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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 Torn H. Okabe

A fundamental study was conducted with the purpose of establishing an environmentally sound recovery process for recycling of valuable metals, by combining scraps containing such metals. As an example, direct extraction and recovery of neodymium (Nd) in magnet scraps was investigated by utilizing liquid metal as an extraction medium. It was found that liquid magnesium (Mg) is a suitable extraction medium and can extract Nd from iron alloys with high efficiency at around I 100 K. The newly developed extraction apparatus for Nd is a mechanically simple and static device without moving parts, where the Mg extraction medium circulates due to differences in the temperature inside the reaction vessel. This developed device can simultaneously accomplish continuous extraction of metal Nd from scraps, re-extraction of Mg from Mg-Nd alloy and the eventual recovery of pure Mg. As a result, metal Nd with 98 % purity was directly recovered from magnet scraps under certain conditions. It was also shown that the extraction agent Mg could be reused. The results of this investigation show the possibility of establishing a new process for the direct extraction of Nd in pure metal form without oxidization.

Jan 1, 2003

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothemlic reduction, hydrometallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By George P. Demopoulos

In this paper the production and stability of crystalline scorodite (FeAsO4·2H2O) is discussed both on the basis of previously published work as well as recent work performed in our laboratory. The production of scorodite, especially from arsenic-rich and iron-deficient sulphate solutions offers a number of operational advantages such as high arsenic content, stoichiometriciron demand, and excellent dewatering characteristics. In addition to hydrothermal production of scorodite the work done over the last 10 years in our laboratory has determined that it is feasible to produce scorodite by step-wise lime neutralization at 90°C. The atmospheric scorodite possesses the same structural and solubility characteristics with the hydrothermally produced scorodite. Long term equilibration tests (up to 66 weeks) in the pH range 5 to 9 and temperatures from 22 °C to 75 °C revealed scorodite to undergo slow incongruent dissolutionyielding a highly metastable nano-sized 2-line ferrihydrite phase. The equilibrium arsenic concentration with this phase was 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7 respectively at 22°C. In the presence of gypsum slightly lower concentrations were measured, this being more pronounced at pH>7. It was tentatively deduced that a Fe-Ca-AsO4 association (in the form of a phase resembling the mineral yukonite) contributes to the lowering of As concentration. Finally thermodynamic calculations determined that scorodite is stable in the presence of ferrihydriteunder oxic conditions up to pH 6.75 at 22 °C or higher pH at lower temperature and gypsum-saturated solutions. Keywords: Scorodite, Crystallization, Arsenic, Solubility, Stability, Precipitation, Disposal, Extraction, Processing, Metals, and Environment.

Jan 1, 2005

By F. H. A. Abdalla

A process is described for the recovery of valuable nonferrous metals from steelmaking dust by suiphatizing roasting using ammonium sulphate. Maximum recoveries of soluble metal sulphates achieved at optimum conditions were> 99.0 %. Selective metal separation of the soluble sulphates in the leached liquors were performed either by controlling the roasting temperature or by adjustment the pH values of the leached liquor ranging from 3.6-6.2. Either pure zinc oxide orland tin oxide could be obtained at optimum conditions, and the products were evaluated chemically and by X-ray analyses. The residues rich in iron oxide can be removed and recycled. The mechanism of sulphatizing roasting process was considered. A general flow-sheet for the overall process of treatment the steel making dust to recover its valuable nonferrous metals was suggested, which ca be applied for other nonferrous bearing materials.

Jan 1, 1996

By J. C. Agarwal

Slags produced by modern smelting furnaces contain copper values which are unacceptably high for discard. The electric arc furnace is employed commercially to clean copper from flash furnace slags but the addition of highly oxidized converter slags to an electric furnace has created operational problems. Highly oxidized Noranda Reactor slags have not been processed successfully in a pyrometallurgical process. These slags, which contain large concentrations of copper (5 to 10 per cent), are treated in slag concentrators (controlled cooling, crushing and milling, and flotation) which produce a copper concentrate that must be resmelted. Though commercially operable, it will be shown that the slag concentrator has important process and cost disadvantages as compared to a pyrometallurgical process. In this paper an economic comparison is made between a pyrometallurgical process and the slag concentrator. For the analysis, five hypothetical smelting plants are considered. Each plant treats 1200 tons of copper concentrate per day and produces 109,000 tons of copper annually. The plant configurations used in this study are:

Jan 1, 1976

By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450°C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Wang Shulan

The synthesis process of BaTiO3 from TiO2 and BaCO3 in the molten NaOH-KOH at 350oC was studied by the A.C impedance technique. The A.C. impedance of molten NaOH-KOH (xNaOH = 0.36) and the variation of the conductivity of the salt with time during the synthesized process were measured. The synthesized reaction of the BaTiO3 and the decomposition reaction of BaCO3 are fast and were finished in 10min. The interaction between TiO2, BaO and BaTiO3 and the molten salt was confirmed by the variation of the conductivity.

Jan 1, 2005

By J. Jakumelt

The coupled simulation of mold filling and solidification for an investment casting process presents difficult. This is due to the complexity of the carious physical process and the geometry, To achieve this task in a precise way, the CFD program FLUENT and the casting simulation tool CASTS were closely coupled. Any physical quantity, such as velocities or temperatures, can be exchanged via files after each time step of the simulation. The communication and operating sequence of the programs is controlled by PERL-scripts. This enables the expertise of FLU ENT for flow simulation and the strength of CASTS, for casting simulation to be combined. The coupled simulation was successful applied to an aerospace investment casting. Several physical models were tested for correct treatment of the casting filters, the porosity of the mold and the viscosity of the liquid metal. The results demonstrate that even complex investment casting geometries can be investigated using CASTS-FLUENT.

Jan 1, 2003

By Etsuro Shibata

The saturated solubility of chromium oxide and the valence of chromium in the slag are important matters when considering how to effectively utilize chromium-containing slags. The experimental data of various types of slags cited in the literature were arranged according to the optical basicity in order to evaluate the effects of the oxygen potential and the slag composition. The saturated solubility of chromium oxide and the Cr2+/ Cr3+ ratio tend to decrease with the increase of the optical basicity of the slag at an oxygen potential below 10.5 atm. However, at an oxygen potential of 0.21 atm, the saturated solubility and the Cr6+/Cr3+ ratio tend to increase with an increase of the optical basicity. A practical approach was suggested to reduce chromium in the stainless steel slag and simultaneously recover it as a ferroalloy by the direct smelting reduction of chromium oxide in the molten slag using some reductant in a small furnace.

Jan 1, 2003

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By W. S. Kirk

World cobalt production in 1987 was estimated to be about 26,600 metric tons (MT) of which Market Economy Country (MEC) production was estimated to be about 22,000 MT. Zaire and Zambia produce about 80 percent of the primary cobalt produced among Market Economy Countries (MEC). Production cutbacks. lowering cobalt grades and mining curtailments in Finland and Zambia in 1987, resulted in lower production than that of 1986. The trend is expected to continue through 1988. Cobalt production from Canadian ores and from Botswana is expected to increase significantly in 1988 as a result of increased nickel production. MEC production in 1988 is estimated to be 22,100 MT, only slightly higher than that of 1987. There are currently no primary cobalt mines. Virtually all cobalt is recovered as a byproduct of copper and/or nickel mining. Zaire, which produces cobalt as a byproduct of copper, is the worlds largest cobalt producer, with over 50 percent of total estimated world cobalt production and nearly 65 percent of MEC production. Zambia follows with about 14 percent and 17 percent, respectively. Zambia's cobalt production also results from copper production.

Jan 1, 1988

By J. M. Shneerson

At Gipronickel Institute a technological flowsheet of pressure leaching of copper from rich copper concentrates (i.e. containing: Cu -59-75%; Ni -D.5-4.64%; Fe -D.2-J.3%; S -21.8-26.9%) was developed. As a result, the possibility of deep decomposition of copper-containing minerals with extraction of elemental sulphur (up to 90-95%) was established. The obtained sulphur concentrates contain 80-90% of elemental sulphur, which can be separated from sulphide residue through autoclave melting and settling. As a rule, sulphide concentrates remaining after extraction of sulphur contain up to 1-2% of noble metals. The sulphide concentrate can be purified to the level of rich concentrates or pure metals using the well-known methods as in the case of tankhouse slimes. The presented research specifies the parameters of main operations: pressure leaching and sulphur extraction. It was established that 98% of copper could be transferred into solution at temperatures of 108-1 10°C and oxygen partial pressure 0.4-0.6 MPa. Experiments were carried out in autoclaves of various volumes using the products of nickel matte processing.

Jan 1, 2003

By Yasuo Ojima

A new copper continuous converting process was investigated to evaluate the possibility of its application in the commercial operation. The tests were performed both in the laboratory and in pilot plant scale. Bath smelting process with the use of the top submerged lance technology was applied in these tests. Furnace shape was modified to a lengthwise eylindrical one with a settling area. The furnace monitor was put in the settling area to check the furnace from inside, FeOx-Si02, FeOx-CaO and FeOx-CaO-Si02 based slag systems were used to check their efficiency, The optimum slag chemistry to have good metallurgical results was discussed and FeOx-CaO system with some Si02 content turned out to be preferable although it has not been practically used, In this pilot plant test feeding rate of I tIH of solid grain matte was charged consecutively for two weeks and continuous converting could be done successively. This process is expected to overcome the problems of existing processes and be easily applied in existing plants.

Jan 1, 2003

By Wilhelm Wendt

About five years ago we showed that it is possible to use the spectral in- formation in the light emitted by the off-gas flame of a PS converter for on-line production control. Very recently measurements have been performed using improved optical equipment and data evaluation software, resulting in both improved accuracy and the establishment of new optical process parameters. Using the optical signals the slag heats could be stopped at a predetermined Cu content of the white metal with an accuracy of +0.2% Cu m the range 74-78% Cu. A good correlation was found between the slag composition and optical data, providing a possibility for on-line monitoring of the SiO2 content of the slag. The measurements indicate the possibility of predicting the optimum end-point of the copper-making stage and having real time information on the impurity removal. Factors influencing the optical parameters, such as blowrate, Pb content, temperature etc. will be discussed.

Jan 1, 1993

By Frank A. Stephens

The process of converting iron ore (principally Fe,03 or Fe30,) into iron carbide (Fe,C) to be used as feedstock for steel-making yields complex mixtures of several Fe-containing compounds as a function of processing conditions. In addition to the above compounds (hematite, magnetite and cementite), the mixtures typically contain wustite (FeO) and metallic iron(Fe). Mossbauer spectroscopy has been developed into aquantitative analytical method for monitoring the degree of conversion to carbide from samples periodically extracted from a fluidized bed reactor type of pilot plant. Calibration of absolute quantities of the above five compounds is based on standards prepared from known mixtures of the high purity individual phases. The PC-based spectrometer allows fitting of the well-known spectral components of each of the five phases, the resulting spectral areas then being compared with the calibration curves via PC software to yield the weight fraction of each. Emphasis has been placed on standardizing and simplifying the analysis procedure for routine use in an industrial environment.

Jan 1, 1993

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By P. M. Tyroler

Inco operates a hydrometallurgical plant to treat the residue from the pressure carbonylation process. The main constituent in the residue is cop¬per. The residue is leached under pressure in an acid sulphate solution in two stages and the copper is recovered via electrowinning. The electrowinning tankhouse is fully integrated into the overall plant flowsheet as spent elect¬rolyte is required in upstream leaching steps. In recent years, the amount of residue had increased and copper removal capacity became the rate limiting factor for the entire plant. Consequently, a major program was undertaken to upgrade the tankhouse with regards to capacity, efficiency, cathode quality, working environment and structual integrity and appearance. This paper will describe current facilities and operation, and detail progress in our up¬grading efforts.

Jan 1, 1987

By M. Omneya El-Hussaini, M. Galal Abdel Wahab, A. Mohamed Mahdy, M. Fathi El Shahat

"Um-Gheig Pb-Zn representative sample was collected from the main adite of Um-Gheig mine along Red Sea coast in Egypt. Its chemical analysis shows that, it contains 16% Zn, 2.3% Pb, 0.1% Cd and 0.1% B as elements of interest. After H2SO4 agitation leaching, the chemical composition of Um- Gheig Pb-Zn deposit ore residue assayed 2.26% Pb, 1.5% Zn, 0.085 % B and 0.01% Cd. This residue was leached with 20% HCl at S/L ratio 1/3 for 2 hours at 80o C. The chloride leach liquor was found to contain 18 g/l Pb, 13 g/l Zn, 0.1 g/l Cd and 0.75 g/l B with the corresponding leaching efficiencies 79%, 86%, 100% and 88% respectively. Lead was precipitated from the chloride leach liquor using concentrated H2SO4 to obtain PbSO4 with precipitation efficiency 96%. While boron was extracted by the selective resin Amberlite IRA743 with loading efficiency of 80%. On the other hand, Zn and Cd were precipitated using Na2S solution with 86.7% and 100% recovery efficiencies respectively.IntroductionLead-zinc ores occur in Egypt in a few localities distributed along the Red Sea coast between El Qusier and Ras Banas.. The reserve of the ore deposits has been estimated by Soviet and German Experts to be about 900,000 Ton, [1]. Onal et al., [2] recovered Pb from Pb–Zn sample containing 10.17 % Pb and 10.98 % Zn from Aladag in Turkey. El-Sherif, [3] used concentrated HCl to leach lead-zinc ore sample of Um-Sammuki area in Egypt. As had been published by Marchioretto et al. [4], the precipitation of heavy metals with lime, sulfide and caustic soda are the most commonly used economical methods for metal removal. Lead was completely removed from the anaerobically digested sludge by precipitation with NaOH and Na2S at waste water treatment plants. Mahdy et al., [5] had successfully extracted boron from the bittern solution of Qaron Lake by ion exchange resin (Amberlite IRA 743). The extraction of boron was mainly depending upon the pH value. They extracted 80% of boron at pH 5.5, while at pH 3.9 about 74% boron was extracted. Kabay et al. [6] used the column-mode to remove 1g/l of boron from geothermal waste water of the Kizildere-Geothermal Power Station by using Diaion CRB 02 Nglucamine- type chelating resins. In this regard, the removal of lead, cadmium and boron allow the residue to be reclassified as non hazardous material."

Jan 1, 2008

By Mark Osborne, Ray D. Peterson, C. Edward Eckert

"The theoretical melting energy requirement for a typical hypoeutectic aluminum-silicon alloy is approximately 520 BTU/lb. It has been demonstrated, however, that even a state of the art secondary processing-automated lost foam casting operation can exceed this value by at least an order of magnitude when the actual thermal energy input from melting to solidification is monitored. Metal transfer and holding operations constitutes over 65% of this expenditure. The authors present relative benchmark energy expenditure information by unit operation for an offsite melting/lost foam casting line with a daily throughput in excess of 100,000 lbs. Efficiency improvements through optimization of the current process, and anticipated energy values at the culmination of a U.S. Department of Energy sponsored project to develop, integrate and demonstrate an advanced melting, transportation, and dispensation system will be cited.IntroductionThe size of the U.S. aluminum remelt pool was approximated to be 14.21 billion kg (31.27 billion pounds) by a recent study?, with the engineered castings (foundry) sector accounting for 3.25 billion kg (7.16 billion pounds) or 23% of that total. This study considered overall process yield and all major contributors to scrap. The values cited, therefore, are more meaningful than simply tabulating annual pounds shipped by sector.The foundry sector consists of Sand Castings, PM Castings and Die Castings categories appearing in Figure 1. All other categories comprise the wrought alloy sector. Wrought alloy production enjoys an energetic benefit from both scale and a relatively continuous operation. Many foundry operations, however, operate in batch mode at less than design metal throughput with characteristically longer melt holding periods. Since any detention of molten metal beyond melting represents an overhead use of energy, melt holding (secondary) energy expenditures can appreciably inflate melting energy requirements in the foundry."

Jan 1, 2009