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By Makoto Ohlsuka

The ternary Ni2MnGa intermetallic compound is an intelligent material which has both a ferromagnetic property and a shape memory effect (SME). The use of the shape memory alloy films for an actuator of micro-machines is very attractive because of its large recovery force. The purpose of the present study is to investigate the effects of fabrication conditions and to clarify the relationships between these properties and fabrication conditions of the Ni-Mn-Ga films. The Ni-Mn-Ga films with a thickness of nearly 5 um were deposited with a radio-frequency magnetron sputtering apparatus using a Ni50Mn25Ga25 or Ni52Mn24Ga24 target. They were heat-treated at various temperatures between 873 and 1273 K for homogenization and ordering and then cooled in a furnace. The composition of the films depended on the sputtering power. The as-deposited films were crystalline and had columnar grains. After the heat treatment the grains widened and the grain boundary became indistinct with the increasing heat treatment temperature. The martensitic transformation temperature of the heat-treated films increased with increasing nickel content. Furthermore the effect of plastic deformation and constraint aging on SME is also investigated. After plastic deformation, the two-way SME was shown through the martensitie transformation and its reversion, The intensity of X-ray diffraction peaks from stress-induced martensitie phase was found. The constraint-aged films also showed the two-way 3ME by thermal cycling.

Jan 1, 2003

By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

By Katsumi Ogi, Hiroto Uchida, Masamitsu Sato, Atsushi Itsuki

"(BTMSE)Ag(hfac) (BTMSE = trans-bis(trimethylsilyl)ethene) was chosen as a suitable precursor for the XeCl laser (308nm) MOCVD of Ag. Iso-propanol solution of (BTMSE)Ag(hfac) was used as a liquid source for the liquid delivery method, high deposition rate 9nm/min at substrate temperatures of 100°C and 120°C were obtained at the vaporizer temperature of 90°C. This deposition rate is three times faster than by conventional bubbling method and life of the source and reproducibility of the deposition were also improved. Electric resistivities of the laser deposited film shows significantly low resistivity of 10-6Q-cm compared to 1 o-3Q-cm of thermal MOCVD film. These results indicates that the laser MOCVD is one of the effective method for the preparation of the high quality silver film.IntroductionSilver films are a potentially important metallization material in electronic and photonic devises due to their lowest resistivity (1.6µ0-cm) among the metals, high optical reflectance and chemical stability. The MOCVD technique has advantages to sputtering or evaporation in the point of conformal growth and better coverage on sharp steps and narrow gaps[l-2]. For MOCVD application, silver precursors must have sufficient vapor pressure without decomposition at their evaporation temperature. To achieve stable precursor gas supply, liquid delivery of precursor material is promising[3-4] especially for materials that have not enough heat stability and high vapor pressure like silver complexes[S-10]. Several new silver complexes for MOCVD and UV irradiation effect to their MOCVD silver film quality were reported by same authors[5]. In this paper new solvent system for liquid delivery system of silver MOCVD were investigated to suite XeCl(308nm) laser MOCVD application."

Jan 1, 1998

By William Petruk

The capabilities of SEM/image analyzers for determining quantitative mineral data which have a bearing on extractive metallurgy have given applied mineralogy a new dimension. The capabilities include automatic mineral identification, unattended operation, search for rare minerals, and measurements of (1) mineral quantities, (2) grain and particle size distributions, (3) liberation characteristics of minerals in ground ores, and (4) mineral associations. Data on mineral quantities define the distributions of elements among minerals, provide background information on characteristics of the samples, and provide a data base for a mineral-materials balance. Size analysis data of the minerals in unbroken ores are used to predict the grind required to liberate minerals. Data on liberation analysis can be used in many ways. One application is to process the image analysis data for feed, concentrate and tails by a materials balancing technique to calculate the recovery of liberated and unliberated grains at each point in a circuit. The calculated recovery data define the behaviour of an ore in a concentrator, pilot plant or bench test, and indicate whether recovery improvements are possible and/or feasible for a particular ore.

Jan 1, 1991

By L. A. Mills

After three years of experience in operating the pilot plant for the Noranda Continuous Smelting Process, the decision was made, in March 1971, to build an 800 ton per day commercial plant at Noranda, Quebec. The de- sign and layout of the plant is discussed and the installed equipment described. Experience previously gained in the pilot plant is mentioned when it has been used in the choice of equipment or plant layout. The full- scale reactor was started up in March 1973 and the operational datacollected and the experience acquired during the first 30 months of operation are described. This includes operation to produce both high grade matte and copper. Areas discussed include refractory wear, fuel consumption and throughput of copper concentrates. Changes made to original equipment and methods of operation are discussed, together with the reasons. The ad- vantages of using solid fuels to handle inert materials and to maximize converting air flowrates and concentrate throughputs are described. Relative efficiencies of oil and natural gas are compared. The addition of oxygen from a 94 ton per day oxygen plant to the reactor converting air was started in August 1975 and the initial operating results are included.

Jan 1, 1976

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

By Tibor Zoltai

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

Jan 1, 1989

By Yanhui Liu, Xuewei Lv, Chenguang Bai

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

Jan 1, 2015

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By I. Gaballah

Jarosite contains up to 15 % of heavy metal compounds 'HMC'. The current waste disposal methods will not be allowed in the near future due to new environmental regulations and pollution risks. For these reasons, thermal treatments of raw or decomposed jarosite, in controlled atmospheres, were investigated. The aim of these treatments is to decontaminate the jarosite and/ or to recover the HMC for recycling. According to physico-chemical characteristics of the samples, the thermal treatments in controlled atmospheres N2, CO+N2 and C12+air lead to the extraction rate that vary from 93 to 98 %. Heavy metal compounds were separated by cooling the gaseous phase. The treatments' residue was almost free from HMC. Between 700 "C and 800 "C, the chlorinating treatment was successful of eliminating more than 97 % of HMC contained in four different samples.

Jan 1, 1999

By Muammer Kaya, Sait Kursunoglu

"The aim of this study was to investigate the effectiveness of ascorbic (C6H8O6) / oxalic (C2H2O4) acid as a reductant for the simultaneous recovery of zinc and manganese from a spent and mixed zinc-carbon and alkaline battery powder in sulphuric acid leaching. The effects of sulfuric acid concentration, ascorbic/oxalic acid dosages, reaction temperature and leaching time on the zinc and manganese dissolutions were investigated according to 2k full factorial experimental design; then, a simple optimization study was carried out for the best reductant. The optimum reductive acid leaching conditions were determined at 3 hours leaching time, 70°C leaching temperature, 0.5M sulfuric acid concentration, 13 g/L ascorbic acid dosage, 1/20 g/mL solid/liquid ratio and 200 rpm stirring speed. Under these conditions, the dissolution efficiencies were 99.9% for Zn and 99.3% for Mn. When our results were compared with the previous results, our findings were better than previous studies.In addition, the manganese dissolution kinetics was undertaken, and the activation energy was found to be 7.04 kJ/mol. Selective precipitations of Zn and Mn from acid solutions were carried out using NaOH and KOH. Using 3M NaOH as precipitating agent at room temperature and at pH 8; 95.4% of Zn and at pH 10; 93.7% of Mn were precipitated from the leaching solution. Under the same conditions, using 3 M KOH at pH 8; 91.6% of Zn and at pH 10, 96.4% of Mn were precipitated. Based on the experimental results obtained, an appropriate flow sheet was proposed to recover zinc and manganese."

Jan 1, 2012

By Hideki Minoura

"Two novel electrochemical techniques for the preparation of highly crystallized CdS film have been presented. One is cathodization of a conductive substrate in an acidic chemical bath containing cadmium salt and thioacetamide, where electroreduction of proton at small current densities induces a growth of highly crystallized CdS thin films, whose growth is not disturbed by the reactions in the solution phase. The other technique is electoreduction of aqueous Cd2+— SCN complex. An advantage of this technique lies in no formation of solid particles in the bulk, of the bath.IntroductionIn recent years much attention has been paid to materials preparation by solution processing because of its advantages in lowering the cost as well as the stress to the environment, as compared to the conventional gas phase techniques which unavoidably require high temperature and/or vacuum. We have been trying to explore novel techniques for preparing functionalized compound semiconductors by aqueous solution process. Semiconductors which we have been mainly focusing on are CdS and ZnO, which are important semiconductors finding applications in various devices. In the present paper, some of the techniques that we have recently established for the preparation of highly crystallized CdS will be presented.Methods of the CdS film processing in solution phase (wet process), which have been reported so far can be divided into two major groups; one is chemical bath deposition (CBD) in alkaline solution containing Cd2+ and thiourea 1)4) and the other is electrodeposition (ED) in acidic solution containing Cd2+ and thiosulfate ions - 5)-8) or organic solutions containing dissolved sulfur 9)-11)."

Jan 1, 2000

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By Paul E. Queneau

The QS (Queneau-Schuhmann) copper converter is a gently sloped, stepped, horizontal kiln-type tilting reactor in which desired bath oxygen activity, compositional and temperature gradients are created by countercurrent flow of matte and slag phases through a series of controlled bubble plume, mixer-settler configurations. Flow of gas and slag is normally concurrent. Copper sulfide concentrates are top-fed, employing oxygen flash burners. Oxygen and oxygen-carbonaceous fuel mixtures are bottom-blown into the smelting bath through judiciously located, independently regulated submerged injectors. Composition and mass flow rates of injector inputs are controlled to produce bubble plumes of desired character, without jetting through and out of the bath. The mixer-settler pattern can be reinforced if desired by employment of suspended shallow baffles. State-of-the-art instrumentation provides timely information required to govern key process variables. The outstanding capabilities of the QS converter for coppermaking have now been indicated by the current success of industrial QSL (Queneau-Schuhmann-Lurgi) leadmaking reactors. Modified converter designs are employed for leadmaking, nickelmaking and steelmaking.

Jan 1, 1993

By B. Mishra

The major waste product of the alkaline extraction of alumina from bauxite [Bayer Process] is known as red-mud. Approximately, a ton of red-mud is produced for every two tons of bauxite that is mined. The red-mud produced from Jamaican bauxite is rich in hematite, alumina and titanium oxide. It has been shown that over 90 wt. pct. alumina can be recovered from red-mud by soda-ash sintering and caustic leaching. Hematite can be carbothermically reduced with a degree of metallization of over 94 pct. At this stage, the product could be charged through the tuyeres in an iron blast furnace or smelted to produce pig iron. The mineralogical characteristics of the reduced product are not amenable to magnetic separation for iron recovery. The problems associated with the use of reduced red-mud as an alternative to direct-reduced iron [DRI] has also been discussed. Special attention has been paid to lower the alkali content of the reduced material. If smelted, the concentration of titanium oxide in the slag will be significantly high justifying its recovery by an acid-leach process. This paper describes the successful efforts of iron and alumina recovery.

Jan 1, 2000

By Thomas J. Keefe, O&apos

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

Jan 1, 1993

By John M. Gaines

Lead concentrates from the Viburnum Trend in Southeast Missouri are sintered, prior to smelting, to bind the particles together, homogenize the feed, and reduce the sulfur content. About 20% of the sinter at some plants is classified as bad sinter. A total of 130 samples of good and bad sinters were studied by reflected light microscopy, scanning electron microscopy-energy dispersive analysis, and electron microprobe analysis to characterize their differences in mineralogy and textures. Good sinters consist predominantly of hardysonite, franklinite, lead silicate matrix, and large crystals of calcium-magnesium-iron silicate, together with minor amounts of lead oxides, lead-zinc silicate, metallic lead, specular hematite, magnetite, lead-iron-bearing zincite, and zinc-lead-magnesium-bearing wustite in a tightly intergrown mesh of crystals and with an evenly distributed porosity of about 15-20%. Bad sinters contain larger amounts of lead silicate matrix, galena, metallic lead, and lead oxides, but smaller amounts of hardysonite, franklinite, and calcium-magnesium-iron silicate, lack intimate intergrowth of the phases, and have lower (0-5%) and unevenly distributed porosity.

Jan 1, 1992

By Maija-Leena Metsärinta

The behaviour of copper and lead in zinc roasting has been studied in laboratory scale roasting experiments as well as in large scale trials in an industrial fluidized bed, with the background of Outokumpu Kokkola Zinc smelter. Commercial zinc concentrates with a low and high ( up to 3 wt % ) copper content and with a low and high (up to 3.5 wt % ) lead content were oxidized to various desulphurisation degrees in the fluidized bed to establish the reaction mechanisms and the paths for copper and lead oxidation in the roasting. Influences of the agglomerate size on the roasting kinetics and micro-scale phenomena were also determined. Optical microscopy was used on the calcine and the findings are presented as numerous photographs of the polished cross sections. SEMIEDS techniques were used for analyzing chemically the phases and particle morphologies present in the samples. Computational thermodynamics was applied to the complex phase equilibria occurring during roasting in the agglomerating calcine. A complete oxidation of zinc concentrate with a high copper and lead content requires a careful control of oxygen coefficient in the roasting in order to maintain a stable operation of the fluidized bed. Oxygen coefficient thus seems to have a significant impact on the hydrodynamic stability of the fluidized bed with fine raw materials.

Jan 1, 2003

By André L. B. Bittencourt

The copper content in the waste slag represents the greatest loss in the process of Caraíba Metais' Smelter. By identifying the variables responsible for copper stabilization in the slag, a minimization on these losses is expected, producing a granulated waste slag with a copper content lower than 0.7%. Statistics resourses such as control charts, Pareto's diagram and correlations curves were applied for the data obtained in the first semester of 1992. The magnetite and the calcium oxide contents in the slag of the Flash Smelter Furnace were most prominent variables. Some operational changes introduced during and after this investigation have shown good results.

Jan 1, 1994

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003