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By D. A. Meyn, R. L. Holtz, C. S. Pande, M. A. Imam, D. J. Singh

"Various theoretical and experimental techniques used to search and develop new metal hydride systems suitable for hydrogen storage are described. The main theoretical technique under study makes the use of electronic structure of the candidate materials. Microstructural characterization techniques like transmission electron microscopy are being used to study the hydride formation. Novel processing techniques for material preparation such as those needed to produce thin films or amorphous phases are also being utilized. The techniques are illustrated with results from Pd, FeTi and Mg2Ni systems.IntroductionOf the four methods of hydrogen storage, compressed gas, cryogenic liquid, metal hydrides, and gas-solid adsorption, the metal hydride storage method is more attractive from the point of view of high volumetric density and safety. Compressed gas storage has disadvantages of extreme pressure, weight, and volume requirements, whereas storage of hydrogen as cryogenic liquid is unattractive due to the requirements of extremely low temperatures and high consumption of primary energy. Moreover, the number hydrogen atoms present in a volume of 10- 22 Cm3 (nH) in liquid hydrogen state (- 20K) is 4.2 whereas number of hydrogen atoms that can be accommodated in a free volume of 10-22 cm3 of various hydrides are as follows: LiH--5.9, TiH2--9.2, ZrH2--9.2, VH2--l0.2. High hydrogen concentration is usually associated with a large H/Metal atomic ratio but is also a function of structure."

Jan 1, 1994

By Levente Becze

The zinc bottom dross is obtained as a by-product from hot dip galvanizing operations and contains at least 92 % zinc, which is recycled mainly by pyrometallurgical processes. The overall costs of such a treatment, however, are often relatively high, and the very strict environmental protection regulations might also cause additional difficulties for the high temperature procedures in the future. Therefore, a novel hydro-electrometallurgical process has been developed in our laboratory, by which one can reclaim zinc of high purity, while attempting to achieve low energy consumption and making allowances for all the environmental restrictions. This aqueous processing technique, based on electrolytic refining in a cell equipped with anion-exchange membrane to separate the anode and cathode compartments, allows the indirect purification of the anolyte. Zinc is dissolved from the anode along with some of the impurity elements, while the intermetallic compounds (Fe-Zn, Fe-AI- Zn) are accumulated in the anode slime.

Jan 1, 2003

By N. Panagiotopoulos

A low-grade (1.06% Ni, 0.06% Co) hematitic type lateritic ore from Triada, Euboea Island, Greece, has been leached with sulfuric acid at atmospheric pressure for the extraction of the contained Ni and Co values. The effect of various parameters, including reaction time and leaching temperature, acid strength, pulp density, etc., on Ni, Co extraction and Fe dissolution was determined. By leaching at 95°C for 4h with a 3N sulfuric acid solution at 25% pulp density, Ni and Co extractions were 82 and 75% respectively, and Fe co-dissolution 28%, yielding a pregnant solution containing 2.7 g/l Ni, 0.16 g/l Co, and 33 g/l Fe. Overall acid consumption was 850 kg/t ore (or 100 kg/kg Nil. Preheating of the laterites at 600°C before leaching resulted in much faster leaching kinetics for Ni, but the final extraction and acid consumption remained unaffected; Fe extraction was not influenced. Three-stage counter-current leaching at 9S°C, using 2N acid strength at each stage and 35% pulp density, reduced acid consumption to 350 kg/t ore (41 kg/kg Nil, and yielded 81% Ni recovery. Percolation leaching of -10 mm laterite at ambient temperature with 3N acid for 7 days resulted in 58% Ni extraction.

Jan 1, 1988

By Z. Zhang, Cuihuan Huang, Zongshu Zou, Nan Wang, Xueqian Xin

"Vitrification is considered as an attractive procedure for municipal solid waste incineration ash, which can realize the volume reduction and innocent treatment of incineration ash, as well as reuse of bottom ash. The main oxide components of molten ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the total mass. The phase relations and thermodynamic properties of the CaO-Al2O3-SiO2-FeOx-MgO-Na2O oxide system is highly required, and is of great scientific significance for optimization of vitrification processing and sustainable resource utilization of melting slag. A study on the equilibria phase relations of CaO-SiO2-MgO-FeOx system was done by using CALPHAD method based on FactSage in this paper. The modeling parameters for the thermodynamic properties of liquid phase in CaO-SiO2-MgO-FeOx system were established and the equilibrium phase relations of MgO-SiO2-FeOx and CaO-SiO2-FeOx-MgO systems were calculated for different temperatures and oxygen partial pressures.IntroductionThe main oxide components of vitrified bottom ash slag are CaO, Al2O3, SiO2, Fe2O3, MgO, and Na2O, accounting for more than 90% of the bottom ash by weight [1]. During slag processing and modification, the knowledge of thermodynamic properties and liquidus temperature in the related slag system is highly required [2-5], which is not yet available. Through literature survey [6-9], it is clear that the systematic information on the concerned complex slag system is scarce. Most binary subsystems except FeOx-Na2O have been investigated well. Among ternary subsystems, few phase relations of the Na2O-MgO-SiO2 ternary system are available. For the phase relations of the system Na2O-MgO-Al2O3, all the studies are focused on the Al2O3-rich region. Investigation on the CaO-Al2O3-FeOx system is limited to Fe2O3-containing system with relatively higher oxygen potential. Most quaternary systems are not studied well except the CaO-MgO-Al2O3-SiO2 system, mainly due to their metallurgical importance. Figure 1 demonstrates the research status of the vitrified bottom ash slag with almost zero effort [10]. The effort here is defined based on the published literature by considering the number of publications, the investigated composition ranges, and the research details. So far the engineers in the field have to make assumptions of the thermodynamic properties of the simplified oxide system, without taking into consideration the interactions of the different oxide components, which hinders the development of the slag valorization and utilization. In order to provide thermodynamic properties for the application of the vitrified bottom ash, the six-component oxide system (CaO-MgO-Al2O3-SiO2-FeOx-Na2O) will be investigated through both experimental approach and computer modeling."

Jan 1, 2011

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By J. K. S. Tee

Using a novel method, zinc has been selectively removed from galvanized steel scrap on a laboratory scale. The separation is based on thermodynamic principles: during chlorination in air-chlorine (10:l) mixtures at 800 OC, zinc forms a volatile product (zinc chloride) while iron does not chlorinate as its oxides are more stable than the respective chlorides. As much as 92 % of zinc is removed from the surface of steel within 10 minutes. This process overcomes tedious and costly preparatory stages associated with leaching - electrowinning methods.

Jan 1, 1999

By J. Shibata

The recovery process of valuable metals, such as Ll, Mn, Ni and Cr from a waste lithium battery was developed n this study. Lithium and Mn are selectively leached from the battery by using dilute mineral acid. Main part of the battery comprises stainless steel, and Fe, Ni and Cr are easily leached by the mixture of dilute HCl and HNO3 Lithium and Mn are precipitated as metal carbonates from the? individual leached solution with sodium carbonate solution. The solution containing Fe,Ni and Cr Is treated by solvent extraction to separate NI and Cr from the leached solution. The experiments are carried out for leaching and separation steps. According to the experimental results, the flow. sheet for a recovery process of valuable metals from a waste lithium battery has been established.

Jan 1, 1995

By Michael P. Heisel

Solinox is a physical scrubbing process capable of removing a number of noxious materials from off-gasses, especially SO2, hydrocarbons, halogens, heavy metals such as dust, etc. As these materials are dissolved physically, (not chemically bound), the solvent is absolutely stable and no by-products are formed in the scrubbing cycle. The process has? been installed in three plants up to now, treating from approximately 30 MMSCFD to approximately 100 MMSCFD. These installations are in a non ferrous metal smelting operation, in a cellulose factory, and in a roasting process.

Jan 1, 1992

By D. P. Cook, Jr. Jones, J. W. Evans

"It is well understood that the flow of liquid metal in the mold region of the caster can have a notable effect on the overall solidification behavior in aluminum casting. Previously our group has characterized the flow in this region in a water model, using particle imaging velocimetry. The flow is significantly effected by the specifics of the metal delivery system, i.e. size, geometry, used during the cast. Recently, a time-averaged 3D numerical model of the nozzle, combo bag and sump region has been developed and its validity has been tested against experimental data. Cases were run for different sized combo bags as well as bags that have been blocked. The results show satisfactory agreement between the physical and mathematical models.IntroductionFluid flow in the head of an electromagnetic (EM) and direct chill (DC) ingots has been shown to effect many important operational parameters in casting such as superheat removal, macrosegregation, and hot cracking. In most cases, the momentum from the nozzle is diverted through a delivery system, termed a bag, before entering the mold region. The specific geometries of the bags vary widely from operator to operator suggesting that there is still some question as to the optimum design. Several studies [1-4] have been carried out to understand the influence of the bag design on the solidification behavior in aluminum casters. However, few studies have included numerical prediction with experimental verification. Unfortunately, many simulations performed today still do not accurately account for flow in such devices.Recently, a significant amount of research into the flow resulting from the metal delivery systems has been performed [5-8]. The thrust of this research has been characterizing the flow patterns by a measurement technique called particle imaging velocimetry. The data suggest that the method of delivering the liquid metal into the mold region has a significant effect on the nature of the flow. With a detailed set of quantitative data from a water model, a numerical model can be built and tested to ensure a proper description of the flow field. The computational model used in these simulations is designed to represent a laboratory scale model of a caster in which ""combo"" bags were simulated. Such bags are mostly of a densely woven glass fiber material with low permeability to aluminum. ""Windows"", of a more open weave, permit aluminum to flow from the bag, see Fig. I. Two different sized combo bags were modeled, each subject to two different outflow window configurations. Furthermore, experimental measurements [9] were used to validate the model results."

Jan 1, 1999

By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

By Nathalie Neveux

For the first time, dehydrated ferrous sulfate was successfully used for the dry synthesis of potassium ferrate. In addition, ferrate ion is stabilized as a solid solution where hexavalent iron is partially substituted by S(V1) leading to a sulfato-ferrate having the following formula K2(Fe,S)04. This substance has an efficient life time of about six months. Ferrate ion is a powerful oxidant ( EO = 2.2V ), a bactericidal agent and possesses coagulant, flocculant properties. Its reduction generates nascent oxygen, hydroxyl groups and Fe(OH)3. Alkali metal ferrate is probably the future global agent for water treatment. Applications of this material in the field of urban and industrial effluents treatment have been investigated. Heavy metals cations such as Cu, Cd, Mn, Ni, Pb, Zn, ... were successfully removed. The results of sulfato-ferrate use for cyanide destruction, decrease in COD, soil, discoloration of pulp and paper effluents will be summarized.

Jan 1, 1999

By K. Abe

Onahama Smelter has two green-charge reverberatory furnaces and the annual smelting capacity is 600 thousand tons copper concentrate. In addition to the concentrate, various kind of industrial wastes has been processed and utilized. First, the brick waste from converter is ground and used as raw material of castable for repairing the copper melt launders. Second, the slag containing calcium-sulfide from other foundry is fed to the reverberatory furnaces. Calcium sulfide is oxidized to CaO. The melting rate of concentrate is accelenlled and the slag loss is decreased. Third, the tip tire made of waste car tire is charged into the reverberatory furnaces as fuel. The steam of waste heat boiler for turbine generators has been increased so as to decrease the electricity cost. Fourth, the sulfur accretion from other chemical plant is blended into the copper concentrate and the sulfur is recovered as the gypsum for sale. Fifth, the processed waste oil has been utilized in the copper concentrate dryer by which the smelting capacity was increased effectively. Consequently, Onahama smelter contributes to the society by processing the wastes to the harmless slag and utilizing them as fuel through the copper smelting.

Jan 1, 1996

By Michael P. Meisel

Solinox is a physical scrubbing process capable of removing a number of noxious materials from off-gasses, especially SO2, hydrocarbons, halo¬gens, heavy metals such as dust, etc. As these materials are dissolved physically, (not chemically bound), the solvent is absolutely stable and no by-products are formed in the scrubbing cycle. The process has been installed in three plants up to now, treating from approximately 30 MMSCFD to approximately 100 MMSCFD. These installations are in a non ferrous metal smelting operation, in a cellulose factory, and in a roasting process.

Jan 1, 1992

By N. Choi

The distribution behavior of selenium and tellurium in nickel sulfide smelting was investigated in the temperature range of 1250-1300 °C under an inert gas atmosphere and various oxygen partial pressures. The distribution coefficients of selenium and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag were detennined in terms of matte and slag compositions, temperature, and oxygen partial pressure. The effect of slag additives such as CaO, MgO, and Ah03 on the distribution coefficients of those elements was also investigated. It was observed that the distribution coefficients of selenium and tellurium increased with increasing matte grade and temperature. The solubility of selenium and tellurium in the slag decreased with increasing the partial pressure of oxygen within the range investigated in this study. The distribution coefficients of selenium and tellurium increased with the amount of CaO and MgO. Tellurium distribution coefficients also increased by the addition of Ah03. Meanwhile, the addition of Alz03 decreased the distribution coefficients of selenium at high matte grade.

Jan 1, 1996

By Satian Niltawach

Iron sulphate jarosite through which iron in zinc sulphide concentrate feed is removed from the production circuit of conventional roast-leach-electrowin process, is chemically unstable and environmentally hazardous even if it is mixed with lime. If zinc silicate ore is used at similar chemical conditions in place of calcine in the jarosite precipitation, the resultant silico-jarosite residue having been mixed with lime is chemically stable and environmentally friendly. The recovery of zinc from silicate ore is also higher than that from calcine.

Jan 1, 1994

By Chen Zhang

Polycrystalline Ti-rich NiTi thin films have been deposited from a single NiTi target using a DC magnetron sputtering system. Free standing film was obtained by using a single crystal silicon substrate. Thickness ofthe thin films is controlled at around 12 pm. In this investigation, the effect of deposition temperature on the microstructure and transformation temperatures of the thin films is studied. Influence of post heat treatment temperatures on the properties of the thin films is also investigated. Transformation temperatures of the thin films are determined by differential scanning calorimetry (DSC). The surface microstructure of the thin films is studied using a scanning electron microscope (SEM), and the crystallinity is determined using x-ray diffractometry. It is found that the thin film deposited on a hot substrate is crystalline even when the substrate temperature is as low as 300°C, while the normal crystallization temperature for an amorphous thin film is around 500°C. The microstructure of the film deposited on a hot substrate shows a very fine grain size. The grain size increases with increasing substrate temperature during deposition. The effect of post deposition heat treatment on grain size is minimal.

Jan 1, 1999

By Takeo Fujino, Nobuaki Sato, Yarong Wang, Kohta Yamada

"Ternary mixed sulfides of some transition metals MTS3 (M=Ba, ·Pb, T=Ti, Zr) were synthesized by a relatively low temperature process using sulfur melt. The mixture of starting materials, such as, metals and/or binary sulfides and a large excess of sulfur was reacted in a vacuum-sealed Pyrex or quartz ampoule at 350- 600 °C for one to three weeks. After the reaction, the remaining sulfur was completely removed by a process composed of filtration of sulfur melt and followed dissolution in CS2• The binary sulfides impurities coexisted in the products were removed by rinsing the products in water and acetone. By using the above method, BaTiS3, PbTiS3 and BaZrS3 'Were obtained in pure form. The effect of addition of halides on the yields of these ternary sulfides were also discussed.IntroductionThere have been a vast number of studies on the preparation and physical and /or chemical properties of mixed metal oxides. As is well known, some of such compounds exhibit excellent materials properties, causing them for use in mechanical, electronic, magnetic and chemical devices. Not a few mixed metal sulfides show similar physico-chemical properties to those of the corresponding mixed metal oxides. However, the study of the mixed sulfide crystals is rather sparse mainly due to difficulties in preparing these compounds. In various methods which have been adopted for preparing mixed sulfides, the simplest method would be the solid-solid reaction of the component binary sulfides or elements. However, there are always diffusional constraints with regard to the reactions in solid phases causing it necessary to heat the reactants at sufficiently high temperatures, viz. 800-1200°C. On the other hand, some mixed sulfides are unstable at high temperatures or to change their materials properties due to sulfur nonstoichiometry and structural modification depending on temperature, i.e., synthesis of such compounds needs to be made at lower temperatures. Processing in alkali halide melts is hopeful to overcome the above problems but to obtain the halide melts the temperatures above ~ 600 °C is needed. Low temperature reaction has been carried out for the preparation of Hg1.24TiS4, which was formed by the ·combination of TiS2 and molten Hg metal at 320°C[l]. Reaction of WS2 with LiBH4 melt at 350°C yielded LixWS2[2]. These sophisticated methods, however, can be applied only to the vary special cases."

Jan 1, 2000

By John Wallace, Chib Iheagwara

"Refinements in sensor design have produced low-cost rugged elements to act as loop coupled with stable detection hardware for eddy current measurement in difficult environments. This has allowed direct dimension gauging of nonferrous and ferrous products above the curie point for absolute dimensions and electrical conductivities independently. The software was developed for the analysis of electrical conductivity profiles in CZ silicon crystal growth, then refined for monitoring bar properties and tube properties. Since in most metal working operations, speeds at the minimum of a few hundred feet per minute are encountered the design of the gauge was optimized for a rapid measurement. Independently extracting electrical conductivity provides data in some metal systems for determining the temperature of the monitored product.IntroductionThe primary reason for the use of eddy currents in gauging is that in hostile environments of metal working techniques such as laser gauging and ultrasonics are not always robust enough for in process measurements. Our goal is to use the technique of eddy current measurement as a quantitative control element in various hot and cold processing operations. Inspection in the early stages of metal and semiconductor processing is usually too costly to introduce in a well developed process and these tools are usually only employed in process development. Until recently there has been no efficient general analysis to allow real time measurements in the cylindrical and the probe geometry that could separate dimensional changes from material property changes both which effect the eddy current response. The basis for these measurements is that forward electromagnetic problem for conductors can be solved exactly for the test geometry which allows an inverse analysis to be made by relaxing the dimensions and conductivity to values which reproduce the measured response[!]. This transformation is based on analysis developed in Robert Siegfried' s thesis and was explored both by modeling and by physical measurement. This analysis was extended over the last few years to allow a more compact data set to be used to exact physical properties. The main result was that the technique would work on high ·quality physical data on as little as three test frequencies with the penalty being that the analysis is computational intensive. The main result of this work was that a quantitative inverse analysis of eddy current response would allow a general instrument to be used for a variety of measurements rather than being tailored for a specific measurement on a specific material test geometry. The development of these instruments has progressed over the last ten years for monitoring real time solidification, crystal growth[2] and hot seamless tube forming where the use of standards in traditional eddy current is limiting. The specific instrument design was dictated by the requirements of the algorithm for both frequency selection and levels of systematic noise that could be tolerated. Because the data is need for real time information this dictated that the system be a parallel multifrequency eddy current instrument feeding the same sensor. The sensor have to be simple and robust and usually a single loop or several loop of heat resistant wire or tube. This presentation is about using inversion of multifrequency eddy current data in real time to produce dimensional and property data on cylindrical conductors and planar conductors in real time. The object of the measurements is to produce dimensional outputs on measurements of conducting material without having to establish a detailed standard for each material or size tested. The dimensional measurements using eddy currents is complicated by material variations in conductivity due to temperature and composition. Those variations that are not geometric are often not of critical interest and complicate the measurement. The dimensional changes are often of more importance"

Jan 1, 1997

By William Petruk

The Kidd Creek base metal deposit near Timmins, Ontario contains around 0.15 wt% Sn, mainly as cassiterite. The cassiterite occurs largely as inclusions in sphalerite, with 85% being in grains smaller than 18.5 micrometres in diameter. Concentrates and tails from the company's Cu, Pb and Zn circuits were studied to determine the liberations and recoveries of cassiterite in the products. The ore had been ground to about 65.% minus 44 micranetres in diameter (-325 mesh); 55% of the cassiterite was liberated. About 92% of the liberated cassiterite and 70% of the unliberated cassiterite were in the concentrator tails, and 20% of the unliberated cassiterite in the zinc concentrate. The company had attempted to recover the cassiterite from the concentrator tails by gravitational methods but recoveries were low. The grain size of the cassiterite in the gravity Sn concentrate was similar to the grain size of the liberated cassiterite in the concentrator tails. Research on flotation of the fine grained cassiterite from Kidd Creek ore has been conducted,

Jan 1, 1990

By P. R. Taylor

Diamond films have been successfully formed in an inductively coupled plasma (ICP) chemical vapor deposition (CVD) system from several gas mixtures: CH,-H,, C2112-112, and C2112-112-02' Our previous thermodynamic study indicated that the substrate temperature could be lowered by the presence of oxygen species at moderate system pressures (0.3-0.5 atm) and that higher volumetric growth rates required a high temperature source and a moderate pressure system in CVD processing. The principal experimental results were consistent with the thermodynamic predictions. The deposited films were characterized by laser Raman spectroscopy, scanning electron microscopy, and X-ray diffraction. The films were well faceted and uniform, with the growth rates over 10 pm/hr on molybdenum substrates. The crystal size ranged between 1 and 2 microns for a two hour experiment. It was possible to decrease the substrate temperature to below 800 °C in this system.

Jan 1, 1995