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By Y. A. Chang, J. Woodford, C. R. Kao

Reactive diffusion studies between NbC and Si were carried out at 1300 °C under a vacuum of 10-5 torr and a uniaxial pressure of 1 MPa. The annealing time ranged from 8 to 100 hours. The Si used was single crystal silicon; the NbC was hot-pressed powder compact. A NbSi2+SiC two-phase reaction layer formed with NbSi2 as the matrix and SiC as discontinuous particles. The microstructure of the reaction product is homogeneous, dense, and fine. The NbSi2 grain size and SiC particle size are in the micron range. The growth of the reaction products follows parabolic kinetics. Extrapolation of the data to zero thickness suggests an apparent incubation time of 3.5 hours. However, for short annealing time «60 hours), the thickness data can be approximated by linear kinetics with an initial growth rate of about 2 11m/hr. Based on these experimental observations, a growth mechanism for the reactive diffusion between Si single crystal and NbC powder compact is proposed. We propose that the nucleation sites for the SiC particles are at the voids of the NbC powder compact. This proposed nucleation mechanism offers a potential way of controlling the SiC particle size by changing the void size and void density of the NbC powder compact. This hypothesis, if proven to be true, will allow us to control mechanical properties of the composites by tailoring the SiC particles formed. It is also pointed out that the microstructure requires Si to be the dominant diffusing species and to diffuse through the reaction layer, while Nb and Conly have to undergo local rearrangement.

Jan 1, 1996

By Tom Lewis

This report discusses the evaluation of the ENVIRO-CLEAN PROCESS, a technology developed by Lewis Environmental Services, Inc. for the recovery of metals such as chromium, mercury, copper, cadmium, lead, and zinc from surface and groundwater streams. This new heavy metal removal process (patent-pending) utilizes granular activated carbon with a proprietary conditioning pretreatment to enhance heavy metal adsorption combined with electrolytic metal recovery to produce a saleable metallic product. The process generates no sludge or hazardous waste and the effluent meets EPA limits. A 50 gpm system was installed for recovering hexavalent chromium from a ground water stream at a site located in Fresno, California. The effluent from the activated carbon system was reinjected into the ground water table with the hexavalent chromium concentration < 10 ppb. The system simultaniously removed trichloroethylene (TCE) to concentrations levels < 0.5 ppb. The activated carbon is regenerated off-site and the chromium electrolytically recovered. The full scale system has treated over 5 million gallons of ground water since installation.

Jan 1, 1996

By Yoon-Bong Hahn

A mathematical model has been developed to analyze and predict the reduction process of iron ore particles in a two-stage fluidized bed system. This model includes the effect of particle degradation to elucidate its effect on reduction of iron oxides. Although the particle degradation is dependent on kind of iron ores, it was found that eighty to ninety percent of overall degradation is occurred in the prereduction stage mainly due to thermal stress and volume expansion. The degradation of particles in the?final stage is not much, but is mainly due to interparticle collision and abrasion. It was also found that to obtain a target reduction degree, it is of great importance to control the bed temperature and the residence time of paarticles in R1 rather than in R2. Optimum range of residence time was 15-20 minutes in the prereduction stage; 30-35 minutes in the final reduction stage.

Jan 1, 1996

By D. J. Chaiko

Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that we have studied are generated by combining an aqueous salt solution with an aqueous polymer solution. We have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. We have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS): In this chapter we review the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.

Jan 1, 1996

By Renato G. Bautista

The chemistry of the separation of metals from each other and from the other undesirable components involve multiple simultaneous chemical reactions. In the case of leaching, the heterogeneous chemical reactions between the solid and the liquid phase may be limited to a few reactions. In the homogeneous liquid phase, the number of simultaneous chemical reactions could be double or triple that of the number of heterogeneous reactions:. The rate of dissolution becomes very dependent on the changing concentrations of the significant chemical species taking part in the multiple reactions in both the heterogenous and homogeneous phase. The rate expression developed for the process must take into account the mechanism of chemical reactions in order to best represent the actual process. This paper also examine the role of mass transfer with chemical reaction in the develpoment of the rate equations for dissolution, liquid-liquid extraction, membrane separation, precipitation, and electrodeposition.

Jan 1, 1996

By Raj Mutharasan

The phenomena of gas-molten metal reactions for the production of metal matrix composites consist typically of a combination of one or more gas transport steps and a liquid gas reaction step. Reaction products include such strength enhancers, grain refiners, or high thermal conductivity phases as TiC, AIN, SIC, Si3N4, TiN in aluminum alloys. Nitrides, carbides and oxides can be produced at various volume fractions and in fairly fine sizes (500 am to 5 um) in laboratory melts by Reactive Gas Injection method (RGI). Gas injection methodology to produce the reinforcements is attractive because it can potentially be scaled to production scales in excess of 10,000 kg/h. For continuous production, the reactant molten metal can be continuously fed into the .crucible where the reactive gas is injected. The molten metal phase reactant may also be involved in a controlling transport step, depending on its concentration and viscosity. It is well known that the reaction product reinforcement size and shape of these phases have significant impact on the physical, mechanical and thermal properties. The current state of knowledge is unable to predict the kinetics and growth of solid reaction products obtained. The primary goal is to develop a fundamental framework for the understanding and prediction of the particle size in such reaction systems. In addition, the role of gas transport, liquid hydrodynamics and decomposition are important issues. A reaction-transport model is being developed using a reaction, transport, and thermodynamic framework, both at macro and at atomistic level to assess gas - liquid interactions.

Jan 1, 1996

By Yoshimasa Oda

The tank house of Tamano Smelter has adopted a high current density electrolysis operation applying PRC (Periodic Reverse Current) method and before 1991, it had materialized both high production capacity of 161,000 tons/year and high labor productivity. However, recent rapid rise of Japanese currency in foreign exchange market has urged us to further exert our efforts in reduction of labor cost. In order to achieve this goal of labor cost reduction, we have completed, in 1994, our phase four production expansion project which incorporated significant re-structuring of the organization and we have accomplished annual production of 191,000 tons/year. This project can be outlined as increase of number of cells for electrode exchange per day in the commercial electrolysis process to meet the increased number of cells and increase of the capacity of impurity treatment process. These improvements were done with minimum installation of new equipment and facilities and with achievements in efficiency and manpower saving of the existing facilities. Together with these improvements, rationalization in the starting sheet section was carried out by changing the material of mother blanks as well as changing their maintenance procedures. At the same time, the crane in this section was modified to enable automatic operation by a fuzzy control. As a result, we were able to save manpower equivalent to 5 operators in this section. With these improvements, the production capacity was increased by 18% and labor productivity by 25%.

Jan 1, 1996

By S. Seetharaman

In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements, In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid, as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences oldie electronic contribution to the conduction of the electrolyte. The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper, The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments&apos; in the field of sensor technology, as applied to metals processing are highlighted.

Jan 1, 1996

By Corby G. Anderson

Hydrometallurgical technology for the pretreatment of refractory gold concentrates has been developed at Sunshine Mining and Refining Company. It employs a patented nitrous-sulfuric acid pressure leaching process which&apos; was proven industrially at the Sunshine refinery. Additionally, pretreatment for removal of antimony and some other impurities is done with alkaline sulfide leaching. This paper will discuss the successful application of these two technologies for pretreatment of a refractory gold concentrate prior to CIL gold recovery. A complex gold concentrate composed of pyrite, arsenopyrite and stibnite was tested. Results of antimony leaching in alkaline sulfide media will be discussed including some details of a novel and selective recovery method for gold leached by polysulfide or thiosulfate" Also, the factors important in and the results of the application of nitrogen species catalyzed pressure leaching to refractory gold concentrates will be detailed.

Jan 1, 1996

By Joel F. Flurnerfelt

Molten Al and Al alloys containing si, Mn, Ti, and y have been lanced with nitrogen-bearing gases. These lancing experiments provided the means for observing what phases form during exposure to nitrogen-bearing gases for finite periods of time, <2 minutes, at high temperatures, >1290oC. The experiments were conducted in sn induction heated drop tube furnace apparatus. The overall premise of these experiments was to select those Al alloys and gas compositions that show promise of forming secondary dispersoid phases, particularly AIN, in the Al matrix. The alloys selected will be atomized using gas atomization reaction synthesis (GARS) using the most favorable conditions. In this case, the chosen Al alloy will be atomized with a nitrogen-bearing gas, such that the Al and gaseous nitrogen species react to form a dispersoid phase within each powder particle. The powder particles that result from this "aggressive" GARS-process would be essentially Al metal-matrix composites within a uniform distribution of dispersoids. To date, only high-purity Al has been atomized using a mild GARS reaction. This work is funded by the Materials Science Division of DOE-BES under contract number W-7405-Eng-82.

Jan 1, 1996

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By Junji Shibata

It is important to recover and reuse the metal values contained in various industrial wastes in a viewpoint of environmental preservation. Most of industrial products are made through the processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. In this paper, some examples of the application of solvent extraction to the treatment of wastes are introduced. The treatment of solid wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse water, etching solution and pickling solution are accomplished using solvent extraction technique.

Jan 1, 1996

By Jillian Spindura

This work investigates the carbothermic reduction of the complex sulphide mineral, pentlandite, in the presence of lime. The effects of change in temperature and the use of different carbon sources are studied and the role of these variables on the reducibility of pentlandite mineral is discussed. The microstructures of the heat-treated pellets are examined using X-ray diffraction and scanning electron microscopic techniques. The latter analytical method also allows any variation in the morphology and composition of the metallic phases formed, with temperature, to be considered. The kinetics of the reduction process is studied and the magnitude of the overall activation energy is determined from the plots of percentage reduction versus time.

Jan 1, 1996

By John J. J. Chen, Barry J. Welch

"The production of primary aluminium can potentially lead to metal that, with minimum treatment, meets a high purity standard. Smelters that can achieve a significant proportion of their production in this manner have a competitive edge which is of growing importance as the use grows for such items as compact discs and the like. Superimposed on the desire to produce high quality metal are stringent environmental requirements that the industry must adhere to. The environmental legislation focuses on fluoride emissions and the approach adopted is towards a zero waste management philosophy. The fluoride recycling process does, however, result in volatile impurities being captured and recycled to the cell. Aluminium has an extremely high reduction potential and this results in a significant proportion of the recycled impurities being reduced at the electrolyte metal interface and thus contaminating the metal. This paper reviews sources of impurities and the impact of the operating procedures adopted on metal treatment.IntroductionSeveral factors have contributed to the immense growth in the aluminium smelting industry. Initially the ready availability of hydro electricity provided a primary reduction energy source for the production of the light-weight metal. Because of its unique properties and innovation in the industry there has been a continued exploitation of its unique properties, especially at the high purity end of the metal. The industry has shown considerably versatility and innovation in adapting to the ever increasing demands of quality and purity. It is however a competitive industry and the ability to produce high purity grade metal (>99.9% pure) gives a competitive edge. Emerging markets such as for CD ROM disc production etc, will keep the quality demand stringent.While the industry has met the continuing demands for metal quality, it has also had to respond to stringent environmental requirements for emissions from the production plant. Like all extractive metallurgical processes carbon dioxide is an inevitable reaction byproduct. However, the volatilization and hydrolysis of the solvent electrolyte leads to fluoride emissions that are potentially harmful. Accordingly, the industry has adopted essentially a zero non-process waste management approach. All cell emissions, including reducible impurities, are recycled back to the cell. This has had a significant influence on the metal treatment processes."

Jan 1, 1996

By T. K. Mukcherjee

The importance of the processing of secondary resources such as solid industrial wastes and liquid effluents as well as byroducts for the recovery of the associated metal values hardly needs any elaboration. Such processing contributes in no small measure.towards the augmentation of the availability and the supply position of resources. As an added benefit, it leads to a reduction in environmental pollution caused by the undesirable waste materials. As some typical examples of secondary resources in the Indian scenario, mention&apos; can be made of spent catalysts, metal/alloy scrap, ash, consumed batteries, flue dust, slag, sludge and slime, pickling solutions, spent acids; plating rinse solutions, spent etchants, waste water from synthetic fibre manufacture and from tanneries etc. These wastes constitute a source of a variety of non ferrous metals. In the processing of secondary resources like these, the techniques of hydrometallurgy such as solvent extraction play a pivotal role. This paper outlines the efforts made to use solvent extraction to recover(1) base metals. such as copper, zinc, nickel and cobalt from a number of secondary resources like cake, and sludge(2) refractory metals like molybdenum and vanadium from sulphidic byproducts and spent catalyst and (3:) nuclear metal like uranium from phosphoric acid. In the case of base metals, process flowsheet involving the use of acidic extractants such as DEHPA and PC88A have been optimised. The problem of iron removal from the leach liquor, "which influences the metal recovery process significantly, has drawn a special emphasis. hi the case of refractory metals, basic extractants .like Alamine 336 has been pressed into service to produce kilogramme. quantities of pure salts of molybdenum and vanadium, Finally, the paper gives a brief account of plant experience in recovering uranium from phosphoric acid, using &apos;a solvent system comosed of DEHPA and TOPO.

Jan 1, 1996

By Luiz A. Teixeira

This paper reports the results of kinetic studies involving the precipitation of arsenic from aqueous solutions as FeAs041 Fe(OH)3&apos; using FeS04 as source of Fe ions, and Air or H202 as oxidizing agents. Both systems lead to an efficient removal of arsenic. The differences in oxidants performances are in the precipitation reaction rate -much faster using hydrogen peroxide. Mechanisms of reactions were suggested based on the following main steps:

Jan 1, 1996

By Liping Li

A comprehensive three-dimensional two-phase mathematical model was developed to represent a channel type reactor with intense bottom gas agitation. Tracer dispersion and particle tracing methods were used to conduct the analysis based on the solution of the Navier-Stokes equations. Different operational parameters, such is gas volume flow rate. bubbler separation aspect ratios and liquid Input flow rates, were investigated for the purpose of reactor optimization. The numerical calculations were compared with experimental results obtained at the University of Missouri and a good general agreement was observed. Relatively low longitudinal mixing was observed characterizing the system as a "plug-flow" type reactor, in contrast to the intense vertical mixing, under the conditions investigated. Some general mixing characteristics are also discussed In connection to the behavior of other metallurgical reactors.

Jan 1, 1996

By Christina V. White

An experimental study was undertaken to investigate the feasibility of utilizing vapor transport for the treatment of heavy metal contaminated smelter soils. The focus of this project was to develop process chemistries that would make incineration a viable process for the treatment these soils. The experimentation concentrated on the elimination of arsenic, cadmium, and lead, and was performed in a laboramry scale rotary kiln setup. Three soil samples from non¬ferrous smelter sites, which contained various concentrations of contaminants, were utilized in the experimentation. Three chemistries were investigated for the volatilization of the heavy metals: Chloridizing volatilization, ferric chloride vapor complex formation, and the use of oxygen potential control. The samples were analyzed for residual heavy metals so that the extractions could be determined. However, the ultimate test was the leachability of the residual arsenic, cadmium, and lead, as determined by the TCLP test. The results firmly establish that incineration is a feasible process for the treatment of metal contaminated soils. It was found that no one process chemistry is suitable for all different soil samples. A two-step process consisting of a reducing step followed by a hydro-chlorination step was required to make Soil Sample-B pass the TCLP tests for all three heavy metals. Soil Sample-A passed the TCLP tests for arsenic, cadmium, and lead using a hydro-chlorination process at a minimum temperature of 700°C. In addition to passing the TCLP mm for Soil Sample-A and Soil Sample-B, 70 to 80 percent removal of the impurities was accomplished. This demonstrates that the leachability of the impurities was decreased primarily due to the removal of a large fraction of the contaminants, Soil Sample-C possessed very high levels of cadmium and lead and only moderate extractions of the impurities were generated from this soil. The arsenic TCLP test was passed at 500&apos;C using a process gas containing ferric chloride and at temperatures of 700°C and above using chlorination of hydro-chlorination.

Jan 1, 1996

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