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By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By Rodney L. Williamson

Optimal estimation theory has been applied to the problem of estimating process variables during vacuum arc remelting (V AR), a process widely used in the specialty metals industry to cast large ingots of segregation sensitive and/or reactive metal alloys. Four state variables were used to develop a simple state-space model of the V AR process: electrode gap (G), electrode mass (M), electrode position (X) and electrode melting rate (R). The optimal estimator consists of a Kalman filter that incorporates the model and uses electrode feed rate and measurement based estimates of G, M and X to produce optimal estimates of all four state variables. Simulations show that the filter provides estimates that have error variances between one and three orders-of-magnitude less than estimates based solely on measurements. Examples are presented that verify this for electrode gap, an extremely important control parameter for the process.

Jan 1, 2001

By K. C. Liddell

"Cu/Ni multilayers exhibiting giant magnetoresistance were deposited from a single electrolyte under stepped potentiostatic control. To enable transport measurements to be made without remounting the multilayer film, we developed a novel method that involved plating on a thin metallic basal layer atop a rigid non-conducting Si substrate. Rotating ring-disk electrode techniques were used to monitor the composition and thickness of individual plated layers. Transmission electron microscopy confirmed that the interfaces between adjacent layers were sharp and that the structure of the layers was uniform throughout the film. Atomic force microscopy images indicated that the film's surface was smooth and free of defects.ELECTRODEPOSITION OF THIN MULTILAYER MAGNETIC MATERIALSI. IntroductionElectrodeposition of compositionally modulated films will in all likelihood continue to be used to produce the read heads for stored magnetic data. However, the next generation of head materials will require both improved sensitivity and reduced film thickness. Certain multi layers consisting of thin alternating ferromagnetic and nonmagnetic layers exhibit giant magneto resistance and consequently are promising candidates for read head applications. We have successfully made multilayer films with giant magnetoresistance that have total thicknesses as low as 25 nm, approximately 120 times thinner than the thinnest similar films reported in the literature. This paper describes early results from our work on electrodeposition and characterization of Cu/Ni multilayers, a model system with enhanced magnetic and mechanical properties, including the GMR effect. The structure and composition of the multilayers were determined using TEM, AFM, and electrochemical methods, and their magnetoresistance was measured by the standard four-probe technique. A novel method developed in this work enabled the transport properties of the ultrathin films to be measured reliably without the need to dissolve the cathode or handle the films. To provide a context for these results, short accounts of other work on giant magnetoresistance and multilayer electrodeposition are also included."

Jan 1, 1997

By F. A. Steward

Copper is one of the trace minerals essential to life. It is added, usually in the form of copper sulfate, to virtually all formulated feedstuffs and to dietary supplements fed to animals on forage. Over the past five years, an improved inorganic copper source trademarked Micronutrients TBCC™, has been developed, tested and commercially introduced. TBCC is a crystalline form of basic copper chloride. Synthesis is accomplished in a continuous neutralization I crystallization process. In current commercial production, the primary sources of copper currently used as feedstocks are the etching solutions used to manufacture electronic printed wiring boards. These solutions have traditionally been managed as hazardous wastes, but their use to manufacture TBCC™ exempts them from regulation as wastes under the "Use/Reuse" provisions of RCRA. Research conducted over five years at multiple universities has shown that animals are healthier when fed this source of copper and that vitamin losses in feed are reduced by its use.

Jan 1, 2000

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By Shilai Yuan, Huimin Lu, Liyuan Zhao, Zhijiang Gao

"A purification process was developed to removal impurity element boron from metallurgical grade silicon by electromagnetic induction slag melting. Vacuum melting furnace was used to purify boron in both Al2O3-MgO-CaO-SiO2 slag system and Al2O3-CaO-SiO2 slag system. The relationship between different slag chemistry and the removal of boron in silicon were studied using Back Propagation (BP) Neural Network model. The best slag chemistry for the removal of boron was predicted by Genetic Algorithm (GA) contributed by the use of Matlab. The results show that the mass fraction of Boron in silicon is reduced from 11.7496×10-6 to 2.3259×10-6 after slag melting in 28.96%Al2O3-3.43%MgO-36.24%CaO-31.37%SiO2 slag system. The relative error obtained with GA-BP Neural Network model was below 0.35%.IntroductionSolar energy, due to its low green house gas emissions, has been paid great attention. Accordingly, the demand for solar grade silicon (SoG-Si) has been growing rapidly. The quest for developing a low-cost method of producing SoG-Si has been moving forward in the last decade. Refining of metallurgical-grade silicon (MG-Si) attracts research interest due to its low material and energy costs, and more environmentally friendly technology in comparison to the traditional Simens process. As such, impurity elements in MG-Si must be removed to low levels for the photovoltaics (PV) cell to operate at optimum efficiency. Most impurities in metallurgical-grade silicon (MG-Si), especially metal elements, can be separated by directional solidification and the zone refining plasma-arc method [1, 2]. The main focus in refining MG-Si to SoG-Si is on the impurities which are the most difficult to remove. Boron has relatively high segregation coefficients (KB=0.8, concentration of Boron in solid silicon divided by its concentration in liquid silicon) [3] and higher vapor tension (the saturated vapor pressure of boron and silicon are 6.78×10-7 Pa and 0.4 Pa, respectively). The vacuum melting and directional solidification methods hence have no effects on boron removal.Slag refining involves melting MG-Si in the presence of a flux to produce a slag phase that can take up the impurity elements. The mechanism of slag refining is considered to include two main steps: the oxidation of boron and the absorption of boron oxide by slag materials. The oxidation of boron, described by the oxygen potential (PO2), resulting from the equilibrium Si and SiO2. The absorption of boron oxide, described as the slag basicity, is interpreted as expected to facilitate their extraction to alkali and alkali-earth oxides in the slag phase. Thus, effective removal may be obtained for a certain slag composition. Researchers [4-5] examined the effect of boron removal in CaO-SiO2 based ternary systems and showed that the addition of excess CaO can decrease the activity of SiO2. Researchers [6-8] studied the boron behaviors in CaO-SiO2-Al2O3, CaO-SiO2-Na2O, Al2O3-BaO-SiO2, CaO-SiO2-Li2O and Al2O3-CaO-MgO-SiO2 slag systems by adding boron in the silicon to a degree. Li2O, Na2O, MgO and BaO are thought to be associated with B2O3."

Jan 1, 2014

By F. Ajersch, P: Tsantrizos, K: Shanker

"TiN films have been deposited on various substrates by a novel reactive plasma technology. In this process, a nitrogen source (NH3 or N2) and TiCl4 are reacted in the jet of a plasma torch, and are deposited onto a substrate forming TiN films at a high growth rate ( > 2µm/min). It was found that the process parameters strongly affect the microstructure, thickness, density, and growth rate of the TiN films. These parameters include source of nitrogen (NH3 or N2, N/Ti ratio, temperature of substrate, and spray distance. In general, it was found that thick and dense coatings were deposited when the N:Ti ratio was kept low, and the substrate temperature was high. Also, for the series of conditions investigated, NH3 was found to give much better results than N2•. The limitations and advantages of this technique are also discussed in this paper.IntroductionTiN is an extremely hard material and is used in many wear applications, particularly as a protective coating on cutting tools to extend their Iife(1.2). Owing to its excellent chemical stability, TiN is also frequently used as a diffusion barrier in the electronics industry for sub-micron Al/TiN/Si ohmic contact systems (3) or as a coating on high-temperature resistant alloys in gas turbine applications (4), based on its good resistance to oxidation. Other applications include decorative coatings in the jewelry industry, and specialized applications such as solar energy absorbers and transparent heat mirrors(5).TiN films can be deposited/formed using various techniques. The main techniques of deposition are CVD (Chemical Vapour Deposition) and PVD (Physical Vapour Deposition). Each of these techniques can have many variations in equipment characteristics, reactants as well as a range of process parameters (pressure and temperature). In the CVD process, TiN is generally deposited onto a heated substrate where a chemical reaction takes place. The reaction can be one of reduction(6) (e.g.: TiCI4 + 0.5N2 + 2H2 --> TiN + 4HCI), of thermal decomposition(7) (e.g. decomposition of titanium dialkylamide), or of displacement (e.g. TiCI4 + NH3 --> TiN + 3HCI + 0.5CI2)' The displacement and reduction reactions are the most common."

Jan 1, 1994

By Run-sheng xu, Hai-yang WANG, Di ZHAO, Teng-fei SONG, Jian-Liang Zhang

This paper was mainly focused on the different semi-cokes and charcoal which could be new fuels for blast furnace injection. Through the comparative study with bituminous coal and anthracite coal, the properties of semi-cokes and charcoal were presented in this research. 10 indexes of different fuels were obtained by different standard experiment, including proximate analysis, ultimate analysis, igniting point, explosivity, transportation characteristic, ash properties, grindability, calorific value, combustibility and reactivity with CO2. According to the data analysis, it provided a theoretical basis for rational utilization of various blast furnace fuels, and helped to broaden the scope of the blast furnace injection fuels. This research could contribute to energy conservation, emissions reduction, and sustainable development of iron and steel enterprises.

Jan 1, 2015

By Y. Z. Zhang

Cyanide has generated environmental concerns because of its toxicity, and it may not respond to the treatment of complex and refractory gold ores. Gold leaching by thiourea is one of the most promising substitutes of cyanide. However, the high reagent consumption has hindered thiourea from its commercial application in gold extraction. The process chemistry and mechanism of thiourea degradation has been discussed on the basis of chemical bonding theory, thermodynamics and electrochemistry in this paper. Progresses on the decreasing of thiourea consumption have been summarised. The potential application of thiourea in gold extraction has been evaluated.

Jan 1, 1996

By Zizheng Zhou

The separation of cobalt from other base metals can be achieved using diffusion dialysis in a two-compartment reactor separated by an anion exchange membrane. In this work, a Neosepta AFX membrane was used to study the separation of various metals in an acid-chloride solution. The separation of one metal from another was investigated on the basis of the various chloro-complex stabilities. The metals investigated included cobalt, nickel, copper(II), iron(III), aluminum, zinc and cadmium. The impact of several critical experimental conditions, including the initial metal and chloride concentration in the feed solution and their initial concentration in the receiving solution, on the separation factor and the metal transfer rate is reported in this work. Effective separation of different metal pairs was achieved under the experimental conditions.

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006

By Run-bo Wang, Zhe Wang, Fan-yi Meng, Jian-Liang Zhang

The influence of semicharcoal substitution for coke breeze on sintering performance was investigated by pot-grate sintering test. At a fixed fuel ratio, sinter productivity and strength decreased with the substitution increasing from 0 to 100% due to better combustibility. To enhance the utilization efficiency of 100% semicharcoal, sintering parameters (moisture and suction pressure) was adjusted. With the moisture increasing, sinter performance of 100% semicharcoal increased because of the suppression of semicharcoal incomplete combustion. As the moisture further increasing to 9.0%, sinter quality gave rise to a decrease trend. The results also showed that the increase of suction pressure was benefit for the increase of heat transfer rate, leading to the improvement of heat utilization energy. Measures to enhance magnetite oxidation during sintering are discussed based on current understanding of the fundamentals that control the sintering process.

Jan 1, 2015

By Y. W. Chung, W. I. Chia

"The interaction of water vapor with single crystal Ni3(Al,Ti) and polycrystalline Ni3Fe, with and without the presence of oxygen, has been studied with Auger electron spectroscopy, photoemission spectroscopy, thermal desorption and isotope exchange. Water dissociates to produce atomic hydrogen above 200 K on both Ni3(Al,Ti) and Ni3Fe surfaces. For Ni3(Al, Ti), the reaction is structure-sensitive. Pre-adsorbed or co-adsorbed oxygen on Ni3(Al,Ti) and Ni3Fe significantly suppresses hydrogen production due to water dissociation. This suppression process occurs more efficiently on Ni3Fe than Ni3(Al, Ti).IntroductionOrdered intermetallic compounds such as aluminides, silicides and titanides are very attractive for structural applications at high temperatures. This is because these intermetallics tend to form adherent oxides in oxidizing environments which protect the base materials from excessive oxidation and corrosion. In addition, they have low density, relatively high melting points and good high-temperature strength. However, the moisture in air severely embrittles many ordered intermetallics such as FeAl [1-3], Fe3A1 [4,5], C03Ti [6,7], (Co,Fe)) V [8], Ni3Si [9], Ni3(Si,Ti) [10], Ni3(AI,Mn) [Ill, and Ni3A1 [12-14], resulting in low 'ductility and brittle fracture at room temperature. Recent studies by Liu and coworkers (see review by George and Liu [15]) provide a qualitative description of the mechanism for this moisture-induced embrittlement. During elongation testing, cracks are formed, thus exposing fresh alloy surfaces. One or more active components of the alloy react with water vapor in the environment to produce atomic hydrogen which penetrates into crack tips and causes hydrogen embrittlement. This is similar to that proposed for moisture-induced embrittlement of aluminum alloys [16]."

Jan 1, 1996

By W. Petruk

The behaviour of galena, chalcopyrite and tetrahedrite during floration of a fine-grained base metal ore from New Brunswick was investigated by image analysis study of the mill concentrates and tailings. The minerals were analyzed to determine the grades and recoveries as related to free and unliberated mineral grains and their size distributions. The results show that only 37 wt % of the galena was liberated but 88 wt % of the free galena was recovered, indicating good mill performance for the lead. The lead recovery was 65 wt %, with the main loss due to unliberated galena. Most of the unliberated galena lost to mill tailings is so fine-grained that galena liberation and Pb recovery would not improve significantly by re-grinding. Chalcopyrite liberation was 56 wt % but only 75 wt % of the free chalcopyrite was recovered. Copper recovery was 45 wt %, with the chalco-pyrite loss in the mill tailings being both as large free grains, and as small and large unliberated grains. It was calculated that copper recoveries could be improved about 8 to 10 wt % by changing the concentrator operations and by regrinding. Concentrator operations hive already been modified and copper recoveries have improved about 5 wt %. About 29 wt % of the silver was lost to tailings mainly as both free and unliberated, large and very small, Silver-bearing tetrahedrite grains. It was calculated that about 25 wt % of the silver in the tailings might be recovered by improved milling conditions and by regrinding.

Jan 1, 1981

By Michael J. McGuire

Rostoker, Inc. has developed a process to smelt solid hazardous/non-hazardous inorganic wastes. Near seven hundred experiments were performed. Actual industrial wastes as well as reagent grade chemicals were used. By mixing a multiplicity of these wastes to proper formulations, then furnacing them, it was determined that saleable end products could be reclaimed; metal, fume and slag. The slag, due to its siliceous structure was tested to be leach resistant (40 CFR). This formed the essence of our patent, #5,180,421 "Method and Apparatus for Recovering Useful Products from Waste Streams". What is unique is that a HTMR (High Temperature Metal Recovery) process has been developed that can treat a multiplicity of wastes within the same furnace. The discussion will include a list of waste streams we have treated, details of proper waste formulation and experimental results.

Jan 1, 1994

By Gopalakrishna M. Rao

"Several industrial and government laboratories are of the opinion that solar--cell technology will grow into a billion-dollar industry by the year 2000, especially if oil prices rise again. Of the variety of materials that have been investigated as the major component of photovoltaic systems, silicon appears to have an outstanding advantage. The cost factor is the primary importance in photovoltaic development, since the technology to make silicon cells of acceptable efficiency and life time has existed since the early stage of the space program. Electrometallurgy is one of the low--cost processes for the production of silicon, since it allows direct, single-stage production from some abundant, inexpensive source materials such as silica and fluorosilicates. Among several systems, two are given particular attention, using inorganic baths with Si0 2 or K2SiF6 as the source of silicon respectively. They appear capable of development to commercial production. Conceptual designs of a commercial--scale cell for silicon production at temperatures above its melting point, and of a pilot' plant for plating silicon from an all-fluoride bath are presented. Energy ProspectsThe major changes in the world energy since the first energy crisis in 1970 have impacted on our community. When oil was $40 a barrel in the mid-1970s, we became obsessed with the energy conservation and a search for alternate energies. Even though the crude oil fell below $15 a barrel during the last several years, our energy security fears continue to haunt us. This time it is not the scarcity, but the abundance of foreign oil and the decline in the domestic production.The prospects of energy depends on the demand and supply of energy. These, in turn, depend on future energy prices, which are linked to economic factors, political events, and unforeseen circumstances. Although no one can predict the future with certainty, three energy consumption patterns used by the Ford Foundation are as shown in Fig. 1."

Jan 1, 1988

By Sheng-li Wu, Guo-liang Zhang, Bo Su

One of the major challenges for the Canadian Gen IV Super-Critical Water-cooled Reactor (SCWR) concept is the selection of fuel cladding materials. The Canadian SCWR concept will operate at a core outlet temperature of 625 oC and 25 MPa of pressure with peak cladding temperature reaching as high as 800 oC. Corrosion resistance is an important factor for material selection. Austenitic stainless steels that contain Cr contents greater than 18 wt.% are generally considered to provide adequate corrosion resistance. In this work, the pressure dependence of the corrosion of austenitic stainless steel 310 containing 24 wt% Cr is assessed at 625 C for exposures of 1000 hours to evaluate the suitability of superheated steam as a surrogate for supercritical water at 25 MPa. Transmission Electron Microscopy (TEM) revealed that 310 exposed to different pressure conditions at 625 oC. (i.e., 0.1, 8 and 29 MPa) had generally the same type of the oxide structure, i.e., a Cr-rich oxide with the spinel structure on outer surface adjacent to the water phase. The material exposed at 8 and 29 MPa had a double layer oxide structure, with the outer oxide layer having a much larger grain size, while the samples exposed at 0.1 MPa showed only a single spinel-phase oxide layer. Cr-depleted recrystallized austenite grains were found underneath the spinel phase oxide. The adjacent large-grained austenite substrate had M23C6 carbides in the grain interior. The implications of these results are discussed.

Jan 1, 2015

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.

By O. Barbosa F.

The thermochemistry of the systems SCN-H2O, Au-SCN-H2O and Ag-SCN-H2O is discussed. Potential-pH diagrams at 25°C are drawn for each system considering several sets of concentrations of the species involved. The information provided by the potential-pH diagrams is.complemented by distribution curves for each series of gold and silver complexes with thiocyanate. The analysis includes comparisons between the thiocyanate systems and the analogous cyanide systems, pointing out analogies and differences between the leaching of gold and silver with thiocyanate and with cyanide. The possibility of using soluble oxidizing agents such as ferric ions, hydrogen peroxide and Caro's acid is evaluated. The thermodynamic data used in the calculations and the chemical reactions represented in the Pourbaix diagrams are all reported in three Appendices. The overall results indicate the thermodynamic conditions for gold and silver leaching by thiocyanate.

Jan 1, 1989

By Baozhong Zhao

The direct smelting of copper concentrates to copper metal in a single furnace offers environmental and energy advantages over conventional two-stage copper smelting processes. However, the direct copper making results in unacceptably high level impurities (As, Sb and Bi) in the anode copper. Experimental studies have shown that it is possible to remove these impurities from molten copper by injection of sulfur-hexafluoride. This paper discusses the experimental findings on the influence of various factors on the rate of removal of impurities, such as the impurity inter-effects, initial oxygen content in the metal and injection rate of SF6.

Jan 1, 1995