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By Carlos A. Nunes

V-AI alloys have been used commercially to produce pure vanadium by Electron Beam Melting (EBM), as well as to obtain Ti-based alloys (ex. Ti-6AI-4V). The aluminothermic reduction of vanadium pentoxide (V205) is the primary method to obtain these alloys. Concerning the obtention of pure vanadium, earlier studies have indicated alloys presenting Al content between 10 and 15wt% as the most suitable alloys for direct EBM. In the present work we investigated the aluminothermic reduction of V205 in order to define process parameters for the obtention of V-AI alloys with composition in the previously mentioned range. It was studied basically the effect of excess AI, CaO addition and reaction atmosphere (air, argon) on the alloy composition (AI, 0, N). In addition, microstructural analysis of selected alloys by SEM (BSE images) and EPMA (WDX) were also performed.

Jan 1, 1996

By H. Soto, J. Jara, F. Nava

A method has been developed to recover cyanide and copper from solutions containing copper complexes and thiocyanate. Copper is precipitated as copper thiocyanate or as copper cyanide depending on pH and the concentrations of thiocyanate and cyanide in the effluent. The copper precipitate assays over 50% copper and presents good dewatering characteristics. After settling it can be separated from the effluent by filtration. The solution containing the bulk of the cyanide is then oxidized with ozone to transform the remaining thiocyanate into cyanide. This results in a regenerated solution rich in free cyanide that can be recycled to the cyanidation process. Careful control of the pH of the solution is required. First, pH of the effluent is lowered to optimize the precipitation and oxidation stages, then the pH is restored to an alkaline value to regenerate the cyanide solution. Recoveries of over 96% copper and cyanide were obtained in laboratory tests using industrial solutions. With this procedure, cyanocidic gold/copper ores could be treated economically by heap leaching, since the cyanide consumed by the copper impurities could be regenerated at very low cost (most of the cost of cyanide regeneration would be compensated by the copper credits). In order to achieve this, a bleed of the barren solution could be treated by the proposed method, and then recycled to the leaching step. The volume of solution to be treated should be large enough to keep a cyanide/copper molar ratio higher than 3:1. This would assure that copper does not cause undue interferences in the leaching or the carbon adsorption stages. If the thiocyanate content is low, the oxidation stage can be avoided, and the solution can be recycled to the leaching stage directly after the solid-liquid separation stage.

Jan 1, 1997

By Jillian Spindura

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

Jan 1, 1996

By W. D. Keller

Scanning electron microscopy (SEM) accompanied by X-ray energy dispersive analysis (XES) is a useful tool in process clay mineralogy. The texture of kaolin, illustrated by SEM, gives a clue to its mode of genesis and probable industrial application. One type of kaolin, originating dominantly by weathering, has an open texture, slakes readily, and is used for filling and coating paper. Another type, in contrast, originates by diagenesis of Al-silicate sediments, and spectacularly resists slaking, thereby enabling it to maintain its bulk density and controlled size and shape of particles after crushing and moistening; this meets an important requirement for the manufacture of refractories. Ratios of elemental Al:Si that may be rapidly determined by SEM and XES yield information on the origin and purity of bauxite and bauxitic clays, and aid in quality control and processing of them. SEM of dissimilar textures of quartz, as in chert and novaculite, are evidence for geothermometry on a stratigraphic scale that is potentially useful in delimiting thermally favorable or unfavorable areas for hydrocarbon exploration, and possibly for unexposed metallic ore deposits.

Jan 1, 1982

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Animesh Jha, Chris Dometakis

"Without the use of a flux, only a poor dispersion of ceramic phase can be achieved. A molten-flux-assisted ceramic phase dispersion technique for producing aluminium alloy metalmatrix composites has been developed. In this paper, we report the physical chemistry for the dispersion of TiB2 in molten aluminium. In particular, aspects of the interfacial energy and the thermodynamics of the dispersion reactions are briefly discussed for enhancing the volume of dispersion phase in the molten metal and for controlling their morphology. This investigation also addresses the role of molten flux in the fabrication of AI-alloy mmc using a casting technique. The morphological aspects of the dispersion are explained on the basis of the classical theory· of nucleation.IntroductionMetal matrix composites (MMCs), have long been recognised as an important class of material due to their greater wear resistance, specific stiffness and temperature capability when compared to conventional monolithic alloys. Particulate reinforced composites produced by melt casting techniques have been amongst the first MMCs to achieve commercial market viability. The advent of melt mixing techniques such as the Duralcan™ process have enabled low cost, easily fabricated composites based on the AI-SiC and AIAlz0 3 systems to be produced. In this process, uncoated ceramic particles with diameters 10ltm and larger, are incorporated into conventional monolithic alloys with reinforcement levels up to 25 volume percent. The AI-7Si-SiC metal-matrix composites have good wear resistance, high strength, low density and high thermal conductivity. The combination of these physical and mechanical properties has become a major attraction for the fabrication of light-alloy composite disc rotor brakes for the automotive sector2. However, in silicon-free alloys, SiC is thermodynamically unstable above the composite melting point and is extensively attacked by the melt to form aluminium carbide3 :"

Jan 1, 1996

By Dorothée Proffit

Characterization of solids containing cyanides is carried out according to recommendations and standard guidelines. Most of these procedures are based on the analysis of leachates collected either on site or after leaching in the laboratory of samples. Unfortunately, these sole results are often insufficient to identify the source of the pollution. To provide 'a more complete characterization of polluted solids, optical and electron microscopy, XRD, Mossbauer spectroscopy, and transmission infrared spectroscopy were combined to analyze leachates and raw or ground samples. This combination of techniques allows the determination of the kind of cyanoferrate complexes are present in the solid state, different from insoluble Prussian Blue, since they do not have the same extraction' behavior. The use of all these techniques to characterize solid samples combined ,to the usual analysis of solutions gives a better understanding of ' the cyanide behavior.

Jan 1, 1998

By C. A. Nogueira, F. Margarido

"A research work has being carried out annmg at evaluating the possibility of treating simultaneously several electrochemical systems of spent batteries using the same process, in order to overcome the high costs and difficulties of selective collection and sorting. Zn-Mn02 systems, representing more than 75% of portable battery market, shall be treated in dedicated processes. The treatment assessment using a single hydrometallurgical process of the other major systems (NiCd, NiMH and Li-ion), having Ni and Co as main metals, was the aim of the research work here reported. Sulfuric acid leaching was demonstrated to be adequate for dissolving more than 90% of the metals of interest contained in batteries. The subsequent separation of metals by solvent extraction, using organophosphorous extractants like DEHPA and Cyanex 272, allowed the production of pure solutions of rare earths, cadmium/manganese, cobalt, nickel and lithium, enabling their further recovering.IntroductionRecycling is the best approach for end-of-life management of spent batteries mainly by environmental reasons but also motivated by resources conservation and, in some cases, by economic profits. Most relevant electrochemical systems of portable cells are Zn-Mn02 (ZMB, alkaline and saline), nickel-cadmium (NiCd), nickel-metal hydride (NiMH) and lithium-ion (LIB). These batteries are collected, sorted and usually treated separately, applying for pyrometallurgical or hydrometallurgical technologies, the former being the most common.Several processes have been developed and some of them industrially applied, as described in some available review papers [l, 2]. In Europe for ZMB systems the oldest processes are Batrec [3] and Citron [4]. Although having differences in details, both are based on pyrometallurgical recovery of zinc by distillation, in metallic or oxide forms, being manganese retained in the slag together with iron. Hydrometallurgical alternatives are also available, like Zincex [5] and Recupyl [ 6] processes, both using sulfuric acid solutions as leachant. The application of the existing technologies to battery recycling, instead of using dedicated processes, is other alternative already tested, being the Waeltz furnace or the Imperial Smelting some examples."

Jan 1, 2012

By A. D. Damodaran

Batch scale and continuous rotary kiln carbothermic metallisation of ilmenite followed by different down-stream treatments such as catalytic rusting, acidic chloride leaching, oxidation-leaching etc. has given rise to a high grade synthetic rutile (98% TiO2). Rotary reactor metallisation experiments had concurrently given important information with respect to mean residence time, dispersion number, hold-up and axial velocity profiles of the solids bed. A mathematical model based on law of additive reaction times has indicated that Boudouard reaction becomes faster than reduction reaction at higher conversions. A possible use of high grade synthetic rutile in paint industry and metallised ilmenite as welding electrode flux material are discussed.

Jan 1, 1992

By David N. Hanlon

The effect of high-temperature plastic deformation of the austenitic phase (y) on the subsequent phase transformation to ferrite (a) has been experimentally investigated, and modelled using a physically-based model. The effect is of importance for steel sheet, in view of me significance of the phase transformation with respect to the eventual properties of the material. In this paper the kinetics of the y ? a phase transformation has been studied after different degrees of prior deformation. The degree of deformation is varied by applying different deformation temperatures and strain rates, and by allowing a varying extent of recovery and recrystallisation. Consequently, both dynamic and static recovery and recrystallisation have been involved. The dilatometric observations on the phase transformation have been modelled using an interface-mobility model, in which the effect of the dislocation structure is introduced as an additional driving-force term. The effect of the stored energy on the nucleation process, which appears to be affected more strongly than the growth of ferrite, is examined in terms of the classical nucleation theory.

Jan 1, 2001

Physical and chemical properties of the salt flux phase play a significant role in the recycling of UBC in Aluminum melting processes. Particularly knowledge of several properties such as salt vapor pressure, melting temperature, loss of aluminum, corrosion of refractories are useful for the process control decisions in order to attain a good quality of aluminum produced. A literature review and analysis of several salt flux systems for the selection of a flux for the Aluminum melter (low temperature natural gas bath melting) process were made. Based on these analysis two salt flux systems are recommended for further studies. These are NaCl?KCl?LiF system and NaF?LiF?KCl system with small amounts of other salt additives. Application of these fluxes to Al industrial processes are discussed.

Jan 1, 1996

By Saeid Pournaderi, Ahmet Geveci, Ender Keskinkilic, Yavuz A. Topkaya

There are mainly three commercial nickel laterites in Turkey: Gordes, Caldag and Sivrihisar. The first two appear in Western Anatolia. The third one, Sivrihisar (Yunusemre) laterites have been found in the first decade of the millennium, in the Central Anatolia region of Turkey. Since then, mining facilities have been continued in Yunusemre. Calcination, prereduction and smelting of Sivrihisar laterites have been extensively studied and published. In the current work, some results of the studies related to characterization of Sivrihisar laterites will be presented.

Jan 1, 2016

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By C. Burton Clark

The important role of the petrographic microscope in the petrology of refractories is discussed, based on 45 years of industrial experience by the author. Highlights of his career are used to illustrate improvements in equipment and techniques during the period. Two specific investigations are described which emphasize the interrelated use of the petrographic microscope with other instruments such as the x-ray diffractometer and scanning electron microscope. Emphasis is placed on the use of phase equilibrium diagrams for guidance in predicting and interpreting reactions that occur under non-equilibrium conditions in the manufacture and use of refractories.

Jan 1, 1982

By S. Ozbilen

"Al-Li binary alloys with nominal Li contents of0.15, 1.1and2.8 (in wt%) were aged naturally at room temperature for two months, aged at low temperatures ( 65 and 1 OOEC) for up to 2 months and aged artificially at 190EC for 4 days after water quenching to 25EC following solutionizing at 530EC for 20 minutes. Ageing behavior of these binary alloys were studied by Vicker's Hardness measurements and DSC thermal analysis. Thermal analysis results indicate the formation of GP zones of Al-Li system in Al-2.8wt%Li binary alloy. In the same alloy, rapid quenching from one phase region (a) gives rise to precipitation of small o' particles in a matrix (a) with still high supersaturation. During ageing of this alloy below lOOEC an additional transformation, i.e., GP zone formation occurs proceeding at a very high rate which is described on the basis of the theoretical analysis for the quenched Al-Li system proposed by Khachaturyan et al [6]. Ageing at temperatures below 11 OEC takes place slowly by the formation of small d' particles of lower thermal stability than the quenched-in d precipitates in addition to GP zones resulting in an increase in hardness compared to water quenched samples. During artificial ageing, GP zones transform by dissolution to d' precipitates while d' particles already in the microstructure coarsen during under aged condition at which hardness increases with time till peak aged condition.IntroductionIn binary Al-Li alloys the d' (Al3Li) fully coherent internally ordered inetastable phase of Li2 structure with a=0.4038d [1-5] forms homogeneously between 120 and 190EC before the formation of stable d' (A!Li) phase and cause the superior mechanical properties. This is due to an appreciable age hardening effect resulting because of the d' precipitation during ageing [1]. The response of d' to decomposition and its formation kinetics have been studied previously and it is believed that the decomposition of the a-supersaturated solid solution occurs in a two stage process; i.e., a 6 d' (Al3Li) 6 d(A!Li). Khachturyan et al [6] theoretically investigated precipitation of the d' phase and gave an interpretation of the transformation paths of the quenched Al-Li alloys. They predict that the disordered supersaturated solid solution congruently orders, and then the uniformly ordered solution decomposes into ordered regions that differ in Li-content. Finally, ordered d' phase forms in the disordered matrix."

Jan 1, 1998

By Patrice Chartrand, Halvor Dalaker, Philippe Ouzilleau

A size-dependant thermodynamical model for the carbon-hydrogen previously developed by Ouzilleau et al. [1] has been expanded here to include chemisorption of methyl groups. Gibbsenergy minimalisation calculations using FACTSAGE software on this model indicates that hydrogen bonding through methyl groups is energetically favoured as an intermediate between bonding as monoatomic hydrogen to edge hexagons (which is more favourable) and as monoatomic hydrogen to corner hexagons (which is less favourable). The model has also been applied to methane decomposition and oxide reduction using natural gas. A C-H solid solution as a thermodynamic description of the solid carbon phase influences calculations of carbon activity in metastable methane, and gives different results than when using graphite.

Jan 1, 2015

By Adrian C. Deneys, David G. C. Robertson

"Fluid flow phenomena on the surface of a molten slag have been documented using video photography in a laboratory scale D.C. arc furnace. The flow on the surface of the slag appeared to be electromagnetically influenced. This was confirmed by varying the position of the anode, which changed the direction of flow on the surface of the slag. Temperature measurements in the bath also confirmed the change in the directional nature of the fluid flow induced by the arc.During some periods, solids were fed into the arc attachment zone (AAZ) down the center of the hollow graphite electrode. Significant movement of the arc around the basal annular surface of the hollow electrode takes place. The point of attachment of an arc on a hollow electrode was more variable than an arc attached to a solid graphite electrode. Video images showed that the solids were rapidly incorporated into the bulk of the slag. Temperature measurements confirmed the existence of a superheated slag layer at the slag-gas interface, which allowed the solids to be rapidly incorporated into the melt.This work has been conducted to study fluid flow, temperatures, and solid behavior during feeding, in the arc attachment zone of a D.C. arc furnace. The work also has relevance to optimizing furnace design for pyrometallurgical slag cleaning processes."

Jan 1, 1999

By B. R. Baldock

The converting of high-grade nickel matte for production of low-sulphur matte or nickel metal is a process which has eluded metallurgists in the past because of the limitations of conventional converting furnaces. The high temperatures required and the refractory nature of nickel oxide has prevented practical success in a process which has been known to be theoretically feasible for a long time. The Ausmelt top submerged lancing system is capable of operating under close control of the smelting conditions. High temperatures and both rapid oxidation and rapid reduction can be achieved. These features have provided the basis for successful pilot plant trials of the desulphurisation of high-grade matte from the Kalgoorlie Nickel Smelter. Sulphur level in product was lowered from 20 to 25% to as low as 0.2%, with iron levels in matte in the range of 1.0 to 3.5%. The theoretical background of matte desulphurisation is surveyed and the pilot plant operations described. The implications of the results in relation to commercial plants and possible refinery operations are summarised.

Jan 1, 1993

At its Copper Cliff Smelter, Inco Limited processes a bulk copper-nickel concentrate in two Inco oxygen flash furnaces, The furnace matte is converted to low iron matte for further processing, and the molten converter slag is recycled to the flash furnaces. The flash furnace slag is discarded. Natural gas or coke supplies a minor proportion of the process heat requirements, thus limiting the flash furnace matte grade to the target 45% CuNiCo. Coke addition to the furnace offers a potential means of establishing a reducing barrier on the surface of the molten bath. Such a practice would be conducive to producing sulfur deficient (partially metallized) matte. At the same iron content, the iron activity of sulfur deficient matte is higher than that of regular matte. A supernatant coke barrier could, therefore, be expected to lead to higher nickel and cobalt recoveries, reduction or even elimination of magnetite furnace bottom build-up and increased sulfur elimination as S02 in the flash furnace. Preliminary experiments were conducted in a miniplant flash furnace to investigate the effect on process metallurgy of the suggested modified scheme. This paper presents the experimental results and discusses key aspects of the possible operation of the Inco flash furnace with a coke barrier separating the freeboard from the molten bath.

Jan 1, 2003