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By Joseph Bloch

The hydriding of bulk metals and alloys is a gas-solid reaction in which a hydride product layer is initially nucleated adjacent to the gas-solid interface and continues to grow until a complete transformation of the parent (a) phase into the hydride phase. The combination of measurements of the overall hydriding kinetics of samples having defined shapes and dimensions, together with examinations of partially hydrided samples, enables the presentation of the reaction rate in terms of an appropriate reaction model. A common and important type of topochemical development of the hydride in bulk metals and alloys involves a hydride layer formed on the metallic surface. The continuity of the layer can affect the reaction rate. The rate of hydrogen absorption in a sample, in the presence of a hydride layer, is usually analyzed using a model combining several sequential steps in which the hydrogen is transferred from the gas phase into the reaction site. Coupling the flux equations across the layer under proper steady state conditions, results in a complex rate equation in which the steady state rate of hydrogen absorption (proportional to the hydride layer velocity) is expressed in terms of the pressure, temperature, the rate constants of the sequential steps and the critical concentrations of hydrogen in the hydride. Generally, the rate constants of the individual microscopic processes are comparable in magnitude, so that the overall rate is not controlled by any of the specific sequential steps. However, there are two limit cases related to the first stage, the adsorption, for which the general rate equation is much simpler, namely, the fast and the slow adsorption approximations. Using this limit cases, equations are derived for the steady state hydriding rate of a given system. These equations provide means to anticipate the pressure dependence of the steady state absorption rate under low pressures, close to Peq and under very high pressures. At the low pressure regime both the fast and slow absorption cases yield linear pressure dependence. For the very high pressure range, it is found that the rate become independent of the applied pressure. The rate is given then by a combination of the individual rate constants of the system and the critical hydrogen concentrations. The model is shown to apply in several real cases, such as ZrCo, LaNi5 and titanium.

Jan 1, 2002

By Adolf Mikula

Lead-tin solders are commonly used in electronic packaging due to their unique combination of electrical, chemical, physical, thermal and mechanical properties. Since it is known that lead and lead containing alloys cause great environmental concern and health hazards it is necessary to replace lead in solder materials. Besides the environmental concerns new technologies in electronic packaging require new and improved solders. In most cases the new solders will consist of ternary or quarternary alloy systems, the main component will be tin or indium and the second element could be bismuth, silver, copper and gold and to improve certain properties a third element will be added. For a third element zinc, nickel, antimony and aluminum can be considered. This report will concentrate on solders containing zinc as an environmental safe element.

Jan 1, 2003

By Charles L. Richman

The effect of the addition of Silver Sulfide on the rate of Chalcopyrite (CP) of Sulfuric acid (H2SD4 leaching is discussed, Although Ag2S in an expensive addition, a theoretical explanation of it's use will aid in the development of a economic substitution. We have used cyclic voltammography to show the presence reaction species at different potentials. Cyclic Voltammography maps the surface reaction current peaks on CP, to regions on the CP Phorbaix diagram. AC Electro-lmpedance spectroscopy (EIS) models the surface impedance properties, which control the rate of electron and ion transfer, and the surface kinetic reactions, with and with out light. EIS and other measurements show that AgCuS u Photo-reactive material- The EIS results are compared with the SEM and EDXA results to show the presence of diffusion pores, and diffusion controlled reactions during CP leaching without the addition of silver sulfate. We hypothesize that AgCuS is an ionic conductor like Ag2S. EIS shows an imposed negative leaching rate greatly. Our theory shows how the formation of Silver Copper (1) sulfide layer at open circuit potential gives an effect similar to negative potential, that is enhanced with illumination. We verify that AgCuAS is an N-type semiconductor that forms a diode type junction with the electrolyte with the Mott-Schoottly relation.

Jan 1, 2001

By Geoffrey S. Plumlee

The Summitville gold mine, located in southwestern Colorado, received tremendous publicity in the 1980's and 1990's for leaks of cyanide solutions from its heap leach facility. As is typical with cyanide spills, real time, geochemically rigorous assessments of the environmental effects were not performed. Past United States Geological Survey (USGS) research used simple mixing experiments to model the influx of alkaline cyanide heap leach solutions from Summitville into a nearby stream, whose waters were highly acidic due to severe acid-rock drainage (ARD) from the mine. These experiments indicated WAD cyanide rapidly degraded due to formation of Fe-Cu-CN solids and lesser HCN volatilization. The alkaline heap leach solutions also precipitated hydrous iron-and aluminum, oxides and hydroxysulfates (iron and aluminum 'supplied by the acid. rock drainage (ARD]), which then sorbed copper and other heavy metals from the ARD. These results indicate that mixing of cyanide heap leach solutions with ARD may be a cost-effective remedial method at mine sites where treatment of both is required. New experiments are currently in progress to further refine a potential remedial process.

Jan 1, 1998

By I-Min Lu

An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces. The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.

Jan 1, 1996

By J. Y. Hwang

Microwave heating is an attractive alternative to conventional heating methods because heat is generated directly within the microwave absorbing materials. It has potential to be utilized for selective heating and removal of specified components from a materials mixture. This investigation was undertaken to explore the potential of selective heating and burning of binders for foundry sand reclamation. Selected raw materials and binders used in foundry operations were tested to determine their receptivity to microwave heating. Time needed to reach 600°C and/or the maximum temperature achieved for samples irradiated by microwaves for twenty minutes under 800 W microwave power are reported. The microwave heating characteristics of the selected materials are summarized and discussed. The interactions between microwaves and the raw materials used in a foundry. such as silica sand. chromite sand and bentonite (clay) binder were studied. The results showed that chromite sand coupled well with microwave energy at ambient temperature while silica sand did not. This was expected because the major component of chromite sand. iron chromite (FeCr2O4). is a good microwave absorber. while quartz, which is the major component of silica sand, is a microwave transparent material at ambient temperature. Bentonite absorbs microwaves well because it contains a hydroxyl functional group and water molecules in its structure. It was found that the structure of bentonite was changed through microwave irradiation. Microwave heating characteristics of silica sand mixed with different amounts of bentonite binders were investigated. The presence of bentonite in the mixture improved the microwave heating of silica sand significantly. and bentonite was deactivated by the microwave processing.

Jan 1, 1995

By Cheryl S. Lim

New technologies such as direct reduction and smelting reduction processes are increasingly being used in iron-making and steel-making in addition to conventional blast furnace technology. Critical parameters for control of these processes include the degree of metallization, degree of pre-reduction, and carbon and silica levels. On-line monitoring of these parameters is difficult because measurements often need to be made on hot ores (at or higher than -1000'C) in circumstances where representative sample streams are not readily accessible. A nuclear analyser has been developed which provides continuous, non¬intrusive, real-time measurements of iron, oxygen, carbon and silicon levels in hot ores undergoing reduction. The analyser has been tested in a plant using a direct smelting process on pre-reduced feed to the smelting vessel-, accuracies of 1% relative, 0.5 w'.96 (25% relative) and 1.0 wt.% (9% relative) were obtained for the degree of pre-reduction, carbon and silica respectively. The underlying method, capabilities and potential applications of the analyser will be discussed.

Jan 1, 2001

By Shunhong Huang

Thirty-five soils were sampled from three sites at different distances from chromium slag heap of a Iron-alloy factory, namely, nine from site A located under the chromium slag and eighteen from Site B in the vicinity of the factory and eight from site C far from the factory. The contents of total Cr in these soils from site A, B and C were 1666.0±1310.9 mg? kg - 1,1136.2±1844.6 mg? kg - 1 ,300.4 ±165.1 mg? kg ? 1, respectively. The contents of water soluble Cr were 59.3±77.57 mg? kg ? 1,0.6 ±0.3 mg? kg - 1 ,0.5±0.3 mg? kg - 1 , respectively. In order to evaluate soil health, the activities of four soil enzymes (catalase, polyphenol oxidase, dehydrogenase, alkaline phosphatases) were analyzed. The results have shown that dehydrogenase activity was greatly depressed by conditions in the heavy chromium-contaminated sites. Negative correlation was observed between dehydrogenase activity and the distance from the chromium slag heap, however, the activities of catalase, polyphenol oxidase, alkaline phosphatases in soils from the three sampling sites mentioned above did not differ significantly. The result imply that of dehydrogenase activity could be used as an indicator for the chromium pollution level in the area of Iron-Alloy factory and for the stability level of the soil ecosystem.

Jan 1, 2008

By Takahiko Okura

Most non-ferrous raw materials are associated with sulphur. To extract the metals, the sulphur is recovered typically as sulphuric acid or liquid SOz, On the other hand, natural gas may contain over 20% of hydrogen sulphide (HzS) and a huge quantity of elemental sulphur is produced through oil and gas refining processes in the world. A large fraction of the sulphur mined from natural sources is eventually returned to the earth as fertilizers, by-products of desulphurisation and neutralisation processes, or as fugitives to the atmosphere. However, the supply and demand for sulphur are in imbalance. Such situation urges to develop a new smelting process without sulphuric acid production. This paper briefly reviews the global sulphur balance and the technologies for recovering elemental sulphur. The core of this paper is a proposal to convert SO2 gas to elemental sulphur by using organic materials. Some results of thermodynamic calculations and experiments are presented.

Jan 1, 2003

By W. R. McDonald

The U.S. Bureau of Mines investigated treatment of gold and silver refractory ores and concentrates that respond poorly to conventional cyanidation techniques due to the complex mineralogy of the ore. Three types of ores were investigated: gold locked placer sands, gold locked in sulfides, and gold that is robbed from the pregnant cyanide solutions by minerals in the ore. Ore treatment included grinding, flotation, cyanidation, air oxidation, pressure oxidation, hypochlorite oxidation, roasting, and carbon in leach.

Jan 1, 1991

By J. L. Watson

The composite nature of titanomagnetites found on the west coast of the north island of New Zealand is an important parameter in the beneficiation of the black beach sands for export to Japan. To investigate this composite nature, borehole and plant samples from the Waipipi Ironsands Ltd property were subjected to a series of separations in heated Clerici solutions at densities varying from 3.2 to 4.6 g/cc. The resulting density fractons were analyzed magnetically and a set of distribution curves for composite grains proposed. In addition the experi¬mental data was plotted to produce titanomagnetite sand 'washability curves" which illustrate the possible problem areas in beneficiation that may arise due to composite titanomagnetite grains. From this data a set of guidelines are suggested for interpreting the curves in terms of ease of gravity concentration. The composite nature or liberation of titanomagnetite grains is shown to favor high and low grade composites with few intermediate compositions being isolated. The relationships between grain size, borehole depth and liberation are examined and related to beneficiation procedures for the black sand deposit.

Jan 1, 1982

By Thomas W. Chapman, Shi-Chern Yen, I-Min Lu

"An electric field was applied to a metal-bearing kaolinite specimen to investigate the efficiency of electro-osmosis in removing heavy metals from contaminated soils. The electric field induces a flow of water through the porous medium, called electro-osmosis, which is superimposed on the hydraulic flow. Because the electro-osmotic flow is relatively stronger in smaller pores, it can enhance the displacement of contaminated solution by fluid convection. Furthermore, local changes in pH caused by the electrode reactions can affect adsorption equilibria and the distribution of solutes between the solution and the solid surfaces.The electro-osmosis experiments were conducted by applying either a constant current or a constant voltage across 8-cm inside diameter, 25 to 30-cm long specimens of kaolinite clay with graphite electrodes. Samples of the pore fluid and of the clay were analyzed to determine metal content, pH, and conductivity as functions of time and position. Results show that removal of heavy metals from soil can be accomplished effectively by electrokinetic treatment of sufficient duration. Approximately 95% of the lead was removed after 189 days.IntroductionRemediation of soils contaminated with toxic chemicals is a difficult and expensive task. Washing or leaching are not particularly effective if the contaminate is sequestered in small pores; hydraulic flows of water pass through larger pores leaving the smaller pores relatively untouched. Electro-osmosis appears to be the most promising new technology for removing heavy metals and organic substances from contaminated soils (Segal, 1980; Hamed et al., 1991, Masliyah, 1994).Electro-osmosis is one of several electrokinetic phenomena that occur through the interactions among an electric field, fluid motion, solute adsorption, and the existence of a net charge on a solid-fluid interface (Newman, 1991, Masliyah, 1994). Electro-osmosis refers to the fluid flow in a porous medium that results when an electric field acts on the mobile region of the electrical double layer, the solution-side region of charge separation that exists at the pore walls."

Jan 1, 1996

By Satu Jyrkönen

A single-particle laminar-flow technique was used to study reactions of sulfidic nickel particles. The studied materials were three natural nickel concentrates and four synthesised nickel mattes. The variables of the experiments were the gas preheating temperature (500 - 1300°C), the composition of the reaction gas (N2 + 0 - 75 vol-% 02) and the ,particle size of the feed. Chemical analysis of the particles was used to determine the oxidation degree of the materials, and optical and scanning electron microscopy were used to detect alteration in their morphology, internal composition and structure. General reactivity of the materials was monitored by the extent of sulfur removal. The reaction mechanism of the studied materials was found to depend primarily on the materials composition as well as oxygen content of the reaction gas.

Jan 1, 1998

By L. A. Neumeier

The Bureau of Mines, U.S. Department of the Interior, is investigating the feasibility of partitioning complex sulfide minerals to simpler sulfide .phases by sulfldation reactions. Such partitioning can afford opportunity to improve selective extraction of mineral constituents of value. This report describes initial research involving sulfidation partitioning of chalcopyrite concentrates. Small chalcopyrite samples were sulfidized with elemental sulfur in glass capsules sealed after evacuating and backfilling with helium, by heating for 1 to 24 h at specific temperatures in the range of 250° to 500° C. which extends from below to above the boiling point of sulfur (-445° C). Above the boiling point of sulfur, the overall reaction with adequate sulfur (13.9 wt pct of CuFeS2) is 5CuFeS2 + 4S g ? Cu5FeS6 + 4FeS2.

Jan 1, 1989

By Joon H. Jang

At a selected pH, hydrothermal oxidation of chalcopyrite was carried out under controlled F+,, at elevated pressures and temperatures (172-200°C) by balancing the rate of oxygen injection against the rate of consumption. Chalcopyrite was converted to covellite (CuS) and digenite (CU1.8S) with rejection of iron and sulfur to the solution. Covellite forms in the first stage, followed by nucleation and growth of digenite in the second stage. The effects of rapid and slow injection of stoichiometric quantities of oxygen are compared. Both the covellite and digenite form a porous layer occupying the same volume as the original chalcopyrite grain. An electrochemical kinetic model is presented to correlate the observed results.

Jan 1, 1993

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By E. Krystad, G. Tranell

"The kinetics of boron removal from liquid silicon during slag refining, as a process step in the production of solar grade silicon, has been investigated by means of small scale mass transfer experimental series at 1600°C, using a graphite crucible. The slags were SiO2-CaO based, with or without addition of approx. 19 wt% MgO. Experiments were carried out at slag-metal ratios of 1 or 2, where the silicon initially contained approx. 250 ppm boron. The metal-slag mass transfer coefficients for boron were found to be in the order of 1-3 · 10-6 m/s and were largely influenced by slag composition. The mass transfer rate was higher for the MgO-containing slag than the slags without MgO. The final equilibrium distribution of boron between metal and slag, LB, was determined to be in the order of 2.3-3.3.I. INTRODUCTIONRecent years have seen a race in industry and research aimed at obtaining a reliable metallurgical route for production of silicon for solar cells (SoG-Si) from metallurgical grade (MG) silicon. Metallurgical routes can successfully challenge the traditional chemical routes for production of SoG-Si if they generate metal of sufficient purity while being less expensive in terms of production cost and energy consumption. Efficient removal of boron is one of the greatest obstacles in the refining of silicon by a metallurgical route, because the segregation coefficient of boron in silicon makes directional solidification unfeasible; in addition, the vapour pressure of boron is not high enough for removal by vacuum refining. However, the thermodynamic properties of boron makes removal from silicon by oxidation possible, and thus the process of slag refining of silicon has been receiving increasing attention as a method for boron removal."

Jan 1, 2012

By Rubén Alvarado

The markets and environmental protection rules are more and more exacting, both of which have determined that copper smelters should look for technological development and global management to ensure their viability and competitivity in the short and long term. The main facilities of the present and future Smelting-Converting Process at Codelco's Caletones Smelter, is based on Teniente Converter reactors with a high operational availability that have reached concentrate processing capacities near 2,000 tpd. These reactors are in operation in most of the smelters in Chile as well as in Zambia, Peru, Mexico and, in ?the near future, in Thailand. Since 1993, the Smelting-Converting process of the Caletones Smelter of Codelco-Chile has been based on one Reverberatory furnace, two Teniente Converters and four Peirce-Smith Converters. These facilities, together with the operation of two Fluidized Bed Dryers, three Slag Cleaning Furnaces, and two Oxygen Plants have allowed the smelter to reach concentrate smelting capacities and copper productions of 1,215 kt/year and 360 kt/year, respectively. This transitional operating scheme, combining together traditional and advanced technological equipment, needs further modernization to successfully face the modern world challenges, especially with relation to the environmental commitment, production costs and wide satisfaction of customers. For this reason, for the period 1997-2000, a Modernization Plan has been worked out. This plan considers an increase of the present throughput, which will permit a significant increase in productivity, as well as finding a definitive solution for meeting the environmental regulations. Among these projects, we can point out the definitive shut down of the Reverberatory Furnace, which is a contaminating piece of equipment of low energetic efficiency. Additionally, it considers the installation of two new Slag Cleaning Furnaces, one additional Oxygen Plant, and the incorporation of two new Sulphuric Acid Plants with a production capacity of 4,500 T/D, that will recover over 92% of the sulphur content, of process off-gases.

Jan 1, 1998