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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

By Mikiya Tanaka

This paper outlines our attempt to establish a recycle process of nickel in the spent baths and waste rinse water of electroless nickel plating plants using solvent extraction and solvent-impregnated support, Solvent extraction studies of nickel from actual spent baths revealed that (i) nickel is efficiently extracted by a hydroxyoxime extractant such as LIX84I at a pH greater than 6 and is readily stripped with sulfuric acid, and (ii) the mixtures of LIX63 and acidic organophosphorus extractants (D2ERP A, PC88A, and Cyanex 272) enhanee the nickel extraction efficiency to a sufficient degree without pH adjustment, but at the same time, reduce the stripping efficiency. The application of acidic organophosphorus extractants to selectively remove impurity metal ions (iron and zinc) from a real spent bath before extracting nickel lead to the finding that PC88A and Cyanex 272 effectively remove iron and zinc without pH adjustment leaving nickel in the raffinate. The removal of nickel from the waste rinse water was also studied. Solvent-impregnated supports with a macroporous resin and oil sorbents made of natural kapok fiber and synthetic fiber as supports were applied using D2EHPA and LIX860 as the extractants. During the batch operation, nickel is removed with a high efficiency without pH adjustment. During the column operation, however, the effective removal is hindered by (i) the dissolution of the nickel-D2EHPA complex into the aqueous phase in the high loading region, and (ii) the slow removal rate of the LIX860-impregnated support.

Jan 1, 2003

By Mariane Costalonga de Aguiar, Carlos Mauricio Fontes Vieira, Sergio Neves Monteiro

"This work evaluates the effect of incorporation of an ornamental rock waste into an industrial clayey body used for roofing tiles fabrication. Formulations with 0, 10, 20 and 30 wt.% of waste were prepared by replacing the sand in the industrial clayey body. The plasticity of the formulations was determined by the Atterberg limits. Specimens were fabricated by 18 MPa press-molding and then fired from 850, 950 and 1050°C. The specimens were tested to determine the water absorption, linear shrinkage and three points bending flexural strength. The results indicated that the waste improves the extrusion performance of the clayey body by decreasing its plasticity. The use of the waste was beneficial to the water absorption and mechanical strength of the fired clayey ceramic at 1050°C.IntroductionOrnamental rock is a natural resource available in the municipal area of Santo Antonio de Padua and located 150 km from the city of Campos dos Goytacazes, northe of state of Rio de Janeiro, Brazil. Intense industrial activity related to ornamental stones, especially gneisses, is traditionally occurring in the region. After mining, the flagstone is submitted to sawing to obtain blocks and then, after a manual operation, the final products are small flagstones [1,2]. During the sawing operation, a sludge composed of water and fine particles of rock is generated. A monthly production of 1000 tons of ornamental rock waste is estimated to be produced at Santo Antonio de Padua. The final disposal of this waste has brought serious environmental problems. Since most industries do not have an adequate sludge treatment, the waste is contaminating the soil and underground waters as well as obstructing rivers and lakes.Ceramic bodies industrially fabricated in the municipal area of Campos dos Goytacazes, 280 km from the city of Rio de Janeiro, are still empirically elaborated using a mixture of local clays. These clays are predominantly kaolinitic mineral, associated with high plasticity. Due to the excessive plasticity of the ceramic bodies, it is common to have dimensional defects in the final products after the drying and firing processes. Moreover, the kaolinitic structure and the presence of aluminum hydroxide confer a refractory behavior to the local clays. This impairs sintering during the firing operation. In the case of clay ceramics for civil construction, this results in greater porosity associated with elevated values of water absorption [3,4]. To avoid this problem, it is necessary to reformulate the ceramic body composition. The addition of both non-plastic materials to reduce plasticity and fluxes to condition the refractoriness is a possible alternative."

Jan 1, 2011

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

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 Raj P. Singh

Applications of cementation in the recovery of metal ions from process solutions have been known for a long time. Cementation reactions involve electrochemical precipitation of a noble metal from solutions of its salts on a more electropositive metal which, in tum, progressively dissolves. For example, addition of zinc metal powder in a solution containing zinc and cobalt ions would allow for the precipitation (separation) of cobalt according to the following chemical reaction. This paper pertains to the recovery of cobalt from cobalt process solutions via a cementation reaction on aluminum shavings (metal scraps from cans etc). Specifically, we report on the characterization of cobalt process solutions, a by-product obtained from cobalt chemicals, and the kinetics of cobalt, nickel and manganese cementation from process solutions on aluminum shavings.

Jan 1, 2000

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide&apos;s smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates &apos;CSO or CSC&apos; under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements&apos; chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By F. F. Aplan, G. Simkovich

"A review is given of the effects of solid state point imperfections upon a number of mineral benefication processes and a metal extraction process. It has been found in numerous flotation studies that small amounts of aliovalent impurities (dopants) in binary compounds may show major effects upon flotation behavior. Both semiconducting and ionic conducting compounds are affected. These effects are also seen in hydrometallurgical studies as well as in electrostatic operations. Additionally, de-copperization of lead melts appears to be strongly influenced by similar defects. It is hypothesized that the effects observed in these studies are present in actual operations and should be considered in designing processes. A few speculations concerning future efforts are advanced. IntroductionImperfections [point (e.g., vacancies, interstials, quasi-free electrons, electron holes, impurity ions), line (e.g., dislocations), two dimensional (e.g., grain boundaries) and three dimensional (e.g., 2nd phases) defects] are generally present in solid materials and these imperfections may, and often do, have important effects upon a variety of properties and processes. In general, one may, in most cases, attain elimination of three dimensional defects by a separation process of one type or another (e.g., gravity, electrostatic, magnetic, flotation, hydrometallurgical etc.,). Thus, this type of defect has rarely been investigated in a systematic fashion. Two dimensional defects are always present in non-single crystal materials but have also escaped systematic studies in processes primarily because the control of such defects is not easily attained. Line defects are non-equilibrium entities which are present in ill-defined quantities so that they present a variable that cannot be easily controlled although through careful systematic experiments one can attain some reproducible relations pertaining to this type of defect.Contrary to the lack of studies concerned with the effects of 1, 2 and 3 dimensional types of defects there has been some activity concerned with point defects and their effects upon a number of mineral/metallurgical processes, especially flotation processes. Thus, this article will present a review primarily of point defects in relation to their effects upon flotation although other processes and defects will also be mentioned."

Jan 1, 1988

By O. Durand

The Cerro Verde Hydrometallurgical Plant, located at Arequipa in the southern part of Peru, started its operation in 1977 with a design capacity of 33,000 MT/year of copper cathodes. The plant has treated 61,055,000 MT of ore mainly oxides with a content of 1.01% total copper and 0.67% of soluble copper. The leaching plant has three pads that produce 4.0 gpl copper solution. The solvent extraction plant has four trains with three extraction stages, two stripping stages with a single mixer in all stages. The mixer-settlers are 316 stainless steel and the pumps are vertical turbines. The flowrates of 1,300 gal/mil of aqueous and 1,300 gal/min of organic at a 1/1 ratio. The electrowinning plant contains 208 commercial cells and 18 starting sheet cells. Each cell has 47 anodes and 46 cathodes. In addition to describing the hydrometallurgical plant, this paper also mentions efforts directed at reducing costs and improving operations. The initial results from leaching secondary sulfides, which started October 1985, are also discussed.

Jan 1, 1987

By James P. Bennett

The U.S. Bureau of Mines, Tuscaloosa Research Center, is conducting a review of the usage of different types of refractories, the current industrial practices to recycle/dispose of spent refractories, and the concerns associated with these practices. This information will serve as the technical basis for initiating a research program to recycle or find alternate uses for spent refractory materials. Approximately 1.6 million metric tons of clay based and 1.2 million metric tons of non-clay based refractory materials were manufactured in the United States in 1992 alone, representing a value of almost 2 billion dollars. Landfill has been and remains the disposal means of choice. Issues such as environmental regulations, concerns over landfill disposal, future liability, and product stewardship programs have brought about increased emphasis for recycling or alternate material use. Information on refractory consumption and the issues associated with recycling or disposing of used materials will be discussed, including current recycling practices.

Jan 1, 1995

By Xiang Zhu

Xidagou is the largest waste water discharge channel of the Anshan Iron and Steel Complex (AISC) with average flow rate of 8000 cubic meters per hour, which is about 75% of the total effluent of the AISC. The waste water from Xidagou seriously polluted the Taizi River Basin. In order to meet the Chinese Class V Standard for Surface Water Discharge and the Standard for Recycled Industrial Water Reuse, with the aid of the World Bank, the AISC began the treatability studies in 1991. Based on the bench-scale test, the AISC carried out pilot-scale treatability studies on three different treatment processes and five different chemical coagulants for more than half a year in 1992. The study results show that the processes of primary sedimentation- chemical mixing and flocculation-secondary sedimentation-filtration can meet the requirement and that PFS and PAM are effective and economic chemical coagulants.

Jan 1, 1994

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By Patricio Ruz, Gabriel Riveros, Carolina Ramirez, Andrzej Warczok, Rober Treimer

"Continuous converting of copper matte produces slag with high cuprous oxide content. The corrosion of chrome-magnesite refractories with slag of high cuprous oxide content is a major problem. Properties of olivine type of slag make the slag very attractive for matte smelting and converting.Analysis of phenomena determining the slag infiltration into the porosity of a refractory and dissolution of refractory components in the slag allowed for better understanding of the mechanisms of refractory destruction.The results of laboratory scale tests of the olivine slag infiltration into open porosity and corrosion showed dominating effects of slag temperature and cuprous oxide content. The optical and X-ray examination of slag samples permitted the definition of the mechanism of formation of new phases and refractory deterioration. 71"

Jan 1, 2009

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By P. M. Swash

The paper describes the use of mineralogical methods in the exploration and evaluation of primary diamond occurrences. The most common methods that are used include the systematic search for kimberlitic indicator minerals, surface textural study of the indicator minerals, (garnet, spinel, ilmenite and chrome diopside) and alluvial macrodiamond studies so as to understand their provenance and guide exploration towards diamondiferous targets. The mineral chemistry of the indicator is used to positively assess the origin of the mineral grains and is also pivotal in the determination of the diamond potential of a deposit. Petrography of the primary deposit is able to identify the body to be kimberlitic and is also a support to the mineral chemistry findings. Unambiguous proof of a prospects potential to contain macrodiamond is proven by the occurrence of microdiamonds in the residues from the rock. The presence of a sufficient number of microdiamonds in the rock is enough to determine a semiquantitative grade estimate and warrant further metallurgical evaluation so as to determine its actual macrodiamond content.

Jan 1, 1991