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By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By Florian Kongoli

The behavior of cobalt as a by-product in the NilCu smelting and converting processes effects directly the quality of the final products as well as the revenues gained from the overall process. An effective way to evaluate and predict this important behavior is thermodynamic modeling which reduces the time and the cost of experimental investigation. In this work a thermodynamic model of cobalt-containing matte phase in NilCu smelting and converting processes is presented. The model predicts a priori the thermodynamic properties and phase relations of the ternary and multicomponent matte based solely upon the optimized parameters of the binary systems. This model can be used with other models such as those of slag, metal, gas etc. to predict various aspects of cobalt behavior such as matte- slag, metal-slag distribution, etc.

Jan 1, 1999

By Andrea Bernardes

Printed circuit boards (PCBs) of varying compositions have been converted by incineration and following melting into an environmental agreeable slag and a copper-nickel-tin alloy, containing the precious metals. The environmental compatibility of the slag was determined according to the German standard DIN 38414 - Part 4; pollutants' concentration in the lixiviates is smaller than the thresholds of drinking water (CE-Standards). Each experiment the charge were 500g scrap from PCBs and ca. 100g slag forming material. The products were a kind of mullite slag, poor on iron, which was recirculated, and an alloy containing up to 0.3% Gold. With a burner to the retort coal gas, the waste gas was burned without soot, and the produced mixed zinc-lead oxide containing silver was collected in the flue dust.

Jan 1, 1997

By Toshiki Kabutomori

In fuel cell powered automobiles, hydrogen is required to be stored in materials that have a hydrogen storage density of over 4 mass%; further, these materials should be capable of supplying hydrogen by using the waste heat from a fuel cell, which is at a temperature of 373 K, in order to match the mileage of gasoline-powered vehicles. A Ti-Cr-V alloy, which exhibits a BCC structure and forms a solid solution, is a promising candidate for onboard hydrogen storage materials. Although it has a large hydrogen storage capacity of over 3.9 mass%, the rechargeable hydrogen capacity is limited to approximately 2.6 mass%. In this study, the effects of fine pulverization of the alloy on PCT (hydrogen pressure-composition-isotherm) characteristics were investigated in order to improve the rechargeable hydrogen storage capacity of the alloy. From the PCT measurements of the finely pulverized samples of the alloy, a plateau in the absorption curve was observed to begin at a hydrogen concentration of 0.5 mass%; further, a rechargeable hydrogen storage capacity of 3.3 mass% was obtained. This was greater than that obtained from the sample that was not finely pulverized, i.e., 2.5 mass%. However, the plateau width in the desorption curve was 2.5 mass%, which was the same as that observed for the sample that was not finely pulverized. The increase in the rechargeable hydrogen capacity during absorption is attributed to the precipitation of the -hydride phase (MH~2) directly from the metal phase (phase). The precipitation of the phase (MH~0.5), which should be formed in low hydrogen concentrations, is suppressed as a result of a possible reduction in the internal defects such as dislocations, vacancies, and grain boundaries by fine pulverization and annealing of the alloy.

Jan 1, 2006

By L. J. Davies

Refractories usage in furnaces for the extraction of nickel from both sulphides and lateritic ores is reviewed. Recent changes in raw materials and basic brick qualities developed to meet the increasing demands of existing and new processes are outlined. Examples of used brick examinations to establish mechanisms of wear are given. The importance of physical and chemical properties are discussed. The use of simulative laboratory testing to aid in refractories development and selection is described.

Jan 1, 1988

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By Emmanuel N. Zevgolis

After the Krupp-Renn process was shown to be unsuitable for treatment of the Greek nickeliferous laterites, the LM process was developed. It involved roasting reduction up to metallic iron in a Rotary Kiln (R/K) and smelting in an Electric Furnace (E/F). Ferronickel (with 15% Ni) produced in the E/F, was upgraded to 90-95% Ni in an 02 converter. Raw Ni was then electrolyzed to pure Ni. The LM process was not applied for very long however, due to various problems. So, the Larco process was developed, i.e., pre-reduction in R/Ks, smelting of the calcine in E/Fs for ferronickel production (15% Ni) and enrichment to 20% Ni, in an O2 converter. Until now, many technological improvements have been invented and applied or adjusted to the process, which have made it a fully reliable and competitive one. sohe of the improvements were the invention and application of a new granulation process for liquid ferronickel, the modification of the existing R/Ks, E/Fs and converters and the design of new ones, and others that are described in the paper. Keywords: Ferronickel, metallurgy, laterites, LM process, Larco process

Jan 1, 2004

By Robert L. Stephens

"It can be argued that one of the most important property of any material is cost, since this property detennines the applications for which a material can be considered. Despite growing demand and production for commodity metals such as copper, nickel, zinc, lead, and tin, the cost of these metals has been steadily decreasing in real terms. The only way that metal miners and producers can remain financially viable in the long term is by continuing to lower their cost curve through the implementation of new metals production technologies. This paper reviews technological developments in the production of copper, nickel, zinc, lead, and tin that have or threaten to redefine the cost curves for these metals.DisclaimerThe opinions expressed in this paper the author's, and are not necessarily those held by the author's employer, Cominco Ltd.IntroductionThis meeting will discuss many novel technologies and processes for producing metals and materials with specific properties that will enhance the applications ranges for the material or will allow entirely new applications to be developed. However, in every real-world case, the cost of the new material or process is an important property that determines which applications the material or process can be used in. Other properties that are important depend on the applications.A recent press report (1) discussing the potential replacement of aluminum radiators with copper radiators in pickup trucks and sport utility vehicles provides an interesting example to reinforce the importance of cost in materials selection. In this case, the displacement of aluminum by copper is being considered because of the more favorable heat dissipation characteristics of copper. Heat dissipation has become more important due to the development of hotter-burning V-8 and V-6 engines. For this application, engineers also consider cost, weight, size, durability, and manufacturing process. The report stated that the development by the International Copper Association (ICA) of the ""CuproBraze"" manufacturing process for heat transfer products was an important development. This technology produces 845 radiators that weigh less, are more uniform in quality, and are potentially more compact. They are also expected to cost less in high production quantities than copper units produced in the past, last three to four times longer than soldered copper radiators, and the process also eliminates the use of lead solder from the manufacturing process."

Jan 1, 2000

By P. Halsall

Smelters of medium or low grade tin concentrates must recover a high proportion of tin from iron-bearing slags or concentrates; the volatility of tin sulphide makes possible the production of iron-free tin fume. Laboratory work defined conditions which would promote the sulphidisation of tin slags and concentrates melted with them, to result in tin recovery as fume, and a residue of less than 0.5% Sn content, which could be controlled to vary with the value of tin. Subsequently pilot-plant work on 6-tonne and 15-tonne scale led to a commercial plant of 45 tonne. capacity (1962), for melting and fuming primary and secondary low-grade tin materials by submerged combustion. Some factors contributing to the rate of Working expressed in terms of the 'half-life and the amount of work done, the 'half-life-tonne' are studied, leading to the design and operation (1972) of the 100-tonne water-jacketed unit, presently in use, treating a wide range of slags and low tin-content ores and residues.

Jan 1, 1983

By G. L. Liu

"Deformation Banding ( DB ) in cold rolled mild steel has been experimentally established by microstructure investigation. Deformation banding model includes such deformation mode when it is applied to rolling texture simulation. The cause for the occurrence of deformation banding is the reduction of the total work for plastic deformation through a relaxation of the deformation constraints. In the first DB model, all grains are assumed to band from the first deformation step. Such an unrealistic assumption has been eliminated in the new model by the introduction of a banding criterion based on an energy minimizing approach. The prediction is closer to the measured texture by applying banding criterion and setting critical resolved shear stresses (CRSS) ratio for { 110 } and { 112 } slip modes to 0.85.IntroductionBased on the continuum theory of plastic flow and deformation mechanism of crystallographic dislocation slip, Taylor's FC ( Full Constrain ) theory [1] has been widely used in texture modeling. As the process of cold rolling of sheet materials produces a microstructure consisting of elongated or equiaxed flat grain or cell, the ""lath"" and ""pancake"" relaxed constraints ( RC ) models [2, 3] were introduced as the successful improvements over the classical FC model. It has been also recognized that crystals may split into different orientations during deformation and the term deformation banding is used to describe such deformation processes [4, 5]. Lee et al. [6, 7] pointed out that the success of the RC theory in predicting textures depends on the physical processes of deformation banding. They developed so called Deformation Banding ( DB ) model by considering DB in the longitudinal plane to be accounted for by the RC method and allowing DB in the rolling plane. DB model was applied to simulate the texture development in bee case [8], the predicted bee rolling textures are in reasonable agreement with the measured textures. In the first DB model, however, all grains are assumed to band right upon the first deformation step. A banding criterion was formulated [7] which states that DB will occur if the work used in DB model is less than that in RC model. Such criterion has been incorporated into the original DB model for texture simulation and is referred to as DBC ( Deformation Banding Criterion ) model."

Jan 1, 1998

By J. C. Agarwal

Slags produced by modern smelting furnaces contain copper values which are unacceptably high for discard. The electric arc furnace is employed commercially to clean copper from flash furnace slags but the addition of highly oxidized converter slags to an electric furnace has created operational problems. Highly oxidized Noranda Reactor slags have not been processed successfully in a pyrometallurgical process. These slags, which contain large concentrations of copper (5 to 10 per cent), are treated in slag concentrators (controlled cooling, crushing and milling, and flotation) which produce a copper concentrate that must be resmelted. Though commercially operable, it will be shown that the slag concentrator has important process and cost disadvantages as compared to a pyrometallurgical process. In this paper an economic comparison is made between a pyrometallurgical process and the slag concentrator. For the analysis, five hypothetical smelting plants are considered. Each plant treats 1200 tons of copper concentrate per day and produces 109,000 tons of copper annually. The plant configurations used in this study are:

Jan 1, 1976

By J. Rastas

The recovery of lead, silver and gold from existing and potential zinc process residues using a sulfidization-flotation method was investigated on a laboratory scale. The following residues were tested: neutral leach residue, high acid leach residue, and hematite residues. The sulfidization of lead and silver is carried out at low pH by the addition of a stoichiometric amount of sulfide at a controlled rate. To increase the particle size of the sulfides, seeding with synthetic lead and silver sulfides -is employed. The flotation is carried out at pH 2-4 using low pH-collectors such as dithiophosphates and dithiophosphinates. Special attention must be paid to the role of oxygen in the conditioning stage. The effect of different parameters on both the sulfidization and the flotation has been evaluated. Recoveries of 85-90, 90-95 and about 80 % were obtained for lead, silver and gold, respectively. Typically, concentrates containing 50-60 % lead, 3-5 kg/t silver and 10-15 git gold were produced.

Jan 1, 1990

By Hiroyuki T. Takeshita

Ca-Ni based alloys were investigated on structures, hydrogenation properties and the effect of additive elements on hydrogenation properties. CaNi, samples were decomposed to form a new hydride with a CsCl-type structure on the constituent metal atoms at high temperatures such as 673K in a hydrogen atmosphere. The candidate of the third element which was added to stabilize the original compound was investigated by using the Miedema's semi- empirical model and, as a result, Pd was chosen. The hydrogenation of CaPd was conducted with a Sieverts' type apparatus and the synthesis of Ca-Ni-Pd ternary alloys was performed by high frequency heating.

Jan 1, 2002

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995

By C. Coetzee

Additives are commonly used in copper electrowinning to improve cathode morphology. Polysaccharides such as guar are generally favoured as additives due to their compatibility with solvent extraction. Polyacrylamides are, however, being considered as possible alternatives. Understanding the influence of the structural chemistry of additives on electrowinning performance is critical to utilise them efficiently. This paper investigated polyacrylamide additives which are structurally different; their effects on copper electrodeposition were characterized and compared to that of guar. Electrochemical impedance spectroscopy (EIS) were used to characterize the effects of molecular weight and ionic charge of the polyacrylamides on electrodeposition. The findings were compared against results obtained with an industrially used guar product. Equivalent circuit modelling of EIS data indicated that an increase in polyacrylamide concentration and a decrease in additive molecular weight increased the overall system resistance.

By M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998

By Wang Shulan

The synthesis process of BaTiO3 from TiO2 and BaCO3 in the molten NaOH-KOH at 350oC was studied by the A.C impedance technique. The A.C. impedance of molten NaOH-KOH (xNaOH = 0.36) and the variation of the conductivity of the salt with time during the synthesized process were measured. The synthesized reaction of the BaTiO3 and the decomposition reaction of BaCO3 are fast and were finished in 10min. The interaction between TiO2, BaO and BaTiO3 and the molten salt was confirmed by the variation of the conductivity.

Jan 1, 2005

By Rajesh Kumar Mishra

About 500,000 troy ounces of Platinum Group Metals (PGM) will be available for recycling each year from spent automobile catalytic converters in North America alone. Platinum Group Metals? from spent catalyst can be extracted by Hydrometallurgical, Pyrometallurgical or Gas Phase volatilization processes. This paper is a review and comparative study of various processes investigated for PGM extraction. A number of processes described in this paper have already been commercialized. The technical and environmental aspects of the important processes are discussed.

Jan 1, 1989