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By B. J. Beaudry

The preparation of alloys containing one to two percent of the volatile lanthanide metals Sm, Eu, Tm and Yb in the high melting point (HMP) rare earth metals Sc, Y and Lu was accomplished by a vapor deposition, diffusion method without crucible contamination. The method avoids the melting of the HMP metals which would introduce impurities from the crucible, generally Ta or W. Plates of the HMP metals were hung from the lid in the upper part of the Ta crucible. The volatile metals were placed on the bottom and the lid welded in place under an atmosphere of helium. By proper selection of thee alloying temperature, the effusion of the metal vapors, through the helium atmosphere was slow enough to permit diffusion to occur and prevent refluxing of the newly formed alloy. Very volatile metals such as Mg required a Knudsen cell with a suitably sized hole to prevent too rapid transfer of the low melting metal. Electron microprobe analysis of a cross-section of the HMP metals showed a homogeneous distribution of the volatile metals. The time and temperature required to obtain a homogeneous rare earth alloy without contamination are given. The use of a Knudsen cell to form magnesium-rare earth alloys is reviewed.

Jan 1, 1992

By Soumendra Basu, Uday Pal, Yang Yu, Srikanth Gopalan, Karl Ludwig, Deniz Cetin, Jacob Davis

"A limiting factor for Solid Oxide Fuel Cell (SOFC) performance is the oxygen reduction reaction (ORR) at the cathode surface. Changes in the surface composition and structure on annealing at 800°C has been studied, since these can influence the ORR. Idealized single crystals of cathode materials La0.8Sr0.2MnO3 (LSM) and La1-xSrxCoyFe1-yO3 (LSCF) were grown as heteroepitaxial thin films on lattice matched single crystal substrates. Changes upon heating the films to operating temperature and pressures were characterized using various synchrotron x-ray techniques. Total Reflection X-ray Fluorescence (TXRF) measurements, which probe compositional changes, were made at high temperature in real time. The LSM surfaces were found to develop manganese enrichment when heated. Highly strontium doped LSCF were found to develop strontium-rich surfaces. HArd X-ray PhotoElectron Spectroscopy (HAXPES) was used to investigate the electronic structure of the materials. Highly strontium doped LSCF precipitates a surface strontium phase that contains both oxide and carbonate contributions.IntroductionSolid oxide fuel cells (SOFCs) are chemical to electrical energy conversion devices that could potentially reshape how energy demands are fulfilled. SOFCs have a potential efficiency over 70%, fuel flexibility, low emissions, and low degradation over long time scales. Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the reaction kinetics of the oxygen reduction reaction at the surface of the cathode is vital to designing a system that will perform well at lower temperatures. A commercialization goal is to reduce operating temperatures without sacrificing performance.In order to exploit the advantages of SOFCs, an understanding is needed of the surface chemical states of cations on the surface of the cathode and how this relates to the oxygen reduction reaction (ORR):"

Jan 1, 2014

By A. V. Tarasov

Emission of sulfur-containing gases causes most adverse impact on the natural environment in the process of nonferrous metals production. Under the conditions of Arctic regions, in particular in the region of the Norilsk Mining and Metallurgical Complex (Russia), this problem requires a special approach taking into account potential economic and socioeconomic consequences. By reducing the iron sulfide content of flotation concentrates by using new flotation reagents inhibiting pyrrhotite flotation and by applying advanced process flowsheets for flotation it is possible to increase the nonferrous metals content of flotation concentrates by 5% or more along with a corresponding reduction in SO2 formation during their subsequent pyrometallurgical processing. The ways used to resolve the environmental problems in the Norilsk region in the process of nickel and copper production, are based on the improvement of methods for elemental sulfur recovery from metallurgical off-gas by non-conventional techniques, the sulfur recovery from metallurgical gases by production of liquid sulfur dioxide and the technology for pyrometallurgical treatment of sulfide concentrates without SO2 formation. Another opportunity is the development and commercial introduction of hydrometallurgical technologies for treating copper-nickel sulfide ores.

Jan 1, 2006

By Angus Hellawell

The application of the common tangent principle to free energy - composition surfaces is considered. It is shown that the construction requires that single phase surfaces on either side of a two phase volume must always exhibit the same sign of curvature - contrary to that shown in many published phase diagrams. In general, these curvatures will be such that the surfaces are mutually concave towards the more stable phase. A number of examples are discussed.

Jan 1, 1991

By Yongxiang Yang

High temperature processing of raw materials in metals production and recycling often involves complex multi-phase fluid flow and heterogeneous chemical reactions at various scales. Good understanding of the process physics and chemistry is crucial for process operation and process development. The traditional scale-up process through laboratory scale ? pilot scale ? commercial scale route has been more and more complemented and partially replaced by full-scale process simulation. Computational fluid dynamics (CFD) has become a very useful simulation tool in process research and development. At the same time industrial applications challenge the CFD development with its complex transport phenomena, often in large-scale reactors with small-scale physics and chemistry. The current paper discusses the applications of CFD to a number of high temperature metallurgical and materials processing applications. The research was carried out by using commercial CFD codes as the framework, and the emphasis was given to the special efforts for the development and implementations of sub-models with process-dependent physical and chemical characteristics. To illustrate the application of CFD simulation to high temperature metallurgical processes and coupling of sub-models to the general-purpose CFD codes, five examples are given: (1) melting of aluminium scrap in a rotary furnace for recycling, (2) molten hot metal flow in a heterogeneous coke-bed of a blast furnace hearth, (3) gas flow heat and mass transfer in a submerge electric arc furnace for phosphorus production, (4) high temperature incineration of hazardous waste in a rotary kiln, and (5) transient heating of metals in heat treatment furnaces.

Jan 1, 2006

By Pragna N. H. Bhakta

The minerals industry is under political and economic pressure to reduce its processing wastes and minimize their impact on the environment: Recycling is one of the means by which the minerals Industry can reduce the quantities of effluents and residues that are discharged to the environment. The wise use of available resources is not only an environmental necessity but also an economic benefit as natural mineral resources are depleted and/or become more complex. The purpose of this paper is to review the technical and regulatory issues that will help shape the future of minerals recycling over the next ten years. Research and development to address technical issues will be discussed with emphasis on the Bureau of Mines recycling research program.

Jan 1, 1992

By Saskia Duyvesteyn

Small ion-exchange resin particles provide faster mass transport than conventional-sized beads. Unfortunately, high pressures are needed to pump solutions through columns containing small resin particles. It is preferable to disperse fine resins in the solution being treated. Screens have been used to separate the resin from the solution, but screens do not retain fines created by attrition of the resin particles. We have developed a separation process based on flotation, which relies on the surface characteristics of the resin, instead of size. The resin is conditioned with a surfactant before dispersing it in the solution to be treated; this increases the hydrophobicity of the resin sufficiently for froth flotation, without introducing surfactant directly into the solution. The surfactant adsorbed on the resin surface does not appear to impair the kinetics of metal ion removal. A flowsheet for an effluent treatment process is proposed; other applications are clearly possible.

Jan 1, 1998

By Guozhu Ye

"One of the most essential problems associated with the treatment of EAF dust is its high content of halogens. For most thermal processes for zinc recovery, such as the plasma processes with a zinc condenser, the halides in the gas stream will form a dross phase that results in a low zinc yield. For those with zinc oxide as main product, such as Waelz oxides, the high halogen content in the product implies a great degradation of the product quality and the product can only be sold at a low price. Further processing of zinc oxide with high halogen content either by pyrometallurgical or hydrometallurgical processes will also result in process problems.This paper will review the pre- and post-treatment alternatives for halogen removal based on the comprehensive characterization work that has been carried out at MEFOS and the preliminary experimental results.The experimental results show that chlorine and fluorine content could be reduced to 450 ppm and 50 ppm respectively by selective sulfation, and to about 200 ppm by soda leaching. Selective sulfation of zinc oxide in the EAF dust will also be discussed."

Jan 1, 2000

By A. V. Tarasov, V. M. Paretsky

"The design is based on the thermal processing of the wastes in· the intensively bubbled melt in the Vanyukov furnace at the relatively high temperatures (1350- 1450 °C), In this case: -the secondary wastes are not formed; - the especially toxic substances at the outlet from the furnace are absent. The technology was tested on a large scale (on semicommersial bases). Technical and economical basis show profitability of recovery complex for processing of hard garbage waste (HGW) using this technology: the period of capital, investments refunding for the, recovery, complex construction with process annual capacity of 240 thousands tons of wastes is 1,5-2,5 years,"

Jan 1, 2000

By A. D. Zunkel

Increasing amounts of electric arc furnace dust (EAFD) are being generated worldwide as more steel is produced from electric furnace melting of galvanized steel scrap. In most countries, the management of this material is a costly technical, economic, and legal problem for minimill steelmakers. Many technologies and processes are being developed and implemented worldwide to manage this material to recover contained zinc, lead, and iron values and render it nonhazardous. These processes are pyrometallurgical, hydrometallurgical, or hybrid in nature. Some produce zinc oxide, some zinc metal, some lead metal, and some lead cement. Some are successful, some have failed, many are dormant. or abandoned, and others continue to be developed and emerge. This paper updates the current status of 20-30 processes in various stages of commercial application and development used worldwide to manage EAFD and recover its nonferrous, particularly zinc and lead, and ferrous values.

Jan 1, 2000

By Robert M. Leary

The Kennecott Utah Copper smelter operates two Outokumpu flash furnaces: a smelting furnace for production of high-grade matte and a converting furnace for production of blister copper. Flash furnaces typically possess several characteristic features that must be considered in process control development such as long lag times associated with settler volume, non-linear input and output responses, large process gains, and unmeasured disturbances. Additionally, the Kennecott smelter possesses certain unique characteristics which must be considered such as single mine concentrate source, limited concentrate blending capacity, and feed preparation facilities that inevitably cause significant lags between furnace control parameters and manipulated set points. In order to improve furnace control and on-line time, a process control system was developed to address these issues. The feed forward control module provides predictive control and operates in response to furnace feed input changes. The feed back control module provides responsive control and is based on furnace output deviations. To provide regular feed back information to the control room supervisors, new sampling methods were developed which provide the operators with molten metal and bulk material samples at regular intervals to provide information for control. The control system was implemented on the Flash Converting Furnace in May 1999 and on the Flash Smelting Furnace in August 1999.

Jan 1, 2000

By L. Cifuentes

Electrodialysis (ED), i.e. a technique based on the effects of electrically charged membranes on ions in solution in an electric field, has been applied to Cu-Fe-As-Sb- H2SO4 electrolytes similar to those used in copper electrorefining and electrowinning operations. The effects of current density, time and species concentration have been studied in a batch ED cell. The technique has shown to be effective in concentrating and separating a range of ions and points to possible new methods of treating copper electrometallurgy effluents.

Jan 1, 1999

By P. Hajiani

Rare earth elements (REEs) are critical materials in many leading-edge technology products. However, REE separation outside China has remained a challenge in addressing environmental concerns of current production. The author has worked on a technique employing the emphasised variability in the electrophoretic mobility (μi) of REE for the purpose of REE separation. In continuation of the results presented in IMPC 2016 [1], this contribution summarizes the progress achieved in 2016 and 2017. The major goal was to increase the REEs concentration by a factor of 1000 and to attenuate the consequent drawbacks, specifically joule heating effect. Amphiprotic hydroxylic solvent was selected to replace water, which has a major impact on the complexation mechanism and buffer requirement. Non-aqueous media result in a significant drop in the specific molar conductivity of the electrolyte, whilst μi reduces several times only. Moreover, a quasi-steady state electrophoretic separation in conjunction with temperature gradient focusing is adapted to improve scalability.

By R. Padilla

Enargite (Cu3AsS4) occurs normally associated with copper sulfides, mainly chalcopyrite. When the enargite content in chalcopyrite concentrates is high, direct smelting of the concentrate presents problems related to environmental pollution and contamination of the final metallic copper. Leaching processes are viable alternatives to treat copper concentrates with high content of enargite. Consequently, in this paper, the pressure leaching of enargite in sulfuric acid-oxygen system is discussed. The leaching rate was studied in the range 160 to 220 °C and partial pressures of oxygen of 74 to 200 psi. The enargite dissolution increased substantially with temperature increase. Complete dissolution of enargite was obtained at 220°C, and 100 psi of oxygen pressure in 90 min. The shrinking core model controlled by surface reaction was used to analyze the kinetics of enargite dissolution. Activation energy of 70 kJ/mol was obtained for the temperature range 160 to 220 oC.

Jan 1, 2008

By Eiichi Kuzuno, Atsushi Shibayama, Toyohisa Fujita, Kazuo Koike, Toshio Miyazaki, Hitoshi Masuda

"A solid sulfur is more useful to recover and store than a sulfuric acid as a by-product in the zinc hydrometallurgy. In this experiment a zin concentrate (sphalerite) was leached with ferric sulfate at about 373 K for 3 to 6 hours. Zinc was leached more than 95%. After a solid-liquid separation, the leached residue contained solid sulfur was obtained. The particles in the residue were dispersed by lignin and the solid sulfur of approximately 85% was recovered as float product by a flotation with frother in the pH 4. The dried float product was heated at 413K for 2 hours. The pure solid sulfur was recovered. On the other hand in the leached liquid a zinc oxide was ·added and ferrous .iron was oxidized to ferric iron by blowing oxygen. This ferric iron was returned to the zinc leached process after solid-liquid separation.IntroductionZinc concentrate is usually roasted as pretreatment in zinc hydrometallurgy and the produced S02 is changed to sulfuric acid. However, recently in Japan the utilization of sulfuric acid has been limited and it is more costly to store. Instead of producing sulfutic acid the solid sulfur recovery has been examined by direct leaching of zinc_ concentrate in this experiment.In the direct leaching, several kinds of effects have been studied for leaching of sphalerite in ferric sulfate solution. The addition of lignine siilfonate1 • 2) and fine· grinding3) increases the · speed arid leaching fraction of sphalerite. The leaching ratio depends on impurities in sphalerite ores4 • 5). Here, the zinc concentrate is leached ferric sulfate solution under atmospheric pressure at 373K. The solid sulfur in leached residue is separated as float products from other solids by sink-float separation and flotation. The sulfur in float products is purified by evaporation at 413K and recovered."

Jan 1, 2000

By David J. Howard, Christine Broadbridge, David C. Paine

"High pressure vapor/solid reactions offer an opportunity for novel synthesis and processing of thin film materials and structures for electronic, optical, and magnetic applications. In this paper we review the use of two high pressure techniques that operate from 25 to 1000 atm (2.5 to 100 MPa) to fabricate thin film oxide structures from Si1-xGex deposited on Si wafers. High pressure synthesis enables temperature-independent control of reaction rates in the oxidation of this multicomponent semiconductor system and hence offers the opportunity to form thennodynamically metastable Si1-xGex<h from the alloy. The thermodynamics of the Si-Ge-0 system are reviewed and a method is described that utilizes selective chemical reduction (via H2 gas) of Si1-xGcx<h to form Ge precipitates in an SiO2 matrix. IntroductionAlloys of Si1-xGex grown epitaxially on Si substrates by chemical vapor deposition (CYD) and molecular beam epitaxy (MBE) have been used to create high performance microelectronic devices1. These devices show improved performance over conventional Si technology because they exploit the Si/Si 1-xGex band-gap discontinuity and take advantage of higher hole mobilities in the Ge containing alloys. While a range of devices based on heteroepitaxial systems have been demonstrated, the Si1_xGex alloys are of particular interest because they are most closely compatable with standard Si device processing. One disadvantage of Si-based materials systems is that they are not typically useful emitters of light. This is important since the use of light (rather than electrons) for transmitting and processing signals into, out of, and within Si-based microelectronics would represent a major technological advance in microelectronics-based communication and computer technologies. Nevertheless, through the use of innovative processing techniques it may be possible to use the Si1_xGex/Si heteroepitaxial system in integrated microelectronic/light-wave technologies."

Jan 1, 1994

By Edgar Blanco

A thermodynamic and experimental investigation to develop a new process for converting molybdenite concentrate to molybdenum dioxide by a water-vapor oxidation process was carried out. In addition, the behavior of rhenium and selenium in molybdenum concentrate during the process was investigated. The kinetics of the reaction were determined by measuring the weight change of a sample with time in water vapor at temperatures between 700-1000°C. The results were analyzed by a Shrinking Unreacted Core model under chemical reaction control, which showed an activation energy value of 102 kJ/mol. To determine the behavior of rhenium and selenium, their concentrations in the molybdenum sulfide and the product molybdenum dioxide were measured by the use of ICP. While most rhenium remained with the molybdenum dioxide after the water vapor oxidation, almost all selenium volatilized. These results agree with thermodynamic analysis.

Jan 1, 2006

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200,000t-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced. The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 2001, As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Yuri Gelfgat

"This paper presents some results of the investigation of the steady magnetic field influence on hydrodynamics and heat/mass transfer in processes of semiconductor single crystal growth (Si, Ge, InSn). The investigation employed mathematical and physical simulation techniques of relevant processes and full-scale experiments on growth facilities. A number of additional MHD phenomena have been found generated in the melt due to the rearrangement of flow pattern, the formation of specific convective cells, and the origin of MHD boundary and shift layer.IntroductionMagnetohydrodynamic (MHD) means of creating forces by contact-free methods in liquid conducting media have been widely used in the production of volume semiconducting single crystals. The goal of this method is to control convective transfer processes in the melt volume and on the crystallization front [1-3]. This is due to the sufficiently high conductivity of semiconductor melts (s = 104 /106 O1m-1 ) and an obvious relationship between the hydrodynamics in the melt and at interfaces and the conditions of formation of single crystals and their quality [ 1].All types of MHD effects rest upon the generation of volume electromagnetic forces in the melt by various means as well as on the possibility to direct them arbitrary in space and to adjust easily their absolute values. Fig. l presents different means how to implement MHD phenomena during single crystal growth. It should be emphasized that in all the modifications given in Fig. l additional energy introduced into the melt cannot influence directly the crystallization process since it is incomparable to the energy of molecular forces. Both the influence and efficiency of MHD means are determined solely by the change of motion, heat and mass transfer characteristics."

Jan 1, 1998

By Dorothée Proffit

Characterization of solids containing cyanides is carried out according to recommendations and standard guidelines. Most of these procedures are based on the analysis of leachates collected either on site or after leaching in the laboratory of samples. Unfortunately, these sole results are often insufficient to identify the source of the pollution. To provide &apos;a more complete characterization of polluted solids, optical and electron microscopy, XRD, Mossbauer spectroscopy, and transmission infrared spectroscopy were combined to analyze leachates and raw or ground samples. This combination of techniques allows the determination of the kind of cyanoferrate complexes are present in the solid state, different from insoluble Prussian Blue, since they do not have the same extraction&apos; behavior. The use of all these techniques to characterize solid samples combined ,to the usual analysis of solutions gives a better understanding of &apos; the cyanide behavior.

Jan 1, 1998