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By Milton Blander

A review of concepts and theories for predicting thermodynamic solution properties of multi- component high temperature liquid solutions is reviewed. During the last 50 years the ability to predict :such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.

Jan 1, 1996

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Mototsugu Matsuno

A new process has been developed to treat fly ash generated from municipal incinerators, which contains not only toxic metals such as lead and cadmium, but also dioxins. The process includes the following steps; fly ash is formed into green pellets with some additives and the pellets are then roasted to eliminate or stabilize the toxic metals and to decompose dioxins. A pilot plant with a capacity of approximately 100 kg/hr was used to test the process, The tests verified that heavy metals were either volatilized or stabilized and dioxins were decomposed by high-temperature roasting. The pelletized ash was found to be non-toxic, so that it can be recycled as artificial lightweight aggregate. It was also found that volatilized metals collected as secondary ash can be recycled as smelting resources.

Jan 1, 2003

By Kumar Ganesan

Elevated mercury levels are expected in aged gold mine tailings due to residual mercury from the amalgamation process, The fate of mercury in tailings is not well understood, Its potential health risk depends mainly on the degree to which mercury is mobile in soil. Mercury is re-moved from soil by evaporation, plant uptake, microbial activities, leaching, and other physico-chemical processes. In this research the amount of mercury lost by evaporation was evaluated. Several aged gold mine tailings in Montana were sampled for total mercury and its flux into the atmosphere. Mercury levels in tailings were higher than the general background levels in most sites. The mercury levels in some cases were as high as 10,000 ug/g. The field measurements using flux chambers indicated a wide range of mercury flux from aged gold mine tailings. The mercury flux ranged from 0-11,000 ng/m2/hr. The mercury loss by evaporation helps rid the soil of mercury but the mercury vapor then will participate in the atmospheric mercury cycle, The low solubility of elemental mercury in water helps to minimize mercury leaching from tailings, however, conversion of elemental mercury to more soluble forms by bio-geo-chemical processes can enhance its mobility posing increased health risk.

Jan 1, 2003

By Bradley C. Bockrath

Some thirty coals were evaluated for liquefaction activity under a mixture of CO and H2 at 425° C. The viscosity of the liquid products was taken as an indicator of the degree of liquefaction. It was found that the direct liquefaction of a particular coal may be beneficially influenced by the presence of pyrite. Active pyrites are often found in the native mineral matter of the coal itself. For example, subbituminous and bituminous coals and lignites of relatively high pyrite content were found to liquefy more readily than similar coals or lignites which were poor in pyrite. The reactivity of inactive coals could be improved by using blends with active, pyrite-rich coals. In addition, pyrite was effective when added separately as pyrite concentrates obtained from coal beneficiation operations. Various other iron- and sulfur-bearing additives were also effective when used in combination as added slurry-phase catalysts, including iron oxides and mineral residues derived from liquefaction of active coals. Under liquefaction conditions, pyrrhotite ( Fe I- x5) is formed from pyrite or from the iron oxides and many sulfur containing species. Pyrrhotite was shown to be a hydrogenation/dehydrogenation catalyst for tetralin but is not active for initiating a variety of free radical reactions that do occur when pyrite is heated with tetralin. The role of pyrite in coal liquefaction is complex and still not well understood.

Jan 1, 1981

By Graham J. C. Carpenter, Marc Charest, Jason Lo

"The method of producing magnesium-based composites with silicon carbide (SiC) particulates embedded in the matrix of magnesium AZ9I D alloy by the squeeze-casting technique are described. This method involves the fabrication of a SiC particulate preform and the subsequent squeezing of molten magnesium into the preform. In this study, alumina, aluminum phosphate and a proprietary binder were used for the fabrication of SiC particulate preforms. The procedures employed in the fabrication of SiC! AZ9ID composites are presented, together with the results of characterization of the composites using optical and transmission electron microscopy. Special attention is given to the reaction products in the bulk alloy and at the interfaces between SiC particles and the AZ9ID matrix alloy.1. IntroductionInterfacial, microstructural and metallurgical characteristics play an important role in determining the mechanical properties of a composite. In theory, reinforcing magnesium with SiC particulates should provide an improvement in strength and modulus of the composite over the unreinforced counterpart. However, many factors resulting from the fabrication process can cause degradation rather than improvements to the mechanical properties. In particular, the interfacial characteristics are known to critically influence the properties of composites [1]. Before evaluating the mechanical properties of a composite, it is always useful to examine the microstructure, which is closely related to the mechanical behavior. This helps to reduce the labor-intensive steps of sample preparation for mechanical property evaluation, which can be particularly difficult as a result of the high hardness of composite materials, as well as providing a wealth of information on the microstructural and interfacial characteristics, particularly the reaction products caused by processing. This information is also pertinent in understanding the factors governing the mechanical properties of the composites.There are many factors which determine the nature of the interfacial characteristics of a SiClMg composites. Qualitative estimations of the interfacial bonding have been performed based on thermodynamics, electronic and electrostatic concepts. In addition, the kinetic conditions during the fabrication play an important role. From an interfacial energy standpoint, the driving force for the formation of a metal/ceramic interface is the decrease in free energy that occurs when intimate contact is established between metal and ceramic surfaces. The simple representation of the energy change per unit area of interface formed (~G) is given by Dupre equation [2]:"

Jan 1, 1996

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide's smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates 'CSO or CSC' under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements' chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By Xiang (Frank) Chen, Mikhail A. Sokolov, Randy K. Nanstad

"Nickel-base Alloy 617 is being considered as a structural material for application in the secondary heat exchanger of the New Generation Nuclear Plant, a very high temperature gascooled reactor. Thermal aging of Alloy 617 plate and welds is being performed with tensile, Charpy impact, and fracture toughness tests conducted at temperatures to 950°C. Results of testing for thermal aging to 5,300 h have been obtained and are presented; varying effects of thermal aging temperature and time on fracture toughness are observed. The 9Cr-1MoV (Grade 91) ferritic steel is a candidate for structural applications in the sodium fast reactor. Fracture toughness testing of unaged Grade 91 steel has been performed to evaluate specimen size effects in preparation for future testing of the material in the thermally aged condition. Results for material in the mill-annealed and heat treated conditions are presented and show that this heat of Grade 91 steel does not indicate a small specimen bias on the fracture toughness Master Curve reference temperature.IntroductionThe behavior of advanced engineering materials will be a critical factor in the performance of Generation IV reactors. In the case of materials utilized for reactor internals and pressure vessels, the effects of irradiation and long time thermal aging are major issues. The environmental conditions for some of the Gen IV reactors are generally beyond present day reactor technology, requiring new experimental data as well as analytical predictions of expected behavior of candidate materials at conditions for which there are only sparse or no experimental data. The radiation environments and several key materials issues for some Gen IV systems are summarized in Section 5 of [l] as a starting point for modeling and microstructural analysis of Generation IV materials. More detailed descriptions of materials research and development needs and recommended activities for the SCWR, VHTR, and GFR are provided in references [2, 3, 4], respectively. Mansur, et. al. provide an interesting comparison of materials needs for Generation IV reactors to corresponding needs for fusion reactors and spallation neutron sources in [5]. The two primary candidate reactor systems currently undergoing significant research and development by the U.S. Department of Energy (DOE) are the New Generation Nuclear Plant"

Jan 1, 2012

By H. Deveci

Bioleaching/biooxidation is essentially a dissolution process with the involvement of acidophilic bacteria acting as the "catalyst" to accelerate the dissolution of metals from sulfide minerals. The contribution of bacteria to the metal dissolution is closely controlled by the growth of bacteria, which is itself affected by the physico-chemical conditions within the bioleaching environment. There are a number of operating parameters controlling bioleaching processes, which are required to be maintained within a certain range in the leaching environment whereby the activity of bacteria with the resultant oxidation of sulfide minerals can be optimized. In this regard temperature, acidity, oxidizing conditions, availability of nutrients, oxygen and carbon dioxide, surface area and presence of toxic ions are of prime importance for control and optimization of bioleaching of sulfide ores/concentrates. Bioleaching processes are temperature and pH dependent with optimum metal dissolution occurring in a particular range where the bacterial strain is most active e.g. mesophiles at 35-40°C and pH 1.6-2.0. Provision of nutrient salts is required to maintain the optimnm growth and hence metal dissolution with the quantity of nutrients apparently being dependent on the availability of substrate i.e. head grade/pulp density of an ore/concentrate. Oxygen transfer is one of the most critical factors since the oxygen levels below 1-2 mgll may adversely affect the oxidizing activity of bacteria. Bioleaching rate tends to improve with increasing the surface area at low pulp densities but, in practice. the pulp density is limited to -20010 w/v. Increasing concentrations of ions such as cr may also adversely affect the oxidative activity of bacteria. Keywords: Bioleaching, Biooxidation, Acidophilic bacteria

Jan 1, 2003

By Kota Nakashima

Residues from titanium smelting tend to contain scandium. The scandiumis discarded because no suitable process exists for its recovery from the residue. Valuable-metal recovery from discharged residue is critical for environmental conservation and to achieve a sustainable society. Since 2015, JXNippon Mining&Metals has been developing a process for scandium recovery from the residue of a titaniumsmelting process. The process consists of the following steps: scandium concentrating by classification or neutralization, selective scandium leaching, impurity removal by neutralization, solvent extraction of scandium by using D2EHPA, purification, and roasting. We optimized the above steps to achieve an effective process to obtain scandium oxide (Sc2O3). In this paper, we introduce results from the bench-scale test of the scandium recovery flowsheet developed by JX Nippon Mining & Metals.

By Eddie C. Chou

Phelps Dodge, Inc. (PD) is currently developing a lateritic nicke/Vcobalt deposit in Madagascar. Hazen Research, Inc. provides technical assistance to PD to investigate recovery processes for nickel and cobalt. Various process options were evaluated in laboratory experiments and pilot plant operations. The process selected for the feasibility study consists of feed preparation, high-pressure acid leach, countercurrent decantation wash, sulfide precipitation, sulfide dissolution, solvent extraction, ion exchange, and electrowinning. Among these unit processes, high-pressure acid leach, sulfide precipitation, and sulfide dissolution are applications of pressure technologies. Process development work and design criteria for commercial operations of these unit processes are presented in this paper. Concerns related to scaling in the high-pressure acid leach and the sulfide precipitation processes are discussed. Corrosion of various metal coupons under these environments was examined.

Jan 1, 2000

By R. Elliott, H. Bayati

"Effect of time and temperature on microstructure and mechanical properties of an austempered ductile iron, ADI, of composition 3.6%C, 2.6%Si, 0.4%Cu, 0.2%Mn are reported. Xray analysis and. microstructural observations indicate that lowering the working temperature, aging temperature, increases the lifetime of ADI significantly. Results show· that lowering the aging temperature increases the strength and reduces the ductility of ADI. DSC traces for ADI austempered at 340°C are presented. Comparison of the DSC analysis and kinetic measurements demonstrates that the DSC traces can be· used to predict the life time of ADI successfully.IntroductionAustempered ductile iron, ADI, is one of the most significant developments in cast iron technology over the past two decades. Outstanding properties of high yield, ultimate strength, ductility, fatigue and wear· resistance make ADI suitable for a range of applications including gears, connecting rods, crankshafts and agriculture machine components. The austempering reaction in cast iron occurs in two stages, Fig. I, in contrast to the single stage reaction in steel. In stage I the relatively low carbon austenite produced during austenitising transforms into ferritic plates and high carbon austenite, a metastable structure called·ausferrite. The high carbon ailstenite and supersaturated ferrite produced in stage I decompose into ferrite and carbide in stage II: to form a structure similar to the bainitic structure in steel. This behaviour exposes a well-defined processing window, t1 - t2, over which the maximum amount of ausferrite is produced, Figure 1. Whereas the bainitic structure determines the properties of austempered steel, ADI properties are mainly affected by volume fraction of retained austenite (VRA), austenite carbon content (ACC), unreacted or martensite volume fraction (UA V), compositiori and amount of carbides, and morphology of ferritic plates[l,2]. Due to the detrimental .effect of martensite and carbides on properties of ADI, an ideal structure of ADI consists only of ausferrite [l,2]. Thus, it is common to determine the processing window for each austempering treatment in order to identify the optimized austempering time. Decomposition of austenite (stage II) signals the end of the life time for an ADI component, therefore, the aging behaviour of ADI at different working conditions can be studied by determining the t2."

Jan 1, 2000

By John J. J. Chen, Barry J. Welch

"As in many industrial processes, the detailed mechanisms involved must first be understood before being able to redesign, or to carry out improvements or optimisation of the process and equipment performance. In a great majority of metallurgical processes, visual observation and actual measurement of process variables are either very difficult or near impossible. Often, the cost and effort involved are prohibitive. Consequently, physical modelling is often used to provide some understanding of the process and for the validation of computer numerical models. In this paper, we summarise some of the work carried out at The University of Auckland on the modelling of the Hall-Héroult electrolytic cell, the in-line melt treatment process, and the steel casting tundish. IntroductionIn any industrial process, it is essential to understand the underlying mechanisms before any optimization or process improvement can be carried out. In many metallurgical operations, the processes are conducted at elevated temperature and under rather hostile environments. Consequently, it is often difficult, and sometimes impossible, to observe the actual processes occurring, or conduct measurements which are pertinent. In some situations, it is possible to formulate mathematical equations purported to describe the process, and obtain the solutions numerically. However, in this latter case, the validity of the simplifying assumptions made are often uncertain. Physical modelling may provide the necessary information for the validation of such numerical models. Furthermore, through an application of the principle of similitude, it is possible to apply data obtained from physical modelling to actual metallurgical processes. This paper will summarise some the work carried out at The University of Auckland on the physical modelling of gas-induced flow in the Hall-Héroult electrolytic cell, an in-line melt treatment unit, and the flow in a steel casting tundish.Gas-Induced Flows in a Hall-Héroult CellIn an aluminium cell, the effects due to electro-magnetic forces have been addressed and various design modifications such as magnetic shielding and the positioning of risers have been carried out to control or lninimise the effects of magnetic fields'. Consequently, the effects of gas-induced flows are now becoming significant providing the impetus for the study of the gas behaviour in the bath. Furthermore, the shape and size, and the rate of evacuation of the anodically generated gases affect the cell voltage affecting the energy efficiency; at the same time, the back-reaction between the anode gas and the metal produced is the predominant cause of the loss of current efficiency. Figure 1 shows a cross-section of a conventional cell in which the gas evolution occurs directly under the anodes, and the gas induced flow is confined mainly to the region occupied by the bath"

Jan 1, 1994

By Shu Yamaguchi

The behavior of halide impurities in pyrometallurgical processes such as Wealtz kiln and MF process has been discussed based on the thermochemical data and the reported data of PbO activity in PbCl2-PbO melts. The role of PbCl(g) has been estimated to be significant in the chloridization evaporation reaction. From reported data on the PbO activity in PbC12-PbO melts, activity of PbCl2 has been calculated by the numerical integration of Gibbs-Duhem equation, and the stability domains and the composition of the liquid phase as well as the vapor pressure of PbCl2 have been estimated as functions of log P2HCI/PH2O and temperature. From the discussion of the path during cooling process on the log P2 HCI . PH2O vs. temperature diagram, the authors proposed a possible dechioridization process that utilize water vapor as a dechloridizer for the direct precipitation of PbO from gas phase.

Jan 1, 2003

By Jose F. Hevia

This study is part of a broader project on the hydrothermal conversion of copper concentrates to metallic copper by solid state reactions in which the copper remains localized in the solid phases. The kinetics of the solid/solid hydrothermal hydrogen reduction of tenorite (CuO) and cuprite (Cu,O) to metallic copper are presented. After an induction period, the process is governed initially by a nucleation step followed by rapid solid state reduction. Nucleation promoter agents decrease the induction period and control the particle morphology. Separate nucleation and reduction rate processes have been identified. Following nucleation, reduction follows a shrinking core process.

Jan 1, 1994

By Masao Suzuki

Over 5 million cars are scrapped yearly in Japan. After dismantling. scrapped automobiles, they are put into a shredder for differential recovery of ferrous and nonferrous metals. The residue, which is called shredder dust, runs over 1.2 million tons per year. This paper reports a entire sequence of scrapping. cars. in Japan with the following sections: (1) production and scrapped car management, (2) material composition, (3) dismantling, (4) shredder plant, (5) differential recovery of metals including specific gravity separation and newly developed color separation.

Jan 1, 1995

By Filippos Patsiogiannis

Laboratory size (4.5 kg) low carbon steel melts were deoxidized using Al and FeAl (33% Al), with and without synthetic fluxes, in alumina and zirconia crucibles. The dissolved oxygen, total oxygen, soluble aluminum, insoluble aluminum, silicon and carbon contents in the melt were determined as a function of refining time and temperature. It was observed that the reaction between aluminum and oxygen in solution closely follows thermodynamic equilibrium. Silica present in the alumina crucibles was found to be a source of oxygen for the melt, while this was not the case for zirconia crucibles. Reoxidation of the melt occurred through oxygen pick-up from the atmosphere. The extent of this reoxidation was found to be a function of oxygen content of the bath and the slag cover on the surface of the melt. The effectiveness of calcium-aluminate based fluxes in protecting the melt from the reoxidation and in increasing the rate of removal of inclusions was evaluated.

Jan 1, 1992

By Patrick R. Taylor

Ilmenite concentrate and methane are fed to a non-transferred arc thermal plasma reactor to produce a powder that is primarily TiC and Fe. This material has promising characteristics for powder metallurgy applications. Free energy minimization plots were used to predict the feasibility of the reaction. An estimate of the optimum molar ratio between the ilmenite concentrate and methane was made based on the mineral composition. Argon-helium mixtures were used as plasma gases. The effects of power input level, carrier gas flow rate, powder feeding rate, and methane-ilmenite molar ratio were studied and the behavior of the system characterized. Two different powder injection angles were tried. A mathematical model to describe the temperature profiles in the reactor was formulated and solved. The product has been characterized by x-ray diffraction and atomic absorption. A conversion of 97 % of Ti to TiC was achieved. It was found that minor amounts of titanium oxides, iron carbide and free carbon are also present. TEM and SEM were used to study the morphology.

Jan 1, 1996

By Leiv Kolbeinsen, Stian Seim, In-ho Jung

"The current work presents new experimental data in the iron-unsaturated region of the FeTiO3-Ti2O3-TiO2 slag system. The samples are prepared by melting pure reactants in a high frequency induction furnace that employs a cold crucible. A similar experimental set-up has been described in literature and proven suitable to investigate high titania slags. The FeO content of the samples range from 3.7 to 21.8 wt% and the Ti2O3 content range from 3.6 to 30.1 wt%. The liquidus temperatures of the samples are measured in-situ by a spectropyrometer and range from 1450 to 1645 °C.In addition, an improved thermodynamic database for the FeO-Ti2O3-TiO2 system has been developed. Ternary parameters have been included and optimized to fit previously published experimental data. This optimization minimizes the discrepancy between experimental data and thermodynamic calculations as previously discussed in literature. New liquidus projection plots are proposed for the FeO-Ti2O3-TiO2 and the FeTiO3-Ti2O3-TiO2 systems.IntroductionIlmenite (FeTiOs) smelting is a relatively small industry world-wide. However, a reasonable focus on the process has been applied in Norway due to the location of one such smelter in Tyssedal, which is located in the western part of Norway. The process is essentially carbothermal reduction, where most of the iron in the ilmenite is reduced to its metallic state, and the titanium oxide is concentrated in the slag product. The metallic iron is sold as a high purity pig iron and finds applications in cast products. The slag concentrate is further processed for the production of TiOvpigment and/or titanium metal. This further processing can be performed through different routes according to the purity of the slag concentrate."

Jan 1, 2012

By Thomas P. Battle

Titanium is the ninth most common element in the Earth's crust, yet only in this century has titanium come into use as an engineering material, particularly in aircraft structures, as the metal, and in pigments, as the dioxide. In this presentation, the metallurgical aspects of processing titanium-containing raw materials will be reviewed. Particular emphasis will be given to the ores and beneficiation techniques which lead to the production of titanium dioxide pigment, which accounts for over 90% of world titanium production.

Jan 1, 1993