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By J. Brent Hiskey

Recently basic concepts of semiconductor electrochemistry and solid-state electronic structure theory have been applied to the dissolution of mineral electrodes. In this paper, fundamental aspects of semiconductor electro- chemistry and interfacial charge-transfer processes are reviewed. Information regarding the electronic and semiconductor properties of chalcopyrite is summarized. The electrochemical response of chalcopyrite in acidic solution is analyzed in terms of initial dissolution processes. The initial charge- transfer reaction involves the consumption of holes. It has been shorn that Fermi level pinning is consistent with observed electrochemical and dissolution behavior. Semiconductor electrochemistry has proved helpful in explaining the formation of intermediate surface films produced during the initial stages of chalcopyrite dissolution

Jan 1, 1993

By Satu Strömberg

Four different nickel concentrates were oxidized in a laboratory scale laminar flow furnace in simulated flash smelting conditions. The major nickel- and iron-bearing minerals in the con- centrates were pentlandite, violarite, gersdorffite, and pyrite and pyrrhotite, respectively. Thermal decomposition, ignition and oxidation behavior of nickel and iron sulfides were examined by using optical and scanning electron microscopy. General reactivity of the concentrates was monitored with sulfur removal which was most effective in violarite-based concentrate. Pentlandite-concentrates needed higher experimental temperatures for complete desulfurization and gersdorffite-based concentrate contained 5 - 10 % of the original sulfur even in the most oxidizing conditions studied (1 100°C, 50 vol-% 02). The reactivity of the iron minerals was found to depend on the other minerals present in the concentrate. In this paper, the observed re- action products and mineralogical changes are presented and preliminary conclusions of possible reaction mechanisms of nickel-bearing minerals are discussed.

Jan 1, 1997

By C. A. Silva

Ladle change-over, during continuous casting of steel, initiates transient flow in the tundish which influences the inclusion content and degree of mixing between two consecutive batches of steel. The mixing behavior in the tundish during this period is determined by the casting rate and the ratios of: inflow to outflow during the refilling period; and, the low liquid level relative to the nominal level in the tundish during the transiency. A 3:10 scale water-model of a typical one strand slab caster was operated in conjunction with a tracer technique to characterize the velocity fields for several combinations of these parameters. Steady operation, a limiting case of the transiency, provided a basis for comparison. High-order moments -- skewness and kurtosis -- of the residence time density function have been utilized as signature elements associated with a particular residence-time distribution for the system. A simple mathematical model incorporating the above parameters as well as a characteristic Peclet Number was successful in simulating the features of the transient period.

Jan 1, 1993

By Thomas P. Battle

Ilmenite (iron titanate) is the source of over 90% of all the titanium produced in the world today. At some point during production of titanium dioxide or titanium metal the iron impurity must be removed. Too often it becomes a waste instead of a product. DuPont and MINPRO have developed a solid-state process which separates the iron and titanium components of ilmenite into different high-purity powders, which can be separated using conventional mineral processing techniques. The main reactor in this process is a unique high-temperature ball mill, where the iron segregates from the ilmenite lattice with the assistance of catalytic quantities of He\. The results of lab, pilot plant, theoretical, and scale-up studies are presented and discussed.

Jan 1, 1996

By Larry M. Southwick

Steel mill electric arc furnace dust is a RCRA listed hazardous waste and its treatment and/or disposal are regulated by a complex set of rules. These regulations were originally established to encourage recovery and recycling of valuable components. For EAF dust, the more valuable constituents include zinc, lead, cadmium and iron. In fact, current trends are in the opposite direction, as the regulations have complicated the ability to commercialize new treatment technologies and created substantial roadblocks and liabilities for processors. As a result, almost half of the EAF dust generated in 1997 will be landfilled. The problems are compounded by difficult processing requirements, less than sterling examples of technology development and mechanical and operating problems. This paper explores some options to simplify the processing requirements and thereby easing difficulties in commercializing new technologies and expediting the recycling of recovered metals. Dust processing usually includes a simple step followed by two complicated steps. The simple step is fuming of heavy metals away from iron and other residues. The complex steps are (1) separating and purifying the heavy metals and (2) upgrading the iron residue. The first complex step can be simplified by producing an intermediate product that is amenable to processing by zinc refiners. This route benefits from the currently underutilized (by dust processors) resource offered by refiners, who have experience in and existing processes for separation and purification of zinc-based heavy metals. Various processes and their associated product options are reviewed and compared. Future directions for dust processing developments are suggested.

Jan 1, 1998

By Thomas E. P. Wechsler

The limiting factor for most pyro-metallurgical processes in secondary cop- per melting is the time required to heat and melt the product. American Combustion's proprietary PYRETRON variable £uel/air/oxygen combustion system improves the throughput of existing scrap melting and heating furnaces for copper and copper alloy production by increasing the rate of heat transfer from the flame to the product. The increased productivity and energy savings obtained from this technology can result in sizable reductions in operating costs for smelting operations.

Jan 1, 1991

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By D. F. Suarez

Spontaneous nodulation leading to growth of well developed glossy spheroids (generally hemispheres) of up to 0.06 cm width in 120 min has been observed during copper electrodeposition with certain levels of glue, thiourea and C1-. Thiourea alone can produce spontaneous nodulation but addition of glue and/or Cl- is required for rapid and sustained growth. In most cases once the glossy nodules develop they consume the majority of the copper deposited; thus, the specific current densities (and hence copper electrodeposition rates) on the glossy nodules are about an order of magnitude or, more greater than on the adjacent planar surfaces. The texture of the adjaoent planar surfaces is not glossy in appearance but is well faceted showing the usual deposition grain structure for such additives. Cathode potentials when spontaneous nodulation occurs are about TOO my more negative than with usual copper electroplating. This fact associated with evidence of extremely high levels of cathode surface passivation based on cyclic voltammograms indicates that the conditions which lead to spontaneous nodulation result from a very tightly adsorbed additive surface film. This film breaks down in specific points initiating the glossy nodules which then grow at extremely rapid rates. Current density is also important in spontaneous nodulation. At equal deposition times a current density of 21.5 mA/cm produced much larger glossy nodules than at 48 mA/cm2. The surface concentration of the glossy nodules was much greater in the latter case, however. The role of current density is still not well understood. The role of it as well as the relative roles of the three additives, thiourea, glue and Cl- in spontaneous nodulation is presented. Preliminary results and some possible correlations of these to help explain spontaneous nodulation are presented. It is believed that tankhouse upsets where cathode nodulation occurs may be related to this phenomenon.

Jan 1, 1987

By James C. Barker

Near Rainbow Mountain in the east-central Alaska Range an ultramafic complex forms a sill-like intrusion composed of dismembered bodies exposed along the south side of the Denali Fault and Broxson Gulch Thrust. The complex comprises dunite and peridotite with lesser gabbro, which together exhibit poorly defined, steeply-dipping compositional layering. The complex hosts four types of copper-nickel occurrences which have characteristic platinum-group elements (PGE), gold, and cobalt distributions. Three of the occurrence-types are considered to have formed as a result of primary mineral segregations which developed during intrusion of the complex. The fourth type of copper-nickel occurrence formed as a result of post-magmatic hydrothermal fluids at intrusive contacts. Scanning electron microscope examination indicates that PGE occur as micron-size telluride and arsenide minerals.

Jan 1, 1987

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By Richard D. Hagni

The techniques of reflected light microscopy and cathodoluminescence microscopy are uniquely suited to the study of the products from many important industrial problems. Ref1 ected 1 ight microscopy provides the means to rapidly identify the mineralogy of an industrial sample, determine the abundance of each phase, and examine the mineral intergrowths or textures. Cathodoluminescence microscopy is a relatively new instrument that provides the means to cause many minerals to cathodoluminescence under the microscopy. The cathodoluminescence of a mineral allows it to be readily distinguished from other phases that differ in cathodoluminescence but are similar in optical properties. Cathodoluminescence microscopy is especially useful to detect cathodoluminescence minerals that are present in only small quantities. Reflected 1ight microscopy and cathodoluminescence microscopy have been successfully applied in studies of beneficiation products, prediction of beneficiation and leaching problems, phosphatic iron ores and mill products, pyrometallurgical products, roasted refractory gold-bearing sulfides, ceramic build-ups, electric arc furnace and smelter dusts, and other industrial products.

Jan 1, 1993

By Anupam Madhukar

The essence of an atomistic unified kinetic model of strained thin film growth and defect initiation is presented along with a comparison of its consequences obtained from computer simulations with experiments. Within the competing kinetics of a strain dependent activated incorporation of atoms and an asymmetry between upwards and downwards inter-layer migration, the model provides a consistent description of 2D versus 3D morphology evolution accompanied by the appearance of surface vacancies and steps at no energy cost. The correlated migration of these precursor defects offers an atomistic mechanism for the emergence of surface half-loops from the growth front (thus accounting for configurational and thermal entropy) governed by activation energies closer to their correlated motion under the evolving strain fields and thus substantially less than those calculated with respect to the perfect crystal as the reference state. The essential mechano-chemical nature of the problem is compared and contrasted with the historical literature of such phenomenon as precipitation hardening and sintering in metallic and ceramic composites.

Jan 1, 1994

By T. T. Chen

Kidd Creek continuously-cast copper anodes are characterized by high levels of Se, Pb and Ag; the anode slimes constituents and their morphologies are controlled by both the anode composition and the casting process. Hollow Cu2Se spheroids and tube-like structures, enveloping Cu-Pb-As oxide and/or Cu2O, are present in the as-cast copper. During electrolysis, the selenides are liberated from the copper and accumulate in the slimes layer; the Cu2O and Cu-Pb-As oxide react rapidly with the electrolyte to form soluble species and PbSO4. Silver, which is present mostly as a solid solution in the anode copper, is also liberated during electrolysis and reacts with the Cu2Se to form (Cu,Ag)2Se. The ultimate composition of the selenides in the slimes layer depends mostly on the Ag and Se contents, but various other elements, including Au and Te, are also structurally incorporated. Although the selenides are the major Ag carrier, metallic silver also is present. A thin layer of Cu2O crystals sometimes forms at the copper surface, and may affect anode passivation. Copper sulphate is a common constituent and serves to agglomerate the slimes. Copper sulphate is present on both passivated and non-passivated anodes, but that observed on the passivated metal is present as a thick compact layer. Copper powder is associated with CuSO4.5H2O only on passivated surfaces.

Jan 1, 1987

By Lloyd R. Nelson

Selective carbothermic reduction is the preferred method of treatment of electric arc furnace (EAF) dust (listed hazardous waste, K061). The process maximizes the recovery of recyclable constituents by concurrent production of saleable zinc metal (directly condensed from the furnace off-gases), an innocuous, disposable iron oxide-rich slag, and some metallic iron. Results of a mineralogical investigation of a foaming slag produced during selective carbothermic reduction treatment of EAF dusts are presented. Wiistite and tricalcium silicate were identified by reflected light microscopy as the primary crystalline phases contained in a glassy matrix, but this technique failed to reveal any solid phases that could have significantly contributed to foam stability. It was concluded therefore, that the foam had been unstable, and had been primarily generated by copious gas evolution associated with the sudden reduction of the slag by an inadvertent addition of carbonaceous reductant. This is consistent with the susceptibility to foaming, when subjected to sudden excesses of carbon, of the slags produced by selective carbothermic reduction, because they still contain unreduced components such as iron oxide.

Jan 1, 1994

By A. G. Cecutti

A brief overview of the known significant health effects of both Nickel and Cobalt will be presented. Some time will be given to the current research activities, especially for Nickel. Emphasis will be placed on some of the controversial issues associated with their health effects.

Jan 1, 1988

By S. L. Pohlman

Physical characteristics of possible importance in the acid leaching of Chrysocolla have been evaluated. Surface area studies and pore size distribution indicate: 1) a large surface area (350 m /gm); 2) an average pore size of 13 or 16 Å , depending upon use of the adsorption, or desorption, branch of the Type IV isotherm in the evaluation; ) the presence of a significant fraction of pores of size less than 15 Å determined by the accumulation surface area method. The initial structure is micro- crystalline on the basis of x-ray powder patterns; the silica leach residue is amorphous and has only 24 m2 /gm surface area, and loses integrity when dry. However, readsorption of copper onto the wet leach residue gives a product with integrity and 100 m2 /gm surface area. Visual observation of the leach residues supports evidence of a non-protective diffusion mechanism of leaching which is well correlated by the shrinking core model previously presented.

Jan 1, 1976

By S. P. Rivers

The stainless steel industry re1ies on nitric-hydrofluoric acid (HNO,/HF) pickling solutions to remove surface contaminants and maintain the corrosion resistance of the steel. More stringent environmental guide1ines are expected to be placed on the disposal of these solutions which could significantly increase processing costs. The U.S. Bureau of Mines has been conducting research to develop a process for recycling depleted pickling solutions, thus reducing the quantity of by product acids generated. Research has shown that F- can be liberated from the predominant iron fluoride species (FeF,') by using oxalic acid in an electrodialysis cell. Ion selective membranes allow dissolved metals in the depleted solution to be replaced with hydronium ions by metathesis, thereby regenerating the HF. The regenerated HN03/HF is then retained in the pick1ing solution. This paper reports on the research effort at the U.S. Bureau of Mines Rolla Research Center to apply electrodialytic recycling to HN03/HF pickling solutions.

Jan 1, 1993

By Roger Altman

The solubility of copper in primary spinel crystals encountered in reverberatory slag samples has been determined by electron microprobe analysis. These spinels, which ranged in composition from 22% A12O3 to pure magnetite, contained small quantities of dissolved copper (0-0.4%). Based on literature data it was estimated that the solubility limit of copper in solid magnetite is no greater than about 1% at 1200°C and about 2% at 1250°C. However, it was found that practically every spinel crystal examined contained significant amounts of matte inclusions. Further examination of converter slag revealed large quantities of irregularly shaped precipitated magnetite crystals which contained a large proportion of copper inclusions. Additional experimentation showed that the total copper content in reverberatory slag samples was greater than the sum of the estimated en- trained plus dissolved matte in the slag. This difference is believed to be significant and is due to the presence of matte inclusions in the spinel crystals. In the present reverberatory slag samples these inclusions accounted for about 1/2 of the amount of sulfide directly entrained in the slag.

Jan 1, 1976

By Sepp Härkki

The energy crisis in Finland after World War I1 together with a sharp rise in the price of energy caused Outokumpu Oy to consider replacing the electric furnace smelting of copper concentrates by some other method. The flash smelting method developed under these circumstances offered a considerable saving of fuel through the utilization of the reaction heat of sulphides and yielded a high recovery of sulphur in the form of acid. The pilot plant testing of the new process was carried out in the years 1947 - 1948. The process was adopted for the smelting of copper concentrates (1) (2) (3) on a commercial scale in 1949 and applied successfullv to the smelting of -nickel concentrates' at the Harjavalta Works in 1959 (4) (5) (6). In 1962 Outokumpu adopted another type of flash smelting where elemental sulphur is recovered from the gases after the thermal decomposition of pyrite in the flash smelting furnace (7) (8): In recent years, the copper-nickel flash smelter and pyrite process have been combined to produce elemental sulphur instead of SO2 from the smelter gases (9) (10). The basic idea of the Outokumpu flash smelting process for sulphidic ores is that the conventional methods with separate roasting and smelting operations are replaced by a combined roasting, smelting and part-converting process carried out in one unit. The heat generated from the exothermic reactions can thus be used for smelting the ore so that only a small amount of additional fuel is needed. The characteristic of the method is also that the dried, fine-grained concentrate is smelted in suspension, which offers the best conditions for rapid reactions. The recovery of waste heat from the furnace off-gases had been considered already in the original flash smelting system. A

Jan 1, 1976