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By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

By C. W. Won

a-etchant solution is the waste material obtained during the etching by ammoniacal solution of printed circuits for PCs. This material contains a substantial amount of copper (13-14%) but is usually discarded after neutralization. In this work, copper recovery from such solutions by electrowinning or cementation using iron scrap was tested. For each method, the effects of temperature, solution pH, initial copper-ion concentration, and reaction time were investigated to obtain optimal conditions for copper recovery.

Jan 1, 1993

By Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998

By S. R. Hutchins

Several refractory sulfide and carbonaceous gold ores were examined to determine whether microbial pretreatment could be used to enhance gold recovery. Test samples were biologically leached using unique. thermophilic microorganisms to solubilize iron sulfide minerals. Gold recovery from sulfide ores and concentrates was enhanced following pretreatment with the thermophiles; responses varied widely for the individual materials. Although bioleaching had little effect on the preg-robbing characteristics of the carbonaceous gold ores, cyanidation of the bioleached residues yielded higher gold recoveries than cyanidation of the native ore. By combining bioleaching with abiotic processes designed to inhibit preg robbing, gold recoveries of 83-98% were obtained from carbonaceous ores yielding 10-50% gold recovery by direct cyanidation.

Jan 1, 1987

By J. Méndez-Nonell

The thermodynamic and chemical properties of SrSO4 and SrS in a gaseous flow of CO and CO2 at high temperature are discussed. The thermodynamic analysis of the system was made using data from the literature. The results obtained from the thermodynamic analysis were experimentally verified using the thermogravimetric technique. The experimental results suggest the formation of a complex compound between SrO and SrSO4. It was also found a change in the chemical mechanism of the process between SrSO4 and CO-CO2 and in the chemical mechanism of the process between SrS and pure CO2.

Jan 1, 1995

By Jean-François Boulanger

The production of rare earth elements from ore usually consists of three steps; the separation of a concentrate of REE bearing minerals; the cracking of the REE minerals to liberate the REE into an aqueous solution and separation of REE into individual elements. This paper describes the results of laboratory tests conducted on a carbonate-rich REE ore containing bastnaesite and monazite. The tests cover the whole processing sequence of beneficiation, preparation of the REE solution using a caustic leach followed by acid leach to break monazite and bastnaesite and liberate REE into an aqueous solution and the partial separation of the REE using solvent extraction. Details on the product quality and process performances (recovery and impurities removal) are given for each studied step. The paper also discusses the economic advantage of separating the REE rather than producing a mixed REO product to be sold to a refinery for REE separation. A mini-pilot plant version of the process is currently planned.

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By Kimio Itagaki, Torn Matsumoto, Makoto Ohtsuka, Kentarou Harada

"The structure and hydrogen-absorption properties of LaNis thin films were investigated in the present study. LaNis thin films were prepared by a sputtering method with a radio-frequency power, Ws, of 50 -400 Wat substrate temperature, Ts, of323 -573 K. Nickel content of the films decreased with increasing Ws, however, there was no dependence on Ts. At low Ws and low Ts, amorphous films were deposited. In other conditions, the films were polycrystalline. The films prepared at high Ws and low Ts, or at low Ws and high Ts, exhibited only a (h k · 0) peak in the X-ray diffraction profiles. This indicates that the c-axis of crystalline films was oriented parallel to the substrate plane. At high Ws and high Ts, the films with columnar structure were obtained. Hydrogen-absorption capacity of the thin films increased with increasing Ws. The pressure plateau did not appear on the pressure-composition isotherms. The films deposited at high Ts represented a higher equilibrium pressure.IntroductionThin films of hydrogen storage alloys can be applied for an electrode of rechargeable battery or fuel cell, a filter for H1 purification and various kind of sensor. Some studies on the preparation of the thin films of LaNi5 intermetallic compound, which is a typical hydrogen storage material, have been done hitherto. Adachi et al. , 2) and Sakaguchi et al. 3) prepared amorphous and crystalline LaNi5 thin films using flash evaporation of alloy powders and measured the pressure-composition isotherm for the prepared film utilizing a quartz crystal mass monitoring (QC:MM) method. It was found that the prepared amorphous film absorbed hydrogen without disintegrating into the powders and the hydrogen-absorption capacity of the films increased with the degree of crystallinity. Sakai et al. 4) reported that the maximum hydrogen storage capacities of amorphous and crystalline LaNi5 thin films, fabricated by a RF sputtering method using combination targets, were about 40 mA h g-1 (LaNisHo.7) and 160 mA h g-1 (LaNi5H2.6), respectively. Uchida et al. 5, 6) prepared LaNi5 thin films using flash evaporation of alloy powders and measured volumetrically the pressure-composition isotherm for the prepared film. It was reported that the hydrogen-absorption capacity of the films changed by the annealing treatment."

Jan 1, 1998

By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By Signe Kjelstrup, Leiv Kolbeinsen, Marit Takla, Odne Burheim

"This paper presents a Seebeck-type solid state thermoelectric power generator unit, designed to investigate the possible recovery of radiant waste heat at a silicon plant in Norway where roughly 703 of the total input energy leaves the process as waste heat. The unit is 0.5 m x 0.5 m and is built of 36 commercially available thermoelectric devices based on bismuth telluride p - and n - type semiconductors. Thermoelectric devices directly convert fractions of a heat flux into an electric current (and vice versa) and may therefore be convenient for recovery of waste heat when the heat source is discontinuously available. The purpose of the thermoelectric unit is to give a proof of principle of direct thermoelectric energy conversion on a large scale. We present the initial test results for the generator. At an average temperature difference between the heat reservoir and the heat sink of 98°C, we measured an open ciruit potential of 23.44 ± 0.06 V and the matched load power output was 39.4 W. At a temperature difference of 220°C, we predict the generator open circuit potential to be 40.8 V, which corresponds to an efficient Seebeck coefficient of 242 µV /K, and matched load power output to be 120 W.IntroductionThe world's power demand increases, driven by population growth and increase in living standards and simultaneously global warming is recognized as one of our most serious environmental problems. According to the International Energy Agency[l], the industrial sector accounted for approximately one third of the total global power consumption in 2005. Increasing the energy efficiency of industrial processes thus represents a benign and substantial route for addressing environmental concerns and energy security.In accordance with the second law of thermodynamics, all real processes are associated with lost work which is energy being dissipated as heat to the surroundings[2]. Improving the energy efficiency of industrial processes is about finding the process path associated with a minimum of lost work. The more evenly the losses are distributed, the smaller are the losses [3, 4]. In addition, exploiting the unavoidable waste heat will contribute to improve the energy efficiency. The waste heat may be utilized for heating purposes and/or it can be upgraded to work for instance via some sort of heat engine."

Jan 1, 2012

By M. Tangstad, H. Mølnäs, J. D. Steenkamp

"Temperature affects several aspects of pyrometallurgical systems, including thermodynamics and reaction kinetics. Reliability of temperature measurements in laboratory and plant applications is thus important from process, safety and financial perspectives. This case study briefly introduces different techniques utilized for temperature validation, and demonstrates temperature validation on laboratory scale utilizing the wire-bridge method. Pt/Ptl3Rh thermocouple hot junctions were constructed by mechanically connecting thermocouple wires through a pure metal bridge consisting of copper, gold, nickel or palladium wire. When heating the wire-bridge thermocouple alongside a regular Pt/Ptl3Rh thermocouple, temperature offsets were quantified as the wirebridge thermocouple short-circuited at the melting points of the pure metals. At the melting points of gold (1064°C) and palladium (1555°C), average measured temperature offsets were -2.1°C ± 2.3°C and 0.2°C ± 0.4°C, respectively. Results from the copper and nickel wire-bridges were inconclusive. The paper concludes with a discussion on the potential industrial applications of the technique.IntroductionThermocouples are probably the simplest of all temperature sensors, but are widely utilized due to simplicity, versatility and ability to handle a variety of experimental conditions and industrial applications. Additionally, thermocouples are often the only option in research laboratories requiring high temperature measurements, and a high level of reliability is usually required from thermodynamic, kinetic as well as safety points of view.The study presented here originated from a test program where the compatibility between different types of carbon-based refractory materials and industrial slag produced in silicomanganese furnaces were investigated on a laboratory scale utilizing the static crucible test[l]. Due to the nature of the silicomanganese production process, the compatibility tests were to be conducted at 1600CC[2]. Details of the experimental set-up utilized for the compatibility tests are discussed in the Experimental Set-up and Method Statement section later in this paper."

Jan 1, 2012

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 Vojteh Leskov?ek

The tribological load is the load on forging tools resulting from the relative motions between the plastically deformed workpiece and the die. In comparison to many other forming processes hot die forging has an especially disadvantageous tribological system. The advantages of the application of hard coatings, which are well known for cutting tools, are to a much lesser extent explored for casting, extrusion, molding and forging tools. Increasing the lifetime of these tools is an important task in surface engineering because of the complex loading conditions and often complicated tool geometry. The plasma-assisted chemical-vapor-deposition (PACVD) technique is well suited to depositing hard coatings onto large dies and molds. The aim of this study is to present and discus results obtained on a duplex PACVD hard coating in an industrial application like the hot forging of automotive parts. A new generation of vacuum-melted and remelted (VMR) hot-work tool steels has been developed; these can reach a hardness of 58 HRc, and have a fracture toughness at this hardness equivalent to that of standard hot-work tool steels at 45 HRc. This offers one of two advantages: the steels can be used at the higher hardness to provide resistance to wear or deformation, or, when used at a hardness of 47?49 HRc for hot forging, to provide temper resistance, nitriding behavior and adhesive wear resistance. The results presented here are from a preliminary investigation. The experimental results indicate that the introduction of a proper duplex PACVD hard coating will lead to an improved wear resistance and a longer lifetime for the hot-forging dies. Furthermore, by using a hard, low-friction coating excellent anti-sticking properties can be obtained. At this stage of the investigation it is also necessary to carry out pilot trials to determine the wear resistance and the tool life in practice.

Jan 1, 2006

By Rikiya Kamezawa, Rudiono, Manabu Takeuchi

"Schottky type solar cells based on phthalocyanine (Pc) thin films were fabricated, and their photovoltaic performance was investigated in various ambient atmospheres. Most of cells prepared in this study showed a good rectification and photovoltaic effects in the visible wavelength region. The introduction ofN02 gas into the measuring chamber was confirmed to increase the current both in dark and under light illumination. However, chemical reaction between the Al electrode and N02 formed some oxide and deteriorated the Schottky barrier, resulting in an increase in cell resistivity. SF 6 gas also showed similar effects on the cell performance.IntroductionPhthalocyanine is one of the typical organic semiconductors, which shows high photoconductive sensitivity in the visible to infrared region. Today, several kinds of metal phthalocyanines are used in electrophotographic photoreceptors. In addition, application of phthalocyanines to solar cells have also been trying by many workers [1, 2]. Many efforts have been made for improving performance of phthalocyanine solar cells by modification of device structure [3, 4], doping by dye or pigment [5, 6] and incorporation of metal clusters [7]. It is known that electrical conductivity in phthalocyanine is increased by adsorption ofNO2 [8, 9]. We tried to improve photovoltaic performance ofphthalocyanine solar cell by adsorption ofNO2. This paper describes the influence of N02 adsorption on the photovoltaic behavior of phthalocyanine solar cells."

Jan 1, 2000

By E. A. Trillo, L. E. Murr, R. D. Flores, J. C. McClure, B. M. Nowak

Complex vortex and swirl-like solid-state flow phenomena have been observed in the residual microstructures characterizing the friction-stir welding (FSW) of copper to 6061 aluminum; 2024 aluminum to 6061aluminum,2024 aluminum to 1100 aluminum, 2024 aluminum to 7039 aluminum and 2024 aluminum to 2195 aluminum. These flow phenomena are characterized by intercalation lamellae composed of dynamically recrystallized grain structures of the dissimilar metals which provide a super-plastic-like mechanism for the FSW flow in the solid state; there is no melting and temperatures at the weld center do not exceed about 0.8 TM (where TM is the absolute melting temperature (K)). In experiments to be described and illustrated, optical or light metallography (LM), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques are utilized in examining residual FSW microstructures corresponding to tool rotation (stirring) speeds ranging from 400 to 1200 rpm, and traverse (or actual welding) speeds of 1 to 2 mrn/s.

Jan 1, 1999

By Alessandro Navarra, Joël P. T. Kapusta

"The converting cost modeling software introduced by Ng et al. in 2005 [1] has been extended to consider the reprocessing of reverts and copper scrap. The original model evaluated the operational costs of a Peirce-Smith converter; algebraic relationships had been implemented with arrays (to represent matrices, vectors and scalar ratios). The new software brings flexibility to the underlying thermochemical balances, by using linked-lists instead of arrays. It is now possible to consider the blending of several feeds, including reverts and scrap.The software computes the length of the converting cycle from the Fe and S content of the charge together with the blowing rate; the times required for other operations (charging, skimming and idle time) are also accounted for. The costs of consumables such as flux, fuel, oxygen or compressed air are all evaluated. Downtime, labor, and materials for converter lining repairs are also considered. The software is easily extended to examine the costs of alternative operating strategies or injection technologies such as sonic single pipe injection and sonic shrouded injection. The potential cost benefits of alternative operating procedures and technologies are discussed through example calculations."

Jan 1, 2009

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By J. L. Johnson

The U.S. Department of the Interior, Bureau of Mines, investigated recovery of concentrates containing tin, tantalum, and niobium from the Kougarok deposit on the Seward Peninsula, AK. To date, 25 million lb of tin has been delineated in occurrences containing 0.36 to 1.32 pct Sn, and the resource potential is estimated to be as high as 25 million short tons at average grades of 0.75 pct Sn, 0.025 pct Ta, and 0,025 pct Nb. Deslimed ore was concentrated to 54 pct Sn, 0.3 pct Ta, and 0.3 pct Nb, with recoveries of 74 pct Sn and 44 pct Ta/Nb using a Humphrey's* spiral followed by a Deister shaking table. Tin values in the slimes were upgraded to a 5-pct-Sn concentrate using a Bartles-Mozley separator followed by flotation. The 5- pct-Sn was further upgraded by fuming to give a concentrate containing approximately 60 pct Sn. The recovery of the two products combined was 80 pct Sn and 46 pct Ta/Nb, A flowsheet with mill-design parameters resulted from the metallurgical testing. An economic analysis was made based on the proposed process.

Jan 1, 1990

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By Ryszard Prajsnar

During copper production in shaft and flash smelting processes at KGHM Polska Miedz S.A., lead bearing material of sulfide, sulfate, and oxide character is generated in forms such as slime from shaft furnace gas handling systems, converter dusts, and dusts from an electric furnace for copper removal from flash smelting slag. These materials are polymetallic concentrates of Pb, Zn, and Cu, with As, Cl, and Cd as impurities. Shaft furnace slime, containing. about 50% PbS and 15% bituminous substances, is the main lead-bearing material. At the Glogów copper mill, a new plant was commissioned in June 2001 to process 80,000 tonnes per year of lead bearing materials to produce 26,000 tonnes per year of crude lead. The plant consists of a feed conditioning system, three (3) rotary rocking furnaces with a capacity of sixteen (16) tonnes of lead feed fired with natural gas and oxygen-enriched air containing up to 45 vol% O2, and a gas handling system. The gas handling system includes a post-combustion chamber, a gas cooling chamber with Cl neutralization, gas mixing chamber, bag filter, and dry limestone scrubbing system for SO2 removal. The lead-bearing feed is smelted with five (5) wt% Na2CO3 and thirteen (13) wt% iron scrap at a temperature of 950 to 1050°C for three (3) hours. The smelting process consists of four (4) stages; feed drying, firing of gaseous hydrocarbons and solid coal from the feed, lead reduction from slag, and separation of molten products. The flow rates of natural gas and oxygen to the burners are controlled to ensure combustion of the bituminous material in the furnace. The process produces crude lead bullion containing (wt%) 0.1 to 0.5% Cu, 0.02 to 0.5% As, 0.05 to 0.07% Bi, 0.1 to 0.5% Sb, and 0.1 to 0.6%Sn. The process also produces a mixture of sodium silicate slag, Fe-Zn-Pb-Cu-S matte, and Fe-As speiss containing (wt%) 5 to 10% Pb, 2 to 6% Cu, 10 to 15% Zn, 1 to 3% As, 10 to 15% S, 0.5 to 3.0% Cl, 2 to 4% K, 4 to 7% Na, 20 to 30% Fe, and 5 to 10% SiO2. The dust is made up of PbO, ZnO, PbSO4, and PbCI2, KCI, and NaCI with a chemical composition (wt%) of 35 to 50% Pb, 5 to 15% Zn, 3 to 6% As, 4 to 8% Cl, 2 to 5% K, and 2 to 5% Na. The construction of the new lead production plant at the Glogów copper mill will process both current lead-bearing materials as well as lead-bearing material that have been stockpiled over the last fifteen (15) years to give a significant improvement in protection of the natural environment.

Jan 1, 2002