Search Documents

By G. Van Weert

Refractory gold ores and auriferous concentrates containing silver tend to form refractory silver jarosites during pressure oxidation. Earlier work with pure Ag2S has shown that the addition of iodine species to the autoclave feed yields cyanide soluble iodargyrite (Agl) instead. Near complete silver extractions from the autoclave product were obtained at a I-/Ag+ ratio of 5 or more. This paper reports on the pressure oxidation and cyanide leaching of two industrial refractory (arseno) pyritic silver-bearing concentrates: 1. from Peru (sulphosalts) and 2. from the USA (pyrite, with acanthite occlusions). While using a I-/Ag+ mol ratio of only 1 in the feed, it has been possible to obtain 98 and 97% Ag extraction from the two autoclave products by cyanide leaching, respectively. This compares to 11 and 54% Ag extraction from the as-received concentrates and 4 and 15% Ag extraction, respectively, after pressure oxidation without KI present. The results of the testwork are discussed in terms of concentrate mineralogy and pressure oxidation conditions.

Jan 1, 1994

By Kent D. Peaslee

When supersonic oxygen jetting is used in electric furnace steelmaking, the lance jet axis is typically inclined at larger angles to the vertical than is used in basic oxygen steelmaking. The supersonic jet is important not only for refining the steel, but for sustaining the foamy slag in the electric furnace. Physical modeling was carried out using a room temperature, two-dimensional slice apparatus in which mercury represented the metal and water-glycerol the slag. High speed video photography with image analysis was used to study the effects of the angle of inclination on the slag/metal bath. Mathematical modeling using FLUENT provided a method of predicting flow patterns and the trajectories of drops injected at various points in the flowfield. A one-half scale water model of the system, in which lance heights, angles, and flowrates simulated those encountered in steelmaking operations, was used to provide a better understanding of some aspects of the oxygen blowing process in electric furnace steelmaking.

Jan 1, 1994

By Ben Q. Li

An efficient numerical algorithm for solving steady state heat transfer and solidification problems is described. The algorithm is of boundary integral type and is based on the formulation of the field variables along the boundary of the domain of interest. Compared with the familiar domain-based methods, such as the finite element and finite difference (or finite volume) methods, this boundary-based method has an advantage of solving fewer unknowns and hence has a potential for reducing computational time significantly. Another and yet more important advantage of the present algorithm is that it is a stable scheme and is not prone to numerical oscillations resulting from convective effects, as often encountered in the domain-based methods. Therefore, no numerical or artificial diffusion (such as streamline upwinding) is necessary. Numerical examples are presented that are drawn from processing systems for producing aluminum-based materials.

Jan 1, 1994

By P. Myllykoski, J. Nylander

"A commercial program package called Crownoff for the simulation of temper rolling in four high mills has been verified against measured data. The agreement between measured and calculated transversal strain distributions of the strip was found to be good. Effects of the strip crown and work roll bending force on the strain distribution were simulated. The results showed that when a single ground camber of work rolls is used for all strip widths; the strip crown should be parabolic, excluding the edge drop. An increase or decrease of the strip crown by 30 % during a coil can be compensated by a 2 to 5 t change in the work roll bending force. The ability to control the strip crown by work roll bending was insensitive to strip width. IntroductionCold rolled steel strips are usually temper rolled after recrystallization annealing, which follows cold rolling. The purpose of temper rolling is to suppress the yield point, finish the strip surface and correct possible flatness errors. The presence of a yield point might otherwise cause problems during subsequent forming processes. The in homogenous yielding in non-temper rolled steels leads to the formation of Lüders bands in the strip surface.The rolling force is influenced by the rolling speed and changes in frictional conditions in the roll bite. Therefore it is very important to plan carefully the mill settings and control algorithms during rolling. The purpose of mill control algorithms is to ensure constant reduction and the best possible strip flatness during the entire coil.Correctly predicting the rolling force is important for determining the mill presettings. Torque, forward slip and power requirements are not usually critical, if the reductions are small. However, the large elastic deformations occurring in the roll bite make the physical description of the process difficult. Physical rolling models developed for cold rolling contain assumptions that lose their validity as the reductions decrease to the level of one per cent."

Jan 1, 1994

By Raymond F. Dalton

Despite the ready availability of numerous zinc sources, the process of solvent extraction- electrowinning (SX-EW) has as yet found little favour in the zinc industry. It is suggested that this is largely due to the previous lack of availability of suitable selective reagents having the particular features required to enable them to fit in to a solvent extraction-electrowinning based process for zinc, particularly with regard to strength and selectivity for zinc over iron. This paper describes work on the development of new selective extractants for the recovery of zinc from both sulfate and chloride aqueous solutions and suggests how they might be integrated into new zinc processes.

Jan 1, 1994

By Luis W. Pommier

The developed processes, the subject of this paper, extract the hydrocarbons, halogenated organic compounds and metal contaminants from hazardous soils, rendering them non-hazardous and ready to be placed back on the ground. The processes first segregate a non-contaminated fraction from the contaminated soil. This initial task is performed using available minerals processing technology: sizing, gravity separation, magnetic separation, froth flotation, etc. The remaining contaminated fraction, is submitted to two leaching operations for the removal of organic and metal contaminants, whenever both are present or to a single leaching operation if only one type of contaminant is present. The decontaminated soil fraction is mixed with the non-contaminated fraction and is placed back on the ground. The leaching liquors, used at neutral pH, are non- hazardous. After decontamination the liquids are processed to extract the contaminants, now valuable materials, for commercialization. Organic contaminants are removed by distillation of the solvents. The metal contaminants are precipitated in their oxide form. In both cases the regenerated solvents are recycled. The decontamination processes are economically competitive with transportation and disposal of the soils to permitted facilities for hazardous materials, and most importantly the developed processes remove the liabilities from the Responsible Parties. The law establishes that these liabilities do not disappear with either fixation nor with transportation and disposal since the environmental liabilities are of the ? cradle to grave? type.

Jan 1, 1994

By T. J. White

Xtaltite is the trade name for a generic technology which exploits the well known insolubility of some minerals, which naturally incorporate toxic waste elements, to consolidate and immobilise a range of inorganic waste products. It is a specific case of synthetic mineral immobilisation technology (SMITE) which is already used to immobilise high level nuclear wastes (HLW. Although HLW is highly toxic, it exists in relatively small volumes, occurs in central facilities and may be stabilised at low waste loading (< 10 wt%). In contrast, heavy metal wastes are of considerable volume, therefore Xtalitite waste forms must routinely accommodate high waste loadings (usually in excess of 30 wt% for a particular toxic oxide or combination of oxides) and be suitable for fabrication in remote locations using relatively simple technology. This paper details the methodology underlying Xtaltite, with particular emphasis given to the interplay between solid state chemistry, durability and economic considerations. Specific reference is made to the treatment of arsenious and mercurial wastes.

Jan 1, 1994

By P. Ret, E. Üstiindag, R. Dieckmann, R. Subramanian, S. L. Sass

"Partial reduction reactions in the Ni-AI-O system, starting with the spinel compound NiAI20 4, are used to form metal-ceramic microstructures. By suitable choice of processing parameters, such as reduction temperature, oxygen partial pressure and time, two different morphologies of nearly pure Ni particles, equiaxed and rod-like, form within a ceramic matrix, which is either a-A12O3 or a metastable ""defect spinel"". Electron microscopy studies were performed for microstructural characterization, phase identification and chemical analysis. The fracture toughness of the Ni-AI2O 3 mixture was significantly improved with respect to that of the original spinel phase. The important issues that must be addressed to form useful metal-ceramic microstructures by partial reduction reactions rue discussed. It is shown that cracking at the original spinel grain boundaries, likely due to the large volume changes associated with the reduction reaction, can be avoided by the addition of small amounts of ZrO2• Initial results illustrating effect of ZrO2 on the microsuuctures are presented.IntroductionEngineering materials used in load bearing circumstances, particularly under extreme conditions (e.g. high temperatures or stresses), generally are formulated with complex microsuuctures. Such composite-like materials can possess properties unobtainable by either of the individual constituents. With metal-ceramic composites, for example, a material can be obtained with an optimum combination of the low density and high strength of the ceramic, and the toughness of the metal. For high temperature service, where demanding conditions are often present, for example, inside jet turbine engines, a successful new material must have low density, high Young's modulus as well as good oxidation resistance, strength, fracture toughness, creep and fatigue resistance. The candidates include intermetallic compounds, and metal-ceramic, intermetallic-ceramic and ceramic-ceramic composites."

Jan 1, 1994

By Gopalakrishna B. Prabhu, David L. Bourell

"Three mol% Yttria-Stabilized Tetragonal Zirconia (YSTZ) was prepared by a sol-gel synthesis technique using zirconium tetrachloride and hydrated yttrium chloride precursors. After drying and annealing at 823K, the particle size was in the range 10 to 20 nm. The zirconia powder was sintered using a uniaxial hot press at an applied stress of 20 to 40 MPa. One hour, isothermal sintering was performed in air after initial heating at 50K/min. Theoretical density was obtained at densification temperatures above 1498K. After sintering, grain coarsening characteristics were studied using constant heating rate anneals followed by quenching, based on a model for grain coarsening in a linear heating rate cycle. The microstructural change was studied using SEM and TEM and the phases were determined using x-ray diffraction.IntroductionThe ability to sinter nanocrystalline materials to full density several hundred degrees below the normal sintering temperatures is one reason for their current interest. [1-5] Yttria Stabilized Tetragonal Zirconia (YSTZ) of grain size of about 300 nm has exhibited superplasticity, with elongations as large as 800%.[6-7] Fine grain size is critical for superplasticity. Retention of the fine grain size during sintering of nanocrystalline powder is important if a material is to exhibit superplasticity or to exhibit physical or mechanical properties associated with the ultra fine structure. This paper investigates the sintering behavior and the grain coarsening characteristics ofnanocrystalline YSTZ.Techniques for synthesizing nanocrystalline materials have been studied in great detail earlier. [8-12] The techniques used to synthesize nanocrystalline zirconia include alkoxide synthesis [9], the chloride method [11], the peroxide method [13] and the acetone-toluene method. [13] In this paper the method used in the synthesis of zirconia is the chloride technique. With this precipitation technique, either zirconium chloride or oxychloride and a corresponding yttrium salt or even pure yttria are used."

Jan 1, 1994

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By W. Marnette

Norddeutsche Affinerie is the largest West European copper producer with an annual output of more than 350,000 tonnes of refined copper, about half of which is produced from copper concentrates. However, in addition to concentrates, Norddeutsche Affinerie processes secondary raw materials and recycling materials which contain a combination of copper and lead. These materials were previously treated in blast furnaces, a technology which has meanwhile been superseded at NA by the electric furnace process, primarily owing to the necessity of complying with the increasingly stringent requirements for environmental protection.

Jan 1, 1994

By G. G. Richards

The zinc slag fuming process is used to recover zinc from molten iron-calcium silicate slags by treatment with pulverized coal and air. The rate of zinc fuming is controlled by the complex interaction of several kinetic factors including the rate of entrainment of coal in the slag, the extent of the coal-slag reaction and the rate of ferrous oxide oxidation to ferric oxide. This paper briefly outlines the mechanism of fuming and, on this basis, optimization of process parameters is discussed. Modelling analysis and recent industrial trials at Cominco show that coal entrainment in the slag, bath temperature, and bath depth are critical variables affecting process rate and efficiency. The first step in process optimization is to assess coal bypass of the bath. In general, changes which promote operation at a higher temperature, greater coal entrainment in the slag and extended residence time of the coal in the bath increase fuming performance. Coal entrainment is controlled by injection conditions whereas bath temperature is a function of coal combustion and ferrous oxide oxidation. Residence time of the coal is largely a function of bath depth. The implication of model predictions for continuous fuming is shown.

Jan 1, 1994

By C. D. Adams, R. T. Tuenge, C. N. King, J. A. Samuels, B. F. Espinoza, R. C. Dye, C. F. Schaus, D. C. Smith, N. M. Peachey

"Recently, doped calcium thiogallate (CaGa2S4) phosphors have been investigated for use in electroluminescent flat panel displays. The current technique used for the deposition of thin film calcium thiogallate is sputtering. Unfortunately, this requires a high temperature annealing process to provide the desired crystallinity of the phosphor. Recent efforts have focused on the possible use of metal-organic chemical vapor deposition (MOCVD) to produce the CaGa2S4 layer. The use of MOCVD provides an attractive alternative to sputtering since it does not require heating above the strain point temperatures of the glass substrates used for the display panels. To accomplish this, the deposition of both Ga2S3 and CaS is investigated as these compounds are intermediate steps in the development of the phosphor deposition. Uniform, crystalline films of both Ga2S3 and CaS were deposited and the process shows promise for successful deposition of the CaGa2S4 phosphor.IntroductionThe lack of a satisfactory blue phosphor having sufficiently high luminances at low power has hampered the development of high resolution flat panel displays. Recently, a new series of blue emitting materials have been investigated for use in thin film electroluminescent (TFEL) devices. l ,2,3 These phosphors are based on a series of alkaline earth thiogallate host materials of the form MGa2S4:RE where M can be either calcium, strontium, zinc, or barium and RE is a rare earth ion. A full-color VGA TFEL panel using CaGa2S4:Ce as the blue phosphor has recently been fabricated and tested. l This FPD provided a luminance of 10 cdlm2 at 60 Hz. The enhanced blue in this display allowed its color capabilities to approach those of the conventional CRT.The method of depositing the phosphor onto the display panels in these test devices has been sputtering. Unfortunately the phosphor as deposited does not possess the crystalline properties required for optimum luminance. The crystalline structure is achieved by subsequent annealing of the deposited material. Although this post deposition anneal provides the desired crystal structure, it occurs above the strain point temperature of ordinary glass. Consequently, the implementation of these phosphors requires the use of glasses capable of withstanding high temperatures, adding to the cost of the final display unit."

Jan 1, 1994

By Stephen K. Pave1

Over 1,100 tons per day of Fluid Catalytic Cracking Unit (FCCU) catalyst is used worldwide. During the cracking reaction, catalyst is contaminated by deposited metals including nickel, vanadium, potassium, copper, iron, sodium, etc. To compensate for contaminants, a portion of the circulating catalyst inventory is withdrawn for disposal and fresh catalyst is added. The DEMETR process takes spent FCCU catalyst and removes a portion of the metal contaminants, enabling the refiner to recycle demetallized catalyst, thus reducing the solid waste from the refinery. Through August, 1993, the operation of one unit for one refiner has resulted in the recycling of over 7,500 tons of spent catalyst.

Jan 1, 1994

By Zvi Rivlin

Classical nucleation theory states that in first order phase transformations, such as liquid to solid transition, nucleation of the product phase starts with the formation of small, unstable clusters (embryos). When the thermodynamic barrier to nucleation is overcome, the embryos grow and attain a critical size, beyond which they are stable, i.e. they become nuclei. If nucle- ation does not occur, the parent, liquid phase remains in metastable equilibrium. At temperature lowers, undercooling increase and atomic mobility decreases. The viscosity change in the undercooled liquid may result in the formation of glassy state. As demonstrated in previous papers [I-21, in solidification involving surface nucleation of the product phase, as the case is in rapid quenching by melt-spinning, both nucleation temperature and nucleation time depend upon the number of atoms available at the isothermal surface in contact with the substrate. As a result of the thinness of the melt-spun ribbons, the embryo clusters that form at the freezing temperature may not be supplied by the amount of atoms necessary for their growth to critical nuclei sizes. In such extreme conditions, the liquid does not crystallize, it forms a metallic glass. A numerical simulation method is proposed for the reactions involved in embryo cluster formation and growth, at the atomic level. The simulation enables the caIcuIation of either the nucleation or the glass transition temperatures. Calculations made for the well-known glass forming CuZr and FeB systems afford prediction of the geometrical and thermodynamically conditions necessary for the formation of either crystalline or amorphous ribbons in melt-spun ribbons.

Jan 1, 1994

By Sridhar Komarneni

"Microwave-hydrothermal processing is a novel technique which combines the conventional hydrothermal processing with microwave field and we previously showed for the first time, that ceramic powders can be rapidly produced by this technique. This review paper deals with the synthesis of unary oxides such as Fe203, Ti02, Zr02, etc., binary oxides such as BaTiO3, SrTiO 3, PbTiO 3, SrZrO 3, KNbO3, etc., and ternary oxides such as NaTi2 (PO4)3 and pyrochlore phases of Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3 etc. and metal powders such as Cu, Ni, etc. below 195°C. This method can be adopted to the synthesis of a large variety of powders by the appropriate control of pH, Eh, temperature/pressure and concentration of chemical species. The main advantages of this method compared to conventional hydrothermal processing are (a) it increases the kinetics of reaction by one to two orders of magnitude, and (b) it can lead to novel phases especially those with layered structures.IntroductionConventional hydrothermal processing is a well-established synthesis technique which has been extensively used in the preparation of fine ceramic powders [1-5], large single crystals [6-8] and massive cement blocks [9]. Technologically important ceramic powders such as BaTiO 3, Al203 etc. made by the hydrothermal process are now commercially available. Although there are numerous methods for materials synthesis, hydrothermal method is truly a low temperature and environmentally benign process. For example, ZrSi04 (Zircon) which is extensively used in ceramic industry can be prepared hydrothermally at 150·C [10] compared to sol-gel or solid-state method [11,12] which require a temperature of about 1000·C. The hydrothermal method is environmentally benign because hydrothermal reactions are carried out in closed systems at low temperatures and the contents can be recovered and recycled after cooling to the ambient conditions. One of the disadvantages with any low temperature processing method is slow kinetics. For this reason we have combined the hydrothermal method with microwaves to enhance kinetics and we named this method as ""Microwave-hydrothermal"" processing [13- 16]. Although the combination of microwave and hydrothermal techniques has been used in the past few years to dissolve all kinds of inorganic (e.g. alumino silicate rocks) and organic materials rapidly for chemical analysis, we were the first to show its potential value for the synthesis of various ceramic powders [13-16]. In this paper, I show that this novel method is applicable to the synthesis of all unary, binary and multinary oxides by the appropriate control of pH, Eh, temperature, pressure and concentration of chemical species. In addition, this method is also found to be useful for the preparation of metal powders."

Jan 1, 1994

By Godwin J. Igwe

For soil remediation technology to be effective, a thorough understanding of the interactions between a targeted contaminant and the soil matrix is crucial. Proper selection of remediation technology, based on understanding the bonding/binding characteristics of the soil and contaminant, can often result in significant remediation cost savings. Contaminated soil cleanup is complicated by both the physical nature of the soil formation and the behavior of contaminants introduced into the formation. Contaminants can exist in the subsurface in different phase attached to the soil surfaces, dissolved in the ground water, or occupying pore spaces as a separate gaseous or liquid phase. Contaminants properties and how they exist in the subsurface influence their toxicity, mobility and treatability with different remediation technologies A soil characterization study was performed to provide information for remediation technology selection for an inorganic lead contaminated soil. The soil pH, TCLP analysis, thermogravimetric analysis, the soluble anions and cations present, equilibrium leaching tests, analysis by x-ray fluorescence, sequential extractions and speciation analysis using scanning electron microscopy, were all used. Results provided many insights into contaminant behavior in the soil, indicating ultimately whether soil washing or solidification/ stabilization remediation technologies were applicable.

Jan 1, 1994

By Ray D. Peterson

The hydrothermal enrichment of chalcopyrite by CuSO, occurs in the absence of oxidizing or reducing reagants. Kinetics of the enrichment process were determined under autoclave conditions in the temperature range of 398°K (125°C) to 473°K (200°C). Covellite (CuS) formed first, followed by digenite (Cu,,,S), with rejection of iron to the solution. The kinetics have been explained by a model which includes diffusion during the first stage formation of covellite followed by surface reaction rate control when digenite be. The effects of particle size, temperature, pH, and cupric and ferrous ion concentrations on the leaching kinetics were examined. Additions of ferrous ion to solution markedly increased the rate of reaction.

Jan 1, 1994

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By C. Beckennann, C. Y. Wang

"Computer simulations of structural and compositional development in equiaxed dendritic alloy solidification are performed using a recently developed multi phase model. The model not only accounts for the transport phenomena occurring on the macroscopic (system) scale, but includes also the grain nucleation and growth mechanisms taking place at various microscopic length scales. In this paper, a numerical technique consisting of a fully implicit control-volume based finite difference method and a multiple time step scheme is developed for accurate and efficient simulations of both micro- and macro-phenomena. Sample numerical results are presented to reveal the effects of liquid now and crystal sedimentation on segregation and the final grain size distribution. In particular, the importance of the interplay between the dendrite microstructure and multiphase now patterns is shown.IntroductionIn recent years, modeling of equiaxed dendritic solidification without convection has experienced considerable progress (1,2]. Nucleation and growth kinetic laws have been coupled with transient heat conduction calculations to determine the solidification microstructure. However, modeling of equiaxed dendritic solidification with melt convection and solid movement has not been attempted so far, largely because of the complications associated with the transport of free equiaxed crystals in the melt. The gravity-induced transport of free crystals is fundamental to the development and extent of the equiaxed zone and also greatly affects the columnar to equiaxed transition. Another possible effect of crystal sedimentation or floatation is to cause severe macrosegregation as well as structural inhomogeneities. The only study available in the literature that accounts for both liquid convection and solid transport is by Ni and Beckermann (3], but deals with globulitic structures (as opposed to dendritic)"

Jan 1, 1994