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By D. Gu, R. G. Anthony, C. V. Philip, 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 column, 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's law with the Nemst-Planck equation as the constitutive equation for diffusive flux. We use a NemstPlanck type model to predict batch experimental data, then evaluate it by comparing it's ability to predict experimental data to that of a more traditional Fick's law type model. The data from this comparison suggests that the Nemst-Planck type model yields better results.IntroductionMillions of gallons of strongly basic, radioactive waste are currently stored in underground storage tanks at Hanford and Savannah River and several locations within the United States. Due to the limited life expectancy of the tanks, there is a pressing need to remediate these wastes. This need has prompted the recent development of new ion-exchange materials for removing radioactive elements from aqueous solutions. A novel material called TAM-5 has been developed jointly by Texas A&M University and Sandia National Laboratories. TAM- 5, a crystalline silico-titanate, is highly selective for Cs + in the complex electrolytic solutions typical of these wastes. It is stable in very basic solutions and in radioactive environments [1, 2 ,3]. In laboratory testing to determine the selectivity of various materials, TAM-5 was superior to other candidate ion exchangers [4, 5]. The selectivities were determined by measuring a distribution coefficient, Kd, which is defined as the concentration, gig or mmols/g of Cs in the solid phase divided by the concentration, mg/L or mmols/mL, of Cs in the liquid phase. The units of Kd are ml/g or L/kg. Table 1 shows Kd values for TAM-5 compared to 9 other candidate materials in a typical waste solution [6]."

Jan 1, 1996

By Ann M. Hagni

"Ceramic matrix composites are inorganic materials that are particularly resistant to heat and abrasion. A magnesia (MgO) and aluminum nitride (AlN) based composite is formed by exposing a magnesia preform to a metallic alloy block in a nitrogen atmosphere at 950°C. The metallic alloy, which is composed primarily of aluminum, is wicked into the preform. Aluminum nitride matrix is grown between MgO particles as the wicked metallic aluminum reacts with nitrogen. Unused metallic alloy, remnant metallic alloy (carcass), and composite produced after 8 hours, 50 hours, and 225 hours of processing are characterized mineralogically. Reflected light microscopy, transmitted light microscopy, scanning electron microscopy, energy dispersive spectroscopy, and X-ray diffraction techniques reveal that in addition to anhedral to euhedral AhNi, AbSbSr, and Al crystallizing in the metallic alloy carcass, AIN and (Al,Si)N have formed as well. Nitride rings and nodules in the carcass may hinder AIN growth in the composite. Fine-grained residual AhNi and AhShSr are dispersed throughout the composite matrix. The nitride matrix is composed of AIN and (Al,Si)N. Rim replacement of MgO by spine! occurs in the composite. Aluminum nitrides in the metallic carcass cathodoluminesce deep violet-blue, unlike non-luminescent AIN in the composite matrix. This distinction in cathodoluminescence suggests a different mode of formation for composite AIN than for carcass AIN. Phase interpretations and textural characterizations deduced from the implementation of sophisticated mineralogical techniques have contributed to the understanding, and will aid in the improvement, of MgO/ AlN-based ceramic matrix compositeprocessing."

Jan 1, 1999

By John Wallace, Chib Iheagwara

"Refinements in sensor design have produced low-cost rugged elements to act as loop coupled with stable detection hardware for eddy current measurement in difficult environments. This has allowed direct dimension gauging of nonferrous and ferrous products above the curie point for absolute dimensions and electrical conductivities independently. The software was developed for the analysis of electrical conductivity profiles in CZ silicon crystal growth, then refined for monitoring bar properties and tube properties. Since in most metal working operations, speeds at the minimum of a few hundred feet per minute are encountered the design of the gauge was optimized for a rapid measurement. Independently extracting electrical conductivity provides data in some metal systems for determining the temperature of the monitored product.IntroductionThe primary reason for the use of eddy currents in gauging is that in hostile environments of metal working techniques such as laser gauging and ultrasonics are not always robust enough for in process measurements. Our goal is to use the technique of eddy current measurement as a quantitative control element in various hot and cold processing operations. Inspection in the early stages of metal and semiconductor processing is usually too costly to introduce in a well developed process and these tools are usually only employed in process development. Until recently there has been no efficient general analysis to allow real time measurements in the cylindrical and the probe geometry that could separate dimensional changes from material property changes both which effect the eddy current response. The basis for these measurements is that forward electromagnetic problem for conductors can be solved exactly for the test geometry which allows an inverse analysis to be made by relaxing the dimensions and conductivity to values which reproduce the measured response[!]. This transformation is based on analysis developed in Robert Siegfried' s thesis and was explored both by modeling and by physical measurement. This analysis was extended over the last few years to allow a more compact data set to be used to exact physical properties. The main result was that the technique would work on high ·quality physical data on as little as three test frequencies with the penalty being that the analysis is computational intensive. The main result of this work was that a quantitative inverse analysis of eddy current response would allow a general instrument to be used for a variety of measurements rather than being tailored for a specific measurement on a specific material test geometry. The development of these instruments has progressed over the last ten years for monitoring real time solidification, crystal growth[2] and hot seamless tube forming where the use of standards in traditional eddy current is limiting. The specific instrument design was dictated by the requirements of the algorithm for both frequency selection and levels of systematic noise that could be tolerated. Because the data is need for real time information this dictated that the system be a parallel multifrequency eddy current instrument feeding the same sensor. The sensor have to be simple and robust and usually a single loop or several loop of heat resistant wire or tube. This presentation is about using inversion of multifrequency eddy current data in real time to produce dimensional and property data on cylindrical conductors and planar conductors in real time. The object of the measurements is to produce dimensional outputs on measurements of conducting material without having to establish a detailed standard for each material or size tested. The dimensional measurements using eddy currents is complicated by material variations in conductivity due to temperature and composition. Those variations that are not geometric are often not of critical interest and complicate the measurement. The dimensional changes are often of more importance"

Jan 1, 1997

By Amy Nelson

In the electrolytic production of zinc, cobalt is removed from the zinc electrolyte by cementation with zinc dust prior to electrowinning. Although the thermodynamics for this reaction are favourable, kinetic barriers to cobalt reduction render the method almost useless in practice unless activators such as copper and antimony or arsenic are added. There is a large body of work studying the effect of these additives, yet the mechanism by which they act is still poorly understood. Even when the target conditions are met, zinc dust consumption is excessively high: satisfactory operation requires up to 300 times the stoichiometric amount of zinc dust. The objective of this work is three-fold: (1) to examine the effects of activators and elucidate the characteristics that make a good activator; (2) to identify new additives that could lead to a more efficient purification process; and (3) to test the new additives with synthetic and real electrolyte solutions. The present paper gives a status report on this project.

Jan 1, 1998

By den Bulck A. Van

In Europe, 50% of the copper originates from recycling. High-Cu containing scraps are regularly rich in impurities like Fe, Ni, Sn and Pb. Many high-Cu containing scraps are fed directly into anode-furnace casting installations or furnaces with limited refining capability. The impurities levels of the anodes produced in these processes should however remain acceptable for further electro-refining. The distribution of Sn between copper and slag has been investigated for conditions relevant to copper converting. Unlike previous studies, this work focuses on the behavior of Sn relevant to fire refining conditions, which are essential for anode refineries.In this study, liquid Cu–1Sn and CuOx–FeOy–SiO2 slag, with CaO additions, were equilibrated at 1300 °C in vacuum sealed SiO2 ampoules. After metal–slag equilibration, the samples were quenched in water. The composition of the slag and Cu metal was investigated with Electron Probe X-ray Microanalysis. The distribution coefficients of Sn between slag and Cu metal were determined as a function of slag composition.

By S. A. Shuey

The present industrial practice used to separate aqueous cobalt from nickel is multistage solvent extraction processing. This paper describes a different but simpler treatment technology. The proposed technology has been applied to cobalt/nickel hydroxide intermediate solids produced from the treatment of Electrochemical Machining (ECM) waste sludge, The process consists of dissolving the cobalt/nickel hydroxides in basic cyanide solutions. Cobalt and nickel form aqueous .solution metal cyanide complexes. Nickel can be selectively precipitated from the solution as a nickellic hydroxide solid. Cobalt can be recovered from the leach solution by precipitation of a cobaltous/cobaltic cyanide double salt. The double salt product can then be subsequently treated to produce an appropriate cobalt product. The process chemistry, proposed fiowsheet and preliminary reagent costs are presented and discussed.

Jan 1, 1998

By Roderick I. L. Guthrie, Donghui Li, Mihaiela Isac, Luis Calzado

The HSBC is an ideal process for the production of BMG strips. The purpose of the present work was to investigate the casting of Ca-based, bulk amorphous strips. The possibility of casting three Ca-based alloys (60Ca-20Mg-20Al, 60Ca-15Mg-10Al-15Zn and 55Ca-15Mg-10Al-15Zn- 5Cu (at.%).) was investigated, using the HSBC simulator. Numerical simulation and mathematical modeling were used to predict temperature variations and cooling rates, under different interfacial gaseous atmospheres (helium and air) near the meniscus region. Given the critical cooling rates and glass temperatures needed to be reached for the vitrification of the respective alloys, this leads to predictions of the critical thicknesses possible with this novel casting process. To validate our predictions, these alloys were then prepared and cast onto the sand-blasted, solid copper substrate mould of the HSBC simulator. The possibility of producing Ca-based metallic glassy strips via the HSBC processes was confirmed, using optical microscopy, X-ray diffraction and Scanning Electron Microscopy, to characterize the glassy properties of the cast strips. It was found that the HSBC process would be able to provide sufficient cooling to form amorphous strips for the 60CA-15Mg-10Al-15Zn and 55Ca-15Mg- 10Al-15Zn-5Cu alloys, but not the 60Ca-20Mg-20Al alloy.

Jan 1, 2014

By John J. Jonas, Sang-Hyun Cho, Ki-Bong Kang

"The recrystallization behavior of Nb micro alloyed steels containing Cr, Mo, Ni and Ti. was studied using hot torsion testing with the aim of modeling the recrystallization processes and the mean flow stress taking into account the microstructural behavior during hot rolling. The kinetics of static and metadynamic recrystallization were characterized and appropriate expressions were formulated for the recrystallization kinetics. These are shown that the recrystallization kinetics depend on steel composition and the processing conditions. The stress-strain curves were determined in order to derive new equations for the peak stress, peak strain, mean flow stress and softening kinetics. The peak strain is influenced by the presence of alloying elements; their addition, which has a solute drag effect, retards the rate of grain boundary motion, shifting the peak to the right. The addition of Nb to the steel results in a significant increment in the activation energy for hot deformation, and Mo has smaller effect than Nb, but Cr has the opposite effect. It was also found that the deformation activation energy in these steels was not altered by the addition of Ni. The rate of metadynamic recrystallization increases with strain rate and temperature and is observed to be independent of strain, in contrast to the observations for static recrystallization.The mean flow stress (MFS) calculations, based on the Sims analysis, are then compared with the predictions of a model based on an improved Misaka mean flow stress equation in which solute effects, strain accumulation, as well as the kinetics of static and metadynamic recrystallization are accounted for. Good agreement between the measured mean flow stresses, which is obtained from the mill logs of POSCO Kwangyang #3 HSM (hot strip mill), and 'predicted ones is obtained over the whole range of rolling temperatures. The results demonstrate that dynamic recrystallization followed by metadynamic recrystallization, supported by the unexpected load drops, sometimes occurs for the rolling schedules studied in the present analysis."

Jan 1, 2001

By H. Hahn, B. H. Kear, K. Kan, S. C. Danforth, G. Skandan, W. Chang

"A new chemical synthetic process for the production of non-agglomeratednano structured ceramic (n-ceramic) powders, starting from metalorganic precursors, is described. The process combines rapid thermal decomposition of a precursor/carrier gas stream in a hot tubular reactor with rapid condensation of the product particle species on a cold substrate. Critical to the success of this Chemical Vapor Condensation (CVC) process are (1) a low concentration of precursor compound in the carrier gas, (2) rapid expansion of the gas stream through an uniformly heated tubular reactor under a reduced inert gas pressure of 1-35 mbar, and (3) rapid quenching of the gas phase nucleated clusters or nanoparticles as they exit from the reactor tube. A wide variety of metal organic precursors is available commercially, all of which can be utilized in the CVC process to produce n-ceramic powders, including single phase, multiphase and multicomponent systems.The CVC process has been used to synthesize non-agglomerated n-SiCxNy and n-ZrOxCy powders, with controlled particle size in the range 2-20 nm. Heat treatment of the assynthesized n-powders in various high purity gas streams causes compositional and structural modifications, including particle purification and crystallization, as well as transformation to a whisker-like morphology. Thus, as-synthesized amorphous n-SiCxNy particles transform to (1) cubic n-SiC particles, when heated in flowing argon at temperatures> 1350 °C, (2) hexagonal n-Si3N4 whiskers, when heated in flowing NH3IH2 at 1400 °C, and (3) cubic nSiC whiskers, when heated in flowing H2 at 1400 °C.Non-agglomerated n-ceramic powders form uniformly dense powder compacts by cold pressing, which can be sintered to theoretical density at temperatures as low as 0.5 Tm' For example, full densification ofn-Zr02 powder compacts under free sintering conditions can be achieved at 1125 °C."

Jan 1, 1994

By Matthew Jeffrey

Due to the increasing environmental and public concerns over cyanidation, there has been a large amount of research into viable alternative lixiviants. Despite these studies, there is little published data directly comparing the kinetics of gold leaching for each of these alternatives: most of the literature is concerned with gold extraction from ores. This paper presents a detailed kinetic study of gold leaching in cyanide, armmonia/thiosulfate and chloride/hypochlorite solutions. The gold leach rates were measured using a rotating electrochemical quartz crystal microbalance (REQCM). This instrument allows the mass of a gold sample to measured in?situ, with a sensitivity of less than 10 ng. From the results of these studies, it is possible to select experimental conditions where the leach rates of the alternative lixiviants are similar to that for the traditional cyanide system.

Jan 1, 1998

By R. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

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' 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 N. D. Schupp

The Doe Run Company's Herculaneum, Missouri lead smelter has existed in continuous operation since 1892. Throughout the history of the plant extensive developments have been made to improve throughput, increase productivity, decrease operational costs and improve technology, while remaining an environmentally responsible producer of high quality primary lead in the international market. This paper provides an overview of the Herculaneum smelter, focusing on the most recent configuration of the operations. The paper includes discussion on all the aspects of primary lead production at the Herculaneum smelter.

Jan 1, 2000

By E. Maziar Sauber

In order to prepare a more desirable feedstock for a rare earth elements separation refinery, cerium, a penalty element in the refinery feedstock, should be removed from the mixed rare earth elements oxide or carbonate feedstock. In this study, cerium (III) to cerium (IV) oxidation by calcium hypochlorite and subsequent precipitation was used to remove cerium from a mixed rare earth elements chloride solution. A factorial design of experiments was used to determine the effect of process variables such as temperature, pH, and oxidizer addition on the oxidation of cerium (III) using synthetic solutions. Under certain test conditions, all of the cerium was successfully removed from the chloride solution, and some REE accompanied cerium and reported to the precipitate. This proposed technology can allow for low cost removal of cerium from mixed rare earth elements chlorides.

By P. Meyers, F. DeSilva, L. Gottlieb

A number of tests looking at lead removal using ion exchange resins of various types from various aqueous streams have been undertaken. The tests focused on strong acid cation (SAC) and weak acid cation 0N AC) resins. It was found that the mechanism of lead removal is partly by lead filtration rather than solely by ion exchange in a large portion of the applications studied. This is not surprising since lead carbonate is essentially insoluble and almost all water supplies contain at least some carbonate alkalinity. Regeneration of lead from exhausted resins containing significant amounts of lead may not be practical in some cases because of the large chemical and waste volumes involved. Since lead, .·along with many other very insoluble metals, is often present as a suspended solid rather than in ionic form, ion exchange is probably not always the best technology for bulk lead removal.

Jan 1, 2000

By Dalene Joalet Steenkamp

Excavation of industrial-scale furnaces allows for the systematic study of reaction sequences by identifying the different reaction zones within the furnace. In 2013, Transalloys excavated a 48 MVA submerged arc furnace that was used for silicomanganese production using the ore-based route. The excavation method was reported elsewhere as was observations made in terms of refractory wear and modes of electrical energy dissipation prior to excavation. The paper presented here, reports on the process reaction zones observed during the excavation and subsequent phase chemical analyses of a number of process samples obtained during the excavation. The zones identified were a loose burden zone, a dry coke-bed zone, a wet coke-bed zone, a hard build-up zone, and an alloy zone. The results are compared to observations made in the excavation of an industrial-scale SAF and a pilot-scale SAF in Norway. The presence of the hard build-up zone below one of the electrodes and absence of a slag zone below all three electrodes are unique features of the SAF excavated at Transalloys.

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By U. M. Mutnti

In order to meet the stringent market requirements for high purity cobalt, ZCCM commissioned the VIR plant in December 1982. The plant comprises a 4.1 tonne/heat vacuum induction furnace with a rated annual capacity of 2,500 MT of barstock. In the VIR furnace, molten cobalt is held under vacuum at 1600°C resulting in the removal of more volatile impurity elements by distillation. Operations todate have demonstrated that Pb, Zn and Cd have good distillation rates in excess of 95%, leading to cobalt containing 1 ppm or less of the above elements. Removal of other impurities such as Se, Bi is about 65% with the finished product still assaying around 1 ppm of each of these elements. Vacuum refining of cobalt offers an economic route for producing higher grades of cobalt from the type of concentrates and treatment processes available within ZCCM. The consistency of VIR cobalt quality has been confirmed by ZCCM and some of its alloy customers.

Jan 1, 1988

By Neng-Wen Yu, Shau-Jun Zhu, Ji-He Wei

The desulfurization process by powder injection and blowing in the RH refining of molten steel and its mechanism have been considered and analyzed. Based on the two-resistance mass transfer theory and the mass balance of sulfur in the system, a kinetic model for the process has been developed. The related parameters of the model, including the mass transfer coefficients and the effective amount of powder in the molten steel being treated for desulfurization, have been more reasonably determined. Modeling and predictions of the process of injecting and blowing the lime-based powder flux under assumed operating modes with the different initial contents of sulfur and amounts of powder injected and blown in a RH degasser of 300 t capacity have been carried out using the model. The relevant circulation rate of the liquid steel and the powder injection and blowing rate were taken to be 100 t/min and 150 kg/min, respectively. The initial contents of sulfur in the liquid steel to be treated and the amounts of powder injection and blowing were respectively assumed to be 0.007, 0.006, 0.005, 0.004, 0.003, 0.002 mass-% and 10, 8, 6, 5, 4, 3 kg/t-steel. The total treatment time for desulfurization under each mode was set up at 24 min, equivalent to eight circulation cycles of the liquid steel to be treated. The results indicated that the predictions made with this model are in good agreement with some data of the industrial experiments and practice. Injecting and blowing the lime-based powder flux with the composition of 85 mass-% lime (CaO) + 15 mass-% fluorspar (CaF2) of 3-5 kg/t-steel, it is possible to decrease the sulfur content in the molten steel to ultralow level below (5-10)x10·4 mass-% from (60-80)x 10·4 mass-%. The total treatment time needed will appropriately be 12-20 min. Intensifying the powder injection and blowing operation and increasing the circulation rate of the liquid steel may effectively' raise the rate of the process in RH refining. The model may be expected to offer some useful information and a reliable basis for determining the reasonable process parameters and help in optimizing the technology of desulfurization by powder injection and blowing in the RH refining of molten steel.

Jan 1, 2000

By Anil Saigal, Jr. Fuller, Said Jahanmir

"All-ceramic crowns, including glass-infiltrated spinel composites, are coming into widespread use because of their superior aesthetics and chemical inertness. This study investigates the residual stresses that are developed in these composites as a result of cool down from the glass-infiltration temperature to room temperature due to slight mismatch in the coefficients of thermal expansion and its effect on the mechanical behavior of these composites. Two-dimensional finite element simulations were performed using an object oriented finite element program OOF. The OOF program is a combination of two programs. The first program, PPM200F, is designed to read an image file such as a micrograph. The individual pixels that constitute the micrograph may be collected into groups and their material properties assigned. PPM200F is then used to create the finite element model/mesh that OOF then reads. The average residual stresses are found to be tensile in the spinel matrix and compressive in the infiltrated-glass. There is large variation in residual stresses and strains from location to location with presence of locations at which the glass is under tensile stress. The crack initiation and initial propagation in glass-spinel composites is at the glass-spinel interface in both the glass and the spinel. The presence of residual stresses can lead to lower crack initiation stresses and degrade the mechanical properties of the composites.IntroductionGlass-infiltrated spinel ceramics are in clinical use as core materials in all-ceramic crowns and as inlays and onlays (1-3). Advantages of ceramic composites include near net-shape forming with high strength in the infiltrated state. Besides, spinel is quite translucent and may potentially be used without a veneer. However, these ceramic composites are subject to damage accumulation from repeat oral contact loading and often fail after a few years of use (4). This paper examines the residual stresses that are developed in these composites, after cooldown from the glass infiltration temperature to room temperature, due to the slight mismatch in the coefficients of the thermal expansion of the two phases."

Jan 1, 2001