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By Patrick R. Taylor

Iron phosphate glasses are promising host matrices for vitrifying actinide rich nuclear wastes materials because of their high solubility of actinide oxides, high chemical durability, and relatively low melting temperatures. An iron phosphate waste form was developed at the University of Missouri-Rolla. The structure and property of the waste form were well characterized by materials techniques. However, to scale the process and advance it to commercial viability, it is necessary to understand the processing parameters, such as the partitioning of waste elements and the viscosity as a function of temperature. Viscosity of 40 Fe203 - 60 P205 mole % iron phosphate melts (prepared with phosphorous pentoxide and ferric oxide) at 1000-1200 C was measured by the rotating-spindle method. It was discovered that this fluid has non-Newtonian behavior. Experiments were performed to study flow properties following the Standard Test methods for Rheological Properties of Non-Newtonian Materials by Rotational (Brookfield) Viscometer (ASTM D 2196-86). Samples prepared using ammonium phosphate and ferric oxide showed Newtonian behavior and the temperature dependence of the viscosity was studied over the range of 1000 to 1200 degrees C. The difference in flow behavior between the two fluids was analyzed in terms of preparation conditions and variation in the final composition and phases. The partitioning behavior of waste elements in the iron phosphate glass was studied by melting in a high temperature furnace and JCP analysis. The experimental results show that the solubility of Ce and Sr in phosphate glasses is significantly higher than the solubility associated with borosilicate glasses. This strengthens the conclusion that iron phosphate may be a viable alternative to borosilicate glass for immobilization of high heavy-metal-content wastes and actinide rich wastes.

Jan 1, 2002

By J. E. Wey

Extraction of cobalt from cobalt sulfide and cobaltite flotation concentrate from the Blackbird Mine, Idaho, was investigated using an adapted strain of Thiobacillus ferrooxidans. Cobalt extractions as high as 100% were realized in the inoculated experiments, whereas only 4% extraction was obtained in the sterile run. The influence of pulp density on the rate and extent of cobalt extraction was also determined. It was found that the extraction of cobalt followed predominantly the indirect mode of bacterial activity. In this process, ferric iron oxidizes cobaltite to cobalt sulfate and ferric arsenate while being reduced to its ferrous state; the bacteria continuously re-oxidize ferrous to ferric iron. Electrochemical measurements using cyclic voltammetry suggested that cobaltite oxidation involved a number of intermediate reactions.

Jan 1, 1993

By Marcelo B. Mourão

An experimental investigation was carried out to -study the rates of reduction of pellets containing iron oxides by carbon dissolved in liquid iron, at temperatures ranging from 1720 K to 1973 K. Several different pellet types were employed; the materials used in the pellet's manufacture were pure hematite, two kinds of commercial iron ores, and mixtures hematite/silica and hematite/lime: Reaction times were determined employing the constant volume pressure increase technique (CVPI). It has been observed that the reaction rate increases as the temperature and the pellet's specific surface area increases. The reaction rate is also affected by the oxide type: pellets made from commercial ores or from mixtures hematite/silica or hematite/lime show reaction rates lower than those made from pure hematite.

Jan 1, 1996

By Tan Pengfu

By using computer-aided techniques of equilibrium calculations for multicomponent and multiphase systems, a computer model has been developed to simulate QSL, KIVCET and Outokumpu flash lead smelting processes. A mathematical description is studied using two zones or three zones, namely smelting zone and slag reduction zone for QSL furnace, or offtake shaft zone, smelting shaft zone and electric furnace zone for KIVCET furnace. The amount of each component in lead, slag and gaseous phases under equilibrium is calculated by using the data of free energies of formation and activity coefficients. The predictions by the present computer model are compared with the known data from QSL-Plant at Korea Zinc Co. in Korea, KIVCET-Plant at Nuova Samim Co. in Italy and Outokumpu Co. in Finland. The agreements between the computer predictions and the known data are excellent, so that the present computer model can be used to monitor and optimize the actual industrial operations of direct lead smelting.

Jan 1, 1998

By R. W. Lawrence

A method by which it is possible at an oxidation potential below 680 mV SHE to achieve quantitative conversion of sulphide sulphur to elemental sulphur instead of sulphate in a biological leach of chalcopyrite and bornite has been investigated. The process chemistry, biological phenomena and process flowsheet options are discussed. Several copper concentrates have been evaluated and have been found to be amenable to th process. Results to study the progression of chalcopyrite decomposition during the leach are presented and mineralogical factors affecting the requirement for silver addition are discussed. A chloride addition method for improving silver recovery is described. The results of a small scale continuous leach test have demonstrated that continuous operation can be carried out with high copper extraction and stoichiometric conversion of sulphide sulphur to elemental sulphur.

Jan 1, 1985

Many studies have been conducted over the past 3 decades on the leaching of gold in solutions containing thiosulfate, ammonia and copper. However, most of these studies have been carried out using ore samples, with very few fundamental studies of this system being attempted. The majority of the published studies have failed to acknowledge the undesirable side reaction between copper(H) and thiosulfate, let alone account for its effect. The fact that the solution chemistry is constantly changing makes it very difficult to perform a fundamental study of gold leaching. With the advent of the rotating electrochemical quartz crystal microbalance (REQCM), such fundamental studies are possible as this instrument measures mass in real time. This has allowed leach kinetics to be measured in a matter of minutes and hence at essentially constant solution conditions; The present paper highlights that a sufficient concentration of copper(II) and ammonia are required in order to achieve appreciable gold leach rates. However, the use of air (oxygen) to maintain the copper(Il) concentration catalyses the undesirable copper(II) reaction with thiosulfate. The presence of ammonium ions is shown to have an effect on this undesirable reaction as well as on the gold leaching ?reaction. Preliminary electrochemical studies into .gold electrowinning using the REQCM show that gold(I) thiosulfate cannot be readily reduced to metallic gold in the potential region at which cementation usually occurs. However, it is well known that gold cementation onto copper occurs rapidly. The current study addresses this discrepancy by studying the effect that copper and silver have on the reduction of gold thiosulfate. It has been found that the presence of both silver and copper enhance gold deposition, particularly at low over potentials. While this is beneficial in cementation, the presence of copper and silver in solution has been found to cause passivation of the cathode surface during electrowinning at 'higher overpotentials.

Jan 1, 1998

By Michael J. Nicol

This paper summarizes some of the results of a study of the reactions involved in the Caron leaching process and identifies the roles of the major dissolved species in the kinetics of dissolution of iron alloy particles formed during reductive roasting. Using rotating disk electrodes and synthetic leach solutions, the reduction of water with the evolution of hydrogen was found not to occur on a dissolving iron surface under typical leach conditions. It has been established that the oxidative dissolution is governed primarily by a reaction involving reduction of Co(III) to Co(II) ions. The reduction of oxygen was also found to make a significant but largely indirect contribution to the kinetics of the dissolution process. The dissolution rates of various iron-nickel-cobalt-copper alloys which simulate the dissolving alloy particles in a Caron plant were measured in synthetic leach solutions under aerobic and anaerobic conditions. The initial dissolution rates of iron, nickel and the iron alloys were found to increase in the presence of thiosulphate, whereas the thiosulphate had a negative effect on the dissolution rates of cobalt and copper. It is shown that the eventual passivation of the iron occurs sooner in solutions rich in Co(II) ions. Whilst these conditions are present in the quench slurry, on-site measurements have shown that due to the very high concentration of reduced dissolved species, passivation does not occur until the slurry is strongly aerated. In the light of these fundamental findings, options for optimizing the rate of dissolution and minimizing the extent of passivation of the iron and iron alloys are discussed. Keywords: Ammonia, leaching, alloy, kinetics, passivation.

Jan 1, 2004

By Kazuhiro Asai

Nippon Mining and Metals Company has an annual indium production capacity of 30 tons at its Saganoseki smelter and refinery. Lately, indium content in the. zinc smelting dust, one of the main sources, has been on the decrease while the amount of impurity in it on the increase. The present process at Saganoseki does not permit efficient elimination of a large. amount of impurity. Therefore, studies were conducted to improve its recovery process. As a result, a new indium recovery process consisting of leaching, solvent extraction and electrowinning has been developed. The new process was tested at a pilot plant and satisfactory results were obtained. This new process is discussed in this paper.

Jan 1, 1995

By F. Chabchoub

A mathematical model has been developed to study the influence of process variables on the horizontal Ohno continuous casting process. The model simulates the heat transfer and fluid flow in a wide plate ingot of pure tin. A two dimensional numerical analysis based on a control-volume finite difference approach, the Semi-Implicit Method for Pressure-Linked Equations algorithm (SIMPLER), and an Enthalpy Transforming Model was used. The shape and position of the solid-liquid interface were calculated at different casting speeds, ingot thicknesses, and cooling device characteristics, as well as various mould temperatures. Results of the mathematical model were compared with

Jan 1, 1992

By Julie M. Melluish

The metallurgical response of the Point Leamington deposit has been studied. Two series of bench tests were conducted and various ore samples and flotation products were examined using image analysis techniques. The majority of sphalerite and chalcopyrite grains in this texturally complex ore were found to be smaller than 10 micrometres. Copper recoveries were low with losses mainly as fine inclusions in pyrite. Sphalerite recoveries were somewhat better due to a generally coarser habit. Gold and silver recoveries were also low and only solid solution silver was identified in the ore. The deposit shows poor economic prospects unless additional tonnage of high grade zinc ore can be delineated.

Jan 1, 1989

By Cesar O. Gomez

A procedure has been developed for mounting at random particles of mineral samples to be characterized using image analysis. The procedure is based on the generation of a random distribution of sample particles in particles of a diluent material. and the embedding of this particle mixture in an epoxy resin without disturbing the initial distribution. Two materials with atomic number similar to that of the epoxy resin were successfully used as diluents: activated charcoal and graphite. The proportion of diluent material to be mixed with the sample to have a large number of mineral particles in the field of view while keeping the occurrence of touching particles at an acceptable level was determined empirically. The randomization achieved with the procedure developed in this work was tested using as samples known mixtures of silica and pyrite particles of the same sieve class. The agreement obtained between the mass ratio of minerals used in the preparation of a particular specimen and that resulting from image analysis demonstrates that the procedure developed is successful in producing a specimen where the embedded particles are randomly distributed.

Jan 1, 1988

By Brian R. Green

Resin-in-pulp (RIP) technology has been developed for recovery of gold. It is now time to look forward to the potential for application of the technology to other situations. Some cases have been identified and have merited preliminary testwork. Four examples, which illustrate the potential of RIP, are dealt with in this paper. These include removal of metal-cyanides from pulps, recovery of manganese that is difficult to wash from filter cakes, recovery of nickel from low grade pulps, and recovery of zinc from process residues. The discussion includes descriptions of the problems, factors that affect the choice of resin, and factors that will affect the economics of the process.

Jan 1, 1998

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By T. Langthaler, H. W. Engl, H. Holl, K. L. Schwaha

"The trend towards near net shape casting requires the development of more complex design and control algorithms for continuous casting ""machines in particular with respect to the solidification process.Compared to conventional continuous casting the reduction in casting thickness allows to influence more directly the solidification rate by control variables like surface cooling and/or casting speed.In order to enable the determination of these control variables for a given solidification profile, an algorithm (inverse solidification analysis) has been developed based on nonlinear constrained optimization. The application of the model is illustrated by practical examples ranging from conventional continuous casting to advanced thin slab casting.IntroductionProcess development in the Iron and Steel Industry is directed towards the realization of continuous process sequences. Since the direct linkage of processes imposes some restrictions onto the individual process steps, more complex algorithms are needed for design of equipment and control of operation. In particular the recent trend to reduce casting thickness, i.e. to cast thin slabs, has made the direct coupling of continuous casting and rolling absolutely necessary. The prospective development in strip production is schematically shown in fig. 1."

Jan 1, 1988

By Susumu Okabe

Top blow injection has been applied to continuous copper smelting and converting by Mitsubishi Materials Corporation since 1974. In this process, injected feeds are captured by and dispersed in the molten bath immediately and effectively, and the reaction is enhanced by the agitation of the bath. The continuous motion of the molten bath, however, may cause severe damage of furnace lining materials, if the injection is not controlled and the furnace is not designed properly. In order to suppress refractory wear, especially at the bath line, surface wave of the molten bath should be moderated. A cold model study was carried out with water bath in a cylindrical vessel and the physical model was derived which correlates the oscillation of gas jet impingement on the bath surface and the surface wave. It was found that a half of the proper frequency of the gas jet impingement coincides the proper frequency of the surface wave.

Jan 1, 1998

By Joel Anderson

Allvac 718Plus is a newly developed superalloy with a good potential for use in fabricated aircraft engine structures when service temperatures exceed 650°C; the limit for standard alloy 718. Fabrication involves welding, where cracking usually is a prohibitive factor. Comparison of the solidification cracking behavior between these two alloys was made by Transvarestraint testing. It was shown that the total amount of cracking was significantly lower for 718Plus alloy, which was associated with a lower amount of ?/Laves or ?/NbC eutectic-type constituents. This in turn is believed to be due to the lower iron content of the Allvac 718Plus material. The analysis of alloying element segregation both within primary dendrite and interdendritic constituents clearly indicates that the segregation of Nb is the controlling factor in determining the final solidification microstructure in these alloys. The Nb concentrations of these constituents are significantly higher compared to the bulk alloy concentration. This was confirmed by the SEM-EDS analysis and calculations assessed with JMatPro, the latter also indicated that alloy 718 is more prone to form Laves and NbC eutectic-type constituents compared to Allvac 718Plus material.

Jan 1, 2008

By Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p' which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

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 Tracie Zoeller, G. Paul Neitzel, Jr. Sanders

"As-cast aluminum alloy microstructures are highly segregated. Coring occurs when solute is rejected during solidification resulting in a non-uniform solute distribution across the dendrite arms. Furthermore, coarse constituent phases are formed in the interdendritic channels as a result of coring. These constituents are either soluble or insoluble and can form from the major solute elements, or the impurity elements iron and silicon. The dissolution of these constituents, or precipitates, is an important consideration in determining the microstructural evolution of an alloy. The properties of an alloy are significantly affected by the morphology of the precipitates. Precipitates can be either beneficial or detrimental to the properties of the alloy. Regardless of the nature of the precipitates present, it is useful to understand the dissolution process. A diffusion-limited dissolution model for planar precipitates is presented and compared to an analytical solution and to models in the literature. Experimental data for the dissolution of AhCu precipitates in a dilute alloy are compared to the proposed model, and found to have good agreement.IntroductionDuring the processing of precipitation hardening alloys, beginning with the solidification step and ending with the final solution heat treatment step, there are a variety of particles that form. Some of these particles must be dissolved and solute redistributed and re-precipitated in a more homogeneous distribution than as it first appears in the as-cast microstructure. The particles can be classified by size as microstructure develops during processing. Coarse particles that form during solidification can either be soluble, partially soluble or insoluble. These particles can be the result of coring of the major solute elements as well as the limited solubility of elements such as iron and silicon. Iron and silicon can combine with the major solute elements such as copper in 2xxx alloys forming coarse phases often referred to as constituents. Figure l(a) shows the as cast microstructure with the constituent phases, Al2Cu and the insoluble phases containing Al-Fe-Mn-Cu-Si [7]. During preheating the soluble phases such as AhCu that were formed by eutectic decomposition must be taken back into solution, whereas the insoluble phases remain essentially unchanged by most thermal operations. Figure l(b) and (c) show some of these constituents after subsequent preheating steps. In Figure l(b), AhCu platelets are shown and in Figure l(c) the remnants of the AhCu phase are noticeable, along with Mn-bearing dispersoid phases. Reduction in the volume fraction and size of these phases improves the ductility and fracture toughness as well as reducing the inhomogeneities that occur during coring. Also adjacent to the dendrite arm boundaries are smaller AhCu phases that precipitate by a solid-state transformation on cooling to room temperature."

Jan 1, 2004

By Fathi Habashi

Solid gas reactions of metallurgical importance can be classified into three groups: Physical processes, e.g., drying and sublimation Chemical processes which may be an addition or a thermal decomposition reaction Electrochemical processes which may be addition, oxidation-reduction, or displacement reactions. Examples are given and the role of the boundary layer is emphasized.

Jan 1, 1996