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By J. D. Budai, D. H. Lowndes, D. P. Norton, D. K. Christen, B. C. Chakoumakos, J. R. Thompson, B. C. Sales

"Artificially-layered structures, consisting of (Sr,Ba,Ca)CuO2 layers in the tetragonal, ""infinite layer"" crystal structure, have been grown by pulsed-laser deposition. Superlattice chemical modulation is observed for structures with SrCuO2 and (Sr,Ca)CuO2 layers as thin as a single unit cell (~3.4 Å). In addition, novel thin film superconductors were formed by using the constraint of epitaxy to stabilize SrCuO2/BaCuO2 superlattices in the infinite layer structure. Using this approach, two new structural families, Ba2Srn-1CUn+l O2n+2+ d) and Ba4Srn-1CUn+3O2n+6+ d, have been synthesized which superconduct at temperatures as high as 70 K. These results represent not only the synthesis of new structural families of superconductors, but also demonstrate that pulsed-laser deposition and epitaxial stabilization can be effectively used to engineer artificially-layered thin-film materials.Advances in the understanding of epitaxial thin-film growth of the cuprates have heightened interest in creating artificially layered superconductors.(1-3) The layered structure of the copper oxide superconductors opens the possibility of forming novel materials by carefully controlling the epitaxial growth of sub-units of the crystal structures. Thin-film growth methods offer unique opportunities for the atomic engineering of new high-temperature superconducting (HTSc) materials through the ability to form artificially layered crystal structures.(4,S) Moreover, the surfaces of single-crystal substrates provide an ""atomic template"" that can be used to stabilize epitaxial films in metastable crystal structures.An important development in forming new HTSc compounds by artificially-layered epitaxy has been the epitaxial growth of (Sr,Ca)CuO2 films in the so-called infinite layer structure.(6-17) This material, which can be considered the parent compound of all of the copper oxide superconductors, has a relatively simple, layered structure consisting of CUO2 planes separated by planes of alkaline earth elements.(18) Bulk synthesis of (Sr,Ca)CuO2 with the tetragonal, infinite layer structure generally requires the use of high pressure and high temperature bulk processing techniques.(19-24) However, recent experiments show that this metastable compound can be epitaxially stabilized at less than atmospheric pressure, resulting in the growth of tetragonal (Sr,Ca)CuO2 single crystal thin films of the infinite layer defect perovskite structure by pulsed-laser deposition (PLD) over a wide range of growth conditions.(6-17)"

Jan 1, 1994

This report presents overview of the authors' results of thermodynamical investigation of some important metallurgical processes and phenomena. Among them: carbo thermal reduction of silica, and boron oxide, silicon carbide obtaining from different precursors, investigations on copper and manganese ores processing, investigations on pollution from different sources. Special attention is paid-to thermodynamical approach to investigation and estimation of multi component multi element compositions stability, developed by the authors. Also are discussed some auxiliary but' important for the thermodynamical investigations issues.

Jan 1, 1997

By Kelly J. Driscoll

Impure zinc (98.5%) was electrorefined to high purity zinc (99.995%) using a fused salt electrolyte of molar composition 1: 1 : 1 :2 ZnCI2:KCl:NaCl:LiCl with a current efficiency of about 90% at 723 K. A recessed channel electrorefining cell was developed which achieved excellent mixing of both the metal and the electrolyte and by ensuring a very small anode to cathode spacing the voltage drop across the cell was 0.16 V and at a current density of 7kA m-2. The physical characteristics of the cell were observed using a low temperature model which showed the formation of droplets and rivulets which provided mixing. The application of this approach to the refining of other non-ferrous metals is discussed.

Jan 1, 1992

By J. D. Sloop

This paper discusses the current state of EAF dust recycling at AmeriSteel's Dust Processing Division in Jackson, Tennessee. Included are a brief history of the plant, a description of the facility, a description of the process, and operating data.

Jan 1, 2000

By Adrien Antenen, Didier Villette

CITRON has developed a new process for the recycling of hydroxide sludge, household batteries, catalysts, automobile shredding residues, grinding sludge and other metal containing organic and inorganic waste. A pilot plant with a capacity of 1,000 tons per year has started operations in April 1998. In August 1999, an industrial plant became operational with an initial treatment capacity of 23,000 tons.

Jan 1, 2000

By W. Kasprzak

Modern light metals processing technologies are very complex and involve a diverse set of variables that must be quantitatively evaluated. The most effective way to design new casting processes that deliver specified metallurgical and mechanical properties is to develop a method of simulating the "real-time" process within a test sample of sufficient size. The results can then be analyzed and the required optimizations can be performed. This paper presents a novel method of simulating the industrial casting processes in a laboratory environment using an experimental apparatus based on the principle of high frequency induction heating. The applicability and accuracy of the proposed analytical method is demonstrated, for example, by simulation of the solidification and heat treatment of a test sample composed of two dissimilar materials. The simulation can be used to develop a stress model for an engine block made from an aluminum based alloy with iron cylinder liner inserts.

Jan 1, 2002

By H. A. F. de Souza, Dana S. Mills, P. E. Burgener

"ICP-MS has moved from a laboratory curiosity to a functional analytical tool. This paper discusses how ICP-MS has been used to solve difficult analytical problems encountered when analyzing various mine materials. Comparisons between analytical techniques applied to the analysis of gold and the platinum group metals illustrate the advantages and problems of ICPMS when. applied to trace levels of some metals iri the presence of ore grade metals. Interferences and matrix effects are compared to ICP, AA and Neutron Activation. The necessity to select chemical extractions which are compatible with ICP-MS are also discussed.The ICP-MS techniques explained in the examples on Au and precious group elements (PGE) have validity in analytical problems encountered in testing of trace metals in the presence of major elements found in mine materials. Exploration and environmental testing are other areas that require the same analytical approach to quantify trace levels in the presence of major interfering elements normally associated with mining environments."

Jan 1, 1999

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By R. W. Harnmack

Hydrogen sulfide generated by the anaerobic respiration of sulfate-reducing bacteria was used to treat pH 2.2 water from the abandoned Rio Tinto copper mine in Nevada. The untreated water contained 550 mg/L Fe, 140 mg/L Al, 90 mg/L Cu, 80 mg/L Mn, 60 mg/L Zn, 4 mg/L Co, and 2 mg/L Ni. The bench-scale treatment system examined consisted of a bioreactor for H2S generation and three precipitator/clarifier units for metal sulfide precipitation and recovery. The treatment system reduced the concentrations of all metals except Mn to less than 0.1 mg/L. Manganese concentrations were reduced by 96 percent to 3.3 mg/L. A CUS/SO concentrate (33 pct Cu) and a ZnS/5° concentrate (28 pct Zn) were produced that may be suitable for metal recovery at existing smelters

Jan 1, 1994

By Richard D. Hagni

The United States is dependent upon foreign sources for more than 93% of its bauxite and alumina supply. Domestic production of bauxite, which comes from Alabama, Georgia and Arkansas, is limited to those bauxite ores containing less than about l ½ % iron. Bauxites with higher iron contents are generally not utilized because they cause problems in bauxite calcining and especially because they produce undesirable brick discoloration and cracking. In order to improve beneficiation and expand the utilization of high-iron or ferruginous bauxites, a mineralogical and textural study has been conducted on selected samples from the Eufaula, Alabama, bauxite district. Reflected light microscopic, petrographic, and X-ray techniques have shown that a variety of iron minerals are present, including hematite, goethite, lepidocrosite, siderite, pyrite, marcasite, and ilmenite. Although the iron minerals may be locally concentrated into concretions and pisolites, most occur as very fine grains that are disseminated and show a variety of intergrowths. Mineralogical and textural observations indicate that the fine-grained iron mineral grains may be amenable to high gradient magnetic separation.

Jan 1, 1981

By J. G. Zafiratos

The leaching of a Greek low-grade manganese dioxide ore, not amenable to conventional mineral processing operations, was studied using a mixed culture of Thiobacillus sp. bacteria. The experiments were carried out in specially designed continuously aerated and stirred tank reactors arranged in two-tank series. The first tank of each series was loaded with an elemental sulfur culture suspension while the second was loaded with a manganese ore high density slurry. The bacterial culture had been previously adapted to grow on elemental sulfur and also in the presence of manganese ore and dissolved manganous ion. A two level full factorial design was constructed in order to study the effects of the ferric ion concentration in the leach solution, the "elemental sulfu weight to ore weight" ratio, the ore pulp density and the composition of the dispersed gas. The responses which were investigated included percentage manganese recovery, co-dissolution of iron and manganese dissolution rate. Parameters with constant values throughout the experiments were the leach solution pH, the nutrient medium composition, the dilution rate and the ore and sulfur grain sizes. It was found that the ferric ion concentration was the most significant factor and had a positive effect on the final percentage extraction of manganese from the ore and also on the rate of manganese solubilization from the ore. The effects of the other factors studied are discussed in detail.

Jan 1, 1997

By M Kolbe

Co-Cu exhibits a metastable miscibility gap in the region of the undercooled melt. Specimens have been undercooled and solidified containerlessly into the metastable miscibility gap in an electromagnetic levitation facility (EML) and in drop tube (DT) experiments. Due to the high undercooling the velocity of the solidification front is very high and the microstructure is frozen in instantaneously. The microstructure of samples processed in the EML is influenced by the electromagnetic stirring due to the induction of electrical currents into the melt. A variety of microstructures has been observed. After undercooling below the binodal the liquid melt separates into the Co-rich L1-phase and the Cu-rich L2-phase. Two basic morphologies of the L1-phase can be observed, they can be attributed to the transition in dendrite growth from diffusionally and thermally controlled to only thermally controlled growth. Transient microstructures are observed after solidification in the vicinity of the binodal. Drop tube experiments, which lead to a rapid solidification of a distribution of droplets under reduced gravity conditions, in contrary allow for the observation of the early stages of demixing: the microstructure shows a homogeneous distribution of spherical particles of the minority phase in the droplets. The cooling rate of the droplets and its dependence on the droplet radius has been calculated. The solidification velocity as a function of undercooling has been measured in the EML for the composition Co-lB.Bat%Cu. The data are analysed in the framework of the LKTlBCT model with a velocity-dependent distribution coefficient as well as within a model of Galenko and Danilov using a kinetic growth coefficient of u=0.22 m/Ks.

Jan 1, 2002

By W. W. Albrecht

I. Introduction Refractory metals like tungsten, molybdenum, rhenium, tantalum and niobium and their compounds are essential ingredients of our modern technology. Especially in purified form, they are used in special alloys, electronics, optics and ceramics. The processing route from raw material to high purity refractory metals and their compounds includes, as a prime option, the following steps: - dissolution of raw materials. - liquid liquid extraction. - precipitation of high purity intermediate compounds. - calcination/reduction to high purity oxides/metals. Especially in the first three steps, major amounts of chemicals like acids or sodium hydroxide are used and, as by-products, substantial quantities of residues and effluents are generated. The impact of environmental regulations on these by-products and the attempt to reduce or minimize the amount of residues and effluents produced will be discussed in this presentation using Ta/Nb chemistry as the example. The basis of our considerations will be the way these by-products are handled at HCST, a major, and in some cases, the biggest producer of refractory metals (tungsten, molybdenum, rhenium, tantalum, and niobium).

Jan 1, 1992

By Pengfu Tan

A thermodynamic model and computer program, CuModel, has been developed to model the distribution behaviors of Cu, Fe, S, O, Ni, Co, Sn, Pb, Zn, As, Sb, Bi, Au and Ag, copper loss in the slag, and heat balance in copper smelting process, matte converting process and copper con-tinuous smelting process. It can be predicted for any set of controllable process parameters such as feed composition, smelting temperature, degree of oxygen enrichment and volume of oxy-gen-enriched air. This model accounts for physical entrainment between matte and slag phases. It can be used in Isasmelt process, copper flash smelting process, Mitsubishi process, P-S con-verting process and Noranda process. The predictions by the present computer model are com-pared with the known commercial data from Guixi Smelter in China, PASAR Corporation in Philippines, Horne Smelter in Canada, MIM Limited in Australia and Naoshima Smelter in Ja-pan. The agreements between the computer predictions and the commercial data are excellent. In this paper, the applications of CuModel in the copper metallurgical industries have been pre-sented. CuModel has been used by Daye Smelter and Guixi Smelter in China, and by PASAR in Philippines as well.

Jan 1, 2004

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By M. K. Mohan

During the processing of metals like Cu, Ni, Co, large quantities of solutions, which contain co- products such as Sb, Cd, Pb etc. are generated. These solutions if processed to recover the metals help in conservation of metals as well as environment preservation. The present study was taken up to recover antimony from process solutions using zeolites. The effect of pH of the solution, time and type of zeolite viz., chabazite, mordenite, erionite and clinoptilolite on the sorption of antimony was investigated. Rate of sorption increases with pH and about 77-pct. antimony sorption was observed with chabazite at a pH of 6. Optimal conditions were established for the maximum recovery of antimony fiom process solutions. The mechanism of sorption for Sb was proposed in terms of adsorption and intraparticle diffusion. The calculated adsorption constants from Langmuir and Freundlich equations indicated that the adsorption of antimony on chabazite was strong.

Jan 1, 1999

By Federico Chavez

The process for recovering lead from battery residues used in several Mexican Plants include lead blast furnace and rotary furnaces. The formers are basically fed with recycled batteries together with the necessary additives to produce metallic lead. One of the by-products generated in the blast furnace is a dust mainly formed by lead sulfide. The rotary furnace is used to recover lead .from lead batteries, dross from the refining-alloying process and the leady fines produced in the blast furnace. This paper describes thennodynamic analysis made to the rotary furnace process to understand the effect that each component of the system has upon the lead recovery. In order to enhance the process, the influence of iron chips composition and excess coke on slag viscosity is discussed. A computer optimization program . has been developed to design the furnace charge based on material and energy balances, .together with the thennodynamic equilibrium calculation.

Jan 1, 1995

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By Keith M. Axler

This report addresses issues specific to the generation of hydrogen fluoride via reaction of calcium fluoride with sulfuric acid. This process has been established on a commercial scale and is under consideration for treatment of calcium fluoride residues from uranium processing. Magnesium fluoride slags are also available as a product of uranium processing. The technique of using sulfuric acid for the production of hydrogen fluoride from magnesium fluoride is also under consideration as a residue processing scheme. In the current study, thermodynamic modeling was used to investigate these chemical processing systems. The results presented herein reveal information relevant to the selection of processing temperatures and conditions. Details include predicted effects in system composition based on operating temperatures for both the calcium fluoride and the magnesium fluoride systems.

Jan 1, 1996

By Mikiya Tanaka, Mikio Kobayashi, Mansour A. S. A1Ghamdi, Kenji Tatsumi, Yukinori Saiki, Hirotaka Senba

"In order to recover nickel ion in a spent electroless nickel - phosphorus alloy plating bath and, at the same time, to remove impurities such as iron and zinc, the applicability of solvent extraction with LlX84I as the extractant has been investigated using actual spent solution. Although the extraction efficiency of nickel from the spent solution is considerably lower than that from the nickel sulfate-nitrate solution, nickel in the spent solution is selectively extracted with high efficiency at the pH of 6 - 7. The extracted nickel is effectively stripped by sulfuric acid at a pH of less .than· 3. On the basis of these results, a· flowsheet for recovering nickel from the spent solution is proposed Chemical equilibrium calculations of the spent solution has shown that the complex formations of nickel with anions such as lactate and phosphonate ions become predominant in the pH range between 2 and 6. This results in the depression of nickel extraction efficiency from the spent solution as compared with that from the .nickel sulfate-nitrate solution. By combining these aqueous equilibrium calculations with the· extraction model considering the extraction stoichiometry and the aggregation of the extractant in the organic phase, the extraction behavior of nickel is quantitatively predicted.IntroductionElectroless plating is indispensable for the recent advanced industries such as the electronic and mechanical industries. Electroless plating baths are repeatedly used by supplying the metal salts; however, the accumulation of the counter anions of the metal ions, the components formed by the oxidation of the reducing reagents in the plating baths, and the metal ions as impurities dissolved from the surface of the objective materials degrades the· quality of the plating. Thus, the baths are finally treated by a precipitation method to form a large amount of metal sludge, which is disposed in dumping sites. Therefore, from the standpoints of environmental protection and resource preservation, it is highly desired to establish a recycling process of the plating baths with minimum emission. Solvent extraction seems to be one of the 'suitable methods to recover metals from the spent electroless plating baths, because the concentration of the metal ion in the baths is relatively high, which is advantageous to solvent extraction as compared with the ion-exchange and adsorption methods. Some studies about the application of solvent extraction have already been carried out using simulated spe11t electroless plating baths [1-3]."

Jan 1, 2000