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By B. Mishra

The application of various bydrometallurgical, pyrometallurgical and electrochemical processes in the extraction, purification and production of radioactive metals as well as the use of various materials, eg. metals and alloys, ceramics, polymers, etc. in the process, construction and handling equipment in the nuclear industry has generated a large stockpile of radioactively contaminated waste material and scrap metal which can not be directly discarded, recycled or considered for long-term storage due to its volume and potential hazards, without the separation of radionuclides. This paper reviews the emerging methods that have been 'investigated and suggested for dealing with some of these wastes' and scrap material. The separation technologies studied for the recovery of radioactive components from the pyrometallurgical and electrochemical processing wastes have been discussed in details with results from some of the recent theoretical and physical modeling work as well as the data obtained? from the actual waste treatment. Specific processes shall be described in terms of its advantages and limitations. These emerging separation technologies are being considered by the US Department of Energy as alternatives for dealing with the issues of environmental management [EMI' and decontamination and decommissioning [D&D].

Jan 1, 1996

By A. M. T. S. Bandara

The solubility of rare earth (RE) salts in aqueous solutions depends on many factors including the type of cations and anions in solution, their concentrations, temperature and the type of solid precipitated. Experiments were conducted using anhydrous La2(SO4)3 and Ce2(SO4)3⋅8H2O as solids and lanthanum(III) perchlorate prepared by dissolving La2O3 in HClO4 solutions as RE-sources. Solutions of H2SO4, H3PO4 and their mixtures in the presence or absence of Na+, Ca2+, Fe(III) or Al(III) as perchlorates served as test solutions. Saturated solutions and precipitated solids were assayed and characterized using standard techniques to show that the La(III) and Ce(III) ions precipitate as hydrated sulphates, phosphates or double salts with sodium, depending upon the solution composition. The change in solubility of RE-salts with solution composition and temperature is the result of the composite effect of changes in solubility products (pKSP) of salts, pKa of acids and other equilibrium constants for ion-association.

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By Evgueni Jak

Pyrometallurgy is an important sector of modern industrial society actively participating in solving current environmental, economic, materials scarcity and other challenges. Recent advances in analytical methods, experimental techniques, thermodynamic, phase equilibria and process modelling tools provide new opportunities to increase the productivity of pyrometallurgical reactors, the treatment of complex feeds and metal recoveries. Fundamental theoretical models can now be used to make a significant next step towards the development and implementation of computerised models describing real industrial processes—Virtual Reactors, and computer-aided smart-decision-making systems that may be called Pyro-GPS by analogy to GPS; these developments can facilitate knowledge-based improvement and optimisation strategies. The implementation of these improvements require ongoing collaboration between researchers, industry and government.

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By Ravi S. Bellur-Ramaswamy, Daniel A. Tortorelli, Robert Haber, Nahil A. Sobh

We optimize continuous quench process parameters to produce functionally graded aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include 1) the process parameters to be optimized, 2) a cost function: the weighted average of the precipitate number density distribution, 3) constraint functions to limit the temperature gradient (and hence distortion and residual stress) and exit temperature, and 4) their sensitivities with respect to the process parameters. The cost and constraint functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine the precipitate particle sizes and their distributions. Both the temperature and the precipitate models are solved via the discontinuous Galerkin finite element method. The energy balance incorporates nonlinear boundary conditions and material properties. The temperature field is then used in the reaction rate model which has as many as 105 degrees of- freedom per finite element node. After computing the temperature and precipitate size distributions we must compute their sensitivities. This seemingly intractable computational task is resolved thanks to the discontinuous Galerkin finite element formulation and the direct differentiation sensitivity method. A three-dimension example is provided to demonstrate the algorithm.

Jan 1, 2001

By Edgar Peek

Lixiviant regeneration is by definition a precondition for any hydrometallurgical process. In chloride hydrometallurgy either HCl or Cl2 has to be regenerated in order to establish an economically viable metallurgical process. One such regeneration process is widely used with steel pickling where HC1 is regenerated through the thermal decomposition of ferrous chloride in either spray roasters or fluid bed pyrohydrolyzers. This standard HC1 regeneration process deserves to be considered as a potential separation process, since thermodynamic calculations show that a fluid bed pyrohydrolyzer can function as a ferrous-nonferrous separator. Several nonferrous,metals such as zinc, lead and cadmium can be volatilized as a chloride under ferrous chloride pyrohydrolysis conditions. If such a nonferrous metal volatilization could be achieved in the case of slurry feeding of "contaminated" iron oxides, then this would increase the Fe/H2O ratio of the (process) feed and thus save on fuel per ton of iron, while yielding a marketable iron oxide product. Previous test work on synthetic materials revealed that the near-complete separation of zinc, lead and cadmium from iron oxide was possible in a pyrohydrolytic atmosphere, even if zinc was present as zinc ferrite (more than 99.5%). This investigation, which was carried out in a tube furnace at 1100 K has now been extended to treat synthetic zinc minerals and also franklinite ore. For the latter, it was found that 85% zinc volatilization could be achieved in 4 hours at 1300 K. It is postulated that complete zinc volatilization could not be attained due to the formation and/or presence of gahnite and hardystonite, which might be stable in HCl/H2O atmospheres at 1100 K. The effect of adding small amounts of calcium chloride to react with gahnite and hardystonite to give zinc chloride and both calcium aluminates and silicates is being discussed. Test work on slurry feeding of this complex ore in a recently constructed 4-inch diameter fluid bed pilot unit has been planned for the near future.

Jan 1, 1995

By Vaughan R. Voller

"The wide range of length and time scales found in solidification processes are outlined and discussed. Methods for Direct Microstructure Simulation (DMS) are introduced. Key features in sharp interface and phase field models are presented. Concepts in micro-macro solidification modeling are covered. Basic details of microstructure and segregation models are provided. A description of a recent segregation micro-macro model is presented in detail.IntroductionA solidification process involves the containment of a liquid region, which, due to cooling, transforms over time to form a fully solid product. The development of the solid microstructure and the segregation of solute components during this transformation are controlled by phenomena that occur across a wide range of length and time scales. A ""successful"" model of a given solidification process needs to account for these phenomena. Standard models of solidification employ a discrete grid of node points and associated volume elements in the special domain, with a discrete time step to track the transient changes of nodal values, describing the composition and microstructure. Through the use of such models significant progress has been made towards a complete understanding of solidification process and phenomena (see the conference proceedings in Refs [1-9]). As solidification models become more sophisticated, however, they all run into the problem of resolving the full range of disparate space and time scales.Two approaches can deal with this problem1. Direct Microstructure Simulation (DMS) where the grid size and time step are chosen to scale with the smallest length and time scales of the given problem.2. Micro-macro modeling where the grid size and time step scale with the macroscopic process scale and phenomena at smaller scales are accounted for via sub-grid modeling and volume averaging.Currently full DMS of solidification is beyond the reach of available computer power and the application and development of micro-macro models is an important and critical research area."

Jan 1, 2001

By D. H. Magoon

The zinc smelter of Cominco Ltd. at Trail, B.C. Is the largest In the western world. A total of 550.000 tonnes of concentrate are proceed at the smelter annually. Approximately 80% of the zinc concentrate is roasted and the remainder Is treated by aqueous oxidation preaaure leaching. The zinc concentrate roasting and sulphur dioxide gas processing plants have undergone many changes over the years. This paper describes the processes and equipment currently used for concentrate roasting, S02 gas cooling and cleaning, mercury removal, sulphuric acid production liquid S02 production, and tall gas S02 scrubbing. The recent Installation of an advanced process control system for the operation of these Integrated processes Is also described.

Jan 1, 1990

By Daudi R. Waryoba

Keywords: Wire Drawing, OFHC Copper, Recrystallization, Orientation imaging Microscopy (OIM), Texture inhomogeneity Textural inhomogeneities have been investigated in oxygen free high conducting (OFHC) copper wire drawn at room temperature to a true strain of 2.31, and isothermally annealed at 250°C and 750°C for annealing times ranging from 10 s to 1 hr. Local orientations were mapped by means of orientation imaging microscopy (OIM). The microtexture of the drawn wires showed a strong <111> + weak <100> duplex fiber texture at the inner core, whereas the mid and surface regions had a comparatively weak texture. Annealing at 250°C resulted into a recrystallization which originated from the mid section, proceed towards the surface regions and ends in the inner core. Recrystallization resulted into a strong<100>+weak<111> duplex fiber texture. A similar textural inhomogeneity was observed during short annealing at 750°C. However, prolonged annealing gave rise to abnormal grain-growth that proceed from the inner core to the outer surfaces with a dominant <111> fiber component at the inner region and mixed components of <111>, <100>, and <112> at the outer surfaces.

Jan 1, 2005

By A. Kontopoulos

Refractory sulfide gold ores or concentrates require an oxidation pretreatment step to yield the contained gold amenable to the subsequent leaching step. The process options for oxidation pretreatment can be broadly classified as follows: roasting, high or low pressure oxidation bacterial oxidation, chemical oxidation, each with a number of alternative suboptions. Roasting and high pressure oxidation are being applied on an industrial scale; the stage of development of the other options range from preliminary laboratory to advanced pilot plant- In this paper, the major technical, environmental and economic aspects of the above processes are being discussed. Future industrial trends will also be considered. Particular emphasis will be placed on the treatment of arsenical ores and concentrates, where safe plant operation as well as, handling and disposal of the arsenic containing products and/or effluents &apos;and residues is of paramount importance.

Jan 1, 1990

By A. H. Rhoades

The modern polarizing microscope with such accessories as cameras, infrared devices, reflectance and/or transmission photometers, indention hardness, and heating stage is used to characterize coal, coke, and other carbon forms. It allows characterization of coke by-products, such as tars and pitches and their insoluble residues. A useful product of the microscopic approach is the coal petrographic analysis which permits the prediction of coke strength carbonization pressure and volume change. Carbonization tests are expensive, time-consuming and require large amounts of coal. Tests on the coke show it to be strong or weak but give no indication of why. Petrographic analysis requires grams of coal and yields data that indicates why the coal produces coke of a given quality. Small samples from drill cores are sufficient for petrographic analysis. These data are also used to optimize blends for coke production. When coke-plant problems occur, ~he microscope can be used to check the coal blend proportions, as well as for weathered coal. Microscopy is useful in spore correlation work which may be a prerequisite to sound coal reserve estimates. Dispersed vitrinoid reflectance studies are used to determine the degree of organic metamorphism which serves to establish oil and gas deadlines. Tars and pitches are examined microscopically for the amount of normal solids as well as the size of undesirable carry-over solids resulting from pollution abatement practices in coke works. The microscope is also used to study coals for gasification and liquefaction.

Jan 1, 1981

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 M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

By J. E. Dutrizac

Fracture-exposed surfaces of sphalerite samples having five different solid solution iron contents ranging from 0.0 wt% to 14.8 wt% Fe were leached for 15 to 120 s at 100°C in 0.3 M Fe(S04)1.5 -0.3 M H2S04 media. The reacted samples were examined using X-ray photoelectron spectroscopy (XPS) which provides chemical state information on the first few nanometers of the solid surface. Surface compositions show that the leaching rate increases with increasing solid solution iron content of the sphalerite. Detailed evaluation of high resolution S2p spectra show that the leaching progresses via the formation of polysulphide species. Disulphide species were not detected in any of the experiments. Examination of the Zn2p and Fe2p spectra indicate little change in the chemical states of these elements over the duration of the experiments. Longer leaching times resulted in the generation of elemental sulphur. The ratios of elemental sulphur to dissolved ferrous ions and zinc suggest that less than 5% of the sulphide is oxidized to sulphate. Morphological studies showed that the elemental sulphur commonly formed at a few isolated sites, such as the grain boundaries. Furthermore, euhedral sulphur crystals were often identified. These observations suggest that at least part of the elemental sulphur forms via dissolved sulphide species which are oxidized in solution by ferric sulphate.

Jan 1, 2003

By T. K. Bundtzen

Placer gold in the Iditarod and Innoko mining camps of western Alaska is derived from a suite of comagmatic, Late Cretaceous to Early Tertiary, alkali-calcic, meta-aluminous. volcanic-plutonic complexes and peralumi-nous rhyolite sills that intrude Mesozoic flysch. Heavy-mineral concentrates from 42 mining operations and streams draining known mineralized areas in the igneous complexes contain placer gold and a variety of ore minerals derived from epithermal to hypothermal conditions of formation. The minerals include cassiterite, ilmenorutile, samarskite, cinnabar, scheelite, chromite, stibnite, silver sulfosalts, monazite, and zircon. Results of the study show that 1) cinnabar. stibnite, and quartz formed with the bulk of the placer gold in an epithermal lode environment, 2) chromite appears to have originated in mafic phases of monzonite plutons and alkalic basalts, and 3) niobium-tin-tungsten-uranium-silver values may have been derived from stockwork accumulations in cupolas of monzonite plutons.

Jan 1, 1987

By Lloyd R. Nelson

The feasibility of producing low carbon (LC) ferromanganese (FeMn) by lime-&apos;ore&apos; melt refining of high-grade ferromanganese silicon (FeMnSi) was investigated. Thermodynamic simulations demonstrated significant benefits in moving from a single-stage ladle operation to a two-stage counter-current reladling operation (to emulate the commercial Penin Process). The theoretical alloy silicon content was predicted to be refined from 1.57 to 0.005 per cent silicon, at a 6.2 per cent higher manganese yield (yield predicted to increase from 82.3 to 88.5 per cent). Extension of this counter-current refining principle, to a multistage Counter-Current Reaction Launder (CCRL) was investigated using the Slag Metal And Gas Klnetics (SMAK) software to model the mass transfer kinetics of the multicomponent coupled reaction system. Simulation results suggested that commercial production of 50 000 tonnes per annum (tpa) of refined LC FeMn, containing less than 0.5 per cent silicon, at manganese yields of up to 90 per cent, should be feasible in a compact CCRL (7 m long by 0.7 m wide).

Jan 1, 1994

By H. Yin, T. Emi

"Advantages of gas/flux injection technology as materialized in the main stay unit processes for steelmaking are depicted covering hot metal pretreatment through secondary refining. Current status of micro-kinetic issues involved in the injection technology are reviewed including gas-in- metal, gas-in-slag, flux-in-metal, metal-in-flux and three-phase dispersion systems with reference to macro-kinetics. Key problems are briefly addressed to further develop injection technology for steelmaking processes.1. FROM PAST TO PRESENTApplication of gas injection to steel industry started in early 1950's when inert gas bubbling via stopper rod, lance, or porous refractory plug was practiced to make the temperature of steel melt in ladle uniform The gas bubbling in ladle was then extended to slightly removing hydrogen ti'om the steel melt tapped from Electric Arc Furnace (EAF) and Basic Open Hearth Furnace (BOH) when vacuum processing facilities were not popular. Later, oxygen gas injection via calorized steel pipe into molten steel bath in BOH Furnace was also put into operation to promote the decarburization to increase the productivity of the process. This line of development has been made in parallel with more profound processes, i.e, top blowing Basic Oxygen Furnace (BOF) for primary steelmaking and side blowing Argon Oxygen Oecarburization (AOD) vessel for decarburizing stainless steels.On the other hand, injection of fluxes into steel bath was first industrialized in Germany in 1960's, Primary objective was to desulfurize steel melt in ladle by injecting CaC2 or CaCrCaO mixture via lance under neutral slag cover with good success. Difficulties in injecting fluxes without clogging and rippling at a desired flux/gas ratio, and durability of injection lance were resolved in due time to bring forth many injection facilities to flourish for versatile refining operation. Top injection of fluxes from main oxygen lance to BOF was also industrialized as LDAC to promote early slag formation. A new process then emerged which injects oxygen gas and fluxes together through concentric annular tuyere, installed at the bottom of the BOE into steel melt. This process, developed in Germany [Oxygen Bottom Maxhutte (OBM)] and brought into maturity in USA (Q-BOP) and Japan in a large scale operation, became the predecessor of the combined blowing (top and bottom blown) BOF which dominates modern steelmaking."

Jan 1, 1996

By Mark Samonds

"Manufacturing processes which involve liquid to solid and solid state transformations in metals encompass a wide variety of physical phenomena. The past twenty years have seen a steady evolution in the complexity and scope of numerical models of these processes, beginning with thermal analyses without phase change. Recently, a few software packages have become available which have true multi-physics capabilities. This permits the treatment of thermal, fluids, stress, electromagnetic, chemical reaction and microstructure development aspects altogether in a fully coupled simulation. This paper will consider various aspects of these types of models.Coupled thermal and fluid flow analyses of continuous castings have been around for fifteen years. Coupled thermal and free surface fluid flow simulations of shape castings have been available for ten years, including view factor radiation models for investment castings. Only recently, however, have fully coupled thermal, fluid, and stress analyses become practical. This implies the reverse coupling of the mechanical deformations to the solution of the energy and momentum equations through modification to the interface heat transfer coefficients and the fluid domain geometry. This has been implemented with a combined eulerian-lagrangian finite element method. Appropriate mechanical constitutive models will also be discussed.Many types of defects need to be predicted in casting processes. Those related to stress include hot tearing, hot cracking, part distortion, and thermal fatigue in dies. Macroporosity, microporosity, and microsegregation are determined by the solidification behavior and microstructure development in a casting. In particular, microporosity is influenced by dissolved gases, the morphology of the mushy zone, the liquid to solid density change, and the local pressure conditions. Macrosegregation is caused by the partitioning of solutes during. solidification and subsequent thermo-solutal convection. An additional transport equation is required for each solute that is being tracked. Computational thermodynamics is being incorporated into these types of analyses to determine transformation temperatures, partition coefficients, densities, and enthalpies. In combination, the microstructure and microporosity models can frequently predict a variety of mechanical models, such as yield strength, tensile strength, and elongation."

Jan 1, 2001

By Adam Powell, David Dussault

"Electric Field-Enhanced Smelting and Refining is a process for driving the reaction between carbon in hot metal and iron oxide in slag, for example, in a steelmaking reactor. This process involves inserting electrodes into the slag and metal phases, such that the overall reaction FeO + C -> Fe + CO is separated into two half-cell reactions: Fe2+ + 2e· -> Fe at the cathode in the slag, and C + O 2 • -> CO + 2e· at the anodic slag-metal interface. Without the electrodes, the reaction is very slow, but with electrodes, the additional surface area available to the ferrous ions for reduction accelerates the reaction even without any applied bias. When a bias is applied to the electrodes, the electric field across the slag further accelerates the overall reaction.With or without applied bias, the process is first-order in the ferrous ion concentration, and limited by ferrous ion transport to the cathode. To complicate matters, as the liquid iron is reduced at the cathode, the Mullins-Sekerka instability leads to formation of dendrite-like liquid iron fingers which grow into the slag. Because of this, the design of the cathode can have a significant effect on the overall process kinetics, and understanding of the dynamics of these fingers and of their effect on mass transfer is necessary for the intelligent design of the overall process and the cathode in particular.Toward this end, a detailed mesoscopic two-phase slag-metal model is presented here which describes multi component diffusion in the slag and fluid flow in both phases in the vicinity of the cathode. Diffusion in the slag is driven by chemical and electrical potentials. The phase boundary is modeled as a diffuse interface using a phase field approach. Because this electrochemical reaction occurs at high-temperature, the kinetics of charge transfer and adsorption through the double layer are fast relative to transport, permitting the use of simple linear reaction kinetics. This also eliminates the need to discretize the double layer, with the result that charge neutrality may be assumed everywhere in the domain. Introducing electric field dependence of the gradient potential and well height coefficients in the free energy function allows the model to capture electrocapillarity at the interface."

Jan 1, 2001