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By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

By Maija-Leena Metsärinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high (up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro-scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEMIEDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By Nathan A. Tiner

Sulfuric acid anodizing process is extensively used in many industrial and consumer products to provide corrosion resistance to aluminum alloys. The anodic coatings produced consist of amorphous alhnum oxide with a pornus structure which is easily sealed and colored with dyes. The coatings may contain defects due to surface flaws, canposition and microstructure of the aluminum alloy, and/or due to the anodizing process conditions. This paper will describe the techniques used in anodizing process, various defects which may be produced in anodic coatings and the methods to control them.

Jan 1, 1992

By Julian Johnson

The effect of changing redox potential (Eh) on the high temperature sulfuric acid leaching of Western Australian dry-land nickel laterite ores has been investigated. In particular, the effect of added reductant (sulfur, sodium sulfite) or oxidant (potassium chromate) on Eh, leaching kinetics, metal extractions, acid utilisation and leach residues has been determined. Three separate ores - nonhonitic ores from Murrin Mumn and Bulong, and limonitic ore from Cawse - were used in the study. Sulfur addition varied from 0 to 7.8 kg/t ore. The total acid loading was kept constant at 430 kg/t (Murrin Murrin ore) and 330 kglt (Cawse ore), whilst acid loading for Bulong ore was varied according to the presence of either reductant or oxidant. The extraction of both nickel and cobalt from limonite ore remained unaffected when small amounts of sulfkr were added, but addition of even small amounts of reductant to nontronitic ore decreased both nickel and cobalt extraction. Increased manganese and iron dissolution were observed as the levels of reductant increased, accompanied by a decrease in chromium dissolution. As the iron dissolution increased, free acidity decreased, with a subsequent decrease in nickel extraction. In contrast, addition of oxidant lead to reduced iron and manganese dissolution and slower extraction of nickel and cobalt. Keywords: Limonite, Nonhonite, Eh, Nickel Extraction

Jan 1, 2004

By S Ivanaj

Oxidation of chalcopyrite from a copper concentrate in an electrochemical cell having separate-anodic and cathodic compartments was studied by potentiodynamic, potentiostatic and galvanostatic experiments. Oxidation of chalcopyrite particles was mainly realized by in-situ electrogenerated FeIII and Cull ions. The use of an ion exchange membrane, in this experimental set, avoids the reduction of the ferric and cupric ions. The effects of particle size, current feeder potential, current intensity and pulp density were studied to optimize the oxidation parameters. Selective complete oxidation of chalcopyrite was achieved. Oxidation of pyrite was negligible. Mom than 85 % of sulfur was obtained in its elemental form. This may allow selective extraction- of copper from the chalcopyrite concentrate without sulfur dioxide emissions.

Jan 1, 1995

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

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 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 Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By C. J. Newman

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to improve gas cleaning capability. The acid plant is reviewed with references to changes? made to accommodate the increased SO2 gas strength resulting from the higher smelting rates.

Jan 1, 1992

By F. R. A. Jorgenson

The ignition of chalcopyrite and pyrite was studied using laminar flow furnace and thermal analysis techniques which were supported by XRD and optical microscopic examination of the products. In air, chalcopyrite and pyrite ignited at temperatures of 400-500'C and 500-600?C respectively. The phase assemblages predicted from thermodynamic analyses were compared with those found by experiment, and the onset of ignition was correlated against changes in the phase compositions. Pyrite and chalcopyrite ignited when pyrrhotite and intermediate solid solution formed thus opening up the structure and allowing ready access of oxygen.

Jan 1, 1989

By R. J. St. Eloi

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year .. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to .generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to 'improve gas cleaning capability. The acid plant is reviewed with references to changes made to accommodate the increased S02 gas strength resulting from the higher smelting rates;

Jan 1, 1992

By P .. R. Ammann

A two-stage pyrometallurgical process has been developed for the recovery of copper (and other non-ferrous metals) from copper smelter slags. All types of slags, including highly oxidized, converter-type slags, are cleaned in an electric furnace which employs mechanical mixers to promote magnetite reduction and copper extraction at high rates. In a 10-ton pilot furnace, it has been demonstrated that slags can be cleaned to 0.2-0.3 per cent copper with economically acceptable usage of raw materials and energy; copper is recovered as a high-grade matte. Pilot plant data have been scaled up to a commercial furnace and engineering designs have been made for a furnace to treat 60 tons per hour of slag from a Noranda Reactor and the associated converters. Plans are being formulated for the construction of a prototype slag cleaning furnace.

Jan 1, 1976

By Jing Zhan

The fibrous precursor can be obtained by coordination precipitation process, using oxalate, cobalt chloride and ammonia. The composition and morphology of fibrous precursor were characterized by XRD, IR, DTA/TGA and SEM analysis. The results show that XRD pattern and composition of the precursor with fibrous morphology precipitated at pH=9.0 were different from that of ß-CoC2O4?2H2O precipitated at pH=1.0. The mechanism on the thermal decomposition of fibrous precursor was addressed. The influences of various conditions in pyrolysis, including the temperature, time, atmosphere, and the morphology of the precursor, on the morphology, average size and specific surface area of the Co powders were investigated in detailed. At last, the final product, fibrous cobalt powders with diameter about 0.3~0.5µm in size and 40~60 in aspect ratio, were produced by thermal decomposition at 400~500? in the weak reducing atmosphere. The structure of pores in cobalt powders was capillary tube with open ports and the majority was mesoporous.

Jan 1, 2009

By T. Innmi

The potential of the nickel matte anode was measured during the matte electrolysis in the commercial cell. The slime layer consists of elemental sulfur and was found to greatly influence the potential of anode. The measurements of porosity and permeability of the slime suggest that the voltage drop of the slime layer dominates the potential. Furthermore, the diffusion of the electrolyte through the slime layer is also one of the factors to determine the potential. In addition, the copper content of the nickel matte anode was found to affect the change in the anode potential during the electrolysis. The role of copper on the anodic dissolution of nickel matte is discussed in this work.

Jan 1, 1988

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

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