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By H. J. Roorda

With an increasing need to obtain metals by processing complex fine intergrown ores, the use of electron-optical techniques will become more important as a tool for mineralogical studies. Electron images enable a higher spacial resolution than can be obtained by optical microscopy and thus provide a powerful and necessary aid for the examination of small grains and finely locked particles. In this paper the mineralogy of Meggen ore was investigated. Both light-optical and electron-optical techniques were used to evaluate the mill feed and products of the concentrator. Detailed examination by reflected-light microscopy to assess the comportment of galena in the complex pyritic ore was inconclusive in establishing the cause for low lead recovery of only forty percent of the ore's lead content. Electron microprobe analyses indicated that the majority of the lead lost to the tailings was accounted for by extreme fine (often smaller than one micron) and complex intergrowths of galena in pyrite. The remainder was lost as fine free galena grains.

Jan 1, 1987

By M. Moinpour, E. Liao, C. Y. Aw, D. J. Brown, P. W. Cheung

"Currently, silicon-based insulated-gate field-effect devices are being widely developed as the basic structural elements in a new generation of chemical microsensors. In this paper, we discuss some of the process considerations related to the fabrication of the Chemically Sensitive Field-Effect Transistor (CHEMFET). This ion-sensitive CHEMFET (or ISFET as it is often called) can be used for pH measurements (i.e., as a pH sensor) when the gate insulator of the electrolyte/insulator interface is made of Si3N4 obtained by the LPCVD method. Effects of processing parameters such as the Si3N4 deposition rate, gas composition, total flow rate, annealing treatment, etc. on Si/Si02, Si/Si3N4 and Si/Si02/Si3N4 structures are discussed in relation to the CHEMFET fabrication. Their effects on the electrical characteristics and chemical response of the sensor are also examined. Capacitance-Voltage (C-V) measurements and ESCA analysis have been used to interpret the results. The Si3N4/Si02 double dialectric layer provides improved ion blocking for the gate insulator in electrolyte solutions with enhanced pH sensitivity over time. The stability and performance of the fabricated CHEMFET sensors were tested by measuring the pH sensitivity in various storage conditions. The SEM analysis was used to evaluate the hydration effect at the ISFET's gate insulator with respect to different storage conditions.IntroductionThere has been a continuous interest in the development and fabrication of various chemical microsensors for chemical and biomedical applications over the last fifteen years. The application of semiconductor (particularly silicon) technology to the area of sensor fabrication has led to an emergence of a new generation of miniaturized, microelectronic, solid-state chemical sensors. There are numerous clinical situations where continuous monitoring of body electrolytes concentrations such as Na+, K+, Ca+2 , etc. and blood gases (pH, Po2 , and PC02) would be essential for the effective diagnosis and management of patients under critical conditions. Solid- state microsensors can be used for direct and continuous in vivo measurement of the above parameters in most instances."

Jan 1, 1988

By Vaughan R. Voller

"Solidification systems from conduction controlled freezing of a pure material through to alloy phase change that include flow and segregation processes are described. The components in a general solidification model-variables, governing transport equations, and local scale relationship-are outlined. A central focus is the presentation of an explicit procedure for coupling between macroscopic and local scale variables.IntroductionSince the seminal work of Byres et al.[!] in the 1940's there has been a steady progress in modeling solidification systems with increasing levels of complexity. The object of this paper is to track the evolution of these solidification models and present a general modeling approach that applicable to a wide range of the solidification systems of current interest.Solidification SystemsIn a broad sense the underlying physics in a solidification process occur at two distinct length scales:1. The macroscopic scale of the process over which the governing transport equations of heat, mass and momentum hold.2. The local scale at the solid-liquid interface where the solidification phenomena are operative."

Jan 1, 1999

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By T. T. Chen

A mineralogical study of copper anodes and copper anode slimes was carried out to elucidate the silver phases present and the behaviour of silver during copper electrorefining. Most of the silver in the anodes is in metastable solid solution in the copper metal. As the copper dissolves, silver also dissolves, but is rapidly removed from solution by a variety of reactions. Some of the silver is precipitated as Ag by cuprous ions and some is precipitated as a complex CU-Ag-Pb-As-Se oxidate phase. Much of the silver, however, reacts with copper selenides to form, progressively, (CU,Ag) 2se, AgCuSe and Ag2se. The reaction commences at the periphery of the selenide grains and progresses inward; the result is commonly a silver-rich species on the outside of a silver-deficient core. Slimes collected periodically throughout the electrorefining cycle show a progressive silver enrichment of the selenides. Traces of Ag2Te also may be present, but the telluride seems to J:ie a rare constituent of most raw anode slimes.

Jan 1, 1989

By Maija-Leena Metsiirinta

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. SEM/EDS 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 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 Alan P. Prosser

The heap leaching of gold ores by cyanide solution was simulated by computer program. The program uses only basic m1neralogical and chemical data; no process testwork data, such as column leach results, are required. The simulation can be used to forecast the consequences of various changes before and during the testwork, design and operation stages of a particular ore-process system. Also, data about the state of different parts of the heap at various times help create an understanding of what is happening. The effects of mineralogical and process variables on the overall performance of the ?heap leaching process are illustrated. Comparisons are made to column leach tests and production data. The potential of the simulation strategy is discussed for making better use of operating experience and for suggesting specific research objectives. It has become clear that more attention should be paid to other metals that dissolve in the solution.

Jan 1, 1989

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thermodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Tibor Zoltai

Asbestos is a generic term for industrially useful fibers recovered from exploitable deposits of the asbestiform varieties of five silicate minerals: chrysotile, anthophyllite, actinolite-tremolite, cummingtonite-grunerite, and riebeckite. Asbestos and asbestiformm fibers of some other minerals are known to be carcinogenic. Minerals crystallized in the asbestiform habit are characterized by unique properties (morphology, strength and flexibility, physical and chemical durability, and defect-free surface structures). The key to the unusual properties, and health effects, of asbestifarm fibers appears to be in their unusual surface structure. In contrast, non-asbestiform crystals of the same minerals, including the five so-called asbestos minerals do not have these properties and are not carcinogenic (1, 2).

Jan 1, 1989

By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By T. Shi, Q. Yuan, S. P. Vanka, B. G. Thomas

"The quality of continuous cast steel is greatly affected by fluid flow in the mold region, especially involving transient phenomena. Mathematical models are being applied to investigate many different aspects of these phenomena, but their accuracy must be validated before they can be applied with confidence. As part of a long-term effort to develop and apply comprehensive models of the continuous casting process, this work evaluates the relative accuracy of models of three different fluid flow phenomena in continuous casting through comparison with measurements.Firstly, transient flow simulations of velocities in the mold region are compared with digital particle image velocimetry (PIV) measurements in a single phase water model. Large-eddy simulations (LES) are found to reasonably match the flow measurements, including transient flow variations, except at long time scales, which could not be modeled owing to the excessive computation costs. The standard K-e model produced very good agreement with time-averaged velocities for relatively little computation time, although it is inaccurate at predicting the transient variations. Secondly, particle trajectory calculations are compared with water model measurements to study the distribution and flotation removal of inclusion particles. The LES model was able to match the measurements both qualitatively and quantitatively. Thirdly, steady, multi phase flow computations are compared with flow patterns observed in both a water model and an operating steel caster with argon gas injection. For the same conditions, the water model and steel caster produced very different flow behavior. The computational model was able to match the measured flow patterns in both cases.This work suggests that computational flow modeling has the potential to match real processes as well or better than water models, especially when complex related phenomena such as particle motion and multiphase flow are involved. Much work is still needed to further improve the models and to apply them in parametric studies."

Jan 1, 2001

By Thomas J. Keefe, O&apos

Results of metal electrodeposition experiments conducted at the University of Brussels and University of Missouri-Rolla over the past few years are reviewed in terms of the relationship and impact on industrial processes. Examples are cited from common electrowinning, electrorefining, or electroplating operations for copper, zinc, nickel, cobalt and silver. The following topics are considered : metallographic structure, crystallographic texture, surface morphology, nucleation and growth, additive monitoring and effects, high current density, substrate related properties including adhesion. The studies were conducted on a variety of scales from laboratory beaker tests to full sized pilot and industrial operating plants.

Jan 1, 1993

By Eric J. Beckman

Recovery of metals from dilute solution, whether the matrix is solid, or liquid, remains a considerable technical and financial challenge. Methods currently exist whereby metals can be extracted from either type of matrix, yet these methods consume significant quantities of reagents and can also generate multiple waste ,streams in the process. Technology developed in our lab allows efficient application of environmentally-benign CO2 to a number of separation problems involving metals. For example, we have employed biphasic mixtures of C02 and water as a green acid leach medium. Metals have been extracted from a steelmaking process residue and then recovered as metal carbonates through depressurization. In this process, metals are extracted and recovered without the use of reagents other than CO2 and water, and CO2 is sequestered as a solid. In addition, through synthesis of Cal-miscible phase transfer agents, we have shown that CO2 can replace the organic solvent currently used in refining of precious metals, The sensitivity to pressure of phase behavior in a CO2-mixture may allow significant streamlining of the process as well. Finally, CO2 soluble chelating agents have been used to extract toxic metals from acidic effluent such as that found in plating facilities.

Jan 1, 1999

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

By Joseph Hamuyuni, Pekka Taskinen

We present experimental results for the liquidus in the system Cu2O - CaO -Al2O3 at 1250 oC. In this study, we quantified the liquidus by the equilibration/quench/analysis technique, with Cu2O, Al2O3, and CaO as primary materials exclusively. Experiments were conducted in air at an at oxygen pressure (p) = 21.3 kPa). Equilibrated specimens were quenched in brine solution of 10 wt% NaCl. We then quantified the liquid chemical compositions by means of Energy-Dispersive X-Ray Spectroscopy (EDS) and Electron probe micro-analyzer (EPMA). This study reveals inconsistences in liquidus surface of the present ternary diagram of the system here in mentioned. Differences of up to 10 wt % compositions of the species have been observed.

Jan 1, 2015

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By Michael J. Nicol

Growing environmental and occupational safety concerns about the use of cyanide in gold processing has increased the interest in more acceptable alternatives. The most likely of these is thiosulfate. However, the thiosulfate process lacks a proven in-pulp method of recovering the dissolved gold, because activated carbon is not effective for the absorption of the gold thiosulfate complex .. Anion exchange resins do offer a possible route for in-pulp recovery. This paper describes work aimed at the evaluation of the effectiveness of commercially available anion exchange resins for the recovery of gold from thiosulfate leach liquors? and pulps. It has been found that strong-base resins are superior to weak-base resins in that they have a larger capacity, which assists in reducing the competition from other anions within a leach solution. Further studies with a selected commercial strong-base resin have shown that competing polythionateanions (particularly tri-and tetrathionate). Lower the maximum possible gold loading but that gold is selectively recovered over other base metal anions in solution. Kinetic experiments found that while? competilig anibns did not affect the initial rate? of gold loading it was important to minimise the contact time of the resin in solution so to prevent displacement of loaded gold by competing anions over longer times. A small-scale resin-in-pulp plant investigation showed gold can be recovered from a leach pulp by a strong-base resin to yield gold loadings of 3000 mg/L, barren pulp containing less than 0.05 mg/L of dissolved gold and. copper loadings of 500 mg/L. Loaded copper was displaced gold and at a loading of 2000 mg/L gold the copper loading was minimal «500 mg/L). The resin was found to recover gold adsorbed on the solids that would, otherwise have. reported to tails if a solid/liquid separation method were used. A patented two-step elution process in which copper and then gold are separately eluted from the resin is also discussed.

Jan 1, 1998

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