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By J. C. Huyhua

The effect or various oxidants on gold and silver dissolution in thiourea solutions (0.05 M in H2SO4) was studied using the rotating disc technique, a.t 2s c and 600 rpm. These studies were carried out at constant (4:1) initial molar ratio or thiourea to oxidant concentrations, to produce 50 % thiourea. oxidation. The initial dissolution rate of gold was approximately four times higher in the presence. of ferric sulfate (5.37 x 10-3mg cm-2 s-1) than in the presence of hydrogen peroxide (H2O2), potassium persultate (K2S2O3), or monopersulfa.te (KHS06). The dissolution rates for silver were considerably lower than gold for the same oxidants. Oxidation of thiourea in the presence of peroxygen and persulta.te compounds is a. fast reaction and it is completed in less than ten minutes. On the other hand, the oxidation or thiourea with? ferric.sulfate is slow, yielding a second-order reaction rate constant k = 6.09 I mol-1 h-1. Sulfur formation in the ferric thiourea system begins when ferric ion reduction approaches to completion. With hydrogen peroxide, sulfur is observed at lower thiourea concentration than ferric. Suifate. The presence of a large excess or free thiourea i.e., s to 20 % thiourea oxidation) retards sulfur formation and maintains favorable dissolution rates. Finally, carbon-in-leach experiments indicate that thiourea solutions a.re stable for several days, with ferric sulfate or hydrogen peroxide. The dissolution rates of gold and silver doubles in the presence or activated carbon when hydrogen peroxide is used as oxidant.

Jan 1, 1989

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By Frederico Muylaert Margem, Jarbas Bravo Neto, Sergio Neves Monteiro

"The mechanical behavior and the fracture characteristics of composites with DGEBA/TETA epoxy matrix reinforced with up to 40% in volume of continuous and thinner ramie fibers were evaluated by tensile tests. Specimens with selected thin fibers aligned along the tensile axis were room temperature tested to rupture. The fracture surface was analyzed by scanning electron microscopy. The results showed significant increase in both the ultimate tensile strength and the elastic modulus. The fracture analysis indicated the possible mechanism for the fiber/matrix interaction, which could be responsible for the composite performance.IntroductionThe fiber reinforced polymer composite emerged in the middle of last century as a versatile engineering material for applications requiring mechanical resistance in association with lightness. Its most commonly used example is ""fiberglass'', i.e., a thermoset polymer matrix composite reinforced with glass fiber. Indeed, ""fiberglass"" has a specific strength of the order of 500 MPa.cm3/g, which is the double of the strongest steels like the maraging. This motivated, at earlier times, ""fiberglass"" to replace many conventional materials including wood and natural fiber composites. Today, ""fiberglass"" has a wide range of uses from aerospace systems and appliances to sport and leisure components. However, its fabrication as well as those of any synthetic fiber such as carbon and aramid composites, requires a relatively large amount of energy. Presently, a growing concern exists regarding the consequences to the environmental by gases like C02 associated with both the energy consumption and the processing of synthetic fibers and their composites. These gases are well known responsible for global warming [1]."

Jan 1, 2011

By J. Phillip Mackey

The Peter Hayes Symposium on Pyrometallurgy, held as part of Extraction 2018, is an acknowledgement of his contributions to the basic science and principles underpinning modern pyrometallurgical processing. After completing his PhD at Strathclyde University, Scotland, in 1974, Peter took up a teaching position at The University of Queensland, Brisbane, Queensland, Australia in 1976. Peter Hayes’ research at the University since then has been focussed on: • The mechanisms and kinetics of heterogeneous solid/solid, gas/solid and liquid/ solid reactions, and • Experimental measurement of phase equilibria in complex high temperature metallurgical systems. This paper provides a brief biography of Dr. Peter Hayes and gives a full listing of Peter Hayes’ publications.

By Sue Xue, Carl C. Nesbitt

A project was completed which investigated the efficacy of recycling lead or lead monoxide from various fire assay wastes including crucibles, cupels and slag. The scope of the project was to determine optimal hydrometallurgical parameters so that direct separation and recovery of lead salts was economically feasible. A process was developed from the study which could use either acetic acid or nitric acid as a leachant, followed by several precipitation processes which could directly recover litharge (PbO) or other lead salts, such as lead carbonate or lead sulfate. The economics of the process is discussed. Analytical equipment such as the atomic absorption spectrophotometer and x-ray diffractometer supplied much of the information required for the study. However some novel analytical approaches using these instruments had to be developed to help in the determination of leaching kinetics and process quality control which are discussed.

Jan 1, 1999

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By Manoj Kumar, Vinay Kumar, Nikhil Dhawan, Manish Wadhwa

"Electronic waste (e-waste) is a collective name given to discarded electronic devices such as Television, Cellular Phones and Personal Computers. Among the heterogeneous metals present in the e-waste are the base metals: copper, aluminium, nickel, tin, zinc, iron and precious metals: gold, silver, palladium, platinum apart from several hazardous and halogens metals. Hence there is a need to recover these metals from electronic scrap by recycling and then re-use, which can meet large amount of metals demand. Hydrometallurgical processing was employed for the recovery of metals from television printed circuit board (TV PCB). Different lixiviants such as hydrochloric acid, Sulphuric acid, and nitric acid were used to understand the dissolution behavior of copper, iron and lead present in the TV PCB. Effect of increasing concentration of nitric acid was also studied. Selective recovery of tin over 95% in the form of tin oxide was precipitated. The precipitated tin oxide was identified by X-ray diffraction technique. Tin oxide of purity more than 99.9% was obtained.IntroductionThe electrical and electronic industries comprising computers, television, mobiles, etc, which are manufactured utilizing printed circuit, boards, capacitors, resistance, soldering material etc. During production, at the end-of service life and degradation due to the advanced version with latest features generate valuable metallic and non-metallic constituents. European Union Council on waste electrical and electronic equipment (WEEE) has classified these into different categories as listed in Table 1 [Streicher-Porte et al., 2005]. Among these the information technology, telecommunications and consumer equipment constitute electronic waste (e-waste) [EC, 2002]. Almost all e-waste consists of an integrated part of printed circuit boards which is a valuable source of several metals such as copper, tin, lead, aluminium, iron, silver, gold, platinum etc. [Relay et al., 1990]."

Jan 1, 2008

By Zhongning Shi, Ramana G. Reddy

"By cyclic voltammetry and potentiostat electrodeposition using Potentiostat/Galvanstat, electrochemical behavior on Ag electrode in electrolyte 0.2M NaOH+0.01MPb(NO3)2-0.01M TeO2 -0.01M TlNO3 solution were also carried out at 298K. The processes of electrodeposition of Tl2Te3 and PbTl4Te3, a thermoelectric material, are reported along with analysis of the composition of the obtained deposits. The results showed that two different underlying processes are occurring depending on deposition potential. One process involves the reduction of TeO3 2- and Tl+ to Tl2Te3 in a potential interval of -0.70V < E < - 0.89V (vs. Hg/HgO). A second process at more negative reduction potentials involves reduction of TeO3 2-, Pb2+ and Tl+ to PbTl4Te3 in a potential interval of -1.02V < E < - 1.19V. The crystalline Tl2Te3 and PbTl2Te3 were deposited electrochemically on Ag substrates at -0.84V and -1.10V respectively. Thermoelectric (TE) material can form a temperature gradient across the material to make electric voltage, which is popular in waste heat utilization and recovery industry. Lead telluride, PbTe, is a small band gap semiconductor of 0.32eV at 300K. PbTe can change its n-type semiconductors with Pb-rich to p-type semiconductors with Te-rich[1]. And it is one of the best TE materials used in thermoelectric generators working between 500K and 600K, or even at a higher temperature of 800K.Three facto,rs play a role in the performance of a thermoelectric material: electrical conductivity (s), thermal conductivity(?), and the Seebeck coefficient (S). These can be combined with absolute temperature (T) to give a figure of merit (ZT) for the material, ZT = s2sT/?. By increasing the electrical conductivity and decreasing the thermal conductivity, which can enhance the ZT value, many efforts, such as alloying with other elements and making the materials nano-sized, have been done to improve its properties recently. Hsu et al. reported that the ZT value of Cubic AgPbmSbTe2+m is increased to 2.2 by doping Ag-Sb to PbTe.[2]."

Jan 1, 2011

By Krishna Parameswaran

This paper discusses sustainability considerations in primary copper smelting using selected examples of practices at ASARCO LLC, an integrated U.S. primary copper producer. Using the classic Brundtland Commission definition of sustainable development, i.e., “development that meets the needs of the present without compromising the ability of future generations to meet their own needs,” the paper discusses how copper mining and smelting practices can be made sustainable. The examples used to illustrate sustainability considerations include: (1) adoption of flash smelting; (2) emission reduction and process improvement associated with anode refining of blister copper and the converter retrofit project, and (3) preliminary research findings on alkali treatment of copper smelting slags and copper mine tailings.

By H. Senoh

For the purpose of clarifying the reason caused a drastic decrease of discharge capacity for MmNi3.6Mn0.4Al0.3Co0.7 electrode at relatively low temperatures, various factors influencing the charge-discharge processes were investigated in the temperature range of 25°C to -40°C. The charge efficiency obviously decreased at low temperatures less than 0°C due to a decrease in the rate of the charge-transfer reaction on the electrode surface. Moreover, both the rate of the hydrogen diffusion from the alloy bulk to surface and the rate of the charge-transfer reaction significantly influenced the high-rate dischargeability. The addition of Mo to MmNi3.6Mn0.4Al0.3Co0.7 alloy was found to be effective for improving the electrocatalytic activity, leading to the improvements of the charge efficiency and the high-rate dischargeability at relatively low temperatures.

Jan 1, 2002

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By Isabela Leao Amaral da Silva, Felipe Perisse Duarte Lopes, Alice Barreto Bevitori, Sergio Neves Monteiro, Ruben Sanchez Rodriguez

"The fibers extracted from the stem of the ramie plant are among the strongest natural lignocellulosic fibers with a potential to be used as reinforcement of polymer matrix composites. Characterization of the ramie fiber has recently been conducted for its physical and mechanical properties. However, the effect of increasing temperature on the ramie fiber behavior has not yet been fully investigated. Therefore, the objective of this work was to perform a thermal analysis on ramie fibers with different diameters within the naturally found range of practical interest. The analysis was conducted by thermo-gravimetric, TGA and DTG, as well as differential scanning calorimetric, DSC, techniques. It was found that the ramie fibers present thermal stability up to 200°C and then suffer a sharp deterioration between 300 and 500°C, resulting in characteristic peaks.IntroductionSince the middle of last century, polymer composites have substituted many conventional monolithic materials in applications ranging from aerospace to sport [l]. The main advantages of these composites are the low density and flexible properties specially using fiber as reinforcement to suit the mechanical performance requirements [2]. These are usually high strength and stiffness requirements that could be reached with synthetic fibers such as glass, carbon and aramid fibers. In recent years, however, the use of synthetic fibers is being questioned in terms of problems caused to the environment. In fact, as non degradable material, synthetic fibers are associated with long term pollution when discarded. Moreover, the expended energy for fabrication and processing can be related to relatively large amounts of C02 emissions and represents a contribution to global warming [3]. Glass fiber, in addition, is toxic and cannot be incinerated as a waste in thermal power plants [ 4]. Possible substitutes for glass fiber are the natural fibers. Many natural fibers are today being considered as viable alternatives to replace glass fiber as reinforcement of polymer composites. In particular, some natural lignocellulosic fiber extracted from plants present a real potential for this replacement [2-8]. Their comparative advantages are lower density and reduced cost as well as renewability, biodegradability, recyclability and neutrality with respect to C02 emission [3]."

Jan 1, 2011

By Larry Southwick

This Peirce-Smith Converting Centennial symposium is celebrating the contributions of two men, William Peirce and E.A.C. Smith, in advancing technology allowing the copper industry to realize its full potential. However, theirs is representative of a larger story: New, simpler technology releasing the stranglehold of older, more complicated technology, new developments in vessel configuration and design finding alternate routes around dead ends in operability, advances in technique and concepts removing roadblocks of cycle time and capacity, and overall innovation opening up vast new reserves around the world to those companies willing to embrace those improvements. Our story is also one of personalities, stubborn smeltermen versus the innovators, those inside the industry versus those from outside. It is a story of an initial borrowing from the steel industry, but also Peirce and Smith, from the refining end of the copper business, taking the ideas of Baggaley from Pittsburgh’s steel and airbrake industry, who built on what Hollway, Manhès and David, Douglas, and others had done in smelter tests, further to compete with the previous primacy and closely held expertise of the copper smeltermen in Wales. These advances have been well recorded in photographs taken over the last 150 years. A number were submitted especially for this symposium. Many others were published in the mining and metallurgy press of the times. Several mining schools also retained copies of photos either taken during field trips, or donated to the school by alumni and operating companies. This presentation will provide a selection and discussion from these sources of “converters in action”, describing the various designs, operations and developments depicted. The focus here will be on the first roughly 60 years of copper converter development, from Bessemer’s days at the dawn of this new idea, up to and slightly past the time of initial adoption of Peirce and Smith’s designs.

Jan 1, 2009

By Hideki Minoura

"Two novel electrochemical techniques for the preparation of highly crystallized CdS film have been presented. One is cathodization of a conductive substrate in an acidic chemical bath containing cadmium salt and thioacetamide, where electroreduction of proton at small current densities induces a growth of highly crystallized CdS thin films, whose growth is not disturbed by the reactions in the solution phase. The other technique is electoreduction of aqueous Cd2+— SCN complex. An advantage of this technique lies in no formation of solid particles in the bulk, of the bath.IntroductionIn recent years much attention has been paid to materials preparation by solution processing because of its advantages in lowering the cost as well as the stress to the environment, as compared to the conventional gas phase techniques which unavoidably require high temperature and/or vacuum. We have been trying to explore novel techniques for preparing functionalized compound semiconductors by aqueous solution process. Semiconductors which we have been mainly focusing on are CdS and ZnO, which are important semiconductors finding applications in various devices. In the present paper, some of the techniques that we have recently established for the preparation of highly crystallized CdS will be presented.Methods of the CdS film processing in solution phase (wet process), which have been reported so far can be divided into two major groups; one is chemical bath deposition (CBD) in alkaline solution containing Cd2+ and thiourea 1)4) and the other is electrodeposition (ED) in acidic solution containing Cd2+ and thiosulfate ions - 5)-8) or organic solutions containing dissolved sulfur 9)-11)."

Jan 1, 2000

By T. Wang, R. G. Reddy

"The corrosion of stainless steel SS316L in a low melting point novel LiNO3-NaNO3-KNO3- NaNO2 eutectic molten salt mixture was investigated at 695K. After long-term isothermal dipping corrosion experiments, the SS316L samples were analyzed using scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS) to determine the topography and corrosion products. Dense and protective lithium iron oxide scale formed on the surface and prevented the SS316L sample from further severe corrosion. Therefore, SS316L is considered to be suitable construction material for solar thermal energy storage materials containers.IntroductionMolten salt mixtures have been considered as potential candidates for thermal energy storage and heat transfer media in solar energy applications. To apply the molten salt in the energy transfer process, the standard pipes made of stainless steel must be utilized to carry the molten salt mixtures in parabolic trough system of solar power production. The pipes encounter continuous flow of hot and cold molten salt every day. Thus corrosion of stainless steel in molten salt mixtures becomes extremely essential for the long-term utilization of the thermal energy storage media. The corrosion of passivity materials inside high temperature molten salt systems have been studied which gives fundamental understanding of basic mechanism about the corrosion process [1-8].The corrosion behavior of Fe-Ni-Cr alloys in an equi-molar LiNO3–NaNO3–KNO3 mixture was studied [9]. According to the XRD analyses, the major phases in the oxide scales were identified as LiFeO2, Fe3O4 and Cr2O3. A HITEC® salt mixture (NaNO3–NaNO2–KNO3) was also tested as a corrosion medium for stainless steel [10] and the corrosion rate was found to be affected by the protective oxide layer. In most cases, the alloys having more than 10wt% chromium show high resistance to corrosion in molten salts."

Jan 1, 2014

By 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 colunm, 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&apos;s law with the Nernst-Planck equation as the constitutive equation for diffusive flux We use a Nernst-Planck type model to predict batch experimental data, then evaluate it by comparing it&apos;s ability to predict experimental data to that of a more traditional Fick&apos;s law type model? The data from this comparison suggests that the Nemst-Planck type model yields better results.

Jan 1, 1996

By Z. Yang, R. W. Smith, Jr. Wharton

"Microorganisms have the ability to remarkably adsorb and/or absorb heavy metal ions. Hence they are being studied widely as a means of removing metal ions from aqueous solutions both in order to clean up toxic streams and to recover valuable metals from these and other streams. It is often difficult to harvest organisms such as bacteria and unicellular algae since they are usually too small to be readily screened out. Froth flotation may prove to be a feasible method to harvest such organisms subsequent to the ad/absortion of the metal Ions. The present paper discusses the surface/electrokinetic properties of microorganisms and the modifier-collect conditions under which they should float. The zeta potential of the green alga Chlorella vulgaris was measured in the presence of AI(III) and Pb(II) ions and in the presence of dodecylammonium chloride and sodium dodecylsulfate. Present and past data suggest that the organisms should behave similarly to other finely divided, charged (polar) solids with their behavior sometimes modified by the non-polar surface regions present.IntroductionThe overall field of bioengineering is growing at a remarkably accelerating rate. Hydrometallurgy and mineral processing are included among those disciplines where there has been actual or proposed commercial use of bioorganisms. Further, the actual or proposed use includes bacterial enhancement of leaching of a number of different types of ores (1-5), modification of the flotation or oil agglomeration separation of minerals by bacteria (6,7) and microorganism (algae, bacteria or fungi) concentration of metal ions present in effluent or other mineral processing or hydrometallurgy aqueous streams (8-23)."

Jan 1, 1988

By Yuhsuke Mizukami

Crude high Cr containing steel such as tool steel, heat-resistant steel or stainless steel is produced by dissolution of high carbon ferro-chromium into molten crude steel. In the refining process, decarburization is performed at the first stage, and deoxidation is followed in the next stage. Therefore, the equilibrium relation between dissolved Cr and 0 in molten Fe-Cr alloy after decarburization is very important when yield of deoxidizer is considered for the ovemll control and optimization of the process. It is well known that the yield of deoxidizer does strongly depend on the kinds of refractories of furnace in the secondary refining process. In the present work, the equilibrium relation between dissolved Cr and O in molten Fe-Cr alloy has been measured in a Cr2O3, MgO or Al2O3 crucible at steelmaking temperature. O contents at given Fe-Cr components have been lower in order of Cr2O3, Al2O3 and MgO crucible. The present results have been discussed based on the activities of the constituents in pure solid Cr2O3, and FeO-Cr2O3, MgO Cr2O3 and (AI,Cr)2O3 solid solutions.

Jan 1, 2003