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By KNona C. Liddell

"Many metal recovery processes involve heterogeneous reactions in porous media accompanied by fluid flow and mass transfer. Modeling such systems is difficult because of the number of rate processes involved and is complicated even further by effects due to the structure of the porous medium. Data on even bulk properties of the medium are often severely limited or unavailable. For many such systems, a cell model may provide an attractive alternative to models based on transport mechanisms in a differential volume. A cell model requires less input data and is computationally efficient. Identical residence time distributions can be obtained with models of both types, and both allow conversion and concentration profiles and histories to be calculated. The formulation and properties of cell models for metals recovery are described in detail.INTRODUCTIONSubsurface mineral leaching, metal ion recovery and environmental remediation are significant modeling challenges. They involve one-, two-, or three-dimensional reactive flow in multi reaction open systems. Dissolution, adsorption, and ion exchange occur at reactive mineral surfaces, and these heterogeneous reactions are accompanied by acid-base, complexation, and redox reactions in the solution phase.Two approaches have been taken to reactive flow problems in geologic media: mixing cell and transport models. Mixing cell models, the subject of this review, are based on a network of connected cells, each with a specified number of input and output streams. Mixing cells are assumed to have no internal solute concentration gradients, that is, each cell behaves like a well-stirred tank. Gradients are represented by step changes between connected cells; this results in a model that is spatially discretized at the outset. Different methods of discretizing the model equations are considered more fully below. Although this is not strictly necessary, it has usually been assumed in subsurface flow applications that all cells in the network have the same volume and identical initial properties."

Jan 1, 1996

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By Peter K. Everett

One of the major driving forces behind the development of the Intec Copper Process has been the increasingly stringent regulations governing SO2 emissions and, in some parts of the world, a declining H2SO4 market. Other incentives include operating cost (9.2 US c/lb Cu), capital cost (US $1400/annual tonne Cu compared with smelter cost of US$3-4000/annual tonne Cu) and the ability to treat low grade and contaminated concentrates. With such advantageous features, widespread use of the process is expected over time, leading to the production of large amounts of residues containing around 25% elemental sulfur, together with approximately 50-60 % akaganeite (FeOOH) and the ganggue minerals originally present in the concentrate feed. This paper briefly describes the Intec process chemistry involved in the formation of elemental sulfur, thereby avoiding atmospheric sulfur dioxide pollution, and the investigations to be carried out either to extract it or to turn the residue into a valuable by-product while minimising any adverse environmental effects, The process is being developed jointly by a group of fifteen major international mining companies.

Jan 1, 1996

By T. T. Chen

Canadian Electrolytic Zinc has developed the "cement-stabilization of jarosite residue" Garofix) process to stabilize zinc plant jarosite residues for disposal. The cement-jarosite mixtures cure quickly, have good mechanical strength and low hydraulic permeability; they possess good neutralizing capability and chemical stability. In the jarofix process, Portland cement partly decomposes jarosite to form (SO4MOH)12.nH2O, ferric hydroxide and an alkali sulphate. Approximately 40% of the jarosite reacts in mixtures containing 30% cement. The jarofix product also contains various Ca-Al-Fesilicate-sulphate-hydrate phases and gypsum, which bond the individual particles together imparting mechanical strength and reducing the permeability. Most of the reactions take place in the first few hours of curing. Ammonium jarosite is slightly more reactive than sodium jarosite but releases NH3 gas; water-soluble Zn in the jarosite residue is stabilized in the cement reaction products.

Jan 1, 1996

By Nagy El-Kaddah

One of the emerging technologies for the production of ultra-clean metals is electromagnetic filtration. The theory and the mechanism of electromagnetic separation of inclusions from molten metal are briefly reviewed along with basic electromagnetic separation systems. This paper focuses on inclusion removal in the induced current separators, with specific reference to a new separator developed at the University of Alabama. A simple analytical model is presented for the analysis of particle separation in such a system. The role of the applied magnetic field on inclusion removal will be discussed. It is shown that particle velocity increases exponentially with increasing magnetic field strength. At moderate field strengths, the velocity of 50 to 100µ inclusions are an order of magnitude larger than those achieved by buoyancy. The separator developed at the University of Alabama is described together with experimental results of laboratory and large scale experiments on purification of molten aluminum. These results demonstrate ?the capability of the system for producing super-clean metals.

Jan 1, 1996

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By R. J. Dippenaar, W. H. Van Niekerk

"An injectable lime-based desulphurization reagent for the treatment of liquid iron was developed. Firstly, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na20 to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. Subsequently, pilot plant and full scale industrial injection trials were conducted. It was found that lime-based slags, containing Na20 and CaF2, are able to desulphurize liquid iron efficiently. By the injection of a lime based reagent consisting of 60% lime, 25% soda ash and 15% fluorspar at a rate of 7 kg reagent/ton hot metal, the sulphur level in the metal (115kg) was reduced from 0,07% to 0,01 % within 5 minutes. The lime-based reagent developed in this study was successfully injected, both from a metallurgical and from a pneumatic point of view, on an industrial scale. The mathematical model utilised in this study, can be used successfully to predict the course and extent of desulphurization by lime-based slags. IntroductionMainly due to environmental difficulties encountered with pure soda ash, dry slag formation with CaC2 and high cost when Mg are used as desulphurizers, much incentive exists for the development of an inexpensive, environmentally friendlier desulphurization reagent. As a first step in the development of such a reagent, selected lime based slags containing small quantities of CaF2 to increase fluidity, and Na2O to increase the basicity, have been evaluated on laboratory scale from a thermodynamic point of view. This was followed by pilot plant injection experiments in which the kinetics of the relevant desulphurization reactions were evaluated. Finally, full scale industrial trials were conducted. All three phases of the investigation will be discussed with the major emphasis being placed on the kinetic study."

Jan 1, 1996

By Milton Blander

"A review of concepts and theories for predicting thermodynamic solution properties of multicomponent high temperature liquid solutions is reviewed. During the last 50 years the ability to predict such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.INTRODUCTIONA number of solution theories and concepts have been developed which reliably predict the properties of multicomponent solutions from those of the lower order systems (often only the binaries). Because there is available data for a large fraction of the important binaries, the capability for making predictions for many multicomponent systems used in metallurgical separation processes is broad and potentially very useful. At the very least, the theories greatly minimize the data necessary for predicting properties of complex multicomponent solutions of molten salts, silicates and metals. It is the purpose of this paper to discuss the concepts which are demonstrably useful. We will discuss simple forms of the theories to make the concepts clear but we will refer to the publications which contain the more complex equations needed to treat the large majority of systems.A simple framework for understanding what we need to know in order to make technologically useful predictions is based on well known thermodynamic principles. In technologies and sciences where molten salts, slags magmas or molten metals are used or studied, one must often calculate the extent of a chemical reaction (or separation) or of phase changes. To do this, one must first write an equilibrium constant, K, for the reaction in terms of the standard free energy change of the reaction, ?G°."

Jan 1, 1996

By E. T. White

The population balance is one of the basic relations for a:n:aIysing particulate minera1 processing operations. It is an exact relation. The principles of the population balance are reviewed and applications in the minerals industry discussed.

Jan 1, 1996

By I. B. Scorzelli

The aim of this paper is to make a detailed mineralogical characterization of a typical brazilian xenotime and zircon from the Pitinga Mine using SEMIEDS techniques, On the other hand, superficial pretreatments with HCI, HN03 and HF were done to evaluate the modifications on surface compositions and the morphology of the particles for flotation purposes, The studies showed that both xenotime and zircon present very small inclusions of thorite; zircon is strongly metamictizated given rise to malacon. The HF pretreatment deeply affected the morphology of the particles as well as the surface properties in relation to flotation.

Jan 1, 1996

By Gabriel A. Torma

This paper provides infonnation on selected technologies available for remediation of metal contaminated soils and industrial effluent solutions. Because some of the industrial sites are contaminated with organics (solvents, gasolines and oils), an effort has been made to introduce the most frequently used cost-effective cleanup methods, such as "bioventing" and "composting." The microorganisms involved in these processes are capable of degrading organic soil contaminants to environmentally harmless compounds: water and carbon dioxide. Heavy metals and radionuclides contaminated mining and industrial sites can be remediated by using adapted heap and dump leaching technologies, which can be chemical in nature or bio-assisted. The importance of volume reduction by physical separation is discussed. A special attention is devoted to the remediation of soils by leaching (soil washing) to remove heavy metal contaminants, such as chromium, lead, nickel and cadmium. Furthermore, the applicability of biosorption technology in the remediation of heavy metals and radionuclides contaminated industrial waste waters and acidic mining effluent solutions was indicated.

Jan 1, 1996

By Ole Rud Bendixen

Topsoe has developed a Wet gas Sulphuric Acid (WSA) process which effectively recovers SO2 in off-gases from non-ferrous smelters and roosters. The product is concentrated sulphuric acid of typically more than 96 wt% irrespective of SO, concentration in off-gas. The process does not generate any waste products or waste water and does not use any absorbents or other chemicals. In the process, up to 99.3% of the SO2 is converted catalytically into SO3, which reacts with water in the gas, hereby forming gaseous sulphuric acid. The acid is condensed in a WSA condenser of proprietary design. Excellent heat economy and practically no sensitivity to the water balance mean that no extra sulphur burning is required at any S02 concentration, The process is especially well suited for treating off-gases where the SO2 content is lower than approx. 5-6%, and it is a good alternative to a complete renovation of a smelter. However, also off-gas from flash smelter may be treated. The process has found good use in both molybdenum and lead roosters. An example from a molybdenum roaster in Chile shows that 97-98wt% acid is produced from a 2.3 % S02 gas. This plant is situated in the outskirts of Santiago and represented a major local source of SO2. The plan was started in May 1993.

Jan 1, 1996

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By Qian Fu

Although chlorine fluxing to remove magnesium has been widely practiced in the aluminum industry for many years, there appear to have been few fundamental studies of the kinetics and transport phenomena involved. The paper describes such a study in which the rates of reaction of individual argon/chlorine bubbles with aluminum/magnesium melts were measured. The detachment of bubbles from a submerged nozzle, at variable depth in the melt, was detected by a microphone and the arrival of the bubble at the top surface by conductivity probes. Analysis of exit gases and mass balances yielded the overall progress of reaction. Experimental results are interpreted in terms of heterogeneous reaction kinetics and mass transport to the bubble-melt interface,

Jan 1, 1996

By T. J. White

A synthetic Mineral Immobilization Technology (SMITE) has been developed for stabilizing municipal and hazardous waste incinerator ash. Tailored additives are introduced to the ash in a' first stage that pre-stabilizes all the toxic metal components in non-volatile forms. and in a second pyrometallurgical stage, these are converted to insoluble mineral analogues. It has been found that a combination of apatitie. spinal, anhydrite and monazite can immobilize all the ash components at high waste loading and high density. Typically the stabilized products contain in excess of 50 wt% ash and have densities of 2.5- 3.0 g.cc-1. Toxicity Characteristic Leach Procedure (TCLP) testing has demonstrated that the products well satisfy regulatory requirements. The cost of production and disposal of SMITE waste forms in 2-5 less expensive than. convential methods of solidification/stabilization. This paper will describe the principles of SMITE design for ash stabilization, outline the fabrication procedure, and present comprehensive microstructural and chemical data to validate waste form performance.

Jan 1, 1996

By Bo Björkman

A controlled dust generation whereby the dust generated would be enriched with specific metals would considerably facilitate the possibilities of recovering metals from such dusts. A basic understanding of the dust forming mechanisms is of fundamental importance to achieve a controlled dust generation. The present study deals with dust formation in a copper converting process. Dust samples collected from various places in the gas cleaning system were characterised for chemical and mineralogical composition using chemical analysis as well as microprobe analysis. Thermodynamic calculations were used to predict the formation of chemically formed dust at various temperatures and amounts of leakage air to the gas system. The results show that a separation of mechanically formed dust. e.g . Si0:2. Cu and chemically formed dust. e.g .? Ph, Zn, As, Bi. could, to some extent, be obtained due to their different particle sizes. A selective condensation of Pb, Zn and As at various temperatures could. according to thermodynamic calculations, he possible at high temperature. A selective condensation of metals requires an airtight gas cleaning system or a gas cleaning system with a limited amount of leakage air in order to maintain the desired temperature level.

Jan 1, 1996

By D. J. Droppert

This paper describes the precipitation-production of crystalline scorodite (FeAs04.2H20) from arsenic-rich sulphate-based metallurgical solutions at ambient pressure (95°C). Arsenic is precipitated by means of a controlled precipitation technique in which the supersaturation of the solution is carefully controlled. By controlling the supersaturation in the presence of seed material. the formation of amorphous ferric arsenate is prevented. Scorodite is known to be the most stable As(V) compound and is therefore preferred as host mineral for arsenic immobilization. The effect of the following parameters on the preCipitation behaviour and kinetics of scorodite are discussed: Type of base seed concentration initial [As]. sulphate concentration. neutralization rate. seed recycling and method of Fe(ll!) addition to Fe-deficient arsenic solutions.

Jan 1, 1996

By S. G. Kumar, R. G. Reddy

"Niobium aluminides offer the advantage of higher high temperature capability compared to other intermetallic aluminides due to the refractory nature of niobium. However, the reaction sequence in Nb-Al system is sluggish and currently there is a great interest in the processing aspects of these materials. In the present study, a systematic investigation was undertaken to compare the effect of different powder metallurgy processing routes on the phase relations and microstructure of 66Nb-22AH2Ti (in atom percent) alloy. The three different process routes adopted were: (i) cold pressing followed by reaction sintering; (ii) cold pressing and hot pressing followed by sintering; and (iii) arc melting, hydride-dehydride process to make the alloy powder followed by cold pressing and then sintering. The samples are analyzed by XRD, Optical Microscopy, SEM-EDS and EPMA. The analysis showed that alloy pellets made from pre-alloyed powders i.e., arc melting followed by hydride-dehydride process, gave good densification and more Nb3Al formation.1. IntroductionTo improve the performance standards of turbine engines, materials scientists are challenged to develop materials that have· high thrust-to-weight ratio with high specific strength, high specific modulus and good environmental properties at elevated temperatures. The conventional high temperature materials like nickel based superalloys are high in density and hence many of the high temperature materials scientists have focussed their attention on intermetallic aluminides like Fe-AI, Nb-AI, Ni-AI and Ti-AI in recent years. The phase relations and properties of alloys based on Fe-AI, Ni-AI and Ti-AI are fairly well known whereas little is known about the alloys based on niobium aluminides."

Jan 1, 1996

By John A. Herbst, William T. Pate

"Plantwide control of mineral processing operations has long been sought for its potential benefits. These benefits include minute-to-minute optimization, reacting to disturbances in ore characteristics and equipment status as they happen, and the coordination of all unit operations in pursuit of the highest performance level. However, several difficult challenges have kept us from fully realizing those benefits. One of these challenges has been to provide fairly complete quantitative descriptions of unit operations to account for critical interactions within and between unit operations. In some cases we understand the physics and chemistry very well and can incorporate that knowledge into phenomenological models. In other cases our knowledge is incomplete, so we must rely on other forms of knowledge such as fuzzy logic or neural nets. Another challenge to be met has been to simultaneously compute a large number of manipulated variables. In the past this challenge was met by optimizing only unit-by-unit, rather than on a global basis to significaritly reduce the number of variables. In this paper, a procedure that globally optimizes one or two important variables is outlined. This procedure comes much closer to true plantwide optimizing control while remaining computationally feasible. Finally, another major challenge is to choose a meaningful global objective that can be calculated with the models and can be effectively optimized. Financial goals seems to be the objectives of choice.This paper discusses recent progress in overcoming the challenges and illustrates a promising approach which is being pursued at Mexicana de Cobre's La Caridad copper ore concentrator. At M de C, advanced control strategies have been installed one at a time in the crushing, grinding and flotation sections. During this period, the throughput of La Caridad, Mexico's largest copper concentrator, increased from 76,000 tpd to 90,000 tpd. Plantwide integration is expected to gain an additional 3% improvement in profitability."

Jan 1, 1996

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