Search Documents

By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Hongmin Zhu, Qiuyu Wang, Shuqiang Jiao, Guojing Hu

"The equilibrium between titanium ions and metal titanium was investigated in fluoride-chloride molten salt. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The equilibrium constant of the equilibrium between titanium ions and metal Ti was calculated in KCI-NaCl- 2.5wt %K2 Tif 6 at the temperature of 1073K.IntroductionTitanium, the ninth most abundant element in the earth's crust, is endowed with high strength, low density, excellent flexibility, strong spring back characteristics, high-temperature performance, corrosion resistance and biocompatibility. These characteristics make titanium eminently suitable to be used in aerospace, marine industries, and harsh chemical environments. Although it has many excellent properties, the application of titanium in industry was limited by its high-cost. Therefore, many methods have been investigated for producing high-purity titanium at low cost. Electrolysis, involving the extraction and preparation of pure metal from ore using an electrolytic process, is considered a promising method for titanium metallurgy. Many studies have focused on the electrochemical behaviour and electrodeposition of titanium in molten chloride, fluoride, and chloride-fluoride electrolytes (1-IOJ. The electroreduction mechanism of Ti3+ ions in molten alkali chlorides has previously been studied by several workers. Two reduction steps, Ti3+ -Ti2+ -Ti, have been observed in various molten alkali chlorides [IJ. One reduction step, Ti3+ -Ti, has been observed in alkali fluoride molten salts l21. The behaviour of Ti4+ in fluoride or chloride-fluoride molten salts has also been investigated in the literature; it was proposed that the reduction of Ti4+ ions in the molten salts proceeded in a two step process: Ti4+-Ti3+-Ti l3l or a three step process: Ti4+ -Ti3+ -Ti2+-Ti ri. 4l Indeed, the stability of the titanium oxidation states depends on the bath composition l5l. The valence state was Ti2+ in alkali chloride melts, which was a lower oxidation state and correspondingly, in alkali fluoride melts, the higher oxidation states ofTi4+ and Til+ were more stable.The aim of the present work is to explore the effect of F/Cl atomic ratio on the equilibrium between titanium ions and metal titanium in fluoride-chloride at the temperature of 1073K. The electrochemical properties of titanium ions in fluoride-chloride were studied on a molybdenum electrode by cyclic voltammetry (CV) and square wave voltammetry (SWV). The solubility product of the equilibrium between titanium ions and metal Ti was calculated."

Jan 1, 2012

By Yang Tian-zu

Sodium pyroantimonate which is widely used as the clarifier in the glass industry and as the synergist in anti-flaming industry respectively has a production history of about 30 years in China. At present there is the production capacity of about 20,000 tons per year in China and China is chief producer of sodium pyroantimonate. In this work the production processes adopted by the producers of China, the operation conditions and the product qualities of sodium pyroantimonate prepared by different preparation methods have been summarized, and on the basis of comparing the advantages and disadvantages for each process the most advanced method - the air-oxidation method was introduced in detail. The production processes of sodium pyroantimonate mainly include the method of oxidation by sodium nitrate, the oxidation method of hydrogen peroxide, the potash salt method, the chlorination method and the air-oxidation method etc. The method of oxidation by sodium nitrate in which the crude antimony oxide, sodium carbonate and sodium nitrate are separately used as the raw material, the flux agent and the oxidant, has the advantage of short and simple technological process, but low grade quality of sodium pyroantimonate and bringing about serious environmental pollution are the disadvantages and this method has been substituted by other methods. Sodium pyroantimonate can be directly prepared by the hydrogen peroxide oxidation method with the advantages of simple technological process, high grade quality of the product and little environmental pollution. High grade quality of sodium pyroantimonate can be also synthesized by the potash salt method, in which industrial antimony white, the hydrogen peroxide, potassium hydroxide and sodium hydroxide are applied as the starting material. The disadvantages of these two preparation methods are high production cost and high requirements on the raw materials. The chlorination method with the crude antimony oxide, hydrochloric acid and chlorine as the raw material has the advantages of low production cost and high grade quality of the product. However complex process, high requirement of anti-corrosion for the equipments and producing plenty of waste water limit its application. The air-oxidation method with stibnite/jamesonite concentrate, sodium sulfide, and sodium hydroxide as the raw material and atmosphere as the oxidant is a newly developed method and its advantages are low production cost and the complex raw material can be treated by this method and its disadvantage is that the quality of sodium pyroantimonate is lower than that prepared by the oxidation method of hydrogen peroxide and the potash salt method.

Jan 1, 2006

By Hong N. Vu, Jitka Jandova

"Gypsum and limestone methods were examined in this study to process zinnwaldite wastes originating from dressing Sn-W ores mined in the Czech Republic. These wastes containing 0.20-0.30% Li and 0.10-0.20% Rb were subjected to magnetic separation to obtain a zinnwaldite concentrate with 1.36% Li and 0.94% Rb. It was observed that processing of the zinnwaldite concentrate with gypsum resulted in almost 96% recovery of Li into aqueous liquors, whilst rubidium extraction was only 25%. At the same time, it is possible to extract almost 92% Li and Rb from the identical zinnwaldite concentrate if the concentrate is processed by limestone method. Lithium carbonate, a final product of both methods was recovered from the refined sulphate solution using K2CO3 as a precipitation agent and/or from unrefined hydroxide solution using gaseous CO2. In the continuation of this study, rubidium will be separated from carbonate solutions after Li2CO3 precipitation as RbAl(SO4)2, an intermediate for Rb2CO3 production. IntroductionLithium is used as an alloying constituent in lightweight alloys, as a heat transfer medium in nuclear reactors and as a component in primary and secondary batteries. With the development of a new generation of electric vehicles, the lithium demand will dramatically grow. Lithium chemicals find extensive application in many industrial branches such as metallurgical, glass, ceramic and pharmaceutical industries. Rubidium compounds are predominantly used in psychiatry and medicine, in magneto-optic modulators, solid-state lasers, phosphors and components of electrolytes for fuel cells. The four most important lithium minerals are amblygonite, spodumene, petalite, and lepidolite. Spodumene LiAlSi2O6 (6.0-7.5% Li2O) and petalite LiAlSi4O10 (3.5-4.5% Li2O) belong to aluminosilcate minerals. Lepidolite (Li.Al)3(Al.Si)4O10(F.OH)2 (3.30-7.74% Li2O), lithium mica, is the most important representative of the mica minerals, a subgroup of the aluminosilicates. It frequently contains 3–5% Rb2O and eventually caesium. Zinnwaldite, which has the general formula K(Li.Al.Fe)3(Al.Si)4O10(F.OH)2 (2-5% Li2O), is regarded as a variety of lepidolite with a high iron content. Commercial amblygonite is a complex phosphate (Li.Na)Al(F.OH)PO4 (up to 9.88% Li2O), however, its deposits have not been commercially exploited because of their small size. Natural brines with a high lithium chloride content are important in the industrial production of lithium [l]"

Jan 1, 2008

By David N. Hanlon

The effect of high-temperature plastic deformation of the austenitic phase (y) on the subsequent phase transformation to ferrite (a) has been experimentally investigated, and modelled using a physically-based model. The effect is of importance for steel sheet, in view of me significance of the phase transformation with respect to the eventual properties of the material. In this paper the kinetics of the y ? a phase transformation has been studied after different degrees of prior deformation. The degree of deformation is varied by applying different deformation temperatures and strain rates, and by allowing a varying extent of recovery and recrystallisation. Consequently, both dynamic and static recovery and recrystallisation have been involved. The dilatometric observations on the phase transformation have been modelled using an interface-mobility model, in which the effect of the dislocation structure is introduced as an additional driving-force term. The effect of the stored energy on the nucleation process, which appears to be affected more strongly than the growth of ferrite, is examined in terms of the classical nucleation theory.

Jan 1, 2001

By D. K. Panda

The behavior of single drops with gas evolution at the interface is of interest because this is one of the important reactions that occur in oxygen steelmaking vessels, where a large amount of iron-carbon drops are dispersed in an oxidizing slag. The carbon dissolved in these drops, reacts with the slag to form CO, which is evolved as a gaseous phase. A room- temperature model was used to study the nature of this type of reaction including the effect of various factors such as viscosity and the presence of surface active impurities. Experiments were done for reacting drops over a wide size range to observe various regimes of behavior. Large single drops were levitated in a counter current flow to produce a sufficiently long residence time to allow the study of the various stages in the reaction. The emphasis of this work was to obtain photographic evidence of a high quality to describe all possible modes of behavior, and so a lot of effort was given to developing and perfecting experimental techniques.

Jan 1, 1994

By Vaughan R. Voller

"Solidification systems from conduction controlled freezing of a pure material through to alloy phase change that include flow and segregation processes are described. The components in a general solidification model-variables, governing transport equations, and local scale relationship-are outlined. A central focus is the presentation of an explicit procedure for coupling between macroscopic and local scale variables.IntroductionSince the seminal work of Byres et al.[!] in the 1940's there has been a steady progress in modeling solidification systems with increasing levels of complexity. The object of this paper is to track the evolution of these solidification models and present a general modeling approach that applicable to a wide range of the solidification systems of current interest.Solidification SystemsIn a broad sense the underlying physics in a solidification process occur at two distinct length scales:1. The macroscopic scale of the process over which the governing transport equations of heat, mass and momentum hold.2. The local scale at the solid-liquid interface where the solidification phenomena are operative."

Jan 1, 1999

By Dian Adisty, Leiv Kolbeinsen, Eli Ringdalen

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types. The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Jan 1, 2014

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

By P. Halsall

Smelters of medium or low grade tin concentrates must recover a high proportion of tin from iron-bearing slags or concentrates; the volatility of tin sulphide makes possible the production of iron-free tin fume. Laboratory work defined conditions which would promote the sulphidisation of tin slags and concentrates melted with them, to result in tin recovery as fume, and a residue of less than 0.5% Sn content, which could be controlled to vary with the value of tin. Subsequently pilot-plant work on 6-tonne and 15-tonne scale led to a commercial plant of 45 tonne. capacity (1962), for melting and fuming primary and secondary low-grade tin materials by submerged combustion. Some factors contributing to the rate of Working expressed in terms of the 'half-life and the amount of work done, the 'half-life-tonne' are studied, leading to the design and operation (1972) of the 100-tonne water-jacketed unit, presently in use, treating a wide range of slags and low tin-content ores and residues.

Jan 1, 1983

By C. P. Broadbent

The process metallurgy of many nickel laterite smelting operations is controlled largely by the physical chemistry of the slag system. Consequently, accurate phase diagram information and physicochemical property data are essential to interpret and predict the behaviour and optimisation of the overall process. The system (SiO2 - MgO - FeO) first described by Bowen et al. between 1914 and 1935 and the system (SiO2 - MgO - FeO - Fe2O3) determined by Muan and Osborne in 1956 are of particular relevance to the study of nickel laterite smelting slags as these systems form a reasonable approximation of many industrial slags. This paper will review the literature for these (and other relevant) phase systems. In addition data available from the ternary and (quasi)ternary phase diagrams will be compared with data obtained from industrial slags. The physico-chemical properties under consideration will include; melting and crystallisation behaviour (solidus and liquidus temperatures), viscosity - temperature relationships, heat flux considerations, electrical conductivity, surface and interfacial tension.

Jan 1, 1993

By S. P. Jupp

A 2-D coupled thermo-mechanical model was developed to simulate hot tandem rolling of AA5056 aluminum alloy using the commercial finite element software package, ABAQUS The model was used to predict the temperature, strain rate and strain distribution in the strip at any position in the roll bite and was verified through comparisons with literature results in terms of both temperature and strain predictions at the roll bite exit. A sensitivity analysis indicated that model predictions of temperature and strain at the roll bite exit were sensitive to the friction coefficient and moderately sensitive to the heat transfer coefficient for the conditions studied. Microstructure equations taken from the literature were used to make predictions at various positions in the strip. The temperature, strain rate and strain vary dramatically through the thickness of the strip in the roll bite. The sensitivity of the microstructure predictions to these parameters was assessed and it was found that using average values of temperature and strain rate in the roll bite versus exit values significantly influenced the resulting microstructure predictions.

Jan 1, 2001

By Dajian Wang

To obtain the thermodynamic properties of a multicomponent liquid alloy system over the whole range of concentration at an arbitrary temperature, the free volume cell theory has been applied to derive the formula of activity coefficients of liquid solutions based on the infinitely dilute solutions at some temperature. The linear logarithmic relationship between activity coefficients of binary dilute solutions and reciprocal of absolute temperature have been verified, and are in good agreement with the experimental values from the literature. The Monte-Carlo algorithm was used to calculate the nonlinear end value equations of binary systems, then the free volume parameters obtained were correlated with the activity coefficients of liquid binary, ternary, and quaternary systems at an arbitrary temperature. Three dimensional a-X-T diagrams of some binary systems representing the temperature and concentration dependence of activities were plotted. The calculated results regarding non-ferrous alloy systems have been statistically examined with the experimental values from the literature. Hence, this simple approach could be useful for analyzing thermodynamic properties of liquid alloy systems.

Jan 1, 2000

By R. C. Hubli

A panial equilibrium model? to simulate the dissolution of millerite (NiS) in aqueous solutions containing copper(II) chloride as the oxidizing species has been developed. The predominant copper(I) and copper(II) species are CuQ3 and CUO2 respectively. The model computes the initial concentrations of the species present in the aqueous phase under the specified input conditions, prior to the simulation of dissolution. During the dissolution of millerite, nickel enters the leach liquor as NiH and it has been found that the H+ decreases as a function of NiS dissolution. The simulation has been accomplished under conditions prevailing during actual dissolution, with only one mineral undergoing dissolution. The model can be applied for the simulation of co-dissolution of two or more sulfides. Under the given conditions, the precipitation of Cu1(OH»)O is negligible but loss of Cu(1l) could be significant if the initial H+ is lower than 0.03 M. The results of the simulation compare favorably with experimental observations.

Jan 1, 1996

By C. Dresen

This paper discussed the reaction kinetics of the reduction of industrial phosphate pellets for P4 production. In the reduction process of various phosphate ores, the following parameters were investigated: Diffusion of the phosphorus oxide and other gaseous products from the reaction mixture after having been reduced on the reductant (coke) surface. Influence of silica on reaction kinetics. Temperature influence. Influence of mineralogy and morphology (different ores). Particle size influence of silica and coke. Experiments were carried out in a vertical tube furnace with 2 ores, 2 types of silica and one type of coke. Selected experimental conditions simulated furnace conditions. The following conclusions could be made: Reaction rate increases with the addition of SiO2 into the pellet. The reaction rate increases above 1350°C (melting temperature of the slag). Mixing different ore types in the pellets leads to differences in reduction kinetics. Particle size of the coke particles influence reduction kinetics. The amount of slag formation is influenced by silica addition, coke size and temperature.

Jan 1, 2002

By P. Peczak

A Monte Carlo simulation technique has been used to study dynamic recrystallization in polycrystals. A continuum microstructure of the polycrystal is modeled employing a discrete lattice. The response of the material to hot deformation is simulated by adding stored energy and recrystallization nuclei continuously with time. The experimentally observed nonuniform character of deformation substructures is modeled by employing a phenomenological expression for inhomogeneous distribution of the stored energy. All simulations were performed on HP-Apollo 9000 Series 700 workstations. A program written in FORTRAN with use of PHIGS graphics library calls was used to interactively monitor the current state of the matrix and all relevant parameters: deformation stress, average grain size and effective nucleation rate. Visual analysis of the simulated microstructure allows a better understanding of the data developed by averaging over a number of very long Monte Carlo runs. Since the essential features of dynamic recrystallization are accurately reproduced by the model, it is used to discuss the role of the controlling mechanisms of the dynamic recrystallization in real polycrystal.

Jan 1, 1993

By H. Fukuyama

The wetting behavior of single crystalline MgO by fayalite-type slag melts has been studied by the sessile drop technique incorporated with high temperature X-ray radiography. The experiments were performed under oxygen partial pressures of 10-6 and 10-4 Pa at 1473 K. Mass ratios of iron to silica, Fe/Si~, in the slag employed were 1.4 and 2.0. To investigate the interfacial reaction, experiments using high density MgO crucibles were also conducted. The reactions at the interfaces were examined by Electron Probe Microanalysis. The contact angles between the slag melts and the MgO substrates were found to be relatively low, ranging from 30 to 10 degrees. The surface tension of the slag was 0.4 N/m for a slag of Fe/Si02 = 2.0. Two phases, magnesiowiistite and olivine, were observed at the interface. Interdiffusivity in magnesiowiistite solid solution was determined as a function of iron oxide content. Phase relations between magnesiowilstite and olivine, and the growth rates of both phases, are also discussed

Jan 1, 1996

By A. E. Isaacson

The U.S. Bureau of Mines is studying the effect of supercritical water, at 400' C and 3,500 psi, and subcritical water, at lower temperatures and pressures, on mixtures of minerals and metals to determine the possible applications of water at high temperature and pressure for processing these materials. This research was conducted using a flow-through bench-scale system. Copper-bearing minerals studied were chalcocite, chalcopyrite, covellite, and cuprite. In general, mixtures of copper minerals and pyrite reacted to form bornite. Intermediate phases formed were chalcopyrite and digenite. Similar reactions occurred between pyrite and metallic copper. A mixture of chalcopyrite and pyrite was inert in supercritical water'. The reaction between cuprite and metallic zinc yielded metallic copper. The cuprite was reduced by hydrogen generated by the reaction between metallic zinc and water. None of the reactions occurred exclusively in supercritical water, but also occurred in water at high temperature and pressure below the critical point. 'Experimental results did show that a dual-reaction process, consisting of solid-state diffusion and fluid transport, was occurring.

Jan 1, 1989

By Xiao Y. Yan

A fused salt electrochemical process was investigated for the synthesis of non-oxide ceramic powders directly from metal oxides, boric oxide, and carbon powders by electro-deoxidation. Sintered pellets of the mixed powders were designed to act as a composite cathode in the electrolytic cell. Electrolysis was carried out in molten CaCl2-NaCl eutectic at 3.1 V and at 600-900 ºC under argon. The favoured cathodic reaction was the removal of the oxygen from the oxides to produce metal atoms that reacted with either the reduced boron atoms, forming a metal boride, or the carbon initially present in the sintered pellets to produce a metal carbide. The technical viability of the process was demonstrated by the electro-deoxidation of sintered pellets of TiO2/B2O3 and TiO2/C to produce TiB2 and TiC, respectively. Compared to existing carbothermic reduction process, this new electrochemical process may be less energy intensive and may lead to lower production costs. I

Jan 1, 2008

By Zhijing Zhang

Long-term thermal stability of ionic liquids is essential for reliable performance of ionic liquids in any engineering applications. TGA studies were carried out on a series of ionic liquids with different cations and anions such as 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), 1-hexyl-3-methylimidazolium chloride ([C6mim]Cl), 1-hexyl-3¬methylimidazolium tetrafluoborate ([C6mim]BF4), 1-hexyl-3-methylimidazolium hexafluorophosphate ([C6mim]PF6), 1-octyl-3-methylimidazolium hexafluorophosphate ([Csmim]PF6), and 1-butyl-3-methylimidazolium bis(trifluromethanesulflonyl)imide ([C4mim][Tf2N]). The short-term thermal stability of ionic liquids was evaluated by measuring the onset temperature of decomposition of ionic liquids, and the long-term thermal stability of ionic liquids was also evaluated by weight loss of ionic liquids over a long period of time at various temperatures. The experimental results showed that the long-term thermal stability of ionic liquids decreased with increasing temperature and was significantly lower than the onset temperature of decomposition of ionic liquids.

Jan 1, 2002