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By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite,(Cu2S) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical equilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By M. Neises, M. Roeb, C. Sattler, S. Stenger

"A two-step thermo-chemical cycle process has been developed and investigated. It is based on metal oxide redox pair systems, which can split carbon dioxide as well as water molecules by extracting oxygen atoms and reversibly incorporating them into their lattice. If concentrated solar radiation is used as the heat source, a promising method exists to produce synthesis gas from water and CO2. An easy way of operation is gained by the combination of a ceramic substrate as the absorber structure, which can be heated to high temperatures with concentrated solar radiation, and of a metal oxide coating which is capable to carry out the redox reactions. The performance and kinetics of a ferrite based redox material coated on ceramic substrates were investigated in a laboratory set-up. CO2 could be reduced with significant conversions. In addition, several side reactions were observed like the formation of carbon and like the Boudouard reaction.IntroductionThe search for alternative energy carriers and for processes able to reuse carbon dioxide stimulates the research for sustainable routes of alternative fuel production. In the scope of this search thermo-chemical processes combined with sources of concentrated solar energy have become more and more attractive. Ideally, the only raw materials for such processes are water (H2O) and carbon dioxide (CO2) enabling not only a process free of emissions, but also allow to reduce emissions of other processes by reusing CO2 to provide synthesis gas, which itself can be applied to produce chemical commodities or even better synthetic fuels like methanol or petrol.In contrast to the direct splitting of those raw materials, thermochemical cycles split water and CO2 in several steps and enable hydrogen (H2) and carbon monoxide (CO) generation at temperatures controllable by today’s technical equipment. One of the most interesting thermochemical cycles is a two-step process using metal oxide based redox systems. During the first step of this cycle (the regeneration step) the metal oxide is reduced setting some of its lattice oxygen free according to reaction (1). In the next step (the splitting) the reduced and activated material is oxidised by withdrawing oxygen from water and CO2 and at the same time hydrogen and CO is set free according to reactions (2a) and (2b) respectively."

Jan 1, 2011

By A. Krishnan

Keywords: Tantalum extraction, SOM Technology, inert anode, membrane stability The Solid Oxide Oxygen Ion conducting Membrane (SOM) technology offers great potential for environment friendly and energy efficient extraction of high-energy content metals. This work was performed to demonstrate the technical and commercial viability of the technology to produce tantalum metal directly from tantalum oxide and ore concentrates using a solid-oxide, oxygen-ion-conducting membrane (SOM). The process can be used to efficiently produce tantalum metal without expensive pre-processing of raw materials and without harmful by products. The work reported in this paper is: the proof that high purity tantalum metal can be produced, study of the electrochemical behavior of the cell and the method to increase membrane stability.

Jan 1, 2005

By Marko Suput

Titanium is a high-strength, low-density metal nearly immune to corrosion, but limited in use by its high price. The high price is due to the cost of smelting and processing the ore. The research on titanium production using the Solid Oxide Membrane (SOM) process aims to consolidate most of the processing steps required for conventional titanium production into a single step making it an energy-efficient and cost-effective method for producing CP billet and ingot and possibly also powders used to make titanium alloys. In the SOM process experiment, a steel crucible contains MgF2-CaF2-TiO2 flux; an inert metal/carbon rod serves as the cathode; an oxygen-ion-conducting yttrium-stabilized-zirconia (YSZ) membrane in the form of a one-end-closed tube contains either a liquid metal that acts as the anode or liquid MgF2-CaF2 ionic flux that connects the YSZ membrane to an anode. During electrolysis, when the voltage between anode and cathode is higher than the reduction potential of titanium oxide, titanium ions are reduced at the cathode and the oxygen ions pass through the YSZ membrane and are oxidized at the anode. The oxygen ions are oxidized at the anode by a reducing agent, hydrogen gas or carbon, forming steam or CO(g), respectively. To date, a suitable MgF2-CaF2-TiO2 flux has been selected and the operating temperature for the SOM process has been determined. Several electrolysis experiments have been performed. As expected, lower valence deposits of titanium oxides have been witnessed at the cathode prior to depositing pure titanium. Continuing work will aim to extend the electrolysis time in order to pass enough charge to produce a significant amount (100 g) of titanium at the cathode.

Jan 1, 2006

By Soobhankar Pati

Solid oxide membrane (SOM) technology has been successfully employed for the production of high energy metals such magnesium, titanium and tantalum by directly reducing their oxides. This paper reports on the recent investigation done for calcium production by SOM process from calcium oxide, dissolved in fluoride and chloride based fluxes. This process employs an inert oxygen-ion-conducting stabilized zirconia membrane to separate the inert cathode in the flux from the anode. When the applied electrical potential between the electrodes exceeds the dissociation potential of calcium oxide, oxygen ions are driven out of the melt and through the zirconia membrane to the anode where they are oxidized. Reduced calcium metal deposits or evolves at the cathode depending on the operating temperature. The SOM cell has been electrochemically characterized, and key concepts related to CaO dissociation, leakage current, solubility of Ca in the flux, and hygroscopic nature of the flux relevant to the SOM process are explained.

Jan 1, 2008

By N. Lohja

Metallurgical industries are generally big producers of solid residues of various kinds. In contrast with the past where environmental sensibilities were not so elevated and the accumulated mass of these residues were not considerable, these days the solid residues are everywhere scrutinized among others in term of their harmful environmental impact and as possible materials for valuable elements extraction or secondary utilisation. As a case study, the present paper gives an overview of the solid residues discharged by the metallurgical industry in Albania for the last tens of years. The results of two monitoring study on the solid residues of copper, iron and ferrochromium producing industries are also summarized. The first deals with the origin, quantities and chemical composition of these residues and the second one with the impact of harmful ingredients of these residues in the environment. Some methods for the processing of these solid residues are also proposed in order to ensure a clean environment and to make not just possible but also economically viable their secondary utilisation. This work is part of a bigger cooperation project among local institutions and foreign expert companies such as Flogen Technologies Inc and other in various countries that will not only monitor the situation but will also develop appropriate technologies for treatment of these specific residues.

Jan 1, 2006

By Virgil Optasanu, Yvon Lacroute, Eric Lesniewska, Tony Montessin, Pauline Vitry, Eric Bourillot, Cédric Plassard

A general challenge in metallic components is the need for materials research to improve the service lifetime of the structural tanks or tubes subjected to harsh environments or the storage medium for the products. One major problem is the formation of lightest chemical elements bubbles or different chemical association, which can have a significant impact on the mechanical properties and structural stability of materials. The high migration mobility of these light chemical elements in solids presents a challenge for experimental characterization. Here, we present work relating to an original non-destructive, with high spatial resolution, tomographic technique based on Scanning Microwave Microscopy (SMM), which is used to visualize in-depth chemical composition of solid solution of a light chemical element in a metal. The experiments showed the capacity of SMM to detect volume. Measurements realized at different frequencies give access to a tomographic study of the sample.

Jan 1, 2015

By J. L. Jambor

Previous crystal-structure determination of magnesian annabergite (Ni,MgMAsO4)2 8H2O indicated that ordering of Ni and Mg occurs in non-equivalent octahedral sites; such ordering supports the possibility of miscibility gaps on the Ni3(AsO4)2 8H2O -MgiAs04)2 8H2O. (annabergite-hornesite) join. In a predecessor study based on analyses of natural specimens, it was proposed that solid solution is incomplete both for annabergite-hornesite and annabergite-erythrite [Co, (AsO4)2 8H2O]. In the current study, syntheses by use of a slow-addition technique and aging of the precipitates indicated that the annabergite-erythrite solid solution is complete, and that no miscibility gap is present on the annabergite-hornesite join to at least 58 mol % Mg. Thus, interpretation of the compositions of these phases in oxidized mill-tailings impoundments can be done with the normal precautions for homogeneity, and without the added concern of the possible presence of miscibility gaps in the ternary system.

Jan 1, 1995

By Stephen C. Britten

An in-situ amperometric slag sensor for measuring the concentration of easily dissociable oxides in slags at temperatures between 1200-1600°C is being developed. The sensor provides the same information as potentiometric sensors while also providing data on the concentration of the transition metal species and the diffision kinetics within the slag. The electrochemical technique utilized in the sensor is similar to methods utilized in aqueous voltammetry.

Jan 1, 1998

By Jun Sugiyama, Hiroyuki Sano, Toshiharu Fujisawa, Hideki Takeuchi, Chikabiuni Yamauchi

"The solid .state electrotransport (SSE) is one of the most promising methods for the elimination of gaseous impurities from chemically active metals, such as rare earth metals. . In the present work, the SSE process was applied for the oxygen removal from praseodymium. The SSE factors, such as effective valence, were measured under the various temperatures, electric field intensities and initial oxygen contents, and the effects of those conditions on the SSE process were discussed. Furthermore, the solubility of oxygen in .solid praseodyillium was also measured·, by using the SSE method and metal-oxide equilibrium method.IntroductionWhen a direct current is passed through a solid alloy, not only electrons but also solute atoms are transported as charge carriers toward the anode or cathode. This phenomenon is referred to as an electrotransport or electromigration. The solid state electrotransport (SSE) is the application technique, based on this principle, to the pUrification of the solid metallic materials.Rare earth metals are used for various functional materials, such as magnetic, optical or electronic materials, therefore their high purity metals are required [l ,2]. However, rare earth metals are chemically active and have a strong affinity with gaseous elements (e.g. oxygen, nitrogen, hydrogen and carbon). In many cases, eliminating operations of gaseous elements have not been always made commercially, because these impurity elements could not be eliminated by usual treatments applied to the purification of ·common metals. As an alternative method, authors have proposed the· application of the SSE process to the elimination of gaseous impurities from rare earth metals. Investigations have been carried out on the yttrium-oxygen and neodymium-oxygen systems and the results were already reported[3,4]."

Jan 1, 2000

By David E. Jones

In any manufacturing process, the generation of secondary, associated or waste products along with the primary product is inevitable. Today there is great emphasis on the concept of waste minimisation. As part of that overall strategy, the search .for markets for these materials formally regarded as wastes, can mean the development of whole new industries. This paper examines some of the work necessary to develop recycling and markets for associated products with particular reference to iron and steelmaking slags.

Jan 1, 1994

By Ray D. Peterson

The hydrothermal enrichment of chalcopyrite by CuSO, occurs in the absence of oxidizing or reducing reagants. Kinetics of the enrichment process were determined under autoclave conditions in the temperature range of 398°K (125°C) to 473°K (200°C). Covellite (CuS) formed first, followed by digenite (Cu,,,S), with rejection of iron to the solution. The kinetics have been explained by a model which includes diffusion during the first stage formation of covellite followed by surface reaction rate control when digenite be. The effects of particle size, temperature, pH, and cupric and ferrous ion concentrations on the leaching kinetics were examined. Additions of ferrous ion to solution markedly increased the rate of reaction.

Jan 1, 1994

By James D. O, DeLa&apos

Multicomponent materials are common in nearly all areas of materials science and technology, yet the use of phase diagrams to represent these complex systems is hampered by the requirement of three or more dimensions for explicit graphical representation. In the present work, the "solid-modeling" capabilities of a computer aided design (CAD) system have been applied to the representation of three-dimensional phase diagrams. Relevant phase diagrams for a hypothetical quaternary eutectic system were constructed and used to demonstrate the capabilities of the technique. These capabilities lead to relative ease of phase diagram construction and improved access to qualitative and quantitative information. Results of this work are contrasted and compared to previous efforts toward computer ,representation of phase diagrams. It is concluded that solid-modeling of three-dimensional phase diagrams can be used to advantage in both education and research.

Jan 1, 1991

By Jeffrey W. Fergus, Shiqiang Hui

"Aluminum is an important alloying addition to the zinc used in the hot-dip galvanization of sheet steel to control the properties and appearance of the resulting coating. Optimization of the galvanization process requires control of the alloy concentration which can be improved through the use of chemical sensors. Aluminum sensors based on molten electrolytes are commercially available but are not widely used because of their high cost. One approach to reducing the cost is to use a solid electrolyte which can simplify the sensor design and thus reduce the cost of fabrication. In this paper, the development of an aluminum sensor based on a solid fluoride electrolyte, specifically magnesium fluoride, will be described.IntroductionThe concentration of the zinc bath used in hot-dip galvanization affects the galvanization process as well as the properties of the resulting coating. Thus, accurate in situ measurement of the alloy composition can be used to improve process control. This paper describes a solid-electrolyte-based aluminum sensor for monitoring the bath composition during hot-dip galvanization."

Jan 1, 1997

By E. A. Trillo, L. E. Murr, R. D. Flores, J. C. McClure, B. M. Nowak

Complex vortex and swirl-like solid-state flow phenomena have been observed in the residual microstructures characterizing the friction-stir welding (FSW) of copper to 6061 aluminum; 2024 aluminum to 6061aluminum,2024 aluminum to 1100 aluminum, 2024 aluminum to 7039 aluminum and 2024 aluminum to 2195 aluminum. These flow phenomena are characterized by intercalation lamellae composed of dynamically recrystallized grain structures of the dissimilar metals which provide a super-plastic-like mechanism for the FSW flow in the solid state; there is no melting and temperatures at the weld center do not exceed about 0.8 TM (where TM is the absolute melting temperature (K)). In experiments to be described and illustrated, optical or light metallography (LM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques are utilized in examining residual FSW microstructures corresponding to tool rotation (stirring) speeds ranging from 400 to 1200 rpm, and traverse (or actual welding) speeds of 1 to 2 mrn/s.

Jan 1, 1999

By Forsén. O.

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means 'that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.

Jan 1, 1987

By Alicia Esther Ares, Alex Iván Kociubczyk, Verónica Liliana Scheiber, Roberto Rozicki

In the present research the horizontal solidification of Sn-Zn eutectic alloys (Sn-8.9wt.%Zn) is performed, with two opposite senses of heat extraction. From the process of solidification, the thermal parameters (local solidification time, cooling rates and interphases velocities) and grain sizes from macrostructures obtained were determined. The presence of defects in the solidified samples was analyzed, observing that they occur largely in the collision zones of solidification fronts advancing in opposite directions in the samples.

Jan 1, 2016

By Nicholas Zabaras, Deep Samanta

"Solidification of metal aluminum and aluminum alloys is modeled on uneven surfaces characterized by sinusoidal curves. Wavelengths and amplitudes of these sinusoidal surfaces are varied to study their effects on processes like solidification, macro-segregation and inverse segregation. Solidification and macro-segregation are modeled using a slightly modified form of a stabilized finite element method developed recently to model high Rayleigh number solidification and porous media flows. For pure metal solidification, the effect of varying amplitudes and wavelengths is observed in heat transfer, fluid-flow ~nd phase change processes. The relative importance of shrinkage driven flow and solutal convection on the redistribution of solute for an alloy solidifying in a rectangular cavity is compared. The analysis is then extended by modifying one of the surfaces to a sinusoid. In this case the effects of varying amplitudes and wavelengths are studied in heat transfer, fluid flow, phase change, macro-segregation and inverse segregation processes.1 IntroductionTransport phenomenon during solidification of alloys is a major cause ofcasting defects such as segregation, micro-voids, hot tears, porosity, internal and surface cracks. Heat flow across metal and mold surfaces directly affects the phase change process and plays an important role in determining freezing conditions within the metal. In alloys, natural convection and shrinkage play an important role in determining the final solute redistribution, macrosegregation and evolution of solid macromorphology. Surface unevenness plays an important role during the early stages of solidification. It influences the heat transfer rate and fluid flow in the melt, which in turn affect the morphology and shape of the solid-liquid interface. The effect of surface unevenness on solute redistribution is important during solidification of alloys, where solute driven flow in the mushy zone is prominent. Thevik and Mo in [7] and [8] used a one dimensional model for studying surface segregation and macrosegregation in alloys under the influence of exudation and solidification shrinkage. Air-gap formation in their model was expressed through a variable convective heat transfer coefficient at the boundary. Tsai et al. in [3] and [4] have modeled macrosegregation in an aluminum-copper alloy driven by shrinkage and solutal convection. They used a single domain model based on mixture theory and solved the transport equations using finite difference methods. Our aim is to model solidification of aluminum followed by macrosegregation and inverse segregation in aluminum-copper alloys on uneven surfaces by finite element methods. These surfaces are modeled as sinusoids characterized by amplitudes, ?s and wavelengths, As, By varying As and ?s, changes in heat transfer, fluid flow, phase-change and macrosegregation are studied."

Jan 1, 2004

By Shichao Zhao, Ke Xie, Qijie Zhai, Wenbin Xia, Yuanyi Guo, Changjiang Song

"This paper investigated the structure evolution and phase formation ofFe-(11,13,15wt.%)Mn alloy under near-rapid solidification conditions. It is found that the area ratio of equiaxed zone in the Fe-13Mn alloy is the largest. And the primary dendrite arm spacing of Fe-(11,13,15wt.%)Mn alloy increased clearly with increasing distance from the surface. The volume percentage of HCP phase increased with increasing manganese content in the range from 11 pct to 15pct.IntroductionThe developing trend of automobile is the energy conservation, enviromnent protection, light weight, and high security. So the material would be required to the higher strength, higher plasticity and more likely to processing of automotive steel. Fe-Mn based alloys is considered as a potential material to the third generation automobile steel for its high damping performance [1], good mechanical properties [2-3], and high young's modulus [4]. And it is important that metastable HCP phases of Fe-Mn based alloys, which attracts technological interest for theoretical and experimental research [5-6].Metastable materials have been extensively used in the area of iron steels. Among various fabrication methods for high performance materials, rapid solidification is one of most popular ways to produce advanced materials by obtaining metastable phases. The solidification of metals in metastable phases provides access to an extended range of materials properties with novel properties [7]. Thus, in this work, Fe-Mn alloy metastable materials prepared by near rapid solidification is studied."

Jan 1, 2013