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By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly. subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fumeless fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

By Yotamu Hara, Animesh Jha

"High Curie temperature and large magnetic anisotropy make cobalt an important magnetic material for power engineering applications of magnets operating above ambient. It is also an essential constituent of modem lithium - cobalt oxide batteries, without which modem electronic gadgets will be functionless. Both these applications of cobalt save energy and reduce C02 emission. Ironically, however the production of cobalt from copper and nickel smelting in the world remains one of the least energy efficient process. The paper analyzes the energy balance, material and process chemistry of overall cobalt recovery and the waste generated, which entail the process limitations. We discuss a novel approach for the reduction of sulphide minerals with CaS04, permitting better separation of metals from slag and generating higher concentrations of S02. Such an approach may seem to be an alternative energy efficient option for processing and further purification of cobalt in metallic form. The results are discussed in the context of process thermodynamics and reaction kinetics for Coalloy production.IntroductionCopper sulphides bearing minerals are predominantly associated with iron and cobalt sulphides minerals. Carrollite (CuC02S4) is a mineral that has both copper and cobalt sulphides [1,2], which may also contain FeS, by substituting either Cu2+ or Co2+ ions in mineral lattice. On smelting copper - cobalt - iron sulphide concentrates, some parts of the cobalt often partition to matte at preferentially low oxygen potential by forming eventually an alloy phase with copper, however a significant fraction is often lost into an oxide slag rich in iron and silica. The slag heaps accumulated in the Copperbelt region in Zambia from last 60 years of mineral processing and metal extraction is reported to be 0.3 to 2.6 wt% of cobalt element, which is high [3]. Cobalt is also available in smaller concentrations in the copper smelting and converter slag, as reported in the investigations on the recycling of such slag materials using leaching with ammonium salt [4], iron chloride [5], and sulphuric acid [6], and solvent extraction [7].The recovery of cobalt from slag, irrespective of the techniques researched so far, does not seem energy efficient because the molten slag at 1300°C is quenched by losing thermal and chemical energy. The quenched slag is again reheated to above room temperature for leaching and above liquidus for carbothermic reduction of residual cobalt oxide. For example, in Mintek DC arc smelting [3], 80% of cobalt and 95% nickel are recovered by expending 600 kW per tonne. Assuming that the mineral carrollite is the starting phase, the univariant calculations for the Co-Ca-Si-S-0, Fe-Ca-Si-S-0, and Co-C-Si-S-0 systems are shown in Figure la, lb, and le, respectively at 1573 K."

Jan 1, 2012

By Edgar E. Vidal

The deposition of ceramic materials onto substrates is of special interest in the development of surface related technologies. Research interest has been placed on using thermal plasma as the deposition method, specifically inductively coupled plasmas. Many different modifications to the same basic principle of deposition have been performed through out the materials research community. Such a technique may have many advantages over more conventional techniques, such as high deposition rates, high surface area coverage, clean energy source, no contamination from electrodes and operation near atmospheric pressures. Materials deposited vary from simple oxide systems like TiO2 to more complex structures like ternary oxides and nitrides. This paper reviews recent developments relative to the inductively coupled plasma deposition of thin films.

Jan 1, 2003

By Flávia Paulucci Cianga Silvas, Otávio da Fonseca Martins Gomes, Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenorio, Guilherme Apostólico Bortolini, Stoyan Gaydardzhiev

"Printed circuit boards (PCB) are particularly problematic to recycle because of the heterogeneous mix of organic materials, metals, and glass fiber. PCBs are found in almost every electroelectronic equipment and their recycling process involves a pre-treatment to separate the products which contain targeted metals. In this work, a physical processing involving sequential shredding and hanuner milling were used to obtain a comminuted sample from scrap printers PCBs. The thus prepared sample was analyzed for particle size distribution and by optical microscopy as well was subjected to pyrolysis, leachabilty and chemical composition determination by XRF. The metals concentration was determined by ICP and AAS. The PCBs have been also analyzed by SEM-EDS (micro-analysis and X-ray mapping). The results show that the studied PCBs are lead free, multilayer with 4 copper layers, have 45% of metals and the copper is present in significantly higher concentration than the rest of the metals.IntroductionThe global generation of e-waste (electrical and electronic equipment waste - WEEEs) grows at a rate of about 40 millions of tons per year [ l].Among this e-waste there are PCBs that are present in almost all electronic equipment. Their composition is heterogeneous and varies according to several factors, including: kind of EEE, when and where it was produced, fabrication technology [2], etc. In printers, the PCBs represent about 6.6- 8 wt.% [3].The PCBs treatment may include physical, pyrometallurgical, hydrometallurgical, ectrometallurgical and more recently bio-hydrometallurgical process. Normally there is a combination between these processes [2, 4, 5, 6, 7, 8, 9, 10].The diversity between the different PCBs composition complicates the recycling process since the composition of metal and others materials can vary according to the models. So characterization is an indispensable step before any processing of PCB to begin. Owing to the above said, the main goal of this work has been set to characterize representative samples of PCBs from printers through physical, chemical and microstructural analyses."

Jan 1, 2014

By Patrick R. Taylor

Sub-micron sized boron carbide powders have been synthesized in a non-transferred arc thermal plasma reactor. Precursors for this synthesis are boric acid or boron oxide powders and methane. The powders produced were characterized in terms of size, shape and purity. Methods to increase the purity of the product were evaluated and included hot water leaching to remove unreacted oxides and controlled temperature, air roasting to remove excess carbon. Theoretical results are also presented on the thermodynamics and mechanisms of the synthesis reactions.

Jan 1, 1994

By Jing Lin, Yuan Xu, Qingcai Liu, Dengfu Cheng

"Smelting reduction technology has been developed greatly in recent years. But one of the key problems for this technology is about the refractory that used as lining material in the molten bath. Investigation and test shown that corrosion rate of refractory was much higher and the corrosion mechanism was much more complexity in the molten bath of smelting reduction with iron bath than that of the blast furnace and rotary furnace technology [l-5]. The corrosion behavior and corrosion rate of Al2OrC-ZrO2 series refractory in the melt of smelting reduction with iron bath have been studied by rotary immersion and quasi-static immersion test in this paper. The major factors that affect the interaction between the melt and refractory were investigated. The test results shown that the corrosion rate of AI2O 3-C-ZrO2 series refractory decreased with the ZrO2 increasing when ZrO2 content was from 3% to 10%. Ferrous oxides content, relative moving speed between the melt and refractory and temperature of the molten bath were the important factors that affect the corrosion rate. But the ferrous oxides concentration was the most important one. The corrosion rate was increased as a linear relation with the rising of ferrous oxides content of the melt. The corrosion rate in the quasi-static immersion was much less than that of the dynamic immersion (rotary immersion) for the Al2O 3-CZrO2 series refractory in the same testing condition. The corrosion mechanism of Al2OrC-ZrO2 series refractory is: graphite oxidized in advance, then interaction between the constituents of refractory and melt taken place and deteriorate layer of refractory and new compounds were formed, the properties of refractory was changed.IntroductionSmelting reduction with iron bath is a typical technology [3, 4, 6]. The obvious features of the melt for smelting reduction technology with iron bath are much higher ferrous oxides and much more complexity melt composition and structure than that of the blast furnace technology [2, 5-8]. The properties of the melt were changed dynamicilly and constantly in reduction process. On the other hand, the behavior of the melt depends on the activity and the reduction rate of ferrous oxides in the molten bath[9]. Because of the high concentration of ferrous oxides in slag and high reduction rate in the molten bath, the corrosion behavior and corrosion mechanism of the refractory lining by melt are an important factor in development of the technology of smelting reduction with iron bath. Up to now, improving refractory quality to anti-corrosion of melt and developing high quality and long term refractory used as the lining refractory materials in the molten bath of the final reduction furnace are also the most important questions for developing smelting reduction technology."

Jan 1, 2000

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 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 Grant E. Casley

Since 1970 Mount Isa fines Limited has made a significant increase in blister copper production from approximately 100,000 to 155,000 mt per annum and in fact 161,040 mt were produced in the calendar year 1974. Flowsheet developments including fluidised bed roasting and converter slag flotation are discussed, particularly their contributions to minimising major equipment changes in smelting and converting. The use of model- ling and simulation techniques for such an exercise is mentioned. The paper reports the alterations made to both equipment and operating techniques in the reverberatory furnace and converter sections to achieve the regular production of 250 mt of blister per converter day from a 41% Cu matte grade. The effects of flux composition on converting performance are highlighted. The air quality control programme is discussed in relation to its restriction of blister copper production.

Jan 1, 1976

By Tianzu Yang, Weifeng Liu, Lin Chen, Deyu Wang

"Due to the gradual exhaustion of easily extractive gold ores, it is vital to make efficient use of refractory gold ores which hold 30% gold storage of the world. However, the disadvantage of current processing technologies for refractory gold ores consists of severe pollution, low gold extraction ratio, high investment, etc, thus great research interests were attracted during recent years. This article provides an overview of the distribution and categories of the refractory gold ores in the world. The state of art in processing refractory gold ores by pyrometallurgy, hydrometallurgy and biometallurgy techniques and their industrial applications are highlighted. Potential environmental conservative techniques for efficient gold extraction are also reviewed.IntroductionResources of Refractory Gold OresAs easily extractive gold ores are going to be exhausted with the large scale mining nowadays, refractory gold ores are becoming more and more important. Gold in the refractory gold ore cannot be fully extracted using conventional method (cyanidation) even with fine grinding. The amount of gold in the refractory gold ores is about 1500~2000t in China, which occupies 30~40% of the total gold storage [1]. Therefore, it is vital to make efficient use of refractory gold ores."

Jan 1, 2013

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

By K. Mansfield

Spent Pot Lining (SPL) is an unavoidable waste product of the electrolytic process in the smelting of aluminium. SPL is considered to be a hazardous waste in various countries because it contains significant quantities of absorbed fluorides along with traces of cyanide. In 1995, Portland Aluminium undertook the investment of AUD$26,400,000 to construct a Research and Development processing facility at Portland, Victoria, Australia, to treat SPL. Extensive research, development and design were carried out over 5 years prior to the investment decision. This study led Portland Aluminium to install an Ausmelt pyrometallurgical furnace to combust and melt the SPL producing a hydrogen fluoride (HF) laden gas, which was cooled and then converted to aluminium fluoride (AlF3). Both the cooling and AIF3 manufacture were processes developed by Portland Aluminium. Many commissioning, equipment reliability and process problems have been encountered that had not been experienced in the trials at Ausmelt or in the developmental process for the treatment of the furnace offgases to form AlF3. Designs based on anticipated process expectations have had to be re-engineered by the SPL team to ensure plant and operational success. In June 2001, the installation of the final major component - a slag granulation process - was completed. This has produced a vitrified (glassy) slag that is expected to have leachability qualities acceptable to the Victorian Environment Protection Authority (EPA) to allow commercial end uses of the slag material to be developed. Today (September 2001), the smelter has successfully used the fluoride product, namely 65- 70% AIF3, in aluminium production and the SPL plant has significantly increased throughput with expectations to be at annual design rates of 12,000 tonne of SPL in early 2002. "The Alcoa Portland SPL Process" has been technically developed and is a proven process for the treatment and recovery of valuable components from SPL materials.

Jan 1, 2002

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 Kenneth N. Han

Thermodynamic and kinetic aspects of nickel and cobalt leaching from metals. minerals and ores in various media have been reviewed and discussed in this paper. A kinetic model developed to delineate the leaching mechanisms for these metals has been discussed in view of experimental observations. The current review also includes the dissolution behavior of nickel and cobalt from various minerals such as oxides, sulrides. ocean floor manganese nodules, and laterites. A particular emphasis has been extended to similarities and differences of the dissolution behavior of these two metals in various media. The leaching of nickel as well as cobalt metal in acidic solutions and arnmoniacal solutions exhibits in most part mass transfer controlling. although at some pH's, chemical controlling or mixed controlling mechanisms seem to prevail. The leaching of nickel and cobalt from oxides in acids and ammoniacal solutions. on the other hand, can be described best by chemical controlling mechanisms.

Jan 1, 1993

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 Eddie C. Chou

Phelps Dodge, Inc. (PD) is currently developing a lateritic nicke/Vcobalt deposit in Madagascar. Hazen Research, Inc. provides technical assistance to PD to investigate recovery processes for nickel and cobalt. Various process options were evaluated in laboratory experiments and pilot plant operations. The process selected for the feasibility study consists of feed preparation, high-pressure acid leach, countercurrent decantation wash, sulfide precipitation, sulfide dissolution, solvent extraction, ion exchange, and electrowinning. Among these unit processes, high-pressure acid leach, sulfide precipitation, and sulfide dissolution are applications of pressure technologies. Process development work and design criteria for commercial operations of these unit processes are presented in this paper. Concerns related to scaling in the high-pressure acid leach and the sulfide precipitation processes are discussed. Corrosion of various metal coupons under these environments was examined.

Jan 1, 2000

By Animesh Jha

"Fine ceramic powders (<500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapour-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapour species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly 'identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.IntroductionThe physical and mechanical properties of ceramic components are strongly dependent on the powder particle size and morphology used for their fabrication. For example the strength (Os) of the structural ceramic components increases with decreasing average grain-size (d) in accordance with the Hall-Petch relationship: Os = 0""0 + k/(d)1/2. Here k is an empirical constant which can be established from the graphical relationship. However as the particle size approaches submicrometer-size range, the dependence of strength on the particle size becomes more complex [1]. The design of ceramic components based on nanometer-size particles have recently become an important field which can offer ceramic materials with properties comparable to their metal counterparts. Several materials based on these concepts have been developed and reported by Niihara [2]. For example, the Al2O 3-SiC nanocomposite, having average B-SiC grain size 0.3-2um with intragranular SiC particulates of 5-10 nm has unusually high strengths (1100 MN/m2) at low and elevated temperatures combined with enhanced fracture toughness (> 4 MN-ml.5) which is an unusual combination in structural ceramics. Besides mechanical properties, as the particle size of ceramic powders approaches the nanometer-size range, the charge transport properties also improve by many times. The effect of particle size on the electrical conductivity of Si3N4-TiN composites has been well documented [3.4]. The size of ceramic particulates without doubt plays a pivotal role in determining the properties of ceramic components."

Jan 1, 1996

By P. N. Anyalebechi

The effects of application of steady and pulsed electric current on the cast microstructures of ingots of a 7050 type aluminum alloy have been experimentally investigated over a solidification rate range of 0.1-10 K/s. This involved the application of an electric current of 465-930 mA/cm2 of melt surface area to laboratory-size ingots solidified in a unidirectional manner. Within the ranges of electric current density and solidification rate investigated, the applied electric current reduced the average dendrite, grain, and second-phase particle size. It also made the size distribution of the second-phase particles more uniform. The mechanism for the observed refinement of the cast microstructure by the applied electric current is not well understood. The potential effects of heat-induced local convections, shear stress-induced fragmentation of dendrites, increased temperature gradient due to Joule heating and the thermal and constitutional supercooling engendered by Peltier, Thompson, and Joule heating are discussed.

Jan 1, 2009

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&apos;), 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 Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002