Guden¹ ; ¹İzmir Institute of Technology, İzmir, Turkey; ²Izmir Katip Celebi University, Izmir, Turkey; ³Izmir Institute of Technology, Izmir, Turkey;
Paper Id: 123 [Abstract]

Concrete is used as a structural material which has a very wide range of applications. Concrete structures may be exposed to a variety of static and dynamic loading conditions in their lifespan. Due to this reason, it is important to investigate and understand the mechanical behavior of concrete under different impact conditions. In literature, the drop weight testing machine was used to investigate the impact behavior of different kind of cementitious material under low-velocity impact [1]. Perforation tests were performed using circular plain and fiber reinforced concrete [2]. In this study, drop weight impact tests on prismatic concrete plates were accomplished using drop tower test apparatus and modeled using finite element software LS-DYNA. In numerical analysis, JOHNSON_HOLMQUIST_CONCRETE (MAT_111) material model was selected to define material model for concrete samples since this material model is well suited for concrete materials subjected to impact loadings [3]. The dynamic mechanical characterization study of concrete material to determine the parameters of the HJC material model was done in the previous work [4]. The test setup consists of 20 mm diameter hemispherical striker tip impacting on a 200x200x20 mm prismatic specimen with the 100 mm hollow specimen holder. To see the effect of striker impact velocity on the behavior of concrete, two different impact velocities (1 m/s and 3 m/s) were applied. The effectiveness of the HJC material model and the validation of the parameters used in the numerical analysis were presented with the comparative study. The results obtained from experimental tests are in a good agreement with the numerical analysis results. Also, numerical results showed similar crack profiles with the experimental results.

References:
[1] N. Banthia, S. Mindess, A. Bentur, and M. Pigeon, "Impact Testing of Concrete Using a Drop-Weight Impact Machine Impact Testing of Concrete Using a Drop-weight Impact Machine," vol. 1106, no. March, pp. 63-69, 1989.
[2] S. Mindess and C. Yan, "Perforation of plain and fibre reinforced concretes subjected to low-velocity impact loading," Cem. Concr. Res., vol. 23, no. 1, pp. 83-92, 1993.
[3] T. J. Holmquist, G. R. Johnson, and W. H. Cook, "A computational constitutive model for concrete subjected to large strains, high strain rates, and high pressures.pdf," 14th International Symposium on Ballistic, Quebec City, Canada. pp. 1-10, 1993.
[4] A. Tasdemirci, M. A. Cankaya, S. B. Seven, C. Uysal, S. Saatci, M. Guden "The effect of strain rate on the compressive mechanical behavior of concrete," Int. J. Impact Eng., vol. under review, 2018.

15:15: [ManufacturingMonPM108]
Hydrogen Segregation in Palladium: Influence of Hydrogen Content, Temperature and Defects
Tahir Cagin¹ ; Han Leng² ; Hieu H. Pham² ; ¹Texas A&M University, College Station, United States; ²Texas A&M University, College Station, United States;
Paper Id: 216 [Abstract]

Atomistic simulations were carried out to investigate the properties of Pd crystals as a combined function of structural defects, hydrogen concentration and high temperature. These factors are found to individually induce degradation in the mechanical strength of Pd in a monotonous manner. In addition, defects such as vacancies and grain boundaries could provide a driving force for hydrogen segregation, thus enhance the tendency for their trapping [1,2]. The simulations show that hydrogen maintains the highest localization at grain boundaries at ambient temperatures. This finding correlates well with the experimental observation that hydrogen embrittlement is more frequently observed around room temperature [3]. The strength-limiting mechanism of mechanical failures induced by hydrogen is also discussed, which supports the hydrogen-enhanced localized plasticity theorem. We will also report on the influence of hydrogen content on thermodynamic properties such as melting point, heat capacity and thermal expansion coefficient and mechanical properties such as elastic modulus and Young's modulus as a function of temperature.

References:
[1] R. B. McLellan and L. Yang, Acta Metallurgica et Materialia 43 (6), 2463-2467 (1995).
[2] T. Mütschele and R. Kirchheim, Scripta Metallurgica 21 (2), 135-140 (1987)
[3] H. Conrad, G. Ertl, and E.E. Latta, Adsorption of Hydrogen on Palladium Single-Crystal Surfaces. Surface Science, 41(2), 435-446 (1974).

SESSION: ManufacturingMonPM2-R4 Precision / Ultraprecision Manufacturing	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Mon Nov, 5 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Tatsuo Sawada; Session Monitor: TBA

15:55: [ManufacturingMonPM209] Keynote
Faultless Steel Production and Manufacturing
Xenia Vourna¹ ; Evangelos Hristoforou¹ ; Athanasios G. Mamalis² ; ¹National TU of Athens, Athens, Greece; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 294 [Abstract]

Faultless steel production and manufacturing (FASTEP) represents a new method and technology for surface and bulk stress distribution monitoring and rehabilitation in steels. The quality of the steel and corresponding products depends on the distribution and level of stresses in its volume and surface, since stress gradient is responsible for steel cracking generation & failure. The existing technology in stress monitoring concerns either surface stress distribution monitoring instruments with unacceptably high uncertainty, or point surface stress sensors, or surface and bulk laboratory techniques not able to operate in industrial environment. Therefore, a method to provide stress tensor distribution monitoring on the surface and in the bulk of steels would be the feedback system to not only monitor stresses but actually to achieve stress rehabilitation. FASTEP solution in achieving stress distribution monitoring in steel production, manufacturing and use, is related to a new method and technology, currently pending for patent, offering stress tensor distribution monitoring on the surface and the bulk of steels, steel welds and products based on them. The achieved uncertainty has been <1% for surface or bulk stress measurements, with speeds as high as 100/s per point of measurement, compared to ~10% uncertainty and speed of 1-10 s per point of the existing state of the art, thus opening a new era in diagnostics & therapeutics in steel industry. Such a technology can be the feedback system for automated stress rehabilitation (annihilation or strengthening) process in steel production and manufacturing, as well as in installed steel structures (end-user applications).

16:20: [ManufacturingMonPM210]
Concurrent Method for Design of Sustainable Multi-stage Manufacturing Processes
Sesh Commuri¹ ; Jelena Milisavljevic² ; Farrokh Mistree² ; Janet Allen² ; ¹University of Nevada, Reno, Reno, United States; ²University of Oklahoma, Norman, United States;
Paper Id: 261 [Abstract]

Multistage manufacturing processes (MMPs) are networked manufacturing systems that have characteristics of mechanical and control systems where different manufacturing operations are performed at each stage [1]. Changing product requirements as well as desire for agility in the manufacturing process impose restrictions on the design of MMPs that could ultimately affect the sustainable operation of the manufacturing process. Some of the challenges that have to be addressed in the design of sustainable MMPs are:<br />- the understanding of the functional attributes of the mechanical and control systems that comprise the MMP and their effect on the properties of the MMP [2];<br />- the selection of sensors and tools and their effect on the dimensional quality of the finished product;<br />- the influence of computational complexity in representing and analyzing the problem [3]; and<br />- manage uncertainty in the models used to represent the MMP which limit the use of traditional design approaches [4]. <br />In this paper, an exploration-based method for the concurrent design of MMPs under uncertainty is presented wherein the attributes of tools and sensors are treated as design variables, thereby allowing the design engineer to assess the impact of design parameters on the performance and ultimately, the sustainability of the manufacturing process. The method is based on the compromise Decision Support Problem (cDSP) construct [5] for MMP, where MMP is described by a Stream of Variation (SoV) model [6]. The proposed method is illustrated using an example of automotive panel stamping process [7].

References:
[1] Shi, J., and Zhou, S., 2009, 'Quality Control and Improvement for Multistage Systems: A survey', IIE Transactions, Vol. 41, no.9, pp. 744-753.
[2] Milisavljevic, J., 2015, 'Accounting for Uncertainty in the Realization of Multistage Manufacturing Processes', Masters Thesis, The School of Aerospace and Mechanical Engineering, University of Oklahoma, Norman, Oklahoma.
[3] Milisavljevic Syed, J., Allen, J.K., Commuri, S., and Mistree, F., 2018, 'A Method for the Concurrent Design and Analysis of Networked Manufacturing Systems under Uncertainty,' Journal of Engineering Optimization, accepted for publication.
[4] Milisavljevic, J., Commuri, S., Allen, J.K. and Mistree, F., 'Concurrent Design Exploration Method (CDEM) of Networked Manufacturing Systems', ASME International Design Engineering Technical Conferences, Cleveland, Ohio, Paper number DETC2017-67557, August 6- 9, 2017.
[5] Smith, W.F., Milisavljevic, J., Sabeghi, M., Allen, J.K. and Mistree, F., 'Accounting for Uncertainty and Complexity in the Realization of Engineered Systems,' ASME International Design Engineering Technical Conferences, Boston, Massachusetts, Paper number DETC2015-46211, August 2-5, 2015.
[6] Ding, Y., Ceglarek, D., and Shi, J., 2000, 'Modeling and Diagnosis of Multistage Manufacturing Processes: Part I - State Space Model', In Proceedings of the 2000 Japan/USA Symposium on Flexible Automation, pp. 23-26.
[7] Apley, D., W., and Shi, J., 1998, 'Diagnosis of multiple fixture faults in panel assembly', Journal of Manufacturing Science and Engineering, vol. 120, pp. 793-801.

16:45: [ManufacturingMonPM211]
A Simple Magnetic Susceptibility Measuring Technique
Giorgios Banis¹ ; Panayiota Tselou¹ ; Angelo Ferraro¹ ; Evangelos Hristoforou¹ ; Athanasios G. Mamalis² ; ¹National TU of Athens, Athens, Greece; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 295 [Abstract]

A simple apparatus able to measure the magnetic susceptibility of spherical samples is demonstrated. The method is based on the equilibrium of the magnetic force applied on the specimen from a coil, and of the Stoke's force applied on the specimen by the flow of a liquid. Acquiring basic materials (coil, tube, power supply), we measured with sufficient accuracy the magnetic susceptibility of materials with unknown magnetic properties. Furthermore, by using a spherical specimen with given magnetic susceptibility, following the reverse methodology, it is possible to define the viscosity of the fluid. Thereby, we present a simple, low cost technique for fast and efficient measuring of specimens' magnetic susceptibility or viscosity of the liquid where the specimen is located.

17:10: [ManufacturingMonPM212]
Parameters Optimization of Rotary Forming Process of Nickel Superalloy Metal Plates
Sandra Puchlerska¹ ; Krzysztof Zaba¹ ;⁰ ; Jaroslaw Pyzik² ; ¹AGH University of Science and Technology, Kraków, Poland; ²AGH University of Science and Technology, Krakow, Poland;
Paper Id: 268 [Abstract]

Nickel-based superalloys can be characterized by resistance to high-temperature corrosion and high-temperature creep resistance. For this reason, they are widely used in the production of jet engine critical parts. One of the commonly used materials is Inconel 625, which will be the subject of this research. For Inconel 625 processing, rotary forming can be applied, which results in axially symmetrical elements. An important property of Inconel 625 is strong strain hardening effect. To improve formability, variety of methods can be applied, including heating of the material. The purpose of the research was optimization of rotary forming process parameters of Inconel 625 to produce jet engine critical parts with high quality requirements. Experimental plans based on orthogonal two-level design was created for 3 selected variables - feed rate, spinning rate, and heating. Optimal process parameters were established using multivariate statistical optimization utilizing GridSearch algorithm for finding set of parameters maximizing general product quality, defined as function of several quality factors measures. These parameters were used to set up processes and obtain product that meet quality requirements.

References:
[1] Superalloys II, C. T. Sims, N. S. Stoloff, W. C. Hagel, Wiley, 1987\n[2] A review of spinning, shear forming and flow forming processes, C. C. Wong, T. A. Dean, J. Lin, International Journal of Machine Tools & Manufacture 43 (2003) 1419-1435\n[3] Optimisation of the shear forming process by means of multivariate statistical methods, J. Kunert, R. \nEwers, M. Kleiner, N. Henkenjohann, C. Auer, Technical Report / UniversitA�t Dortmund, SFB 475 KomplexitA�tsreduktion in Multivariaten Datenstrukturen, No. 2005, 23.

SESSION: ManufacturingMonPM3-R4 Metal Forming / Metal Removal Processing / Non-Conventional Techniques – I	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Mon Nov, 5 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Raul S. Turmanidze; Session Monitor: TBA

17:40: [ManufacturingMonPM313]
Synthesis of ZnSe Films by Electrochemical Deposition for Assembly of Photo-transforming Heterostructures
Dmitri S. Sofronov¹ ; Athanasios G. Mamalis² ; Vadym V. Starikov³ ; E.m. Sofronova¹ ; E.a. Vaksler¹ ; P.v. Mateychenko¹ ; Sergiy N. Lavrynenko⁴ ; ¹SSI "Institute for Single Crystals" of NAS of Ukraine, Kharkiv, Ukraine; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³National Technical University - Kharkov Polytechnic Institute, Kharkiv, Ukraine; ⁴Kharkov Polytechnic Institute, Kharkov, Ukraine;
Paper Id: 170 [Abstract]

The zinc selenide films were synthesized using an electrochemical method in alkaline electrolyte. The influence of deposition options (zinc ions concentration, cathodic current density and electrolysis duration) on ZnSe films formation is discussed. It is shown that the increase of film thickness and its porosity is observed at increase of current density and zinc ions concentration in electrolyte. The most compact films are formed when the zinc concentration in the electrolyte is less than 0.05 M and the current density is not higher than 35 mA/cm². The obtained ZnSe film had p-type conductivity and a resistivity of 10⁵-10⁶ Ohm·m. It was synthesized heterostructure ZnS/ZnSe/Ni including the p-n transition. The parameters of the diode heterostructure were determined by the dark IV-characteristic.

18:05: [ManufacturingMonPM314]
Efficiency of Hard Machining Processes
János Kundrák¹ ; Athanasios G. Mamalis² ; Viktor Molnar¹ ; ¹University of Miskolc, Miskolc, Hungary; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 158 [Abstract]

Machining of hardened surfaces has improved significantly in the past. In addition to long-lasting abrasive machining, machining with cutting tools having geometrically defined single point cutting edges has also appeared, and its productivity gets better and better. This paper analyzes the efficiency of various processes in producing surfaces with the same quality parameters (Rz, IT). The investigated procedures or process variants are: traverse bore grinding; hard-turning with standard insert; hard-turning with Wiper inserts; combined process with standard inserts in hard-turning stage; and combined process with Wiper inserts in hard-turning stage. In the first step, we provide the results of the experimental tests by which we chose the machining data for the different processes, to ensure the required quality in each case. Based on the examination of Material Removal Rate (MRR), Surface Rate (SR), environmental load, and machining flexibility, we determine the order of their application based on the expected operating conditions. It is shown that the Material Removal Rate is most favourable for variants of hard-turning. However, if the operating conditions of a built-in component require a random surface, the most efficient process is combined machining. This order is also advantageous compared to conventional machining because the proposed variants also reduce the environmental load.

References:
[1] Kundrak, J.; Mamalis, A.G.; Markopoulos, A., Finishing of hardened boreholes: Grinding or hard cutting? Mat. and Manuf. Process., Vol.19, No.6, 2004, pp. 979-993.
[2] Mamalis, A.G., Kundrak, J., Gyani, K. On the dry machining of steel surfaces using superhard tools, Int. J. of Advanced Manufacturing Technology, Vol.19, No.3. 2002, pp. 157-162
[3] Kundrak, J.; Varga, G.: Use of coolants and lubricants in hard machining, TEHNICKI VJESNIK-TECHNICAL GAZETTE (ISSN: 1330-3651) (eISSN: 1848-6339) 20: (6) pp. 1081-1086. (2013)

SESSION: ManufacturingTueAM-R4 Non-Ferrous Advanced Materials from Macro- to Nanoscale – I	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Tue Nov, 6 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Mustafa Guden; Session Monitor: TBA

11:20: [ManufacturingTueAM01]
Development, Modeling and Characterization of Shape Memory Alloys and their Utilization in Morphing Structures
Dimitris C. Lagoudas¹ ; ¹Texas A&M University, College Station, United States;
Paper Id: 145 [Abstract]

Phase transforming materials exhibiting significant recoverable inelastic deformations due to reversible solid-to-solid phase transformations have both existing and potential applications in a wide variety of fields. This presentation focuses on Shape Memory Alloys (SMA), which undergo a reversible austenitic to martensitic phase transformation, and covers recent research efforts to characterize and model their behavior to enhance the applicability of these materials in multiple engineering capacities and requirements. We first discuss the recent development of several new SMA beyond NiTi alloys, especially high temperature NiTiHf alloys and their key characteristics and potential for applications. We then review the micromechanical modeling of SMA, modeling of fatigue and fracture of SMA, and modeling of SMA structural components and morphing structures. Since precipitation can adjust their thermomechanical cyclic stability, phase transformation temperatures, and transformation strains, micromechanical modeling of SMAs focuses on the prediction of precipitation hardened SMA's behavior to capture their thermomechanical response. Using SMAs in applications requires understanding their durability and especially their actuation fatigue life and fracture properties, so we investigate the phase transformation induced fatigue under load (actuation fatigue) and fracture under thermal actuation. Finally, we present some applications inspired by origami based designs of foldable morphing structures.

11:45: [ManufacturingTueAM02]
Calorimetric Mechanosensors Consisting of Various Mechanisms: Triboluminescence, Structural Color, and Disassembly of Au Nanoparticles
Mustafa Demir¹ ; Gökhan Topçu² ; Ezgi Inci² ; Athanasios G. Mamalis³ ; ¹Izmir Institute of Technology, Urla, Turkey; ²Izmir Institute of Technology, İzmir, Turkey; ³PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 57 [Abstract]

Fiber-reinforced polymer composites (FRPCs) have been widely used as alternatives for metallic materials in aerospace, defense, transportation, and automotive industries because of their lower weight, higher strength, and stiffness. The use of ultrathin fibers (eg. electrospun nanofibers) of high surface area leads to improvement in the mechanical property of FRPCs associated with the interfacial bonding between nanofibers and polymeric matrices, enhancing the load transfer from the fiber to the matrix. The micrometer-size porous polystyrene (PS) fibers obtained from electrospinning PS/THF solution with the nano-sized (100 to 200 nm) surface porosities were used to fill an epoxy matrix. The effect of incorporation of the PS fibers on the quasi-static and dynamic compression behavior of an epoxy matrix was examined. The addition of PS fibers and increasing strain rate increased the compressive elastic modulus and strength, which was attributed to the interlocking between the resin and fibers by the intrusions of the resin into surface pores on the fibers. In addition, high strain rate deformation experimental data on porous PS fiber-reinforced epoxy matrix was provided. The excessive deformation of the matrix at the interface caused extra energy expenditure to deform the composite.

References:
[1] R. F. Gibson, Compos. Struct. 92 (2010) 2793-2810.
[2] M. M. Demir, N. Horzum, A. Tasdemirci, K. Turan, M. Guden, ACS Appl. Mater. Interfaces. 6 (2014) 21901-21905.

12:10: [ManufacturingTueAM03]
Structure and Optical Properties of Nanocomposite Carbon Films Obtained from Accelerated C60 Ion Flows
Svetlana Rudchenko¹ ; Vladimir Egorovich Pukha¹ ; Vadym V. Starikov¹ ; Athanasios G. Mamalis² ; Sergiy N. Lavrynenko³ ; ¹National Technical University - Kharkov Polytechnic Institute, Kharkiv, Ukraine; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³Kharkov Polytechnic Institute, Kharkov, Ukraine;
Paper Id: 151 [Abstract]

The results of structural and optical investigations of thin carbon films deposited from the mass-separated beam of accelerated C60 ions with energy of 5 keV are presented. The substrate temperature ranged from 100°C to 400°C. It was established that change of the TS from 100°C to 400°C leads to the consecutive formation of diamond-like carbon (DLC) films with amorphous state and superhard nanocomposites consisting nanographite structures (1-2 nm) surrounded by a diamond-like amorphous matrix. For amorphous films the band gap (Eg) was in the range of 1.2 - 1.4 eV. For nanocomposite films on optical absorption spectra, there are two energy components: one with a narrow Eg = 1 eV, which is associated with three-dimensional nanocrystals of graphite, and the other - with a wide optical gap (Eg =3,45-3,55 eV) that corresponds to the diamond-like amorphous matrix of nanocomposite. According to the results of scanning tunneling microscopy (STM) and tunnel spectroscopy (TS), the size of graphite nanocrystals is about 1-2 nm and an amorphous shell around the graphite nanocrystals had a thickness of about 1.5 nm. The graphite component had n-type conductivity and an amorphous component had p-type conductivity. The electrical conductivity of such semiconductor nanocomposite was 103 S/m that to 6 orders higher compared to the DLC film in the amorphous state.

References:
[1] Robertson J. Diamond-like amorphous carbon // Materials science and Engineering. 2002. R37. Р.129-281.
[2] Robertson J. and O'Reilly E.P. Electronic and atomic structure of amorphous carbon // Phys. Rev. B. 1987. Vol.35, 6. P.2946-2957
[3] Robertson J. Electronic and atomic structure of diamond-like carbon // Semicond. Sci. Technol. 2003. Vol.18. Р.S12-S19.
[4] Tay B.K. Optical properties of tetrahedral amorphous carbon films determined by spectroscopic ellipsometry / Tay B.K., Shi X., Cheah L.K., Flynn D.I. // Thin Solid Films. 1997. Vol.308. Р.268-272.
[5] Teo K.B.K. Highest optical gap tetrahedral amorphous carbon / Teo K.B.K., Ferrari A.C., Fanchini G., Rodil S.E., Yuan J., Tsai J.T.H., Laurenti E., Tagliaferro A., Robertson J., Milne W.I. // Diamond and Related Materials. 2002. 11. P.1086-1090.

12:35: [ManufacturingTueAM04]
Properties of the Composite SnO2-Ag (Semiconductor Metal) Ceramic Material
Vladimir Kirko¹ ; Sergey Dobrosmislov² ; Genadii Nagibin² ; Z.i. Popov³ ; ¹Research Institute of Physics and Engineering, Krasnoyarsk, Russian Federation; ²associate professor, Krasnoyarsk, Russian Federation; ³Siberian State Aerospace University, Krasnoyarsk, Russian Federation;
Paper Id: 66 [Abstract]

The SnO₂-based ceramics are being widely used in many industries. Tin dioxide is a semiconductor with the forbidden band energy 3.54 eV, and has unique properties of high electrical conductivity and chemical resistance. Chemically resistant ceramics with high electrical conductivity is of great interest as electrode material operating at high temperatures, for instance in aluminium electrolysis and glass production. In semiconductors, the total electric current is a sum of partial currents, provided by p- and n-type conductivities. In case of contact between a p-type semiconductor and a metal, a space charge region of ionized donors appears, and the blocking contact, or Schottky barrier, forms. This means that the addition of Ag superdispersed particles into the ceramics structure will allow an additional number of charge carriers to appear in the semiconductor-metal contact zone, that will increase the electrical conductivity. Following the research performed, the superdispersed silver particles significantly affect the electrical conductivity of the material. Firstly, a significant drop of the temperature of the percolation beginning is observed. Secondly, the shape of the curve suggests that there is a possibility of the electron passage from the metallic particles into the tin dioxide conduction band. It can also be noted that when the silver portion increases, saturation of the conduction band by charge carriers takes place, and the resistivity no longer depends on the silver concentration. The usage of the silver oxide additives when making SnO2-based ceramics allows the composite material resistivity to significantly decrease, especially at low temperatures, which is associated with silver reduction from its oxide. This effect is associated with the formation of the space charge region in the semiconductor-metal contact zone. Temperature dependencies of the resistivity for materials with 4 and 8 weight % of silver and sintered at 1300°С are practically the same. For the ceramics sintered at 1400°С, an obvious dependence of the resistivity on the concentration is observed. The percolation beginning temperature increases by 150°С compared to that of the material sintered at 1300°С. The sintering temperature increase may lead to silver particles being distributed more uniformly along the grains' boundaries.

References:
[1] Jinhuat L. H2S Detection sensing characteristic of CuO/SnO2 sensor / Jinhuat Liu, Xingjiu Huang, Gang Ye, Wei Lui, Zheng Jiao, Wanglian Chao, Zhongbai Zhou, Zengliang Yu // sensor 2003,3,110-118 p
[2] S. S. Dobrosmislov, Issledovanie fisiko-mehanicheskih i electrofisicheskih svoystv electroprovodyashih ogneupornih keramik na osnove SnO-Sb2O3-CuO / S. S.Dobrosmislov, V.I. Kirko, etc., Ogneupori i tehnicheskaya keramika, 6, 7-10 pp., 2010;

SESSION: ManufacturingTuePM1-R4 Biomechanics / Biomedical engineering	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Tue Nov, 6 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Tetiana Prikhna; Jeremy Ramsden; Session Monitor: TBA

14:00: [ManufacturingTuePM105] Keynote
Glasses for Seeing Beyond the Visible
Jacques Lucas¹ ; ¹University of Rennes, Rennes, France;
Paper Id: 201 [Abstract]

Glasses transmitting light up to 20 micrometers have been discovered in the family base on Se and Te. Those out of equilibrium solids are stable enough to be shaped into two kinds of objects: IR lenses and optical fibers. An original molding technique was used to transform the glass into complex lenses with aspheric configuration. These IR optics are used for night vision systems in IR cameras and all kinds of thermal imaging devices. They provide low cost and sustainable heat measurement systems. Taking advantage of the possibilty to control the viscosity of those glasses as a fonction of temperature it is possible to transform these materials into long infared fibers. From this, we have developed sensors based on Fiber Evanescent Wave Spectroscopy. This technique allows the in-situ collection of the IR spectra of molecules. Applications in medecine with the analysis of biological liquid such as humam serum will be presented. Also the analysis of water pollution for environment control wil be described. Four start up companies located close to the campus were born from this research

References:
[1] X.Zhang, B.Bureau, P.Lucas, C.Boussard-Pledel, Jacques LUCAS. Chem. Euro. J. 2008, 14, 432-444

14:25: [ManufacturingTuePM106]
Au@Pt Core-Shell Nanoparticles with Nanostructured Dendritic Pt Shells as Solid Contacts in Ion Selective Electrodes
Masoumeh Saber Zaeimian¹ ; Anthony Piazza¹ ; Athanasios G. Mamalis² ; Xiaoshan Zhu¹ ; Li Wan³ ; ¹University of Nevada, Reno, Reno, United States; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³Wenzhou University, Wenzhou, China;
Paper Id: 205 [Abstract]

Ion-selective electrodes (ISEs) have been widely used in chemical or clinical analysis for the detection of various ions. Conventional ISEs are fabricated with an ion selective membrane in contact with an inner solution. The inner solution causes short lifetimes of ISEs, complex assembly and maintenance, and difficulties in ISE further miniaturization. Instead of an inner solution, ISEs with an internal solid contact (SC) have been recognized as the next generation of ISEs because they possess important merits in easy miniaturization, simple fabrication and ruggedness [1-2]. Different materials ranging from conducting polymers through to inorganic nanomaterials/nanostructures (e.g., carbon, gold) have been applied as SC for ISEs. In this work, to the best of our knowledge, it is the first time to report using Au@Pt core-shell nanoparticles with nanostructured dendritic Pt shells as an active ion-to-electron transducer layer (or solid contacts) for ISEs. Compared to other reported inorganic nanomaterials/nanostructures, the Au@Pt core-shell nanoparticles possess large and electron-state-rich surfaces for high electrochemical activity, ease synthesis by simply mixing chemical reagents in room temperature, and high stability in environments due to inert noble metal compositions. We anticipate that the merits of the Au@Pt core-shell nanoparticles will enhance the ISE performance in fast response, sensing stability against many interferences, low limit of detection, and wide linear detection range. Specifically, ISE using these nanoparticles for ammonium detection is developed. Ammonium is one of important biological nutrients in soil or environmental water and critical for the plant growth or the blooming/fading of microbiome in water. This ISE can be used for the identification and management of the nutrients for soil/water quality monitoring [3]. Moreover, ammonium is present in blood mostly as a result of the breakdown of proteins [4]. Therefore, the ISE can be used to determine the levels of this cation in plasma and thus to provide extremely relevant physiological information related to the metabolic state of the individual, dietary conditions, or even liver malfunctions. Although our ISE currently is developed on a glassy carbon rod, it can be developed on any flexible substrates for further wearable applications (e.g., detecting ammonium in sweat).

References:
[1] B. P. Nikolskii, E. A. Materova, Ion-Selective Electrode Reviews, 1985, 7, 3-39.
[2] Michalska A, Electroanalysis, 2012, 24, 1253-1265.
[3] K. Sato, W. H. Kang, K. Saga and K. T. Sato, J. Am. Acad. Dermatol., 1989, 20, 537-563.
[4] R. Athavale, I. Kokorite, et al., Anal. Chem., 2015, 87, pp 11990-11997.

14:50: [ManufacturingTuePM107]
Spherical Depth-sensing Indentation in a Liquid Environment: Toward Cardiac Tissue Characterization
Jean-philippe Jehl¹ ; Richard Kouitat Njiwa² ; Pablo Maureira³ ; ¹Institut Jean Lamour - Université de Lorraine, Nancy, France; ²Institut Jean Lamour (UMR 7198 CNRS-Université de Lorraine), Nancy, France; ³INSERM U961, Nancy, France;
Paper Id: 185 [Abstract]

Accurate descriptions for the mechanical behavior of human organs and tissues are required for many clinical applications. They are used for the simulation of surgical procedures (internal training and learning in continuing education) [1, 2], to integrate virtual reality systems, in engineering tissue [3], and in finite element modeling of different organs. The determination of the mechanical properties of soft biological materials is of great interest for imaging, where these material properties can be used to distinguish healthy and pathological tissues [4]. Mechanical tests are carried out to study the mechanical behavior of biological tissues [5], which include different modes of strain compression, tension, and shear. This work proposes to use spherical depth-sensing indentation experiments for the characterization of heart tissue. This tissue dries up and dies quickly, therefore a liquid environment is necessary to characterize its mechanical behavior. The spherical depth-sensing indentation has recently been adapted to operate in such an environment [6]. The experimental protocol and the method of analysis of the obtained results must be rebuilt. The presented work pinpoints the difficulties according to the tests for the cardiac tissue, and proposes some techniques to circumvent these issues. Characterizations of the cardiac tissue are obtained with theory of linear elasticity and nonlinear elasticity. The latter would appear more appropriate to describe the cardiac tissue response under a wide range of deformation.

References:
[1] Misra S, Ramesh KT, Okamura AM. Modeling of tool-tissue
interactions for computer-based surgical simulation: a literature
review. Presence-Teleop Virt 2008; 17: 463-491.
[2] Perrenot C, Perez M, Tran N, Jehl J-Ph, Felblinger J, Bresler L, Hubert J
The virtual reality simulator dV-Trainer is a valid assessment tool for robotic surgical skills. Surgical Endoscopy September 2012, Volume 26, Issue 9, pp 2587-2593
[3] Fung YC. Stress, strain, growth, and remodeling of living organisms.
In: Casey J, Crochet MJ, editors. Theoretical, experimental,
and numerical contributions to the mechanics of fluids and
solids. Basel/Switzerland: Birkh.user Verlag 1995: 469-482.
[4] J-Ph. Jehl and R. Kouitat Njiwa. A (Constrained) Microstretch Approach in Living Tissue Modeling: a Numerical Investigation Using the Local Point Interpolation - Boundary Element Method. Computer Modeling in Engineering & Sciences, Vol.102, No.5, 2014
[5] Gao Z, Lister K, Desai J. Constitutive modeling of liver tissue:
experiment and theory. Ann Biomed Eng 2010; 38: 505-516.
[6] J-Ph. Jehl, A.Voignier, R. Kouitat. On the depth sensing indentation on liquid environment for application to biological tissue. 2016 Sustainable Industrial Processing Summit

15:15: [ManufacturingTuePM108]
Identification of a Peptide that can Enhance Genotoxic Sensitivity Through Cellular Redistribution of Chk1 Protein
Kwang Seok Kim¹ ; Sang Jun Park¹ ; Chun-ho Kim¹ ; ¹KIRAMS, Seoul, South Korea;
Paper Id: 414 [Abstract]

Chk1 protein has been a target in the detectable genotoxic sensitivity of cells and tissues, and a major focus of pharmaceutical development to enhance sensitivity of tumor cells to chemo- and radiotherapy [1]. To take advantage of such biological effects, we identified a specific Chk1-binding 12-mer peptide from screening of phage display library and characterized the peptide in terms of cellular cytotoxicity, and effect on Chk1 activity, and sensitivity to genotoxic agents [2]. Interestingly, polyarginine-mediated internalization of the peptide redistributed nuclear Chk1 with prominent decrease in the nucleus in the absence of DNA damage. Treatment of HeLa cervical cancer cells or NCI-H460 lung cancer cells with the peptide significantly enhanced radiation sensitivity following ionizing radiation (IR). Moreover, IR-induced Chk1 destabilization was aggravated by Chk1 peptide treatment. The approach using the specific Chk1 peptide may facilitate a mechanistic understanding and potential modulation of Chk1 activities and provide a novel rationale for development of specific Chk1-targeting agents [3-4].

References:
1. Zhang Y, Hunter T. Roles of Chk1 in cell biology and cancer therapy. Int J Cancer. 2014;134(5):1013-23
2. KS Kim, KJ Choi, SW Bae. A novel Chk1-binding peptide that can enhance genotoxic sensitivity through cellular redistribution of nuclear Chk1. 2016. Int J Mol Med 38:1490-1498
3. Saladin A, Rey J, Thevenet P, Zacharias M, Moroy G, Tuffery P. PEP-SiteFinder: a tool for the blind identification of peptide binding sites on protein surfaces. Nucleic Acids Res. 2014;42:W221-6.
4. Kawabe T. G2 checkpoint abrogators as anticancer drugs. Mol Cancer Ther 2004; 3:513-9.

SESSION: ManufacturingTuePM2-R4 High Strain-Rate Phenomena / Treatment under Shock Loading–I	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Tue Nov, 6 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Manos Maragakis; Session Monitor: TBA

15:55: [ManufacturingTuePM209] Invited
The Making of UniPore Material Through Explosive Welding Process and the Mechanical Response Under Static and Dynamic Loading
Kazuyuki Hokamoto¹ ; ¹Institute Pulsed Power Science, Kumamoto, Japan;
Paper Id: 7 [Abstract]

Uni-directional porous (UniPore) material is one of the porous materials consisting of many uniformly elongated holes isolated on thin metal walls. It was fabricated through explosive welding process using many small pipes inserted into a large pipe [1]-[3], and such material has potential applications for energy absorption during impact loading and others. For the fabrication, a large pipe was covered by a thick ANFO based explosive cylindrical layer to accelerate the large pipe inward. The pipes were successfully welded tightly and no fracture on the small pipe walls was observed even by using a thin pipe, the thickness of which was 0.2mm. The samples made by copper were cut into short pieces and compressed both statically and dynamically. The mechanical response under static compression tests shows a well-known "plateau region", which is possible to consume energy through large deformation. Furthermore, the dynamic response using a powder gun compressed at 400-600 m/s also shows a plateau through PVDF gauge measurement, and the deformation process is visualized using high-speed camera and compared with numerical simulation using AUTODYN code, which suggests good agreement.

References:
[1] K. Hokamoto, M. Vesenjak, Z. Ren, Mater. Lett. 137 (2014) 323-327.
[2] M. Vesenjak, K. Hokamoto, M. Sakamoto, T. Nishi, L. Krstulović-Opara, Z. Ren, Materials & Design 90 (2016) 867-880.
[3] K. Hokamoto, K. Shimomiya, M. Nishi, L. Krstulović-opara, M. Vesenjak, Z. Ren, Z., J. Mater. Process. Technol. 251 (2018) 262-266.

16:20: [ManufacturingTuePM210]
Preparation of Graphene Nanosheets by Shock Waves
Pengwan Chen¹ ; Xin Gao¹ ; Hao Yin² ; Chunxiao Xu¹ ; Qiang Zhou¹ ; ¹Beijing Institute of Technology, Beijing, China; ²Institute of Systems Engineering, China Academy of Engineering Physics, Mianyang, China;
Paper Id: 159 [Abstract]

Shock wave action of high temperature, high pressure and high strain rate lasting for very short time (~10^-6 s) will cause a series of catastrophic changes of material chemical and physical properties, and herein both detonation-driven high velocity flyer impact loading and electrical explosion technique were employed to induce shock wave for the synthesis of high-quality graphene materials. Using solid CO₂ (dry ice) as the carbon source [1], few layer graphene nanosheets were successfully synthesized by reduction of CO₂ with calcium hydride through detonation-driven flyer impact. Furthermore, by adding ammonium nitrate to the reaction system, nitrogen-doped graphene materials were formed in this one-step shock-wave treatment. Similarly, a few layers of graphene and nitrogen-doped graphene materials were also prepared through the reaction of calcium carbonate and magnesium [2], and the shock pressure and temperature are two important factors affecting the synthesis of few layer graphene nanosheets. Besides that, electrical explosion exfoliation of crystalline flake graphite suspension was achieved to synthesize graphene sheets. Meanwhile, graphite nanosheets, few-layer graphene, and especially, mono-layer graphene with good crystallinity were also produced by electrical explosion of high-purity graphite sticks in distilled water at room temperature [3]. Delicate control of energy injection is critical for graphene nanosheets formation, whereas mono-layer graphene was produced under the charging voltage of 22.5-23.5 kV. The recovered samples were characterized using various techniques such as transmission electron microscopy, scanning electron microscopy, Raman spectroscopy, atomic force microscope, and X-ray photoelectron spectroscopy. Therein, the nitrogen-doped graphene was demonstrated to act as a metal-free electrode with an efficient electrocatalytic activity toward oxygen reduction reaction in alkaline solution. This work provides a simple but innovative route for producing graphene nanosheets.

References:
[1] P. Chen, C. Xu, H. Yin, X. Gao, L. Qu, Carbon 115 (2017) 471-476.
[2] H. Yin, P. Chen, C. Xu, X. Gao, Q. Zhou, Y. Zhao, L. Qu, Carbon 94 (2015) 928-935.
[3] X. Gao, C. Xu, H. Yin, X. Wang, Q. Song, P. Chen, Nanoscale 9 (2017) 10639-10646.

16:45: [ManufacturingTuePM211] Invited
Relationship Between Hardness and Capillary Action-like Phenomena of Nickel Metal Observed in TiB2+TiN/TiNi/Steel-layered Composites Fabricated by Hot Explosive Welding
Ryuichi Tomoshige¹ ; Seiichiro Ii² ; Yasuhiro Morizono³ ; Kanako Sonoda¹ ; ¹Sojo University, Kumamoto, Japan; ²National Institute for Materials Science (NIMS), Tsukuba, Japan; ³National Institute of Technology, Kurume College, Kurume, Japan;
Paper Id: 68 [Abstract]

Our research group has developed a novel welding method that is capable of bonding ceramics, intermetallics, and metal. The welding method is composed of both combustion synthesis and explosive welding. That is, explosive welding is performed just after finishing combustion synthesis of ceramics (for example, TiB₂ or TiC⁺Al₂O₃) and intermetallics (for example, TiNi) on a metal plate. Here, combustion synthesis generates high temperature of around several thousand degrees Celsius due to their exothermic reaction. We have reported that fabricated layered-composites were well-joined among TiB₂ ceramics, TiNi intermetallics, and metal layers, and performed well in resistant-to-thermal shock tests. This is tested by heating the layered material to 550°C and then rapidly cooling it by dropping it into water, due to their high joining strength and pseudo-elastic effect of TiNi layer [1]. In this study, we have fabricated another layered-composite system, that is TiB²⁺TiN/TiNi/steel, by the hot explosive welding technique, and have observed interlayer structures of the obtained layered-composite, especially between ceramics and intermetallics, with electron microscopes. As a result, scanning electron microscopy (SEM) revealed that TiB2 and TiN crystal grains in ceramic layer closely bonded each other. According to observations with transmission electron microscope (TEM), they showed a characteristic crystal orientation relationship, i.e. Blackburn orientation relationship, which is the same as the matter we have revealed it previously in TiB₂+TiN composites prepared by hot dynamic compaction technique [2]. Further detailed scanning TEM (STEM) observations and energy dispersive spectroscopy (EDS) revealed a component of nickel infiltrated from TiNi layer to intergranular regions of TiB2+TiN ceramic layer, which seemed like the capillary action. It was speculated that the phenomena must have generated after finishing the combustion synthesis of ceramic layer, because TiB₂ and TiN phases in the ceramics layer has completely formed. Also, this phenomenon resulted in a decrease in Vickers hardness value in the ceramics layer (around 10 GPa), even though TiB₂ and TiN phases have essentially hardness values of about 33 and 20 GPa, respectively. Here, it is well-known that mechanical properties, including the hardness values, are affected by an aspect of grain boundaries. Therefore, the decrease in hardness must have been caused by the decrease in intergranular bonding strength, as a consequence of the infiltration of metal nickel into boundaries between TiB2 and TiN grains.

References:
[1] R. Tomoshige, S. Ii, and Y. Morizono, 2017 SUSTAINABLE INDUSTRIAL PROCESSING SUMMIT AND EXHIBITION, Vol. 5: Marquis Intl. Symp. / New and Advanced Materials & Technologies for Energy, Environment, and Sustainable Development, pp410-417, (2017).
[2] S. Ii, T. Nishitani, and R. Tomoshige, Materials Science Forum, 561-565, pp.2481-2484 (2007)

17:10: [ManufacturingTuePM212]
Explosive Forming of Metal Tubes for Heat Exchangers
Andras Szalay¹ ; Athanasios G. Mamalis² ; Istvan Zador³ ; Pal Racz⁴ ; Hasebe Toshiaki³ ; ¹S-Metalltech 98 Materials Research and Development Ltd, Budapest, Hungary; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³S-Metalltech 98 Ltd, Budapest, Hungary; ⁴Bay Zoltán Nonprofit Ltd, Budapest, Hungary;
Paper Id: 86 [Abstract]

Large quantities of hot flue gases are generated from kilns, ovens, and furnaces. If some of this waste heat could be recovered, a considerable amount of primary fuel could be conserved. Although the energy lost in waste gases cannot be fully recovered, much of the heat could be recovered by heat exchangers or recuperators, and the loss will be reduced. A heat exchanger is an equipment built for efficient heat transfer from one medium to another. Generally, the two media are separated by a solid metallic wall, so that they never mix. These tubular heat exchangers are widely used in power plants, chemical plants, and metal processing plants. The main requirement for heat exchanger tubes is that the heat transfer between the media inside the tube and outside the tube should be at the maximum. This can be achieved in many ways; the most frequently used solution is the modification of the tubes construction as creation of enhanced surface, or applying spiral strips for causing turbulence in the streaming media. An innovative solution is enhancing the efficiency of the heat exchanger tubes by creating spiral deformations on the tubes. The advantages of the properly designed deformation of the tube material are twofold: on one hand the heat transferring surface of the tubes will be enlarged, and on the other hand the deformations will cause turbulence in the streaming media, enhancing the heat transfer. The task can be solved by explosive tubeforming [1]. The optimal form of the tubes have been designed by thermo-hydraulic computer simulation based on the ANSYS system [2]. The plastic deformation of the tubes is carried out by high pressure shock waves created by explosion of detonating cords positioned on the outer surface of the tubes. The efficiency of the heat exchangers built with explosively formed tubes are cca. 10 % higher than the heat exchangers built with plain tubes. In this presentation we briefly report the results of the simulations and introduce the manufacturing process.

References:
[1] Prümmer R, Explosive Welding, Forming and Compaction. Ed. T.Z. Blazynski, Applied Science, London 1983.
[2]. A.Szalay, A. G. Mamalis, I. Zador, A. K. Vortselas, L. Lukacs: Explosive metalworking: experimental and numerical modeling aspects International Symposium on Explosion, Shock wave and High-energy reaction Phenomena 2013 March 27 - 29, 2013 Nago, Okinawa, Japan

SESSION: ManufacturingTuePM3-R4 Defense / Safety	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Tue Nov, 6 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Kazuyuki Hokamoto; Session Monitor: TBA

17:40: [ManufacturingTuePM313]
Modern Protective Systems for Mitigating Explosions
Nikoloz Chikhradze¹ ; Edgar Mataradze² ; Theodore Krauthammer³ ; Mikheil Chikhradze⁴ ; ¹G. Tsulukidze Mining Institute, Tbilisi, Georgia; ²LEPL Grigol Tsulukidze Mining Institute, Tbilisi, Georgia; ³Director, Center for Infrastructure Protection and Physical Security University of Florida, Geinesville, United States; ⁴Georgian Technical University, Tbilisi, Georgia;
Paper Id: 144 [Abstract]

The major disadvantages of the existing automatic systems of blast suppression are: the long length of response; an inadequate discharge of the blast absorbing agent required for reducing overpressure and temperature to an acceptable value; and the lack of reliability of a blast identification device in difficult conditions of underground openings, especially under long-term operation. Basic design requirements for the protective system are: short response time from the moment of explosion to the system activation; high reliability to rule out false activation and the possibility of failure to detect an explosion; high reduction of shock wave overpressures; capacity to extinguish secondary blasts and ensuing fires— system should remain active for a few minutes; it shall not interfere in the normal functioning of the tunnel and have an ability to adapt to the tunnel shape and size; the system components shall be strong enough to withstand all loads and high shock; low cost of production, installation, and performance monitoring. Subject to these requirements, a new blast protection system has been developed by the G. Tsulukidze Mining Institute and Center for Infrastructure Protection and Physical Security (CIPPS) within the frames of the NATO SPS programme, Shota Rustaveli National Science Foundation (SRNSF) and International Science and Technology Center (ISTC) [1, 2, 3]. The system consists of the following three sub-systems: i) a shock wave high-speed suppression section, in which high pressure is generated upon the initiation of the pyrotechnic gas generator; ii) a suppression section with a long-term action, in which high pressure is obtained by using a pump; iii) a system activating device. The system contains a wireless device for the detection of explosions. This paper presents the results of the testing of the Automatic Protecting System from explosion in an underground structure.

References:
[1] E. Mataradze, N. Chikhradze, T. Krauthammer, GE P 2017, 6632 B
[2] Edgar Mataradze, Nikoloz Chikhradze,2, Irakli Akhvlediani, Nika Bochorishvili1 and Ted Krauthammer, http://iopscience.iop.org/article/10.1088/1755-1315/44/5/052012/pdf
[3] N. Chikhradze, E. Mataradze, M. Chikhradze, T. Krauthammer,IAPS, ISIEMS, Sixteenth International Symposium on the Interaction of the Effects of Munition with Structures, Destin, Florida USA, 9-13 November 2015

18:05: [ManufacturingTuePM314]
Static and Dynamic Compression and Indentation Behavior of Aerated Autoclaved Concrete
Mustafa Sarikaya¹ ; Dogus Zeren¹ ; Burak Akyol¹ ; Taner Kavas² ; Ugur Uzgan³ ; Dogan Soyal⁴ ; Mustafa Guden¹ ; ¹İzmir Institute of Technology, İzmir, Turkey; ²Ayfon Kocatepe University, Ayfonkarahisar, Turkey; ³AKG Gazbeton, Izmir, Turkey; ⁴AKG Gazbeton, İzmir, Turkey;
Paper Id: 113 [Abstract]

The quasi-static and dynamic compression and indentation behavior of the autoclaved aerated concretes (AAC), with the average densities of 490, 405, 400, and 180 kg m-3 were determined experimentally. It has been noted that there are only a few studies on dynamic behavior of light-weight concrete in the literature [1-3]. The quasi-static tests were performed at the nominal strain rates of 0.001, 0.01, and 0.1 s-1. The high strain rate tests were conducted using a modified compression type Split Hopkinson Pressure Bar (SHPB) apparatus in the direct impact mode: the striker bar impinged, with an initial velocity, the concrete samples inserted at the end of the incident bar. The velocity of the striker bar in the direct impact tests was 9 and 30 m s-1, corresponding to the strain rates of 500 and 1500 s-1, respectively. The fracture strength of the quasi-statically and dynamically tested samples were further fitted to the Wiebull cumulative distribution function. The cracks initiated at the compression test plate-sample interface and progressed diagonally to the cylindrical tests sample in the quasi-static strain rates. The facture behavior of the lowest density samples were slightly different in that the cells near the upper and lower compression plate were crushed until about major diagonal or lateral cracks form. The crushing in the direct impact tests started from the impact end of the sample and the samples were completely shuttered into many small pieces, featuring enhanced energy absorption at these strain rates. A similar observation was also made previously [3]. The reduction in the Weibull distribution modulus, m, at high strain rates also showed more brittle behavior of the concrete sample. The indention behavior of the compression tested samples showed somewhat similar behavior of increased resistance to the indenter at increasing strain rates. The results clearly indicated the potentials of these materials to be used against the localized impact, while there existed almost no experimental work on these materials.

References:
[1] Ferrara, L., et al., "Collapsible" lightweight aggregate concrete. Part II: characterization under static and dynamic loadings. Materials and Structures, 2016. 49(5): p. 1747-1760.
[2] Mespoulet, J., F. Plassard, and P.L. Hereil, Strain rate sensitivity of autoclaved aerated concrete from quasi-static regime to shock loading, in Dymat 2015 - 11th International Conference on the Mechanical and Physical Behaviour of Materials under Dynamic Loading, E. Cadoni, Editor. 2015, E D P Sciences: Cedex A.
[3] Belouettar, R., J.R. Klepaczko, and Edps, A study of dynamic behavior of the autoclaved aerated concrete. Dymat 2009: 9th International Conference on the Mechanical and

SESSION: ManufacturingWedAM-R4 Transport / Crashworthiness of Vehicles: Passive and Active Safety	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Ryuichi Tomoshige; Session Monitor: TBA

11:20: [ManufacturingWedAM01]
Perspective Ways for the Development of Endoprosthesis of Human Hip Implants
Sergiy Sheykin¹ ; Athanasios G. Mamalis² ; Raul S. Turmanidze³ ; S. Sohan⁴ ; I. Rostotskiy⁴ ; Dmitrii Vladimirovich Efrosinin⁵ ; ¹Bakul Institute of Superhard Materials, Kyiv, Ukraine; ²PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ³Georgian Technical University, Tbilisi, Georgia; ⁴Bakul Institute of Superhard Materials, Kiev, Ukraine; ⁵Bakul Institute for Superhard Materials, Kiev, Ukraine;
Paper Id: 174 [Abstract]

Nowadays, the greatest spread in the practice of endoprosthesis replacement was obtained by a metal/UHMWPE (Ultra-high-molecular-weight polyethylene) friction pair. As a rule, in this case a CoCrMo alloy is used as the material of the metal component. However, from the point of view of biocompatibility, this alloy is not the best. Among the metals and alloys in this indicator, pure titanium is the best choice. Nevertheless, its usage as a component of the friction pair is hampered by the increased tendency to seize with structural materials (including the UHMWPE) and low mechanical characteristics. To receive the needed level of operating specifications of friction pair, pure titanium/UHMWPE, the technology for modifying the surface layer of the spherical head by surface plastic deformation and subsequent thermal diffusion nitriding was elaborated. This technology made it possible to achieve an optimal combination of strength and adhesive inertness of the working surface of the titanium head [1]. The technology for shaping the working surface of a spherical head was developed, including preliminary precision and finishing. The technologists use tools used at the Institute of Superhard Materials. The technology made it possible to obtain a product conforming to the international standard ISO 7206-2-2013 (Ra <0.05 mm with deviation from non-circularity less than 0.006 mm). Comparative tests of nitrided pure titanium and CoCrMo alloy in pair with the surgeon performed on the ring-plane face friction machine in blood plasma (closest in composition to the synovial fluid of the natural joint) showed a clear advantage of nitrided pure titanium: friction in a pair of nitrided Grade 2 / surgical below by 25%, linear wear by 60%. A promising alternative to the evolutionary development of the traditional endoprosthesis of the femoral head is also considered a fundamentally different technological solution— hybrid endoprosthesis of the femur head with a heart of metal and an outer layer of oxide ceramics [2]. This idea is implemented, for example, in the product with the commercial brand Oxinium™ (Smith & Nephew, Memphis, US). The idea of a multilayer endoprosthesis of the femoral head was suggested by the authors in [3]. The outer part in the form of a spherical shell of artificial sapphire or ZrO₂-ceramics has a cavity filled through a special heat-conducting technological layer in several layers by a metal core. In the metal core, there is a tapered hole for fixing the head. Due to the use of sapphire (it does not have harmful impurities in the interstitial space), such endoprosthesis is chemically inert, is electrically neutral, has an increased wettability of the surface, and has biological compatibility (activity). An additional advantage of this technical solution is the possibility of introducing a layer of polymer material that improves the damping properties of the endoprosthesis.

References:
[1] Increasing of functionality of c.p. titanium/UHMWPE tribo-pairs by thermodiffusion nitriding of titanium component / I.M. Pohrelyuk, S.E. Sheykin, S.M. Dub, A.G. Mamalis, I.Yu. Rostotskii, O.V. Tkachuk, S.M. Lavrys // Biotribology Volume 7, September 2016, Pages 38-45.
[2] Pezzotti, G. Artificial hip joints: The biomaterials challenge / G. Pezzotti, K. Yamamoto / J. Mech. Behav. Biomed. Mat. 3 1 (2014) 3-20.
[3] Спосіб виготовлення головки ендопротеза кульшового суглобу: пат. 105064 U Україна МПК А61F2/32 (2006.1) / С.В. Сохань, Л.Ф. Головко, Н.О. Мельник-Кагляк, 201503079; заявл. 03.04.2015; опублік. 10.03.2016, Бюл. 5-3 с.

11:45: [ManufacturingWedAM02] Keynote
A Composite Nanostructured Material Based on Alumina for Use in an Airocraft Gas Turbine Engine
Athanasios G. Mamalis¹ ; Sergiy N. Lavrynenko² ; Edwin Gevorkyan³ ; Vasily Dutka⁴ ; Maxim Kislitsa⁵ ; ¹PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ²Kharkov Polytechnic Institute, Kharkov, Ukraine; ³Cermet-Ukraine Ltd. Science and Production Company, Kharkiv, Ukraine; ⁴Institute for Superhard Materials of the National Academy of Sciences of Ukraine, Kiev, Ukraine; ⁵Ukrainian State University of Railway Transport, Kharkiv, Ukraine;
Paper Id: 218 [Abstract]

The structure and properties of composite materials, for gas turbine engines based on nanopowders alumina, zirconium dioxide, and tungsten carbide, in the process of hot pressing by electroconsolidation are investigated. Research results on the influence of structure parameters and phase composition on the microstructure, and physical and mechanical properties of alumina composites obtained by electrosparking (electroconsolidation) are described. It has been established that the formation of a composite structure, due to the introduction of nanopowders of alumina and zirconium dioxide into the nanopowder of tungsten carbide, makes it possible to increase some of the physico-mechanical properties of the obtained composite materials.

12:10: [ManufacturingWedAM03]
Challenges in Engineering Devices that Promote Natural Gait in Amputees
Sesh Commuri¹ ; Bhanu Prasad Kotamraju² ; ¹University of Nevada, Reno, Reno, United States; ²University of Oklahoma, Norman, United States;
Paper Id: 266 [Abstract]

State-of-the-art in prosthetic design for below-knee or transtibial amputees is based primarily on the biomechanics of linear walking on level surfaces [1-3]. Existing foot/ankle prostheses tend to be passive devices that cannot accommodate the demands of changing user gait or changes such as surface and slope of the terrain. Limitations on gait imposed by inadequate prosthetic devices can result in musculoskeletal pain and sores that adversely affect the health of the individual [1, 4-6]. Gait asymmetry can also lead to hip/knee replacement surgeries over time. Although some designs recognize the importance of active prosthetic devices, their implementation is complicated due to lack of functional requirements that address user gait under all conditions [7-8]. Recent developments in biomimetic control have resulted in exciting new control strategies that improve the performance of complex systems with human agents [9-10]. While there have been significant advances made in surgical techniques, post-surgical recovery, design and fitting of prosthetic sockets, there has been limited impact on the health outcomes for the amputee. One of the main reasons for the limited improvement is because the available devices cannot easily adapt to user requirements or environments. Fully functional prosthetic feet require real-time detection of gait events to synthesize desired ankle displacements for each gait cycle to mimic natural human locomotion. Dynamic models of human-prosthetic limb system and the foot-ground interaction are also required to implement controllers that can reduce tracking error over each gait cycle (short term objective), while improving the performance over time (long term objective). In this paper, we highlight several of the challenges that have to be addressed in the design of next generation “intelligent” prosthetic devices for transtibial amputees. It is anticipated that the challenges identified in this paper will pave the way to developing a comprehensive solution to the design and control of computer controlled prosthetic ankles and establish benchmarks for their evaluation.

References:
[1] Hansen, A.H., D.S. Childress, S.C. Miff, S.A. Gard, and K.P. Mesplay. The human ankle during walking: Implications for design of biomimetic ankle prostheses. Journal of Biomechanics, 2004. 37: p. 1467-1474.
[2] Winter, D.A. Energy Generation and Absorption at the Ankle and Knee during Fast, Natural, and Slow Casdence. Clinical Orthopaedics and Related Research, 1983. 175: p. 147-154.
[3] Bateni, H. and S.J. Olney. Kinematic and kinetic variations of below-knee amputee gait. Journal of Prosthetics and Orthotics, 2002. 14(1): p. 2-13.
[4] A. Mai, S. Commuri, C.P. Dionne, J. Day, W.W.J. Ertl, and L.J. Regens. Effect of prosthetic feet on end-bearing characteristics in users with Transtibial Osteomyoplastic Amputation. Journal of Prosthetics and Orthotics, 2013. 25(3): p. 151-158.
[5] A. Mai, S. Commuri, C.P. Dionne, J. Day, W.W.J. Ertl, and L.J. Regens. Effect of Prosthetic Feet on End-bearing Characteristics in an otherwise Healthy Male with Transtibial Osteomyoplastic Amputation. Journal of Prosthetics and Orthotics, 2012. 24(4): p. 211-220.
[6] B.P. Kotamraju, S. Commuri, A. Mai, C.P. Dionne, J. Day, K. Veirs, W.W.J. Ertl, and B. Smith. Comparative Study of Residual Muscle Activity in Transtibial Amputees with Osteomyoplastic Amputation and Conventional Amputation during Varied Walking Tasks. Journal of Prosthetics and Orthotics, 2018 (to appear).
[7] Jimenez-Fabian, R. and O. Verlinden. Review of control algorithms for robotic ankle systems in lower-limb orthoses, prostheses, and exoskeletons. Medical Engineering & Physics, 2012. 34(4): p. 397-408.
[8] Rai, J.K., R.P. Tewari, and D. Chandra. Hybrid control strategy for robotic leg prosthesis using artificial gait synthesis. International Journal of Biomechatronics and Biomedical Robotics, 2009. 1(1): p. 44-50.
[9] Commuri, S., and A. Mai. Intelligent control of prosthetic ankle joint using gait recognition, in Recent Advances and Future Directions in Adaptation and Control, Editors Sarangapani, J., and K.G. Vamvoudakis, 2016. Elsevier Publications. p. 635-660.
[10] A. Mai and S. Commuri. Robust Control of Prosthetic Ankle through the Integration of User Intent. IFAC Journal of Control Engineering Practice, 2016. vol. 49, pp. 1-16.

12:35: [ManufacturingWedAM04]
Magnetic Permeability Measurement Device Based on Hall Effect
Spyridon Angelopoulos¹ ; Giorgios Banis¹ ; Xenia Vourna¹ ; Aphrodite Ktena² ; Panagiotis Tsarabaris¹ ; Evangelos Hristoforou¹ ; Athanasios G. Mamalis³ ; ¹National TU of Athens, Athens, Greece; ²TEI of Chalkida, Chalcis, Greece; ³PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 296 [Abstract]

A new, fully portable device is presented, which can be used to measure magnetic permeability and residual stress. The device is based on the use of a Hall sensor and a permanent magnet. The Hall sensor is placed at the edge of a yoke, and consists of two parallel ferromagnetic bars and a permanent magnet. As a result, its output voltage depends on the magnetic field that is produced by the magnet. If the yoke is placed near a ferromagnetic material under test, the Hall voltage output will change accordingly. The optimal placement of the Hall sensor was found through software simulations. The magnetic field measured by the Hall sensor can be correlated to the surface magnetic permeability and the residual stress tensor distribution of the ferromagnetic material under test. Calibration of the sensor was held, in order to provide accurate results. The constructed device includes the aforementioned sensing element, an Arduino-based microcontroller, an RF transmitter, a Bluetooth module, and a battery. The collected data is wirelessly transmitted to a receiving device, and consists of an Arduino-based microcontroller, an RF receiver, an LCD, and a battery. As a result, the output information can be viewed either on the dedicated device or on any other Bluetooth-compatible device (e.g. smartphone or tablet). The sensor is suitable for on-field measurements, as it is wireless, energy sufficient, robust, and conducts high-speed contactless measurements.

SESSION: ManufacturingWedPM1-R4 Energy	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Nikoloz Chikhradze; Session Monitor: TBA

14:00: [ManufacturingWedPM105]
New Designs of Rotors with Variable Geometry Parameters in Dynamics and Their Effective Use in Aviation and Wind Energy
Raul S. Turmanidze¹ ; Paata Kervalishvili¹ ; Giorgi Popxadze¹ ; ¹Georgian Technical University, Tbilisi, Georgia;
Paper Id: 162 [Abstract]

Famous specialists of many leading scientific centers of the world unambiguously prove that, from the date of existence of airscrews, the problem of creating a design for screws with the possibility to change key geometrical parameters in dynamics is particularly acute. It stems from the fact that existing screws are not optimal for all operational phases of units with different functions. The solution to this problem is possible only by using screws of changeable geometry (SCG), which has the capability to simultaneously change the diameter of the screw and a corner of installation, and twist the blades in dynamics. As a result of production and tests for various designs of the screw's demonstration model with changeable geometrical parameters in dynamics, it was proven that, for example, for aircraft use the WHIG gives the chance of especially effective optimization of aircraft flight in vertical takeoff and landing (SVVP), ensuring the maximum diameter and the minimum twist in the hanging mode and vice versa, the minimum diameter and the maximum twist at horizontal flight. In particular, at a variation of diameter of trial model of a rotor, for example, from - 4,1 to - 5,6 m and twists of blades within 80-300 it is possible to increase aircraft loading capacity on average 1.6 times, or to increase flight speed 1.4 times, or respectively to reduce fuel consumption. For wind power installations, especially with big capacities, use of the WHIG will give the chance to expand the range of the maximum efficiency values of installation at changes of wind speed in a wide range from 3 to 20-22 m/s, and also provide installation operability at high wind speeds of 22-35 m/s), at which the existing installations would not be in a functional state. The solution of this problem became particularly salient because of the infamous accident in Fukushima, Japan. These events compelled leaders from major countries of the world to find as many opportunities as possible to replace a share of atomic energy with other types in the overall power balance. Unfortunately, methods that are more effective than wind power in terms of economic and ecological criteria, and potentially mastered volume of energy, do not exist. Preliminary aerodynamic and economic calculations carried out, by means of the design developed by us, proved that it is possible to increase the annual volume of each wind turbine's energy by a minimum of 100%. In the presented work, different options for the rotor designs developed by us, with the indication of their advantages to each case will be analyzed. Further, on the basis of the results from aerodynamic tests of working models that were carried out, recommendations for effective use of each option in these or those concrete branches of equipment, are given. Additionally, the method of accumulation for the received wind and solar energy, which is very effective at prime cost, is an pressing world problem for which there is development costing some hundreds of millions of US dollars annually, will be offered and analyzed. The proposal refers to those countries that have hydroelectric power plants with medium and large capacities— for instance where there are already high dams and reservoirs built . The core of our proposal is that it is possible to mount the greatest possible number of wind stations and solar panels around a reservoir. When there is an order for electric energy they will work for its production, and when orders are not present, they will work for water pumping back from the lower reservoir in its top part. It will give the opportunity to have all power sources working constantly for profit, day and night, day after day, and all the year round. A very effective method of location and operation of solar modules will also be elaborated and presented. The proposed method of accumulation of wind and solar energy gives an opportunity for effective operation of wind and solar stations, the repeated use of accumulated water and, most importantly, fundamentally changing the principle of projecting and constructing of hydroelectric power stations of medium and large capacities. In addition it is necessary to underline the increase of the safety of hydroelectric stations, the reduction in the flooding of the country's cultural values and decrease area of the mirror surface of the reservoir, which adversely affects the changing climatic conditions of this region.

References:
[1] R.Turmanidze, L.Dadone. "Variable Geometry Rotor". Monograph, Publishing House of University of Petrosani. 2003, Romania, 164 p.
[2] R.Turmanidze, L.Dadone, G.Sanadze. Increase of Flight and Technical Characteristics of Flying Vehicles By Means of Application of the Variable Geometry Rotor. Materials of the 5th Forum of the Russian Helicopter Society. Moscow, 2002. p. VI39-VI48. AGARD. 1998. A selection of test cases for the validation of large eddy simulations of turbulent flows. Agard Advisory Report 345. North Atlantic Treaty Organization.
[3] R.Turmanidze, L.Dadone, J.-J.Philippe, B.Demaret, Investigation, Development and Tests Results of the Variable Geometry Rotor. 33 rd. European Rotorcraft Forum. Kazan, 10-14 September 2007, Pages 11.
[4] R.Turmanidze, О.Rukhadze, R.Bidzinashvili, Е.Rukhadze, Designing Fundamentals of Investigation Equipment of Rotors with the Parameters of Variable Geometry. International Scientific Journal "Problems of Mechanics". 1 (42)/2011. Georgia, Tbilisi. 2011. 8 p.
[5] R.Turmanidze, О.Rukhadze, R.Bidzinashvili, Е.Rukhadze, Investigation of the Variable Geometry Rotor in Dynamics. International Scientific Journal "Problems of Mechanics". 2(43)/2011. Georgia, Tbilisi, 2011. 8 p.

14:25: [ManufacturingWedPM106]
Structure and Properties of MgB&lt;sub&gt;2&lt;/sub&gt;- and MT-YBaCuO-based Materials Manufactured Under Pressure
Tetiana Prikhna¹ ; Michael Eisterer² ; Matt Rindfleisch³ ; Athanasios G. Mamalis⁴ ; Michael Tomsic³ ; Vitaliy Romaka⁵ ;⁰ ; Artem Kozyrev¹ ; Myroslav Karpets¹ ; Anton Shaternik¹ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Atominstitut, Technische Universität Wien, Vienna, Austria; ³Hyper Tech Research, Inc., Columbus, United States; ⁴PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ⁵Lviv Polytechnic National University, Lviv, Ukraine;
Paper Id: 121 [Abstract]

The influences of technological parameters (temperature, pressure, type of cladding), composition of precursor powders, and type of additions (Dy₂O₃, Zr, Ti, Ti-O, SiC, Nb) on the superconducting characteristics (transition temperature, critical current density, critical magnetic fields) of MgB₂ wires produced by Hyper Tech Research Inc. and of bulk materials synthesized under ambient, elevated, and high pressures in correlation with their microstructures, were studied. Microstructural observations are in good agreement with ab-initio modeling [1, 2]. The relevant pinning centers of Abrikosov vortices in MgB₂-based materials are oxygen-enriched Mg-B-O inclusions (or nanolayers) and inclusions of high borides MgBx. Their number and size depends on the synthesis parameters and dopants. Ti, Ta, and Zr bind hydrogen, make the formation of magnesium hydride impossible, and thus improve the mechanical characteristics bulk MgB2. Ti, Ta, Zr also affects the formation of higher borides, and Ti, Ta, Zr, SiC, TiC - on the redistribution of oxygen. The critical current density, jc of melt textured YBa₂Cu₃O₇-d (or Y₁₂₃)-based superconductors (MT-YBaCuO) depends on the perfection of texture and the amount of oxygen in the Y₁₂₃ structure, but also on the density of twins and micro-cracks formed during the oxygenation (due to shrinking of the c-lattice parameter). The density of twins and micro-cracks increases with the reduction of the distance between Y₂BaCuO₅ (Y₂₁₁) inclusions in Y₁₂₃. A high level of critical current density demonstrated MT-YBCO oxygenated under 16 MPa oxygen pressure and MgB₂ high pressure (2 GPa) - high temperature synthesized: jc (MT-YBaCuO) at 77 K was nearly 105 A/cm² in self-field and 103 A/cm² at 10 Т, and jc (MgB₂) at 20 K was 106 at 1 T and 103 A/cm² at 8.5 T. The MgB₂ wires with added Dy₂O₃ (4 wt.%, 100 nm) demonstrated Jc=11 kA/cm² at 20 K in 5 T and at 4.2 K in 12.5 T fields.

References:
[1] T.A. Prikhna, V.V. Romaka, A.P. Shapovalov, M. Eisterer, V. Sokolovsky, H.W. Weber, G.E. Grechnev, V.G. Boutko, A.A. Gusev, A.V. Kozyrev, W. Goldacker, V.E. Moshchil, V.B. Sverdun, T. Habisreuther, C. Schmidt, V.V. Kovylaev, V.E. Shaternik, M.V. Karpets, A.V. Shaternik, "Structure and Properties of MgB2 bulks, thin films, and wires", IEEE Trans. Appl. Supercond., vol. 27, Is. 4, 2017, pp. 1-5, DOI: 10.1109/TASC.2016.2638201.
[2] T. А. Prikhna, A. Р. Shapovalov, G. E. Grechnev, V. G. Boutko, A. A. Gusev, A. V. Kozyrev, M. A. Belogolovskiy, V. E. Moshchil and V. B. Sverdun, "Formation of nanostructure of magnesium diboride based materials with high superconducting characteristics", Low Temperature Physics, vol. 42, No 5, pp. 486-505, 2016.

14:50: [ManufacturingWedPM107]
ENERGY CLOUD Service and TOMONI - Holistic Solutions for Energy Intensive Industries
Emmanuel Kakaras¹ ; Michalis Agraniotis¹ ; Christian Bergins¹ ; Torsten Buddenberg¹ ; Nikolaos T. Athanassoulis² ; ¹Mitsubishi Hitachi Power Systems Europe GmbH, Duisburg, Germany; ²Laboratory of Industrial and Energy Economics, NTUA, Athens, Greece;
Paper Id: 80 [Abstract]

European energy intensive industries are considerably affected by today's changing energy market landscape. Securing quality, competitiveness, and low environmental impact of final industrial products by changing conditions in the energy market requires extended efforts from the industry side. More specifically, the ongoing increase of RES' share in energy mix and the European targets on energy efficiency in industry have several implications, as well on technical aspects (additional requirements on flexibility, control reserve, dispatchable power generation, demand side management, energy storage), as also on economic aspects (decrease of whole sale electricity price, increase of taxes and surcharges, disruptive business models). In this changing landscape the task of matching energy supply with energy use following a continuous optimization process becomes of prime importance. Mitsubishi Heavy Industries has developed ENERGY CLOUD Service, an integrated toolbox of solutions assisting large energy users to overcome these challenges. It may support customer's needs in different operating levels, from a) performance monitoring, visualization and O&M optimization, to b) data analysis and evaluation for plant engineering level to c) providing information to management to supporting strategic decisions. Additionally, TOMONI is MHPS's state of the art condition monitoring and maintenance optimization tool, which utilizes advances AI techniques. ENERGY CLOUD Service and TOMONI utilize MHI's and MHPS's vast industrial know how and own developed AI technology, in order to use operating data towards optimization of operation and maintenance of assets and overall plants. In the present paper additional information about successful implementation cases of ENERGY CLOUD Service and TOMONI are reported.

15:15: [ManufacturingWedPM108]
A New Ruthenium(II) Photosensitizer With Bipyridines Containing Electron Donor/Withdrawing Groups
Fernando Federico Salomón¹ ; Mauricio Cattaneo² ; Néstor Katz³ ; ¹INQUINOA, San Miguel de Tucumán, Argentina; ²INQUINOA, San Miguel de Tucuman, Argentina; ³Universidad Nacional de Tucumán, San Miguel de Tucumán, Argentina;
Paper Id: 90 [Abstract]

Ruthenium(II) polypyridyl complexes have interesting physicochemical properties that can be applied in energy conversion processes. Since the development of the Grätzel cell, considerable efforts have been made to find new materials for dye-sensitized solar cells (DSSCs) [1]. In this work, a new polypyridylruthenium(II) complex, of formula [Ru(DMO-bpy)2(Mebpy-CN)]2+, (1), where DMO-bpy = 4,4'-dimethoxy-2,2'-bipyridine and Mebpy-CN = 4-methyl-2,2'-bipyridine-4'-carbonitrile, has been synthesized as a PF6- salt and characterized by spectroscopic, photophysical and electrochemical techniques.<br />Mebpy-CN ligand is an adequate anchoring entity to bind ruthenium photosensitizers to ZnO semiconductor surfaces in DSSCs [2]. The UV-Vis absorption spectrum of (1) in CH₃CN shows two intense bands with maxima at 453 and 492 nm that can be assigned to MLCT transitions from dpi(Ru) orbitals to pi* orbitals of DMO-bpy and Mebpy-CN respectively. The emission spectrum shows a band at a maximum of 679 nm, with a quantum yield Φ = 3x10-3. The redox potential of the RuIII/RuII couple was determined by CV as E1/2 = 1.12 V (vs. SCE). The cathodic shift of E1/2 and the red shifts of both the UV-Vis absorption and emission maxima respect to the corresponding values of [Ru(bpy)3]2+ are the result of destabilization of dpi(Ru) HOMOs induced by two bpys with electron-donor groups [3]. This may prove useful to enhance the efficiency of DSSCs.

References:
[1] A. Hagefeldt, G. Boschloo, L. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110 (2010) 6595-6663.\n[2] J. H. Mecchia Ortiz, C. Longo, N. E. Katz, Inorg. Chem. Comm. 55 (2015) 69-72.\n[3] A. Juris, V. Balzani, F. Barigelletti, S. Campagna, P. Belser, A. Von Zelewsky, Coord. Chem. Rev., 84 (1988) 85-277.

SESSION: ManufacturingWedPM2-R4 Environmental Aspects / Impact on Climate Change	Mamalis International Symposium on Advanced Manufacturing of Advanced Materials and Structures with Sustainable Industrial Applications
Wed Nov, 7 2018 / Room: Sao Conrado (50/2nd)
Session Chairs: Sesh Commuri; Session Monitor: TBA

15:55: [ManufacturingWedPM209] Invited
Smart Cities Under Electric Energy Trends: From Autonomous Building Directive to Prosumer Target
Nikolaos T. Athanassoulis¹ ; Aggelos Tsakanikas¹ ; Antonios G. Kladas² ; ¹Laboratory of Industrial and Energy Economics, NTUA, Athens, Greece; ²NTUA, Athens, Greece;
Paper Id: 51 [Abstract]

The liberalization of the electricity market, in conjunction with actual environmental constraints and provisions, led to considerations for combined urban and electricity market developments promoting buildings' energy autonomy, from the perspective of transforming regional and individual electricity consumers to producer-consumer (prosumer) actors. Such a development favors renewable energy sources, penetration growth, as well as combined electric-thermal production applications with important beneficial environmental issues [1]. The existing incentives for renewable energy exploitation and carbon leakage regulations are expected to be attenuated through the large introduction of prosumers enabling energy and ancillary services optimization by extended combined load management-unit commitment operation based on bid procedures [2]. In this context, energy storage devices are expected to play an important role in increasing the impact of emerging fuels such as natural gas and hydrogen. Such a trend will be facilitated by the spreading of electric traction in all the expected transportation mediums, in order to meet the environmental requirements foreseen. To that respect, battery and fuel cell technologies involved in hybrid/electric vehicles may equally serve the network load leveling issues [3]. Moreover, the transmission and distribution electric network activities will transit to a commonly available commodity, while the necessary extensions and reinforcements will be guided by local marginal price differences. The variety of interacting resources, as well as globalization of tasks and procedures will enable large scale economies and reliability enhancements. The extended distributed regulation necessary will be in close interaction with the centrally controlled large production units through smart grid technologies accommodating the important communication exchanges by convenient internet applications of smart buildings and smart cities underway [4]. The paper undertakes an overview of existing environmental constraints as well as current energy resources developments in the electric energy production sector. Furthermore, technological aspects of available devices involved in small hybrid production units are reported and discussed. Finally, the case study of a typical small autonomous hybrid production plant, convenient for a building prosumer activity, is presented.

References:
[1] S. Choi, S.W. Min, "Optimal scheduling and operation of the ESS for prosumer market environment in grid-connected industrial complex", IEEE Transactions on Industry Applications, (2018), doi: 10.1109/TIA.2018.2794330.
[2] A. Papalexopoulos, "Supplying the generation to meet the demand", IEEE Power and Energy Magazine, (2004) Vol. 2, No. 4, pp. 66-73.
[3] T. Graber, C. Romeis, E. Petrossian, J. Jaeger, "Intelligent prosumer coupling by two galvanically isolated battery storage systems", CIRED - Open Access Proceedings Journal IET, (2017) Vol. 2017, No. 1, pp. 1853-1857.
[4] D. Papaioannou, A. Gakis, N.T. Athanassoulis, A. Rigos and A.A. Mamali, "A review of urban sustainability criteria under global warming stress", Interdisciplinary Environmental Review, (2015) Vol. 16, No. 1, pp. 17-45.

16:20: [ManufacturingWedPM210]
DFT Insights into the Role of Relative Positions of Fe and N Dopants on the Structure and Properties of TiO2
Sahar Ramin Gul¹ ; Matiullah Khan² ; Zeng Yi³ ; Bo Wu¹ ; Athanasios G. Mamalis⁴ ; ¹Multiscale Computational Materials Facility, College of Materials Science and Engineering, Fuzhou University, Fuzhou, China; ²Kohat University of Science and Technology, Kohat, Pakistan; ³State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China; ⁴PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece;
Paper Id: 32 [Abstract]

The location and nature of doped elements strongly affect the structural, electronic, and optical properties of TiO₂. To tailor the band structure and modify the photoelectrochemical properties of TiO₂, a pair of dopants is selected. Fe and N atoms are inserted in the TiO₂ network at substitutional and interstitial sites with different relative distances. The main objective behind the different locations and sites of the doped elements is to banish the isolated unoccupied states from the forbidden region that normally annihilates the photogenerated carriers. Fe at the Ti site and N at the O site doped in the TiO₂ network separated at a distance of 7.805 Å provided a suitable configuration of dopant atoms in terms of geometry and band structure. Moreover, the optical properties showed a notable shift to the visible regime. Individual dopants either introduced isolated unoccupied states in the band gap or disturbed the fermi level and structural properties. Furthermore, the other co-doped configurations showed no remarkable band shift, as well as exhibiting a suitable band structure. Resultantly, comparing the band structure and optical properties, it is argued that Fe (at Ti) and N (at O) doped at a distance of 7.805 Å would strongly improve the photoelectrochemical properties of TiO₂.

References:
[1] Sato, S. Photocatalytic activity of NOx-doped TiO2 in the visible light region. Chem. Phys. Lett. 1986, 123, 126-128, doi:10.1016/0009-2614(86)87026-9.
[2] Shen, Y.; Xiong, T.; Li, T.; Yang, K. Tungsten and nitrogen co-doped TiO2 nano-powders with strong visible light response. Appl. Catal. B Environ. 2008, 83, 177-185, doi:10.1016/j.apcatb.2008.01.037.
[3] Khan, M.; Yi, Z.; Gul, S.R.; Wang, Y.; Fawad, U. Visible-light-active silver-, vanadium-codoped TiO2 with improved photocatalytic activity. J. Mater. Sci. 2017, 52, 5634-5640, doi:10.1007/s10853-017-0798-y.
[4] Liu, X.; Liu, Z.; Zheng, J.; Yan, X.; Li, D.; Chen, S.; Chu, W. Characteristics of N-doped TiO2 nanotube arrays by N2-plasma for visible light-driven photocatalysis. J. Alloys Compd. 2011, 509, 9970-9976, doi:10.1016/j.jallcom.2011.08.003.
[5] Bonch-Bruevich, V.L.K.; Robert, S. The Electronic Structure of Heavily Doped Semiconductors; American Elsevier Pub. Co.: New York, NY, USA, 1966; pp. 55-68.
[6] Di Valentin, C.; Pacchioni, G.; Selloni, A.; Livraghi, S.; Giamello, E. Characterization of paramagnetic species in N-doped TiO2 powders by EPR spectroscopy and DFT calculations. J. Phys. Chem. B 2005, 109, 11414-11419, doi:10.1021/jp051756t.
[7] Wang, Y.; Wu, Y.; Yang, H.; Xue, X.; Liu, Z. Doping TiO2 with boron or/and cerium elements: Effects on photocatalytic antimicrobial activity. Vacuum 2016, 131, 58-64, doi:10.1016/j.vacuum.2016.06.003.
[8] Liu, X.; Khan, M.; Liu, W.; Xiang, W.; Guan, M.; Jiang, P.; Cao, W. Synthesis of nanocrystalline Ga-TiO2 powders by mild hydrothermal method and their visible light photoactivity. Ceram. Int. 2015, 41 Pt B, 3075-3080, doi:10.1016/j.ceramint.2014.10.151.

16:45: [ManufacturingWedPM211]
Reduction of Transport Impact on Air Quality due to New Conception of Hydrogen Storage
Tetiana Prikhna¹ ; Mykola Monastyrov² ; Petro Talanchuk³ ; Athanasios G. Mamalis⁴ ; Fernand Marquis⁵ ; Bernd Halbedel⁶ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Open International University of Human Development Ukraine, Kiev, Ukraine; ³Open International University of Human Development Ukraine, Kyiv, Ukraine; ⁴PC-NAE, Demokritos National Center for Scientific Research, Athens, Greece; ⁵San Diego State University, San Diego, United States; ⁶Technische Universitat Ilmenau, Ilmenau, Germany;
Paper Id: 140 [Abstract]

The new conception of hydrogen production on the board of transport vehicles was due to the reaction of metallic Al powder produced by the developed high productive electroerosion dispersion (EED) method with slightly alkaline water [1]. The developed EED method allows production of Al powder of 98% purity with spherical shape 0.05 - 3-5 microns particles (with near 8 vol.% of 0.05-0.1 microns particles), specific surface up to 120 m2/gr (determined in accordance with the ISO 10076). The poly-dispersed nature of the Al powder permits its dense packing qua PAS. The presence of a nanofraction enables a short reaction induction period. It is mainly due to the presence of nanoparticles that the reaction response time is lowered from 7 to 2 s, which in the case of a transport vehicle will enable the essential volume minimization of the intermediate container. As a result of the reaction of one kilogram of aluminum powder, more than 111 grams of hydrogen are released, which is equivalent to 1.23 m3 of gaseous hydrogen (taking the hydrogen density to be 0.09 kg/m3 at 18°C and 0.1 MPa). The packed density of the aluminium powder was determined with the help of a Scott volumeter according to ISO 3923-2, and was found to be 1240 kg/m3. From a volume of one litre filled with this powder, 1.52 m3 of gaseous hydrogen can be obtained. Further, the systematic approach to reduce heat dissipation and increase efficiency will be realized due to the use of advanced thermoelectrical transformation systems and new type of propulsion engine.

References:
[1] M. Monastyrov, T. Prikhna, A. G. Mamalis, W. Gawalek, P. M. Talanchuk, R. V. Shekera, Electroerosion dispersion-prepared nano- and submicrometre-sized aluminium and alumina powders as power-accumulating substances, Nanotechnology Perceptions. 4 (2008), 179-187

17:10: [ManufacturingWedPM212]
Stroboscopic Method of Fluorescence Analyses of Optically Dense Media
Nugzar Gomidze¹ ; Izolda Jabnidze¹ ; Zhuzhuna Diasamidze¹ ; Lali Kalandadze¹ ; Omar Nakashidze¹ ; Kakha Makharadze¹ ; Miranda Khajishvili¹ ; Zebur Surmanidze¹ ; ¹Batumi Shota Rustaveli State University, Batumi, Georgia;
Paper Id: 275 [Abstract]

Anthropogenic pollution includes various components, and the first place nowadays belongs to oil and oil products, as well as a number of organic compounds. Fighting against this pollution is a modern problem [1,2]. According to statistical data, the annual anthropogenic flow of oil products in the sea is caused by the loss of oil on tankers, and protecting the environment from pollution is closely related to its discovery and then its control. This is a difficult problem, since the pollution factors represent a complex of different complicated organic substances. After being in water, many different processes take place (for instance: transfer in atmosphere, degradation, influence of biological factors etc.), which are less studied. A number of methods of watery media analyses have been applied and studied so far (for instance: infrared spectroscopy method, core magnetic resonance on Shpolski effect, gravitational or weight method, chromatography etc.). It is concluded that the limited accepted concentration in sea water is 50 mkg/L [3,4]. The organic substances are conditionally divided in four classes; they are: photosynthesizing substances, phytoplanktons, amino acids, water humus-like substances, oil, and oil products [5]. There are always fluorescence solved organic substances in water media. Their fluorescence signal makes up a background on oil fluorescence signal, and it significantly blocks its discovery. We receive the fluorescence spectrums simultaneously, which reflect the spectrums received from both oil and other organic substances. There are different ways of separating these spectrums [6], but none of them are perfect. Due to this reason, it is required to investigate the spectrums of fluorescence of additional organic substances apart from oil and oil products. It is rather easy to discover the solid particle floating in the water and substances and to determine their concentration [7]. Nowadays, for discovering and studying the oil products and organic compounds in water, spectral optical methods are used; its principal advantage in contrast to other methods is their express-diagnostics and distance. The express-diagnostics implies the quick discovery of pollution in water via optical methods in order to eliminate the pollution sources on time and liquidation of pollution sources as possible (we mean tankers, terminal etc). Though, there are some differences even among optical methods. One of them is laser fluorescence [8,9]. Fluorescence represents a physical process and is considered as one of the kinds of luminescence. When radiating a substance with light, it is possible for the electron to move among the different levels of energetic levels. The difference of energy among the energetic levels and the frequency of absorbed light oscillation are connected to each other with Bohr's third postulate. While absorbing light, the part of the energy received by the system is used for relaxation and the other part is radiated in the image of photon of determined energy. Schematically, the photon radiation and the absorption is expressed with Iablonski diagram. Fluorescence spectroscopy represents the effective method of studying dynamic processes in solutions. This method will be greatly applied in biology, medicine, material studies, nanotechnology, and of course, ecology. The parameters of fluorescence spectroscopy, such as radiation spectrum, life duration, quantum yield, and fluorescence anisotropy represent the sensitive functions of the processes, which depend of the life duration of excited condition [10,11]. The molecules can participate in these processes which are in 10 nm distance from fluorofore at the moment of excitation. The molecular system is not entirely characterized with the own fluorescence in more or less intensity. Polysaturated, condensed, and of course, aromatic and polyaromatic compounds fluorescence well. Hetero atomic or electron-domain systems should be emphasized. Special organic and non-organic substances fluorescence perfectly, which are used in making displays, monitors, photodiodes and lasers. Natural compounds fluorescence in comparatively less quality [12]. Among natural admixtures which fluorescence well, noteworthy mentions are natural paints, some amino acids (Tryptophan and Tyrosine), and the proteins containing them, cofactors (NADH) and vitamins (riboflavin). Their own fluorescence is the basis of discovering and identifying natural admixtures and oil products.

References:
[1] J. Lakovich. "Principles of fluorescence spectroscopy". Springer Science, 2006. p. 960.
[2] "Fluorescence excitation and emission fundamentals".
http://www.olympusfluoview.com/theory/fluoroexciteemit.html
[3] N. Gomidze, I. Jabnidze, K. Makharadze, M. Khajishvili, Z. Shashikadze, Z. Surmanidze, I. Surmanidze. "Numerical Analyses of Fluorescence Characteristics of Watery Media via Laser Spectroscopy Method". Journal of Advanced Materials Research Vol. 590 (2012), pp. 206-211.
[4] G.G. Stokes. "Ueber die Veränderung der Brechbarkeit des Lichts". Annalen der Physik, B. 163 (11), 1852, S. 480-490
[5] "Lidar Methods of discovering oil pollution sources". (hhtp://ecoline.kiev.ua/articles/pider/lidmru.htmi)
[6] N.Kh. Gomidze., K.A. Makharadze, M.R. Khajishvili, I.N. Jabnidze, Z.Kh. Shashikadze. Some Issues of Fluorescence Characteristics Aqueous Media via Diagnosis of Laser Spectroscopy Method. International Journal of Engineering, Science and Innovative Technology. ISSN No: 2319-5967 (ISO 9001:2008 Certified), 3, issue 3, pp.142-152, 2014. http://www.ijesit.com/Volume%203/Issue%203/IJESIT201403_17.pdf
[7] J.R. Albani. "New insights in the interpretation of tryptophan fluorescence. Origin of the fluorescence lifetime and characterization of a new fluorescence parameter in proteins: the emission to excitation ratio". Journal of fluorescence, 2007.
[8] N.Kh.Gomidze, K.A.Makharadze, M.R.Khajishvili, I.N.Jabnidze, Z.Kh. Shashikadze. "Some Issues of Fluorescence Characteristics Aqueous Media via Diagnosis of Laser Spectroscopy Method". International Journal of Engineering, Science and Innovative Technology. ISSN No: 2319-5967, 3, issue 3, 2pp. 142-152, 2014.
[9] Z. Davitadze, N. Gomidze, K. Makharadze. "Control Laser Spectrofluorimeter with Microcontrollers. Journal of Advanced Materials Research Vol". 590 (2012), pp. 201-205
[10] Z. Shashikadze, N. Gomidze, Z. Davitadze, O. Nakashidze. "Fluoroscence spectrums of water soluble and emulsive oil". RSU works. Series: Natural Sciences and Medicine, Volume 13, pp: 238-241. Batumi.
[11] N.Kh. Gomidze, Z.Kh.Shashikadze, K.A.Makharadze, M.R. Khajishvili, I.N. Jabnidze. "About fluorescence excitation spectrums". 6th International Conference on Advanced Optoelectronics and Lasers. Conference Proceedings. 9-13 September (2013), Sudak, Ukraine, pp. 317-319.
[12] N.Kh. Gomidze, I.N. Jabnidze, Z.J. Surmanidze Stroboscopic Method of Fluorescence Analyses of Optically Solid Media. 2016 IEEE 7th International Conference on Advanced Optoelectronics and Lasers (CAOL). September 12-15, Odessa, Ukraine, pp. 34-36, 2016.

SESSION: SISAMMonAM-R5 SPD Nanomaterials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Mon Nov, 5 2018 / Room: Copacabana A (150/1st)
Session Chairs: Ruslan Valiev; Werner Skrotzki; Session Monitor: TBA

11:20: [SISAMMonAM01] Keynote
Recent Advances in SPD Processing of Nanomaterials with Superior Properties
Ruslan Valiev¹ ; ¹Ufa State Aviation Technical University, Ufa, Russian Federation;
Paper Id: 228 [Abstract]

Multiple studies in recent years have proven severe plastic deformation (SPD) techniques as a very efficient way to produce nanostructured metals and alloys with significantly improved mechanical and functional properties, with the latter affected by several factors, including ultrafine grains and also the atomic structure of boundaries in resulting nanomaterials [1,2]. This report presents the results of complex studies of the formation of different grain boundaries (low angle and high angle ones, special and random, equilibrium and non-equilibrium with strain-distorted structure, as well as with the presence of grain boundary segregations and precipitations) in nanostructured materials processed using SPD with various regimes and routes. This entails materials with superior multifunctional properties [3,4], i.e. the combination of high mechanical and functional properties (corrosion and radiation resistance, electrical conductivity, etc.) that are induced by grain boundary design. Particular emphasis is placed on the physical nature and the use of multifunctional nanomaterials for their innovative applications in medicine and engineering.

References:
[1] R.Z. Valiev, Nanostructuring of metals by severe plastic deformation for advanced properties, Nature Materials, Volume: 3, Pages: 511-516, 2004
[2] R.Z. Valiev, A.P. Zhilyaev, T.G. Langdon, Bulk Nanostructured Materials: Fundamentals and Applications, 2014 by John Wiley & Sons, Inc.
[3] I. Sabirov, N.A. Enikeev, M.Y. Murashkin, R.Z. Valiev, Bulk nanostructured materials with multifunctional properties, Series: SpringerBriefs in Materials, Springer, 2015, IX, 161 p.
[4] K. Edalati, T. Masuda, M. Arita, M. Furui, X. Sauvage, Z. Horita, R.Z. Valiev, Room-temperature superplasticity in an ultrafine-grained magnesium alloy, Scientific Reports, Volume 7: 2662, Pages: 1-9, 2017

11:45: [SISAMMonAM02] Invited
Exploring the Paradox of Strength and Ductility
Terence G. Langdon¹ ; Roberto B. Figueiredo² ; Praveen Kumar³ ; Megumi Kawasaki⁴ ; ¹University of Southampton, Southampton, United Kingdom; ²Federal University of Minas Gerais, Belo Horizonte, Brazil; ³Indian Institute of Science, Bangalore, India; ⁴Oregon State University, Corvallis, United States;
Paper Id: 233 [Abstract]

Processing through the application of severe plastic deformation (SPD) produces exceptional grain refinement to the submicrometer or even the nanometer level. The paradox of strength and ductility was suggested several years ago [1] and has become a major topic in all studies of SPD metals. This paradox relates to the fact that metals may be strong or ductile, but generally they fail to exhibit both high strength and high ductility. Since SPD metals have very small grain sizes, it follows that the strength is usually high but the ductility is limited. This presentation examines the significance of this paradox and discusses possible procedures for at least partially alleviating the low ductility, which tends to be an inherent feature of these SPD nanomaterials.

References:
[1] R.Z.Valiev, I.V. Alexandrov, Y.T. Zhu, T.C. Lowe, "Paradox of strength and ductility in metals processed by severe plastic deformation," J. Mater. Res. Vol. 17, p. 5 (2002).

12:10: [SISAMMonAM03] Invited
Effect of Texture on Shear Banding in ECAP
Werner Skrotzki¹ ; Laszlo Toth² ; Laura Lienshoeft¹ ; Julius Huhn¹ ; Philipp Frint³ ; Martin Franz-xaver Wagner³ ; ¹Dresden University of Technology, Dresden, Germany; ²Lorraine University, Metz, France; ³Chemnitz University of Technology, Chemnitz, Germany;
Paper Id: 270 [Abstract]

Samples taken from a room temperature (RT) extruded aluminium alloy 6060 were deformed by equal-channel angular pressing (ECAP, one pass, RT) [1]. Texture measurements by X-ray diffraction reveal a strong predominant <111> fibre texture in the extruded bar. Depending on the alignment of the fibre axis with respect to the ECAP die, strain localization phenomena in form of shear bands are observed. Local texture measurements by electron backscatter diffraction after ECAP reveal a clear shear texture with certain components dominating. The shear texture is related to the starting texture, which determines the slip system activity. Thus, there is a clear correlation between starting texture and shear banding during ECAP. Texture simulations reproducing the experimental texture show that the Taylor factor is constantly decreasing when shear banding takes place while in the case of homogeneous shear it goes over a maximum. This clearly indicates that geometrical softening leads to the mechanical instabilities.

References:
[1] P. Frint, PhD Thesis, Chemnitz University of Technology (2015)

12:35: [SISAMMonAM04] Invited
A New Continuous Severe Plastic Deformation Process for Metal Sheets: Single-roll Angular Rolling
Hyoung Seop Kim¹ ; Hak Hyeon Lee² ; ¹POSTECH, Pohang, South Korea; ²Pohang University of Science and Technology, Pohang, South Korea;
Paper Id: 324 [Abstract]

A new continuous severe plastic deformation (SPD) process for metal sheets called single-roll angular-rolling (SRAR) is introduced. The SRAR process achieves maximized deformation homogeneity of metal sheets by combining circumferential shear deformation with channel-angular shear deformation. The grain refinement and mechanical properties were investigated experimentally in relation to the number of repetitive SRAR passes. The finite element method was used to demonstrate that the SRAR process provides highly uniform SPD by strengthening the less deformed region that inevitably occurs near the lower part of the workpiece during the channel-angular deformation processes.

References:
[1] R.Z. Valiev, A.V. Korznikov, R.R. Mulyukov, Mater. Sci. Eng. A 168 (1993) 141-148.
[2] H.S. Kim, M.H. Seo, S.I. Hong, Mater. Sci. Eng. A 291 (2000) 86-90.

SESSION: SISAMMonPM1-R5 Current Intelligent Sustainable Advanced Materials like Graphene, CNTs, High Entropy Alloys	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Mon Nov, 5 2018 / Room: Copacabana A (150/1st)
Session Chairs: Yuntian Zhu; Session Monitor: TBA

14:00: [SISAMMonPM105] Keynote
Heterostructured Materials: A New Paradigm for Designing Metals for Superior Mechanical Properties
Yuntian Zhu¹ ; ¹North Carolina State University, Raleigh, United States;
Paper Id: 291 [Abstract]

Strong and tough materials are desired for structural applications such as transportation vehicles for high energy efficiency and good performance. After over a century's research, we have almost reached the limit on how much further we can improve the mechanical properties of metals and alloys. This raises the question if there exists yet-to-be-explored new strategies to make the next generation of strong and tough materials. Recently, heterostructure is found to produce unprecedented strength and ductility that are considered impossible from our textbook knowledge and materials history. Heterostructured (HS) materials consist of domains with dramatic strength differences. A previously not-well-known mechanism, back-stress strengthening and back-stress work hardening, is found responsible for such a dramatic improvement of mechanical properties. This represents a new paradigm for designing strong and tough structural materials. HS materials have recently attracted extensive attention in the academic community as an emerging research field. Moreover, HS materials can be produced by current industrial facilities at large scale and low cost, and has the potential to revolutionize the manufacturing industry. There are many scientific issues with such materials that challenge the communities of experimental materials science and computational material mechanics. In this talk, the authors will present the current advances as well as future challenges and issues in this emerging field.

14:25: [SISAMMonPM106] Invited
Diffusive and Displacive Phase Transformations Driven by High Pressure Torsion
Boris Straumal¹ ; Askar Kilmametov² ; Olga Kogtenkova³ ; Andrey Mazilkin² ; Brigitte Baretzky² ; ¹Institute of Solid State Physics RAS, Chernogolovka, Russian Federation; ²Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Germany; ³Institute of Solid State Physics, Chernogolovka, Russian Federation;
Paper Id: 302 [Abstract]

The influence of high pressure torsion (HPT) on the diffusive and displacive phase transformations in sustainable advanced materials has been studied. In diluted Cu-based binary alloys the HPT drives the competition between deformation-driven precipitation and dissolution of precipitates. The dynamic equilibrium between these two processes is reached already after 1.5-2 anvil rotations. The composition of Cu-matrix in this equifinal state is equal to that which can be reached in equilibrium after long annealing at a certain temperature T_<i>eff</i>. T_<i>eff</i> in diluted Cu-based binary alloys increases with increasing activation enthalpy of diffusion of a second component and its melting temperature Tm [1, 2]. In Cu-Al-Ni shape memory alloys, HPT leads to the combination of displacive (austenite-martensite) and diffusive (decomposition of supersaturated solid solution) phase transitions. On the one hand, the HPT of these alloys led to the precipitation of α1-phase in the Al-pure alloy and to the precipitation of γ1-phase in the Al-rich one (as if they were annealed at an effective temperature T_<i>eff</i> = 620-20°C). As a result of this precipitation, the matrix in the first alloy was enriched and in the second one depleted in Al. The resultant composition change in the Cu-rich matrix changed also the route for the martensitic transformations. After HPT, both alloys contained mainly β'3 martensite with a certain amount of γ'3 martensite. Thus, the HPT-driven diffusive transformations (precipitation of α1- and γ1-phase) influence the followed displacive (martensitic) transformation [3]. The combination of displacive and diffusive phase transitions has been observed also under HPT of Ti-Fe and Ti-Co alloys [4].

References:
[1] B.B. Straumal, V. Pontikis, A.R. Kilmametov, A.A. Mazilkin, S.V. Dobatkin, B. Baretzky, Acta Mater. 122 (2017) 60-1.
[2] B.B. Straumal, A.R. Kilmametov, A. Korneva, A.A. Mazilkin, P.B. Straumal, P. ZiA�ba, B. Baretzky, J. Alloys Comp. 707 (2017) 20-26.
[3] B.B. Straumal, A.R. Kilmametov, G.A. Lopez, I. Lopez-Ferrero, M.L. No, J. San Juan, H. Hahn, B. Baretzky, Acta Mater. 125 (2017) 274-285.
[4] A. Kilmametov, Yu. Ivanisenko, A.A. Mazilkin, B.B. Straumal, A.S. Gornakova, O.B. Fabrichnaya, M.J. Kriegel, D. Rafaja, H. Hahn, Acta Mater. 144 (2018) 337-351.

14:50: [SISAMMonPM107] Keynote
Dislocation Mediated Plasticity During the Deformation of Semicrystalline Polymers
Florian Spieckermann¹ ; Harald Wilhelm² ; Gerald Polt³ ; Mohammad Zareghomsheh³ ; Michael J. Zehetbauer⁴ ; ¹University of Leoben, Leoben, Austria; ²Vienna University of Technology and Plastics Technology Institute LKT-TGM, Wien, Austria; ³University of Vienna, 1090, Austria; ⁴University of Vienna, Wien, Austria;
Paper Id: 132 [Abstract]

Although semicrystalline polymers have become increasingly important for technological applications in the past decades, the micromechanical processes on an atomistic scale occurring during plastic deformation are still a matter of dispute [1]. As an example, this concerns the question whether dislocations in the crystalline phase play a role for the macroscopic strength or not [2]. Based on dedicated experimental methods such Multiple X-ray Line Profile Analysis (MXPA), which allows the verification of the presence of dislocations and their quantification [3-6], and nano-creep experiments, as a mechanical probe for dislocation mediated plasticity with sub-nanometer resolution [7], we discuss recent findings on the molecular processes governing the plasticity of semicrystalline polymers. Special emphasis is given to the generation, mobility, and thermal activation of dislocations in particular, and crystallographic defects and transformations in general for several semicrystalline polymer materials.

References:
[1] Spieckermann, F.; Polt, G.; Wilhelm, H.; Kerber, M.; Schafler, E. & Zehetbauer, M.
Journal of Applied Polymer Science, 2012, 125, 4150-4154
[2] Spieckermann, F.; Wilhelm, H.; Polt, G.; Ahzi, S. & Zehetbauer, M., Polymer, 2014, 55, 1217-1222
Spieckermann, F.; Wilhelm, H.; Kerber, M.; Schafler, E.; Polt, G.; Bernstorff, S.; Addiego, F. & Zehetbauer, M., Polymer, 2010, 51, 4195-4199
[3] Spieckermann, F.; Polt, G.; Wilhelm, H.; Kerber, M. B.; Schafler, E.; Reinecker, M.; Soprunyuk, V.; Bernstorff, S. & Zehetbauer, M., Macromolecules, 2017, 50, 6362-6368
[4] Polt, G.; Spieckermann, F.; Wilhelm, H.; Fischer, C.; Schafler, E.; Bernstorff, S. & Zehetbauer, M., Express Polymer Letters, 2015, 9, 894-900
[5] Polt, G.; Spieckermann, F.; Wilhelm, H.; Kerber, M.; Schafler, E.; Bernstorff, S. & Zehetbauer, M., Mechanics of Materials, 2013, 67, 126-132
[6] Zare Ghomsheh, M.; Spieckermann, F.; Polt, G.; Wilhelm, H. & Zehetbauer, M., Polymer International, 2015, 64, 1537-1543

15:15: [SISAMMonPM108] Invited
Emergence of Industrial Production of High Performance Metals by Severe Plastic Deformation
Terry Lowe¹ ; ¹Colorado School of Mines, Golden, United States;
Paper Id: 345 [Abstract]

Industrial scale nanostructuring via Severe Plastic Deformation (SPD) can alter the properties of metals and alloys to increase their performance, extend their useful life cycles, and thereby diminish their environmental impact. Higher performance and longer lasting metals reduce the amount of natural and other resources needed for multiple applications. Thus, nanostructuring effectively increases the sustainability of using alloys to serve societal needs. We will examine the key advances in SPD-processing that have enabled industrial applications of high performance metals and alloys in various industrial sectors, including energy production and transmission, healthcare, transportation, and electronics. The evolution of scaling of speed, efficiency, and size scale of SPD production will be reviewed. We will also see how the emergence of high performance metals and alloys of aluminum, magnesium, copper, titanium, and iron has been influenced by the convergence of advances in measurement science, process control, and understanding of the microstructural effects of intense shear.

References:
[1] TC Lowe, CF Davis, PM Rovira, ML Hayne, GS Campbell, JE Grzenia, PJ Stock, RC Meagher, HJ Rack, Scientific and Technological Foundations for Scaling Production of Nanostructured Metals, IOP Conf. Series, Mater Sci Eng. 2017; 194 012005.

SESSION: SISAMMonPM2-R5 H2-Storage Advanced Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Mon Nov, 5 2018 / Room: Copacabana A (150/1st)
Session Chairs: Zenji Horita; Christine Borchers; Session Monitor: TBA

15:55: [SISAMMonPM209] Keynote
Severe Plastic Deformation for Production of High-performance Hydrogen Storage Materials
Zenji Horita¹ ; ¹Kyushu University, Fukuoka, Japan;
Paper Id: 271 [Abstract]

High performance of hydrogen storage requires not only fast absorption/desorption kinetics but also lower operating temperature near ambient pressure. A process of severe plastic deformation through high-pressure torsion (HPT) was applied to two major hydrogen storage metallic materials such as Ti-based and Mg-based systems. Microstructures were well refined by the HPT process, so that nanograins were formed in the materials. For the Ti-based system, an HPT-processed TiFe intermetallic no longer requires pre-activation that limits practical use, as it involves exposure to hydrogen atmosphere under high pressures (>3 MPa) at high temperatures (~700 K). The lack of requirement for pre-activation is because hydrogen diffusion is enhanced through introduction of high densities of lattice defects such as grain boundaries [1]. Furthermore, the HPT-processed TiFe was not deactivated even after storage in air [2]. Application of the HPT process to Mg₂Ni made its hydrogen storage performance improved so that hydrogen absorption is feasible at a reduced temperature of 423 K with faster hydrogen kinetics. This was due to the introduction of high densities of planar lattice defects such as grain boundaries and stacking faults [3].

References:
[1] K. Edalati, J. Matsuda, H. Iwaoka, S. Toh, E. Akiba, Z. Horita, Int. J. Hydrogen Energy 38 (2013) 4622-4627.
[2] K. Edalati, J. Matsuda, M. Arita, T. Daio, E. Akiba, Z.Horita, Appl. Phys. Lett. 103 (2013) 143902.
[3] T. Hongo, K. Edalati, M. Arita, J. Matsuda, E. Akiba, Z. Horita, Acta Mater. 92 (2015) 46-54.

16:20: [SISAMMonPM210] Invited
Controlling Hydrogen Absorption and Release Kinetics of Palladium Through Surface Structural Modifications
Shohei Ogura¹ ; Koichi Kato¹ ; Katsuyuki Fukutani¹ ; Ohno Satoshi¹ ; Markus Wilde¹ ; ¹Institute of Industrial Science, The University of Tokyo, Tokyo, Japan;
Paper Id: 391 [Abstract]

The reversible ingress of gas phase H₂ into the interior of hydrogen (H)-absorbing metals is widely utilized in metal hydride storage and H₂ purification. On reactive hydride-forming metals, thin palladium (Pd) surface layers promote barrier-free H₂ dissociation and protection from oxidation. The kinetics of H₂ absorption are of particular interest to industrial Pd-catalyzed olefin hydrogenation (fuel reforming and organic synthesis), for which Pd-dissolved H has been identified as the essential reactive ingredient that drives the H₂ addition to the olefinic C=C double bond [1]. The H₂ transportation mechanism between the gas phase and the metal interior, however, has not been understood very well at the atomic level until recently. It is therefore explained here how we revealed the microscopic H₂ absorption process at structurally well-defined Pd single crystal surfaces through our unique combination of H depth profiling with ¹⁵N nuclear reaction analysis [2] and thermal desorption spectroscopy with isotope-labeled (H, D) surface hydrogen. We thereby demonstrate that the H₂ transfer into the Pd is highly sensitive to the surface atomic structure [3]. Based on this insight into the H₂ absorption mechanism, it is shown how the structure-sensitivity can be exploited by means of deliberate surface structural modifications to control, e.g., the desorption dynamics of Pd-dissolved hydrogen in a wide range of temperatures (160-375 K) [4]. Photoelectron spectroscopy and density functional calculations will further demonstrate that a modification of the surface electronic properties by surface-alloying with gold can even accelerate the H₂ absorption 30-fold compared to pure Pd [5].

References:
[1] M. Wilde, K. Fukutani, W. Ludwig, B. Brandt, J.H. Fischer, S. Schauermann, H.J. Freund, Angew. Chem. Int. Ed. 47 (2008) 9289-9293.
[2] M. Wilde, K. Fukutani, Surf. Sci. Rep. 69 (2014) 196-295.
[3] S. Ohno, M. Wilde, K. Fukutani, J. Chem. Phys. 140 (2014) 134705.
[4] S. Ohno, M. Wilde, K. Fukutani, J. Phys. Chem. C 119 (2015) 11732-11738.
[5] K. Namba, S. Ogura, S. Ohno, W. Di, K. Kato, M. Wilde, I. Pletikosia P. Pervan, M. Milun, K. Fukutani, Proc. Nat. Acad. Sci. (2018) DOI: 10.1073/pnas.1800412115.

16:45: [SISAMMonPM211] Invited
Solute-defect Interaction in the Framework of a Defactant Concept
Christine Borchers¹ ; Reiner Kirchheim² ; ¹Universität Göttingen, Goettingen, Germany; ²Universität Göttingen, 37077 Goettingen, Germany;
Paper Id: 293 [Abstract]

Through severe plastic deformation of metals, defects like vacancies, dislocations, and grain boundaries are generated. These defects are stabilized in metals by segregation of hydrogen and carbon to these defects. Excess vacancies and their clusters are determined by positron annihilation spectroscopy and indirectly by orders of magnitude enhanced diffusion coefficients. Transmission Electron Microscopy (TEM) and Atom-Probe-Tomography (APT) reveal the nanocrystalline microstructure and segregation to grain boundaries. The excess solute reduces defect formation energies and leads to an increased defect density during plastic deformation. This is quantitatively described in the defactant concept [1,2]. According to a theory originating from Gibbs [3], an excess of a different substance at boundaries can reduce their energy, leading to a reduced driving force for their annihilation, the most prominent example of which being the reduction of surface energy by surfactants like foaming agents. This was extended to grain boundaries containing segregated alloying elements, and to general defects like vacancies and dislocations [1,2]. It was proposed that these alloying elements lead to reduced defect formation energies which in turn lead to increased defect densities, the limiting case of which is an amorphization of the structure.

References:
[1] R. Kirchheim, Acta Mater. 55(2007) 5129-5138.
[2] R. Kirchheim, Acta Mater. 55(2007) 5139-5148.
[3] J.W. Gibbs, The Collected Works of Josiah Willard Gibbs, Vol. 1. (Longmans, Green & Company, London 1928).

17:10: [SISAMMonPM212] Invited
Long-term Hydrogen Storage in Mg and ZK60 After Severe Plastic Deformation
Gerhard Krexner¹ ; Michael J. Zehetbauer² ; ¹University of Vienna, Vienna, Austria; ²University of Vienna, Wien, Austria;
Paper Id: 299 [Abstract]

Long-term hydrogen storage experiments are discussed, which were performed on MgH₂ and on the Mg alloy ZK60 following prior Severe Plastic Deformation (SPD). Although SPD processing leads to significant enhancement of hydrogen absorption and desorption rates in both materials, these are not necessarily stable with respect to repeated loading/unloading cycles. Cold Rolled (CR) MgH₂, e.g., shows a reduction of capacity by 30% after 100 cycles. In contrast, in ZK60 (Mg-5Zn-0.8Zr) processed by High Pressure Torsion (HPT), both kinetics and storage capacity are stable for at least 200 absorption/desorption cycles. Analysis starting from Johnson-Mehl-Avrami theory clearly suggests that in the case of CR-MgH₂, nucleation is followed by growth of extended MgH₂ domains, leading to a gradual deterioration of hydrogen diffusion and storage/release characteristics. In the case of HPT-ZK60, however, practically no further growth occurs subsequent to nucleation, thus allowing for permanently enhanced hydrogen diffusion and stable storage/release properties. These results can be understood in terms of the different density and stability of SPD-induced lattice defects acting as nucleation sites in both materials studied [1].

References:
[1] A. Grill, J. Horky, A. Panigrahi, G. Krexner, and M. Zehetbauer,
Int. J. Hydrogen Energy 40, 17144-52 (2015).

SESSION: SISAMMonPM3-R5 H2-Storage Advanced Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Mon Nov, 5 2018 / Room: Copacabana A (150/1st)
Session Chairs: Zenji Horita; Christine Borchers; Session Monitor: TBA

17:40: [SISAMMonPM313] Invited
Effect of Hydrogen on Generation of Lattice Defects and Defect Hardening of Plastically Deformed Palladium
Yuzeng Chen¹ ; Daria Setman² ; Jakub Cizek³ ; Christine Borchers⁴ ; Reiner Kirchheim⁵ ; Martin Deutges⁶ ; ¹Northwestern Polytechnic University, Xi'an, China; ²University of Vienna, Vienna, Austria; ³Charles University in Prague, Prague, Czech Republic; ⁴Universität Göttingen, Goettingen, Germany; ⁵Universität Göttingen, 37077 Goettingen, Germany; ⁶Universität Göttingen, Göttingen, Germany;
Paper Id: 312 [Abstract]

Palladium-hydrogen system is widely used as a model system for investigating behaviors of hydrogen in metals. In this work, we applied different ways of loading on palladium-hydrogen alloys to investigate the effect of hydrogen on generation of lattice defects in palladium subjected to plastic deformation. In cold-rolled palladium-hydrogen alloys, it is shown that hydrogen solute significantly enhances the multiplication of dislocations during deformation, which will give rise to dislocation densities in the cold-rolled metals and results in hardening of the metals. Under the severely plastic deformation condition, the hydrogen solute is found to increase both the densities of deformation induced vacancy agglomerates and of dislocations, while the former also contribute significantly to hardening of the metals. When the alloys are subjected to ultra-fast loading (strain rate up to 10³ s^-1) exerted by a Split-Hopkinson apparatus, the addition of hydrogen leads to the increase in vacancy concentration and dislocation density, too. In this case, the increase in dislocation density is believed to play a major role in hardening palladium.

References:
[1] Y.Z. Chen, X.Y. Ma, X.H. Shi, T. Suo, C. Borchers, K.H. Zhang, F. Liu, R. Kirchheim. Hardening effects in plastically deformed Pd with the addition of Hi. Scripta Materialia. 2015. 98. 48-51
[2] M. Deutges, H.P. Barth, Y.Z. Chen, C. Borchers, R. Kirchheim, Hydrogen diffusivities as a measure of relative dislocation densities in palladium and increase of the density by plastic deformation in the presence of dissolved hydrogen, Acta Materialia 82 (2015) 266-274.
[3] Y.Z. Chen, H. P. Barth, M. Deutges, C. Borchers, F. Liu, R. Kirchheim*. Increase in dislocation density in cold-deformed Pd using H as a temporary alloying addition. Scripta Materialia. 2013, 68(9): 743-746
[4] Melikhova, O.,Cizek, J., Chen, Y.Z., Suo, T., Prochazka, I., Liu, F, Effect of hydrogen on generation of lattice defects in shock-loaded Pd, Journal of Alloys and Compounds, 2015, Vol. 645: S472-S475

SESSION: SISAMTueAM-R5 SPD Nanomaterials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Tue Nov, 6 2018 / Room: Copacabana A (150/1st)
Session Chairs: Malgorzata Lewandowska; Boris Straumal; Session Monitor: TBA

11:20: [SISAMTueAM01] Keynote
Plasticity Induced Grain Boundary Migration
Reinhard Pippan¹ ; Oliver Renk¹ ; Marlene Kapp¹ ; Karoline Komout¹ ; Pradpita Ghosh¹ ; Anton Hohenwarter² ; ¹Erich Schmid Institut of Materials Science, Austrian Academy of Sciences, Leoben, Austria; ²Montanuniversitaet Leoben, Leoben, Austria;
Paper Id: 311 [Abstract]

Grain boundary migration is an important phenomenon during hot working of materials. It is key to understanding the microstructural evolution during the deformation process, and is an essential mechanism for microstructural design of materials. This phenomenon of grain boundary migration during hot forming has been a central research area in material science in the last century. It was long assumed that grain boundary migration during cold deformation does not occur. The generation of ultrafine grained and nanocrystalline material by low temperature heavy plastic deformation has been introduced during the last two decades. In order to understand the minimum grain size, which can be achieved by these processes, it becomes quite evident that grain boundary migration plays a key role. A central question of this grain boundary movement is: "What are the driving forces and what controls the resistance against the movement of the grain boundaries at these low temperatures?" Further important points resulting from this question are: "What is the role of thermally activated processes and what is the contribution of stress and strain induced transfer of atoms from one grain to the other?" This presentation will focus on these central questions by analyzing grain boundary movement as a function of deformation temperature, strain rates, strain paths, impurities, and alloying elements. It will be shown that grain boundary movement during heavy plastic deformation at low temperature has a similar importance as in the case of dynamic recrystallization during hot working, only the driving forces are different. Finally, it will be shown that these phenomena of deformation induced grain boundary migration at low temperatures are important in order to understand the strength of ultrafine grained and nanocrystalline materials.

References:
[1] Recrystallization and related annealing phenomena, F.J. Humphreys and M. Hatherly, Elsevier 2004
[2] O. Renk, A. Hohenwarter, S. Wurster, R. Pippan Acta Mater. 2014;77:401-410
[3] O. Renk, P. Ghosh, R. Pippan Scripta Mater. 2017;137:60-63
[4] D.S. Gianola, S. Van Petegem, M. Legros, S. Brandstetter, H. Van Swygenhoven, K.J. Hemker Acta Mater. 2006;54:2253-2263
[5] M.W. Kapp, O. Renk, P. Ghosh, T. Leitner, B. Yang, R. Pippan J Mater. Res. 2017;32:4317-4326

11:45: [SISAMTueAM02] Invited
Ultrafine-grained Plates with Enhanced Mechanical Properties, Low Anisotropy and Good Formability
Malgorzata Lewandowska¹ ; Marta Ciemiorek¹ ; Lech Olejnik¹ ; Witold Chrominski¹ ; ¹Warsaw University of Technology, Warsaw, Poland;
Paper Id: 239 [Abstract]

Incremental ECAP, unlike conventional ECAP, works in small steps in which deformation and feeding are divided between two different tools acting asynchronously. Incremental processing reduces forces and allows processing in relatively large billets. The major advantage of this technique is that the specimens are in the form of plates with a rectangular shape, which makes them suitable for further processing, e.g. via deep drawing, which may extend the range of potential applications of UFG materials. Plates of 1xxx and 3xxx series aluminum were processed by Incremental ECAP and evaluated in terms of microstructure, mechanical properties, anisotropy and formability. It was demonstrated that incremental ECAP is one of the most effective severe plastic deformation methods in terms of grain size refinement and high angle grain boundaries formation. Eight passes brings about grain size reduction to below 500 nm and very high fraction of high angle grain boundaries of about 80%. The plates exhibit in planar and through thickness isotropy which manifest by the independence of YS, UTS and R -values on the testing direction and fairly uniform distribution of microhardness across thickness. Such properties were attributed to randomized texture developed during processing and uniform microstructure with ultrafine equiaxed grains in all three plate's planes. The values of the parameters describing ability for deep drawing are very promising, as r values only slightly decrease with I-ECAP passes while they became independent on testing direction. This indicates that although the processed plates are slightly prone to wall thinning (typical for aluminum alloys), they are resistant to earing formation, which is one of the main technological problem in deep drawing. The combination of isotropic parameters, enhanced mechanical strength, and suitable ability to deep drawing may yield attractive products with a considerable potential for further forming.

References:
[1] W. Chrominski, L. Olejnik, A. Rosochowski, M. Lewandowska, Grain refinement in technically pure aluminium plates using incremental ECAP processing, Mater. Sci Eng. A636 (2015) 172-180
[2] M. Ciemiorek, W. Chromiński, L. Olejnik, M. Lewandowska, Evaluation of mechanical properties and anisotropy of ultra-fine grained 1050 aluminum sheets produced by incremental ECAP, Mater. Des. 130 (2017) 392-402

12:10: [SISAMTueAM03] Invited
Properties of a Lean Silver Alloy After Equal Channel Angular Pressing and Conventional Post-deformation
Maciej Krystian¹ ; Bernhard Mingler¹ ; Jelena Horky² ; Damien Colas³ ; Frédéric Diologent³ ; ¹AIT Austrian Institute of Technology GmbH, Wiener Neustadt, Austria; ²AIT Austrian Institute of Technology GmbH, Seibersdorf, Austria; ³Varinor SA, Delémont, Switzerland;
Paper Id: 353 [Abstract]

Silver is a soft, precious metal widely used in electronics, medicine, and in the jewellery sector, due to its exceptional properties such as low electrical resistance, antibacterial behaviour, shiny appearance, and resistance to tarnishing. However, final products are usually made of silver alloys to achieve reasonable hardness and strength needed for these kinds of applications. However, alloying is not always the desirable practice, especially in jewellery, as it can reduce tarnishing and corrosion resistance. Therefore, Severe Plastic Deformation is a promising way to improve the mechanical properties [1]. The copper-free silver alloy of the composition Ag 97.2 wt%, In 1.5 wt%, Ge 1.0 wt%, others 0.3 wt% was developed, cast, and cold-drawn. In order to further improve mechanical properties, room-temperature Equal Channel Angular Pressing (ECAP) along with two-step forging (open-die and impression-die forging) and rolling — as two diverse methods of conventional post-deformation — were performed. In this manner, the original grain size of 130 μm was refined to an ultrafine-grained microstructure with mean grain size of 420 nm. Consequently, the combination of ECAP, two-step forging and rolling resulted in outstanding mechanical properties: tensile yield strength of 491 MPa (+355% compared to the as cold-drawn strength), ultimate tensile strength of 550 MPa (+196%), and Vickers hardness of 167 HV1 (+234%). Furthermore, a much more homogeneous hardness distribution over the whole cross-section of the bars was achieved by ECAP. Contrary to some reports on pure silver [2, 3] both, the microstructure and strength remained thermally stable for at least one year at room temperature as well as for at least 100h and 2h at 100°C and 150°C, respectively. Thus, ECAP is able to effectively increase the mechanical properties of this lean silver alloy which exhibits desirable tarnishing and corrosion resistance.

References:
[1] M. Zehetbauer and R. Valiev (Eds.), Nanomaterials by Severe Plastic Deformation, Wiley-VCH, 2006, ISBN: 978-3-527-60494-4
[2] H. Matsunaga and Z. Horita, Softening and Microstructural Coarsening without Twin Formation in FCC Metals with Low Stacking Fault Energy after Processing by High-Pressure Torsion, Materials Transactions 50 (2009) 1633-1637. doi:10.2320/matertrans.MF200921
[3] Z. Hegedűs, J. Gubicza, M. Kawasaki, N.Q. Chinh, Z. Fogarassy and Terence G. Langdon, The effect of impurity level on ultrafine-grained microstructures and their stability in low stacking fault energy silver, Materials Science and Engineering A 528 (2011) 8694-8699. doi:10.1016/j.msea.2011.08.034

12:35: [SISAMTueAM04]
Effect of Equal Channel Angular Pressing on Structure, Texture, and Mechanical Properties of a Magnesium Alloy Containing Rare Earth Elements
Boris Straumal¹ ; Natalia Martynenko² ; Elena Lukyanova² ; Georgy Raab³ ; Sergey Dobatkin² ; Yuri Estrin⁴ ; ¹Institute of Solid State Physics RAS, Chernogolovka, Russian Federation; ²National University of Science and Technology MISiS, Moscow, Russian Federation; ³UGATU, Ufa, Russian Federation; ⁴Monash University, Centre for Advanced Hybrid Materials, Clayton, Australia;
Paper Id: 309 [Abstract]

Magnesium is a promising material for medical applications [1-2], owing to its good biocompatibility. Its high corrosion rate makes it suitable for bioresorbable implants, but it needs to be reduced to match the rate of healing. Addition of Rare Earth (RE) elements promotes the corrosion resistance and strength of Mg, but is usually insufficient. Therefore, the treatment of magnesium alloys by severe plastic deformation, which raises strength and sometimes also the corrosion resistance, seems promising. In this work, a magnesium alloy containing RE elements was processed by equal channel angular pressing (ECAP) in two regimes. Route Bc ECAP was carried with a step-wise decrease in temperature. In the first regime, the temperature was dropped to 350°C after 6 passes at 400°C and further 6 passes were conducted. In the second regime, the temperature was decreased from 425 to 300°C in 25°C decrements, 2 passes being carried out at each temperature. Investigation of the microstructure of the alloy showed that after the ECAP an ultrafine-grained structure with an average grain size of 1.00-0.14 μm and 0.69-0.13 μm for the first and second regimes, respectively. This is to be compared with the average grain size of 70 μm in the initial state. In addition, particles of Mg₄₁Nd₅ phase with an average size of 0.41-0.18 μm and 0.45-0.18 μm were observed for these regimes. The grain refinement achieved was shown to lead to an improvement of mechanical properties. The values of the yield strength, YS=150MPa, the ultimate tensile strength, UTS=220MPa, and the tensile elongation, EL=10.5%, rose to YS=180MPa, UTS=250MPa, and EL=7% and YS=260MPa, UTS=300MPa, and EL=13.2% for the first and the second regimes, respectively. The best combination of properties for the second ECAP regime can be explained by the formation of a sharp prismatic texture, on top of a smaller grain size, as distinct from an inclined basal texture formed after the ECAP by the first regime.

References:
[1] S. Virtanen, Mater. Sci. Eng. B. 176 (2011) 1600-1608.
[2] M. Niinomi, M. Nakai, J. Hieda, Acta Biomater. 8 (2012) 3888-3903.

SESSION: SISAMTuePM1-R5 Amorphous Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Tue Nov, 6 2018 / Room: Copacabana A (150/1st)
Session Chairs: A. Lindsay Greer; Session Monitor: TBA

14:00: [SISAMTuePM105] Keynote
Metallic Glasses: A Range of States Offering Exceptional Mechanical Properties
A. Lindsay Greer¹ ; ¹University of Cambridge, Cambridge, United Kingdom;
Paper Id: 154 [Abstract]

Focusing on metallic systems, we consider developments in understanding and exploiting the glassy state that is formed when a liquid is cooled into a solid state without crystallizing, having in mind that: "The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition" [1]. Metallic glasses are of particular interest for several reasons, not just for their excellent mechanical properties. They not only have a multitude of possible applications, but they also open up the possibility of using mechanical workings to change the structure and properties of glass [2], something hardly explored for conventional oxide glasses. While plastic deformation can be expected to create structural effects, it is more surprising that there can be significant effects even well within the (nominally) elastic regime [3,4]. In this talk, we explore the diversity that can be achieved in the metallic glassy state, from very high energy ("rejuvenated") to very low energy ("relaxed" and even "ultrastable") states [5]. We also explore the extent to which directionality (anisotropy) can be induced in metallic glasses [6]. In each case, we examine the potential applications of the properties (structural and functional) that can be induced.

References:
[1] P.W. Anderson, Science 267, (1995) 1615.
[2] Y.H. Sun, A. Concustell, A.L. Greer, Nature Rev. Mater. 1, (2016) 16039.
[3] S.V. Ketov, Y.H. Sun, S. Nachum, Z. Lu, A. Checchi, A.R. Beraldin, H.Y. Bai, W.H. Wang, D.V. Louzguine-Luzgin, M.A. Carpenter, A.L. Greer, Nature, 524, (2015) 200.
[4] A.L. Greer, Y.H. Sun, Philos. Mag. 96, (2016) 1643.
[5] A.L. Greer, Nature Mater. 14, (2015) 542.
[6] Y.H. Sun, A. Concustell, M.A. Carpenter, J.C. Qiao, A.W. Rayment, A.L. Greer, Acta Mater. 112, (2016) 132.

14:25: [SISAMTuePM106]
Relaxation of Bulk Metallic Glasses After Cryogenic High Pressure Torsion
Florian Spieckermann¹ ; Baran Sarac² ; Erhard Schafler³ ; Viktor Soprunyuk² ; Michael Kerber⁴ ; Jozef Benarczik⁵ ; Juergen Eckert² ; ¹University of Leoben, Leoben, Austria; ²Erich Schmid Institute of Materials Science, Leoben, Austria; ³University of Vienna, Wien, Austria; ⁴University of Vienna, Vienna, Austria; ⁵Deutsches Elektronen Synchrotron DESY, Hamburg, Germany;
Paper Id: 446 [Abstract]

Bulk metallic glasses (BMG’s) combine high strength, hardness and elastic strain limit, they may show good soft-magnetic properties and excellent corrosion resistance as well as high homogeneity and isotropy. The viscous flow workability in the supercooled liquid region makes metallic glasses an excellent candidate for the next generation engineering materials. However, the limited ductility of BMG’s is detrimental for many potential applications. Recent results indicate that structural relaxations on the nanometer scale and their percolation may be involved in the formation of shear transformation zones (STZ) and shear bands that control the ductility of BMG’s. Considerable effects of aging/rejuvenation of BMG’s on their mechanical properties and on structural and dynamic relaxations were reported. Hence, there is fundamental scientific interest in understanding the interplay of structural and dynamic relaxations for equilibrated as well as non-equilibrated BMG’s. In the present study we use in-situ X-ray diffraction to study the structural rearrangements during annealing from 77 K up to the crystallization temperature of CuZr based BMG’s brought out of equilibrium by high pressure torsion performed at cryogenic temperatures. These structural changes are correlated with dynamic mechanical analysis (DMA) and differential scanning calorimetry to determine dynamic relaxations as well as crystallization.

14:50: [SISAMTuePM107] Invited
Rare Earth-containing Multi-component Metallic Glasses
Jean-marie Dubois¹ ; Luka Kelhar¹ ; Saso Sturm¹ ; Spomenka Kobe¹ ; ¹Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 143 [Abstract]

Metallic glasses belong to the class of advanced materials, which exhibit mechanical properties, corrosion resistance, and magnetic properties far superior to that of crystalline materials of similar compositions. Rare earth (RE) containing metallic glasses, which hold some extraordinary properties (such as a very low glass transition temperature), however, have not been extensively studied in the past. Due to the complex electronic and magnetic structure induced by the RE elements, their alloys are expected to possess some excellent fundamental properties. The subject of this paper addresses Ce- and Gd-based metallic glasses, which differ upon their magnetic moments and electronic configurations. At room temperature (RT), cerium reveals paramagnetic behavior with a low magnetic moment of 0.6 μB, while gadolinium, on the other hand, shows the transition into the ferromagnetic state just below RT and possesses one of the highest magnetic moments among REs, with 7.5 μB. Electronic structure of cerium has an unusual 4f electron configuration, which fluctuates up to 4 outer electrons depending on its neibourhood, thus giving Ce and its alloys some unexpected physical properties, such as significant volume change or the emergence of a Kondo state. The fundamental differences between Ce and Gd based metallic alloys originate in different electronic and magnetic structure and the goals of the proposed doctoral dissertation are focused to the experimental analysis of structure, thermal analysis, microstructure and magnetic properties of the multicomponent alloys. Coupling of the fundamental physical and magnetic properties of Ce and Gd, with elements of Al, Fe, and Cu (which by the way are respectively immiscible in each other) is to date unknown. The subject of the proposed talk is to provide fundamental answers and to show a connection between the composition and structure of the alloy and corresponding properties. The purpose here is to investigate the influence of Ce and Gd rare earth (RE) with greatly differing magnetic moments, on the structure, thermal properties, microstructure and magnetic properties of multicomponent Al-RE-Fe-Cu alloys. Formation and stability of glasses can be traced via differential thermal analysis (DTA) and calorimetry (DSC), which also enable the characterization of transformation kinetics. Via pulsed electric current sintering (PECS), powdered samples can be formed into bulk metallic glasses through the process of thermoplastic consolidation in the vicinity of the glass transition temperature (Tg). Magnetic properties of the glasses are analyzed as a function of temperature and time, via controlled crystallization at a temperature 5°C higher than the crystallization temperature (Tx) and time-varying from several minutes to hours. Detailed structural and microstructural characterization is performed via X-ray diffraction (XRD) and electron microscopy, which encompasses scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The field of RE-based metallic glasses has not yet been thoroughly investigated concerning the influence of low and high magnetization RE elements on the structure and magnetic properties. It is of fundamental significance to connect the observed magnetic behavior of glasses with their structural features. In this view, particularly interesting is the coupling between the crystalline lattice and magnetic properties since the behavior of short-range ordered amorphous materials is different from long-range ordered crystalline matter. Another parameter that plays a role is the interlinking effect of the Gibbs free energy and transformation kinetics, in the metastable region of the highly viscous glass when Tg<T<Tx. The hypothesis is based on the fact that the electronic structure and magnetic moments of Ce and Gd are significantly different. It is expected that consequently the difference will also be reflected in the magnetic behaviour of the corresponding alloys. Due to the metastable nature of the glassy materials, heating above Tx will trigger crystallization. However, since some of these alloys possess a well marked Tg that is lower than Tx, we are offered with a temperature gap, which facilitates the study of the transition from viscous glassy state (at Tg) to the crystalline state commencing at Tx. Experimental parameters are varied through the selection of different annealing temperatures and annealing times. Differences in structure, microstructure, and magnetic properties are anticipated with different amounts of crystallites; however, detailed experimental work is essential to provide acute answers.

References:
[1] Klement W, Willens RH, Duwez P, Non-crystalline Structure in Solidified Gold-Silicon Alloys. Nature. 1960;187(4740):869-870. doi:10.1038/187869b0.
[2] Inoue A, Stabilization of metallic supercooled liquid and bulk amorphous alloys. Acta Mater. 2000;48(1):279-306, doi:10.1016/S1359-6454(99)00300-6.
[3] Dubois J-M, Topological instability of metallic lattices and glass formation. J Less-Common Met. 1988; 145:309-326. doi:10.1016/0022-5088(88)90289-5.
[4] Greer AL, Confusion by design. Nature. 1993;366(6453):303-304. doi:10.1038/366303a0.
[5] Ferry M, Direct strip casting of metals and alloys. 1st edition. (Ferry M, ed.). Cambridge: Woodhead Publishing; 2006.
[6] Z. Bian and A. Inoue, Ultra-low glass transition temperatures in Ce-based bulk metallic glasses, Mater. Trans. 46 (2005), pp. 1857-1860

15:15: [SISAMTuePM108] Invited
Using Femtosecond Pulsed Laser Irradiation (FSPLI) to Magnetically Pattern the Surface of Non-ferromagnetic Amorphous Steel
Maria Dolores Baró¹ ; Huiyan Zhang² ; Yuping Feng¹ ; Santiago Surinyach¹ ; Eva Pellicer¹ ; Jordi Sort¹ ; ¹Universitat Autònoma de Barcelona, Bellaterra, Spain; ²Departament de Fisica, UAB, Bellaterra, Spain;
Paper Id: 362 [Abstract]

Periodic ripple and nanoripple patterns are generated at the surface of amorphous steel after femtosecond pulsed laser irradiation (FSPLI). Formation of such ripples is accompanied by the emergence of a surface ferromagnetic behavior, which is not initially present in the non-irradiated amorphous steel. The occurrence of ferromagnetic properties is due to the FSPLI-induced surface devitrification of the glassy structure to form ferromagnetic (a-Fe and Fe₃C) and ferrimagnetic [(Fe,Mn)₃O₄ and Fe₂CrO₄] phases located in the ripples. The generation of magnetic structures by FSPLI turns out to be one of the fastest ways to induce magnetic patterning without the need of any shadow mask. Furthermore, the adhesion force, wettability and nanomechanical properties of the surface treated by FSPLI are also studied and compared to those of the as-cast amorphous alloy. These effects are of interest for applications (e.g., biological, magnetic recording, etc.).

SESSION: SISAMTuePM2-R5 Computational Simulation of ISAM	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Tue Nov, 6 2018 / Room: Copacabana A (150/1st)
Session Chairs: Laszlo Toth; Adelia Aquino; Session Monitor: TBA

15:55: [SISAMTuePM209] Keynote
The Diverse Role of Polycyclic Aromatic Hydrocarbons: Basis for Polyradicaloid Character Leading to New Optoelectronic Devices and Origin for Luminescence in Carbon Nanodots
Hans Lischka¹ ; ¹Tianjin University, Tianjin, China;
Paper Id: 377 [Abstract]

The development of new functionalized materials is one of the key goals in science and technology. Since the discovery of fullerenes, carbon nanotubes and graphene, carbon-based material have attracted peak interest because of its versatility and the outstanding electronic and mechanical properties. In addition to these now well-known compounds, other types of carbon material have been found recently in the form of graphene quantum dots and carbon nanodots, which offer new alternatives to the previously mentioned examples. The key to a successful systematic development of new compounds is the possibility of chemical functionalization by means of covalent and non-covalent derivatization. In the present talk, two aspects in the wide range of applications indicated above are discussed. One is the doping of polycyclic aromatic hydrocarbons (PAHs) by nitrogen with application to the important class of zethrenes [1] as one example. High-level quantum chemical calculations have been performed for the computation of the electronic structure of the different PAHs investigated. The calculations demonstrate clearly how drastic enhancements to the biradicaloid character and reductions of the excitation energy gaps can be achieved by different doping positions. In the second part of the talk, a first approach to the quantum chemical calculation of luminescence properties of carbon nanodots [2,3] is presented. These properties are of great interest since they can be utilized in bioimaging applications, for dye-sensitized solar cells and supercapacitors. The great advantage of the carbon nanodots for the purpose of bioimaging is their low toxicity and excellent biocompatibility. The current challenge is to move their blue fluorescence to the red, which can be achieved by chemical doping. In our investigations, excimer formation and charge transfer in the nanodots have been modeled by means of stacked dimers of pyrene, coronene and circum-coronene sheets. Doping has been performed by replacing carbon atoms by nitrogen atoms or by substituting hydrogen atoms by halogen at the periphery of the PAHs. The absorption and emission spectra have been calculated, which show a characteristic dependence on the doping positions.

References:
[1] Z. Sun, Z. Zeng, J. Wu Acc. Chem. Res. 47 (2014) 2582-2591.
[2] H. T. Li, Z. H. Kang, Y. Liu, S. T. Lee, J. Mater. Chem. 22 (2012) 24230-24253.
[3] S. N. Baker, G. A. Baker Angew. Chem., Int. Ed. 49 (2010) 6726-6744

16:20: [SISAMTuePM210] Invited
A Computational Study of π-π Stacking Interactions Using High-Level Ab Initio Methods and Density Functional Methods
Adelia Aquino¹ ; ¹Tianjin University, Tianjin, China;
Paper Id: 379 [Abstract]

High level ab initio interaction energy calculations based on coupled cluster methods with singles and doubles and non-iterative singles (CCSD(T)) and scaled opposite-spin (SOS) Møller-Plesset perturbation theory (MP2) were performed on several sandwich (S) and the slipped parallel (SP) dimers of selected polyaromatic hydrocarbons (PAHs) up to coronene encircled by three sets of benzene rings (coronene circum-3 dimer, 300 carbon atoms) in an attempt to reliably compute the π-π stacking interactions of extended aromatic systems [1,2]. Results are compared with density functional theory (DFT) using the B3LYP functional and the D3 dispersion correction. Comparison of coupled cluster with SOS-MP2 results show good agreement for smaller linear polyacenes (benzene to anthracene dimer), whereas the unscaled MP2 results demonstrate a well-known overshooting of interaction energies. The SOS-MP2 method reproduces interring distances quite well in comparison to higher level results. Thus, investigations on the stacking properties of larger systems have been continued at this computational level. It was found that the coronene circum-2 dimer complex has a sandwich biconcave structure with a stronger interaction (smaller distances) in the center. The distance of 3.33 Ao is significantly smaller than the van der Waals distance of ~3.60 Ao. Slipped parallel structures have been investigated as well. They are in all cases more stable than the sandwich structures. Comparison in terms of inter-sheet bond distances and interaction energies with sandwich structures will be discussed in the presentation

References:
[1] D. Umadevi, S. Panigrahi and G. N. Sastry, Acc. Chem. Res. 47 (2014) 2574-2581.
[2] X. K. Lu, M. F. Yu, H. Huang and R. S. Ruoff, Nanotechnology 10 (1999) 269-272.

16:45: [SISAMTuePM211] Invited
Insights in the Variations of Deformation Mechanisms in Polycrystals With the Help of Texture Modeling from Macro to Nano Grain Sizes
Laszlo Toth¹ ; ¹Lorraine University, Metz, France;
Paper Id: 308 [Abstract]

It is shown in this work that the crystallographic texture can be efficiently used for getting insight into the deformation mechanisms that take place during plastic deformation. The technique is based on the modelling of the 4D nature of the orientation distribution function (ODF) of the grains (3D) which evolves with strain (1D plus). The changes in the texture are more enhanced when the deformation is extremely high, which can be imparted to the material using the various recent severe plastic deformation (SPD) processes. The most relevant effect in SPD is the grain fragmentation process, which has a strong effect on the grain size and shape. By SPD of alloyed metals nano-range grain sizes can be reached (down to 30 nm) by enhancing in this way the role of the grain boundaries (SPD is a top --> bottom process). Alternatively, nano-polycrystals can be constructed using bottom --> up techniques with even smaller grain sizes (by electro-deposition or powder metallurgy). When such materials are deformed, unusual textures develop. It is shown in this work by polycrystal modelling of the texture evolution that the effect of the existence of the large grain boundary surfaces is a change in the operating slip systems when grains are ultra fine (below 500 nm) or nano-sized (below 100 nm). The main effects are: partial slip, nano-twin formation, grain boundary sliding and migration. The overall behaviour of the polycrystal is also changing; initially, when grain size is still large, heterogeneous deformation from grain-to-grain is valid - which requires the use of a self consistent polycrystal model - while for nano grain sizes the polycrystal approaches more the uniform Taylor polycrystal behaviour. The consequence of the Taylor behaviour is a large reduction in the density of geometrically necessary dislocations which is confirmed by EBSD measurements.

References:
[1] Shear-Coupled Grain Growth and Texture Development in a Nanocrystalline Ni-Fe Alloy during Cold Rolling, L. Li, T. Ungar, L. S. Toth, W. Skrotzki, Metallurgical Transactions, 47 (2016) 6632-6644, DOI 10.1007/s11661-016-3753-7.\n[2] Geometrically necessary dislocations favor the Taylor uniform deformation mode in ultra-fine-grained polycrystals, L.S. Toth, C.F. Gu, B. Beausir, J.J. Fundenberger, M. Hoffman, Acta Materialia, 117 (2016) 35-42. \n[3] Grain size dependent texture evolution in severely rolled pure copper, Materials Characterization, C. F. Gu, M. Hoffman, L.S. Toth, Y.D. Zhang, Materials Characterization, 101 (2015) 180-188.
[4] Nano-enabled orientation alignment via extreme shear strains, Irene Beyerlein, John S Carpenter, Abigail Hunter, Laszlo S Toth, Werner Skrotzki, Scripta Materialia Scripta Materialia, 98 (2015) 52-55.\n[5] Unexpected brass-type texture in rolling of ultrafine-grained copper, Scripta Materialia, C.F. Gu, L.S. Toth, Y.D. Zhang, M. Hoffman, Scripta Materialia, 92 (2014) 51-54. \n[6] New experimental insight into the mechanisms of nanoplasticity, Werner Skrotzki, Andy Eschke, Bertalan Joni, Tamas Ungar, Laszlo S. Toth et al., Acta Materialia, 61 (2013) 7271-7284.

17:10: [SISAMTuePM212] Invited
On The Computational Design Of Ti- and Fe-Based Advanced Materials For Biomedical Applications
Christina Lekka¹ ; J.j. Guttierez Moreno² ; Carla Cutrano¹ ; K Ioannou¹ ; Dimitris Papageorgiou¹ ; Giorgos Evangelakis¹ ; ¹University of Ioannina, Ioannina, Greece; ²University of Tyndall, Tyndal, Ireland;
Paper Id: 246 [Abstract]

Environmentally friendly, biocompatible, and sustainable materials such as Ti-based alloys and Fe-based nanoclusters or coatings are currently under investigation pointing at specific technological demands, thus being promising as non-toxic implants, drug deliverers, and innovative nano-robotic platforms. This lecture presents computational studies on Ti-based and Fe-based metallic and metallic-hybridic materials, aiming to reveal the electronic origin of the structural, magnetic, and mechanical properties, for the design of materials with predefined properties suitable for new technological applications. The calculations cover different scales, from 'first principles' up to large-scale semi-empirical simulations, always comparing with available experimental data. <br />As a first example, ab-initio results reveal the electronic rules for the Ti bcc instability that are related to the electronic band structure characteristics along the phonon critical directions and the electronic occupation at the Fermi level. In Ti-based alloys, Nb composition, phase coordination number, and sp dopants enrich these electronic rules. The mechanical stability conditions and the elastic constants predict the TiNb bcc stabilization only for Nb-rich compositions while the directional Youngs modulus along [100] turns out to be smaller than that of bone (about 30 GPa) which makes these compositions most suitable for non-toxic orthopedic implants. This work was supported by the BioTiNet ITN (No. 264635) FP7 Marie Curie project.<br />The Fe-based nanoclusters and thin coatings with non-magnetic (Cu) or magnetic (Co) substitutions, the Fe surface/edge atoms with Cu first neighbors exhibit the highest magnetic moment of 3.6μ_B ( Fe bcc has 2.1μ_B) for the smallest icosahedral. This moment smoothly decays towards thin film and bulk shape as the size of the cluster increases. Although the Fe-Cu clusters show higher local Fe moment, the average is always highest for the Fe and Fe-Co clusters, due to the difference of d Fe spin up-down electron occupation. These results, supported by SELECTA (No. 642642) H2020-MSCA-ITN-2014 project, could be a basis for the design of environmental sustainable smart alloys with superior magnetic properties.

References:
[1] M. BAnisch, A. Panigrahi, M. Stoica, M. Calin, E. Ahrens, M. Zehetbauer,W. Skrotzki, J. Eckert, Giant thermal expansion and a-precipitation pathways in Ti-Alloys, \n[2] Nature communications, 1429 (2017) \n[3] Billas I M L, Chatelain A, de Heer W A. Magnetism from the Atom to the Bulk in Iron, Cobalt, and Nickel Clusters. Science. 1994;265:1682-1684\n[4] M. Calin, A. Helth, J. J. Gutierrez Moreno, M. BAnisch, V. Brackmann, L. Giebelera, Th. Gemming, Ch. E. Lekka, A. Gebert, R. Schnettler, J. Eckert, Journal of the Mechanical Behavior of Biomedical Materials 39 (2014) 162\n[5] Ch.E. Lekka, J.J. Gutierrez-Moreno, M. Calin, Electronic origin and structural instabilities of Ti-based alloys suitable for orthopaedic implants, J.Phys.Chem.Solids 102 (2017) 49-61\n[6] J.J Gutierrez Moreno, M.Bonisch, N.T.Panagiotopoulos, M. Calin, D.G.Papageorgiou, A. Gebert, J. Eckert, G.A.Evangelakis, Ch.E.Lekka, Ab-initio and experimental study of phase stability of Ti-Nb alloys, JALCOM 696 (2017) 481-489\n[7] C. S. Cutrano and Ch.E. Lekka Structural, magnetic and electronic properties of Cu-Fe nanoclusters by density functional theory calculations, JALCOM 707 (2017)

SESSION: SISAMTuePM3-R5 ISAM Industrial Applications	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Tue Nov, 6 2018 / Room: Copacabana A (150/1st)
Session Chairs: Laszlo Toth; Adelia Aquino; Session Monitor: TBA

17:40: [SISAMTuePM313] Invited
Socioeconomic Pathways and Their Guidance Towards a Renewable Power Generation Dominated Market
Tamer Turna¹ ; ¹TES Energy Consulting, Istanbul, Turkey;
Paper Id: 298 [Abstract]

Global GDP projections for the 21st century have been updated recently. The newly developed shared socio-economic pathways (SSPs) in 2016 represent a set of widely diverging narratives; they show that in 2050, the loss in global GDP between SSP5 will mean Taking the Highway (fossil fuels development) dominated growth path vs. the Taking the Green Road (Sustainability) path, which means a totally renewables originated energy sourcing of 2%. The global GDP is projected to be in the range of $200 to $300 trillion, which could mean a calculated loss of 4 to 6 trillion USD. When considering the total stock market capitalization of fossil fuel companies today is about $5 trillion and the GDP of 2016 was $75.6 trillion USD, the need of a viability analysis on the economic sustainability of fossil-fueled development emerges. Further, if action is taken to tackle climate change and to keep temperature rise under 2°C, most of the coal, oil, and gas reserves will have stay in the ground. The technological development of renewables-sourced power generation in meeting merchant market requirements is dizzy, backed by ground progress within the latest RES power supply auctions. Lithium and Vanadium Ion batteries, hydrogen storage, and many other storage technologies provide promising progress, whereby settlement of further technological challenges is still needed. This paper addresses how the Renewable Energy Sources stand and perform in the market on merchant basis, and how their future is expected to evolve under free market conditions.

SESSION: SISAMWedAM-R5 Nano-Analytic Methods	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Wed Nov, 7 2018 / Room: Copacabana A (150/1st)
Session Chairs: Erhard Schafler; Golta Khatibi; Session Monitor: TBA

11:20: [SISAMWedAM01] Keynote
X-ray and Neutron Diffraction for Characterizing Microstructure
Tamas Ungar¹ ; ¹University of Manchester, Manchester, United Kingdom;
Paper Id: 193 [Abstract]

Materials performance depends on the microstructure. Different electron microscopy techniques characterize microstructures almost perfectly and comprehensively, but there are still issues hidden from the scrutiny of electron microscopy: residual and internal stresses [1,2]; load partitioning [1-3]; strain fields [4]; very small lattice defects [5]; bulk average quantitative density numbers [6-8]; and others. Diffraction peak broadening or line profile analysis proves to be a valuable tool complementing electron microscopy for characterizing and quantifying these issues [9]. Modern line profile analysis procedures are based on physically modeled profile functions of different microstructural elements [7,9-11]. In a recent development, the Marquard-Levenberg analytical method has been combined with a special statistical Monte-Carlo procedure, providing global optimization of the physical parameters of microstructure properties [12]. We shall cover the correlation between TEM or X-ray determined dislocation densities in plastically deformed single crystals [1,2,6], in high pressure torsion deformed Ta and Nb [13]; the long range internal stresses in dislocation cell-structures [1,2,6,14], lath martensite steels [3], or the planar defect structure in high temperature sintered SiC [15]. It will be shown how the synergy between electron microscopy and line profile analysis adds to a more comprehensive characterization of substructures. The synergy between the two techniques renders a more complete understanding of both the qualitative and quantitative properties of microstructure elements in terms of dislocation types and densities, dipole character of different dislocation arrangements, internal stresses, or planar defect densities [1-15].

References:
[1] H. Mughrabi, T. Ungar, W. Kienle and M. Wilkens, Phil. Mag. 53 (1986) 793-813.
[2] E. Schafler, K. Simon, S. Bernstorff, P. Hanak, G. Tichy and T. Ungar and M. Zehetbauer Acta Mater. 53 (2005) 315-322.
[3] T. Ungar, S. Harjo, T. Kawasaki, Y. Yomota, G. Ribarik and Z. Shi, Met. Mater. Transact. A48 (2017) 159-167.
[4] T. Ungar, Ph. A. Dubay, G. Kostorz, Acta Metall. 38 (1990) 2583-2586.
[5] T. Seymour, P. Frankel, L. Balogh, T. Ungar, S.P. Thompson, D. Jadernas, J. Romero, L. Hallstadius, M.R. Daymond, G. Ribarik and M. Preuss, Acta Mater. 126 (2017) 102-113.
[6] T. Ungar, H. Mughrabi, D Rönnpagel and M. Wilkens, Acta Metall. 32 (1984) 333-342.
[7] P. Scardi and M. Leoni, Acta Cryst. A58 (2002) 190-200.
[8] M. Zehetbauer, T. Ungar, R. Kral, A. Borbely, E. Schafler, B. Ortner, H. Amenitsch and S. Bernstorff, Acta Mater. 47 (1999) 1053-1061.
[9] G. Ribarik and T. Ungar, Mater. Sci. Eng. A528 (2010) 112-121.
[10] T. Ungar, I. Dragomir, A. Revesz and A. Borbely, J. Appl. Cryst. 32 (1999) 992-102.
[11] T. Ungar, J. Gubicza, G. Ribarik and A. Borbely, J. Appl. Cryst. 34 (2001) 298-310.
[12] G. Ribarik, B. Jóni, and T. Ungar, in preparation.
[13] B. Jóni, E. Schafler, M. Zehetbauer, G. Tichy and T. Ungar, Acta Mater. 61 (2013) 632-642.
[14] T. Ungar and M. Zehetbauer, Scripta Mater. 35 (1996) 1467-1473.
[15] J. Gubicza, S. Nauyoks, L. Balogh, J. Labar, T.W. Zerda and T. Ungar, J. Mater Res. 22 (2007) 1314-1321.

11:45: [SISAMWedAM02] Invited
In-situ X-ray Synchrotron Profile Analysis during High Pressure Torsion Deformation
Erhard Schafler¹ ; Michael Kerber² ; Florian Spieckermann³ ; ¹University of Vienna, Wien, Austria; ²University of Vienna, Vienna, Austria; ³University of Leoben, Leoben, Austria;
Paper Id: 241 [Abstract]

X-Ray Line Profile Analysis is a powerful method to characterize the microstructure of deformed materials, especially when high energy and brilliant Synchrotron radiation enables investigations with high time and spatial resolution. Parameters like dislocation density, dislocation arrangement, scattering domain size, and its distribution are parameters of a physical model of peak broadening, which can be applied to high quality diffraction measurements. A small sample high-pressure-torsion-machine was designed in order to perform in-situ diffraction experiments during the deformation process at hydrostatic pressures up to 8GPa in order to follow the strain as well as pressure induced microstructural characteristics of any deformed material. This was possible with the ideal design and equipment at the High-Energy-Materials-Science-beamline at PETRA III in Hamburg. Recent and first results of experiments on HPT-deformed Ni, Ti and BMGs are presented [1].

References:
[1] E. Schafler, M.B. Kerber,F. Spieckermann, T. Fischer, R. Schuster, C. von Baeckmann in: Magnesium Technology 2017, ed. K.N. Solanki, D. Orlov et al., Springer, pp. 645-651 (2017)

12:10: [SISAMWedAM03] Invited
Liquid Environment Spherical Depth Sensing Indentation: Toward the Mechanical Characterization of Living Tissue
Jean-philippe Jehl¹ ; Richard Kouitat Njiwa² ; Pablo Maureira³ ; ¹Institut Jean Lamour - Université de Lorraine, Nancy, France; ²Institut Jean Lamour (UMR 7198 CNRS-Université de Lorraine), Nancy, France; ³INSERM U961, Nancy, France;
Paper Id: 211 [Abstract]

Nowadays, it is increasingly understood that the mechanical characteristics of living systems play a fundamental role in their function. Their determination is quite difficult and are required in many applications; for instance, the manufacture of dummies used in the surgical simulation procedures (internal training and learning in continuing education) [1, 2], the manufacture of specialized neo-tissue [3], and the numerical investigation of tissue response to external stimuli. The determination of the mechanical properties of soft biological materials is of great interest for imaging, where these material properties can be used to distinguish healthy and pathological tissues [4]. Mechanical tests are carried out to study the mechanical behavior of biological tissues [5]. This work proposes to use spherical depth sensing indentation experiments for the characterization of soft tissue (cardiac tissue). The tissue dries up quickly and therefore a liquid environment is necessary to perform the experiment. The spherical depth sensing indentation has recently been adapted to operate in such an environment [6]. The present work focuses on the results obtained for cardiac tissue samples. The built-up procedure appear to be effective in a wide range of deformations.

References:
[1] Misra S, Ramesh KT, Okamura AM. Modeling of tool-tissue
interactions for computer-based surgical simulation: a literature
review. Presence-Teleop Virt 2008; 17: 463-491.
[2] Perrenot C, Perez M, Tran N, Jehl J-Ph, Felblinger J, Bresler L, Hubert J
The virtual reality simulator dV-Trainer is a valid assessment tool for robotic surgical skills. Surgical Endoscopy September 2012, Volume 26, Issue 9, pp 2587-2593
[3] Fung YC. Stress, strain, growth, and remodeling of living organisms.
In: Casey J, Crochet MJ, editors. Theoretical, experimental,
and numerical contributions to the mechanics of fluids and
solids. Basel/Switzerland: Birkh.user Verlag 1995: 469-482.
[4] J-Ph. Jehl and R. Kouitat Njiwa. A (Constrained) Microstretch Approach in Living Tissue Modeling: a Numerical Investigation Using the Local Point Interpolation - Boundary Element Method. Computer Modeling in Engineering & Sciences, Vol.102, No.5, 2014
[5] Gao Z, Lister K, Desai J. Constitutive modeling of liver tissue:
experiment and theory. Ann Biomed Eng 2010; 38: 505-516.
[6] J-Ph. Jehl, A.Voignier, R. Kouitat. On the depth sensing indentation on liquid environment for application to biological tissue. 2016 Sustainable Industrial Processing Summit

12:35: [SISAMWedAM04] Invited
Lifetime and Reliability of Small-scaled Multilayered Structures
Golta Khatibi¹ ; Bernhard Czerny¹ ; Thomas Walter¹ ; Agnieszka Betzwar¹ ; Martin Lederer¹ ; ¹TU Wien, Vienna, Austria;
Paper Id: 407 [Abstract]

Small-scaled materials are used in a broad range of applications, from microelectronic systems to medical devices with a continuous trend towards further down-scaling and function integration. The micro-systems are composed of networks of interfaces separating layers of dissimilar materials with a broad range of chemical, physical and mechanical properties. Interfaces have been recognized as potential sites of failure as a result of incompatibility and thermal mismatch in the multilayered materials. Knowledge of fatigue and degradation behavior and understanding the related micro-mechanism of damage with respect to microstructural characteristics of the constituent materials with focus on their interfaces is a prerequisite for design and fabrication of functional and reliable devices. The common practice for reliability assessment and lifetime estimation of electronic devices are accelerated passive and active thermal cycling tests. In the recent years device manufactures are seeking for highly accelerated and realistic reliability assessment methods to respond to the requirements of the rapidly growing technology and keeping up with market demands. In this context, accelerated isothermal fatigue testing has been introduced as an efficient alternative to conventional thermal procedures. A considerable reduction of testing time is achieved by using dedicated high frequency mechanical fatigue testing set-ups in order to replace the thermally induced strains by equivalent mechanical strains. Based on a physics of failure approach, the relevant failure modes in the material interfaces are induced enabling detection of weak sites of the devices in a very short duration of time. Detailed microstructural investigations and failure analysis provide insights into the micro-mechanism of deformation. On the basis of experimental data and numerical methods, the proposed method is used for prediction of lifetime and delamination growth behavior of small scaled multilayered structures. In this talk, exemplary studies on the application of accelerated isothermal mechanical fatigue testing for lifetime assessment of small scaled interconnects and thin multilayered structures are presented and the advantages and limits of the proposed method is briefly discussed.

References:
G. Khatibi, B. Czerny, A. Lassnig, M. Lederer, J. Nicolics, J. Magnien, E. Suhir, A Novel Approach for Evaluation of Material Interfaces in Electronics, IEEE 2016, Aerospace Conference
A. Lassnig, R. Pelzer, C. Gammer, G. Khatibi, Role of intermetallics on the mechanical fatigue behavior of Cu-Al ball bond interfaces, Journal of Alloys and Compounds, 646 (2015) 803 - 809
B. Czerny, M. Lederer, B. Nagl, A. Trnka, G. Khatibi, M. Thoben, Thermo-mechanical analysis of bonding wires in IGBT modules under operating conditions, Microelectronic Reliability 52 (2012) 2353-2357
B. Czerny, G. Khatibi, Interface Reliability and Lifetime Prediction of Heavy Aluminium Wire Bonds, Microelectronics Reliability 58 (2016) 65-72
J. Magnien, G. Khatibi, M. Lederer, H. Ipser, Investigation of interfacial behavior in miniaturized solder interconnects, Materials Science & Engineering A 673 (2016) 541-550
T. Walter, M. Lederer, G. Khatibi, Delamination of polyimide/Cu films under mixed mode loading, Microelectronics Reliability 64 (2016) 281-286
A. Mazloum-Nejadari, G. Khatibi, B. Czerny, M. Lederer, J. Nicolics, L. Weiss Reliability of Cu Wirebonds in Microelectronic Packages, Microelectronics Reliability 74 (2017) 147-154
A. Betzwar Kotas, G. Khatibi, Isothermal bending fatigue response of solder joints in high power semiconductor test structures, Microelectronics Reliability 85 (2018) 1-11

SESSION: SISAMWedPM1-R5 Functional Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Wed Nov, 7 2018 / Room: Copacabana A (150/1st)
Session Chairs: Ernst Bauer; Gerda Rogl; Session Monitor: TBA

14:00: [SISAMWedPM105] Keynote
Spinodal Decomposition in High-Entropy Half-Heusler Thermoelectrics with High ZT~1.5
Peter Rogl¹ ; ¹University of Vienna, Faculty of Chemistry, Wien, Austria;
Paper Id: 189 [Abstract]

Besides skutterudites and Zintl phases, Half Heusler (HH) alloys are currently the most promising candidates for thermoelectric (TE) devices at elevated temperatures; they can be used in a wide range of temperatures, and their starting materials are abundant and cheap [1]. In particular, the nanostructuring of TiNiSn-based thermoelectric materials - not only by ball-milling but also by preferably system-inherent phase separation - has accomplished multicomponent HH alloys with attractive ZTs for n-type TE materials based on (Ti,Zr)-Ni-Sn. These values could be achieved on the basis of a profound knowledge not only on isothermal phase relations, temperature dependent solubilities, but also on solidification behavior. The detailed experimental investigation of the constitution of the (Ti,Zr)-Ni-Sn systems, including liquidus projections, Scheil solidification diagrams, as well as CALPHAD modelling, provided the necessary basis for an elaborate synthesis (annealing/hot-pressing) route in order to get a suitable and reproducible microstructure. In addition, exploiting inherent but coherent binodal/spinodal demixing at subsolidus temperatures within the sections TiNiSn-ZrNiSn and TiNiSn-HfNiSn, we were able to achieve for the n-type half Heusler alloy Ti0.5Zr0.25Hf0.25NiSn a ZTmax = 1.5 at 825 K. The demixing is a balanced effect of destabilisation of the solid solution by a positive enthaphy of mixing, compensated by elastic strain energy (coherent binodal) but also by the entropy of mixing. In this respect, the five component thermoelectric material can be considered as a so-called pseudoternary high-entropy alloy system. The experimental data are backed by SEM/TEM analyses as well as by DFT results.

References:
[1] G. Schierning, R. Chavez, R, Schmechel, B. Balke, G. Rogl, P. Rogl, "Concepts for Medium-high to High Temperature Thermoelectric Heat-to-Electricity Conversion: A Review of Selected Materials and Basic Considerations of Module Design", Translational Materials Research 2, 025001, 1-26 (2015)

14:25: [SISAMWedPM106] Invited
Bulk and Thin-film Stoichiometric and Off-stoichiometric Full Heusler Thermoelectric Systems
Ernst Bauer¹ ; Bernhard Hinterleitner¹ ; Michael Poneder¹ ; Christoph Eisenmenger¹ ; Johannes Rehak¹ ; Rene Moser¹ ; Raimund Podloucky² ; Takao Mori³ ; Xing-qiu Chen⁴ ; ¹Technische Universität Wien, Vienna, Austria; ²Technische Universität Wien, Wien, Austria; ³NIMS Tsukuba, Tsukuba, Japan; ⁴NIMS Tsukuba, Shenyang, China;
Paper Id: 226 [Abstract]

Among the various families of thermoelectric materials, half-Heusler and full-Heusler systems are appreciated for their excellent mechanical properties and an outstanding thermal stability. While half-Heusler materials are also known for their superior thermoelectric performance as characterized by the so-called figure of merit, ZT, reaching ZT values above 1, the thermoelectric efficiency of full-Heusler systems is still moderate and does not exceed ZT ~ 0.1 - 0.2. The latter finding is based on the unfavorable fact that the total thermal conductivity of such Heusler phases is pretty large, exceeding that of well-behaving thermoelectric materials by more than one order of magnitude. Nevertheless, the power factor of Heusler systems like those based on Fe₂VA1, is comparable, or even exceeds that of well behaving and excellently performing materials based on Bi-Te. In this contribution, the influence of substitution on different lattice sites (e.g., V/W or Fe/Ni) on the thermoelectric performance is studied, both from experiments as well as from first principles DFT calculations. In addition, we show that thin film preparation of Heusler systems results in an significant enhancement of the power factor pf substantial drop of the lattice thermal conductivity and thus in an dramatic increase of the figure of merit ZT. A number of microscopic observations are accounted for to explain this boost.

14:50: [SISAMWedPM107] Invited
Severe Plastic Deformation via High Pressure Torsion in Thermoelectrics
Gerda Rogl¹ ; Peter Rogl² ; Ernst Bauer³ ; Michael J. Zehetbauer⁴ ; ¹Christian Doppler Laboratory for Thermoelectricity, Wien, Austria; ²University of Vienna, Faculty of Chemistry, Wien, Austria; ³Technische Universität Wien, Vienna, Austria; ⁴University of Vienna, Wien, Austria;
Paper Id: 188 [Abstract]

Thermoelectric materials are able to directly convert thermal energy into electrical energy, and vice versa. The potential of a material for thermoelectric applications is determined by the dimensionless figure of merit, ZT, which is directly proportional to the Seebeck coefficient squared and the temperature, and inversely proportional to the electrical resistivity and thermal conductivity, the latter consisting of an electronic and phonon part. As the Seebeck coefficient, the resistivity and electronic part of the thermal conductivity, are interdependent, one way to enhance ZT is to reduce the phonon part by enhancing the scattering of the heat carrying phonons. High pressure torsion (HPT) is known as an outstanding technique in the methods of severe plastic deformation (SPD) to produce bulk ultra fine grained and nano crystalline materials, by introducing many grain boundaries as well as defects like dislocations and point defects [1,2,3]. In the first step, HPT-mediated nano crystallization was used to reduce the thermal conductivity of ball milled (BM) and hot pressed (HP) skutterudites. The samples, which were HPT processed after BM and HP, show enhanced ZT values up to a factor of 2 in comparison to BM and HP samples. In the second step, HPT at elevated temperatures and in argon atmosphere was used to directly consolidate skutterudite powders into a solid. This way, time and energy consuming BM and HP can be avoided [4,5]. In this paper, we compare the grain sizes as well as dislocation densities and structural, physical, and mechanical properties of BM + HP samples with BM + HP + HPT samples, along with HPT produced samples (synchrotron diffraction data, collected from 300 - 800 K, SEM and TEM investigations reveal the modifications).

References:
[1] M.J. Zehetbauer, Y.T. Zhu (eds), Modeling of Strength and Strain Hardening of Bulk Nanostructured Materials in: Bulk nanostructured materials, Wiley VCH, Weinheim (2009).
[2] M. Zehetbauer, H.P. Stuewe, A. Vorhauer, E. Schafler, J. Kohut, Adv. Eng. Mater. 5 (2003) 33.
[3] T. Ungar, M. Zehetbauer, Scr. Mater. 35 (1996) 1467.
[4] G. Rogl, P. Rogl, E. Bauer, M. Zehetbauer, Severe plastic deformation, a tool to enhance thermoelectric performance, in: Thermoelectric Nanomaterials, K. Kuomoto, T. Mori (eds), Springer Series in Materials Science 182, Springer Verlag Berlin (2013).
[5] G. Rogl, A. Grytsiv, J. Bursik, J. Horky, R. Anbalagan, E. Bauer, R.C. Mallik, P. Rogl, M. Zehetbauer, Phys. Chem. Chem. Phys. 17 (2015) 3715.

15:15: [SISAMWedPM108] Invited
Advanced Mechanical Processing of ZK60 and ZK60 + Mm Alloys for Hydrogen Storage Applications
Daniel Rodrigo Leiva¹ ; Erenilton Pereira Silva¹ ; Juliano Soyama² ; Haroldo Cavalcanti Pinto³ ; Claudio Shyinti Kiminami⁴ ; Tomaz Toshimi Ishikawa¹ ; Walter Jose Botta⁵ ; ¹Departamento de Engenharia de Materiais, Universidade Federal de São Carlos, São Carlos, Brazil; ²Faculdade de Engenharia Mecânica, Universidade Estadual de Campinas, Campinas, Brazil; ³Departamento de Engenharia de Materiais, Universidade de São Paulo, São Carlos, Brazil; ⁴Departamento de Engenharia de Materiais, Universidade Federal de São Carlo, Sao Carlos, Brazil; ⁵Departamento de Engenharia de Materiais, Universidade Federal de São Carlos, Sao Carlos, Brazil;
Paper Id: 409 [Abstract]

Magnesium alloys as ZK60 are interesting materials for hydrogen storage in the solid state, due to the high volumetric and gravimetric capacities that can be attained, and to the relatively low relative cost of these materials. The development of simpler and more cost effective processing routes of Mg alloys for H2 storage is an important challenge of applied research, in order to make possible the replacement of the intensive time and energy consuming processes based on high-energy ball milling, HEBM. We have explored different alternatives of advanced processing to ZK60 or ZK60 modified with Mm (mischmetal) [1-3], aiming to produce refined microstructures and enhanced H2 storage properties, especially faster activation (first hydrogenation) kinetics. Due to the Mm addition, a network of intermetallic particles is formed at the grain boundaries of the modified ZK60 alloy. Equal-channel angular pressing (ECAP) or rapid solidification by melt-spinning (MS) were combined with a subsequent step of extensive cold rolling (CR). The additional processing by CR caused further grain refinement and breakage of intermetallic particles, as well as favoring crystallographic texture in the (002) direction. All these features promoted a significant improvement in the hydrogen storage capacity. Another approach applied for the ZK60 alloy consisted in the combination of friction stir processing (FSP) with filing. The pulverization of the ZK60 alloy, already grain refined by FSP, has shown to be also an interesting strategy to produce materials with better H-absorption/desorption kinetics.

References:
[1] E. P. Silva, D. R. Leiva, H. C. Pinto, R. Floriano, A. M. Neves, W. J. Botta, International Journal of Hydrogen Energy 43 (2018) 11085- 11091.
[2] J. Soyama, R. Floriano, D. R. Leiva, Y. Guo, A. M. Jorge, E. P. Silva, H. C. Pinto, C. Bolfarini, C. S. Kiminami, W. J. Botta, International Journal of Hydrogen Energy 41 (2016) 11284-11292.
[3] J. Soyama, M. R. M. Triques, D. R. Leiva, A. M. Jorge, E. P. Silva, H. C. Pinto, C. Bolfarini, C. S. Kiminami, W. J. Botta, International Journal of Hydrogen Energy 41 (2016) 4177-4184.

SESSION: SISAMWedPM2-R5 Functional Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Wed Nov, 7 2018 / Room: Copacabana A (150/1st)
Session Chairs: Spomenka Kobe; João Paulo Sinnecker; Session Monitor: TBA

15:55: [SISAMWedPM209] Keynote
Magnetism in Micro and Nanostructures: Magnetic Recording and Magnonics
João Paulo Sinnecker¹ ; Elis Helena De Campos Pinto Sinnecker² ; Danilo Froes Batista³ ; ¹Centro Brasileiro de Pesquisas Físicas, Rio de Janeiro, Brazil; ²Instituto de Fisica, UFRJ, Rio de Janeiro, Brazil; ³Centro Brasileiro de Pesquisas Fisicas, Rio de Janeiro, Brazil;
Paper Id: 381 [Abstract]

This work will address the research in the area of micro and nanomagnetism, showing results in artificial magnetic micro and nanostructures for high-density magnetic recording and magnonics. New technological high-density storage systems investigations over the past decades have followed the study of artificial magnetic nanostructures as single storage elements. The reduction of the memory elements' size has been used to increase the storage density [1,2]. We have studied the magnetic behavior of T-shaped magnetic micro and nanostructures, experimentally and by micromagnetic simulations. T-shaped magnetic nanostructures have stable magnetic states resulting from the configurational anisotropy, in which stable magnetic states have been predicted for one single element, allowing the storage of two bits of information. Depending on the direction of the applied field, T-shapes can be prepared in four magnetic states. Magnonics is an emerging research field in which spin-waves are used for information transmission and processing. The data can be encoded either in the amplitude or phase, and the absence of charge transport eliminates Joule losses. Spin-wave propagation is usually done in patterned structures that require the continuous application of an external magnetic field, which jeopardizes its efficiency [3]. Magnetic domain walls as propagation channels have been proposed [4] as they exist in remnant magnetic states. The domain walls act as potential wells confining the spin-waves. We have simulated the spin-wave along 180° walls in permalloy slabs. We show that, up to 2 GHz, spin-waves are strongly confined within the wall. The dispersion relation for the confined waves resembles a magnetostatic-dominated Damon-Eschbach mode [5]. We have fabricated rectangular permalloy structures by electron-beam lithography and obtain Landau configuration reproducibly, as confirmed by Kerr microscopy images. This study is aimed to evaluate the suitability of these spin-waves for magnonics.

References:
[1] RA Escobar et al, Appl. Phys. Lett. 104, 123102 (2014)
[2] RA Escobar et al, JAP 117, 223901 (2015)
[3] E. Albisetti et al., AIP Advances 7, 055601 (2017)
[4] F. Garcia-Sanchez et al., Phys. Rev. Lett. 114, 247206 (2015)
[5] R. W. Damon and J. R. Eshbach, J. App. Phys. 31, S104 (1960)

16:20: [SISAMWedPM210] Invited
Magnetostriction of Current Fe-based Alloys: An Overview
Cristina Bormio Nunes¹ ; Guilherme O. Fulop¹ ; Mateus B. S. Dias¹ ; Fabio M. Cardoso¹ ; ¹Universidade de São Paulo, Escola de Engenharia de Lorena, Lorena, Brazil;
Paper Id: 368 [Abstract]

Magnetostriction is an important magnetic property of soft magnetic materials, which provides different kinds of applications. Low- and high-magnetostriction materials are of interest. For reducing noise in transformers and electric machines, low-magnetostriction materials are desired. However, for sensors and actuator applications, high-magnetostriction materials are the target. In conjunction with magnetostriction, other magnetic properties need to be suitable for applications such as high permeability and low coercive force. A review of the most promising materials will be presented. In order to understand the high magnetostriction in Fe-based alloys, the lecture focuses on its microscopic origin while building on microscopic investigations. Low magnetostrictive material Fe-Si will also be discussed. Results of magnetic properties on a new low magnetostrictive alloy, Fe-Ti, will be presented.

16:45: [SISAMWedPM211] Invited
Cobalt Ferrite — New Aspects in Magnetization Behaviour
Reiko Sato¹ ; ¹Technical University ov Vienna, Institute of Solid State Physics, Vienna, Austria;
Paper Id: 264 [Abstract]

Recently, CoFe₂O₄ is of more physical and technological interest, because among the ferrites, it exhibits the highest magnetocrystalline anisotropy as well as a high magnetostriction (100=590 ppm), high strain sensitivity (one order larger than that of polycrystalline terfenol (λ_s = 1000 ppm)), and low raw material costs, whose properties are appropriated for non-contact sensor and sonar detection field. Additionally, CoFe₂O₄ is an insulator that is one of the few materials which can be used for bulk magnetoelectric composites. The grain size, magnetic properties, and cations distributions in octahedral and tetrahedral sites depend strongly on the production method. With forced hydrolysis method, a grain size of 3 nm could be achieved [1], which is very important for biomedical applications. Pressing ball milled cobalt ferrites under high pressure and sintering in a high external field can obtain a magnetostriction up to 400 ppm [2]. Low temperature magnetization measurements on single crystalline Co_0.8Fe_2.2O₄ gave evidence of a first order magnetic process (FOMP) transition, which occurs when applying the external field in the [111] direction [3]. This transition is also well visible in the magnetostriction data. Such transition gives evidence of two competing anisotropy directions or two no equivalent magnetization sites, which may be due to different valent states at 3d atoms. Due to the complex preparation methods of single crystal cobalt ferrite, more attention has been given on polycrystalline cobalt ferrites to obtain high magnetostriction. In this work, special emphasis will be given on the temperature dependence of enhanced magnetostriction of CoFe₂O₄ by annealing the sample (produced by ball milling and sintered at 1000°C for 12 h) with strong magnetic field of 10 T, at 300 °C for 3 h and cooling down to room temperature with the presence of field. These results will be compared with those data obtained for the sample before the magnetic field annealing.

References:
[1] Giap V. Duong, R. Sato Turtelli, N. Hanh, D.V. Linh, M. Reissner, H. Michor, J. Fidler, G. Wiesinger, R. Grössinger, J. Magn. Magn. Mater. 307 (2006) 313-317.
[2] Atif Muhammad, Reiko Sato-Turtelli, Martin Kriegisch, Roland Grössinger, Frank Kubel, and Thomas Konegger, Journal of Applied Physics 111, 013918 (2012).
[3] Martin Kriegisch, Weijun Ren, Reiko Sato-Turtelli, Herbert Müller, Roland Grössinger, and Zhidong Zhang, Journal of Applied Physics 111, 07E308 (2012).

17:10: [SISAMWedPM212] Invited
Novel Multicomponent Magnets Using Less Critical Raw Materials for Sustainable Use
Tomaž Tomše¹ ; Jean-marie Dubois² ; Spomenka Kobe³ ; ¹Jožef Stefan Institute, Ljubljana, Slovenia; ²Institut Jean Lamour, Nancy, France; ³Josef Stefan Institute, Ljubljana, Slovenia;
Paper Id: 306 [Abstract]

This talk will address the general issue of energy production and use, while limiting the consumption of critical raw materials and restraining the impact on the environment that are the pillars of sustainability, which is derived from the framework of this summit series. The magnetic properties of Nd-Fe-B magnets originate in the intrinsic properties of the hard magnetic Nd₂Fe₁₄B phase (exhibiting large magnetocrystalline anisotropy) [1], but the overall performance of the bulk Nd-Fe-B magnets heavily depend on the material's microstructure, which is determined by the manufacturing route and chemical composition of the alloy [1], [2]. The maximum energy product ((BH)max) of anisotropic sintered Nd-Fe-B magnets is often used as a figure of merit, which is much higher than the (BH)max values of other magnetic materials developed in the past (cobalt magnet steel) and other permanent magnets, that are currently on the market (hard ferrites, alnicos and Sm-Co). For the same performance, less magnetic material is needed, which effectively leads to miniaturization of devices [3]. The disadvantage of sintered Nd-Fe-B magnets is the fact that their intrinsic coercivity (Hci), which is a measure of the magnet's capability to withstand the external demagnetizing fields, especially at high temperatures, heavily depends on the use of heavy rare earth (HRE) elements, dysprosium, and terbium. These elements substitute the Nd atoms in the Nd₂Fe₁₄B phase and adds up to 10 wt. % are common in the high-coercivity magnets [4]. As a result, the magnetocrystalline anisotropy, a property of hard magnetic phases, is increased. But at the same time, the saturation magnetization of the system is lowered due to the antiferromagnetic coupling of the magnetic moments of Dy and Tb atoms with the moments of iron, which weakens the field produced by the magnet. The values of remnant magnetization (Br) and maximum energy product are thus reduced [5]. In addition, the HRE elements are far less abundant than Nd (except in China), and therefore much more expensive [4][6]. In some applications, like traction motors of (hybrid) electric vehicles and electric power steering (EPS) motors, magnets suffer from demagnetization due to the large reverse magnetic fields. Although the standard approach is to use HREs throughout the magnet body to increase its Hci value, certain parts of the magnet are more exposed than others [7][8]. Based on the facts shown above, the purpose of this work is to address the issue of the growing need for critical HRE elements. This was achieved in two ways. Firstly, nanostructured materials that employ less HREs to achieve high intrinsic coercivity, compared to the microcrystalline materials, were considered for the preparation of the bulk magnets. Secondly, novel Nd-Fe-B magnets were prepared by using a combination of magnetic powders obtained with one or more of the established manufacturing techniques and condense them into a so-called multicomponent bulk magnet in a fast consolidation step by using a special kind of a hot pressing technique called Pulsed Electric Current Sintering (PECS). By minimizing the process time and using low consolidation temperatures, the magnetic properties of the respective hard magnetic materials were preserved and tailored. During this study, we optimized the PECS process parameters for each type of the Nd-Fe-B magnetic powders in order to avoid the deterioration of the magnetic properties. We found a suitable combination of magnetic powders with different magnetic properties that can be processed together in a single consolidation step, and we prepared a multicomponent magnet by using a HRE-free and HRE-containing powder. We avoided the diffusion of the HRE element from the HRE-containing into the HRE-free part of the magnet during consolidation. Based on numerical simulations, we have shown that the demagnetizing fields have significant effects only on certain parts of the magnet that are located near their edges. As a consequence, only those parts need to be protected against demagnetization. Therefore, the highly inventive idea was to develop a magnet with a large volume fraction of its body HRE-free and only using HREs in the exposed parts to significantly improve the performance and to address the issue of the resource efficiency at the same time.

References:
[1] M. Sagawa, S. Fujimura, N. Togawa, H. Yamamoto, and Y. Matsuura, "New material for permanent magnets on a base of Nd and Fe (invited)," Journal of Applied Physics, vol. 55, pp. 2083-2087, 1984.
[2] O. Gutfleisch, "Controlling the properties of high energy density permanent magnetic materials by different processing routes," Journal of Physics D: Applied Physics, vol. 33, p. R157, 2000.
[3] B. D. Cullity and C. D. Graham, Introduction to Magnetic Materials. Hoboken: Wiley, 200
[4] D. Brown, Z. Wu, F. He, D. Miller, and J. Herchenroeder, "Dysprosium-free melt-spun permanent magnets," Journal of Physics: Condensed Matter, vol. 26, p. 064202, 2014.
[5] J. Coey, "Intrinsic magnetic properties of compounds with the Nd2Fe14B structure," Journal of the Less Common Metals, vol. 126, pp. 21-34, 1986.
[6] K. Binnemans and P. T. Jones, "Rare earths and the balance problem," Journal of Sustainable Metallurgy, vol. 1, pp. 29-38, 2015.
[7] Y. Matsuura, "Recent development of Nd-Fe-B sintered magnets and their applications," Journal of Magnetism and Magnetic Materials, vol. 303, pp. 344-347, 2006.
[8] D. D. TREMELLING, "Layered permanent magnet with conductive cage rotor construction," ed: Google Patents, 2015.
[9] J. Jaćimović, F. Binda, L. G. Herrmann, F. Greuter, J. Genta, M. Calvo, T. Tomše, R. Simon, "Net Shape 3D Printed NdFeB Permanent Magnets" Advanced Engineering Materials, pp. 1700098-n/a, 2017
[10] T. Tomše, J. Jaćimović, L. Herrmann, F. Greuter, R. Simon, S. Tekavec, J.-M. Dubois, S. Kobe, "Properties of SPS-processed permanent magnets prepared from rapidly solidified Nd-Fe-B powders" (ACCEPTED TO JOURNAL OF ALLOYS AND COMPOUNDS)

SESSION: SISAMWedPM3-R5 Functional Materials	Zehetbauer International Symposium on Science of Intelligent and Sustainable Advanced Materials (4th Intl. Symp. on Science of Intelligent and Sustainable Advanced Materials (SISAM))
Wed Nov, 7 2018 / Room: Copacabana A (150/1st)
Session Chairs: Spomenka Kobe; João Paulo Sinnecker; Session Monitor: TBA

17:40: [SISAMWedPM313]
Optimization of Mechanical and Corrosion Properties of Biodegradable Mg-Zn-Ca Alloys by SPD-Processing and Additional Heat Treatment
Michael J. Zehetbauer¹ ; Andrea Ojdanic¹ ; Erhard Schafler¹ ; Jelena Horky² ; Bernhard Mingler³ ; Dmytro Orlov⁴ ; ¹University of Vienna, Wien, Austria; ²AIT Austrian Institute of Technology GmbH, Seibersdorf, Austria; ³AIT Austrian Institute of Technology GmbH, Wiener Neustadt, Austria; ⁴Lund University, Lund, Sweden;
Paper Id: 424 [Abstract]

This lecture reports the changes in hardening and corrosion of biodegradable Mg-Zn-Ca alloys caused by HPT-processing and long-term heat treatments, which have been applied in order to strengthen the alloy and to adapt the Younga's modulus of the alloy to that of the human bone, for suitable application as an biodegradable implant material. The structural changes are represented by the evolution of precipitates as well as of deformation induced defects like dislocations and vacancy clusters. The studies aimed to quantify the individual effects of the structural modifications to strength and to corrosion rate, with the final goal to optimize the alloy for the use as biodegradable implants with respect to mechanical properties as well as corrosion rate [1]. The thermomechanical procedure used in this work follows that of Orlov et al. [2] applied to Mg-Zn-Zr alloy ZK60. Both the precipitates as well as the vacancy clusters achieve strength increases; in case of the latter, the Zn atoms act as trapping sites not only for HPT-induced dislocations but also for vacancies. So far, overall increases of strength of up to 250% were reached. Quantitative estimations show that the vacancy clusters contribute far more to the total strength increase than the precipitates. Furthermore, vacancy concentrations of at most 10-5 cause the hardness increase measured [3]; the experimental results, however, exhibited vacancy concentrations till to even 10-3 which means that a significant part of the HPT-induced vacancies stays single and thus does not contribute to hardening. The corrosion rate as well as the Younga's modulus remained unchanged during the processing history consisting of both HPT deformation as well as heat treatments, thus making these alloys a very attractive biodegradable material. This work has been supported by projects J2-7157 of the Slovenian Research Agency ARRS, and I2815-N36 of the Austrian Science Fund FWF.

References:
[1] Hofstetter J., Becker M., Martinelli E., Weinberg A.M., Mingler B., Kilian H., Pogatscher S., Uggowitzer P.J., Loeffler J.F. (2014) JOM, 66, 566-572
[2] Orlov D., Pelliccia X., Fang L., Bourgeois L., Kirby N., Nikulin A.Y., Ameyama K., Estrin Y. (2014) Acta Mater. 72, 110-124
[3] Kirchner H.O.K. (1976) Z.Metallk. 67, 525-532

18:05: [SISAMWedPM314] Invited
Novel Biocompatible Ni- and Cu-free Ti-based Amorphous Alloys: Thermal Stability, Corrosion Resistance and Apatite-forming Ability
Mariana Calin¹ ; Somayeh Abdi¹ ; Juergen Eckert² ; Annett Gebert¹ ; ¹IFW Dresden, Dresden, Germany; ²Erich Schmid Institute of Materials Science, Leoben, Austria;
Paper Id: 30 [Abstract]

Metallic glasses, also known as amorphous alloys or liquid metals, are relative newcomers in the field of biomaterials. They have gained increasing attention during the past decades, as they exhibit an excellent combination of properties and processing capabilities desired for versatile biomedical implant applications [1]. In the present study, we developed new Ti-based glassy alloys without any harmful additions, with potential for orthopaedic and dental applications. Ti₇₅Zr₁₀Si₁₅ and Ti₆₀Nb₁₅Zr₁₀Si₁₅ glassy alloys were obtained by melt spinning and their crystallization behavior, corrosion resistance, and apatite-forming ability were investigated [2,3]. These compositions are marginal glass formers and cannot lead to bulk glass formation. Upon devitrification on heating, the Ti-(Nb)-Zr-Si glassy alloys exhibit nanophase composite microstructures, which lead to a remarkable improvement of mechanical properties. The corrosion and passivation behavior of the alloys in their homogenized melt spun states in Ringer solution at 37°C in comparison to their cast multiphase crystalline counterparts and to cp-Ti and beta-type Ti-40Nb was studied. All tested materials showed very low corrosion rates as expressed in corrosion current densities icorr<50 nA/cm². Electrochemical and surface analytical studies revealed a high stability of the new alloys passive states in a wide potential range. The addition of Nb does not only improve the glass-forming ability and the mechanical properties, but also supports a high pitting resistance even at extreme anodic polarization. With regard to the corrosion properties, the Nb-containing glassy alloy can compete with the beta-type Ti-40Nb alloy. Simulated body fluid (SBF) tests confirmed the ability for formation of hydroxyapatite on the melt-spun alloy surfaces. All these properties recommend the new glass-forming alloys for applications as wear- and corrosion-resistant coating materials for implants.

References:
[1] A.L. Greer, Materials Today, 12 (2009) 14
[2] M. Calin et al., Mat. Sci. Eng. C, 33 (2013) 875
[3] S. Abdi et al., J. Biomed. Mat. Res. B, 104 (2016) 27.

SESSION: AdvancedMaterialsMonAM-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Mon Nov, 5 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Fernand Marquis; Alain Tressaud; Session Monitor: TBA

11:20: [AdvancedMaterialsMonAM01] Keynote
Design of Lanthanide-based Phosphors Using Quantum Chemical Calculations
Werner Urland¹ ; ¹Private Institute of Theoretical Chemical Physics, Muralto, Switzerland;
Paper Id: 52 [Abstract]

Phosphors doped by divalent or trivalent lanthanides are in the spotlight of scientific investigations due to its possible applications as domestic lighting, laser materials, or scintillator crystals. Quantum chemical calculations (semi-empirical and non-empirical) are used to design new phosphors by predicting their luminescence properties. The model using Density Functional Theory is based on an effective Hamiltonian that includes electrostatic, spin-orbit, and ligand field contributions. From these calculations the multiplet energy levels arising from the ground [Xe]4fⁿ and excited [Xe]4f^n-15d¹ electron configurations of Ln²⁺ and Ln³⁺ in their chemical environment are obtained. The results are in good agreement with the experimental investigations, validating the usefulness of the theoretical modelling to understand and characterize the luminescence spectra of phosphors.

References:
[1] Amador García-Fuente, Fanica Cimpoesu, Harry Ramanantoanina, Benjamin Herden,Claude Daul, Markus Suta, Claudia Wickleder, Werner Urland (2015): A ligand field theory-based methodology for the characterization ofthe Eu2+ [Xe]4f65d1 excited states in solid state compounds, Chem. Phys. Lett., 120 (2015), 622. DOI: doi:10.1016/j.cplett.2015.01.031
[2] Harry Ramanantoanina, Fanica Cimpoesu, Christian Göttel, Mohammed Sahnoun, Benjamin Herden, Markus Suta, Claudia Wickleder, Werner Urland, Claude Daul (2015): Prospecting Lighting Applications with Ligand Field Tools and Density Functional Theory: A First-Principles Account of the 4f7–4f65d1 Luminescence of CsMgBr3:Eu2+, Inorg. Chem., 54 (2015), 17, 8319. DOI: 10.1021/acs.inorgchem.5b00988

11:45: [AdvancedMaterialsMonAM02] Invited
Development of Hybrid Reinforced Corrosion Resistant Polymer Concretes
Nikoloz Chikhradze¹ ; Fernand Marquis² ; Guram Abashidze¹ ; Davit Tsverava³ ; ¹G. Tsulukidze Mining Institute, Tbilisi, Georgia; ²San Diego State University, San Diego, United States; ³LEPL Grigol Tsulukidze Mining Institute/M.Sc. Student of Georgian Technical University, Tbilisi, Georgia;
Paper Id: 59 [Abstract]

Polymer concretes, unlike common concrete (produced based on cement, as cohesive material), are notable for high durability on compression 50-90 MPa, and especially, on tension 6-10 MPa, with unique corrosion resistance. However, they are also associated with negative properties, such as high creep deformability. Because polymer concretes work well on tension, their application is prospective for the production of shock resistant construction materials, but for this, strengthening by additional reinforcing mechanisms is necessary. In addition, because of differences in the durability and deformability on compression, as well as on tension, it is important to reinforce the polymer concrete's tensile and bended properties. This work presents and discusses the reinforcement of polymer concrete by hybrid fibers. The major goal of this work is the production of such polymer concretes with high durability on tension and high shock resistance that preserves these properties under the effect of aggressive environments. The primary cohesive materials are unsaturated polyester resins, as polymers. The fiber reinforcements (coarse and fine) are primarily three types of basalt, polypropylene, two types of metal fibers, andesite and quartz, all selected for their chemical resistance and durability. The technological parameters for the production and processing of nano and ultrafine dispersive powders from rocks using vibration and planetary mills, and the physical and mechanical properties of these concretes are presented and discussed. The data on the corrosion resistance of these processed polymer concretes (corrosion resistance coefficient, diffusion coefficient of aggressive liquids, coefficient of liquids- sorption, and the coefficient of liquids penetration in the concretes) are also presented and discussed.

12:10: [AdvancedMaterialsMonAM03]
Climbing the Pyramid to Clean, Commercially Useful, Acid Induced Polymerizations
Stewart Lewis¹ ; ¹Pyramid Polymers LLC, New Kensington, United States;
Paper Id: 19 [Abstract]

Acids are ubiquitous to many chemical processes, including polymerization. The first synthetic polymer was derived from the action of sulfuric acid on natural olefins (i.e., terpenes) in 1789. Fast forward to today and a large variety of commodity goods, essential to everyday life, are the sole products of this (i.e., cationic) technique. They include adhesives, synthetic oils, and certain rubbers. Although its industrial use is somewhat limited in scope (ca. 3.5x106 tons of polymers are derived from cationic polymerization of vinyl monomers every year), the route is capable of polymerizing > 2,000 olefins. Despite its long history and utility, such chemistry is plagued by environmental issues. Examples are the difficulty in recycling acid components, the toxicity of the acid components and the solvents employed, sensitivity to moisture, and the need for cryogenic T to reach high molecular weight. This talk covers advances (most, previously undisclosed) made by the speaker that overcome the above obstacles such a number of aqueous cationic polymerization systems for olefins, hydrocarbon soluble forms of AlCl3, heterogeneous initiators, and a highly recyclable Lewis acid in addition to detailing results from some pilot plant studies. Finally, a unique resource on the cationic methodology is provided to the audience that will be of value to both those skilled in this art as well as the newcomer.

References:
I will have to fill this in at a later date

12:35: [AdvancedMaterialsMonAM04]
Climbing the Pyramid to Clean, Commercially Useful, Acid Induced Polymerizations (Part II)
Stewart Lewis¹ ; ¹Pyramid Polymers LLC, New Kensington, United States;
Paper Id: 339 [Abstract]

Acids are ubiquitous to many chemical processes, including polymerization. The first synthetic polymer was derived from the action of sulfuric acid on natural olefins (i.e., terpenes) in 1789. Fast forward to today and a large variety of commodity goods, essential to everyday life, are the sole products of this (i.e., cationic) technique. They include adhesives, synthetic oils, and certain rubbers. Although its industrial use is somewhat limited in scope (ca. 3.5x106 tons of polymers are derived from cationic polymerization of vinyl monomers every year), the route is capable of polymerizing > 2,000 olefins. Despite its long history and utility, such chemistry is plagued by environmental issues. Examples are the difficulty in recycling acid components, the toxicity of the acid components and the solvents employed, sensitivity to moisture, and the need for cryogenic T to reach high molecular weight. This talk covers advances (most, previously undisclosed) made by the speaker that overcome the above obstacles such a number of aqueous cationic polymerization systems for olefins, hydrocarbon soluble forms of AlCl3, heterogeneous initiators, and a highly recyclable Lewis acid in addition to detailing results from some pilot plant studies. Finally, a unique resource on the cationic methodology is provided to the audience that will be of value to both those skilled in this art as well as the newcomer.

References:
I willl update this later.

SESSION: AdvancedMaterialsMonPM1-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Mon Nov, 5 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Janina Molenda; Michael Zharnikov; Session Monitor: TBA

14:00: [AdvancedMaterialsMonPM105] Keynote
Fabrication and Potential Applications of Novel Poly(ethylene glycol) Hydrogel Films and Nanomembranes
Michael Zharnikov¹ ; ¹Heidelberg University, Heidelberg, Germany;
Paper Id: 74 [Abstract]

Whereas biorepulsive oligo- and poly(ethylene glycols) (OEGs and PEGs) are widely used for different applications, they have not been utilized yet as materials for free-standing nanomembranes. In this context, I discuss fabrication and potential applications of novel PEG hydrogel films and membranes, abbreviated as PHFs and PHMs, respectively. They were prepared by thermally activated crosslinking of amine- and epoxy-terminated, star-branched PEG oligomers, and characterized by tunable thicknesses of 4-300 nm [1]. These systems possess a variety of useful properties, including biocompatibility, robustness, and extreme elasticity [1,2]. They can serve as a basis for hybrid materials, advanced nanofabrication, and lithography, using electron irradiation and ultraviolet light as writing tools [1-3]. They can also be used as highly sensitive elements in MEMS as well as in humidity sensors and moisture-responsive nanoelectronic devices, relying on optical or resistive transduction technique. In particular, their resistance changes by ca. 5.5 orders of the magnitude upon relative humidity variation from 0 to 100%, which is an unprecedented response for homogeneous materials [4]. The PHFs and PHMs are also able to host protein-specific receptors, providing, at the same time, protein-repelling and humidity-responsive matrix with a characteristic mesh size up to 8.4 nm [5]. A noticeable grafting density of the test avidin protein, specifically attached to the biotin moieties, coupled to the free amine groups in the PHMs, was achieved, whereas non-specific protein adsorption was efficiently suppressed. The engineering of PHMs with biomolecule-specific receptors and their loading with biomolecules are of potential interest for sensor fabrication and biomedical applications, including tissue engineering and regenerative therapy.

References:
[1] N. Meyerbröker, T. Kriesche, M. Zharnikov, ACS Appl. Mater. Interfaces 5 (2013) 2641-2649.
[2] N. Meyerbröker, M. Zharnikov, Adv. Mater. 26 (2014) 3328-3332.
[3] N. Meyerbröker, M. Zharnikov, ACS Appl. Mater. Interfaces 6 (2014) 14729-14735.
[4] M. Khan, S. Schuster, M. Zharnikov, J. Phys. Chem. C 119 (2015) 14427-14433.
[5] M. Khan, S. Schuster, M. Zharnikov, Phys. Chem. Chem. Phys. 18 (2016) 12035-12042.

14:25: [AdvancedMaterialsMonPM106] Invited
A Concept of Embedded Dipole in Interfacial Engineering and its Applications in Organic Electronics
Michael Zharnikov¹ ; ¹Heidelberg University, Heidelberg, Germany;
Paper Id: 75 [Abstract]

The energy level alignment between the metal electrodes and adjacent organic semiconductor, as well as between the buffer layers and adjacent electrode/active layer is a key issue in organic electronics and photovoltaics. A frequently used approach in this context is the introduction of a suitable interfacial dipole by modification of the electrodes/buffer layers with a self-assembled monolayer (SAM). For this purpose, SAMs are usually decorated with a specific dipolar terminal group, attached to the molecular backbone, which, however, can affect the growth of organic semiconductor and be easily modified itself, thus distorting the desirable energy level alignment. An alternative novel concept involves embedding of a dipolar functional group into the backbone of the SAM constituents, thus decoupling dipole control and interfacial chemistry [1,2]. The validity of this concept is demonstrated by the example of several model SAMs, containing embedded dipolar groups with different chemical compositions and orientations. Combining molecules with oppositely oriented dipolar groups in a mixed SAM allows continuous variation of the interfacial dipole in a broad range, enabling its exact adaptation to the requirements of a particular device. Using a specific spectroscopic signature of the embedded groups, within the concept of electrostatic shift, the morphology of the mixed films can be precisely monitored down to the molecular scale by X-ray photoemission spectroscopy [3,4]. As an example of potential usefulness of this novel class of SAMs in organic electronics and photovoltaics, their application in organic field-effect transistors is demonstrated, resulting in decrease of the contact resistance by ca. three orders of magnitude accompanied by significant improvement in the performance and stability of the devices. As a continuation of these activities, application of novel dipolar SAMs in organic solar cells is now under consideration [5].

References:
[1] T. Abu-Husein, S. Schuster, D. A. Egger, M. Kind, T. Santowski, A. Wiesner, R. Chiechi, E. Zojer, A. Terfort, M. Zharnikov, Adv. Funct. Mater. 25 (2015) 3943-3957.
[2] O. M. Cabarcos, S. Schuster, I. Hehn, P. P. Zhang, M. M. Maitani, N. Sullivan, J.-B. Giguère, J.-F. Morin, P. S. Weiss, E. Zojer, M. Zharnikov, D. L. Allara, J. Phys. Chem. C 121 (2017) 15815-15830.
[3] T. C. Taucher, I. Hehn, O. T. Hofmann, M. Zharnikov, E. Zojer, J. Phys. Chem. C 120, (2016) 3428-3437.
[4] I. Hehn, S. Schuster, T. Wachter, T. Abu-Husein, A. Terfort, M. Zharnikov, E. Zojer, J. Phys. Chem. Lett. 7 (2016) 2994-3000.
[5] Q. Zhang, W.-T. Wang, C.-Yu Chi, T. Wachter, J.-W. Chen, C.-Yi Tsai,Y.-C. Huang, M. Zharnikov, Y. Tai, and D.-J. Liaw, Energy Environ. Sci. 11 (2018) 682-691.

14:50: [AdvancedMaterialsMonPM107] Invited
The Impact of Cathode Electronic Structure on the Parameters of Lithium and Sodium Batteries
Janina Molenda¹ ; ¹AGH University of Science and Technology, Kraków, Kraków, Poland;
Paper Id: 22 [Abstract]

The author of this work, based on her own investigations of A_xMO₂ cathode materials (A=Li, Na; M=3d), has demonstrated that the electronic structure of these materials plays an important role in the electrochemical intercalation process. The proposed electronic model of intercalation [1-3] is universal and has outstanding significance with regard to tailoring the properties of electrode materials to the most efficient application in Li-ion and Na-ion batteries. The paper reveals correlation between electronic structure, transport, and electrochemical properties of layered Li_xCoO₂, Na_xCoO₂ and Li_xNi_1-y-zCo_yMn_zO₂ cathode material and explains of apparently different character of the discharge/charge curve in Li_xCoO₂ (monotonous curve) and Na_xCoO₂ systems (step-like curve). Comprehensive experimental studies of physicochemical properties of Li_xNi_1-y-zCo_yMn_zO₂ cathode material (XRD, electrical conductivity, thermoelectric power) are supported by electronic structure calculations performed using the Korringa-Kohn-Rostoker method 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. Furthermore, the variations of the electromotive force of the Li/Li⁺/Li_xNi_1-y-zCo_yMn_zO₂ cell (for 0 < x < 1) remains in quite good agreement with the relative variation of EF on DOS calculated from the KKR-CPA method.

References:
[1] J. Molenda, D. Baster, M. Molenda, K. Świerczek, J. Tobola, Phys. Chem. Phys. Chem. 16 (2014) 14845
[2] J. Molenda, D. Baster, M. U. Gutowska, a. Szewczyk, R. Puźniak, J. Tobola, Funct. Mater. Lett. 7 (2014) 144000
[3] J.Molenda, A.Milewska, W. Zajac, M.Rybski, J. Tobola, Phys. Chem. Phys. Chem. 19, (2017)25697

15:15: [AdvancedMaterialsMonPM108] Invited
Fabrication of Nanocomposites by Mechanical Alloying and Explosive Consolidation
Nikoloz Chikhradze¹ ; Guram Abashidze¹ ; Fernand Marquis² ; Mikheil Chikhradze³ ; ¹G. Tsulukidze Mining Institute, Tbilisi, Georgia; ²San Diego State University, San Diego, United States; ³Georgian Technical University, Tbilisi, Georgia;
Paper Id: 212 [Abstract]

Bulk nanostructure materials are characterized by high specific strength, hardness, corrosion, and wear resistant properties, and in particular, conditions by super-plasticity [1, 2, 3]. They exhibit specific electrical, thermal, magnetic, optical, chemical and other properties. Accordingly, the demand on nanoparticles and bulk nanocomposites in increased for practical application. Therefore, the development of new technologies for fabrication of bulk nanocomposites is big challenge. This paper consists of an experimental investigation and manufacture of multifunctional bulk nanostructured composite materials in Ti-Al-B-C, Si-B-C, SiC-B-C B₄C-SiC, B₄C-Si-C systems. The coarse crystalline Ti, Al, amorphous Boron and Carbon (Graphite) elementary pure (at least 98%) powders were used as precursors. The blend with different percentage contents of the powders were prepared. The high energetic "Fritsch" Planetary ball mill was used for blend processing, mechanical alloying, amorphization, and nanopowder production. The time of processing varied in range of: 1-36h. The optimal technological regimes for nanopowder preparation are determined experimentally. Ball milled blend compacted by explosive consolidation technology and bulk composite materials are fabricated. 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 and the structure-properties relationship are presented and discussed in the paper.

References:
[1] The Second World Space Congress, 10-19 October, 2002, Houston, TX, USA., I-4-03IAF, 34th COSPAR Scientific Assembly
[2] R. Mania, M. Dabrowski et all, International Journal of Self-Propagating High-Temperature Synthesis. 2003 v. 12, #3, 159-164
[3] R.M. Da Rocha, Chapter in Ceramic Engineering Science Proceeding, Jan., 2010

SESSION: AdvancedMaterialsMonPM2-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Mon Nov, 5 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Joseph Newkirk; Session Monitor: TBA

15:55: [AdvancedMaterialsMonPM209] Keynote
Creating the Materials of Tomorrow
Joseph Newkirk¹ ; ¹Missouri University of Science & Technolgy, Rolla, United States;
Paper Id: 27 [Abstract]

When I was young I was fascinated by projections of future technologies. The future looked like an exciting place and I could not wait to see it. Many new technologies have been introduced in my lifetime and most were enabled by new materials. What future technologies are awaiting new materials and how do we develop them? Is it possible to create materials that will provide a leap in performance compared to existing materials, rather than just an incremental change? What can we learn from previous developments? This presentation will look briefly at the history of the impact of structural materials development on our culture and society. In addition, the lack of sufficient quantities of key elements will be shown to have a devastating effect on societies. Drawing from lessons learned from this review, the possibility of new culture shocking technologies will be discussed. Today the pace of technological change is moving faster than the development of new materials, and many initiatives are designed to improve the rate of introduction of new materials. However, a vision as to what the materials needs of the future are is required in order to direct the development required. The requirements of these new technologies are basically hindered by the lack of compact power sources and light-weight structural materials. Some solutions to these dramatically higher performance materials will be suggested, with the goal of stimulating new discussions and research into material systems.

References:
[1] J.W. Newkirk and F. Liou, "High Performance Materials by Laser Deposition" Materials Science Forum, Vols. 783-786, p. 2365-2369, 2014.
[2] T. Amine, J.W. Newkirk, and F. Liou, "An Investigation of the Effect of Direct Metal Deposition Parameters on the Characteristics of the Deposited Layers" Case Studies in Thermal Engineering 3, pp. 21-34. 2014.
[3] A.T. Sutton, C.S. Kriewall, M.C. Leu, and J.W. Newkirk, "Powder Characterization Techniques and Effects on Part Properties in Powder Bed Fusion Processes: A Review" Virtual and Physical Prototyping, pp. 1-27, 2016.
[4] L. Yan, W. Li, X. Chen, Y. Zhang, J. Newkirk, F. Liou, D. Dietrich, "Simulation of Cooling Rate Effects on Ti-48Al-2Cr-2Nb Crack Formation in Direct Laser Deposition" JOM, Vol 69, No. 3, pp. 586-591, 2017.
[5] W. Li, F. Liou, J. W. Newkirk, K. Taminger, W. Seufzer, "Investigation on Ti6Al4V-V-Cr-Fe-SS316 Multi-layers Metallic Structure Fabricated by Laser 3D Printing" Scientific Reports, 7(1), December 2017, p. 7977.

16:20: [AdvancedMaterialsMonPM210] Invited
Electroerosion Coagulation and Dispersion for Complex Water Purification, Waste Recycling and Manufacturing of Metals, Oxides, and Alloys Nanopowders
Mykola Monastyrov¹ ; Tetiana Prikhna² ; Bernd Halbedel³ ; Gennadii Kochetov⁴ ; Fernand Marquis⁵ ; ¹Open International University of Human Development Ukraine, Kiev, Ukraine; ²Institute for Superhard Materials, Kiev, Ukraine; ³Technische Universitat Ilmenau, Ilmenau, Germany; ⁴NATIONAL UNIVERSITY OF CONSTRUCTION AND ARCHITECTURE, Kyiv, Ukraine; ⁵San Diego State University, San Diego, United States;
Paper Id: 122 [Abstract]

The application of electroerosion coagulation together with in-situ manufactured polyvalent powdered aluminium oxides and iron oxides allowed efficient water purification from heavy metal ions and radioactive alkali ions (Fe, Cr, Cu, Mo, Zn, Co, Ni, Cd, Mn, As, Sn, Pb, Al, Ba, Cs and Sr) as well as from organic contaminations (from the liquid waste landfills, in particular) [1]. The method of electroerosion dispersion is very effective for production of nanopowders (5-500 nm) of metals, oxides, nitrides and carbides, as well as for recycling of any conductive materials such as cemented carbides, alloys of heavy metals, any metallic granules or chips, cans, etc [2]. The iron magnetic nanoparticles produced by electroerosion dispersion have considerable interest in many fields of research and application due to their attractive properties. They have high potential for applications in the field of biomedical sciences (diagnostics and therapy), ferrofluids, catalysis, colored pigments, high-density magnetic recording, printer toners, Li-ion batteries, wastewater treatment and absorption of electromagnetic waves.

References:
[1] M. Monastyrov, T. Prikhna, B. Halbedel, P. Talanchuk, G. Kochetov, A. Vasiliev, M. Eisterer, F. D. S. Marquis, New technology for the integrated treatment of industrial and landfills waste water using iron and aluminum oxides nanopowders, In: Proceedings 2017 Sustainable Industrial Processing Summit and Exhibition, Volume 5: marquis Intl. Symp./ New and Advanced Materials &Technologies for Energy, Environment, and Sustainable Development, Edited by: F.Kongoli, F. Marquis, N. Chikhradze, Flogen, 2017, 346-355.
[2] M. Monastyrov, T. Prikhna, A. G. Mamalis, W. Gawalek, P. M. Talanchuk, R. V. Shekera, "Electroerosion dispersion-prepared nano- and submicrometre-sized aluminium and alumina powders as power-accumulating substances, Nanotechnology Perceptions", 4 (2008), 179-187

16:45: [AdvancedMaterialsMonPM211]
The Quest for Electronic Ferroelectricity in Organic Charge-transfer Crystals
Alberto Girlando¹ ; ¹Parma University, Parma, Italy;
Paper Id: 108 [Abstract]

Organic ferroelectric materials that can operate at room temperature are in demand in the emerging field of lightweight and environmentally friendly electronics. In recent years, attention has focused on mixed stack charge-transfer (ms-CT) co-crystals, made up by planar pi-electron donor (D) and acceptor (A) molecules alternating along the stack direction. These materials are characterized by r, the degree of CT, ranging from 0 to 1, with r ~ 0.5 separating the neutral (N) from the ionic (I) ground state. Increase of the Madelung energy, following lattice contraction by lowering temperature, may induce a peculiar phase transition, the N to I one, with r crossing the N-I borderline. Ionic systems are subject to the Peierls instability, yielding to dimerization of the stack, hence potential ferroelectricity. Indeed, the prototypical ms-CT crystal Tetrathiafulvalene-Chloranil (TTF-CA) becomes ferroelectric in the low temperature (below 80K) I dimerized phase [1]. The TTF-CA ferrolectricity is electronic in nature, rather than ionic, being characterized by higher polarization and fast response to the electric field [2]. However, the search for other ms-CT crystals exhibiting electronic ferroelectricity at higher temperatures proved to be very challenging [3], since ionic or intermediate ionicity systems are relatively rare, and other conditions have to be met. In this paper, the quest for electronic ferroelectricity will be shortly reviewed. A strong electron donor, 3,3,5,5-Tetramethylbenzidine (TMB) has been coupled with a series of pi-electron molecules of increasing acceptor strength [4]. The co-crystal of TMB with Tetracyanoquinodimethane (TCNQ) undergoes a valence instability transition around 200 K, ending in the same ferroelectric structure as TTF-CA. Unfortunately, the ferroelectricity could not be directly tested, since the crystals are damaged at the transition. Other systems in the series are currently being investigated. Results on other ms-CT crystals with polar structure will be presented, even if they do not exhibit true ferroelectricity. The aim is to find the conditions which have to be met to obtain electronic ferroelectricity, so that suitable systems can be properly engineered.

References:
[1] K. Kobayashi, S. Horiuchi, R. Kumai, F. Kagawa, Y. Murakami and Y. Tokura, Phys. Rev. Lett. 108 (2012) 237601.
[2] S. Horiuchi, K. Kobayashi, R. Kumai and S. Ishibashi, Chem. Lett. 43 (2014) 26-35.
[3] A. S. Tayi, et al., Nature 488 (2012) 485-489. G. Da'Avino et. al., Nature 547 (2017) E9.
[4] N. Castagnetti, M. Masino, C. Rizzoli, A. Girlando and C. Rovira, Phys. Rev. Mater. 2 (2018) 024602.

17:10: [AdvancedMaterialsMonPM212] Keynote
Understanding the Behaviour of Advanced Alloys is Critical to Safe and Reliable Performance of Modern Equipment in the Energy Sector
Jonathan David Parker¹ ; ¹EPRI, Charlotte, United States;
Paper Id: 327 [Abstract]

Most electricity generating plants must be able to achieve greater flexibility of operation than was traditionally the case. Thus, high energy components must exhibit reliable, long-term performance under cyclic operating conditions. Historically, assessment of the performance of these components focused on defining the transients related to hot, warm, and cold starts and stops. The complexity and range of cycles in many plants now include rapid changes in generating output to operating levels of 30% of rated capacity. In many cases, the desirable levels of low load operation are below the values considered in the original design. EPRI programs have thus been working with utilities to implement monitoring campaigns which record the changes in local pressure, temperature, and flow with time at different locations within a system, and to undertake analysis to assess the influence of these effects on performance. This work is challenging since both the cycles and the low load operation can lead to problems associated with thermal and/or mechanical loading, as well as potential issues with control of water chemistry, oxidation, and corrosion. The present review summarizes EPRI achievements linked to transient effects in modern generating plant, with particular emphasis on the behavior of creep strength enhanced steels. These steels, typically based on 9 to 12% Cr, offer significant benefits to the design and fabrication of components in high efficiency fossil fuelled plants because when properly processed tempered martensitic steels offer an excellent combination of strength and toughness. However, assessment of in-service experience demonstrates that cracking in CSEF steel components has occurred relatively early in life. In many cases, the occurrence of damage has been linked to less than optimal control of steel making, processing, and component fabrication. The results of EPRI facilitated collaboration to establish best practice guidelines for component design and the use of these steels in high efficiency plants are discussed, and the ongoing commitment to knowledge creation and technology transfer is described.

References:
1. R. Viswanathan and W.T. Bakker, Materials for Ultra Supercritical Fossil Power Plants, Report TR-114750, EPRI, Palo Alto, (January 2000).
2. F. Masuyama, ISIJ International, 41 (2001), No. 6, p. 612-625.
3. "The CURC-EPRI Coal Technology Roadmap. August 2012: Update." Available at: www.coal.org
4. International Energy Agency - OECD/IEA, (2012) Available at: www.iea.org
5. B. Diczfalusy. "HELE Coal Technology Roadmap." IEA Clean Coal Centre Workshop: on Advanced ultrasupercritical coal-fired Power Plants, Vienna, Austria (2012).
6. O. Hamart, Vallourec, Private communication
7. J. R. DiStefano and V. K. Sikka, "Summary of Modified 9Cr-1Mo Steel Development Program," 1975-1985. ORNL-6303, Oak Ridge National Laboratory, (1986).
8. J. Shingledecker, R. Purgert and P. Rawls, Seventh Int Conf on Advances in materials Technology for Fossil Power Plants, EPRI / ASM, (2013)
9. H. Shigeyama, Y. Takahashi and J.D. Parker, Proceedings of the ASME 2015 Pressure Vessels & Piping Conference, PVP2015 - 45252, (2015), Boston, USA
10. J.D. Parker, Int. J. of Pressure Vessels & Piping, 101, (2013), p. 30-36.
11. J.D. Parker, Int. J. of Pressure Vessels & Piping, 114 - 115, (2014), p.76 - 87.
12. Guidelines and Specifications for High-Reliability Fossil Power Plants: Best Practice Guideline for Manufacturing and Construction of Grade 91 Steel Components. EPRI, Palo Alto, CA.1023199, (2011) updated as EPRI 3002006390 (2015).
13. J.D. Parker, Advances in Materials Technology for Fossil Power Plant, EPRI / ASM (2014), p 714
14. Y. Gu, G.D. West, R.C. Thomson and J.D. Parker, Advances in Materials Technology for Fossil Power Plant, EPRI/ASM (2014), p 596
15. Standard Test Method for Creep-Fatigue Testing, ASTM, Designation: E 2714 - 13.
16. D.W. Gandy, J. Shingledecker, L. Lherbier & D. Novotnak, Powder Metallurgy Methods for Producing Large Components, Nuclear Exchange, (2011).

SESSION: AdvancedMaterialsMonPM3-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Mon Nov, 5 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Krzysztof Wierzbanowski; Andrzej Baczmanski; Session Monitor: TBA

17:40: [AdvancedMaterialsMonPM313] Invited
Microstructure, Texture and Mechanical Characteristics of Polycrystalline Copper After Asymmetric Rolling
Agnieszka Uniwersał¹ ; Krzysztof Wierzbanowski¹ ; Mirosław Wrobel¹ ; Sebastian Wronski¹ ; Marcin Wronski¹ ;⁰ ; ¹AGH University of Science and Technology, Kraków, Poland;
Paper Id: 200 [Abstract]

In the recent years, asymmetric rolling has attracted the attention of metallurgists and material scientists. This deformation process has a number of advantages: it can be used to improve material properties as well as some technological rolling parameters [1-5]. This geometry of deformation is relatively easy to implement on existing industrial rolling mills, and it can provide large volumes of a material. The study of microstructure, crystallographic texture, and stored energy in asymmetrically rolled polycrystalline metals (copper, aluminum and titanium) are presented in this work. The characteristics above were examined using the EBSD technique, X-ray diffraction, and calorimetric measurements. The mechanical aspects of the process were examined experimentally and studied using the Finite Element Method. The rolling asymmetry was realized using either two identical rolls rotating with different angular velocities, or two rolls with different diameters rotating with the same angular velocity. <br />It was found that asymmetric rolling leads to important microstructure modifications, grain refinement, texture rotation and its homogenization. The mechanical strength and hardness of the processed material are improved. The estimated stored energy accumulated during deformation is higher after asymmetric rolling, which influences the subsequent annealing process. The material bending, resulting in this process, can be partly controlled by an appropriate choice of rolling process parameters. The rolling normal force is reduced and distribution of torques between two work rolls is modified in asymmetric rolling process, as compared with the symmetric one.

References:
[1] M. Wronski, K. Wierzbanowski, S. Wronski, B. Bacroix, P. Lipinski, Int. J. Mech. Sci., 87 (2014) 258-267\n[2] M. Wronski, K. Wierzbanowski, S. Wronski, B. Bacroix and P. Lipinski, Arch. Metall. Mater., 62 (2017) 1991-1999\n[3] M. Wronski, K. Wierzbanowski, M. Wrobel, S. Wronski, B. Bacroix, Met. Mater. Int., 21 (2015) 805-814\n[4] A. Uniwersal, M. Wronski, M. Wrobel, K. Wierzbanowski, A. Baczmanski, Acta Mater., 139 (2017) 30-38\n[5] A. Uniwersal, M.Wrobel, K. Wierzbanowski, S. Wronski, M. Wronski, I. Kalemba-Rec, T. Sak, B. Bacroix, Mater. Charact., 118 (2016) 575-583

18:05: [AdvancedMaterialsMonPM314] Invited
Intergranular Stresses and Micro-damage Process in Two-phase Materials Studied Using Diffraction and Self-consistent Model
Andrzej Baczmanski¹ ; Elzbieta Gadalinska² ; Sebastian Wronski³ ; Przemyslaw Kot³ ; Christian Scheffzuek⁴ ; Gizo Bokuchava⁴ ; Lea Le Joncour⁵ ; Yuchen Zhao⁵ ; Chedly Braham⁶ ; ¹AGH University of Science and Technology, Faculty of Physics and Applied Computer Science, Krakow, Poland; ²Institute of Aviation, Warszawa, Poland; ³AGH-University of Science and Technology, WFiIS, Krakow, Poland; ⁴FLNP, Joint Institute for Nuclear Research, Dubna, Russian Federation; ⁵ICD-LASMIS, Universite de Technologie de Troyes, Troyes, France; ⁶PIMM, Arts et MA�tiers ParisTech (ENSAM), Paris, France;
Paper Id: 213 [Abstract]

As a selective and non-destructive method, the diffraction method applied for in-situ tensile test is particularly useful in analysing the evolution of phase behaviour during elastic and elasto-plastic deformation of polycrystalline materials [1-3]. This experimental technique enables determination of the mechanical properties for group of grains inside the gauge volume defined by diffraction condition. The measurements are carried out using selected hkl reflections during tensile/compression tests. In the case of multiphase polycrystalline materials, the measurement of separate diffraction peaks enables independent investigations of the mechanical behaviour of each phase.<br />In this work, a methodology combining diffraction experiments and self-consistent calculations was used to study behaviour of phases within two-phase polycrystalline materials (Al/SiCp composite and duplex austenitic-ferritic steel). Special attention was paid to the role of first and second order stresses on the yield stresses of the phases, as well as on the evolution of these stresses during the deformation process. The stresses were determined from lattice strains measured in situ during tensile tests and after sample unloading [4,5] using neutron diffraction (JINR, Dubna, Russia and ISIS, RAL, UK) and diffraction of X-ray synchrotron radiation (ID15B, ESRF, Grenoble, France).<br />Comparison of the elasto-plastic self-consistent model with measured lattice strains allowed the determination of micro-mechanical properties of each phase in two-phase polycrystalline materials. The partitioning of the load between phases were correctly predicted by the self-consistent model. It was shown that the developed version of this model can be used to predict the consequences of damage processes occurring in a given phase. <br />The experimental and model results obtained in this work were used to study slip on crystallographic planes, localisation of stresses in polycrystalline grains [4,5] and initiation of micro-damage [6] occurring during plastic deformation.

References:
[1] M.R. Daymond, H.G. Priesmeyer, Acta Mater. 50 (2002) 1613a-1623.\n[2] M.L. Young, J.D. Almer, M.R. Daymond, D.R. Haeffner, D.C. Dunand, Acta Mater. 55 (2007) 1999-2011.\n[3] D. Gloaguen, G. Oum, V. Legrand, J. Fajoui, S. Branchu, Acta Mater. 61 (2013) 5779-5790.\n[4] A. Baczmański, R. Levy-Tubiana, M.E. Fitzpatrick and A. Lodini, Acta Mater., 52 (2004) 1565-1577.\n[5] A. Baczmanski, L. Le Joncour, B. Panicaud, M. Francois, C. Braham, A. M. Paradowska, S. Wroński, S. Amara and R. Chirone, J. Appl. Cryst, 44 (2011) 966-982.\n[6] A. Baczmański, Y. Zhao, E. Gadalińska, L. Le Joncour, S. Wroński, C. Braham, B. Panicaud, M. Francois, T. Buslaps, K. Soloducha M., Int. J. Plasticity 81 (2016) 102-122.

SESSION: AdvancedMaterialsTueAM-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Tue Nov, 6 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Raphael Semiat; Alexander Yarin; Session Monitor: TBA

11:20: [AdvancedMaterialsTueAM01] Keynote
Environmental and Energy Issues in Water Treatment Processes
Raphael Semiat¹ ; ¹Technion IIT, Haifa, Israel;
Paper Id: 10 [Abstract]

The growth in population and in the standard of living in developing countries, coupled with inefficient use of water and pollution of available water resources, have driven desalination to be a major source of fresh water for both domestic and industrial purposes. The challenges in water management are among the most important problems facing the world today. The shortage of clean water is at the heart of critical health issues in developing countries, and is the focus of ecological and safety concerns even for the highly developed nations. To provide water for drinking and agriculture, we must desalinate and clean natural water sources, reclaim polluted water, purify water with different degrees of contaminants, and improve the effectiveness of water handling (storage and delivery) systems ranging from large desalination plants to waste water treatment facilities and down to family's water purification systems. We must remove contaminants that include inorganics (metals and ions), organics (e.g. toxic waste, pharmaceuticals) and microorganisms (bacteria, viruses, etc.). At the heart of these diverse problems stands the need for new ways to clean water, to safely dispose of the extracted waste, to properly reuse the cleaning systems and to keep the environment clean. The cost of desalinated water is higher than the cost of natural water if available in the vicinity but can be lower if natural water is brought from long distance. The popular concept is that desalination consumes high energy; however, like in the process industry, the cost is based on optimization of all parameters involved, not only the energy. It is not only the cost of the process components, but also most importantly, the environmental parameters that need to be properly considered. The potential environmental impacts of desalination are related to the energy generation process as well as to the design and management of the desalination process. The importance of these impacts depends on the type of technology used. Energy consumption of desalination processes is very low in comparison with the total national energy consumption for electricity and transportation. It was shown that the energy consumption of most desalination processes constitute only a small fraction of the total national energy consumption. For example, the energy requirement to produce an annual desalinated water capacity of 600 million m3/y in Israel is less than 1.3% of the Israeli national energy consumption. It should be noted that it is easier to save 1.3% of the national energy consumption than about 80% of the urban water consumption. Energy consumption depends on the location of the plant and the distance of the plant from the seawater suction point, and the energy cost is highly dependent on the type of energy source. Other environmental issues may also affect the water cost, and it is important to keep the environment intact while keeping desalinated costs to the possible minimum. In literature and in real life there are considerable concerns regarding the environmental impacts of desalination technologies. The main concerns are related to emission of air pollutants and greenhouse gases, entrapment of marine life on the intake side, and discharge of relatively high-temperature, salinity-elevated and chemical-laden concentrate. Nevertheless, limited research is available on these possible ecological and biological impacts, particularly on the long term effects on the marine environment. Existing data revealed that only a small area, adjacent to the concentrate disposal point, is affected by elevated salinity and temperature after which complete dilution with the seawater diminishes any further affects. Israel made significant steps to provide affordable solutions based on a wide distribution system, desalination (80% of the urban water consumption), tertiary treatment of wastewater for irrigation, drip irrigation for reduction of water consumption, and improved agriculture techniques. However, there is always room for improvements. It is essential to improve desalination steps in order to reduce the cost. New directions may include improved membranes—especially UF membranes, improved pretreatment processes, and increased recoveries as applied effectively near zero liquid discharge in inland brackish water desalination. It is essential to improve wastewater treatment by better techniques like MBR and better treatment for removal of tracers of organic and inorganic contaminants. An important subject is the treatment of produced water from the gas and oil industry, treatment of polluted aquifers, development of small water treatment and recovery for remote communities, and more. Priority should be given in the near future to development of renewable energy sources and water supplies that meet sustainability and environmental requirements. This presentation summarizes the environmental impacts of most aspects of desalination processes, highlighting the recognized problems and their available industrial solutions. The aspects related to techniques, energy and environmental issues investigated in our water research program would also be discussed.

11:45: [AdvancedMaterialsTueAM02] Keynote
Self-healing Nano-textured Engineering Vascular Materials
Alexander Yarin¹ ; ¹University of Illinois at Chicago, Chicago, United States;
Paper Id: 14 [Abstract]

The nature-inspired self-healing strategies have been explored in biomimetic engineering designs with a goal of repairing structural damages or facilitating the anti-corrosion protection by means of systematic transport of healing materials, which can be cured and polymerized at the damaged sites. Microscopic capsules filled with healing agents, which were proposed first, are certainly viable and require no external energy to trigger the healing process but such capsules is inherently thick due to their bulky size. A different approach with a much smaller confinement for the healing materials and a capability of multiple healing is desired. Here we overview the efforts of our group and the other research groups toward development and testing of nano-textured vascular self-healing materials and discuss the state-of-the art in the field of such materials, which emerged to mimic multiple natural materials, for example, those characteristic of our own body (skin, bones healed by means of vascular system) [1,2]. Self-healing materials formed by electrospinning and solution blowing are expected to be capable of self-restoring their mechanical properties, e.g. stiffness, toughness, adhesion and cohesion. It is important to heal the invisible and practically undetectable fatigue cracks, which endanger airplanes, and multiple other composite-made vehicles and constructions. Nano-textured vascular self-healing also prevent or delay delamination in composites on ply surfaces [3]. Another field where nano-textured vascular self-healing materials are extremely desirable is the anti-corrosion protection. Numerous corrosion protection approaches are hindered by toxicity of the chemical paints and other problems related to the cost, as well as to the environment, remain as serious concerns. Accordingly, the bio-inspired vascular self-healing techniques have been recently explored as alternative approaches for prevention corrosion. We discuss in detail the extrinsic self-healing based on nano-textured vascular nanofiber networks and demonstrate successful performance of such materials in healing cracks in the anti-corrosion protection layers [4,5].

References:
[1] Lee MW, An S, Yoon SS, Yarin AL. 2018. Advances in self-healing materials based on
vascular networks with mechanical self-repair characteristics. In: Advances in Colloid and
Interface Science, Volume 252. p. 21-37.
[2] Lee MW, Yoon SS, Yarin AL. 2017. Release of self-healing agents in a material: What
happens next? In: ACS Applied Materials & Interfaces, Volume 9. p. 17449-17455.
[3] Lee MW, An S, Jo HS, Yoon SS, Yarin AL. 2015. Self-healing nanofiber-reinforced
polymer composites: 1. Tensile testing and recovery of mechanical properties. In: ACS Applied
Materials & Interfaces, Volume 7. p. 19546-19554.
[4] Sun Z, Zussman E, Yarin AL, Wendorff JH, Greiner A. 2003. Compound core/shell polymer
nanofibers by co-electrospinning. In: Advanced Materials, Volume 15. p. 1929-1932.
[5] Yarin AL, Pourdeyhimi B, Ramakrishna S. 2014. Fundamentals and Applications of Microand
Nanofibers. Cambridge University Press, Cambridge.
[6] Lee MW, An S, Lee C, Liou M, Yarin AL, Yoon S. 2014. Self-healing transparent core-shell
nanofiber coatings for anti-corrosion protection. In: J. Mater. Chem. A, Volume 2, 7045-7053.
[7] Lee MW, Yoon SS, Yarin AL. 2016. Solution-blown core-shell self-healing nano- and
microfibers. In: ACS Applied Materials & Interfaces, Volume 8, p. 4955-4962.
[8] Lee MW, An S, Jo HS, Yoon SS, Yarin AL. 2015. Self-healing nanofiber-reinforced polymer
composites: 2. Delamination/debonding, and adhesive and cohesive properties. In: ACS Applied
Materials & Interfaces, Volume 7. p. 19555-19561.
[9] An S, Liou M, Song KY, Jo HS, Lee MW, Al-Deyab SS, Yarin AL, Yoon SS. 2015. Highly
flexible transparent self-healing composite based on electrospun core-shell nanofibers produced
by coaxial electrospinning for anti-corrosion and electrical
insulation.In: Nanoscale, Volume 7. p. 17778-17785.
[10] Lee MW, An S, Lee C, Liou M, Yarin AL, Yoon SS. 2014. Hybrid self-healing matrix
using core-shell nanofibers and capsuleless micro-droplets. ACS Applied Materials &
Interfaces In: ACS Applied Materials & Interfaces, Volume 6. p. 10461-10468.

12:10: [AdvancedMaterialsTueAM03] Keynote
Wear-resistant MAX phases-based Materials of Ti-Al-C System for Electrical Transport
Tetiana Prikhna¹ ; Orest Ostash² ; Vladimir Sverdun¹ ; Viktoriya Podhurska² ; Fernand Marquis³ ; Myroslav Karpets¹ ; Semyon Ponomarov⁴ ; Alexandra Starostina¹ ; Thierry Cabioc'h⁵ ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Karpenko Physical-Mechanical Institute of the National Academy of Sciences of Ukraine, Lviv, Ukraine; ³San Diego State University, San Diego, United States; ⁴Institute of Semiconductor Physics, Kiev, Ukraine; ⁵Universite de Poitiers, CNRS/Laboratoire PHYMAT, Chasseneuil Futuroscope Cedex, France;
Paper Id: 125 [Abstract]

MAX phases combined best properties of metals and ceramics [1-3]. Short-time synthesis under relatively low (10-15 MPa) pressures using hot pressing technique allowed us to obtain MAX-phase-based materials suitable for manufacturing of current-loaded inserts of pantographs. The most effective appeared to be the material containing 93% Ti₃AlC₂, 4% TiC and 3% Al₂O₃. Its wear after the 5 km of friction path in contact with copper under 0.25 MPa load (which is typical for pressing pantographs to electrical wire) was 0.0003 g, and the wear of the counter body (copper M1) at this was 0.0011 g. The wear of MAX-phase-based material was 20 times less than the wear of silumin AK (which is used for electrical transport pantographs manufacturing) and the wear of copper in contact with MAX phase occurred to be 10 times less than its wear in contact with silumin AK. It has been found that the amount of Ti₃AlC₂ (or 312), Ti₂AlC (or 211), TiC and the material density effect the wear resistance of MAX-phases-based materials. The wear of highly dense materials based on MAХ phases containing both phases of structural types 312 and 211 (61% Ti₃AlC₂, 22% Ti₂AlC, 17% TiC (I) and 40% Ti₃AlC₂ + 60% Ti₂AlC (II)), when rubbed in pairs with copper M1 under 0.25 MPa, after 5 km of the path was 0.0005 g and 0.0018 g of composition (I) and (II), respectively, while the wear of the silumin was much higher: 0.0228 g and 0.022 g, respectively.

References:
[1] Barsoum M., In: Prog. Solid St. Chem. 28 (2000) 201-81.
[2] Prikhna T, Starostina A, Petrusha I, Ivakhnenko S, Borimskii A, Filatov Yu, Loshak M, Serga M, Tkach V, Turkevich V, Sverdun V, Klimenko S, Turkevich D, Dub S, Basyuk T, Karpets M, Moshchil' V, Kozyrev A, Il'nitskaya GD, Kovylyaev V, Lizkendorf D, Cabiosh T, Chartier P., Journal of Superhard Materials 36(1) (2014) 9-17.
[3] J. Halim, P. Chartier, T. Basyuk, T. Prikhna, E.N. Caspi, M.W. Barsoum, T. Cabioc'h, 37 (2017) 15-21.

12:35: [AdvancedMaterialsTueAM04]
One-dimensional Nanomaterials for Emerging Energy Storage
Liqiang Mai¹ ; ¹Wuhan University of Technology, Wuhan, China;
Paper Id: 209 [Abstract]

One-dimensional nanomaterials can offer large surface area, facile strain relaxation upon cycling, and efficient electron transport pathway to achieve high electrochemical performance. Hence, nanowires have attracted increasing interest in energy related fields. The authors designed a single nanowire electrochemical device for in situ probing the direct relationship between electrical transport, structure, and electrochemical properties of the single nanowire electrode, in order to understand the intrinsic reason for capacity fading. The results show that during the electrochemical reaction, conductivity of the nanowire electrode decreased, which limits the cycle life of the devices. We have developed a facile and high-yield strategy for the oriented formation of CNTs from metal organic frameworks (MOFs).The appropriate graphitic N doping and the confined metal nanoparticles in CNTs both increase the densities of states near the Fermi level and reduce the work function, hence efficiently enhancing its oxygen reduction activity. Then, we fabricated a field-tuned hydrogen evolution reaction (HER) device with an individual MoS₂ nanosheet to explore the impact of field effect on catalysis. In addition, we demonstrated the critical role of structural H₂O on Zn²⁺ intercalation into bilayer V₂O₅·<i>n</i>H₂O. The results suggest that the H₂O-solvated Zn²⁺ possesses largely reduced effective charge and thus reduced electrostatic interactions with the V₂O₅ framework, effectively promoting its diffusion. Through preparing CaV₄O₉ nanowires, we also identified exciting electrochemical properties (including high electric conductivity, small volume change, and self-preserving effect) and superior sodium storage performance of alkaline earth metal vanadates. The work presented here can inspire new ideas in constructing novel one-dimensional structures and accelerate the development of energy storage applications.

References:
[1] L. Q. Mai, Y. J. Dong, L. Xu and C. H. Han, Nano Lett.,10 (2010) 4273.
[2] L. Q. Mai, M. Y. Yan and Y. L. Zhao, Nature,546 ( 2017) 469.
[3] J. S. Meng, C. J. Niu, L. H. Xu, J. T. Li, X. Liu, X. P. Wang, Y. Z. Wu, X. M. Xu, W. Y. Chen,Q. Li, Z. Z. Zhu, D. Y. Zhao and L.Q. Mai. J. Am. Chem. Soc., 139 (2017)8212.
[4] J. H. Wang, M. Y. Yan, K. N. Zhao, X. B. Liao, P. Y. Wang, X. L. Pan, W. Yang, L. Q. Mai, Adv. Mater., 29 (2016).
[5] M.Y. Yan, P. He, Y. Chen, S. Y. Wang, Q. L. Wei, K. N. Zhao, X. Xu, Q. Y. An, Y. Shuang, Y. Y. Shao, K. T. Mueller, L. Q. Mai, J. Liu, and J. H. Yang, Adv. Mater., 1703725(2017).
[6]. X. M. Xu, C. J. Niu, M. Y. Duan, X. P. Wang, L. Huang, J. H. Wang, L. T. Pu, W. H. Ren, C. W. Shi, J. S. Meng, B. Song and L. Q. Mai, Nature Commun., 2017, 8, 460.

SESSION: AdvancedMaterialsTuePM1-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Tue Nov, 6 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Barbara Szpunar; Jerry Bernholc; Session Monitor: TBA

14:00: [AdvancedMaterialsTuePM105] Keynote
Application of State-of-the-Art Calculations in the Design of Accident Tolerant Nuclear Materials
Barbara Szpunar¹ ; ¹University of Saskatchewan, Saskatoon, Canada;
Paper Id: 300 [Abstract]

Numerous nuclear accidents clearly illustrate the risks associated with the present design of reactors based on pure uranium dioxide fuel, with low thermal conductivity that deteriorates with temperature increase and upon further oxidation. Additionally, zircaloy cladding reacts rapidly with water at higher temperatures (> 800°C) and highly explosive hydrogen can be released. Although many factors need to be investigated before alternative nuclear materials can be adapted to the service of the harsh environment in the nuclear reactor, the suitable fuels must have a high thermal conductivity. We use density functional theory to calculate thermomechanical properties since it has predictive power, which is needed when there are no experimental results available. We investigate thoria [1], since it has been considered as an alternative fuel with a high melting point and higher thermal conductivity than urania. It has desirable properties, as our calculations also confirm onset of a significantly higher oxygen diffusion (due to oxygen lattice pre-melting) at higher temperatures than in urania. It also has higher retention of fission products (FP) and thermal conductivity of thoria does not deteriorate because it does not oxidize. We also investigate metallic alternative nuclear fuel, since they have high thermal conductivity that increases with increasing temperature [2]. Additionally, using finite difference method, we demonstrate that thoria and metallic fuels would not only be safer due to a higher thermal conductivity, allowing faster dissipation of heat and thus lowering the centerline fuel temperature, but they would have higher longevity due to reduced thermal stress [3].

References:
[1] B. Szpunar, J.A. Szpunar, Ki-Seob Sim, J. Phys. and Chem. Solids, 90, 114 (2016).
[2] B. Szpunar, L. Malakkal, E. Jossou, J.A. Szpunar, Materials for Nuclear Energy, Springer, ISBN 978-3-319-51647-9, DOI 10.1007/978-3-319-52333-0, Part XIV (2017).
[3] B. Szpunar, L. Malakkal, S. Chung, et al., MATEC Web of Conferences, 130, 03001 (2017).

14:25: [AdvancedMaterialsTuePM106] Keynote
Computational Exploration and Design of Nanoscale Sensors and Devices
Jerry Bernholc¹ ; ¹NC State University, Raleigh, United States;
Paper Id: 333 [Abstract]

We describe large-scale ab initio simulations of nanoscale sensors and transistors, which can predict the best-performing structures. In the sensors part we focus on mechanisms of detection of small molecules: ammonia, nitrogen dioxide, glucose and ethylene by nanotube-based sensors, and on a novel nano circuit involving a nanotube functionalized with a fragment of polymerase I enzyme. The nano circuit monitors replication of a single-stranded DNA and can potentially be used to sequence DNA by detecting electrical signatures of the adding bases. We discuss modifications that should enable reliable distinction between some of the bases, and our work towards complete sequencing. We also describe computational optimization of graphene nanoribbon (GNR) structures and devices, including the determination of atomically precise polymer-GNR conversion mechanism due hole injection, the design of realistic, experimentally realizable negative differential resistance device based on 7-GNR, and optimization of transistor structures consisting of a GNR channel, BN insulating layers and an Al gate.

14:50: [AdvancedMaterialsTuePM107]
The Importance of Polymer Topology in Surface Absorption
Giuseppe Pellicane¹ ; Mesfin Tsige² ; Francis Gaitho¹ ; ¹University of KwaZulu-Natal, Pietermaritzburg, South Africa; ²University of Akron, Akron, United States;
Paper Id: 282 [Abstract]

Physical techniques for surface modification of plastics use surface-active agents, which are allowed to self-assemble at the surface. Many techniques, which are important in modern technologies, use polymer blends, and there is considerable interest in understanding the composition extent of the surface layer differs from that in the bulk for molten polymer mixtures. Dynamical and structural properties of polymers in the melt state are strongly influenced by molecular architecture [1-4] and blending polymers with different molecular topologies could be potentially exploited to control interfacial segregation of the polymer film, and to achieve optimal mechanical properties of the plastic material [5,6]. However, a deep understanding of the role of chain architecture and molecular mass in determining which species preferentially adsorb at a given interface is lacking. Experiments to resolve the matter are typically conducted by mixing polymers possessing the same repeat chemistry, but different molecular architecture [10-14]. Here we show the results obtained in large-scale molecular dynamics simulations of linear-cyclic polymer films, and we find clear evidence of enhancement of linear polymers at the interface [7], in agreement with recent experimental results [8]. The behavior predicted by the self-consistent field theory (SCF), i.e., enhancement of cyclic polymers at the interface [9], emerges for relatively long chains. In our presentation, we provide a picture of the microscopic mechanisms through which the chain length arbitrates the competition between the different packing constraints imposed by the loop and linear geometry of the two polymers. We also discuss the role of enthalpic and entropic factors of the interfacial free energy of the system in determining which species in the blend preferentially adsorbs at the interface.

References:
[1] Kapnistos, M; Lang. M; Rubinstein, M; Roovers, J.; Chang, T; Vlassopoulos, D., Soc. Rheol. Annu. Meeting 2006.
[2] Robertson, R. M.; Smith, D. E., Proc. Natl. Acad. Sci. U.S.A. 2007, 104, 4824-4827.
[3] Iyer, B. V. S.; Lele, A. K.; Shanbhag, S., Macromolecules 2007, 40, 5995.
[4] Subramanian, G.; Shanbhag S., Macromolecules 2008, 41, 7239-7242.
[5] Wu, S. L.; Polymer Interface and Adhesion, Marcel Dekker: New York, 1982.
[6] Garbassi, F; Morra, M; Occhiello, E., Polymer Surfaces: From Physics to Technology; John Wiley and Sons: New York,1994.
[7] G. Pellicane, M. Megnidio-Tchoukouegno, G. T. Mola, and M. Tsige, Physical Review E Rapid Communications, 93, 050501 (2016); M. Megnidio-Tchoukouegno, F. M. Gaitho, G. T. Mola, M. Tsige, and G. Pellicane, Fluid Phase Equilibria, 441, 33-42 (2017); F. M. Gaitho, M. Tsige, G. T. Mola, and G. Pellicane, Polymers, 10, 324 (2018).
[8] Wang, S-F; Li, X.; Agapov, R. L.; Wesdemiotis, C.; Foster, M. D., ACS Macro Letters, 2012, 1, 1024-1027. (2016).
[9] Wu , D. T.; Fredrickson, G. H., Macromolecules 1996, 29, 7919-7930.

15:15: [AdvancedMaterialsTuePM108]
Thermionic Generators with Linear and Non-linear Electron Dispersion Relations: Chances and Limits
York Christian Gerstenmaier¹ ; Gerhard Wachutka² ; ¹Institute for Physics of Electrotechnology, Technische Universitaet Muenchen, Munich (Muenchen), Germany; ²Institute for Physics of Electrotechnology, Technische Universität Muenchen, Munich (Muenchen), Germany;
Paper Id: 248 [Abstract]

Direct heat to electricity energy conversion by use of thermionic electron emission from hot elec-trodes is a long standing issue; however, it suffers from several shortcomings. In this work, a thermionic theory for general electron dispersion relations E(k), relating electron wave number k to its energy in the electrode-material and depending only on the magnitude of wave-vector k, will be presented. The theory does not require the construction of a model-Hamiltonian for the electrode's materials. Instead use is made of band-structure data, as e.g. the parabolic E(k) ap-proximation for the Richardson-Dushman equation and linear E(k) as used for Dirac semimetals. The new theory confirms previous findings on parabolic E(k), e.g. that the emission current is independent of effective electron mass in the material as long as it is larger than the electron mass m0. For effective mass lower than m0 , the emission is reduced and tends to zero for vanishing effective mass. It turns out that linear E(k) dispersion for the Dirac semimetals, does not have the potential to surpass Richardson emission. Also, a more rigorous electron emission theory is established by utilizing the real anisotropic band-structure data En(k) of a periodic crystal elec-trode-material. However, the theory is incomplete, for lack of a general theory relating the elec-tron's wave-numbers transverse to the 1D electric field in the vacuum to the wave-numbers in the material which are integrated over. In the special case of collimated electron emission normal to the surface, the transverse wave-numbers can be set to zero, i.e. the transverse derivatives of En(k) disappear or are very small. It is not known, whether such electrode-materials can exist. If so, a considerable increase of electron emission is possible compared to the Richardson- Dush-man theory, especially for small lattice constants perpendicular to emission direction. For realistic values, an increase of the emission current by a factor 100 or more can be achieved. The new findings may pave the way for optimized material design with respect to thermionic emission.

References:
[1] S. W. Angrist, Direct Energy Conversion, 3rd edition, Boston: Allyn and Bacon, 1977.
[2] G. N. Hatsopoulos, E.P. Gyftopoulos, Thermionic Energy Conversion, Volume I, II MIT Press, 1973, 1979.
[3] Y. C. Gerstenmaier and G. Wachutka, "Efficiency of Thermionic and Thermoelectric Converters", AIP Conference Proceedings Volume 890 (a��7th World Conference on Thermophotovoltaic Generation of Electricity (TPV7)a��), Melville, New York, 2007, pp. 349-359.
[4] Y. C. Gerstenmaier and G. Wachutka, Phys. Rev. E 86, 056703 (2012).
[5] Y. C. Gerstenmaier and G. Wachutka, J. Appl. Phys. 122, 204501 (2017).
[6] A. Geim, "Graphene: Status and Prospects", Science, 324 (2009).
[7] S. M. Young et al, Phys. Rev. Lett. 108, 140405 (2012).
[8] J. Xiong et al., Science, 350, 413 (2015).
[9] Z. K. Liu et al., Science, 343, 864 (2014).
[10] R.H. Fowler, L.W. Nordheim, Proc. R. Soc. London, A119, 173-181 (1928).
[11] Y. Hishinuma, T.H. Geballe, B.Y. Moyzhes, Appl. Phys. Letters, 78, 2572-2574 (2001).
[12] Y.C. Gerstenmaier, G. Wachutka, a��Thermionic Refrigeration with Planar and Nonplanar Electrodesa�� in 11th THERMINIC, 2005, pp. 372-379.
[13] N.W. Ashcroft, N.D. Mermin, Solid State Physics, Philadelphia, PA: Holt, Rinehart, Winston, 1976.
[14] R.H. Good, E.W. Mueller, a��Field Emissiona�� in Handbuch der Physik, 21, Berlin, 1956, pp. 176-231.
[15] R. Gomer, Field Emission and Field Ionization, Cambridge, MA: Harvard Univ. Press, 1961.
[16] M.S. Chung, P.H. Cutler, Miskovsky, T.E. Sullivan, J. Vac. Sci. Technol. B12, 727-736 (1994).
[17] G.M. Fleming, J.E. Henderson, Phys. Rev. 58, 887-894 (1940).
[18] Q. D. Gibson et al., Phys. Rev. B 91, 205128 (2015).

SESSION: AdvancedMaterialsTuePM2-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Tue Nov, 6 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Ephraim Eliav; Raphael Semiat; Session Monitor: TBA

15:55: [AdvancedMaterialsTuePM209] Keynote
Fluoride Materials for Advanced Technologies, Energy, and Sustainable Issues
Alain Tressaud¹ ; ¹ICMCB-CNRS, University Bordeaux, Pessac, France;
Paper Id: 357 [Abstract]

Inorganic fluorine-based compounds are present today as components in many advanced technologies, in particular energy storage and conversion, such as Li-ion batteries, F- ion-based all-solid-state batteries, and fuel cells [1]. Other than these types of applications, fluoride materials are also decisive elements in microphotonics, fluorescent chemical sensors, solid-state lasers, nonlinear optics, etc. 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) are tested as electrodes active materials in primary lithium batteries. In secondary Li batteries, 3d-transition metal fluorides and oxyfluorides are proposed as electrodes. - Among the huge variety of solid-state d-transition metals fluorides derived from the perovskite, layered BaMF₄ and iron fluorides (TTB- K₃Fe₅F₁₅), are noticeable multiferroics, in which magnetism and ferroelectricity coexist. - Finally, functionalization processes and surface modifications using various fluorination treatments yield nanosized materials, high surface area fluorides, switchable hydrophobic/hydrophilic coatings. Concerning environmental issues, new alternatives are proposed to substitute CFCs, HCFCs and HFCs, by molecules much favorable for our troposphere because of their lower GWP. In many areas of the world where the level of fluorine in water is dangerously high, various defluoridation processes improve the quality of drinking water, lowering the risks of fluorosis and bringing most promising development for these populations [3]. <i>Acknowledgements: This presentation was made possible with the support of ARC Corp. (Dr. Dayal Meshri, CEO) </i>

References:
[1] "Progress in Fluorine Science", A. Tressaud Series Editor, Elsevier, USA Vol. 1 - "Photonic & Electronic Properties of Fluoride Materials", A.Tressaud & K. Poeppelmeier Eds. (2016) ; Vol. 2 - "New Forms of Fluorinated Carbons", O. Boltalina & T. Nakajima, Eds. (2016); Vol. 3 - "Modern Synthesis Processes and Reactivity of Fluorinated Compounds", H. Groult, F. Leroux & A. Tressaud, Eds. (2017); Vol. 4 - "Fluorine & Health: Pharmaceuticals, Medicinal Diagnostics, and Agrochemicals", G. Haufe, & F. Leroux Eds. (to appear, 2018).

[2] Fluorine Chemistry, a thematic issue, Chemical Reviews, V. Gouverneur, K. Seppelt, Eds., Chem. Rev. 115 (2015) 563-1306.

[3] "Fluorine and the Environment" Vol.1: F-emissions and atmospheric chemistry. Vol.2: Green Chemistry, Water, Agriculture, and Analytical aspects", Advances in Fluorine Science , A. Tressaud, Series Ed. Elsevier (2006)

16:20: [AdvancedMaterialsTuePM210] Invited
Nanotechnologies for Removing Contaminants From Water
Raphael Semiat¹ ; ¹Technion IIT, Haifa, Israel;
Paper Id: 11 [Abstract]

The challenges in water management are among the most important problems facing the world today. The shortage of clean water is at the heart of critical health issues in developing countries, and is the focus of ecological and safety concerns in even the most highly developed nations. To adequately provide water for drinking and agriculture, we must reclaim polluted water, purify water with different degrees of salinity, and improve the effectiveness of water handling (storage and delivery) systems, ranging from desalination plants to waste water treatment facilities to home water purification systems. We must remove contaminants that include inorganics (metals and ions), organics (e.g. toxic waste, pharmaceuticals) and microorganisms (e.g. bacteria). At the heart of these diverse problems stands the need for new ways to clean water, to safely dispose of the extracted waste, and to properly reuse the cleaning systems. Nanotechnologies stem from new developments in micro-electronics; however, new tools developed recently allow us to better understand problems related to water. Many of the problems that exist are related to nano-size and smaller particles, like viruses and molecular size contaminants. Nanotechnology may be used for modern, improved water treatment techniques. Nanoparticles can be used for water purification, provided their proper removal from the product. This is essential, since some of those materials may be dangerous for drinking, off spec for purified water, or cause problems to membranes, as in higher cleaning steps. In nano-particles categories, those based on oxides of iron, titanium, and other metals may be included, as they act as catalysts for oxidation of dissolved organic matter to water and CO2. They may also act as nano-adsorbents for removal of heavy metals and other molecules from water. Other uses of nanoparticles are in new membranes design, controlling the known properties of current membranes and/or production of new types of membranes that may possess better properties. Uses of properties of nano-particles, as monitors in modern devices, may give proper information on water quality and contaminant content. The thickness of the active layer of a reverse osmosis membrane is currently in the range of 40-150 nanometers, and is reduced for newer membranes. Controlling pore sizes and pore size distributions in different membranes is comparable to problems associated with the control of lines in modern semi-conductor devices. This presentation will summarize the current situation related to water and nanotechnology, followed by some examples under development.

16:45: [AdvancedMaterialsTuePM211] Keynote
Electronic Structure and Energetic Properties of Relativistic Quantum Dots
Ephraim Eliav¹ ; ¹School of Chemistry, Tel Aviv University, Tel Aviv, Israel;
Paper Id: 161 [Abstract]

Excited, ionized, and electron attached states of 3-D parabolic quantum dots (often referred to as "artificial" atoms) are treated with the relativistic 4-component multi-reference Intermediate Hamiltonian Fock-space coupled cluster method [1]. Collective excitations, spin-orbital splittings, and quasi-degenerate structure of many open shell quantum dots are important, implying the need for accurate inclusion of dynamic and non-dynamic correlation effects, along with first principles relativistic treatment of excitation spectra. The effects of correlation and relativity on structure and properties of n-electronic quantum dots (with 1<n<60) has been shown by calculating them at the high and low electronic density regions, as a function of the potential strength parameter I. Electronic correlation plays an important role, especially for low values of confining potential, where it constitutes a few percent of the total energy. Relativistic effects are more pronounced, when large values of confining potential are used. The spin-orbit effects are more dominant than scalar relativistic effects. Unlike in real atoms, in quantum dots relativistic effects are not affected by the systems' size, but only by the confining potential strength. In contrast to the case of the 2-D confining potential, where the magic numbers representing a closed shell structure are 2, 6, 12, 20, etc., in the 3-D potential case, one can clearly identify the shell structure 1s, 2p, 3d, 2s, 4f, 3p, 5g, etc., which is similar to the shell structure of the periodic table. Recently few-electrons quantum dots, confined by 3-dimensional isotropic harmonic potentials, with impurities that mimic finite-size atomic nuclei, have been also studied [2]. The relative weight of the correlation correction is significant for these systems, in particular for small systems with weak confining potentials and low impurity charges Z, where it constitutes up to 17% of the total energy. Strong nonadditivity is observed for some low values of Z and I, where correlation increases with Z and I, opposite to the effect of each of these potentials separately. A suggestion is made to investigate quantum dots with impurities off the dot center.

References:
[1] H. Yakobi, E. Eliav, U. Kaldor, J. Chem. Phys., 134 (2011) 054503/1-054503/11.
[2] E. Eliav, H. Yakobi, U. Kaldor, Computational & Theoretical Chemistry 1040-1041 (2014) 61-71

17:10: [AdvancedMaterialsTuePM212]
Inkjet Printing Nano-functionalization of Energy Materials
Rumen Tomov¹ ; T Mitchell Williams¹ ; Simon Hopkins² ; Vasant Kumar³ ; Bartek A. Glowacki¹ ; ¹University of Cambridge, Cambridge, United Kingdom; ²Research Fellow, Geneva, Switzerland; ³University of Cambridge, Cambridge, United Kingdom ;
Paper Id: 393 [Abstract]

The future of the international accord on mitigating the impact of climate change is linked to the successful implementation of nano-technology. The latter is strongly dependent on finding commercially viable methods for nano-functionalization of the energy related materials. Drop-on-demand inkjet printing methods combining scalability and low equipment cost with high-resolution ink delivery have been proven a feasible solution in various areas: 2D functionalization — (i) fabrication of multifilamentary superconducting YBCO structures by inkjet printing of a low-fluorine YBCO precursor solution on SS/ABAD-YSZ/CZO substrates creating a multifilamentary structure by an inverse technique (Jc of up to 3 MA cm-2 at 77 K) [1]; (ii) in situ fabrication of conductive silver coatings without additional heat treatment from micron-sized elongated silver flakes [2].<br />3D functionalization — Composite solid oxide fuel cells LSCF/CGO cathodes were nano-engineered via "dual" inkjet printing infiltration. The structure was found to extend the active three-phase boundary and to promote adsorption/dissociation/surface exchange reactions. Electrochemical impedance tests showed a reduction in the polarisation resistance of between 1.5 and 7.0 times.

References:
[1] S.C. Hopkins, T.B. Mitchell-Williams, D.R. Vanden Bussche, A. Calleja, V.R. Vlad, M. Vilardell, X. Granados, T. Puig, X. Obradors, A. Usoskin, M. Soloviov, M. Vojenciak, F. Gomory, I.V. Driessche, M. Backer, B.A. Glowacki, IEEE Trans. Appl. Supercond., 26 (2016) 1-5.\n[2] C. Nash, Y. Spiesschaert, G. Amarandei, Z. Stoeva, R.I. Tomov, D. Tonchev, I. Van Driessche, and B.A. Glowacki, J. of Electronic Materials 44 (2015) 497-510.\n[3] R.I. Tomov, T.B. Mitchel-Williams, R. Maher, G. Kerherve, L. Cohen, D.J. Payne, R.V. Kumar and B.A. Glowacki, J. Mater. Chem. A, 6 (2018) 5071-5081.

SESSION: AdvancedMaterialsTuePM3-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Tue Nov, 6 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Pengwan Chen; Werner Urland; Session Monitor: TBA

17:40: [AdvancedMaterialsTuePM313] Keynote
Synthesis and Densification of Heterogeneous Ultrafine and Nanostructured Materials by High Rate Energy Processes
Fernand Marquis¹ ; Nikoloz Chikhradze² ; Tetiana Prikhna³ ; Pengwan Chen⁴ ; Eugene Olevsky¹ ; ¹San Diego State University, San Diego, United States; ²G. Tsulukidze Mining Institute, Tbilisi, Georgia; ³Institute for Superhard Materials, Kiev, Ukraine; ⁴Beijing Institute of Technology, Beijing, China;
Paper Id: 422 [Abstract]

Because the strength, toughness, and other engineering properties of heterogeneous materials are strongly 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 issues 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 and strength and toughness of typical heterogeneous materials.

18:05: [AdvancedMaterialsTuePM314] Keynote
Shock Induced Elemental Doping of Materials
Pengwan Chen¹ ; Xin Gao¹ ; Chunxiao Xu¹ ; Jianjun Liu² ; Xiang Gao¹ ; ¹Beijing Institute of Technology, Beijing, China; ²State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing, China;
Paper Id: 421 [Abstract]

Shock wave action generates high temperature, high pressure, and high strain rate that last for a very short time (~10^-6 s), which may cause a series of catastrophic changes to the chemical and physical properties of materials. Shock induced doping is a new method to realize elemental doping in specific materials. Two types of shock-induced doping are realized in our experiments; one is pressure-induced diffusion doping, the other is in-situ doping through shock-induced chemical reaction. Shock wave action has been successfully utilized for enhancing certain properties of materials by elemental doping. This work provides a simple but efficient route for elemental doping of materials. In this work, elemental doped TiO₂ nanopowders are synthesized through shock induced doping method. A shock-loading apparatus is designed for generating shock wave and recovering the doped powders, consisting of a sample container, a flyer, and a cylindrical explosive container with an explosive and a detonator. A mixture of dopants and TiO₂ powder is filled in the sample container and impacted by a detonation-driven high-velocity flyer, leading to the doping of N, S, B, Ga in TiO₂powder under high temperature and high pressure. The characterizations of recovered samples confirm the presence of elemental doping. The visible light photocatalytic activity and photo-electrochemistry of shock doped TiO₂ are tested. N-doped graphene nanopowders are synthesized using the mixture of carbon source, strong reductant and nitrogen source through shock waves. Under the impact action of detonation-driven high-velocity flyer, the carbon source is reduced to form carbon atoms with the decomposition of nitrogen source under high temperature and pressure. Subsequently, as the formation of graphene nanosheets occurs from carbon atom deposition, the nitrogen atoms are doped in the formed graphene nanosheets. The nitrogen-doped graphene demonstrates and acts as a metal-free electrode with an efficient electrocatalytic activity toward oxygen reduction reaction in alkaline solution.

SESSION: AdvancedMaterialsWedAM-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Patrick Ching-Ho Hsieh; Udo Schwingenschlogl; Session Monitor: TBA

11:20: [AdvancedMaterialsWedAM01] Keynote
Nanotechnologies for Targeted Delivery of Cardiovascular Therapeutics
Patrick Ching-ho Hsieh¹ ; ¹Academia Sinica, Taipei, Taiwan;
Paper Id: 8 [Abstract]

Human clinical trials of protein or cell therapy for ischemic cardiovascular diseases have shown disappointing outcomes, mainly because of the poor uptake and retention by the targeted site. We aim to develop novel strategies using nanomaterials and nanotechnologies for improving targeted delivery of cardiovascular therapeutics. Several examples will be highlighted, including (1) instructive nanofiber scaffolds with a protein drug VEGF to establish an intramyocardial engineered vascular niche which attracts endogenous stem cells to home to the injury site for tissue regeneration (Lin et al. Sci Transl Med. 2012), (2) functionalized nanoparticles allowing local or systemic injection to prevent thromboembolism or tissue injury following ischemia (Tang et al. ACS Nano. 2012; Chang et al. J Control Release. 2013), (3) a drug capture system using a mixture of hyaluronan hydrogel and anti-PEG antibodies to capture systemically injected PEGylated therapeutics at injection sites (Wu et al. Sci Transl Med. 2016), and (4) platelet-like proteoliposomes which biomimic platelet interactions with circulating monocytes, allowing an EPR-independent drug delivery to the heart infarct (Cheng et al. Adv Healthc Mat. 2016). These strategies improve the efficacy of cardiovascular therapy and can be applied to other biomedical applications.

11:45: [AdvancedMaterialsWedAM02] Keynote
Ab-initio Calculations of the Thermoelectric Properties of MXenes
Udo Schwingenschlogl¹ ; ¹King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia;
Paper Id: 285 [Abstract]

This presentation gives an overview of ab-initio calculations [1-3] addressing the thermoelectric performance of MXenes. Specific examples include a comparison of Ti₂CO₂, Zr₂CO₂, and Hf₂CO₂ in order to evaluate the role of the metal atom. The lattice thermal conductivity is demonstrated to grow along the series Ti-Zr-Hf in the temperature range 300-700 K, resulting in the highest figure of merit in the case of Ti₂CO₂. Flat conduction bands promote the thermopower in the case of n-doping. Functionalization effects are studied for Sc₂C, which is semiconducting for various functional groups, including O, F, and OH. The lowest lattice thermal conductivity is found for OH functionalization. Therefore, despite a relatively low thermopower, Sc₂C(OH)₂ may be interesting for intermediate-temperature thermoelectric applications due to a high electrical conductivity. We also discuss results on heterostructures built from MXenes and transition metal dichalcogenide monolayers. Low frequency optical phonons are found to occur as a consequence of the van der Waals bonding. They contribute significantly to thermal transport and compensate for reduced contributions of the acoustic phonons (strong scattering in heterostructures), such that the thermal conductivities become similar to those of the constituent MXenes.

References:
[1] A. N. Gandi, H. N. Alshareef, and U. Schwingenschlogl, Chem. Mater. 28 (2016), 1647-1652.
[2] S. Kumar and U. Schwingenschlogl, Phys. Rev. B 94 (2016), 035405.
[3] A. N. Gandi, H. N. Alshareef, and U. Schwingenschlogl, J. Phys.: Condens. Matter 29 (2017), 035504.

12:10: [AdvancedMaterialsWedAM03]
High Effective Surface Area Electrodes by Electrochemically-induced Swelling of Aligned CNT Fibers
Katarzyna Krukiewicz¹ ; Roman Turczyn¹ ; John Bulmer² ; Krzysztof Koziol³ ; ¹Silesian University of Technology, Gliwice, Poland; ²University of Cambridge, Cambridge, United Kingdom; ³University of Cambridge, Cranfield, United Kingdom;
Paper Id: 310 [Abstract]

Fibers made purely of aligned carbon nanotubes (ACNT) exhibit remarkable properties, such as high specific strength, stiffness, electrical and thermal conductivity, as well as extreme flexibility [1-3]. The uniqueness of ACNT fibers lies in the fact that during the application of certain potentials they undergo the unusual process of swelling [4]. Since this process leads to the increase in radial dimension and effective surface area, swollen ACNT fibers can be considered as advantageous materials for electrodes in ion batteries and supercapacitors. In this paper, we demonstrate that through the process of swelling, the effective surface area of ACNT fiber can be significantly increased. The effect of swelling on the enlargement of effective surface area is extensively investigated by means of chronoamperometry in the function of applied potential and time of potential application. It is shown that by the careful choice of swelling process parameters, it is possible to increase the effective surface area of ACNT fiber up to 450 times when compared with the initial geometric area of the fiber, reaching the specific effective surface area of 7.5 m2 g-1.

References:
[1] K. Koziol, J. Vilatela, A. Moisala, M. Motta, P. Cunniff, M. Sennett, et al., Science 318 (2007) 1892-1895.
[2] C. Paukner, K. Koziol, Sci. Rep. 4 (2014) 3903-3909.
[3] A.S. Wu, T.W. Chou, Mater. Today 15 (2012) 302-310.
[4] K. Krukiewicz, J.S. Bulmer, K.K.K. Koziol, J.K. Zak, Electrochem. Commun. 64 (2016) 30-34.

12:35: [AdvancedMaterialsWedAM04]
Maintenance of the Cell Motility in the Tunic of Halocynthia Roretzi
Yoko Kato¹ ; ¹Tohoku Gakuin University, Tagajo, Japan;
Paper Id: 273 [Abstract]

The previous reports have indicated that the tunic of Halocynthia roretzi, which has chitin sulfate-like polysaccharide and cellulose Ibeta, responds to various stimulus, including mechanical stimuli and neurotransmitters, and deforms as a result [1 -4]. Moreover, the water content of the tunic was changed when the deformation occurred [1]. While the tunic in the artificial seawater increased its mass at 5 °C, whose temperature reduced the activity of the metallo-protease secreted from the cells in the tunic, the propagation of bacteria in the tunic would be prevented [1]. However, whether or not the condition of the cells in the tunic could be maintained at 5 °C has been barely examined. If the activity of the cells in the tunic is maintained in the artificial water, the conditions of the tunic could be controlled on its own. In this study, the motility of the cell obtained from the tunic, kept at 5 °C for 10 days, by centrifugation (1000G, 7 min) was examined. In addition, the contents of the dissolved organic matter and nitrate in the supernatant and seawater used for keeping the tunic were evaluated by the absorbance at 250 -350 nm and 220 nm in the spectroscopic analysis, respectively. The actively moving cells observed although the tunic were just kept in the artificial seawater. In the meantime, the contents of the dissolved organic matter and nitrate in the supernatant were more than those in the artificial seawater used for keeping the tunic. When these two types of the solutions were kept for 10 days at 5 °C, most of the samples indicated the decrease in the contents of the dissolved organic matter and nitrate. The tunic of Halocynthia roretzi could maintain its condition suitable for the cells independently.

References:
[1] Y. Kato, Journal of Biomechanical Science and Engineering, Mar. 2010; 5(2): 163-174. \n[2] Y. Kato, Proceedings of ISOPE-2011, Maui.\n[3] Y. Kato, Proceedings of ASME 2012 International Mechanical Engineering Congress and Exposition, Nov. 2012: 607-613.\n[4] Y. Kato, Open Chemistry Journal, 2018; 5: 1-17.

SESSION: AdvancedMaterialsWedPM1-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Marina Nisnevitch; Session Monitor: TBA

14:00: [AdvancedMaterialsWedPM105]
Biodiesel Production from Brown Grease
Marina Nisnevitch¹ ; Faina Nakonechny¹ ; Mirit Kolet¹ ; Daniel Zerbib¹ ; ¹Ariel University, Ariel, Israel;
Paper Id: 202 [Abstract]

Massive use of fossil fuels has led to an increase in the CO₂ concentration in the atmosphere, and this has caused global climate changes. In contradistinction, biofuels, which are produced from plant sources, and in particular biodiesel, do not affect the greenhouse gas balance. Conventional sources of biodiesel are agricultural crops, such as corn, soybean, canola, cotton, mustard, and palm. However, use of these crops for biodiesel leads to the depletion of global food resources. The aim of the present study was to develop a scheme for rapid and efficient production of biodiesel from brown grease, i.e. cooking oil waste, which has a high free fatty acids content. Biodiesel is produced by free fatty acid esterification and triglyceride trans-esterification [1]. These processes can be performed under thermal activation and classical homogeneous catalysis; however, this scheme cannot serve for production of biodiesel in a continuous regime [2]. The present research proposes performance of continuous biodiesel production using heterogeneous catalysts. Application of this process can help replace fossil energy sources by renewable biofuels, decrease greenhouse gas exhausts, and contribute to wastewater treatment.

References:
[1] A. Demirbas. Biodiesel Fuels from Vegetable Oils Via Catalytic and Non-Catalytic Supercritical Alcohol Transesterifications and Other Methods: A Survey. Energy Convers. Manag. 44 (2003) 2093-2109.
[2] C. V. McNeff, L.C. McNeff, B. Yan, D.T. Nowlan, M. Rasmussen, A.E. Gyberg, B.J. Krohn, R.L. Fedie, T.R. Hoye. A Continuous Catalytic System for Biodiesel Production. Appl. Catal. A Gen. 343 (2008) 39-48.

14:25: [AdvancedMaterialsWedPM106]
Ionic Liquid Based Artificial Cellulase Type Catalysts for Cellulosic Ethanol Process
Ananda Amarasekara¹ ; ¹Prairie View A&M University, Prairie View, United States;
Paper Id: 50 [Abstract]

Efficient hydrolysis of lignocellulosic biomass to fermentable sugars is a challenging step and the primary obstacle for the large scale production of cellulosic ethanol. 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 functionalized Brönsted 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 water 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 a recyclable, simple enzyme mimic type catalysts we have studied quantitative structure activity relationships (QSAR) of BAIL catalysts and found that activity decreases as: imidazolium > pyridinium > triethanol ammonium [4]. Furthermore, we have investigated the effects of selected metal ions on 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. BAIL solution at 140 - 170 °C using Cr³⁺, Mn²⁺, Fe³⁺, Co²⁺ Ni²⁺, Cu²⁺, Zn²⁺, and La³⁺ chlorides as co-catalysts. 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 paper will present the development of BAIL based artificial cellulase type catalysts, QSAR, catalyst immobilizations, biomass applications (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. Technol., 2016, 6, 426.
[4] A.S. Amarasekara et al., Sustain. Energ., 2014, 2(3), 102.

14:50: [AdvancedMaterialsWedPM107] Invited
Hot Pressed Aluminum Dodecaboride- and Boron Carbide-based Ceramics
Tetiana Prikhna¹ ; Pavlo Barvitskiy¹ ; Viktor Moshchil¹ ; Vladislav Domnich² ; Fernand Marquis³ ; Myroslav Karpets¹ ; Sergey Dub¹ ; Semyon Ponomarov⁴ ; Richard Haber² ; ¹Institute for Superhard Materials, Kiev, Ukraine; ²Rutgers University, New Brunswick, United States; ³San Diego State University, San Diego, United States; ⁴Institute of Semiconductor Physics, Kiev, Ukraine;
Paper Id: 119 [Abstract]

The results of a structural and mechanical properties study of aluminum dodecaboride (a-AlB₁₂, AlB₁₂C₂, a-AlB₁₂-TiB₂-TiC)- and boron carbide (B₄C and B₄C-SiC)-based ceramics, hot pressed at 30 MPa, 1950 - 2240°C, and high pressure (2 GPa) as well as high temperature (1200-1400°C) sintered and synthesized, will be under discussion. The materials can be used as protective armor or constructional ceramics for nuclear power plants, additives to the boron-carbide-based materials, or as solid fuel, abrasives, explosives, etc. [1-5]. The materials were manufactured from a-AlB₁₂, AlB₁₂C₂, C nanopowders and B₄C, SiC, TiC micropowders. The preliminary mixtures of powders were prepared using high speed planetary activator. The a-AlB₁₂ powder with and without carbon additions can be sintered to the dense state of 1200-1400°C, 2 GPa, 1 h, while the hardness of the materials was not high (12.5-17.8 GPa at 49 N-load). The AlB₁₂C₂ nanopowder sintered at 1400°C, 2 GPa, 1 h contained 89 wt.% AlB₁₂C₂ and 11 wt.% of admixture Al₂O₃ (according x-ray diffraction study) and demonstrated hardness HV(49 N-load)=26.6-0.6 GPa, fracture toughness K_1<i>c</i> (49 N)=5.9-0.5 MPa-m0.5, density g=2.73 g/сm³. The materials obtained at 30 MPa, 2240-1950°C had much higher characteristics. γ-AlB₁₂ (94-98 wt.%, p=2.53-2.58 g/cm³) showed HV(49 N)=24.1 GPa; K_1<i>c</i> (49 N)=4.9 MPa-m0.5; bending R_bs=336 MPa and compressive R_cs=378 MPa strengths. Composite 74 wt.% AlB₁₂C₂, 22 wt% TiB₂ , 4 wt% Al₂O₃ (p=3.1 g/сm3) had HV(49N)=37.65-6.74 GPa, K_1<i>c</i>(49 N)=5.2 MPa-m0.5, R_bs = 646 MPa and R_cs =795 MPa. B4C(p=2.52 g/сm3) demonstrated HV(4.9 N)=40 GPa, K_1<i>c</i> (3-point bending)=4.89 MPa-m0,5, R_cs=392 MPa, R_cs=1551 MPa and B₄C-20%SiC (p = 2.67 g/cm³) had HV(49 N)= 35 GPa, K_1<i>c</i>(3-point bending)=5.9 MPa-m0,5, R_bs=474 MPa, R_cs=1878 MPa.

References:
[1] Kisly, P. S., Neronov, V.A., Prikhna, T. A., Bevza, Yu.B. (1990). Aluminum borides, Kiev, Naukova Dumka, 1-192. (in Russian) (Кислый П. С., Неронов В. А., Прихна Т. А., Бевза Ю. В. Бориды алюминия. К.: Наук. Думка, 1990. 192 с).
[2] Whittaker, M. L., (2012) Synthesis, characterization and energetic performance of metal boride compounds for insensitive energetic materials, Thesis for the degree of Master of Science : - The faculty of the University of Utah Department of Materials Science and Engineering, University of Utah.
[3] Domnich, V., Reynaud, S., Haber, R.A., Chowalla, MJ. Am. Ceram. Soc., 94 (2011) 3605-3628.
[4] Prikhna, Т. A., Barvitskiy P. P., Karpets М. В., Muratov V. B., Sverdun V. B., Haber R., Kartuzov V. V., Moshchil V. E., Dub S. N., Loshak M. G., Alexandrova L. I., Kovylaev V. V., Garbuz V.V., Marchenko A. A., J. Superhard Materials, 39(5) (2017) 299-307.
[5] Prikhna, Т.А., Haber, R. A., Barvitskiy, P. P., Sverdun,V. B., Dub, S. N., Muratov, V. B., Domnich , V., Karpets, М. V., Moshchil, V. E., Loshak, М. G., Kovylaev, V.V., Vasiliev O.O., Proceedings of the 41st International conference and exposition on advanced ceramics and composites, January 22 - 27, 2017, Daytona Beach, Fla., USA., http://acumen-va-publish.com/ACerS/ICACC_2017/toc.html.

15:15: [AdvancedMaterialsWedPM108] Keynote
Process Intensification in Biorefineries – the Way to High Added Value Products
Ludo Diels¹ ; ¹VITO/UA, Mol, Belgium;
Paper Id: 314 [Abstract]

The global trend towards sustainability and resource efficiency urges us to transform our concept of chemical plants and strive for compact, safe, energy-efficient, and environment-friendly sustainable processes. These developments share a common focus on process intensification. At the level of core conversion processes in a biorefinery, one way to achieve process intensification entails combining reaction and separation in such a way that the overall result is more sustainable, delivers better product quality, reduces the equipment size, lowers the solvent use both for (i) bioprocesses and (ii) chemical processes. Several bio-based processes are plagued by limited product titers and volumetric productivities due to product inhibition. Other processes suffer from side reactions decreasing the yield of the process. Many enzymatic reactions are characterized by suboptimal reaction equilibria. For such processes, it can be advantageous to invest in a recovery technology that allows the selective separation of the product during fermentation or biocatalysis. In-situ product recovery (ISPR) is a key technology platform to intensify bioprocesses. Specific cases will be presented and the benefits for the selected processes explained. Clever integration of separation technology can also be beneficial for chemical processes requiring high dilution to prevent precipitation or intramolecular reactions or processes that suffer from substrate inhibition. The concept of volume intensified dilution not only allows to get similar or better yields and purities, but also a considerable reduction of solvent use. In upstream and downstream processing, proper pretreatment of feedstocks to remove inhibitory components and selective separations in downstream processing are essential as well. Bioprocesses have the disadvantage to operate under quite dilute conditions. This means that concentrating the product, re-using the water and desalinating the water are becoming key challenges for the success of future bio-based processes. These challenges will be explained via different examples from practice.

SESSION: AdvancedMaterialsWedPM2-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Hervé Martinez; Xijia Wu; Session Monitor: TBA

15:55: [AdvancedMaterialsWedPM209] Keynote
New Surface Science Investigations for the Knowledge of Electrochemical Energy Storage
Hervé Martinez¹ ; ¹Université de Pau et des Pays de l'Adour - IPREM CNRS UMR 5254, Pau, France;
Paper Id: 9 [Abstract]

It is now generally accepted that the performance of all lithium ion or lithium batteries (including liquid or solid electrolyte) depends on the surface chemistry developed on the electrode / electrolyte interface system. This work presents a contribution to the knowledge of the solid electrolyte interface (SEI) from two different examples: The first one concerns Spinel Li₄Ti₅O₁₂ (LTO) which is considered as a good alternative negative electrode material for Li-ion batteries. The reactivity of LTO toward commons carbonates based electrolytes has been evidenced by surface analysis and an important gassing occurring at the electrode/electrolyte interface was reported. Therefore it is essential to better understand the interfacial phenomena. A precise understanding of the Spinel Li₄Ti₅O₁₂ (LTO) electrode/electrolyte interfaces in relation with batteries (Li₄Ti₅O₁₂/Li half-cells) electrochemical performances is presented. The influence of various parameters (cycling temperature, electrode and electrolyte composition, cycling potential window) upon the SEI formation and dissolution through cycles is investigated. Finally, full cells as Li₄Ti₅O₁₂/LiMn₂O₄ cells having potential assets in term of cost and safety will be investigated, in order to point out the changes in the SEI formation due to interactions between both electrodes. The samples are analyzed using 3 complementary extreme surface characterization techniques XPS-AES-TOF-SIMS (analysis depth 1-10 nm), operating at different spatial resolutions. The second example is related to the recent technological development of miniaturized systems which has induced a strong demand for developing compact power sources with high efficiency and small dimensions that are suitable for portable devices. Among these systems, the lithium microbattery may be relevant for a wide range of applications (microelectronic devices). An all solid state battery LiCoO₂ / LiPON / Li is considered and more specifically the behaviour of the interface between the positive electrode and the solid electrolyte, studied by ion milling cross section / Auger Spectroscopy coupling.

References:
1. T. Ohzuku and A. Ueda (1994) Why transition metal (di) oxides are the most attractive materials for batteries. Solid State Ion., vol. 69, no. 3-4, pp. 201-211
2. D. P. Abraham, E. M. Reynolds, E. Sammann, A. N. Jansen, and D. W. Dees (2005) Aging characteristics of high-power lithium-ion cells with LiNi0.8Co0.15Al0.05O2 and Li4/3Ti5/3O4 electrodes, Electrochimica Acta, vol. 51, no. 3, pp. 502-510
3. J.B. Gieu, V. Winkler, C. Courriges, H. Martinez (2017) New insights in the characterization of the electrode/electrolyte interfaces within LiMn 2 O 4 /Li 4 Ti 5 O 12 cells, by X-ray Photoelectron Spectroscopy, Scanning Auger Microscopy and Time-of-Flight Secondary Ion Mass Spectrometry. Journal of Materials Chemistry A, 5 (29)
4. Salot, R.; Martin, S.; Oukassi, S.; Bedjaoui, M.; Ubrig, J. (2009) Microbattery Technology Overview and Associated Multilayer Encapsulation Process. Appl. Surf. Sci., 256 (3 SUPPL.), S54-S57
5. Uhart, J.B. Ledeuil, B. Pecquenard, F. Le Cras, M. Proust, H. Martinez (2017) Nanoscale chemical characterization of solid state microbattery stacks by means of Auger Spectroscopy and ion-milling cross-section preparation. ACS Applied Materials & Interfaces, 9 (38), pp 33238-33249

16:20: [AdvancedMaterialsWedPM210] Keynote
Material Life Prediction for Sustainable Development
Xijia Wu¹ ; ¹National Research Council Canada, Ottawa, Canada;
Paper Id: 199 [Abstract]

Sustainable development demands advanced materials to transform or conserve energy, which have to satisfy the durability requirements under working conditions with enhanced energy performance. Constitutive modeling and life prediction are core tasks for durability design, especially with thin margins at increasing operating temperature and lowering weight. Traditionally, these two tasks were handled separately, via phenomenological approaches that employ too many empirical correlations, with parameters that do not physically connect to each other. This is not the way to go, when facing the challenges of sustainable development. Recently, an integrated creep-fatigue theory (ICFT) has been developed, which constructs the material constitutive law based on physical decomposition of the total deformation as the sum of elastic strain, rate-independent plastic strain, intragranular dislocation glide, climb, as well as grain boundary sliding [1]. This mechanism-based approach allows delineation of inelastic deformation in creep, fatigue, and thermo-mechanical fatigue into mechanism strains, which in turn describes the various forms of physical damage, such as persistent slip bands, grain boundary cavitation and cracking in relation to the responsible mechanism(s), respectively. Furthermore, the holistic damage accumulation in a material under random thermomechanical loading generally consists of nucleation of surface/subsurface cracks by fatigue [2], environmental effects, and their propagation in coalescence with internally distributed damage such as cavities promoted by creep. Application of ICFT to creep has led to a deformation mechanism-based true-stress (DMTS) model that describes the three-stage creep behaviour with the influence of oxidation [3]. The DMTS model can be used for long-term creep life prediction. Application of ICFT to low-cycle fatigue and thermomechanical fatigue of ductile cast iron and austenitic cast steels has demonstrated that the complicated hysteresis behaviors are governed by fundamental deformation mechanisms operating under the corresponding loading profiles [4,5,6]. In general, ICFT provides an integrated approach to constitutive modeling and life prediction with the physics-based "genome" to include all effects of environment and material internal damage, enabling a holistic durability analysis for materials under user-specified loading profiles.

References:
[1] X.J. Wu, Key Engineering Materials 627 (2015) 341-344.
[2] X.J. Wu, Fat. Fract. Eng. Mat. & Struct. (2017) DOI: 10.1111/ffe.12736.
[3] X.Z. Zhang, X.J. Wu, R. Liu, J. Liu, M.X. Yao, Materials Science & Engineering A 689 (2017) 345-352.
[4] X.J. Wu, G. Quan, R. MacNeil, Z. Zhang, C. Sloss, Metall. and Mater. Trans. 45A (2014), 5088-5097.
[5] X.J. Wu, G. Quan, R. MacNeil, Z. Zhang, X. Liu, C. Sloss, Metall. and Mater. Trans. 46A (2015) 2530-2543.
[6] X. J. Wu, G. Quan, and C. Sloss. Metall. and Mater. Trans A. 48A (2017) 4058-4071.

16:45: [AdvancedMaterialsWedPM211]
MIEC-type A₂BO₄ Ceramic Membranes with Enhanced Oxygen Permeation
Konrad Swierczek¹ ; ¹AGH University of Science and Technology, Faculty of Energy and Fuels, Krakow, Poland;
Paper Id: 194 [Abstract]

Membrane technology is successfully commercialized in various industrial applications, e.g. in treatment of chemicals, food, gas, water or wastewater. Recently it has also emerged in clean and renewable power applications [1]. In particular, dense ceramic membranes having mixed ionic-electronic conductivity (MIEC) can be used for the production of a high purity hydrogen and oxygen via gas separation route, but also for preparation and processing of syngas, e.g. by a partial oxidation of methane. Such membranes can be applied as well in gas separation technology [2]. For instance, oxygen can be preferentially transferred from a gas mixture through the MIEC membrane, allowing to obtain a high-purity O₂ for further usage. Many considered MIEC-type oxides, candidate membrane materials which exhibit high mixed ionic-electronic transport properties, and possess either perovskite-type or perovskite-related crystal structure. In such compounds, the electronic component of the electrical conductivity is governed by a double exchange mechanism, while the ionic component in ABO_3-δ perovskite-type oxides proceeds by the oxygen vacancy mechanism. However, depending on the chemical composition, temperature, and the oxygen partial pressure, A₂BO_4±δ compounds may exhibit ionic transport through the oxygen vacancies or the interstitial oxygen. Movement of the interstitial oxygen is unique, due to a low activation energy but also nature of the transport, which is described as the interstitialcy mechanism [3, 4]. Unfortunately, due to the 2D-type conduction in A₂BO_4±δ, the observed macroscopic conductivity of polycrystalline sinters is relatively low. In this work, various approaches are discussed concerning methods of enhancement of the oxygen permeation through A₂BO_4±δ ceramic membranes, including preparation of a functional layer having 3D conductivity and introduction of the A-site nonstoichiometry and the B-site doping. It is shown that the A-site deficient A_2-xCu_1-yNi_yM_zO_4±δ (A - larger lanthanides, M - Sc³⁺, Ga³⁺) possess excellent transport properties, and are a suitable basis for the development of a highly-conducting, barium-free, dense ceramic membranes, which can be further enhanced with the functional layer.

References:
[1] A. Gugliuzza, A. Basile (Editors), Membranes For Clean And Renewable Power Applications, Woodhead Publishing Limited, 2014.
[2] K. Li, Ceramic Membranes For Separation And Reaction, John Wiley & Sons Ltd, 2007.
[3] A.C. Tomkiewicz, M. Tamimi, A. Huq, S. McIntosh, J. Mater. Chem. A 3 (2015) 21864.
[4] T. Ishihara (Editor), Perovskite Oxide for Solid Oxide Fuel Cells, Springer, 2009.

17:10: [AdvancedMaterialsWedPM212]
Application and Results of Oxipyr®-diluted Combustion in Aluminum Furnaces
Michael Potesser¹ ; Johannes Rauch¹ ; ¹Messer Group GmbH, Gumpoldskirchen, Austria;
Paper Id: 117 [Abstract]

Diluted, mild, or flameless oxyfuel combustion has shown huge successes in past years as an optimization tool for different high temperature applications. This innovative combustion technology has a lower flame temperature, more uniform temperature distribution, and low concentrations of oxygen as well as nitrogen inside the furnace, leading to low fuel consumption and very low NOx levels. In this work, we analyze the optimization processes of different types of rotary and reverberatory furnaces (fix, tiltable) with Messer Oxipyr® burners, which led to impressive savings, dross reduction, and ecological improvements for the customers. A review of the available literature on this topic is also given.

References:
[1] Davis F.W.: Report of Investigations no. 2502, Washington, D.C.: Bureau of Mines, July 1923
[2] Wünning J.W.: Thermprocess Symposium 2003
[3] Wünning J.A., Wünning J.W.: Prog. Energy Combust.Sci.Vol.23., 1997, p.81-94
[4] Anderson J.E.: Symposium of Industrial Combustion Technologies, 1986, p.329-334
[5] Ryan H.M. et al.: Dilute Oxygen Combustion - Phase I Report, Report No. DOE/ID/1331-T1, U.S. Department of Energy, Washington, DC, October 1997
[6] Riley M.F., Kobayashi H., Deneys A.C.: JOM, May 2001, p.21-24
[7] Spoljaric D., Potesser M., Holleis B., Demuth M., Rauch J.: Proceedings of the 3rd Euroasia Mena Steel Summit, 22-23.January 2013.
[8] Potesser M., Holleis B., Demuth M., Spoljaric D., Zauner J.: Cu 2010, Vol.2, Pyrometallurgy I,(2010), GDMB, pp.1051-1060
[9] Potesser M., Holleis B., Spoljaric D., Antrekowitsch H.: Stahl und Eisen 2008, Pages 59-63
[10] Potesser M., Holleis B., Spoljaric D.: BHM, 153. Jg. (2008), Heft 3, S 121-125
[11] Blasiak W.,Yang W. H., Narayanan K., Sche'ele J.: Journal of the Energy Institute 2007, Vol. 80, No. 1, p.3-11
[12] U. Boin, T. Linsmeyer, F. Neubacher, B. Winter: Stand der Technik in der Sekundäraluminiumerzeugung, Band 120, M-120, Wien, 2000.
[13] U.S. Energy Requirements for Aluminum Production, Historical Perspective, Theoretical Limits and Current Practices, February 2007
[14] D.Spoljaric and D.Wieck: Recycling aluminium with oxygen combustion technology, Aluminium International Today, July/ August 2003, p.26-28.

SESSION: AdvancedMaterialsWedPM3-R6	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Guaratiba (60/2nd)
Session Chairs: Pavle Radovanovic; Session Monitor: TBA

17:40: [AdvancedMaterialsWedPM313] Keynote
Plasmonic Semiconductor Nanocrystals as Multifunctional Materials
Pavle Radovanovic¹ ; ¹University of Waterloo, Waterloo, Canada;
Paper Id: 380 [Abstract]

Synthesis, properties, and applications of plasmonic nanostructures with tunable localized surface plasmon resonance (LSPR) have been a subject of intense investigation over the past decade. Unlike typical metal nanoparticles, colloidal plasmonic semiconductor nanocrystals have LSPR frequencies tunable in the near- to mid-infrared region, which can potentially allow for their applications in terahertz imaging, heat-responsive devices and surface-enhanced infrared spectroscopic techniques [1]. Furthermore, the ability to control type and concentration of charge carriers, as well as their activation, trapping, and scattering via nanocrystal composition and/or surface chemistry allows for fine tuning of the energy, band width, and quality factor of LSPR in semiconductor nanocrystals. Besides expanding the LSPR range, semiconductor nanocrystals bring about numerous other opportunities related to single-phase plasmon-exciton interactions. However, non-resonant nature of the LSPR and exciton in semiconductor nanocrystals has been a major obstacle toward realizing such opportunities. This talk will first introduce the general properties of colloidal plasmonic semiconductor nanocrystals and compare them with those of noble metal nanoparticles. Then, various ways of generating and controlling the type, concentration, and mobility of charge carriers in these materials [2] will be reviewed. The second part of the talk will focus on the results of our recent work on structure and composition dependent plasmonic properties of transparent metal oxide nanocrystals [3,4], and particularly on generating robust electron polarization in degenerately-doped In₂O₃ nanocrystals owing to non-resonant magnetic-field-induced plasmon-exciton coupling [5]. Applications of these materials for photocatalysis, solar energy conversion, and new energy-efficient and sustainable electronic and quantum information technologies will also be discussed. The talk will conclude with general outlook, and future research directions.

References:
[1] Comin, A.; Manna, L. Chem. Soc. Rev. 2014, 43, 3957-3975.
[2] Runnerstrom, E. L.; Bergerud, A.; Agrawal, A.; Johns, R. W.; Dahlman, C. J.; Singh, A.; Selbach, S. M.; Milliron, D. J. Nano Lett. 2016, 16, 3390-3398.
[3] Wang, T.; Radovanovic, P. V. J. Phys. Chem. C 2011, 115, 406-413.
[4] Fang, H.; Hegde, M.; Yin, P.; Radovanovic, P. V. Chem. Mater. 2017, 29, 4970-4979.
[5] Yin, P.; Tan, Y.; Fang, H.; Radovanovic, P. V. Nat. Nanotechnol. 2018, 13, 463-467.

18:05: [AdvancedMaterialsWedPM314]
Self-regulation of Living Spaces Through Material Multi-functionality
Tahir Cagin¹ ; Ergun Akleman² ; Terry Creasy² ; Negar Kalantar² ; Zofia Rybkowski³ ; ¹Texas A&M University, College Station, United States; ²Texas A&M University, college station, United States; ³Texas A&M University, college Station, United States;
Paper Id: 255 [Abstract]

We envision living spaces and structures that could self-regulate their comfort and utility levels such as temperature, light, or air purity, in response to cyclic external environmental changes occurring in nature. The concept of self-regulation is natural for biological structures such as plants, which can regulate their internal parameters that do not require a centralized control. With current advances in materials science and engineering focusing on development of multi-functional materials, design and control of materials' microstructures, as well as advances in architectural design of functional units and architectured materials, it has become possible to construct self-regulatory structures without sensors or centralized control. By using materials that can self-modify their form and morphology in response to localized environmental cues such as gradient changes in temperature, vapor pressure, mechanical pressure, and pH, there exists the potential to modify permeability of air, water, and heat transfer across a structure's skin, as well as modulate light and other comfort related parameters. The design principle underscoring this perspective is to apply non-equilibrium statistical thermodynamics, which governs the behavior of dynamic systems as a function of field gradients; eg.. temperature gradient leading to energy flow, concentration gradients montioring mass flow and potential gradient guiding eurrent flow. The level and treshold of the flows is guided by the materials response functions — thermal conductivity, viscosity, resistivity, and other coupled transport coefficients. There are many existing highly active functional materials, such as shape memory alloys, bi-metallic strips, stimuli-responsive polymers, dendritic or star polymers, abundant phase changing materials and piezoelectric materials, that can provide such self-regulatory behavior [1-5]. We will describe various materials systems that provide opportunities in design materials and material systems for construction of self-regulating structures.

References:
[1] J.B. Haskins, A. Kinaci, T. Çağın, “Molecular Dynamics Simulations of Piezoelectric Materials for Energy Harvesting Applications,” Materials Science Forum 792, 54-64 (2014).
[2] S. Ozdemir Kart, M. Uludogan, I. Karaman, and T. Çağın, “DFT Studies on Structure, Mechanics and Phase Behavior of Magnetic Shape Memory Alloys: Ni2MnGa” Phys. Stat. Sol. (a) 205, 1026-35 (2008).
[3] T. Çağın, G. F. Wang, R. Martin, N. Breen, W. A. Goddard, “Molecular Modeling of dendrimers for nanoscale applications,” Nanotech. 11, 77-84 (2000).
[4] A. Chakrabarty, T. Çağın, “Thermo-mechanical Properties of a piezoelectric polyimide carbon nanotube composite: Assessment of Composite Theories,” Comp. Mater. Sci. 92, 185-191 (2014).
[5] P. K. Maiti, T. Çağın, S-T Lin, and W. A. Goddard, III, Effect of Solvent and pH on the Structure of PAMAM Dendrimers, Macromol. 38, 979-991 (2005).

SESSION: Non-ferrousMonAM-R7	6th Intl. Symp. on Sustainable Non-ferrous Smelting and Hydro/Electrochemical Processing
Mon Nov, 5 2018 / Room: Pontal (50/2nd)
Session Chairs: Margarita Gutierrez-Ruiz; Gustav Hanke; Session Monitor: TBA

11:20: [Non-ferrousMonAM01] Plenary
Applications and Market of Rare-earths
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 334 [Abstract]

Rare-earths have many applications in the high-technology industry, especially for magnets and luminescent phosphors, which are also important for lasers and optical fibers. This paper reviews the current trends of the market, wherein a crisis emerges: although the typical rare-earth ore - monazite - has ~45% Ce, 30% La, 15% Nd, and 5% Pr, cerium and lanthanum are at 1/25 of the price of neodymium. Elements as Cerium and Lanthanum often do not have a market and need to be stockpiled by the mining companies. Thus, the rare-earth market is now driven my magnets, and elements such as terbium, dysprosium, and holmium are among the most needed by the market, besides neodymium and praseodymium. Until recently, europium was strongly used as phosphor in all TVs, including plasma TVs. But now LED TVs obtain white color principally by mixing blue LED and a yellow phosphor that uses the cheap yttrium and cerium. In this presentation, a review of the present situation of the Brazilian rare-earth industry [1], and methods for rare-earth reduction, are provided.

References:
[1] M. F. de Campos,D. Rodrigues, J. A. de Castro. Perspectives for the Brazilian Industry of Rare-Earth Magnets Materials Science Forum v. 869 (2016), 602-607.
[2] J. A. de Castro, D. Rodrigues, M. F. de Campos. Model development based on transport phenomena principles for simulating neodymium reduction within electrowining cells. Proceedings of 24rd International Workshop on Rare Earth and Future Permanent Magnets and Their Applications REPM 2016, 2016, Darmstadt, Germany. p. 664-671.

11:45: [Non-ferrousMonAM02] Keynote
Characterization Strategies for Metallurgical by-Products: Case Study Jarosite
Juergen Antrekowitsch¹ ;⁰ ; Gustav Hanke¹ ; ¹University of Leoben, Leoben, Austria;
Paper Id: 447 [Abstract]

Metallurgical treatment of ore concentrates produces high amounts of different by-products. These materials often contain high grades of different metals, but are dumped in many cases as there is actually no method of an economical treatment available. For developing, or adapting a proper process, detailed knowledge of the materials characteristics is needed. The chemical composition is relatively easy to determine using standard analytical methods but can only be seen as a first, very general step. Mineralogical characterization is of prime importance to identify and quantify phases carrying the metals of interest as well as valueless phases. The final aim is to develop a characterization procedure which defines the appropriate analytical methods for specific materials. Actually precipitation- and leach-residues from hydrometallurgical zinc production (jarosite) are in the focus of research at University of Leoben. The material contains different valuables such as zinc, lead, copper and silver. Various methods (XRF, ICP-MS, etc.) have been used for chemical analysis as well as XRD for identification of major phases. Scanning electron microscopy is the tool of choice for identifying minor phases and chemical analysis of single grains. So far, the value of the material has been proven. Further work will focus on quantification of already accomplished results.

References:
[1] Balladares E, Kelm U, Helle S, Parra R, Araneda E. 2014. Chemical-mineralogical characterization of copper smelting flue dust. Dyna. Volume 81(186). p.11-18.

[2] Piatak N M, Seal R R, Hammarstrom J M, Meier A L, Briggs P H. 2003. Geochemical Characterization of Slags, Other Mine Waste, and Their Leachate from the Elizabeth and Ely Mines (Vermont), the Ducktown Mining District (Tennessee), and the Clayton Smelter Site (Idaho). US Geological Survey. Open-File Report 03-260.

[3] Rizescu C, Bacinschi Z, Stoian E, Polinescu A. 2010. Characterisation of steel mill electric-arc furnace dust. In: Advances in waste management. 4th WSEAS International Conference on Waste Management, Water Pollution, Indoor Climate (WWAI �10). p.139-143.

[4] Vere� J, �epel�k V, Hredz�k S. 2015. Chemical, mineralogical and morphological characterisation of basic oxygen furnace dust. In: Mineral Processing and Extractive Metallurgy, Volume:124(1), p. 1-8.

[5] Jamieson H E, Walker S R, Parsons M B. 2015. Mineralogical characterization of mine waste. In: Applied Geochemistry. Volume 57. P. 58-105.

[6] Hanke G, Antrekowitsch J. 2018. Characterisation and pyrometallurgical recycling of jarosite type residues out of zinc primary metallurgy. In: World of Metallurgy � Erzmetall. Volume 71.1. p. 25-30.

[7] Pappu A, Saxena M, Asolekar S R. 2006. Jarosite characteristics and its utilization potentials. In: Science of the Total Environment. Volume 359.1. p 232-243.

[8] Sinclair R J. The Extractive Metallurgy of Zinc. Victoria (Australia): Australasian Institute of Mining and Metallurgy; 2001. p.31-105.

[9] Onuk P, Melcher F, Mertz?Kraus R, G�bler H E, Goldmann S. 2017. Development of a Matrix?Matched Sphalerite Reference Material (MUL?ZnS?1) for Calibration of In Situ Trace Element Measurements by Laser Ablation?Inductively Coupled Plasma?Mass Spectrometry. In: Geostandards and Geoanalytical Research. Volume 41(2). p. 263-272.

[10] Wilson S A, Ridley W I, Koenig A E. 2002. Development of sulfide calibration standards for the laser ablation inductively-coupled plasma mass spectrometry technique. In: Journal of Analytical Atomic Spectrometry. Volume 17(4). p. 406-409.

11:45: [Non-ferrousMonAM02]
Characterization and Process Development for Leaching Residues
Gustav Hanke¹ ; ¹University of Leoben, Leoben, Austria;
Paper Id: 359 [Abstract]

Currently, Zinc is mainly produced via the hydrometallurgical route, generating huge amounts of iron precipitation residues. These materials are mainly dumped, due to missing economic treatment options. For the development of possible processes, detailed knowledge of the materials characteristics is mandatory. Beside chemical composition, mineralogical characterization is of importance to identify present phases containing valuable components. University of Leoben has a special focus on such precipitation residues with the aim to develop guidelines how to evaluate such materials which show a certain challenge, especially because of the fineness of the residue. Nevertheless, it has been found at many sites worldwide that, depending on the primary zinc winning process, interesting values of lead, zinc and silver are present, turning the waste into an interesting secondary resource. Various methods (XRF, ICP, XRD etc.) have been used for chemical analysis and the identification of major phases. Scanning electron microscopy is an appropriate choice for the definition of minor phases and chemical analysis of single grains. The successful characterization of such materials forms the base for different processing concepts to utilize currently unused secondary resources.

12:10: [Non-ferrousMonAM03] Keynote
Determination of Bioaccessibility of As and Pb in Soils Polluted With Mining Wastes: A New Equipment That Simplifies the Gastric and Intestinal Phases Measurements
Thalia Rodriguez¹ ; Margarita Gutierrez Ruiz² ; Daniel Quiroz Vivanco² ; Agueda Ceniceros² ; Tania Tavares³ ; Arturo Aguirre Gomez⁴ ; ¹Faculdad de Quimica, UNAM, Mexico, Mexico; ²UNAM, Mexico, Mexico; ³UFBA, Rio de Janeiro, Brazil; ⁴FES Cuautitlan UNAM, Cuautitlan, Mexico;
Paper Id: 365 [Abstract]

The Mexican environmental standard for the remediation of polluted soil (NOM-147) contains an option to determine the remediation objectives based on human health risk assessment, using as a correction factor the bioavailability in vitro (bioaccessibility) [1, 2], in the gastric phase. Some studies in animals show that to determine bioaccessibility, it is better to take into consideration the gastric and intestinal phases [2].<br /> <br />To expedite the measurements of bioaccessibility a simple and low-cost equipment was developed which allows pH control and the addition of reagents without interrupting the process. This simplifies the measurement in the gastric and intestinal phases based on physiological extraction method (PBET) [3]. The new equipment was evaluated by measuring the bioavailability and bioaccessibility of As and Pb on standard reference soil (NIST Montana 2710). The results were compared with those reported by 14 laboratories [4]. The bioaccessibilties of Pb and As, considering only the gastric phase, were they like the results obtained "in vivo". The results including both phases were out of the "in vivo" range but were similar to the international results. We recommended the substitution of the equipment required by the NOM-147 [5] with the new extraction equipment designed to improve the procedure.

References:
[1] Boros K., Fortin, D, Jayawardene I., Chenier M. Levesque C. and Rasmussen, P.E, 2017. Int J Environ Res Public Health. 14(1): 92.\n[2] Brooke N. S. [Dissertation] Graduate School of The Ohio State University. 2016. 176 p.\n[3] M,V. Ruby, A. Davis, R. Schoof, S. Eberle, M. Sellstone, M. Environ. Sci. Technol. 30 (1996) 422-30.\n[4] I. Koch, et al., Journal of Environmental Science and Health, Part A: Toxic/Hazardous Substances and Environmental Engineering, 48 (2013) 641-655.\n[5] NOM-147. The official Mexican Standard NOM-147-SEMARNAT/SSA1-2004, that establishes the criteria to determine the concentrations of remediation of soil contaminated by heavy metals.

12:35: [Non-ferrousMonAM04] Keynote
Application Study on Technology of Reducing Copper Content in Discarded Slag
Zhi Wang¹ ; Ruimin Bian¹ ; Chuanbing Wei¹ ; Baojun Zhao² ; Haibin Wang¹ ; Wenzhao Cui¹ ; ¹Dongying Fangyuan, Dongying, China; ²The University of Queensland, Brisbane, Australia;
Paper Id: 65 [Abstract]

Effects of flux, vulcanizing agent and reductant on slag cleaning in new-type slag cleaning furnace (Φ3.6×8.1m) were investigated under the conditions including smelting temperature of 1200°C and 1250°C, settling time of 30 min and 60 min, and Fe/SiO2 of 1.7-1.9. The results show that addition of SiO2, B2O3 or CaF2 into original copper smelting slag can improve settling separation effect. Though no effect on copper recovery, addition of FeS can provide heat required by reaction with oxygen and reduce copper dissolution in spinel phase and slag. Copper content in discarded slag can be controlled at 0.26% under the optimum comprehensive conditions with ratio of oxygen to natural gas of 1.6.

References:
[1] BIAN R M. ZHAO B J. LI X. National and international S&T cooperation project, technical report of "Associated research and development of the technology and apparatus of reducing Cu content in discarded slag"[R]. Dongying Fangyuan Nonferrous Metals Co., Ltd, 2013.\n[2] MA X D. ZHAO B J. Progress report of Fangyuan copper smelting slag cleaning by pyro metallurgical route [R]. Chemical and Engineering Academy of UQ. 2014. \n[3] BIAN R M. YUAN J Z. CHEN J H. Copper smelting slag cleaning method and techno-economic analysis [J]. Nonferrous Metal (Smelting Section). 2012. 14-17.\n[4] CHEN M.CUI Z. ZHAO B. Slag chemistry of Bottom Blown Copper Smelting Furnace at Dongying Fangyuan[C]//Proceedings of 6th International Symposium on High-Temperature Metallurgical Processing. 2015:257-264.\n[5] CHEN M. ZHAO B J. Viscosity measurements of SiO2-FeO-CaO system in equilibrium with metallic Fe [J]. Metallurgical and Materials Transactions. 2015.46(2):577-584.\n[6] SHUI L. CUI Z. MA X.et al. Mixing phenomena in a Bottom Blown Copper Smelter; A water model study[J].Metallurgical and Materials transactions B. 2015.46(3):1218-1225.

SESSION: Non-ferrousMonPM1-R7	6th Intl. Symp. on Sustainable Non-ferrous Smelting and Hydro/Electrochemical Processing
Mon Nov, 5 2018 / Room: Pontal (50/2nd)
Session Chairs: Pavel Kozlov; JiWhan Ahn; Session Monitor: TBA

14:00: [Non-ferrousMonPM105] Plenary
A New Sustainable Process for the Gasification Coal Fines and Recovering of Metals and Alumosilicates from their Ashes
Valentin Tsymbal¹ ; Inna Rybenko¹ ; Alexey Olennikov² ; Pavel Sechenov¹ ; Florian Kongoli³ ; ¹Siberian State Industrial University, Novokuznetzk, Russian Federation; ²Tyumen State University, Tyumen, Russian Federation; ³FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 208 [Abstract]

This new process makes possible the gasification of any pulverized coal waste in a suspended layer of slag and produces a synthetic gas, various metals that are simultaneously reduced from the coal ash and a highly porous aluminosilicate slag-microspheres that can be used in various fields. The input stream consists only of coal from waste and other reactants, including oxygen for burning the coal are obtained internally within the same process flowsheet. This process is based on the previously developed jet-emulsion reactor technology SER, intended for direct reduction of pulverized metallurgical wastes and ores. It is a sustainable process since it does not produce any waste and is energetically self-sufficient. It can also be designed in a mobile version that can be placed near waste generation sites or in remote places from electrical networks.

References:
[1] V.P. Tsymbal, S.P. Mochalov, I.A. Rybenko, R.S. Ayzatulov, V.V. Sokolov, A.G Padalko, V.I. Kozhemyachenko, S.Y. Krasnopyorov, K.M. Shakirov, S.N. Kalashnikov, L.A. Ermakova, A.A. Olennikov, A.M. Ognev, S.V. Szczepanov, A.A. Rybushkin, E.V. Suzdaltsev, Moscow: Metallurgizdat, (2014) 488.\n
[2] V.P. Tsymbal, A.A. Olennikov, V.I, Kozhemyachenko, I.A. Rybenko, F. Kongoli, SIPS 2015 (Sustainable Industrial Processing Summit), Volume 2, (2015) sips15_2_453FS.\n
[3] V. Tsymbal, A. Olennikov, I. Rybenko, V. Kozhemyachenko, E. Protopopov, F. Kongoli, Sustainable Industrial Processing Summit & Exhibition SIPS 2016 Volume 1: FLOGEN Star Outreach. (2016) 214-227.\n
[4] V. Tsymbal, A. Olennikov, I. Rybenko, P. Sechenov, F. Kongoli, Sustainable Industrial Processing Summit & Exhibition SIPS 2017 Volume 9: FLOGEN Star Outreach. (2017) 104-115.\n
[5] V.P. Tsymbal, S.P. Mochalov, I.A. Rybenko, Yu.V. Tsymbal, Patent 2371482 Russia C1, Publ. 27.10.2009, Bul. 30.\n
[6] G.A. Terentev, V.M. Tyukov, F.V. Smal, Мoscow, Chemistry (1989) 271.\n
[7] N. Plate, Journal Science and life (2004) 11, 66-68.\n
[8] G-D. Shilling, B. Bonn, U. Kraus, Мoscow, Nedra (1986) 175.\n

14:25: [Non-ferrousMonPM106] Keynote
Feasibility of Producing Caustic Calcined Magnesia in Multiple Hearth Furnaces
Musa Rizaj¹ ; Nurten Deva² ; Edward Z. Obrien³ ; Florian Kongoli⁴ ; ¹Prishtina University, Prishtina, Kosovo; ²Public University of Mitrovice - Isa Boletini - , Faculty of Geosciences, Republic of Kosova, Mitrovice, Kosovo; ³FLOGEN Technologies, Wilmington, United States; ⁴FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 386 [Abstract]

The magnesite (MgCO₃) obtained from the magnesite mine in Strezovc, Kosovo is used as the raw material to produce caustic calcined magnesia (CCM) using roasting in rotary furnaces. The process takes place at temperatures between 600-850°C, which enables complete dissociation of magnesium carbonate and produces CCM as a very active powder. The ore enters at one end of the rotary furnace, passes through it in rotary movement, while the temperature increases and CCM is obtained at the end of the furnace. One the disadvantages of this process is the large amount of dust in the gas that reaches up to 30-35% of the total amount of raw materials. An alternative technology of producing CCM is the Multiple Hearth Furnace, which is a vertical furnace with a number of circular hearths on top of each other, a central shaft, rakes and rabble arms. The ore enters in the upper parts of the furnace and moves toward the floor through multiple hearths while gases go in opposite directions, heating the materials that come down towards the floor. The object of this work is to evaluate, in cooperation with FLOGEN Technologies Inc. Canada/USA, the feasibility of producing CCM in the Multiple Hearth Furnace instead of the rotary furnace in terms of technical, economic, and environmental aspects.

15:15: [Non-ferrousMonPM108] Keynote
Hydrometallurgical Processing of Industrial Copper Waste With Tin Recovery
Pavel Kozlov¹ ; A. Panshin² ; Sergey Yakornov³ ; ¹UMMC-Holding, Moscow, Russian Federation; ²UMMC-Holding, Verkhnyaya Pyshma, Russian Federation; ³UMMC-Holding, Verkhnya Pyshma, Russian Federation;
Paper Id: 406 [Abstract]

Pyrometallurgical processing of copper-containing secondary raw materials and concentrates at industrial copper plants produce annually more than 1 million tons of furnace and converters dusts that are polymetallic materials with complex composition, containing mainly zinc, lead, tin as well as copper, iron and other impurities such as halogens and arsenic, that are undesirable for hydrometallurgical processing of zinc. A technology has been developed to treat these dusts that consists of two combined stages of pyrometallurgy and hydrometallurgy. Lead is removed during the pyrometallurgical stage while zinc recovers into the solution during the hydrometallurgical stage. Iron, copper, and other calcine components are dissolved, and a solid residue is obtained that concentrates tin. The purpose of this paper is to describe the hydrometallurgical stage that consists of high-temperature leaching of calcine and washing of cake. During this stage the zinc recovery into the solution is more than 98% and the tin recovery into solid product is 85%. Depending on tin percent in the original feed, the expected content of tin in the obtained concentrate is 14-20%, which makes a sellable product to the plants that specialize in the processing of tin-containing materials

SESSION: Non-ferrousMonPM2-R7	6th Intl. Symp. on Sustainable Non-ferrous Smelting and Hydro/Electrochemical Processing
Mon Nov, 5 2018 / Room: Pontal (50/2nd)
Session Chairs: Shefik Imeri; Andrej Ivanič; Session Monitor: TBA

15:55: [Non-ferrousMonPM209] Invited
Production of Glass Wool From the Liquid Slag of a 42 MW Electric Arc Furnace for Fe -Ni Production in Newco Ferronickel
Shefik Imeri¹ ; Florian Kongoli² ; ¹MIM-GOLESH, Prishtina, Kosovo; ²FLOGEN Technologies Inc., Mont-Royal, Canada;
Paper Id: 60 [Abstract]

The liquid slag with chemical composition 55- 70 % SiO₂; 0 - 7 % Al₂O₃; 0 - 5 % Fe₂O₃; 5 - 13 % CaO and 0 -5 % MgO, is sufficient raw material for glass wool production [1]. Part of the electric arc furnace slag, which is currently being discharged as a sterile material, can be used directly from a 42 MW electric arc furnace for Fe-Ni production, in a liquid state to produce glass wool. The liquid slag from the electric arc furnace flows continuously through a special channel via a feeder to the fiberizing machine for the fiberizing process (creation of the fibers), and the blanket then passes through a curing oven, normalizing its structure and achieving its final thickness as a final glass wool product. Glass wool production as a new product will have positive impacts of increasing the profits of the company and significantly decreasing the production cost of Ni. In a subsequent future article, an overall glass wool production line, with all details and technical explanations will be presented.

References:
[1] Analysis of the composite materials having a structure of the mineral fibers based on the non-invasive spectroscopic methods. Wioleta ŚMISZEK-LINDERT, Anna BAJOREK, Jerzy KUBACKI.(CHEMIK 2015, 69, 7, 411-418)

16:20: [Non-ferrousMonPM210]
Studying Effective Parameters in Reduction Waste Copper of Electrical Resistance Furnace Slag in Khatoonabad Smelter
Moein Koochaki¹ ; ¹National Iranian Copper Industries Company, Tehran, Iran, Iran;
Paper Id: 326 [Abstract]

The process of extracting copper in the copper smelting plant in Khatoon Abad is by the method of flash smelting. Copper slay is a byproduct produced from matte smelting and copper refinery. This slay contains 1-3% of copper. Electric resistance furnace is mainly used for copper recycling from slay under 1% of output copper and production with value added. In this research, sampling of in input slay, output matte and slay within 6 months has been done for reduction of output copper percentage from electric furnace. XRF and XRD experiments, mesh copper particles and photomicrography of samples were determined, and the temperature variations of input slay and output matte, height variations of electrode immersion in the slay and its power consumption, and proportion of Fe/SiO₂ of input slay were investigated. The result demonstrates that coke charge reduces oxidizing copper and reduces its loss in the slag, as well as the position of electrode in slay bath and the depth of slay lager change in the energy distribution. As for operational conditions of profile furnace and variations of proportion of Fe in ferro silicate, slay is effective with more filtration of slay from copper, and granularity of copper particles in input and output slay is effective with better extraction of copper. By controlling these cases, on average the percentage of copper in the output slay decreased to 0/5 weight percent, and that created significant savings.

References:
[1] John w. Goth, August, 1951. AN INVESTIGATION OF THE ELECTRIC SMELTING OF COPPER CONCENTRATES. McGill University: Montreal, Canada
[2] R.H. Eric, Jan. 2004, Slag properties and design issues pertinent to matte smelting electric, South African Institute of Mining and Metallurgy
[3] Basic design of factory 2001

16:45: [Non-ferrousMonPM211] Invited
Freeze/Thaw Performance of Concrete with Addition of Fly Ash and Recycled Rubber
Andrej Ivanič¹ ; Sebastian Toplak¹ ; Samo Lubej¹ ; ¹University of Maribor, Maribor, Slovenia;
Paper Id: 236 [Abstract]

The concrete industry is one of the major consumers of natural resources. The main aim of sustainable development is to find alternative resources, which could decrease negative effects of the concrete industry on the environment and contribute to the preservation of natural resources. Huge amounts of waste tires accumulated all over the world are recognized as a good supplement for natural aggregates in concrete [1], while the fly ash is used as a replacement for Portland cement in concrete owing to its pozzolanic properties [2]. It is important to protect the environment, conserve the topsoil, and prevent dumping of fly ash from thermal power stations on land and to promote utilization of fly ash in the manufacture of building materials and construction activity. In this paper, an experimental investigation of the freeze/thaw performance on the concrete with recycled waste tire rubber and fly ash addition was conducted. As a partial substitute for the Portland cement, two types of fly ash were used and the specific part of mineral aggregate was replaced by recycled rubber particles. Half of the samples were subjected to freeze/thaw cycles in order to compare their mechanical properties with concrete samples not treated in the temperature chamber. All samples were also tested for compressive strength and modulus of elasticity. Test results indicated that there was a significant improvement of concrete resistance to freezing and thawing, which was also observed by other researchers [3]. However, the freezing and thawing did not affect the compressive strength and modulus of elasticity as much as these features were affected by the choice of fly ash.

References:
[1] D. Bjegović, A. Baričević, M. Serdar, Durability Properties of Concrete with Recycled Waste Tyres, International Conference on Durability of Building Materials and Components, Porto, Portugal, 2011.

[2] A. N. Scott, M. A. D. Thomas, Evaluation of Fly Ash From Co-Combustion of Coal and Petroleum Coke for Use in Concrete, ACI Materials Journal 104 (2007) 62-70.

[3] R.Siddique, T. R Naik, Properties of concrete containing scrap-tire rubber : an overview, Waste Management 24 (2004) 563-569.

17:10: [Non-ferrousMonPM212]
Extraction of Creatinine by Adsorption Onto Pure Micro- and Mesoporous Silica Materials
Hadj Hamaizi¹ ; Leila Kharbouche² ; Ghazala Benbakhta² ; Mustapha Mokhtari³ ; María Dolores Gil García³ ; María Martínez Galera³ ; ¹, Oran, Algeria; ²University of Oran, Oran, Algeria; ³University of Almería, Almeria, Spain;
Paper Id: 15 [Abstract]

This report describes the compositional and structural design strategy of a micro- and mesoporous silica materials mesh for the efficient removal of uremic toxins towards blood purification application. Our investigation gives the results of the syntheses involving nonionic surfactants and tetraethylorthosilicate (TEOS) as silica precursors for the extraction of urea and creatinine from human blood. The procedure of materials preparation is widely used in the synthesis of mesoporous solids. By using various amounts of non ionic surfactants (Brij S 100 and TRITON X-114) never used before in the synthesis, micro- and mesoporous purely silica samples were obtained. Structural and textural parameters indicated the presence of mesopores interconnected with micropores in a "wormhole-like" or cubic disposition. Adsorption of urea and creatinine, waste biological molecules, onto silica materials was studied and a drastic diminution of creatinine concentration from blood plasma was observed, by a simple contact at ambient temperature. The synthesis protocol, the characterization of materials as well as the results of creatinine adsorption are detailed and a discussion is proposed in this work. Micro- and mesoporous silica are convenient for both research and biomedical applications.

References:
[1] P.T. Tanev, T.J. Pinnavaia, Science, 267 (1995) 865-867
[2] S.A. Bagshaw, E. Prouzet, T.J. Pinnavaia, Science, 269 (1995) 1242-1243
[3] Y. Cao, Y. Gu, K. Wang, K, J.Taiwan Institute of Chemical Engineers, 66 (2016) 347-356
[4] R. Takai, R. Kurimoto, Y. Nakagawa, Y. Kotsuchibashi, K. Namekawa, M. Ebara, Journal of Nanomaterials, (2016) http://dx.doi.org/10.1155/2016/5638905.

SESSION: Non-ferrousMonPM3-R7	6th Intl. Symp. on Sustainable Non-ferrous Smelting and Hydro/Electrochemical Processing
Mon Nov, 5 2018 / Room: Pontal (50/2nd)
Session Chairs: Eugene Wong; Cibele Sanchez Roboredo; Session Monitor: TBA

17:40: [Non-ferrousMonPM313]
Advantages of Using Low Alkali Cements and Industrial Waste Materials in Prevention of Alkali-silica Reaction in Concrete
Cibele Sanchez Roboredo¹ ; Paul Thomas² ; Kirk Vessalas² ;⁰ ; ¹, Sydney, Australia; ²University of Technology Sydney, Sydney, Australia;
Paper Id: 238 [Abstract]

Manufactured cement has to comply with the requirement of containing less than 0.60% sodium oxide equivalent (Na₂Oeq) to meet the standard alkali content specified by codes of practices worldwide, such as ASTM C150 [1]. This limit has been adopted since the 1940s for the purpose of preventing deleterious expansion due to alkali-silica reaction (ASR), which has the potential to compromise the mechanical performance of concrete structures in service. Limiting the amount of sodium and potassium alkalis in cement is one method of lowering the alkali content [2]. However, raw materials used to manufacture cement may often contain alkali contents exceeding this limit. These raw materials are thus often discarded for use in cement manufacture. Another challenge to contend with is the need to conserve naturally occurring resources. Therefore, alternative solutions proposing the use of industrial by-products raw materials need to be considered [3].<br />The use of supplementary cementitious materials (SCMs), like fly ash and slag, generated as industrial waste can be recycled in blended cements [4], which provides a viable option for lowering the alkali content of cement permitting the use of raw materials that would otherwise be discarded to landfill. This paper reviews the advantages of using SCMs to lower the alkali content of cement and allow a wider range of raw materials to be employed in cement manufacture whilst conserving natural resources and decreasing the CO₂ emissions associated with cement manufacture [5].

References:
[1] Kerenidis, K.; Hooton, R. D., Mitigating alkali-silica reaction when using high-alkali cements. Concrete International 2011, 33 (5), 34-39.\n[2] Hill, E. D., Alkali limits for prevention of alkali-silica reaction: A brief review of their development. Cement, Concrete, and Aggregates 1996, 18 (1), 3-7.\n[3] Thomas, M., The effect of supplementary cementing materials on alkali-silica reaction: A review. Cement and Concrete Research 2011, 41 (12), 1224-1231.\n[4] Hill, E. D., Alkali limits for prevention of alkali-silica reaction: A brief review of their development. Cement, Concrete, and Aggregates 1996, 18 (1), 3-7.\n[5] Barker, D. J.; Turner, S. A.; Napier-Moore, P. A.; Clark, M.; Davison, J. E., CO2 Capture in the Cement Industry. Energy Procedia 2009, 1 (1), 87-94.

18:05: [Non-ferrousMonPM314] Invited
Synthesis and Characterization of High Performance Magnesium Nanocomposites
Eugene Wong¹ ; Manoj Gupta² ; ¹Newcastle University in Singapore, Singapore, Singapore; ²National University of Singapore, Singapore, Singapore;
Paper Id: 116 [Abstract]

Magnesium is the lightest structural metal with a density that is two-thirds of aluminium, and possesses great potential for weight critical engineering and biomedical applications [1-3]. The addition of micron-size reinforcements is one method to improve the mechanical properties, but often results in further deterioration of the limited ductility of magnesium. In recent years, an improvement in both strength and ductility of magnesium can be achieved with the addition of nano-size reinforcements [4]. In this paper, the synthesis of magnesium nanocomposites via two innovative methods—disintegrated melt deposition and hybrid microwave sintering— will be highlighted. Both of these techniques are able to produce nanocomposites with improved properties. Hybrid microwave processing can also reduce production time and energy by up to 80% [5]. The effects of the addition of ceramic, metallic and hybrid reinforcements will be discussed to illustrate the improvement in mechanical properties such as tensile, compressive, dynamic, fatigue, corrosion, and wear properties.

References:
[1] H.Z. Ye, X.Y. Liu, Review of recent studies in magnesium matrix composites, J. Mater. Sci. 9 (2004) 6153-6171. doi:10.1023/B:JMSC.0000043583.47148.31.
[2] M.P. Staiger, A.M. Pietak, J. Huadmai, G. Dias, Magnesium and its alloys as orthopedic biomaterials: a review., Biomaterials. 27 (2006) 1728-34. doi:10.1016/j.biomaterials.2005.10.003.
[3] V.H. Hammond, Magnesium Nanocomposites: Current Status and Prospects for Army Applications, (2011).
[4] M. Gupta, W.L.E. Wong, Magnesium-based nanocomposites: Lightweight materials of the future, Mater. Charact. 105 (2015). doi:10.1016/j.matchar.2015.04.015.
[5] M. Gupta, W.W.L. Eugene, Microwaves and Metals, 2011. doi:10.1002/9780470822746.

SESSION: Non-ferrousTueAM-R7	6th Intl. Symp. on Sustainable Non-ferrous Smelting and Hydro/Electrochemical Processing
Tue Nov, 6 2018 / Room: Pontal (50/2nd)
Session Chairs: Zhigang Zak Fang; Vasiliy Kryukovskiy; Session Monitor: TBA

11:20: [Non-ferrousTueAM01] Keynote
Hydrogen Assisted Magnesium Reduction of TiO&lt;sub&gt;2&lt;/sub&gt; (HAMR Process)
Zhigang Zak Fang¹ ; ¹University of Utah, SALT LAKE CITY, United States;
Paper Id: 127 [Abstract]

Titanium metal production has been a focus of the research community around the world for several decades. The strong affinity of titanium to oxygen makes the conventional Ti metal production by either the Kroll or the Hunter process energy intensive. A new approach is designed to prepare high-purity Ti metal powder from commercial purified TiO₂. Pure TiO₂ is subjected to Mg reduction, followed by a de-oxygenation process using Mg. Both the Mg reduction and the deoxygenation processes are carried out in hydrogen atmosphere. It can be shown that hydrogen destabilizes Ti-O system and enables Mg to reduce oxygen content in Ti to extremely low levels. The processes are also conducted in molten salt medium. It has been successfully demonstrated that this two-step hydrogen assisted Mg reduction process, i.e. the reduction plus deoxygenation, can produce low oxygen Ti metal powder with oxygen content as low as a few hundred ppm.

11:45: [Non-ferrousTueAM02]
Alternative Aluminium Production Technologies
Vasiliy Kryukovskiy¹ ; ¹RUSAL, Moscow, Russian Federation;
Paper Id: 128 [Abstract]

A successful development of the Bayer-Hall-Héroult process (pot amperage-600kA, power consumption-12,500kWh/t, and current efficiency-95%) during the past 20 years has been significant for pre-baked anode smelting efficiency, which is close to peak performance. It is obvious that under the circumstances, even the slightest increase of any indicator requires such huge costs that they might never be recouped, considering growing prices of raw materials, energy, and transportation. At the same time, there are pending issues with greenhouse gas pollution and contamination of land and water with red mud and spent pot lining. In this environment, it is logical to address well-known technologies which have not been practiced for various reasons. Among them are: low-consumption and bipolar electrodes[1], electrolysis of aluminum chloride through chlorination of non-bauxite aluminum containing ore (Toth Aluminum Corporation)[2], carbothermal production of alumosilicic alloys from sillimanite, caoline and others. The current studies have proven that the main problem with commercialization of the low-consumption electrodes is that it has been tested on a classic pot design with horizontal carbon anodes, whereas changes in mass and heat transfer require a new pot design, alumina, and current feeding as well as MHD control. Unfortunately, sporadic tests on cells with vertical and bipolar electrodes, with low-melting bath and alumina suspensions have not become pilot. The same happened to electrolysis of aluminum chloride: alumina chlorination issues unsolved by Alcoa and All-Russian Aluminum and Magnesium Institute (VAMI) stopped further development of the advanced technology right when Toth Aluminum Corporation announced and Fluor Daniel confirmed a technical feasibility of the aluminum chloride production by chlorination of low-quality alumina containing ore (caoline, sillimanite and others). This problem remained unsolved in the Alcoa-VAMI technology. In this regard chlorination of high-silicon ore and smelting of chloroaluminate is an interesting process researched by Academy Fellow А. Marakushev [3]. The carbothermal process developed by VAMI to produce alumosilicic alloys was used in the USSR in 1980s [4]. The advantages are as follows: there is no expensive alumina refining and caustic/ acid mud stacking in the cycle; there are no costs on production of expensive electrode materials; there are no transportation costs associated with bauxite mining, delivery and processing, which reduces aluminum cash cost; CAPEX on construction of the alumosilicic alloy carbothermal area is minimal compared to costs on construction of alumina production and smelting area with the equal capacity. The use of the carbothermal process to produce primary alumosilicic alloy will help build up aluminum and aluminum-based production, and will reduce emissions significantly. RUSAL, one of the largest aluminum companies in the world, addresses these and other subjects by investing hundreds of millions of dollars every year into the environment and acting as a global leader in the reduction of GHG emissions and production of low carbon aluminum. The report will cover projects RUSAL is implementing or has implemented in relation to topical issues associated with alternative production of aluminum and value-added products, including scandium alloys, mud stacking and aluminum waste processing.

References:
[1] Galasiu I., Galasiu R., Thonstad J. Inert anodes for aluminium electrolysis. 1-st edition, Aluminium-Verlag, Germany: 2007. 209 p.
[2] Toth Аluminium Corp., Patent USA 4514373A, 1983.
[3] Маrакushеv А.А. и др. ЕР 0611837,1992.
[4] Saltykov A.M., Baymakov A.Y. Development of electro thermal aluminium-silica alloys production. Zvetnye Metally, N7, 2003.

12:10: [Non-ferrousTueAM03]
High Value-added Products Development From Solid Wastes
Cang Da Qiang¹ ; Lingling Zhang¹ ; Yanbing Zong¹ ; Yu Li¹ ; Xiaoming Liu¹ ; ¹University of Science and Technology Beijing, Beijing, China;
Paper Id: 347 [Abstract]

New products with higher value for construction materials and industrial utilization (e.g. ceramic, glass-ceramic, inorganic fiber, water permeable brick etc.) were developed from different solid wastes from different industrial sectors and municipalities, such as: iron and steel slag, coal ash, red mud, slurry, mining taillings etc. Some of them were pre-disposed in high temperature liquid phase (changing the composition of the slag in order to use the sensible heat from it) and some were disposed in normal temperature. The market oriented green products composition design was made by Faxsage software, and the preparation process was finalized by different experiments in LAB. The properties of the products were tested according to the National Standard with different instruments. The results showed that the higher value-added products could be made from different solid wastes with higher strength and economic and environmental profit. In particular, the harmful elements such as heavy metals could be sealed in the glass phase and the crystal structure, so that the heavy metal leakage rate is a an acceptable standard for the National Standard. One of the products, ceramic preparation process from solid wastes, and its properties were introduced in this paper.

12:35: [Non-ferrousTueAM04]
Pyrometallurgical Recovery of Gold From Refractory Gold Ledge Ores
Sultanbek Kozhakhmetov¹ ; Sergey Kvyatkovskiy¹ ; Ruslan Seisembayev¹ ; Anastasiya Semenova¹ ; ¹Institute of Metallurgy and Ore Benefication, Almaty, Kazakhstan;
Paper Id: 84 [Abstract]

The problem concerning effective processing of gold ledge ores extremely refractory to loosening has been considered. [1]. Among gold ledge ores in Central Kazakhstan, ores from the Sayak-4 gold-arsenic-cobalt deposit discovered in 1950s have not been processed until the present as they are extremely refractory to loosening and beneficiation. [2, 3]. This papers is devoted to experimental study of the Reducing Pyrometallurgical Selection (RPS process) of refractory gold-arsenic-cobalt ledge ores from the Sayak-4 (Gold) deposit, under the conditions of concentrating gold in mattes and reduction melting with the recovery of precious metals into collecting iron-copper alloys [4]. Scaled-up tests were carried out using the Sayak-4 ores containing, %: Au - 3.5 g/t; Ag - 1.76 g/t; Fe - 3.95; Cu - 0.01; C - 1.93; S - 1.0; As - 3.3; Co - 0.05; SiO2 - 38.30; CaO - 23.6; Al2O3 - 4.56; MgO - 0.73. During experiments of gold collecting in mattes has shown the possibility to obtain slags containing Au - 0.1 g/t and Ag - 2.0-2.16 g/t. Reduction melting with additional charging of iron oxide, copper oxide and coke to the ore shows the possibility to obtain collecting iron-copper alloys containing Au - 7.5-8.14 g/t and Ag - 2.09-3.87 g/t. The obtained slags contained 0.38-0.50 g/t of Au and 0.2-3.2 g/t of Ag. Direct recovery of gold into collecting mattes reached 97%, and into metal alloy - 90.9%.

References:
[1] Zakharov V. A., Meretukov M. A. Gold: Refractory Ores. Moscow : "Ore and Metals" Publishing House (2013) 456. \n[2] Naumov E. A., Kalinin Yu. A., Kovalev K. R., Borisenko A. S. Eastern Kazakhstan gold ore deposits in carbonaceous terrigenous-carbonate complexes and their isotropic-geochronological characteristics. Materials of International Symposium. "Huge gold deposits of Central Asia: Strengthening of Kazakhstan gold ore potential". Almaty, 13-14 March (2014) 123-126.\n[3] Antonov Yu. A. Bakyrchik deposit and its reserve increase perspectives. Materials of International Symposium. "Huge gold deposits of Central Asia: Strengthening of Kazakhstan gold ore potential". Almaty (2014) 56-60.\n[4] Kozhakhmetov S. M., Bekturganov N. S., Kvyatkovskiy S. A., Dzhumabaeva Z. Sh., Esetov U. E. Refractory gold ore pyrometallurgical selection technology development on Sayak-4 deposit's example with gold to matte recovery. Materials of International Symposium. "Huge gold deposits of Central Asia: Strengthening of Kazakhstan gold ore potential". Almaty, (2014) 182-184.

SESSION: MineralTuePM1-R7	5th Intl. Symp. on Sustainable Mineral Processing
Tue Nov, 6 2018 / Room: Pontal (50/2nd)
Session Chairs: Francisco Souza; Paul Slatter; Session Monitor: TBA

14:00: [MineralTuePM105]
The Impact Of Sustainable Industrial Practice On Process Suspension Rheology
Paul Slatter¹ ; ¹Sheridan College, Perth, WA, AUSTRALIA., Perth, Australia;
Paper Id: 330 [Abstract]

The industrial processing industry is under continuous sustainability pressure from environmental, legal, and financial quarters to use less water, and industrial processing plant designers and operators are obliged to consider the option of operating at higher concentration [1]. As the concentration of fine particle industrial processing suspensions increases, viscous stresses also increase, and inevitably become non-Newtonian in nature. For some years, our industrial flow process research group has been researching the behaviour of high concentration non-Newtonian suspensions in pipes, valves and fittings, pumps and launders, and these will form the focus of the paper. The aim of this paper is to highlight the important practical aspects of these fundamental issues [2], and their implications for design for industrial process suspension handling. In particular, the objective is to present the principal conceptual issues that underpin sound design for industrial process suspensions. The introductory detail of the design process for handling industrial suspensions will be presented in this paper. The important point to make at the outset is that the foundation of sound design for industrial suspension handling does not revolve around the task of choosing or producing special materials and plant - although these are often required. The foundation lies rather in having a good understanding of the industrial suspension fundamental viscous properties, and sustainable industrial process design and operation [3], which is the basis of this paper and our work at the industrial flow process research group.

References:
[1] Souza Pinto, T.C., Moraes Junior, D., Slatter, P.T. and Leal Filho, L.S., 2014 Modelling the critical velocity for heterogeneous flow of mineral slurries, International Journal of Multiphase Flow 65, pp. 31-37.
[2] Souza Pinto T.C., Slatter P.T., Matai P.H., Leal Filho L.S., 2016 The influence of hematite particle shape on stratification in pipe flow, Powder Technology 302, pp 75-80.
[3] Myers T.G., Mitchell S.L., Slatter P 2017 An asymptotic analysis of the laminar-turbulent transition of yield stress fluids in pipes, Journal of Physics: Conf. Series 811 (2017) 012007.

14:25: [MineralTuePM106]
The Challenges of Artisanal Mining of Kaolin in Junco do Serido, Paraiba, Brazil - Social, Environmental Implications and Small Miner's Health
Francisco Souza¹ ; Joelson Souza Isidro Dos Santos¹ ; Antonio Sobrinho² ; ¹Federal Institute of Education, Science and Technology of Paraiba, Campina Grande, Brazil; ²Priest Jeronimo Lawen School, Santa Luzia, Brazil;
Paper Id: 115 [Abstract]

The Northeast of Brazil, essentially in the Borborema Province [1], have small-scale mining as a secular activity, promoting livelihood and economic development of cities with mining vocation [2][3]. Junco do Seridó is a town located in the Brazilian State of Paraiba, with privileged rich geology in pegmatite fesdspatic bodies with low iron levels, fastened in quartzites of the Equador Formation. The chemical weathering in acidic conditions [4] in the region promoted degradation of pegmatites, turning feldspars and other silicates in kaolinite with impurities of quartz, muscovite, iron oxides-hydroxides, tantalite and several clay minerals. The kaolin is drawn by hand, initially in open pit front. With the advancement of depth, the mining evolves underground, always handmade, rustic, dangerous, and unhealthy. The goal of this study is to show how the artisanal mining of kaolin influences livelihoods and promotes the economic development of the municipality, but on the other hand causes environmental impact and serious damage to the health of miners. The precariousness of working conditions associated with the lack of surveillance, mining planning of technological innovation, and the absence of recovery projects of degraded areas, altogether cause a mismatch between economic development, social welfare, occupational health, and environmental balance in small-scale mining.

References:
[1] F.F.M. de Almeida. Evolução da Plataforma Brasileira. Rio de Janeiro: DGM (1967) p. 36
[2] F.A. Souza, P.S.S. Barros, A.P.C.L. Sobrinho. Open Pit and Undergound Mining: A Mixed Method for Small Mineral Exploration on Pegmatitie Bodies of Central Borborema Province, in Paraiba State, Brazil. Sustainable Industrial Processing Summit/Schechtmam International Symposium. Volume 1: Mining. Edited by Florian Kongoli (2014) 395-401.
[3] F.A. Souza, P.S.S. Barros, A.P.C.L. Sobrinho. Mining and Mineral Processing on Pegmatities: Example of Serido Microregion, Paraiba State Brazil. Sustainable Industrial Processing Summit/Schechtmam International Symposium. Volume 2: Mineral Processing. Edited by Florian Kongoli (2014) 287-296.
[4) W.A. Deer, R.A. Rowie, J. Zussman. Na Introduction to the Rock Forming Minerals. Longmans Green and Co. Ltd. London. 1966. p. 558

14:50: [MineralTuePM107]
Investigation of Microwave Route for Beneficiation of Low-grade Iron Ore
Nikhil Dhawan¹ ; Veeranjaneyulu Rayapudi² ; ¹IIT-Roorkee, roorkee, India; ²IIT-ROORKEE, ROORKEE, India;
Paper Id: 332 [Abstract]

India's 2030 vision requires a huge amount of quality iron ore, and the utilization of low-grade iron ores such as banded iron ores will play an important role to achieve the same. The absence of alumina impurities in the Banded Hematite Jasper (BHJ) ore provides it an edge over other low-grade iron ores, and has a promising potential as feed material in a blast furnace. The conventional beneficiation techniques such as magnetic separation, spiral concentration, and washing are ineffective in producing suitable feed (Fe~60%) for the blast furnace. It is found that microwave exposure provides significant enrichment to the low-grade iron ore and can be used as a pretreatment step in the beneficiation of similar low-grade iron ores. The above study reveals that hematite and magnetite are strongly susceptible to microwave exposure, which enhances separation of iron values from impurities. The pretreatment process for beneficiation includes only microwave exposure, and no chemical additive and may prove economical and industrially feasible. Under optimal conditions, an iron-enriched concentrate with 61%Fe, 85% Fe recovery at 50% yield can be achieved from feed ~37 % Fe, whereas the carbothermal reduction in the microwave reactor yields ~68% Fe at 95% iron recovery under optimal conditions.

References:
[1] Rath, S., Dhawan N., Rao, D. S., Das, B., Mishra, B.K., 2016, Beneficiation studies of a difficult to treat iron ore using conventional and microwave roasting, Powder Technology, 301, 1016-1024.

15:15: [MineralTuePM108]
Quantitative Assessment of Heavy Metals in Tannery Waste by the Exposure of Atomic Absorption Spectroscopy
Muhammad Pervaiz Bhatti¹ ; Asima Munawar¹ ; Zohaib Saeed¹ ; Muhammad Yousaf² ; Ahmad Adnan¹ ; ¹Government College University Lahore, Lahore, Pakistan; ²Government College University Faisalabad, Faisalabad, Pakistan;
Paper Id: 166 [Abstract]

Atomic absorption spectrophotometer technique was employed to measure the contents of the heavy metals in the effluents directly released from tannery industries. These effluent samples were first subjected through wet acid digestion process for decomposition of organic substances and concentration of the metals being measured in the samples. The measured concentration of the heavy transition metals by AAS technique was analyzed and it was concluded that this spectrophotometer method can analyze a remarkable concentration of the effluents metals. Therefore, the quantitative measurement of most of the metals in tannery waste is preferable by AAS method. These results overall give a picture that the environments are greatly being contaminated due to high Cr, Fe, Pb concentrations as well as other toxic chemicals found in the discharged effluents from tanneries

References:
[1] Y. Li., S.-H. Yang., C.B. Tang , Y.-M. Chen ., J. He and M.-T. Tang., J. Min. Metall. Sect. B-Metall. 54 (1) B (2018) 73-79.
[2] A.S. Tanaino and A.A.Lipin J. Min. Sci., 40 (2)(2004) 188-198.
[3] A.A. Repin., B.N. Smolyanitsky., S.E.Alekseev., A.I.Popelyukh., V.V.Timonin, and V.N.Karpov J. Min. Sci., 50 (2014) 943-952.

SESSION: MineralTuePM2-R7	5th Intl. Symp. on Sustainable Mineral Processing
Tue Nov, 6 2018 / Room: Pontal (50/2nd)
Session Chairs: Nikhil Dhawan; Session Monitor: TBA

15:55: [MineralTuePM209]
Development of an Eco-friendly Tailing Disposal System of Iron Ore Tailing and Study of Issues
Rajan Kumar¹ ; Tvs Subramanyam² ; G E Sreedhar³ ; ¹, Hyderabad, India; ²Biocon, Bangalore, Pakistan; ³NMDC Limited, Hyderabad, Pakistan;
Paper Id: 351 [Abstract]

The major environmental impacts from tailing disposal can be divided into two categories: (1) The loss of productive land following its conversion to tailing dump, and (2) the introduction of sediment, acidity, and other contaminants into the ecosystem. The tailing system continues to generate opposition from local communities, the general public, and non-government organizations (NGO). The project was completed as follows: (1) Identification, characterization and settling study; (2) Preparation of synthetic tailing mixtures; (3) Characterization and settling studies; (4) Pressure filtration and paste thickening studies; (5) Study of flow properties of filtered tailings and rheology of thickened (paste) tailings; (6) Assess the transportability of filtered and paste tailings; (7) To evaluate the flow properties and paste rheology (8) Address issues related to the storage and transportation. The project concluded that tailing samples are amenable for paste thickening as well as filtration. It is possible to get a paste with 56-72% solids and yield stress in the range of 75-300 Pa. The tests revealed that it is possible to produce a filter cake with moisture content ranging from 14 to 24%.

References:
[1] Williams D L, Management of Solid Wastes - Environmental Management in the Australia Minerals and Energy Industries - Principles & Practices
[2] Tailing Management - pp 232 - 338, Mining Magazine - May 2002
[3] Thickened Tailings Disposal - pp 7 - 12, Mining Environmental Management -September, 2001

SESSION: EnvironmentalWedAM-R7	7th Intl. Symp. on Environmental, Policy, Management , Health, Economic , Financial, Social Issues Related to Technology and Scientific Innovation
Wed Nov, 7 2018 / Room: Pontal (50/2nd)
Session Chairs: Kyoshik Park; Ludo Diels; Session Monitor: TBA

11:20: [EnvironmentalWedAM01] Plenary
Creating a Sustainable Future: Industrial Processing and Productive Chains
Pedro Prates Valério¹ ; Elém Patrícia Alves Rocha² ; Jesus Maria Frias Celayeta³ ; Marcelo Cardoso² ; Erika Cristina Cren² ; ¹University Center of Belo Horizonte (UNIBH), Belo Horizonte, Brazil; ²Federal University of Minas Gerais, Belo Horizonte, Brazil; ³Dublin Institute of Technology, Dublin, Ireland;
Paper Id: 395 [Abstract]

The chemical and food industries have been responsible for most of the growing global demand for raw materials around the world. In this framework, it should be highlighted that industrial sustainability may involve assessing trade-offs among multiple dynamic goals and striving for continual improvement, rather than achieving a specific state. In this sense, there is a clear need for knowledge on new sources of feedstock as a way of strengthening the global economy and meeting impending industrial demands worldwide [1,2]. Certainly, this scenario brings challenges that need to be overcome regarding processing industries and sustainable research. In this context, ongoing studies carried out by our Research Group at Federal University of Minas Gerais (DEQ/UFMG) in collaboration with international research have provided valuable data and procedures that not only covers thermal conversion processes and chemical kinetics but also physical-chemical properties of lignocellulosic-based materials (forestry waste, agricultural residues and agro-industrial waste) [3,4] contributing to the outcome of significant applications in the fields of Science and Technology as well as of Sustainable Industrial Processing. Results obtained are an environmentally friendly alternative relating to edible oils extraction and energy conversion technologies in connection to biorefining. The study has identified some of the main agricultural and forest residues demonstrating the importance of adding value to waste steam (activated coal; vegetable coal; animal feed; nutraceutical food; cosmetics) by the generation of co-products from the processing of alternative raw materials.

References:
[1] M. C. Rulli, D. Bellomi, A. Cazzoli, G. Carolis, P. D'Odorico, Nature 6 (2016) 1-10.\n[2] K. L. Kline, S. Msangi, V. H. Dale, J. Woods, G. M. Souza, P. Osseweijer, J. S. Clancy, J. A. Hilbert,\nF. X. Johnson, P. C. McDonnell, H. K. Mugera, Bioenergy 9 (2017) 557-576. \n[3] E. P. A. Rocha, F. J. B. Gomes, E. Sermyagina, M. Cardoso, J. L. Colodette, Energy & Fuels 29 (2015), 7975-7984\n[4] P. Palmero, L. Lemmens, A. Ribas-AgustAi��, C. Sosa, K. Met, J. D. Umutoni, M. E. Hendrickx, A. M. Van-Loey. Food Chem 141 (2013) 2036-2043

11:45: [EnvironmentalWedAM02] Plenary
Challenges and Perspectives — Department of Mechanical Engineering Pontificia Universidade Católica do Rio de Janeiro
Mônica F. Naccache¹ ; ¹Pontificia Universidade Católica do Rio de Janeiro, Rio de Janeiro, Brazil;
Paper Id: 402 [Abstract]

The Department of Mechanical Engineering is committed to excellence in education and research. The undergraduate program was created in 1948, and in 1964 the graduate program was launched. Since then, it has been rated as one of the best in the country. The graduate program is rated at the top four in the country, with the highest grade given by CAPES evaluation. It has a significant presence in the national and international scientific community, and a strong interaction with industry. Our students are encouraged to participate in interchange experiences, and in extra-curricular activities such as Scientific Initiation, the Baja and robotics teams. In general, the alumni are very well rated in the job market. In this presentation I will present some initiatives and perspectives in our department in the Brazilian context.

12:10: [EnvironmentalWedAM03] Plenary
Biobased Aromatics – Challenges, Hurdles, and Opportunities
Ludo Diels¹ ; ¹VITO/UA, Mol, Belgium;
Paper Id: 313 [Abstract]

Aromatics are among the most important resources for the chemical industry. Many materials are made from aromatics and lead to higher or better performance. Brand owners are on the search for more sustainable molecules (e.g. bio-based). But also the introduction of higher performance and safety issues can be seen as the most important driver for this development. Currently virtually all aromatic building blocks are made from fossil oil. This presentation is anticipating the expected growing shortage of aromatics from the petrochemical industry and the widely shared ambition to green the chemical industry. On top of that one of the main drivers is to develop innovative molecules that are safer and more performing. This lecture will give an overview of the problems linked to wood-based refineries and the availability of lignin sources. Next, it will give an overview of the different approaches worldwide to valorize lignin and to produce bio-based aromatic molecules. It will indicate the hurdles, challenges and needs for value chain approaches. A nice example in integrated approach is the The Shared Research Center, Biorizon. Biorizon, an initiative of TNO, ECN, VITO and the Green Chemistry Campus, develops technologies to produce aromatics derived from plant-based (waste) streams. Biorizon brings together global leaders (large industry and SMEs) in the fields of feedstock, conversion, equipment, building blocks, materials and end-products. Biorizon aims to be a world leader in the development of biobased aromatics to provide the chemical megacluster around the Netherlands, Flanders (Belgium) and Nordrhein Westfalia (Germany) with innovative, sustainable building blocks leading to many different applications in the products marketed by brand owners and small companies. The objective is to make commercial production feasible for industrial partners by 2025 at the latest. Biorizon utilizes plant-based streams such as wood or its fractions lignin and sugars to develop functionalized biobased aromatics for performance materials, chemicals & coatings. Biorizon is based on the open innovation methodology, bringing together collective intelligence of various industries, companies and knowledge organizations. The multi-disciplined technological need, as well as the long term roadmaps based on thermochemical conversion, sugar chemistry for furanes and lignin depolymerisation-based chemicals for functionalized aromatics lead to a large network of applied research projects with more than 40 industrial partners, sharing research, intelligence, investments, risks and workload in different projects.

References:
[1] www.biorizon.eu/community

12:35: [EnvironmentalWedAM04]
A Study of High Accident Risk for Chemical Process
Donghoon Lee¹ ; Hern Kim² ; Yong Taek Ju¹ ; Kyoshik Park³ ; ¹United Safety Consulting Co., Ltd, Seoul, South Korea; ²Myongji University, Seongnam, South Korea; ³Myongji University, Yongin-si, Republic of South Korea;
Paper Id: 303 [Abstract]

High accident risk was studied by analyzing the Chemical Accident Tracking System (CATS) in Korea. At the top of the accident analysis taxonomy hierarchy, are accidents in facilities due to worker carelessness, inadequate facility management, and transportation vehicle accidents. Chemical processes were classified according to its typical components, such as transportation facility, unloading facility, storage facility, transport facility, process facility, and emission treatment facility. Each facility was further analyzed to have typical components in the industry. As a result of chemical accident analysis, the number of leaks due to vehicle accidents in transportation facilities was the highest, and the next is due to the leakage of process facilities. The following are major consequences of chemical accidents in Korea: accident frequency, corrosion, fatigue cracks, and repair work. For further study, a new hierarchical method of accident taxonomy was suggested in order to prepare effective countermeasures on how to reduce or manage chemical accidents.

References:
[1] Chemicals Control Act, Ministry of Environment, 2016.
[2] Pack, J. G., Suh, Y. W., Gan, S. Y., and Lee, S. W., "Improvement Measures for Chemical Accident Policies in the Chemicals Control Act and Measures to Support the Industry", Korea Environment Institute., 2016.
[3] Chemical Accident Tracking System(CATS), http:// csc.me.go.kr
[4] Crowl, D.A. and Louvar, J.F., Chemical Process Safety: Fundamentals with Applications, Prentice-Hall, New Jersey, 2nd Ed., 2001
[5] Jo, Y. B., Hazardous Substances Industrial Health Manual, KOSHA, 1-21, 2006.
[6] Ministry of Environment, Environmental statistics yearbook, 2003~2014.
[7] Korea Occupational Safety & Health Agency, Analysis of case on major accident, 1999~2013.

SESSION: EnvironmentalWedPM1-R7	7th Intl. Symp. on Environmental, Policy, Management , Health, Economic , Financial, Social Issues Related to Technology and Scientific Innovation
Wed Nov, 7 2018 / Room: Pontal (50/2nd)
Session Chairs: Xin Hu; Heap-Yih Chong; Session Monitor: TBA

14:00: [EnvironmentalWedPM105]
A Novel Multi-agent Conceptual Framework for Stakeholder Management in Infrastructure Projects
Heap-yih Chong¹ ; Xin Hu² ; Xiangyu Wang² ; ¹Curtin University, Cannington, Australia; ²Curtin University, Perth, Australia;
Paper Id: 28 [Abstract]

Off-site manufacturing (OSM) has been confirmed as an efficient production approach in the construction industry, benefiting the industry stakeholders in many ways, such as the improved sustainability and productivity [1]. A variety of stakeholders are involved into the development of an OSM project [2], and the successful project implementation requires a highly integrated level of collaboration among the stakeholders [3]. However, limited studies are available to explore this important issue. Therefore, this discussion paper aims to develop a novel multi-agent conceptual framework to facilitate the management of OSM stakeholders. An integrative review method was adopted to achieve the aim. The proposed framework will enrich the current understanding of stakeholder management in OSM projects and promote a new collaborative working platform in a large scale social environment. It also promotes the establishment of the theoretical foundation of collaborative planning in infrastructure projects.

References:
[1] Pan W, Gibb AG, Dainty AR. 2012. Strategies for Integrating The Use of Off-site
Production Technologies in House Building. Volume 138. Journal of Construction
Engineering and Management. p. 1331-1340.
[2] Boyd N, Khalfan MM, Maqsood T. 2012. Off-site Construction of Apartment Buildings.
Volume 19. Journal of Architectural Engineering. p. 51-57.
[3] Teng Y, Mao C, Liu G, Wang X. 2017. Analysis of Stakeholder Relationships in The
Industry Chain of Industrialized Building in China. Volume 152. Journal of Cleaner
Production. p. 387-398.
[4] London K, Pablo Z. 2017. An Actor-network Theory Approach to Developing An
Expanded Conceptualization of Collaboration in Industrialized Building Housing
Construction. Volume 35. Construction Management and Economics. p. 553-577.
[5] Blismas N, Wakefield R. 2009. Drivers, Constraints and The Future of Offsite
Manufacture in Australia. Volume 9. Construction Innovation, p. 72-83.
[6] Arif M, Goulding J, Rahimian FP. 2012. Promoting Off-site Construction: Future
Challenges and Opportunities. Volume 18. Journal of Architectural Engineering, p. 75-78
[7] Torraco RJ. 2005. Writing Integrative Literature Reviews: Guidelines and Examples.
Volume 4. Human Resource Development Review. p. 356-367.
[8] Mullens MA, Armacost RL, Swart WW. 1995. The Role of Object Oriented CAD in A
Generic Simulator for The Industrialized Housing Industry. Volume 4. Automation in
Construction. p. 29-43.
[9] Doran D, Giannakis M. 2011. An Examination of A Modular Supply Chain: A
Construction Sector Perspective. Volume 16. Supply Chain Management: An
International Journal. p. 260-270.
[10] Wood DJ, Gray B. 1991. Toward A Comprehensive Theory of Collaboration. Volume
27. The Journal of Applied Behavioral Science. p. 139-162.
[11] Bildsten L. 2014. Buyer-supplier Relationships in Industrialized Building. Volume 32.
Construction Management and Economics. p. 146-159.
[12] Abanda FH, Tah JHM, Cheung FKT. 2017. BIM in Off-site Manufacturing for Buildings.
Volume 14. Journal of Building Engineering. p. 89-102.
[13] Lee CY, Chong HY, Liao PC, Wang X. 2017. Critical Review of Social Network
Analysis Applications in Complex Project Management. Volume 34. Journal of
Management in Engineering, p. 1-15.
[14] Hughes D, Williams T, Ren Z. 2012. Differing Perspectives on Collaboration in
Construction. Volume 12. Construction Innovation. p. 355-368

14:25: [EnvironmentalWedPM106]
A Transformative Supply Chain Conceptual Framework for Infrastructure Projects
Xin Hu¹ ; Heap-yih Chong² ; Xiangyu Wang¹ ; ¹Curtin University, Perth, Australia; ²Curtin University, Cannington, Australia;
Paper Id: 29 [Abstract]

Off-site manufacturing (OSM) has proven to be an innovative and effective approach of addressing low productivity and sustainability issues in construction projects [1]. Supply chain management is an indispensable component of the OSM project management [2]. Nevertheless, issues have emerged in the supply chain management while using it in infrastructure projects due to their transient, fragmented, and complex nature as well as the large number of stakeholders involved [3]. The development of a collaborative supply chain has significant values in addressing the issues in the OSM supply chain management for infrastructure projects. However, limited explorations about this issue are available. Therefore, this discussion paper aims to develop transformative supply chain conceptual framework for improving the efficiency and effectiveness of OSM infrastructure projects. An integrative review method was adopted to achieve the aim. The proposed framework will improve the productivity and sustainability performance of the infrastructure sector through advancing supply chain management performance with other advanced technologies. It contributes to the creation of new knowledge of supply chain management in infrastructure engineering.

References:
[1] Department of Infrastructure and Regional Development and Cities. 2017. Australian Infr
astructure Statistics Yearbook 2017. https://bitre.gov.au/publications/2017/files/yearbook
_2017.pdf
[2] Department of Infrastructure and Regional Development and Cities. 2018. Infrastructure I
nvestment Program. http://investment.infrastructure.gov.au/
[3] Infrastructure Australia. 2016. Australian Infrastructure Plan. http://infrastructureaustralia
.gov.au/policy-publications/publications/files/Australian_Infrastructure_Plan.pdf
[4] Blismas N, Pasquire C, Gibb A. 2006. Benefit Evaluation for Off-site Production in
Construction. Volume 24. Construction Management and Economics. p. 121-130.
[5] Wang T, Wang J, Wu P, Wang J, He Q, Wang, X. 2018. Estimating the Environmental
Costs and Benefits of Demolition Waste Using Life Cycle Assessment and Willingnessto-pay:
A Case Study in Shenzhen. Volume 172. Journal of Cleaner Production. p. 14-26.
[6] Abanda FH, Tah JHM, Cheung FKT. 2017. BIM in Off-site Manufacturing for Buildings.
Volume 14. Journal of Building Engineering. p. 89-102.
[7] Zhu J, Wright G, Wang J, Wang X. 2018. A Critical Review of the Integration of
Geographic Information System and Building Information Modelling at the Data Level,
Volume 7. International Journal of Geo-Information. p. 1-16.
[8] Simatupang TM, Sridharan R. 2002. The Collaborative Supply Chain. Volume 13. The
international Journal of Logistics Management. p. 15-30.
[9] Torraco RJ. 2005. Writing Integrative Literature Reviews: Guidelines and Examples.
Volume 4. Human Resource Development Review. p. 356-367.
[10] Shuck B. 2011. Four Emerging Perspectives of Employee Engagement: An Integrative
Literature Review. Volume 10. Human Resource Development Review. p. 304-328.
[11] Downe-Wamboldt B. 1992. Content Analysis: Method, Applications, and Issues. Volume
13. Health Care for Women International. p. 313-321.
[12] El-Abbasy MS, Zayed T, Ahmed M, Alzraiee H, Abouhamad M. 2013. Contractor
Selection Model for Highway Projects Using Integrated Simulation and Analytic
Network Process. Volume 139. Journal of Construction Engineering and Management. p.
755-767.
[13] Li X, Yi W, Chi HL, Wang X, Chan APC. 2018. A Critical Review of Virtual and
Augmented Reality (VR/AR) Applications in Construction Safety. Volume 86.
Automation in Construction. p. 150-162
[14] Song Y, Tan Y, Song Y, Wu P, Cheng JCP, Kim MJ, Wang X. 2018. Spatial and
Temporal Variations of Spatial Population Accessibility to Public Hospitals: A Case
Study of Rural-urban Comparison. GIScience & Remote Sensing. p. 1-27.
[15] Tao S, Wu C, Sheng Z, Wang X. 2018. Space-Time Repetitive Project Scheduling
Considering Location and Congestion. Volume 32. Journal of Computing in Civil
Engineering. p. 04018017.
[16] Gu N, London K. 2010. Understanding and Facilitating BIM Adoption in the AEC
Industry. Volume 19. Automation in Construction. p. 988-999.
[17] Lee CY, Chong HY, Liao PC, Wang X. 2018. Critical Review of Social Network
Analysis Applications in Complex Project Management. Volume 34. Journal of
Management in Engineering. p. 04018017.
[18] Alam Q, Kabir MH, Chaudhri V. 2014. Managing Infrastructure Projects in Australia: A
Shift from a Contractual to a Collaborative Public Management Strategy. Volume 46.
Administration & Society. p. 422-449.
[19] Corsten D, Kumar N. 2005. Do Suppliers Benefit from Collaborative Relationships with
Large Retailers? An Empirical Investigation of Efficient Consumer Response Adoption.
Volume 69. Journal of Marketing. p. 80-94.
[20] Lumineau F, Henderson JE. 2012. The Influence of Relational Experience and
Contractual Governance on the Negotiation Strategy in Buyer-supplier Disputes. Volume
30. Journal of Operations Management. p. 382-395.
[21] Matopoulos A, Vlachopoulou M, Manthou V, Manos B. 2007. A Conceptual Framework
for Supply Chain Collaboration: Empirical Evidence from the Agri-food Industry.
Volume 12. Supply Chain Management: An International Journal. p. 177-186.

14:50: [EnvironmentalWedPM107]
Hydrological Characterization and Simulation of Processes in a Semi-arid Mountainous Catchment of the Cape Fold Belt
Faith Tatenda Jumbi¹ ; Dominic Mazvimavi¹ ; Julia Glenday² ; ¹University of the Western Cape, Cape Town, South Africa; ²South Africa Earth Observation Network, Cape Town, South Africa;
Paper Id: 109 [Abstract]

Knowledge of key hydrological processes and the scale at which they are dominant is still a gap in understanding how mountain catchments function [1]. This is crucial for the sustainable management of water resources as mountain areas are regarded as water towers where the bulk of fresh water is generated [2]. The general effects of land cover types on hydrological processes are known, but estimation of the specific effects in a given catchment is still problematic [3]. This study is examining how herbaceous wetlands dominated by palmiet plants (Prionium serratum) and stands of invasive woody plants (Acacia mearnsii) affect flow paths as well as surface and ground water levels in valley bottoms within a catchment context. An assessment of the appropriate level of complexity required for the prediction of vegetation impacts on hydrological processes is also undertaken. The Kromme and Baviaanskloof River catchments in the Eastern Cape Province of South Africa were used as case study sites because of their unique nature (narrow valleys with relatively flat valley bottoms) and regional importance for water supply. Through physical characterization, the nature of the groundwater-surface water interactions is being determined and how the valley bottoms are linked to their adjacent steep hillslopes. Data being collected include rainfall, groundwater levels, soil moisture and stream flow. Two models (MIKE SHE and FLEXI Topo) are used for prediction. Preliminary conceptualization of the catchment's hydrology shows that it is highly responsive to rainfall of high intensities, which are attributed to changes in land cover types; stream flow duration is also prolonged even in small tributaries, and this could be due to groundwater discharge from the fractured bedrock aquifer. The project forms part of a larger research study on participatory hydrological modelling, which involves stakeholder engagement in the selection of options being considered in the modeling process for sustainable water management.

References:
[1] Viviroli, D., Archer, D.R., Buytaert, W., Fowler, H.J., Greenwood, G.B., Hamlet, A.F., Huang, Y., Koboltschnig, G., Litaor, M.I., López-Moreno, J.I., Lorentz, S., Schädler, B., Schreier, H., Schwaiger, K., Vuille, M., Woods, R., 2011. Climate change and mountain water resources: overview and recommendations for research, management and policy. Hydrol. Earth Syst. Sci. 15 (2011) 471-504.
[2] Viviroli, D., Weingartner, R., The hydrological significance of mountains: from regional to global scale. Hydrol. Earth Syst. Sci. Discuss. 8 (2004) 1017-1030.
[3] Nolin, A.W. Perspectives on Climate Change, Mountain Hydrology, and Water Resources in the Oregon Cascades, USA. Mt. Res. Dev. 32 (2012) S35-S46.

15:15: [EnvironmentalWedPM108]
Quantitative Assessment of Heavy Metals in Tannery Waste by the Exposure of Atomic Absorption Spectroscopy
Muhammad Pervaiz Bhatti¹ ; Shakeel Ahmad¹ ; Ayoub Rashid¹ ; ¹Government College University Lahore, Lahore, Pakistan;
Paper Id: 167 [Abstract]

The availability of fresh and good quality drinking water has become one of the major problems of the contemporary era. So, there are increasing apprehensions in the world for occupation of good quality water reservoirs. The exploitation of natural resources and rapid industrialization are directly or indirectly related to the dearth of fresh and good quality drinking water in the world. All kinds of industries release their waste products directly into the environment, making it polluted and unhealthy for human beings. Leather industries also appear to pollute the soil and water bodies with their discharged toxic wastes [1]. These are responsible for uncontrolled contamination of water by their lethal discharge comprised of metals and other substances that is proving poisonous for all kinds of living organisms on the earth [2]. The progress in technological development is assumed to bring prosperity in every sphere of life, but unfortunately some bitter fruits are also being cultivated by them in the form of deteriorating ecosystems. When crops are being irrigated by metal-based polluted water, it not only seems to impede on their proper growth and development, but also yields nutritionally deficient products [3]. Atomic absorption spectrophotometer technique was employed to measure the contents of the heavy metals in the effluents directly released from tannery industries. These effluent samples were first subjected through wet acid digestion process for decomposition of organic substances and concentration of the metals being measured in the samples. The measured concentration of the heavy transition metals by AAS technique was analyzed, and it was concluded that this spectrophotometer method can analyze remarkable concentration of the effluents metals. Therefore, the quantitative measurement of most of the metals in tannery waste is preferable by AAS method. These results overall give a picture that the environment is being greatly contaminated due to high Cr, Fe, Pb concentrations, as well as other toxic chemicals found in the discharged effluents from tanneries.

References:
[1] Malarkodi M., Krishnasamy R., Kumaraperumal R and Chitdeshwari T. Characterization of heavy metal contaminated soils of Coimbatore district in Tamil Nadu, J. Agrono, 2007, 6 (1), 147-151.
[2] Navneet K., Sinha D.K. Drinking water quality management through correlation studies among various physicochemical parameters: A case study. Inter. J. of Environ. Sci, 2010, 1(2), 253-259.
[3] Aschner M. Neurotoxic mechanism of fish-bone methylmetry, Environ.Toxico. Pharma,2002, 12, 101-102.

SESSION: EnvironmentalWedPM2-R7	7th Intl. Symp. on Environmental, Policy, Management , Health, Economic , Financial, Social Issues Related to Technology and Scientific Innovation
Wed Nov, 7 2018 / Room: Pontal (50/2nd)
Session Chairs: Moustafa El-Shenawy; Lokendra Ohja; Session Monitor: TBA

15:55: [EnvironmentalWedPM209]
Microbiological Quality of Bivalves and Their Water Beds Along the Mediterranean Coast of Egypt
Moustafa El Shenawy¹ ; ¹National Research Center, Cairo, Egypt;
Paper Id: 20 [Abstract]

There is widespread concern about the safety of shellfish, which are harvested from quite shallow locations along the Mediterranean coast of Egypt. Investigation of some microbiological properties of the collected bivalves and their water beds, and surface and bottom areas, were done during four seasonal sampling cruises from March, 2016 to February, 2017 at eleven stations. All samples were analyzed for the total plate count, fecal pollution indicators, bacteria (total coliforms, E.coli, and fecal streptococci), and the prevalence of three emerging food-borne pathogens, including Listeria monocytogenes, Campylobacter, and E.coli 0157:H7. In addition, some environmental parameters of the coastal water samples, including temperature, salinity, dissolved oxygen, and pH were also measured. Sampling techniques were done according to IOS standers, and the membrane filtration technique was applied using the total plate count agar and the respective selective media. Identification using the biochemical tests was done and the final counts were calculated as cfu/100ml/gm water/meat. Fecal pollution bacterial counts ranged from <1 to 104 of all the detected microorganisms, depending on the investigated area and dates of sampling. The incidence of Listeria monocytogenes in the examined water samples varied widely from 0 to 15%. Campylobacter was found in percentages of 2 to 20%. E.coli 0157:H7 was detected in 3 to 25% of the investigated locations. There was an association between the fecal contamination indicators and the presence of the studied pathogens. The same trend was observed in the oyster meat samples. These results may help to develop sanitary strategy/strategies for better Mollusca shellfish safety.

References:
[1] Pierce, Melissa L. ; Ward, J. Evan ; Holohan, Bridget A. ; Zhao, Xiaowei ; Hicks, Randall E./ The influence of site and season on the gut and pallial fluid microbial communities of the eastern oyster, Crassostrea virginica (Bivalvia, Ostreidae) : community-level physiological profiling and genetic structure. In: Hydrobiologia. 2016 ; Vol. 765, No. 1. pp. 97-113
[2] Bayat, Zeynab; Hassanshahian, Mehdi; Hesni, Majid A./Enrichment and isolation of crude oil degrading bacteria from some mussels collected from the Persian Gulf. In: Marine Pollution Bulletin. 2015; Vol. 101, No. 1. pp. 85-91
[3] Lasa, A., Diéguez, A.L. & Romalde, J.L. Antonie van Leeuwenhoek (2014) 105: 335.

16:20: [EnvironmentalWedPM210]
A Cost Effective and Sustainable Approach to Using Ladyfinger Flower (Abelmoschus Esculentus) as a Natural Indicator in Titration
Lokendra Ohja¹ ; ¹REGIONAL INSTITUTE OF EDUCATION, NCERT, BHOPAL, India;
Paper Id: 25 [Abstract]

The role of indicators in acid base titration is very vast, and the synthetic indicators used for this work at a large scale. A sustainable effort has been made to replace these synthetic indicators by natural indicators. Abelmoschus Esculentus flowers appear to have very good indicating properties in acid- base titration. Indicators are used to show the end point of reaction, and this end point mainly deals with change in color, disappearance of color and precipitate formation. Three different sets of titration, viz. strong acid vs strong base, weak acid vs strong base, strong acid, and weak base, have been tested. The result of titration viz. strong acid and strong base (10mL by natural indicator and 9mL by synthetic indicator), weak acid and strong base (9mL by natural indicator and 8.7mL by synthetic indicator), strong acid and weak base (2.5mL by natural indicator and 2.8mL by synthetic indicator) showed that the natural indicators are very much effective in this regard. These values are almost similar to that obtained from synthetic indicators. Results shown above concluded that natural indicators could be an excellent replacement for synthetic indicators since they are cheap, readily available, simple to extract, not toxic, and user and environmentally friendly.

SESSION: CompositeMonAM-R8	6th Intl. Symp. on Composite, Ceramic and Nano Materials Processing, Characterization and Applications
Mon Nov, 5 2018 / Room: Grego (50/3rd)
Session Chairs: Pawel Rokicki; Marcos de Campos; Session Monitor: TBA

11:20: [CompositeMonAM01] Plenary
Aviation Coatings for Volcanic Environments
Pawel Rokicki¹ ; Marek Goral¹ ; Andrzej Nowotnik² ; ¹Rzeszow University of Technology, Research and Development Laboratory for Aerospace Materials, Rzeszow, Poland; ²Rzeszow University of Technology, Rzeszow, Poland;
Paper Id: 107 [Abstract]

Environments that contain volcanic ashes can lead to serious damage of static and rotating elements of the jet engine. The mechanism standing behind the issue are complex, and concern not only erosion processes but also chemical interactions in elevated temperature reaching up to 1500°C [1]. Volcanic ash melts inside the engine, and in such a form hits the surface of the blade/vane. Nowadays, the most commonly used thermal and environmental barrier coatings (TBC/EBC) for turbine blades is yttrium stabilized zirconia dioxide (YSZ) [2,3]. It is a part of a whole coating consisting of two interacting layers, namely bond coat and top coat. The main role of the bond coat is to provide proper adhesion to sustain all the other surface parameters responsible for the efficiency of the whole blade. As the YSZ is characterized by proper thermal properties, it does not provide sufficient chemical resistance to the volcanic ash environment [3,4]. Thus, the research presented in the paper aims to develop a technology for manufacturing a coating that would be resistant to not only erosion, but also to chemical meaning in complex environments. This paper presents a step-by-step technology of EB-PVD, thermal, and plasma spraying processes leading to the manufacture of environmental barrier coatings based on YSZ and gadolinium zirconate (GZO). The coating obtained in the research were analysed by means of optical and electron microscopy, which allows a full description of their structure.

References:
[1] Goral M., Kotowski S., Nowotnik A., Pytel M., Drajewicz M., Sieniawski J. 2013. Surface and Coatings Technology Volume 237, 51-55
[2] Goral M., Kubaszek T. 2017. Advances in Manufacturing Science and Technology, Vol 41. No 2. 63-72
[3] Goral M. 2016. Materials Science Forum Vol. 844, 193-196
[4] Steinberg L., Naraparaju R., Heckert M., Mikulla C., Schulz U., Leyens C. 2018. Journal of the European Ceramic Society, Vol 38, Issue 15, 5101-5112
[5] Arunkumar, P., Aarthi, U., Sribalaji, M., Mukherjee, B., Keshri, A. K., Tanveer, W. H., Babu, K. S. 2018. Journal of Alloys and Compounds, Vol. 765, 418-427
[6] Swadzba R. 2018. Applied Surface Science, Vol 445, 133-144
[7] Dudziak, T. Medvedovski E., Homa M. 2018. Journal of Materials Engineering and Performance Vol. 27, Issue 8, 4317-4335
[8] Drexler J. M., Gledhill A. D., Shinoda K., Vasiliev A. L., Reddy, K. M. Sampath S., Padture N. P. 2011. Advanced Materials Volume 23, Issue 21, 2387-2496.
[9] Mechnich P., Braue W. 2013 Journal of the American Ceramic Society. Vol 96, Issue 1958-1965.
[10] R.W. Fawley, Superalloys (1972) 3-29.

11:45: [CompositeMonAM02]
Improved Nanocrystalline Structures for Magnetic Recording
Marcos De Campos¹ ; Jose Adilson De Castro¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 336 [Abstract]

This paper will discuss in detail the adequate microstructural structures for magnetic recording. The maximum coercivity is obtained for single domain size particles [1], also known as Stoner-Wohlfarth particles. It was found that the squareness of hysteresis is improved with texture optimization, which is relevant as good squareness of hysteresis is an important issue for the magnetic recording industry. Detailed overviews on the texture effects of Stoner-Wohlfarth particles, as well as the effects of particle interaction, are given and discussed in detail. Additionally, modifications of the Stoner-Wohlfarth model, and the Callen-Liu-Cullen [2] model are analyzed. The spring effect observed in hysteresis curves of isotropic nanocrystalline materials can be explained with the Stoner-Wohlfarth model. Theories for magnetostic coupling between particles are also reviewed.

References:
[1] S.A. Romero, M.F. de Campos, A.J. Moreira,
F.J.G. Landgraf, The Effect of the Cu and Sm
content on the anisotropy field of Sm(CoFeCuZr)z
isotropic nanocrystalline alloys. In: H. Fukunaga, S.
Sugimoto (Eds.), Proceedings of the 22th
International Workshop on Rare- Earth Permanent
Magnets and Their Applications, Nagasaki, Japan,
2012, pp. 44-47.
[2] E. Callen, Y.J. Liu and J.R. Cullen. Initial
magnetization, remanence, and coercivity of the
random anisotropy amorphous ferromagnet.
Physical Review B Vol. 16 (1977), p. 263

12:10: [NanomaterialsMonAM03]
Batteries: Trends in the Market and Research
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 337 [Abstract]

General trends in battery research and development are discussed. The renewable energy industry, such as solar and wind, will increase the demand for rechargeable batteries in a near future. Other possibilities for energy storage are also discussed, as for example the fly-wheel, and hydro energy storage. For large scale batteries, the Vanadium redox type is considered as possibly the most promising. For vehicles, however, energy density is very important. Lithium ion batteries of the NMC type (N = Nickel, M = magnese and C= Cobalt) have been preferred for electric cars. For trucks and buses, batteries of the lithium iron phosphate have been used, especially in China. Batteries of the Ni-M-H have been gradually falling to disuse now (Ni = Nickel, M= metal as lanthanum and H is hydrogen). Nickel cadmium batteries are now considered obsolete. The mild-hybrid cars will increase the demand for batteries, but a big issue still is the cost of batteries [1]. There is a trend to avoid batteries based on heavy metals as cadmium. However, due to cost reasons, the market of lead acid batteries is still the largest in rechargeable batteries. Fast charging is also one of the most relevant issues of batteries today. Some companies, however, already announced solutions for fast charging, one of which involves high voltage charging.

References:
[1] Bjorn Nykvist & Mans Nilsson.
Rapidly falling costs of battery packs for electric vehicles.
Nature Climate Change volume 5, pages 329-332 (2015)

12:35: [CompositeMonAM04]
Optimized Materials for Wind Turbines and Electric Motors
Marcos De Campos¹ ; ¹UFF - Federal Fluminense University, Volta Redonda, Brazil;
Paper Id: 338 [Abstract]

At least almost half of the electric energy of the world is consumed by electric motors.Thus, there is big pressure on increasing the efficiency of electric motors, and rigorous specifications such as IE4 - (Super Premium Efficiency) are now requested by the European Union [1]. Electric vehicles need machines with very high efficiency, and this can be achieved with improved materials. For example, axial flux machines may use amorphous or nanocrystalline soft magnetic materials, and wind turbines can be improved with better magnetic materials. Off-shore wind turbines need to be without gearbox (i.e. direct drive) in order to reduce maintenance problems. Rare-earth magnets are necessary for direct drive wind turbines. Moreover, the correct choice of the magnetic materials can lead to significant weight reduction of the turbines, and thus the turbines can be built taller. Tall wind turbines are necessary because strong and constant winds are found at heights of about 150 meters or more. The proper choice of materials is essential for better motors and generators, which will ultimately reduce the energy consumption in the entire world. In this study, different possibilities of magnetic materials are discussed and compared.

References:
[1] https://ec.europa.eu/energy/en/topics/energy-efficiency/energy-efficient-products/electric-motors

SESSION: CompositeMonPM1-R8	6th Intl. Symp. on Composite, Ceramic and Nano Materials Processing, Characterization and Applications
Mon Nov, 5 2018 / Room: Grego (50/3rd)
Session Chairs: Raman Singh; Gabor Patonay; Session Monitor: TBA

14:00: [CompositeMonPM105] Plenary
Ultra-thin Graphene Coating on Metals for Corrosion Resistance: Opportunities and Challenges
Raman Singh¹ ; ¹Monash University, Monash University, Australia;
Paper Id: 168 [Abstract]

Corrosion of engineering alloys and its mitigation measures cost any developed economy ~4% of their GDP (i.e., ~$8b annually to Australia and ~$250b to USA). Traditional measures such as development of corrosion-resistant alloys and conventional coatings have not always provided durable corrosion resistance, particularly in highly demanding situations. Thus, a novel and disruptive approach is immensely commercially attractive. This presentation will discuss graphene coating as a disruptive approach to durable corrosion resistance [1-2], chronological evolution of the field, and success in circumventing the related challenges. The presenter's group demonstrated that just 1-2 atomic layers of graphene coating can improve corrosion resistance of copper (Cu) by two orders of magnitude in an aggressive chloride solution (similar to seawater) [2]. However, the improvement in corrosion resistance of Cu due to graphene coating vary remarkably in different studies, i.e., from >2 orders of magnitude [2], to only 10 times [3] to little improvement [4]. In fact, a few subsequent studies [5,6] have categorically demonstrated graphene coated Cu to show remarkably inferior long-term oxidation resistance to bare Cu. The presenter's recent investigations [7,8] have provided mechanistic understanding of such variabilities. The group also had considerable success in circumventing the factors/challenges that contributed to the development of deleterious defects in graphene film that trigger accelerated corrosion (instead of protection) as reported in other studies [5,6]. The graphene developed the most recent studies [7,8] have been demonstrated to provided durable corrosion resistance to nickel [7] (see Figure 1) and copper [8]. However, developing graphene on most common engineering alloys (e.g., mild steel) by CVD poses a few fundamental scientific challenges that this presentation will discuss.

References:
[1] Chen, L et.al., Oxidation Resistance of Graphene-Coated Cu and Cu/Ni Alloy, ACS Nano, 5 (2011) 1321.
[2] RK Singh Raman et.al., Protecting Copper from Electrochemical Degradation by Graphene Coating, Carbon, 50 (2012) 4040.
[3] D Prasai et.al., Graphene: Corrosion-Inhibiting Coating, ACS Nano, 6 (2012) 1102.
[4] N Kirkland et.a., Exploring graphene as a corrosion protection barrier, Corros Sci, 56 (2012) 1. S
[5] M Schriver et.al., Graphene as a Long-Term Metal Oxidation Barrier: Worse Than Nothing, ACS Nano, 2013, 10.1021/nn4014356.
[6] F Zhou et al, Enhanced Room-Temperature Corrosion of Copper in the Presence of Graphene, ACS Nano, 7 (2013) 6939
[7] MR Anisur, RK Singh Raman, Controlling Hydrogen Environment and Cooling during CVD Graphene Growth on Nickel for Improved Corrosion Resistance, Carbon, 127 (2018) 131.
[8] A Tiwari, RK Singh Raman, Durability of Corrosion Resistance of Copper due to Ultra-thin Surface Layers of Graphene, Materials, 10 (2017) 1112.

14:25: [CompositeMonPM106]
Effects of Various Additives and Sintering Temperature on Phase Evolution and Properties of Carbon-Clay Ceramic Composites
Fatai Olufemi Aramide¹ ; Olusola Dayo Adepoju² ; Patricia Abimbola Popoola³ ; ¹Department of Metallurgical and Materials Engineering, Federal University of Technology, Akure, Nigeria; ²Metallurgical and Materials Engineering, Federal University of Technology, Akure, Nigeria; ³Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Pretoria, South Africa;
Paper Id: 89 [Abstract]

Effects of Ifon clay, various additives, and sintering temperature on the phase development and physico-mechanical properties of mullite-carbon ceramic composite were investigated. Powders of Ifon clay, kaolin from Okpella, and graphite of known mineralogical composition were thoroughly blended in a ball mill for 3 hours at a speed of 60 rev/min using a predetermined ratio. From the blended powders, standard samples were produced by uniaxial compression. This was followed by sintering in an electric furnace at 1400°C, 1500°C and 1600°C for one hour. The sintered samples were characterized for various physical and mechanical properties. The phases developed in the sample during sintering were also investigated using X-ray diffractometer (XRD). Morphology and microanalysis of the sintered ceramic composite samples were determined using ultrahigh resolution field emission scanning electron microscope (UHR-FESEM) equipped with energy dispersive spectroscopy (EDS). It was observed that the Ifon clay addition to the sample favours the formation of microcline over mullite at temperatures between 1400°C and 1500°C in sample A. As the sintering temperature increases to 1600°C, there is the formation of mullite phase and pores in sample A [1]. For sample B, 10% SiC served as nucleating point for SiC around 1400°C [2, 3]. 10% TiO₂ led to the development of 2.5% TiC at 1500°C which increased to 6.8% at 1600°C. Ifon clay in the sample led to the development of anorthite and microcline in the samples. 10% TiO₂ is effective as anti-oxidant for graphite up to 1500°C in sample C [3]. For sample D, the addition of TiO₂ and SiC in the sample led to the formation of TiC in the sample at 1400°C and 1600°C. This takes place through high temperature solid state reaction (reaction sintering) of TiO₂ and SiC. This also contributes to the reduction in the apparent porosity of the sample with increased sintering temperature [4, 5]. The presence of titania in the sample does not favour the stability of anorthite beyond 1400°C. The formation of 50.6 % mullite in the sample at 1500°C gave it the highest cold crushing strength and absorbed energy. The sample D sintered at 1500°C is considered optimal.

References:
[1] F. O. Aramide, Effects of sintering temperature on the phase developments and mechanical
properties Ifon clay, Leonardo J. of Sc., 14, 26, (2015), 67-82.
[2] Forrest, C. W.; Kennedy, P.; Shennan, J. V. Special Ceramics. 5 (1972) 99.
[3] Kennedy, P. Non-Oxide Technical and Engineering Ceramics; Hampshire, S. Ed.; Elsevier: New York, (1986) 301-317.
[4] Sawyer, G. R.; Page, T. F. J. Mater. Sci. 13 (1978) 885.
[5] Ness, J. N.; Page, T. F. J. Mater. Sci. 21 (1986) 1377.

14:50: [CompositeMonPM107]
How to Generate More Fluorescence with Less: Silica Nanoparticle Encapsulated Dyes
Gabor Patonay¹ ; Eman Alsolmy¹ ; Maged Henary¹ ; Walid Abdelwahab¹ ; Gala Chapman¹ ; ¹Georgia State University, Atlanta, United States;
Paper Id: 227 [Abstract]

The use of fluorescence in many chemical applications often requires extrinsic fluorophores, especially when intrinsic fluorescence of the molecule of interest is weak or in a spectral region that is prone to interference in the matrix. Introducing extrinsic fluorophores in the molecule of interest may require chemistry that utilizes a reagent that is less environmentally friendly or may require significant amounts of the fluorescent dyes. This is especially true if a fluorophore is used to authenticate the origin of industrial products, such as hydrocarbons, paints, etc. This is due to the fact that the fluorescence intensity of a single molecular label or reporting group can be relatively weak, requiring a larger amount of chemicals per unit product. Frequently the product itself may cause quenching of the fluorophore. All these concerns may be alleviated by encapsulating fluorophores in silica nanoparticles. Silica nanoparticles are biologically and environmentally friendly and can be designed for many applications. Covalently copolymerized dyes in silica nanoparticles are free from leaching; even non-covalently encapsulated dyes are often virtually free of leaching. The outside of the silica nanoparticles can be designed to mach the product chemistry, and can be hydrophobic or hydrophilic or anything between. The encapsulated dye can serve as a simple reporting label or as a sophisticated molecular probe. Due to the large number of dye molecules that can be encapsulated in a single silica nanoparticle, the number of labels are very small, requiring minimal amount of chemicals. Silica nanoparticle synthesis is conducive for the introduction of covalently copolymerized fluorescent dyes by using modified TEOS reactive analogues that are inexpensive and widely available. The outside layer of the silica nanoparticle surface that can be modified by regrowth technique can also serve as chemical reagent or sensor. This study reports how copolymerized silica nanoparticles can be made using a wide array of fluorophores and how its surface properties were modified by adding hydrophobic or hydrophilic molecules to achieve compatibility. Surface hydrophobicity controlled fluorescent silica nanoparticles are excellent candidates for many applications, including sensitive analytical detections. Copolymerization of multiple dyes or other molecules will also be discussed to achieve large Stokes' shift using fluorescence energy transfer.

References:
[1] Patonay G, Beckford G, HAänninen P. UV-Vis and NIR Fluorescence Spectroscopy, in Handbook of Spectroscopy: Second, Enlarged Edition, Wiley-VCH Verlag GmbH & Co. KGaA, Published Online: 2 APR 2014, DOI: 10.1002/ 9783527654703. ch26.
[2] Patonay G, Chapman G, Beckford G, Henary M, Ellis M. Use of Fluorescent NIR Dyes in Silica Nanoparticles and as Enzyme Substrates in Bioanalytical Applications, Proc. SPIE. 8956, 89560U /1-89560U/11 (2014).
[3] Chapman G, Solomon I, Patonay G, Henary M. Synthesis and pH-Dependent Spectroscopic Behavior of 2,4,6-Trisubstituted Pyridine Derivatives, J. of Heterocyc Chem (52) 3, 861-872 (2015).
[4] Ebeid WM, Salim MM, Elkady EF, Asmaa A, Ramzia A, El-Bagary Patonay G. Simultaneous Determination of Valsartan, Amlodipine besylate and Hydrochlorothiazide using CZE in their Combined Dosage Form, PHARMAZIE, 70, 368-373, (2015).
5. Patonay G, Henary M, Chapman G, Emer K, Crow S, Fluorescent silica nanoparticles containing covalently bound dyes for reporter, marker, and sensor applications Proc. SPIE. 97230Q; doi:10.1117/12.2217869 (2016).

15:15: [CompositeMonPM108]
Thermoelectric Properties of the Layered Rhodates K&lt;sub&gt;x&lt;/sub&gt;RhO&lt;sub&gt;2&lt;/sub&gt; and Na&lt;sub&gt;x&lt;/sub&gt;CoO&lt;sub&gt;2&lt;/sub&gt;
Udo Schwingenschlogl¹ ; Nirpendra Singh¹ ; Yasir Saeed¹ ; ¹King Abdullah University of Science and Technology (KAUST), Thuwal, Saudi Arabia;
Paper Id: 290 [Abstract]

We discuss the structural and thermoelectric properties of the layered compounds K_xRhO₂ [1] in comparison to isostructural and isovalent Na_xCoO₂. The optimized structure of K_1/2RhO₂ exhibits a remarkable deviation of the c/a ratio from the experimental result as well as from c/a ratios of related compounds. This indicates that a hydrated phase of K_xRhO₂ exists and the experimental structure determination refers to this hydrated phase. The calculated Seebeck coefficient of pristine K_1/2RhO₂ amounts to 50*10^-6 V/K at 300 K, which is close to the experimental value of 40*10^-6 V/K. More importantly, we observe high values for the Seebeck coefficient and power factor for hydrated K_xRhO₂ in the whole temperature range from 0 to 700 K. At 100 K we find for hydrated K_7/8RhO₂ a value of Z = 3*10^-3 K^-1, which is the highest power factor observed at this temperature. It exceeds also the exceptionally high value of Na_0.88CoO₂ by more than 50%. Our results, hence, demonstrate that hydration is an effective approach to modify the lattice parameters and, as a result, enhance the thermoelectric performance. The Na_xRhO₂ oxides [2] are found to form a new class of materials with exciting thermoelectric features, even outperforming the 2H phases of the K_xRhO₂ system. In the latter the optimal thermoelectric performance is achieved at low temperature, whereas the modified stacking of the atomic layers in the 3R phases of Na_xRhO₂ results in a reduced interlayer coupling and, in turn, in a dramatically enhanced thermoelectric response in the technologically relevant high temperature range. We find that Na vacancies in Na_xRhO₂ avoid clustering and that the RhO₆ octahedra are modified depending on the amount of Na deficiency. Analysis of the induced changes in the density of states close to the Fermi level indicates that the Rh^3+d d_3z2-r2 states control the transport properties of the compounds. A substantial figure of merit of 0.35 at 580 K is found in hydrated Na_0.83RhO₂ due to the enhanced effective mass of the charge carriers. In general, the figure of merit can be further increased by reduction of the Na vacancy concentration to increase the resistivity.

References:
[1] Y. Saeed, N. Singh, and U. Schwingenschlogl, Adv. Funct. Mater. 22 (2012), 2792-2796.
[2] Y. Saeed, N. Singh, and U. Schwingenschlogl, Sci. Rep. 4 (2014), 4390.

SESSION: CoatingsMonPM2-R8	5th Intl. Symp. on Sustainable Surface and Interface Engineering: Coatings for Extreme Environments
Mon Nov, 5 2018 / Room: Grego (50/3rd)
Session Chairs: TBA Session Monitor: TBA

15:55: [CoatingsMonPM209]
Characterization of Polymer Solutions with TiO2; Applied on Substrates and Used in Construction for Sustainable Photocatalysis
Aline Hernández¹ ; Natalia Loera² ; Gerardo Pérez² ; Luis Fischer³ ; Francisco Blockstrand³ ; María Jóse Contreras⁴ ; Diana Sánchez⁴ ; ¹Facultad de Ingeniería, Estado de México, Mexico; ²Anahuac University Mexico, Huixquilucan, Edo. de México, Mexico; ³Facultad de Ingeniería, Huixquilucan, Edo. de México, Mexico; ⁴Universidad Anáhuac México, Huixquilucan, Edo. de México, Mexico;
Paper Id: 269 [Abstract]

Air pollution is one of the main environmental and health hazards in several countries, which affects children under 5 years of age and adults aged 50-75 the most. The World Health Assembly approved the WHA68.8 resolution in 2015, in which air quality guidelines were defined in order to achieve sustainable development. Some of the main regulated air pollutants are PM₁₀, PM_2.5, NO₂, O₃ and SO₂. Hence, this article covers the characterization of the photocatalytic reaction efficiency of two polymer solutions, which use TiO₂ as photocatalytic active [1] in different substrates for its potential application as primer or paint [2]. A Sampling Conditioning Unit was used in order to prove that the pollutants such as NO_x, SO_x and CO₂ decrease when the solutions are applied. Additional tests were performed in SEM (Scanning Electron Microscope), to measure the adherence quality of the paint to the substrate, and later analyze changes at the altered surfaces with added solutions [3]. The results presented a decrease of 47.8% on CO₂, and 30.7% on SO_x at constant flux.

References:
[1] F. Fresno, R. Portela, S. Suarez, J. M. Coronado, Photocatalytic materials: recent achievements and near future trends, J. Mater. Chem. A, 2, (2014), 2863-2884 .
[2] R. Portela, M.D. Hernández-Alonso, Environmental Applications of Photocatalysis, Design of Advanced Photocatalytic Materials for Energy and Environmental Applications, (2013), 35-66
[3] J. Clavijo, Caracterizacion de materiales a travos de medidas de microscopia electronica de barrido (SEM), Revista Elementos. 3 (2013) 133-146.

16:20: [CompositeMonPM210]
Rice Husks Fibre Reinforced Polypropylene Composites for Structural Reuse - A Technological Solution to an Environmental Challenge in Sub-Saharan Africa
Edward Odhong¹ ; Alex Munyasya Muumbo² ; Abel N. Mayaka³ ; ¹Multimedia University of Kenya, NAIROBI, Kenya; ²The Technical University of Kenya, Nairobi, Kenya; ³Multimedia University of Kenya, Nairobi, Kenya;
Paper Id: 26 [Abstract]

Africa is facing a serious crisis, due to serious environmental degradation arising from the economic exploitation of its forests. A possible mitigating measure would be the development and provision of alternative cheap structural materials to replace timber.
A good cheap alternative material is plant fibre reinforced polymer composite. Use of rice husk fiber reinforced polymer composite minimizes environmental pollution due to characteristic biodegradability [1]. Engineering materials fail when loaded beyond their elastic limit by fracture or plastic deformation. Structures made from healable materials have significantly prolonged service life [2]. A rice husk fibre reinforced polypropylene composite will undergo failure that involves crack initiation, propagation, and complete fracture [3]. Rice husk fibre reinforced polypropylene composite forms a chemical or frictional bond, whose strength largely depends on strength of the interface [4].
In this research, rice husk fibres were prepared by hammer milling, heated to reduce moisture content and surface modification done to increase wettability by the matrix. Polypropylene wastes were shredded and used as matrix [5]. Composite test pieces were produced by film stacking technique and by injection moulding. Respective standards were applied during destructive testing and mechanical properties were compared with existing published results. The resulting strengths were: Tensile 85 MPa, bending 56 MPa, Compressive 178 MPa, impact 61 J/mm² and hardness BHN 480. These results gave mechanical performance sufficient to conclude that the reinforced composite material could be used to replace timber and save forests which are depleting.
The fractured test pieces were repaired / healed and then retested for respective mechanical properties. Percentage recovered strengths from tensile, impact and compressive strength tests were 81, 98.36 and 95 respectively. It could be concluded that repaired rice husk fibre reinforced polypropylene composites could be reused for their original specific structural functions thus further minimizing need for forest products for similar applications.

References:
[1] HGB. Premalal, H. Ismail, A. Baharin Comparison of the mechanical properties of rice husk powder filled polypropylene composites with talc filled polypropylene composites. Polymer Testing. 2002;21(7):833-9.\n[2] M. Hautier, D. LAi��vAi��que, C. Huchette , and P. Olivier. 2015. Investigation of a composite repair method by liquid resin infusion. 29 av. de la Division Leclerc, 92322 Chatillon, France *UniversitAi�� de Toulouse, UPS, IUT P. Sabatier, IGM-LGMT DAi��pt. GMP - 133C av. de Rangueil, B.P., 67701 - 31077 Toulouse CEDEX 4, France mathieu.hautier@onera.fr. \n[3] H.S. Yang, J.K. Kim,, J. Son,, H.,J. Park, B.,J. Lee, T.,S. Hwang, Rice husk\nflour filled polypropylene composites; mechanical and morphological study,\nComposite Structure, 2004; 63, p.305-312. [4] F. Uchenna, O. Dimzoski, G. Bogoeva-Gaceva, G. Gentile, M. Avella and A. Grozdanov, "Polypropylene-based Eco-composites Filled with Agricultural Rice Hulls Waste", Chem. Biochem. Eng. Q. 23 (2), Page No. 225-230, 2009.\n[5] B. Hayes. 2014.Improved Resin Injection Repairs for Polymer Composite Materials Applied Poleramic, Inc. 6166 Egret Court. Benicia, California, 94510- 94569.

16:45: [CompositeMonPM211]
Applications of Microsphere Monolayers on Solar Cells and LEDs
Chia-hua Chan¹ ; Chii-chang Chen¹ ; ¹National Central University, Taoyuan, Taiwan;
Paper Id: 278 [Abstract]

Thus far, solar cells are the main component for efficiently converting energy from the sun to electricity. To generate light from electric energy to the optical energy, LEDs are the main devices. The light reflection of the optical interface in these two devices is the main barrier to enhance the efficiency of the devices. In this study, we demonstrate a cost-effective method of depositing anti-reflection coatings on glass [1], GaAs [2], sapphire [3] and GaN wafers [4]. The anti-reflection layers are formed by monolayer of microspheres. The deposition is realized by dip coating method. For GaN LEDs, the microspheres can enhance the external efficiency (the output coupling of the light). The microspheres deposited on sapphire before the crystal growth can ameliorate the crystal quality of the GaN to improve the electric property of the GaN LED. The coating is also used on the glass to enhance the transmission of the light at the interface in the OLEDs. The microspheres deposited on GaAs-based solar cell can enhance the transmission of the light into the materials to improve the efficiency. We demonstrate theoretically and experimentally the concept and the devices using the monolayer of the microspheres. We have developed a novel technique to deposit the monolayer of microspheres on any flat wafers without the limit of the wafer size. We will show the monolayers of microspheres on 2-inch sapphire wafer and 4-inch silicon wafer.

References:
[1] Chia-Hua Chan, Alexis Fischer, Amanda Martinez-Gil, Philippe Taillepierre, Chien-Chieh Lee, Song-Lin Yang, Chia-Hung Hou, Hung-Ta Chien, Dong-Po Cai, Kuei-Chu Hsu, Chii-Chang Chen, "Anti-reflection layer formed by monolayer of microspheres," Appl. Phys. B. vol. 100, p.547, 2010.
[2] Te-Hung Chang, Pei-Hsuan Wu, Sheng-Hui Chen, Chia-Hua Chan, Cheng-Chung Lee, Chii-Chang Chen, Yan-Kuin Su, "Efficiency Enhancement in GaAs Solar Cells Using Self-assemble Microsphere," Opt. Express. vol. 17, p. 6519, 2009.
[3] Chia-Hung Hou , Shao-Ze Tseng , Chia-Hua Chan, Tsing-Jen Chen , Hung-Ta Chien , Fu-Li Hsiao , Hua-Kung Chiu , Chien-Chieh Lee , Yen-Ling Tsai , Chii-Chang Chen*, "Output power enhancement of light-emitting diodes via two-dimensional hole arrays generated by a monolayer of microspheres," Appl. Phys. Lett. Vol. 95, p. 133105, 2009..
[4] Guan-Ting Chen, Jen-Inn Chyi*, Chia-Hua Chan, Chia-Hung Hou, Chii-Chang Chen, Mao-Nan Chang, "Crack-free GaN grown on AlGaN/(111)Si micropillar array fabricated by polystyrene microsphere lithography," Appl. Phys. Lett. vol. 91, p. 261910, 2007.
[5] Chia-Hua Chan, Chia-Hung Hou, Chih-Kai Huang, Tsing-Jen Chen, Shao-Ze Tseng, Hung-Ta Chien, Cheng-Huang Kuo, Kuo-Huang Hsieh, Yen-Ling Tsai, Kuei-Chu Hsu and Chii-Chang Chen*, "Patterning periodical motif on substrates by monolayer of microspheres: Application on GaN LEDs," Jpn. J. Appl. Phys. vol. 48, p. 020212, 2009.

17:10: [CompositeMonPM212]
Influence of the Structural Parameters on the Optical Properties of Nano-dispersive Nickel
Lali Kalandadze¹ ; Omar Nakashidze¹ ; Nugzar Gomidze¹ ; Izolda Jabnidze¹ ; ¹Batumi Shota Rustaveli State University, Batumi, Georgia;
Paper Id: 276 [Abstract]

In general, the optical properties of nano-dispersive structures are very different from the properties of the bulk materials, and depend on the following structural parameters: the occupancy of the volume of the ultrafine medium with nanoparticles (q); the size and shape of the particles (f); the order of the particles; and the properties of the medium and surrounding nanoparticles (λ₀) [1,2]. This was predictable because these structures contain from some atoms to thousands of atoms and take a middle place between atoms and massive substances, and subsequently, they have properties different from both of them. In the present paper, using the discontinuous Ni films as examples, we consider theoretically and experimentally the influence of the structural parameters on the optical properties of the ultrafine structures. In this work, the optical properties of nano-dispersive structures are represented within the theoretical Maxwell-Garnett model [3,4]. The behavior of the optical spectra of thin Ni films was explained in the framework of the effective medium approximation in two cases: q<0.5 and 0.5< q<1. In this approach, an effective refractive index (n-ik) of the nano-dispersive structures can be calculated as a function of the λ₀, q, and particle shapes. These calculations proved a good agreement between the experimental results and the theoretical calculations.

References:
[1] LV Nikitin, LG Kalandadze, MZ Akmedov, SA Nepijko, AP Ostranitsa, journal of Magnetism and Magnetic Materials 148 (1995) 279-280.
[2] Nakashidze O. and Kalandadze L., New Developments in Materials Science; Nova Publishers; (2013), 119-126
[3] Nakashidze O. and Kalandadze L. 2016IEEE 7th international conference on Advanced Optoelectronics and Lasers; (2016), pp. 17-20
[4] Kalandadze L. Journal of Sensor Letters. American Scientific Publishers.V5, Number 1, (2007), pp. 13-14

SESSION: CompositeTueAM-R8	6th Intl. Symp. on Composite, Ceramic and Nano Materials Processing, Characterization and Applications
Tue Nov, 6 2018 / Room: Grego (50/3rd)
Session Chairs: Fakhra Aziz; Jean-Charles Dupin; Session Monitor: TBA

11:20: [CompositeTueAM01]
The Spectroscopies of Electrons for the Control and the Development of Surface Technologies in the Transport Industry
Jean-charles Dupin¹ ; ¹IPREM UMR5254 CNRS - University of PAU, PAU, France;
Paper Id: 284 [Abstract]

Nowadays, many industrial sectors, and among them transport, are intended to improve both mechanical and chemical properties of surfaces to increase their durability, such as thermochemical broadcast treatments; surface treatments by wet - chemical - electrochemical - plasma routes; inorganic, organic, and hybrid coatings, etc. Whether as support for the development and for the optimization of surface treatment in accordance with regulations (ex: REACH), or as a means of control and audit materials and failures, the electron spectroscopies show a real interest for R&D activity. It is thus now that the XPS and Auger spectroscopies, only dedicated to fundamental academic research in past decades, are making a remarkable contribution in the innovation of new processes for improvement of surfaces and facilitating their transfer to industry. As part of (electro)chemical surface treatment of metal alloys, from the initial preparation of the substrate up to its protection by a thin coating, varied and complementary examples will come to account for the extraordinary potential of the electron spectroscopies. Spectral signature, whether from surface or in depth, or from chemical mapping survey (Figure 1), will have as many opportunities to identify phenomena at interfaces or to reveal unexpected behaviors. Different industrial issues will be reviewed, such as adhesion of rubber to steel in reinforcement material in belted radial tires, and eco-friendly anti-corrosion coatings for aircraft aluminum alloys.

References:
[1] Appl. Surf. Sci. 298 (2014) 199-207; Corrosion Protection of Magnesium Alloys: From Chromium VI Process to Alternative Coatings Technologies. In Magnesium Alloys. InTech. (2017);

11:45: [CompositeTueAM02]
Capacitive Humidity Sensor Based on Polymer Composite Thin Film
Fakhra Aziz¹ ; Nosheen Fatima² ; Lih W. Lim³ ; Khaulah Sulaiman³ ; ¹University of Peshawar, Peshawar, Pakistan; ²Capital University of Science and Technology (CUST), Islamabad, Pakistan; ³University of Malaya, Kuala Lumpur, Malaysia;
Paper Id: 17 [Abstract]

Nowadays humidity sensors are used in every industry, such as in food, pharmaceuticals [1], medicine, [2] and agriculture [3, 4]. These commercial humidity sensors are quite expensive, complicated in operation, and have low sensitivity and stability because of the materials used as a sensing element [5]. It is difficult to maintain their operational cost, power losses, sensitivity and stability [4]. Therefore, it is essential for a sensor to have high sensitivity and stability, low cost, small hysteresis, wide linear range, simple operation, short response, and short recovery time [5, 6]. Electrical conduction is affected significantly by dipoles of water molecules, which makes it important for researchers to investigate the magnitude of change in impedance and capacitance of the samples with respect to varying relative humidity. The investigation becomes more important for composite materials due to the contribution of properties by two or more ingredients. Changing the constituting ratio of the ingredients in the composites results in modification of properties in composite materials. The choice of compatible ingredients is also important to fabricate stable samples so as to overcome the degradation processes [7]. The present work demonstrates a humidity sensor based on a composite of polythieno [3,4-b]-thiophene-co-benzodithiophene (PTB7) and [6,6]-phenyl-C-butyric-acid methyl ester (PCBM). The capacitive type humidity sensor is fabricated using simple cost effective spin coating approach in the Al/ PTB7:PCBM/Al surface type geometry with different ratios of PTB7: PCBM i.e., 1:0, 1.5:1, 1:1, 1:1.5 and 0:1 respectively. The sensing behavior of the prepared devices has been observed at ~1V of AC operational bias over a wide range of relative humidity i.e. 20-95 % RH. The sensors are also examined at different frequencies i.e., 100 Hz, 1 kHz, 10 kHz and 100 kHz. The optimum frequency and volumetric ratio are selected as 100 Hz and 1.5:1 (PTB7:PCBM). The sensor shows better sensitivity of 1.325 nF/%RH with negligible hysteresis. The composite sensor indicates remarkable improvement in the sensing behavior as compared to single material based sensors. These properties make it a potential candidate for the state-of-the-art sensor applications.

References:
[1] M. V. Fuke, P. Kanitkar, M. Kulkarni, B. Kale and R. Aiyer, "Effect of particle size variation of Ag nanoparticles in Polyaniline composite on humidity sensing," Talanta, vol. 81, pp. 320-326, 2010.
[2] N. Camaioni, G. Casalbore-Miceli, Y. Li, M. Yang and A. Zanelli, "Water activated ionic conduction in cross-linked polyelectrolytes," Sensors and Actuators B: Chemical, vol. 134, pp. 230-233, 2008.
[3] A. Ramaprasad and V. Rao, "Chitin-polyaniline blend as humidity sensor," Sensors and Actuators B: Chemical, vol. 148, pp. 117-125, 2010.
[4] R. Nohria, R. Khillan, Y. Su, R. Dikshit, Y. Lvov and K. Varahramyan, "Humidity sensor based on ultrathin polyaniline film deposited using layer-by-layer nano-assembly," Sensors and Actuators B: Chemical, vol. 114, pp. 218-222, 2006.
[5] J.-R. Huang, M.-Q. Li and J.-H. Liu, "A novel conductive humidity sensor based on field ionization from carbon nanotubes," Sensors and Actuators A: Physical, vol. 133, pp. 467-471, 2007.
[6] Z. Ahmad, M. Sayyad, M. Saleem, K. S. Karimov and M. Shah, "Humidity-dependent characteristics of methyl-red thin film-based Ag/methyl-red/Ag surface-type cell," Physica E: Low-dimensional Systems and Nanostructures, vol. 41, pp. 18-22, 2008.
[7] S. B. Khan, M. T. S. Chani, K. S. Karimov, A. M. Asiri, M. Bashir and R. Tariq, "Humidity and temperature sensing properties of copper oxide: Si-adhesive nanocomposite," Talanta, vol. 120, pp. 443-449, 2014.

12:10: [CompositeTueAM03]
Experimental Investigation of Drilling Carbon Fiber Reinforced Plastic Composite Materials
Kamlesh Phapale¹ ; ¹Bharat Forge Ltd., Pune, India;
Paper Id: 91 [Abstract]

Composite materials are the emerging material for enormous applications in various engineering domains in place of conventional material, due to its extremely high strength to weight ratio and corrosion resistance properties. The composite laminates are difficult to machine materials, which results into low drilling efficiency and drilling induced delamination. These problems can affect mechanical properties of produced parts, therefore, lower reliability. Drilling is a widely used technique to assemble components specifically, in more complex structures. This paper presents the experimental characterization to understand the effect of cutting parameters used for drilling holes on the thrust force, delamination extent, and hole surface roughness using two-flute solid carbide twist drill of diameter 6.35mm. It also describes the identification of critical thrust force below which no damage occurs. Results show that the feed rate plays dominant role in delamination, thrust force and hole surface roughness than the spindle speed.

References:
[1] Tsao C.C, Chiu Y.C., Evaluation of drilling parameters on thrust force in drilling carbon fiber reinforced plastic (CFRP) composite laminates using compound core-special drills, International Journal of Machine Tools & Manufacture 51(2011),740-744.
[2] Gaitonde V.N, Karnik S.R, Campos Rubio J, Esteves Correia A, AbrA�o A.M and Paulo Davim J. A study aimed at minimizing delamination during drilling of CFRP composites, Journal of Composite Materials 2011 45: 2359
[3] Gay D, Hoa SV, Tsai SW. Composite materials design and applications. New York: CRC Press; 2003.
[4] Davim JP, Reis P, Antonio CC. Experimental study of drilling glass fiber reinforced plastics (GFRP) manufactured by hand lay-up. Compos Sci Technol 2004; 64:289a��97.
[5] Stone R, Krishnamurthy K. A. Neural network thrust force controller to minimize delamination during drilling of graphite-epoxy laminates. Int J Mach Tools Manuf 1996; 36:985a��1003.
[6] Tsaoa C.C, Hocheng H. Computerized tomography and C-Scan for measuring delamination in the drilling of composite materials using various drills. Int J Mach Tools Manuf 2005; 45:1282a��1287.
[7] Krishnaraj V, Zitoune R, Collombet F, Davim P. Challenges in drilling of multilaterals. Mater Sci Forum 2013; 763:145a��68.
[8] Tsaoa C.C, Hocheng H. Computerized tomography and C-Scan for measuring delamination in the drilling of composite materials using various drills. Int J Mach Tools Manuf 2005; 45:1282a��1287.
[9] DeFu Liu, YongJun Tang, W. L. Cong. A review of mechanical drilling of composite laminates. Composite Structures 94 (2012):1265a��1279.
[10] Pierre RahmA�, Yann Landon, FrA�dA�ric Lachaud, Robert Piquet & Pierre Lagarrigue. Analytical models of composite material drilling. Int J Adv Manuf Technol (2011); 52:609a��617.
[11] Khashaba UA. Drilling of polymer matrix composites: A review, Journal of Composite Materials 2013 47: 1817 originally published online 10 July 2012.

12:35: [CompositeTueAM04]
Electron Beam Surface Hardening of AISI H13 Tool Steel
Sandeep Thakare¹ ; ¹Bharat forge limited, pune, India;
Paper Id: 147 [Abstract]

AISI H13 is an excellent hot work tool steel commonly used for manufacturing dies. These dies are subjected to working conditions with continuous cyclic thermo-mechanical loading, which results into surface failure of dies. So in order to enhance the service life of the die, surface hardening by electron beam is proposed. In this paper, effect of electron beam scanning speed on the hardening case depth of an AISI H13 sample was studied. Microstructure of EB hardened layer has been characterized by optical microscope. The tribological performance of hardening was investigated by pin on disk wear testing. It is found that effective case depth increases with decrease in the scanning speed.

References:
[1] M. Newishy, Microstructure and mechanical properties of AISI H13 tool steel processed by laser surface melting.
[2] J. Toshiki Hirogaki, In-situ heat treatment system for die steels using YAG laser with a
machining center, Precision Engineering, 25, 212-217, 2001.
[3] A.I. Katsamas, Surface hardening of low-alloy 15CrNi6 steel by CO2 laser beam.
Surface and Coatings Technology 115, 249-255, 1999.
[4] T.I. Khan, The effect on wear behaviour of H13 tool steel surfaces modified using a
tungsten arc heat source Wear 244, 154-164, 2000.
[5] John C. Bergeron, Failure Analysis of H13 Gear Blank Forging Dies, Department of
Materials Science and Engineering, Michigan Technological University, May 22, 2004
[6] Tauqir A, Zaigham H, Hashmi FH, Khan AQ. J Mater Sci 1997;32:465.
[7] Electron beam hardening , Katsuyuki Matsui, Shiroh Uchida, Takayuki Hirata, Masahiko Kumano Int. J. of Materials and Product Technology, 1990 Vol.5, No.3, pp.220-230

SESSION: CompositeTuePM1-R8	6th Intl. Symp. on Composite, Ceramic and Nano Materials Processing, Characterization and Applications
Tue Nov, 6 2018 / Room: Grego (50/3rd)
Session Chairs: Emrah Ozensoy; Pragati Kumar; Session Monitor: TBA

14:00: [CompositeTuePM105]
Enhanced Precious Metal-free LaCo&lt;sub&gt;x&lt;/sub&gt;Mn&lt;sub&gt;1-x&lt;/sub&gt;O&lt;sub&gt;3&lt;/sub&gt; Hybrid Perovskite Catalysts with Fine-Tunable Redox Properties
Emrah Ozensoy¹ ; ¹Bilkent University, Ankara, Turkey;
Paper Id: 221 [Abstract]

Simple (LaMnO₃ and LaCoO₃) and complex hybrid perovskites (LaCo_xMn_1-xO₃) were synthesized, and their catalytic functionality and thermal/chemical durability were investigated in a comparative manner. Structural properties as well as catalytic behavior of these hybrid perovskite structures were examined comprehensively, using a multitude of in-situ and ex-situ characterization techniques such as XRD, BET, TEM-EDX, STEM, ICP-MS, TPR, and ex-situ and in-situ XANES, and were compared to that of LaMnO₃ and LaCoO₃ benchmark systems. Adsorption and desorption properties of NOx species examined by in-situ FTIR and TPD revealed a superior NOx storage capacity (NSC) and thermal stability for LaCo_0.7Mn_0.3O₃ and LaCo_0.8Mn_0.2O₃ hybrid perovskites as compared to that of LaMnO₃ and LaCoO₃.TPR and in-situ XANES results suggested that Mn addition enhances thermal stability by suppressing the sintering of Co at high temperatures and enhances NOx storage by increasing the number of NOx adsorption sites. Ex-situ XANES and XPS results suggested that Mn addition alters the oxidation state of Mn and Co via Mn³⁺+ Co³⁺ -> Mn⁴⁺ +Co²⁺ leading to a stoichiometrically defective but functionally enhanced structure. Hybrid perovskites were also found to facilitate N-O bond activation. NOx TPD results point out that treatment with H₂(g) further enhances the NSC of hybrid perovskites due to the formation of oxygen vacancies and OH^- radicals. These results suggest that B-site cations of perovskites play a crucial role both in catalytic activity and stability. Current findings reveal valuable molecular-level insights regarding the origins of the fine-tunable redox/catalytic behavior of mixed perovskite systems, which could be applicable to a large variety of catalytic systems to enhance catalytic activity, structural durability, and selectivity.

References:
[1] K. E. Ercan, Z. Say, M. Kurt, M. Karatok, G. Pantaleo, L., F. Liotta, E. Ozensoy, submitted (2018)
[2] Z. Say, Z., M. Dogac, E. I. Vovk, Y. E. Kalay, C. H. Kim, W. Li, E. Ozensoy, Applied Catalysis B: Environmental, 154-155 (2014) 51.
[3] M. Kurt, Z. Say, K. E. Ercan, E. I. Vovk, C. H. Kim, E. Ozensoy, Topics in Catalysis, 60 1-2 (2017) 40.

14:25: [CompositeTuePM106]
Nanotwinning in Materials: A Worthy Defect for Superior Properties
Pragati Kumar¹ ; Prateek Uttam¹ ; Nupur Saxena¹ ; ¹Central University of Jammu, Jammu, jammu, India;
Paper Id: 242 [Abstract]

This article reviews current primary analysis on twin boundaries defect at nano-regime. We emphasis essentially on studies that intent to understand, through modelling, experiments, or both, the origin and effects of twinning at elementary level. We foresee that, by imparting an extensive viewpoint on the happening progress in twinning, this analysis will pitch in the juncture for designing or tracing new metallic and semiconductor materials with modified alter properties like thermoelectric¹, mechanical², optical^3,4, ferroelectric and magnetic⁵ etc. Since it is nearly unworkable to slog with defect free or impurity free materials, it is vital to comprehend how defects and impurities modify the properties of the materials. To be specific, it is more necessary to differentiate between distinct types of impurities (defects) and decide if their existence is favourable or not, so that we can use it as per our requirement and can be used in different application by enhancing various properties of the material. We have analysed these issues and provided an updated overview of the current characterization tools able to identify and detect defects in different forms of materials, and also made an overview on the possible applications

References:
[1] G. Li, S.I. Morozov, Q. Zhang, Q.An, P. Zhai, and G.J. Synder, Physical Review Letter 119 (2017) 215503.
[2] I.A. Ovidako and A.G Sheinerman, Rev.Adv.Mater.Sci.44(2016)1
[3] Y.Q. Wang, R. Smirani and G.G. Ross Nano Lett. 4, (2004) 2041.
[4] P. Kumar, N. Saxena, F. Singh and A. Agarwal, Physica B:Condensed Matter 407 (2012) 3347
[5] X. Li, C. Lu, J. Dai, S. Dong, Y. Chen, N. Hu, G. Wu, M. Liu, Z. Yan and J.M Liu, Scientific Reports 4 (2014) 7019

SESSION: MathematicsTuePM2-R8	3rd Intl. Symp. on Sustainable Mathematics Applications
Tue Nov, 6 2018 / Room: Grego (50/3rd)
Session Chairs: Peter Rowlands; Constantin Udriste; Session Monitor: TBA

15:55: [MathematicsTuePM209] Plenary
The "Unreasonable" Effectiveness of Mathematics in Physics
Peter Rowlands¹ ; ¹University of Liverpool, Liverpool, United Kingdom;
Paper Id: 217 [Abstract]

The ‘unreasonable’ effectiveness of mathematics in physics was famously proposed as a problem by Eugene Wigner in 1960. The explanation is far from obvious, as the vast bulk of mathematics has never found a significant physical application, while the physical world often resists the easy extensions that mathematics could provide. It is easy, for example, in mathematics to create theories of physics with 10 and 11 dimensions, yet the physical world we observe obstinately refuses to allow more than 3 dimensions of space and 1 of time. Something in physics causes this restriction, which is not a logical outcome of the mathematics. There must be another principle at work. We will propose that the mathematics most successfully used in physics is not an ‘application’ of a pre-existing independent system but a natural growth that emerges with the fundamental concepts it describes, and that nature operates on an astonishingly simple algorithm which is similar to but not identical with the principles of computer science. The physics that results effectively creates its own mathematical structure, which also seems to have applications in biology and other areas of science.

References:
[1] E. P. Wigner, E. P., Communications on Pure and Applied Mathematics (1960) 13: 1-14.

16:20: [MathematicsTuePM210] Invited
Multitime Optimal Control in Resource Economics
Constantin Udriste¹ ; ¹University Politehnica of Bucharest, Bucharest, Romania;
Paper Id: 191 [Abstract]

Multitime optimal control theory has been recently used in economics. Here, we develop some ideas using the context of optimal control and differential geometry. Specifically, two problems are analysed: (i) multitime evolution of reproducible resources, and (ii) multitime evolution of non-reproducible resources. The technique is to associate each problem with proper functional (like multiple integral or curvilinear integral) and appropriate constraints (geometric PDEs like m-flows, Goursat-Darboux PDEs, parallelism PDEs, and specific isoperimetric constraints like integrals). When the Hamiltonian is linear affine in the control, we focus on bang-bang and singular optimal controls.

References:
[1] C. Udriste, M. Ferrara, Multi-time optimal economic growth, Journal of the Calcutta Mathematical Society, 3, 1 (2007), 1-6.

[2] C. Udriste, M. Ferrara, Multitime models of optimal growth, WSEAS Transactions on Mathematics, 7, 1 (2008), 51-55.

16:45: [MathematicsTuePM211]
Reconsideration of Continual and Statistical Mechanics Based on Scalar Representation of Deformation
Valeriy Ryabov¹ ; ¹Department of Nuclear Technology, National Research Centre, Obninsk, Russian Federation;
Paper Id: 175 [Abstract]

Theory of particle and continuous mechanics is developed, which allows a treatment of deformation in terms of molecular variables "coordinate-momentum-force", instead of the standard treatment in terms of tensor-valued variables "strain-stress". The new concept is based on a representation of the classical mechanics on the surface of Euclidean 6-torus. The six parameters representing the topological dimensions of the torus are responsible for three stretches and three angles related to their orientation in a deformed body. A withdrawal of the strain description from the coordinate system of deformed body to an extended one changes and simplifies essentially all computational basis in particle, continual and statistical mechanics. Instead of stress-strain relation the new constitutive equations contain a dependence of generalized tension forces acting on each atom (or small element of mass) on scalar deformation parameters. In other words, any notions of surface or volume forces could be excluded from statistical and continual mechanics. The novel concept generates a new type of ensemble with constant tension force NfE. The much simpler principle of virtual work implicit there gives a serious advantage over the widespread isostress ensemble NtE in molecular dynamics (MD) simulations. Besides, the equality of internal tension forces to the boundary forces (traction) enables fully atomistic MD calculations of deformation. In thermodynamic limits, instead of the pressure and volume as state variables, this ensemble employs deformation forces measured in energetic unit and stretch ratios. So the changes might be spread even to formulas in school textbooks. The governing equations of nonlinear elastostatics for inhomogeneous medium are also formulated. Unlike the standard theory, there is no need for compatibility conditions or the Saint-Venant's principle to justify solutions to boundary value problems in elasticity theory. It suggests a completely different strategy in continual mechanics computations. The conventional algorithms use a finite element analysis for strain-driven constitutive equation. Unlike this, a discretization schema in terms of scalar deformation variables is dealing directly with coordinate dependence of large scale deformation based on fully atomistic foundation. But the most important consequence of derived approach is that the continual mechanics ceases to be a separated and independent branch of theoretical physics, and instead goes over to a part of particle physics. Several key examples illustrate the implementation of the new theory in calculations of statics and dynamics and thermodynamics of deformed solids.

References:
[1] V.A. Ryabov, Mechanics of deformations in terms of scalar variables. Cont. Mech. Thermodyn. Springer, 29, 3, 715 (2017).
[2] V.A. Ryabov, Implementation of isotension ensemble in molecular dynamics. Comp. Meth. Appl. Mech. and Eng., Elsevier, accepted for publication (2018).

17:10: [MathematicsTuePM212]
Steady Biomagnetic Flow Along a Nonlinearly Stretching Surface with Magnetic Dipole
Ferdows Mohammad¹ ; Maria Mahbub² ; E.e. Tzirtzilakis³ ; ¹, Dhaka, Bangladesh; ²M.SC stdent, dhaka, Bangladesh; ³Professor, Patras, Greece;
Paper Id: 354 [Abstract]

A mathematical analysis has been put forward that deals with, in particular, the flow of a heated Ferro-fluid over a linearly stretching sheet under the action of a magnetic field generated by a magnetic dipole [1]. Mathematical models have been developed for investigating the flow of a biomagnetic viscoelastic fluid over a stretching sheet, as well as in a channel with stretching walls under the action of an externally applied magnetic field generated by a magnetic dipole [2]. A great amount of significant work has been done on sheet stretched with nonlinear velocity. Fluid flow over a nonlinearly stretching sheet has been investigated [3]. In this study, the flow of a biomagnetic fluid over a sheet stretched with a non-linear velocity is studied with an applied magnetic field present in the fluid due to a magnetic dipole and heat transfer in the flow. This study mainly emphasizes the properties of biofluid flow considering two specified circumstances: one is magnetic field and the other one is non-linear velocity of the stretching sheet. Nevertheless, the magnetic field that has been produced by the dipole is strong enough to saturate the biomagnetic fluid flow. A non-linear system of ordinary differential equations has been introduced with some appropriate boundary conditions. They will be consistent with the principles of Ferrohydrodynamics (FHD) and Magnetohydrodynamics (MHD). Through performing non-dimensionalization in the variables involved and then by solving them using a suitable dsolve routine in Maple software graphical representations are produced to show how the flow properties vary with some dimensionless parameters. The parameters that have effects on them are Prandtl number (Pr), biomagnetic interaction parameter (B) and nonlinear stretching parameter (n). After comparing with previously published work, the achieved results seem to be in good agreement. Hopefully, this study is helpful for more accurate understanding of blood flow in human body suffering from arterial or vascular diseases.

References:
[1] E. E. Tzirtzilakis and N. G. Kafoussias, Biomagnetic fluid flow over a stretching sheet with nonlinear temperature dependent magnetization, Zeitschriftfur Angewandte Mathematik und Physik, 54(4), 551-565 (2003).
[2] J. C. Misra and G. C. Shit, Biomagnetic viscoelastic fluid flow over a stretching sheet, Applied Mathematics and Computation, 210(2), 350-361 (2009). 41) K. Vajravelu, J.R. Cannon, Fluid flow over a nonlinearly stretching sheet, Applied Mathematics and Computation, 181(1), 609-618(2006).
[3] K. Vajravelu, J.R. Cannon, Fluid flow over a nonlinearly stretching sheet, Applied Mathematics and Computation, 181(1), 609-618(2006).

SESSION: AdvancedMaterialsWedAM-R8	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Grego (50/3rd)
Session Chairs: Michael Potesser; Session Monitor: TBA

11:20: [AdvancedMaterialsWedAM01] Invited
Layered Double Hydroxides-based Materials as Catalysts for Sustainable Chemical Processes
Ioan-cezar Marcu¹ ; ¹Laboratory of Chemical Technology & Catalysis, Faculty of Chemistry, University of Bucharest, Bucharest, Romania;
Paper Id: 169 [Abstract]

Layered double hydroxides (LDH) belong to the anionic clays family, having the general formula M²⁺_1-xM³⁺_x(OH)₂A^n-_x/n·mH₂O with a M²⁺/M³⁺ molar ratio between 1.5 and 4 [1]. M²⁺ and M³⁺ are bivalent (e.g., Mg²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺) and trivalent (e.g., Al³⁺, Ga³⁺, In³⁺, Cr³⁺, Mn³⁺, Fe³⁺) cations, respectively, with ionic radii not too different from that of Mg²⁺ [2]. They are hexa-coordinated to hydroxyl groups, forming brucite-like sheets which stack to create a layered structure. A large variety of inorganic and organic counter-anions A^n- can be intercalated in the inter-layer space to compensate the positive charge introduced by the M³⁺ cations partially replacing M²⁺ cations in the layers. Two or more cations can simultaneously enter the brucite-like sheets, where they are homogeneously distributed and intimately mixed together. Due to their structure, along with their compositional flexibility, the LDH possess versatile physico-chemical properties which make them good candidates as multifunctional nanostructured catalysts and catalyst precursors [1, 3].<br />Various transition metals cations can be introduced into the layers of the LDH structure, but also into the inter-layer space as heteropolyanions and organometallic complexes where they are responsible for the redox properties of these materials and, therefore, for their catalytic properties in oxidation reactions. They can be used as such, particularly for low-temperature liquid-phase oxidation and epoxidation processes, or as mixed oxides obtained by their controlled thermal decomposition for high-temperature gas-phase selective oxidation, oxidative dehydrogenation, and total oxidation processes [4].<br />The thermal decomposition of the LDH leads to highly homogeneous mixed oxide structures with high specific surface areas, thermal stabilities, and tunable acid-base and redox properties. Due to these properties, the transition-metal-containing mixed oxides obtained from LDH precursors have been recognized as very promising catalysts for sustainable chemical processes, such as catalytic selective oxidation for obtaining chemicals and intermediates and complete oxidation as a promising valuable technology for the destruction of volatile organic compounds [4].<br />Through a number of examples selected mainly from our own research work, the high potential of transition-metal-containing LDH-based materials as catalysts for sustainable oxidation processes will be clearly demonstrated based on the correlation preparation method— physico-chemical characteristics— catalytic performance.

References:
[1] D. Tichit, B. Coq, CATTECH 7 (2003) 206-217.
[2] F. Cavani, F. Trifiró, A. Vaccari, Catal. Today 11 (1991) 173-301.
[3] G. Fan, F. Li, D. G. Evans, X. Duan, Chem. Soc. Rev. 43 (2014) 7040-7066.
[4] I. C. Marcu, A. Urdă, I. Popescu, V. Hulea, in Sustainable Nanosystems Development, Properties and Applications, M.V. Putz, M.C. Mirică (Eds.), IGI Global, Hershey, 2017, Ch. 3, p. 59-121.

11:45: [AdvancedMaterialsWedAM02]
Advanced Experimental Design and Optimization Methods for New Building Materials Developed in Civil Engineering
Daniel Lepadatu¹ ; Loredana Judele¹ ; Ion Antonescu¹ ; ¹Technical University Gheorghe Asachi of Iasi, Faculty of Civil Engineering and Building Service, IASI, Romania;
Paper Id: 176 [Abstract]

In civil engineering, the development of new materials has been highly dynamic, when taking into account the progress of research as well as the high demand driven by society. Due to the constantly diminishing primary natural resources, the global economy is increasingly focusing on recycling waste and reintroducing it into the circuit of creating new materials with improved properties. In this context, the current paper aims to present advanced experimental designs and optimization methods as alternatives to existing ones, as they not only involve very high additional costs, but whose capacity is also being surpassed. Thus, we present a set of methods that by their specific nature contribute to diminishing the time of the research, development, and obtaining of new materials, but also to the drastic reduction of the costs related to the experimental calibration. "It's about Design of Experiments", together with "Response Surface Methodology", offers to researchers an advanced approach to experimental designs with the possibility of quantifying the influence of different factors on this process, and the needed combination to optimize certain characteristics of them. Artificial Neural Networks are another way to obtain this time by learning from the examples of the required combination to optimize. A comparison of the two methods will also be presented. All these will have both a theoretical approach and also one based on the scientific work of the authors, and not only using these methods. Thus, the new materials developed in civil engineering will be produced using experimental design adapted to the complexities of physical phenomena, which are often unknown, involved in this process, and also optimizing their properties by obtaining some characteristics that respond to the requirements of safety, security, and durability.

References:
[1] Douglas C. Montgomery, Design and Analysis of Experiments, John Wiley & Sons, (2012).
[2] Bliuc I., Lepadatu D., Iacob A., Judele L., Bucur, R. D. Assessment of thermal bridges effect on energy performance and condensation risk in buildings using DoE and RSM methods European Journal of Environmental and Civil Engineering, Taylor & Francis, 21 (2017) 1466-1484.
[3] Barbuta M, Marin E., Cimpeanu S. M., Paraschiv G., Lepadatu D., and Bucur R. D., Statistical Analysis of the Tensile Strength of Coal Fly Ash Concrete with Fibers Using Central Composite Design, Advances in Materials Science and Engineering, Volume (2015) 7 pp.
[4] Samarasinghe S, Neural Networks for Applied Sciences and Engineering: From Fundamentals to Complex Pattern Recognition, by Auerbach Publication, (2012).
[5] Lepadatu D, Barbuta M., et all., Mechanical characteristic prediction on polymer concrete with silica fume using artificial neural network, Proceedings of 14th SGEM GeoConference on Nano, Bio And Greena-Technologies, Vol. 2 (2014) 235-242.

12:10: [AdvancedMaterialsWedAM03]
Modern Methods of Determining Road Bitumen Adhesiveness to Natural Aggregates
Loredana Judele¹ ; Daniel Lepadatu¹ ; Iulian Cucos² ; Mihaela Movila¹ ; ¹Technical University Gheorghe Asachi of Iasi, Faculty of Civil Engineering and Building Service, IASI, Romania; ²Technical University Gheorghe Asachi of Iasi, Faculty of Hydrotechnical Engineering, Geodesy and Environmental Engineering, IASI, Romania;
Paper Id: 186 [Abstract]

Asphalt coatings are preferred for the construction and/or rehabilitation of highways. They are very common in the world, and have the advantage of being more easily executed and maintained than cement concrete. The use of new technologies using added and/or modified bitumen, fiber additions (cellulose, synthetics, etc.) has been observed in recent years, allowing for improved performance in terms of increased lifetime and widening the thermal domain where the mix improves its properties. Adhesion between bitumen and natural aggregates is a key factor in the service life of wearing courses. Very often, the cause of the defects appearing on the surface of the road can be attributed to an inadequate adhesiveness between the bitumen and the natural aggregates. The main function of the bitumen is to act as an adhesive, and its good adhesiveness to the mineral aggregate is essential for obtaining a mixture of high quality asphalt. The need to ensure a link between aggregates and asphalt is very important and that is why we use, more and more often, the doping of bitumens, namely to add small amounts additive (0.1-0.5%) in the bitumen mass. Analyzing and assessing wetted materials in the laboratory is not an easy mission. They are based especially on the expert opinion (assessment) of the technician that performs the assays, even if some of the mechanical characteristics are quantified or standardized. Although the incidence of premature failure due to adhesiveness is relatively rare, fractures can involve significant costs when they occur. The goal of this research is to compare the adhesiveness results of a set of bitumen (achieved through quantitative determination method and Rolling Bottle Method (RBM) like classic methods) to the results achieved through experimental trials on the same set using the "Average Percentages of Black" (APB) method and PHP program. Not only are the two sets of results compared, but also the two methods—a traditional and a modern one, each with their own advantages and disadvantages.

References:
[1] Nasler I., H. Beckedahl, Adhesion between aggregates and bitumen - performance testing of compacted asphalt specimens by means of the dynamic indirect tensile test, Euroasphalt&Eurobitume Congress; Barcelona (2000).
[2] Gugiuman G. Bitume routier avec adjouvant- Euroasphalt&Eurobitume Congress; Barcelona (2000).
[3] Mohammad I. Hossain, Rafiqul A. Tarefder, Determination of Adhesive and Cohesive Damages in Asphalt Concrete by Finite Element Method, International Journal of Civil Engineering and Structures, ISSN: 2160-6676, 1,1, (2012).
[4] Judele L., M. Barbuta, D. Lepadatu, Structure and role of additive in bitumen adhesion to natural aggregates, 14th SGEM GeoConference on Nano, Bio And Green - Technologies For A Sustainable Future, Vol. 2, No. SGEM2014 Conference Proceedings, ISBN 978-619-7105-21-6, 2, (2014), 307-314.
[5] Judele L., THE MECHANISM OF BITUMEN ADHESION TO AGGREGATES THE INFLUENCE OF MINERALOGYC NATURE, Bulletin of the Polytechnic Institute of Iassy, Tom LVII(LXI), 2, (2011), 175-181.

12:35: [AdvancedMaterialsWedAM04] Invited
Applications of Chalcogenides: S, Se, and Te
Gurinder Ahluwalia¹ ; ¹COLLEGE OF THE NORTH ATLANTIC, Labrador City, Canada;
Paper Id: 164 [Abstract]

The changing landscape of research, from pure scientific ventures towards industrial applications, necessitates investigation of novel materials for several applications. In the present work, I will discuss various aspects of research on materials for industrial applications, with emphasis on use of chalcogenides for optical fibers, electrochemical sensing, imaging and detection, biochemical sensing, data storage, photovoltaics and infrared detection. The peculiar properties of chalcogenides arise due to the lone pair orbitals forming the valence band as a result of their electronic configuration. At the same time, dangling bonds play an important role to modify the electrical behavior of chalcogens in amorphous forms. In particular Sulfur (S), Selenium (Se) and Tellurium (Te) find applications in a variety of devices used in the electronics and optoelectronics industry. Sulfur based materials exhibit interesting properties such as a high refractive index, large Kerr non-linearities, ability to be directly patterned by exposure to near band gap light, good transmission in the IR beyond 1.5m. Selenium based materials find wide applications in rectifiers, solar cells, photographic exposure meters, xerography and anticancer agents. It is also used in the glass industry to eliminate bubbles and remove undesirable tints produced by iron. In addition, selenium also has a high reactivity towards a wealth of chemicals that can be potentially exploited to convert selenium into other functional materials such as CdSe, ZnSe, Ag2Se and so on. Selenium based materials in amorphous form are used for imaging and biomedical applications. In crystalline form, their combination with other materials such as lead (Pb), Copper (Cu) and Indium (In) are widely used for photovoltaic and photo-detection applications. Se and Te are lone pair, polymeric divalent materials with chain structures. They can be designed to bond with cross-linking elements of different bond strengths such as Ge, Sb and As. The cross linked Te/Se alloys have a huge number of non-bonded lone pair electrons which could easily be excited by optical and electrical fields. When the amorphous phase cannot contain the excitation energy, a phase change to a crystalline phase occurs. Such polymeric lone pair structures are vibronic in nature wherein electronic transitions are made possible by vibrational motion of the chains. These simultaneous vibrational and electronic transitions form the basis of optical and electrical phase change memories. Tellurium based materials are widely used for data storage devices based on phase change characteristics exhibited by them. Applications such as optical fibers for communication and sensing, X-ray imaging, electrochemical sensors, data storage devices, biomedical applications, photovoltaics and IR detectors will be presented and the future scope and expected improvements to existing technologies will be discussed depending on the availability of time.

References:
[1] Applications of Chalcogenides: S, Se and Te. Ed Gurinder Kaur Ahluwalia, Springer 2017

SESSION: AdvancedMaterialsWedPM1-R8	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Grego (50/3rd)
Session Chairs: Yashika Gupta; Jarugu Narasimha Moorthy; Session Monitor: TBA

14:00: [AdvancedMaterialsWedPM105]
Investigating Reasons for Poor Performance of CdS/p-SnS Solar Cells
Yashika Gupta¹ ; Arun Palakkandy² ; ¹University of Delhi, Delhi, India; ²S.G.T.B. Khalsa College, University of Delhi, Delhi, India;
Paper Id: 190 [Abstract]

Search for an efficient and low cost alternative to Silicon-wafer solar cells has led to the popularity of thin film photovoltaics. Tin Sulphide (SnS), being an earth abundant, cheap, and less toxic semiconducting material [1,2] with a high absorption coefficient (> 104 cm-1) in visible range [3], stands out as a potential candidate. Theoretical simulations by Loferski et al. [4] predicted 24% efficiency for SnS based solar cells, however maximum efficiency achieved to date is far less than the predicted value. In this work, a detailed analysis of the poor performance of CdS/p-SnS heterojunction solar cells is carried out. ITO/CdS/p-SnS/Au solar cells with varying thickness of p-SnS absorber layer were made using a thermal evaporation technique. Best conversion efficiency of 0.005% was obtained for the cell having p-SnS layer of thickness 1068nm. Defects present in p-SnS thin films along with the band misalignment at the interface of CdS/SnS layers lead to poor performance of the cell by increasing the trap-assisted tunneling recombinations at the junction. Ideality factor was calculated from the dark J-V characteristics, using the modified piecewise model [5] to quantify the junction characteristics. It was found that the ideality factor has a direct impact on the device performance, with efficiency decreasing as the ideality factor of the junction increases.

References:
[1] H.Noguchi, A.Setiyadi, H.Tanamura, T.Nagatomo, O.Omoto, Sol. Energ. Mater. Sol. Cells 35 (1994) 325.
[2] C.Gao, H.Shen, L.Sun, Z.Chen, Mater. Lett. 65 (2011) 1413.
[3] G.H.Yue, D.L.Peng, P.X.Yan, L.S.Wang, W.Wang, X.H.Luo, Alloys Compd. 468 (2009) 254.
[4] J.J.Loferski, J. Appl. Phys. 27 (1956) 777.
[5] Y.Gupta, P.Arun, JAPED (accepted, 2017).

14:25: [AdvancedMaterialsWedPM106]
Stimuli-Responsive Materials: Bottom-Up Control of Material Properties by De Novo Molecular Design
Jarugu Narasimha Moorthy¹ ; ¹Dept of Chemistry, IIT Kanpur, IIT Kanpur, India;
Paper Id: 192 [Abstract]

The properties of bulk organic materials are determined by organization of their constituents' molecules. Implicit within is the fact that the structures of organic molecules that make up the bulk materials crucially control the properties of the latter. We believe that organic structure is essential to control both reactivity as well as molecular organization, and hence the properties of materials. I will demonstrate how organic compounds may be maneuvered by a diligent design to control photoreactivity[1] and molecular self-assembly to develop functional materials.[2] As to the latter in particular, I will present our very recent de novo approaches to the development of stimuli-responsive 2D metal-organic framework nanosheets (MONs).[3]

References:
[1] Moorthy, J. N.; Mandal, S.; Parida, K. Org. Lett, 2012, 14, 2438. (b) Moorthy, J. N.; Mandal, S.; Mukhopadhyay, A.; Samanta, S. J. Am. Chem. Soc., 2013, 135, 7872. (c) Mukhopadhyay, A.; Maka, V.; Moorthy, J. N. Eur. J. Org. Chem. 2015, 1403. (d) Mukhopadhyay, A.; Maka, V.; Moorthy, J. N. Photochem. Photobiol. Rev. C. 2016, 29, 73.

[2] Seth, S.; Savitha, G.; Moorthy, J. N. J. Mater. Chem. A. 2015, 03, 22915. (b) Seth, S.; Savitha, G.; Moorthy, J. N. Inorg. Chem. 2015, 54, 6829. (c) Chandrasekhar, P.; Mukhopadhyay, A.; Savitha, G.; Moorthy, J. N. Chem. Sci. 2016, 07, 3085. (d) Chandrasekhar, P.; Savitha, G.; Moorthy, J. N. Chem. Eur. J. 2017, 23, 7297.

[3] Chandrasekhar, P.; Mukhopadhyay, A.; Savitha, G.; Moorthy, J. N. J. Mater. Chem. A. 2017, 5, 5402. (b). Mukhopadhyay, Maka, V.; Savitha, G.; Moorthy, J. N. Chem (Cell Press), 2018, ASAP.

14:50: [AdvancedMaterialsWedPM107]
The Multi-layer Structures Based on TiO₂ for Multifunctional Glazing Surface
Luminita Andronic¹ ; ¹Transilvania University of Brasov, Brasov, Romania;
Paper Id: 215 [Abstract]

Multi-layer structures based on TiO₂ have been designed, developed, and assembled into functional nanostructures at the molecular-level to control the materials' properties. Controlling microstructure and homogeneity of nano-sized materials with well-defined properties will be done by sol-gel method and dip-coating methods. Due to the possibility of controlling the hydrolysis, condensation, and densification processes, the sol-gel method offers the opportunity to synthesize a large variety of new materials. The glazing surfaces with photocatalytic water pollutants decontamination, low-E and thermochromic properties were obtained by epitaxial growth of nanostructures on commercial low-E glass substrate, thus ensuring multi-functionality of existing materials on the market, for the next generation of integrated windows in buildings with low energy consumption. The thin films with multi-layers structure had following structure: substrate (low-E glass)/layer 1/layer2. Layer 1 is an oxide thin film of TiO₂ formed on the substrate, and acts as a barrier to prevent Na⁺ from diffusing into the thermochromic layer. Layer 2 is a thermochromic layer of V_xO_y. Characterisation of coating on low-E glass in terms of crystallinity, roughness, morphology, band gap energy, functional properties of glazing, and optical properties (transmittance, reflectance, and absorbance) will be performed. Materials that have transmittance of <70% are considered non-compliant with the target of at least 80% for which the glazing had kept the visual comfort. The coatings passed the stability and durability tests in climate chamber, humidity, salt spray testing, and exposure of glazing to a dry atmosphere at a temperature of 0-50°C, according to the ISO/ASTM standards. Photocatalysis standard tests of pollutants degradation consist in efficiency evaluate of methylene blue (MB) photodegradation in aqueous solution, according ISO 10678/2010.

References:
[1] A. Hosein, G. Hoseini, N. Dalilah Dahlan, U. Berardi, A. Ghaffarian Hoseini, N. Makaremi, M. Ghaffarian Hoseini, Renewable and Sustainable Energy Reviews 25 (2013) 1-17.
[2] K. Midtdal, P. Jelle, Bjorn, Solar Energy Materials and Solar Cells 109 (2013) 126-141.
[3] L. Long, H. Ye, Solar Energy 107 (2014) 236-244.

15:15: [AdvancedMaterialsWedPM108]
Heusler Alloy Thin Films Fabricated by DC Magnetron Co-sputtering
Jan Lancok¹ ; Stanislav Cichon² ; Katerina Horakova² ; Vladimir Chab² ; ¹Institute of Physics ASCR, Prague 8, Czech Republic; ²Institute of Physics ASCR, Prague, Czech Republic;
Paper Id: 257 [Abstract]

Heusler compounds have composition XYZ (so called half-Heuslers) or X₂YZ (so called full-Heusler). Their tuneability originates from large number of elements. This provides the opportunity to adjust electronic structure and hence material properties in many desired directions, such as: half-metallic material for spintronic applications, zero-gap topological semiconductors etc [1]. The properties of Heusler alloys are very sensitive to any non-stoichiometry and crystalline defect. Due to this, in our work we presented the fabrication of the thin films by DC magnetron sputtering in Ar gas by co-sputtering from three single elements targets with independent controlled powers supplies, when the film composition was controlled by DC power. Depositions were carried out in an UHV vacuum chamber evacuated before deposition to pressure 5x10^-8 Pa. The plasma composition and energy of the species were monitored by mass spectroscopy using a Hiden 500 spectrometer. The relation between plasma properties and films structured was carefully examined. The spatial distribution of particular metals were characterised by means of EDX analyses performed at 3 inch Si substrate placed at the same target substrate distance. With this method, we fabricated two different kinds of Heusler alloys (i) magnetic Rh₂MnBi films with high (ii) ultrathin Fe₂ZrSi corrosion protection films. The structural properties of all films were studied by surface techniques such as STM, AFM, and by NanoESCA (Oxford instruments Omicron Nanoscience) instrument, which is based on a PEEM (Photoelectron Emission Microscope) and PES (Photoelecton Spectroscopy). The structural properties were characterized by XRD and SEM equipped by EDX and EDSB techniques. Firstly, the epitaxial Rh-Mn-Bi crystalline films were grown at substrate temperature from RT up to 500 °C on the MgO substrates. Theoretical calculations predict very high magnetic moment for Rh₂MnBi, Ai<i>μ_B</i> = 5 Bohr magnetons per formula unit. Another study reports calculations showing enhanced magneto-optical response of the material. However, in case of the Rh-Mn-Bi system, there is a huge dissimilarity among the metals; a) The melting temperature of Rh reaches 2000 °C b) Although the Mn melting temperature is relatively medium high, 1250 °C, it has a relatively high vapor pressure ; c) Mn oxidizes easily; d) The Bi melting temperature is only 271.4°C, and its vapor pressure is very high, which make the fabrication of these films very difficult. Our attention was focused on the relation of the deposition parameters on the structural and following magnetic properties of the films characterized by vibrating sample magnetometer and by Magneto-optical Kerr effect.<br />Secondly we studied initial stages of Fe and Si atoms interactions with Zr (0001) surface. Ultrathin Fe-Si films were evaporated on the Zr(0001) surface [2]. The formation of the stable corrosion resistance Fe₂ZrSi or FeZrSi Heusler alloys was formed. Following by means of DC magnetron sputtering, the multicomponenct gradient films Fe-Si-Zr from Zr, Fe and Si targets were fabricated on polycrystalline disc Zr (99%) with diameter 12 mm. The depositions were carried out in UHV conditions in pure argon atmosphere at substrate temperature varied from 20-700 °C [3]. Electrochemical Impedance Spectroscopy was employed to analyse the corrosion characterization of Zr with protective Heusler-like films. The effect of Fe-Si-Zr films composition and structure on surface chemistry, morphology, and corrosion behaviour of Zr was examined and evaluated.

References:
[1] T. Graf, S. S. P. Parkin, C. Felser, IEEE Transactions on Magnetics 47 (2011) 367.\n[2] K. Horkova, S. Cichoň, J. Lancok, P. Sajdl, V. Chab , Initial astages of Zr-Fe-Si alloy formation on Zr(0001) surface, Surface Science 657 (2017) 28-34.\n[3] K. Horakova, S. Cichoň, J. Lancok, I. Kratochvilova, L. Fekete, P. Sajdl, A. Krausova, J. Macak, V. Chab, Corrosion protection of zirconium surface based on Heusler alloy Pure and Applied Chemistry 89 (2017) 553-563.

SESSION: AdvancedMaterialsWedPM2-R8	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Grego (50/3rd)
Session Chairs: Firoz Babu Kadumudi; Adedeji Badiru; Session Monitor: TBA

15:55: [AdvancedMaterialsWedPM209]
Laponite-reinforced Nanocellulose: A Wood-based Substrate for Recyclable and Foldable Electronics
Firoz Babu Kadumudi¹ ; Mehdi Mehrali¹ ; Alireza Dolatshahi Pirouz¹ ; ¹Technical University of Denmark, Kgs Lyngby, Denmark;
Paper Id: 258 [Abstract]

The quantity and speed of electronic waste (E-waste) discard has increased rapidly in recent years. Research to develop electronics that disappear has progressively gained importance, as it's a necessity to assure a sustainable environment [1, 2]. Interest in emerging green electronics follows from possibilities for broad types of applications that cannot be addressed with traditional rigid electronics, such as flexibility and foldability. Flexible devices that can be easily fabricated on polymeric substrates, which typically constitute the majority of the weight in a device, are suitable for a broad range of applications to empower conformal devices and displays[1]. Nanocellulose, extracted from wood, has been explored as bio-derived and biodegradable materials due to its good thermo-mechanical properties[3]. Even still, the current substantial thermal mismatch between nanocellulose and inorganic electronics, can result in the malfunction of electronic devices[4]. In this work, we have developed rollable nanoclay incorporated nanocellulose free standing films for flexible and recyclable electronics with improving their coefficient of thermal expansion (CTE) and thermo-mechanical properties. Specifically, we have used Laponite® nanoclay to generate nacre mimetic nanocellulose films. The electrostatic interaction of Laponite® with nanocellulose formed a flexible film with mechanically stable, thermally stable (310 °C) and low CTE (40 ppm/°C) properties. Electronic patterns were deposited on Laponite®-nanocellulose films using lithographic techniques through a shadow mask, and demonstrated their possibility in foldable electronics applications. Note: Laponite® is a trademark of BYK Additives Ltd.

References:
[1] X. Liu, Y.-Z. Long, L. Liao, X. Duan, Z. Fan, ACS nano 2012, 6, 1888.\n[2] M. Irimia-Vladu, Chemical Society Reviews 2014, 43, 588.\n[3] D. Klemm, F. Kramer, S. Moritz, T. Lindstrom, M. Ankerfors, D. Gray, A. Dorris, Angewandte Chemie International Edition 2011, 50, 5438.\n[4] H. Zhu, W. Luo, P. N. Ciesielski, Z. Fang, J. Zhu, G. Henriksson, M. E. Himmel, L. Hu, Chemical reviews 2016, 116, 9305.

16:20: [AdvancedMaterialsWedPM210]
Achieving Sustainable Industrial Processing Through an Integrative Systems Engineering Framework
Adedeji Badiru¹ ; ¹Air Force Institute of Technology, Dayton, United States;
Paper Id: 301 [Abstract]

This paper introduces an integrative systems engineering framework for pursuing and achieving sustainable industrial processing. The environment is the setting, surroundings, or conditions in which living objects operate. Several concepts come together for sustainable industrial processing. The basic questions include the following: What needs to be done? What can be done? What will be done? Who will do it? When will it be done? Where will it be done? How will it be done? The aspects that are critical to sustainability are the most basic ones. These include the environment, chemistry, natural resources, energy, air, water, and their proper use, and finally the understanding of physics, chemistry, biology, and geology. As humans, we must be economical so that none of these resources become depleted without completing industrial processing goals. Many may ask, "Why should I protect my environment, and why should I be economical?" The answer is simple, it is for the well-being of all living and inanimate things. This well-being can be of an individual person, an organization, resources, work, proper living manners, production infrastructure, and personal satisfaction. Without being sustainable, our environment will suffer from aspects such as pollution and not having enough renewable resources, especially the essential ones. The same aspects that are considered in everyday life for our own well-being should be considered for our work environment as well. Emissions are powerful and must be reduced to be successful. Some companies are mandated to only pollute a certain percentage into the environment during industrial operations. Because of the multi-faceted aspects of sustainability, it is only through a structured and integrative systems view that sustainable industrial processing can be successful. Sustainable industrial processing is everyone's responsibility. We must all work together to pursue and implement intellectual initiatives and research to advance sustainable industrial processing. Systems engineering is essential for achieving this goal.

References:
Agustiady, Tina and Badiru, A. B. (2013), Sustainability: Utilizing Lean Six Sigma Techniques, Taylor & Francis CRC Press, Boca Raton, FL

Badiru, Adedeji B., John Elshaw, and Ibrahim Ade Badiru (2015), "Quality Insights: Systems-based product quality assessment for customer preferences," International Journal of Quality Engineering and Technology (IJQET), Vol. 5, No. 3/4, 2015, pp. 266-280.

Badiru, A. B. (2014), "Quality Insights: The DEJI Model for Quality Design, Evaluation, Justification, and Integration," International Journal of Quality Engineering and Technology, Vol. 4, No. 4, pp. 369-378.

Badiru, A. B., "The Many Languages of Sustainability," Industrial Engineer, Nov 2010, pp. 31-34.

Badiru, A. B. and M. N. Goltz, "Holistic Systems Approach to Sustainability: Bridging Environmental and Social Dimensions," in Proceedings of Industrial Engineering Research Conference, Reno, Nevada, May 22-25, 2011

16:45: [AdvancedMaterialsWedPM211] Keynote
Engineering of Magnetic Softness and GMI Effect in Thin Magnetic Wires
Arcady Zhukov¹ ; Paula Corte Leon¹ ; Mihail Ipatov¹ ; Juan Maria Blanco¹ ; Valentina Zhukoa¹ ; ¹Dept. Phys. Mater., UPV/EHU, San Sebastian, Spain;
Paper Id: 328 [Abstract]

Recently, studies of amorphous magnetic wires have attracted great attention, owing to excellent magnetic properties such as magnetic bistability, excellent magnetic, mechanical, and corrosion properties, Giant Magnetoimpedance (GMI) effect [1]. Aforementioned GMI effect consisting of a large change of the impedance of a magnetic conductor under magnetic field is quite interesting for magnetic sensors applications [1]. Recent tendency in devices miniaturization stimulated development of thin (few micrometer diameters) and soft magnetic microwires prepared using Taylor-Ulitovsky method. Excellent soft magnetic properties and GMI effect have been reported for properly prepared and processed Co-rich microwires [1]. Less expensive Fe-rich microwires are preferable for the applications. But amorphous Fe-rich materials exhibit rather high magnetostriction coefficient and consequently present quite low GMI effect [1]. <br /> The most common method for magnetic softness optimization is the annealing. Nevertheless, recently the optimization of soft magnetic properties and GMI effect after are reported mostly for brittle devitrified Fe-rich microwires [1]. <br />From previous studies of Co-rich amorphous materials it is known that stress annealing can considerably affect the magnetic properties of amorphous materials [1]. <br />Consequently, the purpose of this paper is to present our recent experimental results on influence of stress- annealing on magnetic properties and GMI effect of Fe- and Fe-Co based glass-coated microwires. <br />We observed that Fe-rich microwires annealed under stress at appropriate annealing conditions (time and temperature) can present low coercivity, considerable magnetic softening and enhanced GMI effect. For interpretating observed changes of hysteresis loops after stress annealing, we considered internal stresses relaxation and different mechanisms of stress-induced anisotropy. Observed versatile properties of stress annealed glass-coated microwires with enhanced and tunable soft magnetic properties make them suitable for technological sensing applications.

References:
[1] A. Zhukov, M. Ipatov and V. Zhukova, Advances in Giant Magnetoimpedance of Materials, Handbook of Magnetic Materials, ed. K.H.J. Buschow, 24: chapter 2 (2015) 139-236.

17:10: [AdvancedMaterialsWedPM212]
Microcrystalline Silicon Grown on Glass for Photo- and Thermophotovoltaic Applications
Karen Gambaryan¹ ; Torsten Boeck² ; ¹Department of Physics of Semiconductors and Microelectronics, Yerevan State University, Yerevan, Armenia; ²Leibniz Institute for Crystal Growth,, Berlin, Germany;
Paper Id: 411 [Abstract]

Thin-film Si solar cells on glass have the potential to reduce both material usage and production costs as compared to wafer-based Si solar cells [1-3]. The first sample under consideration was prepared first by deposition of a-Si onto glass substrates by physical vapor deposition at room temperature, followed by heating from the front side to ~300°C and deposition of an indium metallic solvent. Droplets form and move along the surface, leaving traces of c-Si, a process referred to as amorphous-liquid-crystalline transition [4,5]. At the preparation of the second sample, an additional silicon layer with the thickness of 400 nm was deposited on an ALC layer. A sample, when after that a c-Si was grown on the seed layer by steady-state liquid phase epitaxy from indium solution will be referred as a third sample. SEM characterization shows that microcrystalline Si layer with grain sizes of up to several tens of micrometers was grown. Fourier-transform infrared spectrometry has shown that the resulting samples have a strong absorption edge in the mid-infrared region around 1960 cm−1. I–V measurements show that the lower surface resistance (1.3 kΩ) has sample #2, but higher one (35.7 kΩ) – sample #3, due to the high purity of crystallites grown by SSLPE. Magnetic field dependence of the electric sheet resistance was measured in Faraday geometry at room temperature. On MR curves, six well-resolved oscillations with an average period of δB=0.1214 T were revealed. Either Aharonov–Bohm effect or kinetic phenomena taking place in the grains boundaries at current flow are responsible for those oscillations. Since the period of A–B oscillations is given by δB=4Φ0/πDe2, where Φ0=h/e is the quantum flux, a diameter of De=215±10 nm is obtained. Presented results will be promising with regard to the designated use in photo- and thermophotovoltaics.

References:
[1] L. Carnel, I. Gordon, D. Van Gestel, G. Beaucarne, J. Poortmans, Thin Solid Films 16 (2008)
6839-6843.
[2] M.A. Green, Appl. Phys. A 96 (2009) 153-159.
[3] A. Gawlik, J. Plentz, I. Hoger, G. Andra, T. Schmidt, U. Bruckner, F. Falk, Phys. Status
Solidi 212 (2015) 162-165.
[4] D. Amkreutz, J. Haschke, T. Haring, F. Ruske, B. Rech, Solar Energy Materials and Solar
Cells 123 (2014) 13-16.
[5] R. Bansen, C. Ehlers, T. Teubner, K. Bottcher, K. Gambaryan, J. Schmidtbauer, T. Boeck,
Journal of Photonics for Energy 6 (2016) 025501-025501-10.

SESSION: AdvancedMaterialsWedPM3-R8	4th Intl. Symp. on New and Advanced Materials and Technologies for Energy, Environment and Sustainable Development
Wed Nov, 7 2018 / Room: Grego (50/3rd)
Session Chairs: Mayya Kulikova; Sholpan Itkulova; Session Monitor: TBA

17:40: [AdvancedMaterialsWedPM313]
Synthesis Gas Processing Over Ultrafine Catalysts Based on Composite Material
Mayya Kulikova¹ ; O.s. Dementyeva¹ ; M.i. Ivanstov¹ ; M.v. Chudakiva¹ ; V.b. Tsvetkov¹ ; ¹A.V. Topchiev Institute of Petrochemical Synthesis, Moscow, Russian Federation;
Paper Id: 87 [Abstract]

Due to the ability to control the structure and properties of nanocomposites, they are very promising for use as catalysts for petrochemical processes based on synthesis gas (mix of CO and H₂), such as Fischer-Tropsch synthesis, methanol synthesis, dimethyl ether synthesis, etc. [1] The original approach to the synthesis of composite materials with high activity in reactions based on CO and H₂ was created in A.V. Topchiev Institute of Petrochemical Synthesis (Russia) [2,3]. Using active component metal-polymeric composite particles leads to formation of fundamentally new catalytic active particles with unique properties. The selectivity and activity of composites in reactions based on H₂ and CO can be controlled by the polymer nature, polymer concentration, and a method of introducing a polymer composition in the composite material. Synthesized composites were characterized by complex phys-chemical methods: magnetometry in situ, IR- spectroscopy, dynamic light scattering, and transmission electron microscopy. Nanoheterogeneous contacts distributed in solid organic matrix were synthesized by method of polymer-containing composite materials. Initial organic matrixes represent polyconjugated systems decomposing to carbon during formation of the catalyst. These particles of 10-20 nm in size formed metal from salts immobilized on polymers. The polymers' flexibility and its effect on coils formation was determined by molecular modeling method. [4] Analysis of the polymers folding into coils, and a comparative study of their geometry revealed significant differences of the final structure of the polymer molecules, forming a complex metal-containing particle - polymer structure.

References:
[1] M.V. Kulikova, M. I. Ivantsov, L. M. Zemtsov, G. P. Karpacheva, S.N. Khadzhiev. XII international conference on Nanostructured Materials (NANO 2014) . p. 1038.
[2] Chudakova M.V., Kulikova M.V., Ivantsov M.I., Bondarenko G.N., Efimov M.N., Vasil'ev A.A., Zemtsov L.M., Karpacheva G.P., Khadzhiev S.N.// Petroleum Chemistry. 2017. V. 57. 8. P. 694-699.
[3] Ivantsov M.I., Kulikova M.V., Gubanov M.A., Dement'eva O.S., Chudakova M.V., Bondarenko G.N., Khadzhiev S.N.// Petroleum Chemistry. 2017. V.57. 7. P. 571-575
[4] Tsvetkov V.B., Kulikova M.V., Khadzhiev S.N.// Petroleum Chemistry. 2017. V. 57. 7. P. 600-607.

18:05: [AdvancedMaterialsWedPM314]
Hydrogen Production by Biogas Reforming Over Sol-gel Made Nanocatalysts
Sholpan Itkulova¹ ; Sholpan Kussanova¹ ; Kirill Valishevskiy¹ ; Yerzhan Boleubayev¹ ; ¹D.V. Sokolsky Institute of Fuel, Catalysis and Electrochemistry, Almaty, Kazakhstan;
Paper Id: 99 [Abstract]

Hydrogen is the most accredited fuel for the future, and hence, several efforts are focused towards the development of processes and catalysts for producing hydrogen rich syngas from bio-fuels, including biogas. Conversion of biogas to produce syngas (a mix of hydrogen and carbon oxide) is not yet a commercially used process, due to the lack of highly effective catalysts with resistance to or absence of coke formation. The sol-gel method, as one of approaches to create nanomaterials, is extensively applied to prepare nanosized catalysts. This strategy leads to narrow size distribution of metal particles, their high thermal resistance against agglomeration, and low deactivation rate. This work deals with the design and synthesis of catalysts prepared by the sol-gel method (Pechini) and their testing in biogas reforming to produce hydrogen rich syngas. The multicomponent Co-based catalysts with varied metal content were synthesized according to the slightly modified procedure [1]. The catalysts were studied by a number of physico-chemical methods (TEM, SEM, BET, TPR etc.) The catalytic properties of new nanomaterials were tested in dry and steam reforming of a model biogas with a ratio CH₄/CO₂=1in a flow tubular reactor under atmospheric pressure, gas hourly space velocity - 1000 h-1, and varying temperature within 300-800°C and steam amount within 0-2 vol. parts. The synthesized catalysts perform a high stable activity in both dry and steam biogas reforming with producing hydrogen rich syngas. At 700°C, P=0.1 MPa, and GHSV=1000 h-1, methane conversion reaches 99.0% and syngas produced gets a ratio of H₂/CO =1.8.

References:
[1] H. Li. H. Xu. J. Wang. J Nat Gas Chem 20 (2011) 1-8.

SESSION: BatteryMonAM-R9	5th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Mon Nov, 5 2018 / Room: Asian (60/3rd)
Session Chairs: Vasant Kumar; Miles Freeman; Session Monitor: TBA

11:20: [BatteryMonAM01] Keynote
Lead-acid Battery Recycling - A Different Way
Athan Fox¹ ; Miles Freeman¹ ; Robert Liu¹ ; Johdie Harris¹ ; Vasant Kumar² ; ¹Aurelius Environmental, Dudley, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom ;
Paper Id: 426 [Abstract]

The lead-acid battery (LAB) market is forecast to reach $84 billion USD by 2025.¹ Despite intense competition from alternative and emerging energy storage solutions, LABs continue to deliver the most proven, low-cost, safe and affordable option for electrical energy storage. Indeed, LABs are used widely in automobiles (for starting, lighting and ignition), traction and heavy industry (for example electric forklifts and trucks), telecommunications, emergency lighting, renewable energy systems, medical equipment, railway backup systems, oil and gas exploration, and more.<br /><br />The recycling of LABs via current methods is energy intensive and wasteful. In some parts of the world it produces "smelter smoke", a toxic mixture of sulphur dioxide, nitrogen dioxide and very often lead metal particles. For this reason, although LABs are the world's most successfully recycled commodity product,² and a perfect example of a successful multi-million tonne circular economy, the incumbent recycling processes are in dire need of improvement and technological innovation.<br /><br />At Aurelius, our aim is to revolutionise the art of recycling through science, ethical practice, sustainability and technology. Our vision is a web of industries, where one stream's waste is another stream's feed-stock: bridging linear and wasteful processes to create circular, energy efficient, non-polluting, zero waste industries. Our stepping stone towards this vision is a technology for the recycling of LAB paste.<br /><br />Invented in 2006 by Professor Vasant Kumar at the University of Cambridge,^3-5 UK, the technology was licensed exclusively in 2016 to Aurelius for further development, scaling up and commercialisation. Our piloting efforts are funded by two Innovate UK awards and a Horizon 2020 (Phase 2) SME grant. To date, we have raised more than 2 million USD in grant funding, while our annual turnover from the collection, dismantling and processing of more than 10,000 tonnes of LAB scrap per year is also used to fund our technology and innovation.<br /><br />The patented hydrometallurgical process, branded as Fenix^Pb, brings about a critical improvement to the lead recycling industry.⁶ It enables conversion of spent battery paste to leady oxide (Pb/PbO) without producing or handling an intermediate ingot, and without utilising electrowinning. In fact, our process reduces the carbon footprint by 80-89%; eliminates noxious gases (including sulphur dioxide) at no added cost; reduces slag by more than 90%; and produces energy (this is because a key stage in the process is highly exothermic, releasing rather than consuming energy).<br /><br />Our leady oxide is also a step-change in lead-acid battery technology. Laboratory tests carried out at the University of Cambridge have shown that batteries produced from our leady oxide have a 30% improved energy density. This innovation is largely due to the particle size; indeed, our advanced leady oxide is a nano-crystalline solid. Moreover, our process delivers a scalable means of controlling accurately the free metallic lead content (%Pb) and ratio between the alpha and beta phases of the oxide - enabling battery manufacturers to fine-tune their batteries' active materials dependant on its properties and applications.

References:
1) Lead Acid Battery Market Size & Trend Analysis By Product (SLI, Stationary, Motive), By Construction Method, By Application (Automotive, UPS, Telecommunication, Electric Bikes, Transport Vehicles), By Region And Segment Forecasts 2014 - 2025, Report ID 4076564, Research & Markets, January 2017 (URL: https://www.researchandmarkets.com/research/kvf4lb/lead_acid_battery)\n2) Lead Action 21, Environmental and social responsibility for the 21st Century, International Lead Association, November 2015 (URL: https://www.ila-lead.org/UserFiles/File/ILA9927%20FS_Recycling_V08.pdf)\n3) M.S. Sonmez, R.V. Kumar, Hydrometallurgy, 95 (2009), 82-86.\n4) M.S. Sonmez, R.V. Kumar, Hydrometallurgy, 95 (2009), 53-60.\n5) J. Yang, R.V. Kumar, D.P. Singh, J. Chem. Technol. Biotechnol., 87 (2012), 1480-1488.\n6) A. Fox and M. Freeman, SciTech Europa Quarterly, 28 (2018), 118-121.

11:45: [BatteryMonAM02] Keynote
Preparation of High-Performance Cathode and Anode Materials for Sodium-Ion Batteries and Investigating the Reaction Mechanism
Ghulam Ali¹ ; Ji Young Kim¹ ; Hee-dae Lim¹ ; Kyung Yoon Chung¹ ; ¹Korea Institute of Science and Technology (KIST), Seoul, South Korea;
Paper Id: 389 [Abstract]

The demand for energy storage systems (ESS) has increased tremendously in the last decade due to their use in a variety of applications ranging from mid- to large-scale. The most important factors in the development of ESS include high-performance and cost-effective systems. At present, lithium-ion batteries (LIBs) are being used as storage devices but their application is limited to small- to medium-scale. The main reasons to not use LIBs at large-scale are high production cost and limited lithium resources. While searching for alternatives, sodium-ion batteries (SIBs) have emerged as a potential candidate for the use of ESS, which is considered cost-effective and also share similar electrochemical principle to LIBs. However, high-performance cathode and anode materials are urgently required for the commercialization of SIBs.
In the search of high-performance electrode materials, we have prepared several cathode and anode materials for SIBs. I will briefly discuss the preparation and electrochemical properties of the high-performance cathode materials, which include FeF₃.0.5H₂O and olivine-type NaFePO₄, and also discuss the investigated reaction mechanism. The nanocomposite of FeF₃.0.5H₂O and reduced graphene oxide has shown high sodium storage performance where it delivers a capacity of 266 mAh g^-1 while NaFePO₄ has shown excellent cyclability with a capacity retention of 94% after 100 cycles. Further, alloying-based SnF₂ anode material was prepared and the electrochemical properties, as well as reaction mechanism, were systematically investigated. The nanocomposite of SnF₂ and acetylene black has shown promising electrochemical performance where it delivers a high capacity of 563 mAh g^-1. In-situ XRD and synchrotron-based X-ray absorption spectroscopy (XAS) were used to investigate the reaction mechanism of the above-mentioned materials. The details of the investigated reaction mechanism will be discussed in my presentation.

References:
[1] Ali, G., S. H. Oh, S. Y. Kim, J. Y. Kim, B. W. Cho and K. Y. Chung, Journal of Materials Chemistry A 3(19): 10258-10266 (2015)\n[2] Ali, G., J. H. Lee, D. Susanto, S. W. Choi, B. W. Cho, K. W. Nam and K. Y. Chung, ACS Applied Materials & Interfaces 8(24): 15422-15429 (2016).\n[3] Ali, G., J. H. Lee, S. H. Oh, H. G. Jung and K. Y. Chung, Nano Energy 42: 106-114 (2017).

12:10: [BatteryMonAM03]
Enabling Cost Effective Implementation of Next Generation Active Materials for Post Lithium Ion Batteries with Nitrogen-doped Single-walled Carbon Nanohorns
Claudio Capiglia¹ ; ¹Recruit R&D, Tokyo, Japan;
Paper Id: 97 [Abstract]

Single-Walled Carbon Nanohorns (SWCNHs), are a kind of carbon material with graphene type surface structure characterized by horn shaped graphitic tubules (2-5 nm diameter and 40-50 nm tube length) to form dahlia-like structures. They can be mass produced (tons/year) using a novel proprietary process technology, making them attractive for various industrial applications. SWCNHs can be considered as the next generation of graphene-based materials. Thanks to their particular 3D structure, they do not stack as in the case of 2D graphene-based materials, and keep their original chemical-physical proprieties at the powder state. Inspired by their unique structure, Nitrogen doped Single-Walled Carbon Nanohorns (N-SWCNHs) were used as a conductive substrate with various post lithium ion batteries active materials such as Sulfur (cathode), Germanium, and Tin (anodes). The choice of nitrogen doping is motivated by the quest for improved interaction between SWCNHs and the surrounding active material. N-SWCNHs were used as porous conductive host for encapsulating sulfur, using a simple melt diffusion method. Electrochemical results obtained from N-SWCNHs-Sulfur composite as cathode for lithium sulfur batteries showed high gravimetric capacities of 1650 mAh/g (almost the theoretical capacity), with high sulfur content of 80% by weight. Furthermore, N-SWCNHs were exploited by growing 5-10 nm germanium nanocrystal around the cones of N-SWCNHs. The Ge@N-SWCNHs composite, when used as anode material, provided extremely stable and high gravimetric capacities of 1400 mAh/g at 0.1C after 100 cycles. Similarly, results were obtained for Sn@N-SWCNHs composites, where a strong reducing agent (Lithium Naphthalenide) was used to decorate Sn nanocrystal on the surface of N-SWCNHs. Capacities as high as 735 mAh/g were achieved at 0.1C even after 140 cycles. The detailed results will be presented and discussed at the symposium.

References:
[1] Nitrogen-Doped Single-Walled Carbon Nanohorns as a Cost-Effective Carbon Host toward High-Performance Lithium-Sulfur Batteries. C.Capiglia et. al., ACS Appl. Mater. Interfaces 2018, 10, 5551-5559.

12:35: [BatteryMonAM04] Invited
Development of Nanostructured Electrode Materials for High Performance Secondary Batteries Using Ammonium Fluoride
Jinyoung Chun¹ ; ¹Korea Institute of Ceramic Engineering & Technology (KICET), Jinju, Republic of South Korea;
Paper Id: 371 [Abstract]

The development of advanced electrode materials for secondary Li batteries is essential to meet the increased energy demands posed by portable electronic devices and the rapid growth of electrical vehicles and energy storage systems.[1] In order to replace the intercalation reaction-based materials that have capacity limitations, many researchers have focused on new electrode materials reacting through conversion or alloying reactions, which can take up multiple Li-ions per unit formula.[2] In this study, using ammonium fluoride (NH₄F), we developed a new synthetic route to fabricate metal fluoride (MF_x) nanocomposites for conversion reaction-based high capacity cathodes and nanostructured silicon (Si) for alloying reaction-based high capacity anodes. At first, we discovered that various anhydrous MF_x can be obtained through simple heat treatment of metal precursors with NH₄F under an inert atmosphere. Based on this process, MF_x/mesoporous carbon nanocomposites were successfully synthesized.[3] From the reaction mechanism of this synthetic method, we expected that residual impurities in the raw Si materials, such as SiO₂, could be easily removed using NH₄F. Interestingly, the reaction of raw Si materials with NH₄F not only removed residual SiO₂, but also generated nanopores on Si. When used as electrodes in Li batteries, the MF_x nanocomposites and nanostructured Si showed noticeable improvements in electrochemical performance. It is expected that this study will motivate further research into the synthesis of advanced electrode materials for secondary batteries using NH₄F.

References:
[1] J. B. Goodenough, Y. Kim, Chem. Mater., 2010, 22, 587-603\n[2] J. Cabana et al., Adv. Mater., 2010, 22, E170-E192\n[3] J. Chun et al., ACS Appl. Mater. Interfaces, 2016, 8, 35180-35190

SESSION: BatteryMonPM1-R9	5th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Mon Nov, 5 2018 / Room: Asian (60/3rd)
Session Chairs: Claudio Capiglia; Jim Zheng; Session Monitor: TBA

14:00: [BatteryMonPM105]
NovoPb - A Complete Lead Recycling System to Enhance Brazilian Sustainability
Deise Menezes Santos¹ ; Yandiara Larissa Barros² ; Marcos Benedito Jose Geraldo De Freitas³ ; André Gustavo De Sousa Galdino⁴ ; Matheus Carvalho⁵ ; Francklin Jonas De Paula⁶ ; Vasant Kumar⁷ ; ¹Universidade Federal do Espírito Santo, Vitoria, Brazil; ²Instituto Federal do Espirito Santo, Vitoria, Brazil; ³Universidade Federal do Espirito Santo, Vitoria, Brazil; ⁴Instituto Federal do Espírito Santo, Vitória, Brazil; ⁵Instituto Federal de Minas Gerais, Governador Valadares, Brazil; ⁶Faculdade Pitagoras, Governador Valadares, Brazil; ⁷University of Cambridge, Cambridge, United Kingdom ;
Paper Id: 385 [Abstract]

Pyrometallurgy lead-acid battery recycling causes pollution and is energy-intensive. This research aims to implement an alternative hydrometallurgical process of recycling lead-acid battery paste, NovoPb, by developing processes to make it economically viable in the current market and to ensure the quality of the newly recycled batteries in a 1 ton capacity pilot plant at Minas Gerais - Brazil.<br />NovoPb is based on a paste-to-paste route using a biomass source, citric acid. The new intermediary lead compound is calcined at a much lower temperature (340°C) than usual smelted lead (1200°C), saving energy and reducing hazardous gas emissions such as Pb and SOx, to directly generates nanostructured PbO for battery paste. <br />The process to be deployed in Brazil has as a first challenge the battery scrap characterisation, to measure the use of reagents per ton of scrap, which is not standard protocol in the current pyrometallurgical process. The study of the characterisation forms will be carried out in the laboratory to define the route to be followed in the pilot plant, which will be built by the British partners.<br />The determination of the optimal reaction conditions will be designed by factorial modelling. The influence of the impurities will be evaluated from a pure standard mixture of the main species that compose the battery paste. The optimization of the pilot process will be carried out by application of artificial neural networks after controlled operation.<br />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 and the British company, Aurelius Technology.

References:
1. Zentner LEA, Rond-PHC. Lead contamination among pregnant Brazilian women living near a lead smelter. Int J Gynecol Obstet. 2004;87(2):147-8. \n2. Sun Z, Cao H, Zhang X, Lin X, Zheng W, Cao G, et al. Spent lead-acid battery recycling in China : A review and sustainable analyses on mass flow of lead. Waste Manag [Internet]. 2017;64(1):190-201. Available from: http://dx.doi.org/10.1016/j.wasman.2017.03.007\n3. Zhang W, Yang J, Wu X, Hu Y, Yu W, Wang J, et al. A critical review on secondary lead recycling technology and its prospect. Renew Sustain Energy Rev. 2016;61:108-22. \n4. Kumar RV. LEAD RECYCLING. UNITED KINGDOM; WO 2008/056125 A1, 2008. p. 35. \n5. Sonmez MS, Kumar R V. Leaching of waste battery paste components. Part 1: Lead citrate synthesis from PbO and PbO2. Hydrometallurgy. 2009;95(1-60. \n6. Sonmez MS, Kumar R V. Leaching of waste battery paste components. Part 2: Leaching and desulphurisation of PbSO4 by citric acid and sodium citrate solution. Hydrometallurgy [Internet]. 2009;95(1-6. Available from: http://dx.doi.org/10.1016/j.hydromet.2008.04.019\n7. Ifes. Polo de Inovaio firma convinio com empresas para implantar processo mais limpo na reciclagem de baterias [Internet]. 2018 [cited 2018 Jul 7]. 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\n8. Kumar D, Jain VK, Shanker G, Srivastava A. Citric acid production by solid state fermentation using sugarcane bagasse. Process Biochem. 2003;38(12):1731-8. \n9. Li L, Zhu X, Yang D, Gao L, Liu J, Kumar RV, et al. Preparation and characterization of nano-structured lead oxide from spent lead acid battery paste. J Hazard Mater [Internet]. 2012;203-204:274-82. Available from: http://dx.doi.org/10.1016/j.jhazmat.2011.12.021

14:25: [BatteryMonPM106]
Solution-based Synthesis of Li₃PS₄ Solid Electrolytes
Hee-dae Lim¹ ; Xing Xing² ; Ping Liu² ; ¹Korea Institute of Science and Technology (KIST), Seoul, South Korea; ²University of California, San Diego (UCSD), San Diego, United States;
Paper Id: 384 [Abstract]

Sulfide-based solid electrolytes have attracted much attention due to their high conductivities, which are far beyond those of oxide-based solid electrolytes. [1,2] However, They (Li₂S-P₂S₅ system, i.e., LPS) have been normally synthesized by solid state synthesis such as mechanical ball milling. These methods require rigorous control of reaction environment as well as high temperature heat treatment and repeated pelletizing steps. In contrast, solution-based synthesis methods can induce chemical reaction among precursor particles (Li₂S and P₂S₅) at low temperatures resulting in the formation of conductive phases of Li₃PS₄ and Li₃P₇S₁₁ with only moderate thermal treatment.[3,4] The method deserves great attention since it simplifies synthesis process, yields products of great purity, and may facilitate the fabrication of composite electrodes with improved interfaces. <br />In this work, we have developed an efficient method to form a thin solid electrolyte layer directly on Li metal using the liquid coating techniques. The formation of LPS (Li₂S-P₂S₅) based electrolyte is achieved by rational design of the solvent and the Li, P, and S precursor ratios. The solution electrolyte can be directly coated and formed on Li metal through the in-situ formation of the solid electrolyte layer, which does not require the complex synthesis process and high temperature sintering step. Layers of thickness of < 50 um can be fabricated and electrochemical cycling of lithium is achieved. This liquid-phase coating is a simple and straightforward technique for making a thin solid electrolyte and can be applicable to anode surface with complex contours. The new liquid coating technique holds the promise to overcome the limitations of current state solid electrolytes.

References:
[1] Kamaya, N. et al. A lithium superionic conductor. Nature Mater. 10, 682-686 (2011).\n[2] Yamane, H. et al. Crystal structure of a superionic conductor, Li7P3S11. Solid State Ion. 178, 1163-1167 (2007).\n[3] Ito, S. et al. A synthesis of crystalline Li7P3S11 solid electrolyte from 1,2-dimethoxyethane solvent. J. Power Sources 271, 342-345 (2014).\n[4] Liu, Z. et al. Anomalous High Ionic Conductivity of Nanoporous Li3PS4. J. Am. Chem. Soc. 135, 975-978 (2013).

14:50: [BatteryMonPM107] Keynote
Internal Hybrid Li-ion Battery-Capacitor Energy Storage Cells
Annadanesh Shellikeri¹ ; Mark Andrew Hagen¹ ; Jin Yan² ; W.j. Cao² ; Richard Jow³ ; Jeffrey A. Read³ ; Jim Zheng¹ ; ¹Florida A&M University and Florida State University, Tallahassee, United States; ²General Capacitor LLC, Tallahassee, United States; ³U.S. Army Research Laboratory, Adelphi, United States;
Paper Id: 283 [Abstract]

As a new generation of supercapacitor, the Li-ion capacitor (LIC) is an advanced energy storage device which consists of an electric double-layer capacitor (EDLC) cathode and a pre-lithiated anode [1,2], between which the ions shuttle during charge and discharge processes. Because of using pre-lithiated and low surface anode materials, the LIC can be charged to a maximum voltage as high as 4.0 V, which is much higher than of EDLCs and comparable to Li-ion batteries (LIBs); therefore, it allows the LIC and LIB to be assembled in one package as a LIB/LIC hybrid energy storage cell. We have demonstrated a new hybrid energy storage cell that combines the advantages of both the LIB and the LIC [3], thereby avoiding their inherent defects, while bridging the gap between the high energy densities offered by batteries and the high power densities seen in EDLCs. The energy density and power density of the hybrid cell can be designed to meet the requirements by a reasonable distribution of the ratio between LIB and LIC electrode materials in the internal hybrid cell. For example, we show a hybrid LIC consisting of a Li nickel cobalt manganese oxide (NMC)/activated carbon (AC) composite cathode in combination with an ultra-thin Li film (u-Li) pre-loaded hard carbon anode. Additionally, we show that by utilizing three design approaches: dry composite electrode fabrication method, cathode to anode capacity ratio design, and pre-lithiation method using u-Li, we can demonstrate an energy storage device with excellent cycle life, and that can be tailored by composite ratios within the cathode to fit different applications. Shown here is an in-depth look at various composite material ratios, pre-lithiation calculations and hybrid Li-ion battery-capacitor energy storage device creation based on targeting essential energy-power performance characteristics.

References:
[1] W.J. Cao and J.P. Zheng, "Li-ion Capacitors with Carbon Cathode and Hard Carbon/SLMP Anode Electrodes", J. Power Sources, 213, 180 (2012).
[2] W.J. Cao, J. Shih, J.P. Zheng, and T. Doung, "Development and characterization of Li-ion capacitor pouch cells", J. Power Sources, 257, 388 (2014).
[3] Zheng, J.-S., Zhang, L., Shellikeri, A., Cao, W., Wu, Q., & Zheng, J. P. (2017). A hybrid electrochemical device based on a synergetic inner combination of Li ion battery and Li ion capacitor for energy storage. Scientific Reports, 7, 41910.

15:15: [BatteryMonPM108]
New Possibilities in the Next Generation of Lead-Acid Batteries
Vasant Kumar¹ ; ¹University of Cambridge, Cambridge, United Kingdom ;
Paper Id: 382 [Abstract]

Lead acid batteries have been well established for over 150 years and remain the largest segment of batteries in use. The market continues to grow in the automotive sector in ICVs, HEVs and EVs, e-bikes, small vehicles, energy storage, and back-up UPS. Furthermore it is well supported by a strong recycling infrastructure which is the envy of all other battery technologies. New recycling methods offer opportunities for controlling the morphology and structure of electrode components in order to derive new energy and power benefits from nanotechnology. New materials offer options for long-life electrode grids that are light and corrosion resistant. A doubling of capacity and rate at a lower cost will offer a paradigm shift in creating new markets for lead-acid batteries.

References:
1. A critical review on secondary lead recycling technology and its prospect, Zhang W, Yang J, Wu X, Hu Y, Yu W, Wang J, Dong J, Li M, Liang S, Hu J, RV Kumar, Renewable and Sustainable Energy Reviews 61:108-122 01 Aug 2016
2. A novel leady oxide combined with porous carbon skeleton synthesized from lead citrate precursors recovered from spent lead-acid battery paste, Hu Y, Yang J, Zhang W, Xie Y, Wang J, Yuan X, Vasant Kumar R, Liang S, Hu J, Wu X; Journal of Power Sources 304:128-135 01 Feb 2016.
3. A novel ultra-fine leady oxide from spent lead pastes for application as cathode of a lead acid battery, D Yang, J Liu, Q Wang, X Yuan, L Li, W Zhang, Y Hu, X Sun, RV Kumar, J Yang, J Power Sources, 257, 27-36, 2014.
4. Electrochemical performance of leady oxide nanostructure prepared by hydrometallurgical leaching and low temperature calcinations of lead paste, J L Gao, J Liu, X Zhu, D Yang, Q Wang, L Li, D He, RV Kumar, J Yang; Electrochem. Soc., 160(9), A 1559-64, 2013.

SESSION: BatteryMonPM2-R9	5th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Mon Nov, 5 2018 / Room: Asian (60/3rd)
Session Chairs: Thierry Djenizian; Vimalnath Selvaraj; Session Monitor: TBA

15:55: [BatteryMonPM209] Invited
Crystal Growth of High-quality Lithium Metal Phosphates and Its Derivative by Using Flux Method
Tetsuya Yamada¹ ; Katsuya Teshima¹ ; ¹Center for Energy & Environmental Science, Shinshu University, Nagano, Japan;
Paper Id: 323 [Abstract]

Nowadays, improvement of functional materials is a sought after issue, with the aim of combining high-energy consumption and sustainable society. It is known that functionality of materials depends on crystallographic characteristics. Regarding to battery materials, ionic diffusion in bulk becomes easier by increasing specific surface area and improving crystallinity, whose ionic conductivity depends on crystal face. So, crystallographic controls of battery materials should be one of the crucial concerns to realize innovation in next-generation energy applications. Flux method is one of the crystal growth techniques in liquid phase. This technique enables us to achieve various crystallographic characteristics, in terms of crystallinity and morphology, such as size, shape, and also habits. We have studied flux growth of battery materials. So far, lots of unique and functionalized crystals have been grown. For example, polyhedron, cylinder, flower-type LiCoO₂ crystals are representative morphology. Since they have never been grown by other technique, we expected that flux method is a suitable method to improve battery by means of crystallography. Recently, we are focusing on designing lithium metal phosphates and its derivative, formulated as Li<i>M</i>PO₄ and Li₂MPO₄F (<i>M</i>=Fe, Mn, Ni). Although they show poor conductivity, their electrochemical stability and high energy density are attractive advantages as active materials. We aimed to control crystal facets of Li<i>M</i>PO₄ and Li₂<i>M</i>PO₄F, which exhibits higher conductivity, by using the flux method. As a result, we grew Li<i>M</i>PO₄ and Li₂<i>M</i>PO₄F crystals with idiomorphic, high-crystalline natures. Some of them showed anisotropic morphology along to one direction, which may be typical due to flux method. In the SIPS2018 conference, we will report the flux growths, crystallographic characteristics, battery properties, and growth manners of a series of Li<i>M</i>PO₄ and Li₂<i>M</i>PO₄F.

16:20: [BatteryMonPM210]
Dissolution of Spent Lead Acid Battery Paste for Lead Recovery, Bio-sensing and Bio-removal of Residual Pb Ions
Vimalnath Selvaraj¹ ; Vasant Kumar² ; Carsten Schwandt³ ; Subramanian Sankaran⁴ ; ¹University of Cambridge, Cambridge, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom ; ³University of Nizwa, Nizwa, Oman; ⁴Indian Institute of Science, Bengaluru, India;
Paper Id: 392 [Abstract]

A spent lead acid battery consists of four parts, namely the electrolyte, lead and lead alloy components (for example the battery grid and plate), lead paste (the "redox", otherwise known as active, component of the battery) and organics or plastics with weight percentages of 11-30%, 24-30%, 30-40% and 22-30% respectively [1]. The spent battery paste is arguably the most complex component to recycle. It is complex as it is made up of a multitude of materials including PbSO₄ (~60%), which dominates in spent batteries, PbO₂ (~28%), PbO (~9%), free metallic lead (~3%) and a small but substantial concentration of impurities such as iron, antimony, tin and barium [1,2]. The recovery of Pb from spent lead paste is achieved conventionally through pyrometallurgical process requiring relatively elevated temperature (>900°C) for the decomposition of PbSO₄ [3]. The elevated temperature releases SO₂ gas and lead particulates into the environment, raising serious environmental concerns [4]. Hydro-electro metallurgical processing, which has been developed as an alternative, also consumes high energy and uses toxic acids like HBF₄ or H₂SiF₆ [5]. There is a need for eco-friendly method. In this study, a hydrometallurgical process for complete dissolution of spent lead paste at room temperature has been developed. Post recycling of the dissolved spent lead paste, the residual Pb ions are determined and removed using an eco-friendly biological method. The complete dissolution of spent lead acid battery paste is achieved in the presence of sodium hydroxide (NaOH), nitric acid (HNO₃) and hydrogen peroxide (H₂O₂). The concentration of Pb ions in the processed water is determined by deploying bacterial cells, Pseudomonas aeruginosa, using differential pulse anodic stripping voltammetry (DPASV). The parameters namely, pH, time, biomass loading and Pb ions concentration were optimized for maximum Pb ions removal by the selected bacterial cells.

References:
1. Zhu, X., Li, L., Sun, X., Yang, D., Gao, L., Liu, J., ... & Yang, J. (2012). Preparation of basic lead oxide from spent lead acid battery paste via chemical conversion. Hydrometallurgy, 117, 24-31.
2. Chen, T. T., & Dutrizac, J. E. (1996). The mineralogical characterization of lead-acid battery paste. Hydrometallurgy, 40(1-2), 223-245.
3. Yanakieva, V. P., Haralampiev, G. A., & Lyakov, N. K. (2000). Desulphurization of the damped lead battery paste with potassium carbonate. Journal of Power Sources, 85(1), 178-180.
4. Sonmez, M. S., & Kumar, R. V. (2009). Leaching of waste battery paste components. Part 1: Lead citrate synthesis from PbO and PbO2. Hydrometallurgy, 95(1-2), 53-60.
5. Yang, J., Kumar, R. V., & Singh, D. P. (2012). Combustion synthesis of PbO from lead carboxylate precursors relevant to developing a new method for recovering components from spent lead-acid batteries. Journal of Chemical Technology & Biotechnology, 87(10), 1480-1488.

16:45: [BatteryMonPM211]
High Performance of Chemically Modified TiO₂ Nanotubes for Lithium-ion Microbatteries
Thierry Djenizian¹ ; ¹Ecole des Mines Saint-Etienne, Gardanne, France;
Paper Id: 203 [Abstract]

Modern microelectronic devices such as backup power for computer memories, MicroElectroMechanical Systems (MEMS), medical implants, smart cards, Radio-Frequency Identification (RFID) tags, and remote sensors have necessitated the development of high performance power sources at the microscale. In this context, the development of three-dimensional (3D) microbatteries forms a viable alternative to provide high volumetric energy densities to meet the demands of these devices.[1] The development of nano-architectured electrodes is one of the most promising approaches to realize the 3D paradigm of microbatteries.[2] Among all the potential anode materials, TiO₂ nanotubes (TiO₂-NTs) possess remarkable characteristics for the design of 3D Li-ion microbatteries. Self-organized nanotubular materials allow a good diffusion of Li ions in the porous structures, and the 1D morphology allows an efficient charge transfer along the axis of the tube that results in a good apparent electronic conductivity of the TiO₂-NTs layer, when compared to a film composed of nanoparticles [3,4]. Anatase TiO₂ can accommodate only 0.5 Li⁺ per formula unit, corresponding to a theoretical capacity of 168 mAh g^-1. Hence, several approaches have been investigated to improve the overall performance of TiO₂-NTs for the design of high-performance Li-ion microbatteries. Doping with aliovalent ions like Niobium (Nb⁵⁺) is also a facile strategy to modify the electronic properties of titanium oxide and thereby enhance the electrochemical performance.[5,6] <br />We report the fabrication of self-supported Nb doped TiO₂-NTs by anodization of Nb/Ti alloys devoid of any carbon additives or binders. An increase in the capacity of the TiO₂-NTs was observed as the Nb doping concentration increased. Such a composition of 10 wt.% Nb doped TiO₂-NTs (Nb10-TiO₂-NTs) showed a first cycle capacity of 200 mAh.g^-1 (0.144 mAh.cm^-2) compared to pristine TiO₂-NTs, which gave a capacity of 115 mAh.g^-1 (0.078 mAh.cm^-2) at C/10. Galvanostatic cycling tests at various C-rates revealed the influence of Nb doping in the TiO₂-NTs. Compared to pristine TiO₂-NTs, the discharge capacities of doped nanotubes are improved and almost doubled when the Nb concentration reaches 10 wt.%. Besides a good cycling behaviour at multiple C-rates, an overall capacity retention of 87 % is achieved after 100 cycles. According to Electrochemical Impedance Spectroscopy measurements, the enhanced electrochemical performance of the Nb-doped TiO₂-NTs is attributed to their higher electronic conductivity.

References:
[1] B.L. Ellis, P. Knauth, T. Djenizian, Three-Dimensional self-supported metal oxides for advanced energy storage, Adv. Mater. 26 (2014) 3368-3397.\n[2] J.W. Long, B. Dunn, D.R. Rolison, H.S. White, Three-Dimensional Battery Architectures, Chem. Rev., 104 (2004), 4463-4492.\n[3] G.F. Ortiz, I. Hanzu, T. Djenizian, P. Lavela, J.L. Tirado, P. Knauth, Alternative Li-Ion Battery Electrode Based on Self-Organized Titania Nanotubes, Chem. Mater., 21 (2009), 63-67.\n[4] T. Djenizian, I. Hanzu, P. Knauth, Nanostructured negative electrodes based on titania for Li-ion microbatteries , J. Mater. Chem., 21 (2011), 9925-9937.\n[5] Y.Wang, B. M Smarsly, I. Djerdj, Niobium Doped TiO2 with Mesoporosity and Its Application for Lithium Insertion, Chem. Mater., 22 (2010), 6624-6631.\n[6] M. Fehse, S. Cavaliere, P. E. Lippens, I. Savych, A. Iadecola, L. Monconduit, D. J. Jones, J. Roziere, F. Fischer, C. Tessierand, L. Stievano, Nb-Doped TiO2 Nanofibers for Lithium Ion Batteries, J. Phys. Chem. C, 117 (2013), 13827-13835.

17:10: [BatteryMonPM212] Keynote
Flux-Crystal Growth Engineering Toward Next-generation Batteries: Electrode Material and Interfacial Designs
Katsuya Teshima¹ ; Tetsuya Yamada¹ ; Shuji Oishi² ; Nobuyuki Zettsu¹ ; ¹Center for Energy & Environmental Science, Shinshu University, Nagano, Japan; ²Center for Energy & Environmental Science, Shinshu University, Nagano, Japan;
Paper Id: 322 [Abstract]

Lithium ion secondary 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 level of safety. All solid-state LIBs provide many advantages in terms of size, flexibility, cost, and performance. However, there are serious problems to be solved toward practical uses. For example, diffusion of lithium ions at the interface between different solid materials is still poor for operating charge/discharge in batteries. Our group has studied high-quality crystals for applications as energy and environmental materials by using a flux method. Flux method is a nature-mimetic liquid-phase crystal growth technique. It is possible to construct molten reaction field at any temperature with facile setup and give designed crystals shape, including crystal faces, which has never been achieved using other methods like solid state reaction. Recently, we have 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 control of active materials, (II) construction of good interfaces in electrodes among cathodes, 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 using flux method would provide new aspect to make innovation in all solid state LIBs as next-generation energy storage. The details of interfacial and crystal designs of battery materials will be introduced in the SIPS2018 conference.

SESSION: BatteryMonPM3-R9	5th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Mon Nov, 5 2018 / Room: Asian (60/3rd)
Session Chairs: Hee-Dae Lim; Session Monitor: TBA

17:40: [BatteryMonPM313] Keynote
Fracture in Anodes for Li-ion and Na-ion Batteries
Katerina Aifantis¹ ; ¹University of Florida, Gainesville, United States;
Paper Id: 425 [Abstract]

Si and Sn are the most promising anodes for Li-ion and Na-ion batteries, respectively. Despite their high capacity upon the formation of Li and Na rich alloys, the main drawback in commercializing these promising electrodes lies in the severe volume expansion and subsequent fracture they experience upon electrochemical cycling. The present talk, hence, focuses on capturing and modeling this severe fracture, by electrochemically cycling Si and Sn films with respect to Li and Na. Scanning electron microscopy can illustrate the extent of fracture and reveal that additional plasticity mechanisms occur in the case of Na-Sn. The experimental data are complemented by a phase field model, which can accurately predict the fracture in patterned Si anodes during lithiation. This is the first rigorous correlation between experiments and modelling in fracture of anodes and paves the way for developing design criteria that predict the onset of fracture initiation based on the anode material and geometric properties.

References:
Rethore J.R., Zheng H., Li H., Li J., Aifantis, K.E. A multiphysics model that can capture crack patterns in Si thin films based on their microstructure, Journal of Power Sources, 400, p. 383-391, 2018.

18:05: [BatteryMonPM314]
New Approaches in the Development of Advanced Lithium-sulfur Batteries
Jiazhao Wang¹ ; Xin Liang¹ ; Mohammed Rejaul Kaiser¹ ; Fang Li¹ ; Huakun Liu¹ ; ¹Institute for Superconducting and Electronic Materials, University of Wollongong, Wollongong, Australia;
Paper Id: 82 [Abstract]

Lithium Sulfur (Li-S) batteries are one of the most promising next generation battery technologies due to their high theoretical energy density, low materials cost, environmental friendliness, and relative safety [1]. Nevertheless, sulfur is an electrically insulating material, which leads to poor electrochemical accessibility and low utilization in the electrode. The polysulfide anions that are generated during cycling are highly soluble in the organic electrolyte solvent. The diffusion of polysulfides to the lithium anode results in low active material utilization, low Coulombic efficiency, and short cycle life of the sulfur electrode. In terms of making the lithium/sulfur batteries suitable for operation, carbon and conducting polymers are the promising conducting material to improving performance. Ternary composites with porous sulfur/dual-carbon architectures were synthesized by a single-step spray-pyrolysis/sublimation technique, which is an industry-oriented method that features continuous fabrication of products with highly developed porous structures [2]. A double suspension of commercial sulfur and carbon scaffolding particles was dispersed in ethanol/water solution and sprayed at 180°C using a spray pyrolysis system. In the resultant composites, the sulfur particles were subjected to an ultrashort sublimation process, leading to the development of a highly porous surface, and were meanwhile coated with amorphous carbon, obtained through the pyrolysis of the ethanol, which acts as an adhesive interface to bind together the porous sulfur with the scaffolding carbon particles, to form a ternary composite architecture. This material has an effective conducting-carbon/ sulfur-based matrix and interconnected open pores to reduce the diffusion paths of lithium ions, buffer the sulfur volumetric expansion, and absorb electrolyte and polysulfides. Because of the unique structure, the composites show stable cycling performance for 200 cycles and good rate capability of 520 mAh g-1 at 2°C. This advanced spray-pyrolysis/sublimation method is easy to scale up and shows great potential for the commercialization of Li-S batteries. Sulfur-conducting polymer composites were also investigated to improve the performance of Li-S batteries. A PPy@S@PPy composite with a novel three-layer-3D-structure was synthesised by the oxidative chemical polymerization method and chemical precipitation method. The discharge specific capacity of the PPy@S@PPy composite cathode is 554 mAh g-1 after 50 cycles, representing approximately 68.8% retention of the initial discharge specific capacity of about 801 mAh g-1 [3]. A free-standing sulfur-PPy cathode and a PPy nanofiber coated separator were designed for flexible Li-S batteries. The as-prepared PPy film not only has a rough surface, which can enhance adhesion of the active materials and trap dissolved polysulfides, but also possesses elastic properties, which can accommodate the volume expansion and maintain the integrity of electrode during cycling. On the other hand, the PPy-separator not only acts as a reservoir for soluble lithium polysulfides, but also acts as an upper current collector to accelerate the kinetics of the electrochemical reactions. Moreover, PPy is electrochemically active and could contribute to the capacity of Li-S batteries. Benefiting from the advantages above, the flexible Li-S battery can deliver an initial discharge capacity of 1064 mA h g-1, and retain a capacity of 848 mA h g-1 after 20 cycles at 0.1 C. After repeated bending of 10 times, the capacity remains almost the same. In addition, the soft-packaged Li-S battery could power a device containing 24 white LEDs, both before and after bending, indicating its great potential application in flexible electronics. We believe that this flexible electrode structure may provide guidance for fabricating high energy, flexible electrochemical energy-storage devices [4].

References:
[1] M. R. Kaise, S. L. Chou, H. K. Liu, S. X. Dou, C. S Wang, J. Z. Wang, Adv. Mater., 29 (2017) 1700449.
[2] X. Liang, M.R. Kaiser, K. Konstantinov, R. Tandiono, Z. Wang, C. Chen, H..K. Liu, S. X. Dou, and J. Z. Wang, ACS Appl. Mater. Interfaces, 8 (2016) 25251.
[3] X. Liang, M. Zhang, M. R. Kaiser, X. W. Gao, K. Konstantinov, R. Tandiono, Z. X. Wang, H. K. Liu, S. X. Dou and J. Z. Wang, Nano Energy, 11 (2015) 587.
[4] F. Li, M. R. Kaiser, J. Ma, Z. P. Guo, Z., H. K. Liu, J. Z. Wang, Energy Storage Materials, 13 (2018) 312.

SESSION: BatteryTueAM-R9	5th Intl. Symp. on Sustainable Secondary Battery Manufacturing and Recycling
Tue Nov, 6 2018 / Room: Asian (60/3rd)
Session Chairs: TBA Session Monitor: TBA

11:20: [BatteryTueAM01] Invited
Novel Electrode Materials as Anodes for High-Performance Na-ion Batteries
Ghulam Ali¹ ; ¹Korea Institute of Science and Technology (KIST), Seoul, South Korea;
Paper Id: 157 [Abstract]

There is a need to develop cost-efficient and high-performance large-scale batteries for intermittent energy sources. In this regard, sodium-ion batteries (SIBs) have emerged as a potential candidate for the use of electrical energy storage systems (ESS), which share similar electrochemical principles to the comparatively high-cost lithium-ion batteries (LIBs). However, high-performance electrode materials are required for the realization of SIBs. In this presentation, the development of anode materials for SIBs will be discussed. Our group has contributed to a variety of materials such as carbonaceous, intercalation-based metal oxides, conversion-based metal oxides, and alloying materials as anodes for SIBs. The results show that novel carbon-based anodes possess the capability of high energy and power density. The intercalation-based anodes such as TiO2 have also shown good stability over long cycling, thus demonstrating the suitability as anodes for SIBs. Conversion-based metal oxides also show promising electrochemical properties when used as a full sodium-ion cell. Finally, the nano-sized alloying-based SnF2 material was tested as anodes, and the electrochemical results, as well as the reaction mechanism of the material using synchrotron-based X-ray absorption spectroscopy, are measured. All of the above will be discussed in detail during the talk.

11:45: [BatteryTueAM02]
Hydrometallurgically Generated Nanostructured Lead(II) Oxide from discarded Lead-Acid Batteries: From Laboratory to Pre-Pilot Scale-up
Robert Liu¹ ; Vimalnath Selvaraj² ; Marcel Yiao² ; Vasant Kumar³ ; Steve Andrew¹ ; Spencer Lowe¹ ; Miles Freeman¹ ; Johdie Harris¹ ; Athan Fox¹ ; ¹Aurelius Environmental, Dudley, United Kingdom; ²University of Cambridge, Cambridge, United Kingdom; ³University of Cambridge, Cambridge, United Kingdom ;
Paper Id: 429 [Abstract]

The recycling of lead-acid batteries (LABs) is currently an energy intensive, inefficient and polluting procedure. An alternative hydrometallurgical recycling route using citric acid(1)(2) has been proven to effectively and efficiently facilitate the extraction of lead from discarded LAB paste material to form an intermediate that can be further processed to be potentially reused again in new LABs. This citric acid route has been extensively trialled in the laboratory at the University of Cambridge and has recently been through several concurrent iterative experimental trials at a pre-pilot scale at Aurelius Environmental Ltd in Tipton, UK. The procedure of scaling up any process from the laboratory to pilot and, if successful, to full commercial scale is a journey that is well trodden. The current review paper will seek to describe some of the challenges and successes that has thus far been encountered in scaling up this promising recycling route. As the author, associates and collaborators attempt to translate what has been shown in the laboratory to a pre-pilot scale, the ultimate aim is to transition to a full pilot scale and beyond in the near future. The progress and future aims of this nascent technology will be outlined and discussed in order to inform and educate a wider audience of this exciting and sustainable recycling method.

References:
[1] Sonmez MS, Kumar RV. Leaching of waste battery paste components. Part 1: Lead citrate synthesis from PbO and PbO2. Hydrometallurgy. 2009;95(1-2):53-60.
[2] Sonmez MS, Kumar RV. Leaching of waste battery paste components. Part 2: Leaching and desulphurisation of PbSO4 by citric acid and sodium citrate solution. Hydrometallurgy. 2009;95(1-2):82-6.
[3] Yang J, Kumar RV, Singh DP. Combustion synthesis of PbO from lead carboxylate precursors relevant to developing a new method for recovering components from spent lead-acid batteries. Journal of Chemical Technology & Biotechnology. 2012;87(10):1480-8.

SESSION: EnergyTuePM1-R9	5th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Tue Nov, 6 2018 / Room: Asian (60/3rd)
Session Chairs: Manfred Mauntz; Harold Dodds; Session Monitor: TBA

14:00: [EnergyTuePM105] Plenary
Electricity Production Choices and Consequences - 2018 Update
Harold Dodds¹ ; ¹University of Tennessee, Knoxville, United States;
Paper Id: 163 [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 work considers the various choices, or options, for producing electricity and the consequences associated with each option. The options are fossil, renewables, and nuclear. 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 being continually updated. This presentation will provide updated information through October of 2018.

References:
References will be provided during the oral presentation.

14:25: [EnergyTuePM106] Keynote
Deep Online Analysis of Dielectric Parameters for Lubricants and Insulation Oils: Identification of Critical Operation Conditions of Gearboxes and HV Transformers for Live Time Enhancement
Manfred Mauntz¹ ; Jorn Peuser¹ ; ¹cmc Instruments GmbH, Eschborn, Germany;
Paper Id: 112 [Abstract]

The online oil sensor system measures the components conductivity kappa, the relative permittivity epsilon r and the temperature T independently from each other. For insulation oils, the system calculates the loss factor tan delta with a very high precision. Changes in acidification, humidity, and break down voltage can be identified in real time. The new approach utilizes sensor detection of chemical aging of the insulating oil and its inhibitors. Based on a very sensitive measurement method with high accuracy, even small changes in the conductivity and dielectric constant of the transformer oil composition can be detected reliably. The new sensor system effectively controls the proper operation conditions of High Voltage Transformers, oil-filled circuit breakers, oil regeneration, and filtration systems. In wind turbine applications, the system enables damage prevention of the gearbox by an advanced warning time of critical operation conditions and an enhanced oil exchange interval realized by a precise measurement of the electrical conductivity, the relative permittivity, and the oil temperature. A new parameter, the WearSens® Index (WSi) is introduced. The mathematical model of the WSi combines all measured values and its gradients in one single parameter for a comprehensive monitoring to prevent wind turbines from damage. Furthermore, the WSi enables a long-term prognosis on the next oil change by 24/7 server data logging. Corrective procedures and/or maintenance can be carried out before actual damage occurs. Raw data and WSi results of wind turbine installations with different lubrication oils are shown. Short-term and long-term analysis of the data show significant trends and events, which are discussed more in detail. Once the oil condition monitoring sensor systems are installed on the high voltage transformer or a wind turbine's gearbox, the measured data can be displayed and evaluated elsewhere in sense of a full online condition monitoring system. 24/7 monitoring of the system (HV transformer or gearbox) during operation enables specific preventive and condition based maintenance 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: Allsensorsystem- Sensorsystem zur Messung von Komponenten der komplexen Impedanz elektrisch gering leitender und nichtleitender Fluide, dessen Realisierung und Anwendung, patent application no. 10 2008 047 366.9, German Patent Office, Munich, (2008)
[4] M. Mauntz, U. Kuipers and J. Peuser: New oil condition monitoring system, WearSens® 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: 978-967-13625-0-1, S. 179-180, (2015)

14:50: [EnergyTuePM107] Invited
Microstructural Design in Hydrogen Fuel Storage
Jerzy Szpunar¹ ; ¹University of Saskatchewan, Saskatoon, Canada;
Paper Id: 366 [Abstract]

The storage of hydrogen will also require structural modification of the storage system. One of storage systems that was developed by us will be discussed. We designed a Pd-graphene composite for hydrogen storage with spherical shaped nanoparticles of 45 nm size, homogeneously distributed over a graphene substrate. This new hydrogen storage system has attractive features like high gravimetric density, ambient conditions of hydrogen charge and low temperature of the hydrogen discharge. The palladium particles produce a low activation energy barrier to dissociate hydrogen molecules These Pd particles, have to be nano-size and homogeneously dispersed on the graphene surface, to serve as efficient hydrogen receptors and further facilitate a dissociation and diffusion of hydrogen and storage in graphene via a spillover process. The hydrogen storage capacity in such a combined metal-graphene system could be significantly increased compared to storage in graphene or in metal. In this project, we optimized the structure of Pd/graphene to allow a hydrogen uptake at ambient conditions and discharging of hydrogen at low temperature. In particular, with hydrogen charging pressure of 60 bar, the Pd/graphene composite system with a Pd loading amount of 1 at. % captures 10 wt. % of hydrogen.

References:
1. Razavi-Tousi, J.A. Szpunar, Effect of addition of water-soluble salts on the hydrogen generation of aluminium in reaction with hot water, Journal of Alloys and Compounds, 679 (2016) 364-374.
2. Razavi-Tousi, J.A. Szpunar, Microstructural evolution and grain subdivision mechanisms during severe plastic deformation of aluminum particles by ball milling, Philosophical Magazine, 95 (2015) 1425-1447.
3. C.Y. Zhou, J.A. Szpunar, X.Y. Cui, Synthesis of Ni/graphene nanocomposite for hydrogen storage, ACS Applied Materials & Interfaces, 8 (2016) 15232-15241.
4. A. Choudhary, L. Malakkal, R.K. Siripurapu, B. Szpunar, J.A.Szpunar, First principles calculations of hydrogen storage on Cu and Pd-decorated graphene, International Journal of Hydrogen Energy, 41 (2016) 17652-17656.
5. O. Faye, U. Eduok, J. Szpunar, B. Szpunar, A. Samoura, A. Beye, Hydrogen Storage on bare Cu atom and Cu-functionalized boron-doped graphene: a first Principles study, International Journal of Hydrogen Energy, 42 (2017) 4233-4243.

15:15: [EnergyTuePM108] Invited
Some of the Physical Contents of Thermodynamic Inequalities Leading to Nonequilibrium Thermodynamics and the Fifth Law of Thermodynamics
Anil A. Bhalekar¹ ; ¹R. T. M. Nagpur University,, NAGPUR, India;
Paper Id: 78 [Abstract]

The origin of thermodynamic inequalities was traced systematically, which helped us in understanding the physical contents of them. The thermodynamic functions that appeared— the entropy, S, the Gibbs function, G, the Helmholtz function, A, the enthalpy, H, etc.— belong equally to the end equilibrium states and end nonequilibrium states. The former category of inequalities does not lead us to nonequilibrium thermodynamics, but provides classification of accessible/inaccessible equilibrium states from initial equilibrium state, that produces thermodynamic criteria of equilibrium in terms of these functions. Whereas, the latter category of inequalities leads us to develop nonequilibrium thermodynamic description. This we could demonstrate by adopting the steps of generation of entropy function for nonequilibrium states directly from the cyclic form of the celebrated Clausius' inequality, described by Eu and Garcia-Colin (1996). Once S function for nonequilibrium states become available, that too, based on the second law of thermodynamics, was straightforward to define all other thermodynamic functions for nonequilibrium states. Next, for spatially uniform systems, the only irreversibility that is permitted to exist is due to non-vanishing rates of chemical reactions. The method adopted in quantification of this irreversibility is the De Donderian method that was adopted earlier by Prigogine and Defay (1954). That surfaces out the internal composition variation parameter as an independent thermodynamic variable, Whereas for spatially non-uniform systems all the thermodynamic functions at the local level for existing nonequilibrium conditions follows from standard fluiddynamical integration, and they are the per unit mass quantities represented as s, u, h, a, and G. Herein, the suitable composition variables are the mass fractions x_{k,C}, the mass fraction of the component k in internal translational energy state determined by its peculiar or chaotic velocity C. The fifth law of thermodynamics follows therefrom, which asserts that for spatially non-uniform systems the functional dependence of entropy is s = s (u, v, x_{k,C}), which is the expression of local thermodynamic equilibrium (LTE), that permits the development of thermodynamic description of corresponding irreversible processes. The fourth law of thermodynamics has been recently formulated (2017) by us, that asserts that all processes which are describable by dS/dt = d_{e}S/dt + d_{i}S/dt, with the rate of entropy production d_{i}S/dt > 0 a positive definite quantity, are stable in Gibbs-Duhemian sense. Another demonstration is that the thermodynamics of chemical reactions is indeed the thermodynamics of irreversible phenomena, which has been asserted earlier by Prigogine and Defay (1954).

References:
1. S. Glasstone, Thermodynamics for Chemists, Princeton/D. Van Nostrand, New Jersey/New York (1964/1947)
2. B. C. Eu and L. S. Garcia-Colin, Irreversible processes and temperature. Phys. Rev. E 54(3), 2501-2512 (1996).
3. I. Prigogine and R. Defay, Chemical Thermodynamics, London: Longmans Green, 1954. Translated by D. H. Everett.
4. A. A. Bhalekar and B. Andresen, Thermodynamic stability of irreversible processes. A Gibbs-Duhem type theory and the fourth law of thermodynamics, In: F. Kongoli, A. Buhl, T. Turna, M. Mauntz, W. Williams, J. Rubinstein, P. L. Fuhr, M. Morales-Rodriguez (eds.), 2017 Sustainable Industrial Processing Summit and Exhibition, vol. 2, pp. 109 - 122. FLOGEN 2017 (2017).

SESSION: EnergyTuePM2-R9	5th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Tue Nov, 6 2018 / Room: Asian (60/3rd)
Session Chairs: Peter Wasserscheid; Meng Tao; Session Monitor: TBA

15:55: [EnergyTuePM209]
Naphthalene and Pyrene Degradation by Novel Bacterial Strains Isolated From an Oil-polluted Site in the Arabian Gulf
Assad Al Thukair¹ ; ¹King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia;
Paper Id: 5 [Abstract]

Brevibacillus brevis (T2C2008), Proteus mirabilis (T2A12001) and Rhodococcus quinshengi (TA13008) were tested to unravel their degrading efficiency for low molecular weight (LMW) and high molecular weight (HMW) polycyclic aromatic hydrocarbons (PAHs). The strains were isolated in previous research that focused on the microbial community structure and potential degraders of hydrocarbons in oil-contaminated sites in the Arabian Gulf. The bacterial isolates PAHs degrading efficiency was trialed at temperatures 25°C and 37°C and pH values 5.0 and 9.0. Each media was spiked with 100 mg/L naphthalene and pyrene, and followed by incubation at the chosen temperatures and pH. Rhodococcus qinshengi metabolized close to 56% pyrene at 37°C. Naphthalene was completely mineralized in R. qinshengi inoculated media at 37°C. At room temperature (25°C), Brevibacillus brevis metabolized over 80% naphthalene. Approximately 94% naphthalene biodegradation was observed in P. mirabilis and R. qinshengi incubated media. Rhodococcus qinshengi showed unique degradation potentials under varying pH conditions as the strain's mineralization was above 50% pyrene across the pH values investigated. Given that Proteus mirabilis and Brevibacillus brevis actively mediated the degradation naphthalene, the strains could be suitable for decontamination of environments polluted with LMW PAHs. Rhodococcus qinshengi biodegradation overall, exceeded half the concentration of the spiked naphthalene and pyrene, at varying temperatures and pH, implying that the strain could be suitable for degrading PAHs in suboptimal environments contaminated with hydrocarbons.

References:
[1] Abed, R.M., Al-Thukair, A. and De Beer, D., 2006. Bacterial diversity of a cyanobacterial mat degrading petroleum compounds at elevated salinities and temperatures. FEMS microbiology ecology, 57: 290-301.
[2] Agarry, S.E. and Aremu, M.O., 2012. Batch equilibrium and kinetic studies of simultaneous adsorption and biodegradation of phenol by pineapple peels immobilized Pseudomonas aeruginosa NCIB 950. British Biotechnology Journal 2: 26.
[3] Al-Thukair, A.A. and Malik, K., 2016. Pyrene metabolism by the novel bacterial strains Burkholderia fungorum (T3A13001) and Caulobacter sp (T2A12002) isolated from an oil-polluted site in the Arabian Gulf. International Biodeterioration and Biodegradation 110: 32-37.
[4] Al-Thukair, A.A., Abed, R.M.M. and Mohamed, L., 2007. Microbial community of cyanobacteria mats in the intertidal zone of oil-polluted coast of Saudi Arabia. Marine pollution bulletin 54: 173-179.
[5] Andreolli, M., Lampis, S., Zenaro, E., Salkinoja-Salonen, M. and Vallini, G., 2011. Burkholderia fungorum DBT1: a promising bacterial strain for bioremediation of PAHs-contaminated soils. FEMS microbiology letters 319: 11-18.
[6] Balachandran, C., Duraipandiyan, V., Balakrishna, K. and Ignacimuthu, S., 2012. Petroleum and polycyclic aromatic hydrocarbons (PAHs) degradation and naphthalene metabolism in Streptomyces sp.(ERI-CPDA-1) isolated from oil contaminated soil. Bioresource technology 112: 83-90.
[7] Bisht, S., Pandey, P., Kaur, G., Aggarwal, H., Sood, A., Sharma, S., Kumar, V., and Bisht, N.S., 2014. Utilization of endophytic strain Bacillus sp. SBER3 for biodegradation of polyaromatic hydrocarbons (PAH) in soil model system.European Journal of Soil Biology 60, 67-76.
[8] Chang, H., Nie, M., Ge, B., Liu, C., Yang, Q., Zhou, L., Fan, X., Sun, C., Wei, R. and Jiang, X., 2013. Effects of rhamnolipid on oil degradation by Pseudomonas aeruginosa strain NY3. Chin J Environ Eng. 7: 771-776.
[9] Chen, K., Zhu, Q., Qian, Y., Song, Y., Yao, J. and Choi, M.M., 2013. Microcalorimetric investigation of the effect of non-ionic surfactant on biodegradation of pyrene by PAH-degrading bacteria Burkholderia cepacia. Ecotoxicology and environmental safety 98: 361-367.

16:20: [EnergyTuePM210] Invited
Terawatt Solar Photovoltaics: Roadblocks and Opportunities
Meng Tao¹ ; ¹Arizona State University, Tempe, United States;
Paper Id: 146 [Abstract]

Global power demands are projected to reach 46 terawatts by 2100. Solar photovoltaics has to reach a scale of tens of peak terawatts in order to meet a meaningful portion of the demands. The enormous scale required creates a number of roadblocks for photovoltaic technologies, which are unprecedented in other semiconductor technologies. Some of the roadblocks include scarce raw materials used in today's solar cells, high energy input for silicon solar cells, life-cycle management of solar modules, storage of intermittent solar electricity, and high production/installation costs for solar cells/modules. In this talk an analysis will be presented, as quantitatively as possible, on some of these roadblocks under the best scenarios, i.e. the maximum possible wattage from each of the current commercial cell technologies. It is concluded that without significant technological breakthroughs, the current commercial cell technologies combined would not be able to make a noticeable impact on our energy mix or carbon emissions. Based on this analysis, several strategic R&D directions are identified for a scalable and sustainable solar photovoltaic technology.

References:
[1] M. Tao, Terawatt Solar Photovoltaics: Roadblocks and Opportunities (Springer, London, 2014)

16:45: [EnergyTuePM211]
Recyclability of Heterogeneous Palladium Catalysts for the Dehydrogenation of Aqueous Formic Acid
Axel Kosider¹ ; Patrick Preuster² ; Andreas Boesmann¹ ; Peter Wasserscheid¹ ; ¹Friedrich-Alexander-Universitat, Erlangen, Germany; ²Helmholtz Institute Erlangen-Nürnberg for Renewable Energy, Erlangen, Germany;
Paper Id: 237 [Abstract]

Our limited supply of fossil fuels leads to an increasing demand for alternative energy sources. A promising and often considered option is hydrogen, because it is a renewable energy source. However, the storage and transportation of hydrogen is inconvenient, complex, and expensive. In addition to physical storage, hydrogen can be stored chemically so that these challenges are circumvented. One possibility is to use formic acid as a chemical hydrogen carrier, which has a hydrogen content of 4.4 wt.-% [1, 2]. Formic acid can be produced from biomass and it is decomposed to hydrogen and carbon dioxide with high selectivity [3]. Heterogeneous palladium catalysts decompose aqueous formic acid at ambient pressure and temperature, so that hydrogen generated from sustainable formic acid can be used as a renewable energy source [4]. However, during the dehydrogenation of formic acid, a drastic decrease in catalytic activity is observed and active centers of the catalyst become poisoned. For economic reasons, regenerating the deactivated material is crucial.
We investigate the decomposition of aqueous formic acid at room temperature, as well as deactivation and reactivation of the catalytic active material with commercial heterogeneous palladium catalysts. In batch-experiments, we determine the gas production rate, the gas composition, and the liquid phase composition in order to determine activity and selectivity of the catalysts. Furthermore, the catalyst is treated at different conditions after each experiment in order to examine the regeneration of the poisoned material.
Commercial palladium catalysts have high activity and selectivity for the decomposition of aqueous formic acid to hydrogen and carbon dioxide at room temperature and ambient pressure. Poisoning of the active material leads to a strong decrease in activity so that a regeneration is necessary. Post-treatment of the deactivated palladium shows a regeneration of the catalytic active material and facilitates recycling of the precious metal catalyst.

References:
[1] S. Enthaler, J. von Langermann, T. Schmidt, Energy Environ. Sci. 3 (2010), 1207-1217.\n[2] M. Yadav, Q. Xu, Energy Environ. Sci. 5 (2012), 9698-9725.\n[3] P. Preuster, J.Albert, Energy Technol. 6 (2018), 501-509.\n[4] M. Jeon, D. Han, K. Lee et al., International Journal of Hydrogen Energy 41 (2016), 15453-15461.

17:10: [EnergyTuePM212]
Utilization of Green Cement (CSA) with CFBC Coal Power Plant Byproducts for 3D Printing Construction Materials for Sustainable Society
Jiwhan Ahn¹ ; Thriveni Thenepalli² ; Ramakrishna Chilakala² ; ¹KIGAM (Korea Institute of Geoscience and Mineral Resources), Daejeon, Republic of South Korea; ²Hanil Cement Co Ltd.,, Daejeon, South Korea;
Paper Id: 367 [Abstract]

Global warming, caused by the use of extensive fossil fuels and pollutants generated in several industrial facilities, has reduced the quality of our lives and clouded society's sustainable development [1]. In South Korea, the yearly emissions are 749 Mt CO₂e/a. The BAU of greenhouse gas in the goal year of 2020 is 776 million tons of CO₂, which will be reduced to 543 million CO₂ if the reduction goal of 30% is reached [2]. Furthermore, core technologies will be developed and demonstrated in the fields of CCS and CCUS for CO₂ reduction technology, which has high development potential and energy efficiency. This sustainable development is fundamentally based on resource recycling [3]. The green cement with circulating fluidized bed combustion (CFBC) coal power plants by products and it utilizes this green cement for 3D printing construction materials. 3D printing technology is the 4th industrial revolution technology and fabrication of 3D printing is compass of the new digital transformation and the key to the future of the global manufacturing economy [4,5]. 3D printing makes it possible to construct buildings in a short period of time and at low cost contributing to the construction of eco-friendly, low-carbon self-reliance by utilizing the rapid hardness, high strength, and eco-friendliness of Green Cement (CSA).

References:
[1] Jim Krane, MRS Energy and Sustainability: A Review Journal 4(2017)1-12.
[2] Ministry of Environment, Korea, Greenhouse Gas reduction Road Map.
[3] A.P. M. Velenturf, Phil Purnell, Sustainability 9(9) (2017), 1603-1619.
[4] D.E.Editors, History of 3D Printing Timeline. Digital Engineering, 29 Apr. 2016, www.digitaleng.news/de/history-of-3d-printing-timeline/.
[5] M.Gebler, A. J.M. Schoot Uiterkamp, C.Visser, Energy Policy 74 (2014) 158-167. Energy Policy 85 (2015) 511.

SESSION: EnergyWedAM-R9	5th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Wed Nov, 7 2018 / Room: Asian (60/3rd)
Session Chairs: Puzhen Gao; Tshimangadzo Saddam Munonde; Session Monitor: TBA

11:20: [EnergyWedAM01]
Nanostructured NiFe₂O₄ Composites as Electrocatalysts for Hydrogen Evolution Reaction (HER) in Acidic Solutions
Tshimangadzo Saddam Munonde¹ ; Philiswa Nomngongo² ; Haitao Zheng¹ ; Mphoma Matseke¹ ; ¹The Council for Scientific and Industrial Research (CSIR), Pretoria, South Africa; ²University of Johannesburg, Johannesburg, South Africa;
Paper Id: 210 [Abstract]

Water electrolysis has recently progressed as the most efficient and attractive way of producing hydrogen [1]. However, to ensure the effective production of hydrogen yielding high current densities at a low overpotential, a catalyst is needed. Present advancements in the water electrolysis process have opened pathways leading to the synthesis of a variety of non-precious materials as electrocatalysts, in place of Pt based catalyst [2,3]. In this work, we present the hydrothermal synthesis of the non-precious nickel ferrite (NiFe₂O₄) nanocomposites for hydrogen evolution reaction (HER). To increase the conductivity and therefore enhancing the activity of NiFe₂O₄ catalyst, the various carbon materials (carbon black, carbon nanofibers, etc.) were composited with NiFe₂O₄ nanoparticles. Post-treatment for NiFe₂O₄ composites were applied to further boost the catalytic activity of the NiFe₂O₄ composites. The composites show comparable activity and durability with commercial Pt/C for HER. The synthesized NiFe₂O₄ material was characterized using the XRD, FTIR, SEM and TEM, EDX and XPS etc. techniques.

References:
[1] Shi, Y., Zhang, B. (2016).. Chem. Soc. Rev, 45(6), 1529-1541.
[2] Lv, H., Xi, Z., Chen, Z., Guo, S., Yu, Y., Zhu, W., Mu, S. (2015). J. Am. Chem.Soc, 137(18), 5859-5862.
[3] Xu, X., Sun, Y., Qiao, W., Zhang, X., Chen, X., Song, X., Du, Y. (2017). Appl. Surf. Sci., 396, 1520-1527.

11:45: [EnergyWedAM02]
Nuclear Education and Training at Harbin Engineering University, China
Puzhen Gao¹ ; ¹Harbin Engineering University, Harbin, China;
Paper Id: 148 [Abstract]

Nuclear power is developing quickly in China. Peaceful and safe use of nuclear energy requires not only advanced technology, but also an extensive and intensive safety culture. Large number of personnel with nuclear safety technology and nuclear safety vision is in demand. Universities play an important role in providing nuclear engineering professionals. This presentation will introduce the nuclear engineering education in China, and specifically at Harbin Engineering University (HEU). HEU is a national key university with a long history and rich heritage. The nuclear academic program at HEU was founded in 1958; with the support of Chinese government and IAEA, the College of Nuclear Science and Technology (CNST) has become the largest nuclear education and training base in China. CNST annually trains and outputs about 400 students with different degrees. This presentation will cover: nuclear education and training at HEU, including application of simulators and virtual reality tools; teaching labs; the nuclear power simulation center; the virtual reality lab; student academic activities; international cooperation; student exchange.

References:
[1]http://cnst.hrbeu.edu.cn/en15/
[2]http://cnst.hrbeu.edu.cn/

12:10: [EnergyWedAM03]
Technological Treatment of Hazardous Chemical Waste
Mitar Lutovac¹ ; Sonja Stefanov² ; Rade Biocanin³ ; ¹University UNION Belgrade, Belgrade, Belgarde, Serbia and Montenegro; ², Novi Sad, Serbia and Montenegro (formerly Yugoslavia); ³State University of Novi Pazar, Novi Pazar, Serbia and Montenegro (formerly Yugoslavia);
Paper Id: 21 [Abstract]

Incineration, as a way of eliminating hazardous waste, is widely accepted in the petrochemical or chemical processing industry. This paper presents the results of many years of research on the management of hazardous solid waste, as well as on the achievement of the technology that destroys hazardous chemical waste. In this paper, the efficiency of this approach is presented both from the point of view of environmental protection and in the overall financial effect that can be achieved. Based on the considerations of the level of development of science and technology and relevant market needs, we propose advanced technologies and plans for complete treatment-incineration of hazardous chemical waste for quantities up to 100 kg / day, which is classified in the so-called "small" plants. This solution represents a modest contribution to the modern technologies of hazardous waste disposal in general, but has enormous significance for the eco-security and sustainable development in countries of the Ex Yugoslavia, the Balkans, and beyond.

References:
[1] Bahl S. European Plastics News, Vol.26., No.3.,27-28, 1999.
[2] Biocanin R., Obhodjas S. Environmental pollutants , IUT Travnik, 2011.
[3] Clayden Jonathan, Nick Greeves, Stuart Warren, Peter Wothers (2001). Organic chemistry. Oxford, Oxfordshire: Oxford University Press. ISBN 0-19-850346-6.
[4] Dillon A.P. Hazardous waste incineration engineering. Noyes data corporation, New Jerse, USA.1981.
[5] Djuricic R. M., Nenadic S. M., Milutinovic I. I., Acimovic-Pavlovic Z., Development of a neutralization and combustion plant for hazardous medical waste , Zlatibor 06-09-april 2009.
[6] Holoubek I., Hrdinka C., Environmentalni aspekty antropogennich technologii (07) Nemocnioni odpady, RECETOX, Masaryk University, Brno, CR, Available on Web site: http://recotex, muni.cz

12:35: [EnergyWedAM04]
Management of Sand Production in Oil and Gas Reservoirs
Abdollah Esmaeili¹ ; ¹Cyprus International University (CIU), Nicosia, Cyprus;
Paper Id: 36 [Abstract]

Sand production is a serious problem in oil and gas reservoirs worldwide. It can drastically affect production rates. The adoption of a sand management strategy is crucial for prolonging economic reservoir development for sand producing reservoirs. Significant gains in production (acceleration) and reserves (IOR) can result from the pursuance of sand management in these fields. Such a strategy requires that the sand production is managed in a safe and controlled manner, where the negative consequences of sand production are manageable and predictable. Sand management has been identified as one of the key issues in field development in most of the world's oil and gas fields. Sand management is not just about selection of sand control systems - it is about maximizing and maintaining production while managing sand at acceptable rates. Successful sand management can only be achieved with a fully integrated, multi-disciplinary team. Facilities' sand management is tasked with the goal of ensuring sustained hydrocarbon production when particulate solids (i.e. sand) are present in well fluids, while minimizing the impact of these produced solids on surface equipment. Particle size and total concentration of formation sand determines their net effect on production and the resulting operability of surface facilities. Conventional sand management control focuses on sand exclusion from the wellbore, either by production limits or completion design. Completions may adversely affect inflow due to skin buildup and both controls impede maximum hydrocarbon production. Alternatively, co-production of fluids and solids, with subsequent sand handling at surface facilities, is an inclusion paradigm that allows sustained hydrocarbon production. Produced solids are removed at the wellhead upstream of the choke using fit-for-purpose equipment. This methodology allows for increased or recovered hydrocarbon production, while their removal upstream of the choke protects facilities operations.

References:
[1] Abass H.H., A.H. Habber, A. Shebatalhamd, "Sand control during drilling, perforation, completion and production", SPE 81492, (2003)
[2] Goodman R. E. (1989) "Introduction to Rock Mechanics", 2nd edn. John Wiley,Chichester
[3] Hall, C.D., Harrisberger,W.H. "Stability of sand arches: A key to sand control". J. Petr. Tech.22, 821-829. (1970)
[4] Haugen, K., Kvernvold, O., Ronold, A., Sandberg, R. (1995). "Sand erosion of wear resistant materials: Erosion in choke valves". Wear 186-187, 179-188.
[5] Van den Hoek, P.J., Hertogh, G.M.M., Kooijman, A.P., de Bree, Ph., Kenter, C.J., Papamichos, E. (2000a). "A new concept of sand production prediction: theory andlaboratory experiments". SPE Drilling & Completion 15, 261-273.
[6] Morita, N. (1994), "Field and laboratory verification of sand-production prediction models", SPE Drilling & Completion 9, 227-235.
[7] Morita, N., Whitfill, D.L., Massie, I., Knudsen, T.W. (1989a). "Realistic sand production prediction: Numerical approach". SPE Production Eng. 4, 15-24.
[8] Risnes, R., Bratli, R.K., Horsrud, P. (1982). "Sand stresses around a wellbore". Soc.Petr. Eng. J. 22, 883-898.
[9] Skjaerstein, A., Tronvoll, J., Santarelli, F.J., Joranson, H. (1997). "Effect of water breakthrough on sand production: experimental and field evidence". SPE38806. In: SPE ATCE, San Antonio, TX, October 5-8.
[10] Han, G., Dusseault, M.B. (2002). "Quantitative analysis of mechanisms for water related sand production". SPE73737. In: SPE International Symposium on Formation Damage Control, Lafayette, LA, February 20-21.
[11] Tronvoll, J., Dusseault, M.B., Sanfilippo, F., Santarelli, F.J. (2001), "The tools of sand management", SPE71673. In: SPE ATCE, New Orleans, LA, September 30-October 3.
[12] Tronvoll, J., Fjaer, E. (1994), "Experimental study of sand production from perforation cavities", Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 31, 393-410.
[13] Bouhroum, A., & Civan, F., "A Critical Review of Existing Gravel-Pack Design Criteria," Journal of Canadian Petroleum Technology, Vol. 34, No. 1, 1995, pp. 35-40.
[14] Geilikman, M. B., Dusseault, M. B., & Dullien, F. A. L., "Sand Production as a Viscoplastic Granular Flow," SPE 27343 paper, SPE International Symposium onFormation Damage Control, February 9- 10, 1994, Lafayette, Louisiana, pp. 41-50.
[15] Hayatdavoudi, A., "Formation Sand Liquefaction: A New Mechanism for Explaining Fines Migration and Well Sanding," SPE 52137 paper, SPE Mid-Continent Operations Symposium, March 28-31, 1999, Oklahoma City, Oklahoma, pp. 177-180.
[16] Saucier, R. J., "Successful Sand Control Design for High Rate Oil and Water Wells, "J. of Petroleum Technology, Vol. 21, 1969, p. 1193.
[17] Saucier, R. J., "Considerations in Gravel-Pack Design," J. of Petroleum Technology, Vol. 26, 1974, p. 205.
[18] Skjaerstein, A., & Tronvoll, J., "Gravel Packing: A Method of Wellbore Re-enforcement or Sand Filtering?," SPE 37506 paper, SPE Production Operations Symposium, March 9-11, 1997, Oklahoma City, Oklahoma, pp. 871-879.
[19] Tiffin, D. L., King, G. E., Larese, G. E., & Britt, R. E., "New Criteria for Gravel and Screen Selection for Sand Control," SPE 39437 paper, SPE Formation Damage Control Conference, February 18-19, 1998, Lafayette, Louisiana, pp. 201-214.
[20] Penberthy, W.L. and Shaughnessy, C.M., "Sand Control", SPE Series on Special Topics, Volume 1, 1992.
[21] Suman, G.O. Jr., Ellis, R.C., and Snyder, R.E., "Sand Control Handbook", Second Edition, Gulf Publishing Company, Houston, Texas, 1991.
[22] Sparlin, D.D., "Sand and Gravel - A Study of Their Permeabilities", SPE Paper 4772, SPE Symposium on Formation Damage Control, New Orleans, Louisiana, February 7-8,1974.
[23] Ledlow, L.B., "High-Pressure Packing With Water: An Alternative Approach to Conventional Gravel Packing", SPE Paper 26543, SPE 68th Annual Technical Conference and Exhibition, Houston, Texas, October 3-6,1993.
[24] Wong, G.K., Fors, R.R., Casassa, J.S., and Hite, R.H., "Design, Execution, and Evaluation of Fracture and Pack (F&P) Treatments in Unconsolidated Sand Formations in the Gulf of Mexico", SPE 26563, 68th Annual Technical Conference and Exhibition, Houston, TX, 3 - 6 October, 1993.

SESSION: EnergyWedPM1-R9	5th Intl. Symp. on Sustainable Energy Production: Fossil; Renewables; Nuclear; Waste handling , processing, and storage for all energy production technologies; Energy conservation
Wed Nov, 7 2018 / Room: Asian (60/3rd)
Session Chairs: Abdollah Esmaeili; Session Monitor: TBA

14:00: [EnergyWedPM105]
Sand Production in an Oil Well and Its Prediction Methods
Abdollah Esmaeili¹ ; ¹Cyprus International University (CIU), Nicosia, Cyprus;
Paper Id: 35 [Abstract]

In formations where the sand is porous, permeable, and well cemented together, large volumes of hydrocarbons which can flow easily through the sand and into production wells are produced through perforations into the well. These produced fluids may carry entrained sand, particularly when the subsurface formation is an unconsolidated formation. Produced sand is undesirable for many reasons. When it reaches the surface, sand can damage equipment such as valves, pipelines, pumps and separators and must be removed from the produced fluids at the surface. Further, the produced sand may partially or completely clog the well, lead to substantially poor performance in wells, ultimately inhibit production, and thereby making an expensive work-over necessary. In addition, the sand flowing from the subsurface formation may leave a cavity, which may result in caving of the formation and collapse of the casing. Sand production in oil and gas wells can occur if fluid flow exceeds a certain threshold, governed by factors such as consistency of the reservoir rock, stress state, and the type of completion used around the well. The amount of solids can be less than a few grams per cubic meter of reservoir fluid, posing only minor problems, or a substantial amount over a short period of time, resulting in erosion and in some cases filling and blocking of the wellbore. Although major improvements have been achieved in the past decade, sanding tools are still unable to predict the sand mass and the rate of sanding for all field problems in a reliable form. This paper provides a review of selected approaches and methods that have been developed for sanding prediction. Most of these methods are based on the continuum assumption, while a few have recently been developed based on discrete element model. Some methods are only capable of assessing the conditions that lead to the onset of sanding, while others are capable of making volumetric predictions. Some methods use analytical formulae, particularly those for estimating the onset of sanding, while others use numerical methods, particularly in calculating sanding rate.

References:
[1] Abass H.H., A.H. Habber, A. Shebatalhamd, "Sand control during drilling, perforation, completion and production", SPE 81492, (2003)
[2] Goodman R. E. (1989) "Introduction to Rock Mechanics", 2nd edn. John Wiley,Chichester
[3] Hall, C.D., Harrisberger,W.H. "Stability of sand arches: A key to sand control". J. Petr. Tech.22, 821-829. (1970)
[4] Haugen, K., Kvernvold, O., Ronold, A., Sandberg, R. (1995). "Sand erosion of wear resistant materials: Erosion in choke valves". Wear 186-187, 179-188.
[5] Van den Hoek, P.J., Hertogh, G.M.M., Kooijman, A.P., de Bree, Ph., Kenter, C.J., Papamichos, E. (2000a). "A new concept of sand production prediction: theory andlaboratory experiments". SPE Drilling & Completion 15, 261-273.
[6] Morita, N. (1994), "Field and laboratory verification of sand-production prediction models", SPE Drilling & Completion 9, 227-235.
[7] Morita, N., Whitfill, D.L., Massie, I., Knudsen, T.W. (1989a). "Realistic sand production prediction: Numerical approach". SPE Production Eng. 4, 15-24.
[8] Risnes, R., Bratli, R.K., Horsrud, P. (1982). "Sand stresses around a wellbore". Soc.Petr. Eng. J. 22, 883-898.
[9] Skjaerstein, A., Tronvoll, J., Santarelli, F.J., Jaeranson, H. (1997). "Effect of water breakthrough on sand production: experimental and field evidence". SPE38806. In: SPE ATCE, San Antonio, TX, October 5-8.
[10] Han, G., Dusseault, M.B. (2002). "Quantitative analysis of mechanisms for water related sand production". SPE73737. In: SPE International Symposium on Formation Damage Control, Lafayette, LA, February 20-21.
[11] Tronvoll, J., Dusseault, M.B., Sanfilippo, F., Santarelli, F.J. (2001), "The tools of sand management", SPE71673. In: SPE ATCE, New Orleans, LA, September 30-October 3.
[12] Tronvoll, J., Fjaer, E. (1994), "Experimental study of sand production from perforation cavities", Int. J. Rock Mech. Min. Sci. Geomech. Abstr. 31, 393-410.
[13] Bouhroum, A., & Civan, F., "A Critical Review of Existing Gravel-Pack Design Criteria," Journal of Canadian Petroleum Technology, Vol. 34, No. 1, 1995, pp. 35-40.
[14] Geilikman, M. B., Dusseault, M. B., & Dullien, F. A. L., "Sand Production as a Viscoplastic Granular Flow," SPE 27343 paper, SPE International Symposium onFormation Damage Control, February 9- 10, 1994, Lafayette, Louisiana, pp. 41-50.
[15] Hayatdavoudi, A., "Formation Sand Liquefaction: A New Mechanism for Explaining Fines Migration and Well Sanding," SPE 52137 paper, SPE Mid-Continent Operations Symposium, March 28-31, 1999, Oklahoma City, Oklahoma, pp. 177-180.
[16] Saucier, R. J., "Successful Sand Control Design for High Rate Oil and Water Wells, "J. of Petroleum Technology, Vol. 21, 1969, p. 1193.
[17] Saucier, R. J., "Considerations in Gravel-Pack Design," J. of Petroleum Technology, Vol. 26, 1974, p. 205.
[18] Skjaerstein, A., & Tronvoll, J., "Gravel Packing: A Method of Wellbore Re-enforcement or Sand Filtering?," SPE 37506 paper, SPE Production Operations Symposium, March 9-11, 1997, Oklahoma City, Oklahoma, pp. 871-879.
[19] Tiffin, D. L., King, G. E., Larese, G. E., & Britt, R. E., "New Criteria for Gravel and Screen Selection for Sand Control," SPE 39437 paper, SPE Formation Damage Control Conference, February 18-19, 1998, Lafayette, Louisiana, pp. 201-214.
[20] Penberthy, W.L. and Shaughnessy, C.M., "Sand Control", SPE Series on Special Topics, Volume 1, 1992.
[21] Suman, G.O. Jr., Ellis, R.C., and Snyder, R.E., "Sand Control Handbook", Second Edition, Gulf Publishing Company, Houston, Texas, 1991.
[22] Sparlin, D.D., "Sand and Gravel - A Study of Their Permeabilities", SPE Paper 4772, SPE Symposium on Formation Damage Control, New Orleans, Louisiana, February 7-8,1974.
[23] Ledlow, L.B., "High-Pressure Packing With Water: An Alternative Approach to Conventional Gravel Packing", SPE Paper 26543, SPE 68th Annual Technical Conference and Exhibition, Houston, Texas, October 3-6,1993.
[24] Wong, G.K., Fors, R.R., Casassa, J.S., and Hite, R.H., "Design, Execution, and Evaluation of Fracture and Pack (F&P) Treatments in Unconsolidated Sand Formations in the Gulf of Mexico", SPE 26563, 68th Annual Technical Conference and Exhibition, Houston, TX, 3 - 6 October, 1993.

14:25: [EnergyWedPM106]
Local Thermal Effect on Vapor Extraction (VAPEX) Process for Heavy Oil Enhanced Recovery
Abdollah Esmaeili¹ ; ¹Cyprus International University (CIU), Nicosia, Cyprus;
Paper Id: 37 [Abstract]

Heavy oil has a high viscosity, so production form heavy oil reservoir is very difficult. One of the methods which are used to increase recovery factor from this reservoirs is miscible injection. Among miscible injection methods is vapor extraction method via injection the vapor of hydrocarbon solvent which is a suitable constitute for thermal methods in reservoir where heat loss is high. The vapor extraction (VAPEX) process, a solvent-based enhanced oil recovery process has been found promising for some heavy oil reservoirs. Viscosity of heavy oil will be decreased by injection the vapor of hydrocarbon solvent into it. This phenomenon is the base of vapor extraction (VAPEX) method. One of the disadvantages of VAPEX process which has been reported by most of previous researchers is its low production rate. In this paper, effect of temperature on increasing recovery and production rate of this process has been investigated. Obtained results show that by increasing temperature, oil recovery and production rate by this process will be increased.

References:
[1] Das, S. K. and R. M. Butler, (1998). "Mechanism of the Vapor Extraction Process for the Heavy Oil and Bitumen", Journal of Petroleum Science and Engineering, Vol.2 PP 43-59.
[2] Azin, R., Kharrat, R., Ghotbi, C., Vossoughi, S. (2005). "Applicability of the VAPEX Process to Iranian Heavy Oil Reservoirs", SPE 92720
[3] Laherr, J. H.,(1996). "Upstream Potential of the Middle East in the World Context", SPE
[4] Karmakar, K. and Maini, B. B.,(2003) "Applicability of the Vapor Extraction Process to Problematic Viscous Oil Reservoirs.", SPE 84034
[5] Butler, R.M., Mokrys, I. J. (1989). "Solvent Analog Model of Steam-Assisted Gravity Drainage", AOSTRA Journal of research, Vol. 5, P. 17
[6] Das, S. K. and R. M. Butler, (1998). "Mechanism of the Vapor Extraction Process for the Heavy Oil and Bitumen", Journal of Petroleum Science and Engineering, Vol.2 PP 43-59.
[7] Karmaker, K., Maini, B.B. (2003). "Experimental Investigation of Oil Drainage Rates in the VAPEX Process for Heavy Oil and Bitumen Reservoirs", SPE 84199.
[8] Redford, D. A. "the Use of Solvents and Gases with Steam in the Recovery of Bitumen from Oil Sands", J. Cdn. Pet. Tech., 1982
[9] Harding, T. G., Farouq Ali, S M., and Flock, D. L., "Steam Performance in the Presence of Carbon Dioxide and Nitrogen", J. Cdn. Pet. Tech., Vol. 30, 1983
[10] Nasr, T. N., Prowse, D. R. and Fraunfeld, T. W. J., "the Use of Flue Gas With Steam in Bitumen Recovery from Oil Sands", J. Cdn. Pet. Tech.,Vol. 62, 1987
[11] Bagci, S. and Gumrah, F., "Steam-Gas Drive Laboratory Tests for Heavy-Oil Recovery", In Situ (1998) 22, No. 3, 263
[12] Butler, R. M. and Mokrys, I. J.(1991) "A New Process (VAPEX) for Recovering Heavy Oils Using Hot Water and Hydrocarbons Vapor", JCPT, Vol.30, No.1.
[13] Butler, R. M. and Mokrys, I. J., "In-Situ Upgrading of Heavy Oils and Bitumen by Propane Deasphalting: the Vapex Process", SPE 25452, 1993.
[14] Ted W. J. F., Kissel G. and Zhou s., "PVT and Viscosity Measurements for Lloydminister-Aberfeldy and Cold Lake Blended Oil Systems", SPE 79018, 2002.
[15] Salama, D. A., Kantzas, (2005). "Experimental Observation Miscible Displacement of Heavy Oils with Hydrocarbons Solvents", SPE 97854
[16] Azin, R., Kharrat, R., Ghotbi, C., Vossoughi, S. (2005). "Applicability of the VAPEX Process to Iranian Heavy Oil Reservois", SPE 92720
[17] Salama, D. Kantzas A., (2005). "Monitoring of Diffusion of Heavy Oils with Hydrocarbon Solvents in the Presence of Sand", SPE 97855
[18]] Luo, P. (2005). "Effects of Asphaltene and Solvent Concentration on Heavy-Oil Viscosity", SPE 97778
[19] Goite, J.G., Mamora, D. D., Ferguson, M. A. (2001). "Experimental Study of Morichal Heavy Oil Recovery Using Combined Steam and Propane Injection", SPE 69566.
[20] Mamora, D. D., Rivero, J. A., Venturini, G. J., "Experimental and Simulation Studies of Steam-Propane Injection for the Hamaca and Duri Fields", SPE 84201, (2003).
[21] Zhao L. "Steam Alternating Solvent Process", SPE 86957, 2004.
[22] Palmgren C., "High Temperature Naphtha to Replace Steam in the SAGD Process", SPE 30294, 1995.