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By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By J. K. Brimacombe

Plant trials have been conducted at the Tacoma Smelter of ASARCO to assess the effect on tuyere blockage and refractory erosion at the tuyere line, of increasing the injection pressure of air into a Peirce-Smith con¬verter. Four tuyeres each having an ID of 19.1 mm (3/4 in) were installed toward one end of the tuyere line of the No. 4 Converter. Air and oxygen-enriched air were injected at 414 kPag (60 psig) through these tuyeres and at the usual 83 kPag (12 psig) through the remainder of the tuyeres in an otherwise normal converter campaign. The test campaign consisted of 88 charges and lasted for 89 days. During this period, punching of the high-pressure tuyeres was found to-be unnecessary; and when, as a precaution, the tuyeres were cleaned by hand at the end of a charge, they were always open. Also it was observed that the flow of high-pressure air remained constant. Accretion formation around the tip of the high-pressure tuyeres varied from charge to charge and was influenced by the matte grade and the level of oxygen enrichment.

Jan 1, 1983

By S. Raghavan

The thermodynamic activities of MgO in the solid solutions that can exist in the system NiO-Mg0-Zn0 are determined by measuring the EMF of the cell: O2 (g), Pt / MgO, MgF2 // MgF2 // x MgO + yNiO + (1-x-y)ZnO / Pt, O2 (g) / MgF2 in the temperature range 1190-1237 K. Equilibrium phases were prepared along the quasi- binary lines MgO/NiO = 0.1765,0.3333, 1.0,3.0 and 5.667 with the ZnO contents being 0.1, 0.2, 0.25, 0.35, 0.5, 0.75 and 0.9. The crystal structures of the phases were identified by X-ray diffraction. Results obtained so far show that a single phase MgO-rich cubic solid solution exists upto 0.2 ZnO content and for compositions above 0.25 ZnO, a second ZnO rich wurtzite phase forms in addition. Activity measurements show that for low MgO and ZnO contents, the MgO activities exhibit ideal to slight positive deviation from ideality and at higher MgO contents, a negative deviation is shown. Further studies are in progress.

Jan 1, 1993

By Mariana H. Staia

The present communication reports the results obtained by applying different concentration methods, at laboratory level, to the black sands from Estado Bolivar, Venezuela, with the aim of obtaining an adequate ilmenitic concentrate for the subsequent chlorination process. Sizing analysis was performed and plasma emission spectroscopy method was used to determine the chemical composition. It was found that from the two hydrogravimetric methods used, the Humphrey spirals is much more effective than Wilfley tables, leading to a 85% recovery. The most convenient particle size group for these concentration methods was the one corresponding to ASTM 40-140 mesh. When magnetic concentration was applied to the concentrate, obtained as a product from Humphrey spiral, a recovery of ilmenite more than 90% was obtained in the first step. It has been shown that the ore would respond to the separation techniques employed, giving individual minerals: ilmenite, zircon and silica as concentration products.

Jan 1, 1995

By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By Cledwyn Mangunda

Mining operations generate Acid Mine Drainage (AMD) that poses a significant threat to the natural environment. AMD treatment using Ca(OH)2 leads to the precipitation of a sludge dominated by a mixture of ferri-oxyhydroxides. This sludge has poor dewatering tendencies and is deposited in landfills with potential for metal remobilization. This study investigated the dewatering behaviour of a precipitate formed during elevated temperature treatment of a primary, pre-settled sludge from the neutralisation of aqueous acidic Fe2(SO4)3 and Ca(OH)2 solutions in an MSMPR reactor. The resulting treated precipitates were analysed for micro-properties, with results showing that an increase in the secondary reactor temperature from 25 °C up to 50 °C led to an increase in mean particle size, a decrease in the number of particles and improved dewatering behaviour at a ferric concentration of 300 mg/L. This was ascribed to the attainment of a circum-neutral surface charge that favoured agglomeration and a change in micro and nano-structure that allowed for better water passage.

By Jana Dobrovska

Solidification and cooling of a continuously cast slab and simultaneous heating of a mould is a very complicated problem of transient heat and mass transfer. Nowadays, the solving of such a problem is impossible without numerical models of the temperature field not only of the slab itself, while it is being processed through the whole concasting machine (Caster), but of the mould as well. Two original numerical models have been developed and used in the investigation of a continuously cast steel slab. The first (one of two) 3D model of the temperature field of a concasting is capable of simulating the temperature field of a caster. Experimental research and data acquisition have to be conducted simultaneously with the numerical computation-not only to confront it with the actual numerical model, but also to make it more accurate throughout the process. After computation, it is possible to obtain the temperatures al each node of the network, and at each time of the process. The utilization of the numerical model of solidification and cooling of a concasting plays an indispensable role in practice. The potential change of technology-on the basis of computation-is constantly guided by the effort to optimize, i.e. to maximize the quality of the process. The user can therefore choose any appropriate longitudinal or cross-section of a slab and display or print the temperature field in a 3D or 20 graph whenever necessary. The second numerical model of dendritic segregation of elements assesses critical points of slabs from the viewpoint of their increased susceptibility to crack and fissure. In order to apply this model, it is necessary to analyze the heterogeneity of samples of the constituent elements (Mn, Si and others) and impurities (P, S and others) in characteristic places of the solidifying slab. The numerical model, based on measurement results obtained by an electron micro-probe, generates distribution curves showing the dendritic segregation of the analyzed element, together with the distribution coefficients of the elements between the liquid and solid states. The combination of both models enables the prediction of cracks and fissures in critical points of the continuously cast carbon-steel slab. Both models had been applied in the industrial investigation of a cast low-carbon-steel slab.

Jan 1, 2003

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

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 SIMON TIMBILLAH

The chalcopyrite-molybdenite (Cu-Mo) flotation industry is increasingly turning to organic depressants as suitable replacements for inorganic reagents, such as NaHS, due to environmental and safety concerns as well as high consumption rates of the inorganic reagents. This presents an opportunity for improvements or design and synthesis of alternative reagents. Disodium carboxymethyl trithiocarbonate (Orfom® D8) depressant is an organic depressant with a carboxylate group on one end and a trithiocarbonate group at the other end. Fundamental results are shown regarding the interaction of the Orfom® D8 depressant in the bulk flotation of a Cu-Mo concentrate from an operating North American mine. Cyclic Voltammetry on pure copper and Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS) measurements on pure chalcopyrite with Orfom® D8 depressant treatment are also reported. Through such characterization techniques a potential adsorption mechanism of Orfom® D8 on the mineral surface was identified and its depressant characteristics in the Cu-Mo flotation systems explained.

By G. Laird, N. B. Gray, N. Lawson

"Photographic, video, laser, hot film and conductivity methods are used in the experimental study of gas-liquid flows. A discussion of their capabilities and limitations are given in this paper illustrating the wide range of phenomena that can be studied. Most of these methods are limited to physical models at room temperature with transparent fluids, although they can be extended for use with opaque and hot fluids. A number of these techniques have been used by the GKW CRC in studies on industrial plants and their usage is increasing although a number of technical difficulties still need to be overcome. An in-depth discussion of the laser doppler anemometry (LDA) and particle image velocimetry (PIV) methods is given with experimental results on the flow field of an air plume in water based on advanced development of the techniques and studies carried out at the GKW CRC. The LDA method provides high resolution data on the velocity profiles, while the PIV method provides an overall view of the complex flow structure occurring at the gas-liquid regions. These two methods complement each other in providing experimental data for validating numerical models and exploring the complexities of multi phase flows.IntroductionThe injection of gases into melts is an important operation in the metallurgical industry. It is used in converters, anode furnaces, blast furnaces, ladles, bath smelters, zinc fumers and many other smelting processes. In many of these processes, the gas is injected into a molten bath resulting in the formation of bubbles that promote reaction, mixing, alloying and heat transfer. The study of gas-liquid systems presents enormous challenges to the researcher due to the complexity of the mathematical and physical modelling which require innovative numerical and experimental skills."

Jan 1, 1996

By Masao Suzuki

Over 5 million cars are scrapped yearly in Japan. After dismantling. scrapped automobiles, they are put into a shredder for differential recovery of ferrous and nonferrous metals. The residue, which is called shredder dust, runs over 1.2 million tons per year. This paper reports a entire sequence of scrapping. cars. in Japan with the following sections: (1) production and scrapped car management, (2) material composition, (3) dismantling, (4) shredder plant, (5) differential recovery of metals including specific gravity separation and newly developed color separation.

Jan 1, 1995

By S. R. Hutchins

Several refractory sulfide and carbonaceous gold ores were examined to determine whether microbial pretreatment could be used to enhance gold recovery. Test samples were biologically leached using unique. thermophilic microorganisms to solubilize iron sulfide minerals. Gold recovery from sulfide ores and concentrates was enhanced following pretreatment with the thermophiles; responses varied widely for the individual materials. Although bioleaching had little effect on the preg-robbing characteristics of the carbonaceous gold ores, cyanidation of the bioleached residues yielded higher gold recoveries than cyanidation of the native ore. By combining bioleaching with abiotic processes designed to inhibit preg robbing, gold recoveries of 83-98% were obtained from carbonaceous ores yielding 10-50% gold recovery by direct cyanidation.

Jan 1, 1987

By Achilles J. B. Dutra, Carlos M. Juarez

"The use of thiourea as a gold leaching reagent has been extensively studied by many researchers, and it has proved to be promising for some cases as refractory ores. Otherwise, the recovery of gold from these solutions did not receive so much attention. In this paper the electrowinning of gold in acidic thiourea solutions was studied by voltarnmetry and chronopotentiometry. An adsorption step was detected prior to Au(I) reduction and the diffusion coefficients at 25°C for Au-TU complex and FD were found to be 1.00 x 10.5 cm2 S-I and 1.98 x 10-5 cm2 S-I respectively. At -0.350 V (SCE) a passivation probably due to TU adsorption was observed. For higher overpotentials hydrogen evolution was the main reaction.IntroductionThe use of acidic thiourea solutions for the extraction of gold and silver has shown to be a promising alternative to the traditional process of cyanidation, specially for certain refractory ores (1-3) and electronic scrap (4). In some cases, the industrial scale was reached (1,5). The thiourea leaching of precious metals presents advantages over cyanidation, as faster kinetics, lower toxicity and lower sensibility to base metals; however the costs due to high thiourea consumption impairs its use.The majority of the publications on thiourea processing of gold is on leaching. Many are review papers (5-7). Recently, the adsorption and desorption of the gold-thiourea complex on activated carbon and ion exchange resins have been studied (8-11).Little research has been done on the electrowinning of gold from acidic thiourea solutions, most of it has been carried on the seventies and beginning of the eighties in the former USSR (12-17) and concerned the eletrolytic extraction of gold in tridimensional cathode cells.The present paper concerns the cathodic behavior of the gold-thiourea complex in the presence of formamidine disulfide in order to provide information on the electrowinning of gold from solutions obtained directly from leaching or from an elution process."

Jan 1, 1997

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By N. El-Kaddah, V. L. Acoff, M. Arenas

"Control of the weld penetration, weld pool shape and temperature field in arc welding is critical to achieve the desired microstructure and mechanical properties in the resultant welds. This is particularly important in welding gamma titanium aluminides (y-TiAl) where the weld pool is relatively shallow and the temperature gradient in the heat-affected zone is quite steep. This paper investigates theoretically and experimentally the evolution of the shape of the weld pool for stationary gas tungsten arc welds in y-TiAl alloys. A mathematical model has been developed for predicting the electric current flow, the resultant electromagnetic forces in the metal, and the transient development of the temperature and velocity fields in the molten pool generated by a spatially variable heat flux at the arc-striking zone. The governing equations were solved numerically using the control volume technique. Welding experiments were carried out to determine the shape of the weld pool and the extent of the heat affected zone at different welding times for model validation. The numerical predictions were found to be in reasonable agreement with measurements. It is suggested that the model presented in this paper is likely to provide the information needed for predicting the microstructure and mechanical properties of y-TiAl welds. IntroductionIn recent years, there has been considerable interest in the welding of gamma titanium aluminides as a means of manufacturing high-temperature, high-performance components for turbine and automobile engines. These alloys are highly reactive, and must be welded in vacuum or inert gas atmosphere, rendering electron beam, and inert gas tungsten arc welding (GTA) to be the only suitable welding techniques for joining these materials [1-3]. The GTA welding is especially attractive because of its flexibility and relative cost-effectiveness. However, previous studies on the weldability and weld properties of these alloys using this process revealed a decrease in the mechanical properties in the fusion zone [4]. This is generally attributed to the change of the original duplex structure to a dendritic structure amplified by the shallowness of weld spot. Quantifying the effect of arc operating parameters on the geometry and temperature profile of the welding pool prior cooling is the first step for controlling the fusion zone microstructure and mechanical properties."

Jan 1, 1999

By Donald R. Fosnacht

An investigation was initiated to obtain the scope of the problems associated with recycling various waste oxide materials generated at Inland Steel and to identify and? test techniques that could possibly aid in increasing the amount of waste oxide materials recycled to primary. operations. Based on the results of this work, several new techniques were developed ?and tested on ?a plant or laboratory scale. These include the use of cold-bond agglomeration methods for producing waste oxide agglomerates for use as a cooling agent or scrap substitute in steelmaking operations, and the use of various techniques for beneficiating blast furnace flue dust and soaking pit rubble so that the upgraded materials can be utilized in sinter plant or ironmaking operations. The physical and chemical characteristics of the waste oxide materials and the results of the laboratory and plant testing are discussed in this paper.

Jan 1, 1985

By J. P. Evans

The modem 'copper smelter today utilizes tonnage oxygen for smelting concentrates. ,generating a high strength S02 off-gas leaving the smelter vessel. This gas stream. which also contains any unreacted oxygen, plus CO2; N2 and H20. also carries with it the volatilized portion of heavy metals in the feed, plus partly oxidized sulfide concentrates, The time/temperature history and subsequent treatment of this off-gas stream emerging from the smelting furnace exit up to the acid plant can influence the partitioning and segregation of heavy metals, in the off-gas circuit. Depending on this history. the type and characteristics of the chemical and physical reactions which occur in the gas handling system 'can be influenced. This fact can also be used as a tool to adjust the separation of copper from heavy metals. In this paper, the impact of different time/temperature histories of the gas, due to different furnace geometries and design. on the subsequent formation and characteristics of the smelter dust is examined. Based on the available data. several case histories drawn from examples using both bath and flash smelting technologies are analyzed from this perspective.

Jan 1, 1992