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By Thierry De Nys

A direct leaching process of sulphidic zinc-based concentrates in aqueous sulphuric acid solutions has been developed by the V.M. R & D Department. By a very accurate control of the oxidation potential of the leach solution, this process enables a separate recovery of the zinc, copper, silver, lead and sulphur of the concentrate and makes it extremely attractive for treating more complex ores. The iron, solubilized during leaching, is eliminated out of the zinc solution by means of the V.M. goethite process. Alternative flow sheets for a conventional zinc electrolysis plant are presented.

Jan 1, 1990

By Mikhail Mikhaylenko

Natural and technogenic sources of rare earth elements (REE) and other rare and scattered metals are remarkable for their chemical diversity. The pregnant solutions going to processing for the valuable metals have very complex compositions. Both targeted elements and competing impurities are present in the solutions in different chemical forms. Thus processing of such materials demands application of different technological tools addressing numerous specific tasks on the way to the final product. Screening work was undertaken to identify the best resins among developmental and commercial products addressing typical cases in the hydrometallurgy of scandium and REE. The cases outline typical sources of scandium and REE, such as streams of TiO2 production, extracted phosphoric acid, barren uranium solutions and others. Specially designed ion exchange resins can be effective tools.

By Muammer Kaya, Sait Kursunoglu

"The aim of this study was to investigate the effectiveness of ascorbic (C6H8O6) / oxalic (C2H2O4) acid as a reductant for the simultaneous recovery of zinc and manganese from a spent and mixed zinc-carbon and alkaline battery powder in sulphuric acid leaching. The effects of sulfuric acid concentration, ascorbic/oxalic acid dosages, reaction temperature and leaching time on the zinc and manganese dissolutions were investigated according to 2k full factorial experimental design; then, a simple optimization study was carried out for the best reductant. The optimum reductive acid leaching conditions were determined at 3 hours leaching time, 70°C leaching temperature, 0.5M sulfuric acid concentration, 13 g/L ascorbic acid dosage, 1/20 g/mL solid/liquid ratio and 200 rpm stirring speed. Under these conditions, the dissolution efficiencies were 99.9% for Zn and 99.3% for Mn. When our results were compared with the previous results, our findings were better than previous studies.In addition, the manganese dissolution kinetics was undertaken, and the activation energy was found to be 7.04 kJ/mol. Selective precipitations of Zn and Mn from acid solutions were carried out using NaOH and KOH. Using 3M NaOH as precipitating agent at room temperature and at pH 8; 95.4% of Zn and at pH 10; 93.7% of Mn were precipitated from the leaching solution. Under the same conditions, using 3 M KOH at pH 8; 91.6% of Zn and at pH 10, 96.4% of Mn were precipitated. Based on the experimental results obtained, an appropriate flow sheet was proposed to recover zinc and manganese."

Jan 1, 2012

By H. Kaffash

Ferromanganese is a ferroalloy with high manganese content which finds many uses for example as deoxidizer in steelmaking industry. However, there is very little data on the dissolution rate of carbonaceous materials in Mn containing metals. In this paper, the kinetic analysis of carburization reactions is investigated for Mn–Fe alloys. Dissolution rate of graphite in pure iron and four different alloys with 10 wt%, 40 wt%, 60 wt% and 85 wt% manganese at 1823 K was studied. Results showed that the dissolution rate of carbon from graphite increased with increasing time for all alloys. The dissolution rate constant increased with the increasing manganese content from 6.5 × 10−3 cm/s for 0%Mn to 23.6 × 10−3 cm/s for 85%Mn.

By Hiroshi Nakazawa

An acid mine drainage in abandoned Horobetsu mine in Hokkaido, Japan, contains arsenic and iron ions; total arsenic ca.10ppm, As(III) ca. 8.5ppm, total iron 379ppm, ferrous iron 266ppm, pH1.8. Arsenic occurs mostly as arsenite (As (III)) or arsenate (As (V)) in natural water. As(III) is more difficult to be remove than As(V), and it is necessary to oxidize As(III) to As(V) for effective removal. 5mL of the mine drainage or its filtrate through the membrane filter (pore size 0.45m) were added to arsenite solutions (pH1.8) with the concentration of 5ppm. After the incubation of 30 days, As(III) was oxidized completely with the addition of the mine drainage while the oxidation did not occur with the addition of filtrate, indicating the microbial oxidation of As(III). In this paper, we have investigated the microbial oxidation of As(III) in acid water below pH2.0.

Jan 1, 2006

By Y. F. Jia

Arsenic constitutes a major contaminant for the hydrometallurgical industry. Its removal and immobilization from process effluents typically involves lime neutralization and co-precipitation with ferric iron (Fe (III)/As(V)>3). Alternatively, precipitation of scorodite (FeAsO4?2H2O (cr)) may be applied to arsenic fixation. The mechanism of arsenic fixation in the former process has been suggested to be surface adsorption. Unequivocal characterization of these products is difficult because of their amorphous nature hence a variety of methods need to be applied including the particularly powerful method, extended x-ray absorption fine structure (EXAFS) spectroscopy. In this study, we have investigated the preparation of arsenate-adsorbed ferrihydrite with the purpose to compare its structure to that of Fe(III)-As(V) co-precipitates and scorodite (both amorphous and crystalline). Furthermore the solubilities of these Fe(III)-As(V) solids are measured as a function of pH. Their structures are elucidated and correlated to their solubilities and thereby the application of these findings to the practice of arsenic removal and disposal is assessed.

Jan 1, 2003

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By D. Gu, R. G. Anthony, C. V. Philip, M. E. Huckman

"In this paper, we review the equations needed to construct an ion exchange column model. These models contain three major components: 1) a differential material balance around the column, 2) a differential material balance around an ion exchange particle, and 3) a constitutive equation for diffusive flux. We then examine the ability of a fairly simple mathematical model to predict ion exchange column experimental data. This model contains the traditional absorption theory equations and is used to predict the behavior of a column filled with a hydrous crystalline silico-titanate and which is removing trace amounts of Cs+ from a high pH, complex electrolyte solution. Finally, we propose replacing Fick's law with the Nemst-Planck equation as the constitutive equation for diffusive flux. We use a NemstPlanck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model. The data from this comparison suggests that the Nemst-Planck type model yields better results.IntroductionMillions of gallons of strongly basic, radioactive waste are currently stored in underground storage tanks at Hanford and Savannah River and several locations within the United States. Due to the limited life expectancy of the tanks, there is a pressing need to remediate these wastes. This need has prompted the recent development of new ion-exchange materials for removing radioactive elements from aqueous solutions. A novel material called TAM-5 has been developed jointly by Texas A&M University and Sandia National Laboratories. TAM- 5, a crystalline silico-titanate, is highly selective for Cs + in the complex electrolytic solutions typical of these wastes. It is stable in very basic solutions and in radioactive environments [1, 2 ,3]. In laboratory testing to determine the selectivity of various materials, TAM-5 was superior to other candidate ion exchangers [4, 5]. The selectivities were determined by measuring a distribution coefficient, Kd, which is defined as the concentration, gig or mmols/g of Cs in the solid phase divided by the concentration, mg/L or mmols/mL, of Cs in the liquid phase. The units of Kd are ml/g or L/kg. Table 1 shows Kd values for TAM-5 compared to 9 other candidate materials in a typical waste solution [6]."

Jan 1, 1996

By Dinesh P. Amalnerkar, Nagegownivari Munirathnam, Tirthalli Prakash, Katia Vutova, Vania Vassileva, Veliko Donchev

"A time-dependent model for electron beam melting and refining (EBMR) of different metals and alloys is developed. The model is 3D axi-symmetrical and an adapted numerical scheme of Pismen-Rekftord type is applied. The developed computer program computes the thermal fields in the metal ingots during EBMR process as well as the dynamics of the thermal streams and the geometry of the molten metal pools. Calculated results for different regimes of EBMR of titanium are obtained and discussed in the paper. Experiments are performed and impurities' concentration data are presented. Simulation results are compared with experimental data and are used for optimization of the EBMR process in the case of Ti.IntroductionElectron beam melting and refining (EBMR) has an important role in the special electrometallurgy[ 1-6] and it is approved for obtaining of pure titanium [7]. EBMR of metals and alloys is being recognized as a competitive and even the single method for obtaining new materials for all areas of human activity.The principal scheme of the EBMR drip process is shown in Fig.1. A thin layer of molten metal is formed on the front part of the feeding rod during the e-beam processing and generated droplets fall into the molten pool in the crucible where the ingot is formed. The refining is mainly realized at the boundary liquid metal - vacuum. There are three zones in EBMR (Fig.1) - on the front part of the feeding rod (zone I in Fig.1 ), on the surface of the generated droplets (zone II in Fig.1) and the surface of the molten pool in the water-cooled copper crucible (zone III in Fig.1)."

Jan 1, 2013

By F. T. Principe

In order for solvent extraction technology to be acceptable as an alternative to existing jarosite precipitation circuits, iron must be cleanly separated and concentrated into a feed stream suitable for downstream iron by-product recovery which meets market specifications and economics. Ten years ago, significant progress was made in a joint McCill University/CANMET project that involved iron extraction with mono(2-ethylhexyl) phosphoric acid and stripping with HCI. Our iron solvent extraction research was reactivated recently by looking into this and other members of the organophosphorus extractant family. Our research focuses on the mechanisms and control of anion (SO42/CI) transport across the various phases (Rafinate/Organic/Strip), iron build-up in the strip liquor, and extractant stability/selectivity. In this paper, these issues along with some other performance parameters are discussed using data derived from an extensive search of the two commercially available and best known members of the organophosphorus family, di-2-ethylhexyl (D2EHPA) and mono-2-ethylhexyl (M2EHPA) phosphoric acid. Further in this discussion, the challenges lying ahead in the development of sx systems that overcome the deficiencies of D2EHPA and M2EHPA are outlined. In particular, the necessity of considering secondary separation technologies that can further concentrate iron values in the chloride strip liquor to levels economically attractive for the production of saleable iron oxide by pyrohydrolysis is addressed.

Jan 1, 1998

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 Chen Ya

Layered LiMn0.5Ni0.3Co0.2O2 was prepared from Mn(NO3)2, Ni(NO3)2, Co(NO3)2 and LiOH by co-precipitation and solid state reaction. XRD, C-V and galvanostatic charge-discharge methods were used to examine the structural and electrochemical characteristics. The LiMn0.5Ni0.3Co0.2O2 delivered a high discharge capacity of 167 mAh/g between 2.5 and 4.3 V with excellent cycling stability.

Jan 1, 2006

By Edgar Peek

"The two dominant metallurgical problems in treating most base metal sulphide concentrates in both the chloride and sulphate system are iron removal and sulphur elimination, respectively [1-3]. In this paper the opportunities, limitations and fundamentals of the chloride metallurgy system are described against this background. Only the treatment of oxide and sulphide ores is considered. Both hydrometallurgical and pyrometallurgical unit process operations are highlighted, since most successful base metal processes are based on a combination of the two. Hence, an overview of the technical and also some economical aspects of chloride metallurgy are presented.This overview summarizes the successful applications of chloride metallurgy, but it will not give exhaustive process and plant descriptions. It predominantly focuses on the essential technical features of the metallurgical unit process operations, while providing numerous references separately."

Jan 1, 2011

By Kuniaki Murase, Tetsuji Hirato, Yasuhiro Awakura

"Electrodeposition of CdTe was studied using aqueous ammonia-alkaline electrolytic baths in which Cd11-and Te1V-ions are dissolving as Cd11(NH3)/+ and Te1vol-ions, respectively. Ca-thodic polarization curves of the baths suggest the presence of strong interaction between the Cd11-and Te1V-ions; electrodeposition of tellurium is inhibited by the presence of Cd(NH3)/+ ions. The interaction makes it possible to electrodeposit CdTe films with stoichiometric composition. Polycrystalline CdTe thin film of about 1 µm thickness was electrodeposited at 343 K from ammonia-alkaline solutions (pH= 10.7) containing TeO32-(<20 mmol dm-3) and Cd(NH3)/+ ( < 60 mmol dm-3) ions. Increasing Cd(NH3)/42+/TeO32- mole ratio or decreasing total concentration of ammonia/ammonium-ion gave flat and smooth crystalline CdTe deposits at constant cathode potential-0.70 to -0.30 V vs SHE at 343 K.IntroductionCadmium telluride (CdTe) is well-known as a compound semiconductor whose band gap, i.e. 1.44 eV, is suitable for solar energy conversion with a photovoltaic cell. Various methods, such as CVD (chemical vapor deposition) and electrodeposition, of preparing CdTe thin films for solar cells have been investigated.Acidic sulfate solutions with a pH of 1-2 are usually employed for CdTe processing by electrodeposition.1-3) The electrodeposition of compound semiconductors is usually achieved (i) at a higher cathode potential than the redox potential of less-noble species, can in this case, and (ii) under the condition of diffusion-limiting current of a more noble species, Te1Y.4) There-fore, a suitable CdII/TeIV concentration ratio in the acidic electrolytic baths, resulting in the deposition of stoichiometric CdTe, is determined by the diffusion-limiting current density of TeIV- reduction, i.e. the concentration of HTeIVO2+ · Since the solubility ofTe1v species HTeIVO2+ in the acidic solutions is quite low, the rate at which CdTe is deposited from the acidic solutions is extremely slow."

Jan 1, 1998

By Laurent Cohen

Since the 1970s, Solvent Extraction (SX) in hydrometallurgical processes has been a key enabling technology in the production of high-purity metals. Examples include copper, rare earth oxides, uranium, cobalt and nickel. Notwithstanding incremental improvements in extractant formulations, few breakthroughs can be recounted in this industry outside of the initial amine-, oxime- or phosphine-based reagent chemistries. However, the advent of lithium-ion batteries and their stringent requirements for critical materials (lithium, cobalt and nickel) offer new challenges and opportunities for SX. Solvay recently introduced a new extractant for lithium, CYANEX® 936, and developed unique modeling software capabilities in cobalt/nickel separation using CYANEX® 272, zinc SX using DEHPA® and rare earth separations using CYANEX® 572. This paper discusses trends in SX and provides insight on processing of critical materials essential to energy sources. It also summarizes the technical and economic benefits based on extractant selection and advances in modeling.

By Gopalakrishna B. Prabhu, David L. Bourell

"Three mol% Yttria-Stabilized Tetragonal Zirconia (YSTZ) was prepared by a sol-gel synthesis technique using zirconium tetrachloride and hydrated yttrium chloride precursors. After drying and annealing at 823K, the particle size was in the range 10 to 20 nm. The zirconia powder was sintered using a uniaxial hot press at an applied stress of 20 to 40 MPa. One hour, isothermal sintering was performed in air after initial heating at 50K/min. Theoretical density was obtained at densification temperatures above 1498K. After sintering, grain coarsening characteristics were studied using constant heating rate anneals followed by quenching, based on a model for grain coarsening in a linear heating rate cycle. The microstructural change was studied using SEM and TEM and the phases were determined using x-ray diffraction.IntroductionThe ability to sinter nanocrystalline materials to full density several hundred degrees below the normal sintering temperatures is one reason for their current interest. [1-5] Yttria Stabilized Tetragonal Zirconia (YSTZ) of grain size of about 300 nm has exhibited superplasticity, with elongations as large as 800%.[6-7] Fine grain size is critical for superplasticity. Retention of the fine grain size during sintering of nanocrystalline powder is important if a material is to exhibit superplasticity or to exhibit physical or mechanical properties associated with the ultra fine structure. This paper investigates the sintering behavior and the grain coarsening characteristics ofnanocrystalline YSTZ.Techniques for synthesizing nanocrystalline materials have been studied in great detail earlier. [8-12] The techniques used to synthesize nanocrystalline zirconia include alkoxide synthesis [9], the chloride method [11], the peroxide method [13] and the acetone-toluene method. [13] In this paper the method used in the synthesis of zirconia is the chloride technique. With this precipitation technique, either zirconium chloride or oxychloride and a corresponding yttrium salt or even pure yttria are used."

Jan 1, 1994

By E. Fockedey

he destruction of free cyanide on a Co3O4 doped carbon felt was studied. The experiments were done with an eiectrochemical filter press cell on dilute alkaline solutions containing 250 mg/l NaCN. No chloride ions were added to the solutions. The cobalt oxide protects the felt against corrosion and has a catalytic effect on the degradation of the cyanide. This kind of electrode allows working with current density as high as 1200 Aim without any visible degradation of the felt. The most interesting results were obtained with a current density of 400 Aim&apos; at which the cyanide concentration can be lowered to 5 mg/l with a current efficiency of more than 70 % and a specific energy consumption of about 10 kWh/ kg CN.

Jan 1, 1998

By George S. Dulikravich

An advanced semi-stochastic algorithm for constrained multi-objective optimization has been adapted and combined with experimental testing and verification to determine optimum concentrations of aJ10ying elements in heat-resistant and corrosion-resistant H-Series austenitic stainless steel alloys. The objective was to simultaneously maximize a number of alloy&apos;s mechanical properties. This research will result in a rigorous tool for the design of high-strength H-Series steels and other types of alloys unattainable by any means existing at the present time. Such a material-by-design tool will also be able to reduce or minimize the need for the addition of expensive elements such as Cr, Ni, Co, Nb, Ti, V, etc. and still obtain the optimum properties of an aJ1oy.

Jan 1, 2003

By Michael B. Tessieri

With the increasing environmental demands and higher fuel efficiency standards on auto manufacturers, the use of aluminum in automotive applications is expected to show significant growth for the balance of this decade. Cast and wrought aluminum usage is reviewed by auto part, and alloy family for the year 2000 automobile. The analysis addresses the effect of this increased volume on the recycling infrastructure and identifies issues and opportunities, which will face the recycling industry.

Jan 1, 1995

By M. M. Kim

Zn-27% Al was pressure infiltrated into a column of 20 micron diameter abrasive grade SiC particles to give billets with particle loading of 50 voli.une %. Some billets were heated to a temperature where they became semi-solid and diluted with liquid Zn-27% Al alloy to give billets with particle loadings of 12 and 16 volume %. Some of these billets were then extruded into wire with an area reduction of approximately 98%. Tensile properties of the as-cast billets were always inferior to those of the matrix alloys; however, the extruded composite samples showed at 37% improvement in ultimate tensile strength compared to their extruded conventional counterparts. The fracture surfaces of these samples are described.

Jan 1, 1990