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By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By A. L. Paverd

The petrology of a number of pyrometasomatic mineral deposits in north Queensland, Australia, were studied to evaluate the use of mineralogy and major element chemistry in the exploration for copper, lead and zinc-bearing skarns. Results indicate a direct correlation between the character of the mineralization and the composition and nature of the host rock. The study of garnet compositions proved the most useful. Economic mineralization was limited to limestone-derived skarns containing garnet of And60-90, whereas skarns containing garnet of less than contained less than 1And55 contained less than 1% total sulfide. Skarns containing garnet of And60-8S host the best mineralization; above And8S' copper, lead and zinc sulfides decrease and magnetite and pyrrhotite become the dominant ore minerals. Similar correlations were found for pyroxene, amphibole and 'the bulk composition of the skarns.

Jan 1, 1981

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015

By T. Feldmann

Despite the ubiquity of applications for germanium, there is a lack of practically useful solubility data in acidic solutions. Previous studies were done at ambient temperature and only for commonly used acids (H2SO4, HCl). Hence, an investigation of the solubility of GeO2 in different acids was undertaken. Several inorganic and organic acids were studied in the concentration range of 1–11 mol/L and at 23, 40, and 60 °C. In the case of H2SO4 and HCl previous data was confirmed. Lower acidity resulted in a higher solubility for Ge at all tested temperatures. Tests done at 40 and 60 °C and low to moderate acidity levels, gave slightly increased solubility values at higher temperatures compared to 23 °C. This wasn’t the case at higher acidity levels, i.e., the solubility curves at different temperatures converge at high acidity. Lastly, a relationship of water activity and GeO2 solubility in different acid media was established.

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By Yuanbo Zhang, Zhixiong You, Guanghui Li, Peidan Wen, Tao Jiang

Sn-bearing iron ore containing small amount of Zn, Pb and As is one of the typical complex polymetallic ores in China. This kind of ore is not extensively utilized due to the complicated relationships between iron and other associated nonferrous metal minerals. Excessive contents of these elements would adversely affect the metallurgical operation as well as the quality of steel products. In this study, reduction behavior of Sn was detailedly investigated using H2 or mixed H2/CO as reductant. The results revealed Sn volatilization was improved in the presence of H2 than individual CO/CO2 atmosphere. Simultaneous volatilization of these elements was realized by roasting under weak H2/CO reducing potential, and metallization reduction was advantageous for further Zn volitilization. A metallic pellet (DRI) with Fe metallization greater than 90%, residual Sn, Zn, Pb and As content of 0.054%, 0.012%, 0.0045% and 0.09% was prepared via a simulated reducing gas of coal gasification.

Jan 1, 2015

Heap leaching with thiosulfate is only used in one location for the treatment of a refractory preg-robbing gold ore initially pre-treated with bio-oxidation. The chemistry of thiosulfate leaching is complex. Further work is required to develop a better control of the system. A mild refractory gold ore containing pyrite and chalcopyrite was used in this study to investigate the use of thiosulfate as an alternative heap leaching technology. Preliminary bottle rolls tests indicated that similar gold extraction was obtained with cyanide and thiosulfate. In the column leach test, effects of thiosulfate, copper and ammonia concentrations, and their ratio on both gold extraction and reagent consumption, were assessed. The range of reagent concentration were: 0.1 - 1.0M (NH4)2S2O3, 0.03 - 0.10M CuSO4*5H2O, 1.0 - 6.0M NH4OH. The solid-liquid ratio was in the range of 0.83:1 to 5: 1. Best results showed that 72% of gold was extracted in 50 days with 0.3M (NH4)2S2O3, 0.05M CuSO4*5H2O and 6M NH4OH or a combination of 1.0M (NH4)2S2O3, 0.03M CuSO4*5H2O and 3M NH4OH. The reagent consumption at solid/liquid ratio of 3:1 was 37 - 48.6 kg/t (NH4)2S2O3 and 0 - 0.62 kg/t CuSO4*5H2O. The results of thiosulfate leaching were also compared with cyanide leaching.

Jan 1, 1999

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By R. Schuhmann

The thermodynamic data and calculations which underlie the design of the Q-S process for coppermaking are summarized. The efficient production of crude copper and slag of low copper content in a single con¬tinuous converter requires the establishment and control of gradients in oxygen activity and other physico-chemical variables throughout the reactor. These gradients are established by stagewise introduction of oxygen and solid feed materials to provide: (a) flash oxidation of sulfides above the bath, utilizing the great bulk of the oxygen, (b) conversion of high grade matte or white metal to crude copper by bottom blowing with restricted bath turbulence, (c) close approach to equilibrium staging of converting and deconverting reactions along the length of the slag layer, from a maximum oxygen activity near the metal discharge end to a minimum at the slag discharge end, and (d) completion of slag cleansing by deconverting. In terms of the Phase Rule, the Q-S process involves a system with a minimum of 5 components (Cu, Fe, S, O, and SiO2) and several liquid, solid, and gaseous phases. Accordingly, basic data from previously reported studies on simpler systems are utilized to prepare an equilibrium diagram for the 5-component system and to generate a quantitative thermodynamic model for the Q-S process. This model shows in particular the ranges of oxygen activities (measured by equivalent CO2/CO ratios) involved in the Q-S process and the relations of oxygen activity to temperature and other important physico-chemical variables of coppermaking.

Jan 1, 1976

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thermodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Ahmad-Bitar¸ Riyad N., Shadia J. Ikhmayies

"CdSi-xTex thin films with O<x<0.3 were prepared on glass substrates by the annealing of CdS:In thin films produced by the spray pyrolysis technique. The annealing was performed in nitrogen atmosphere at 400 --,C in the presence of Te vapor. The compositions of the films were determined by energy dispersive X-ray detection (EDAX) measurements. Scanning electron microscopy (SEM) was used to investigate the morphology of the films. The transmittance of the films was measured at room temperature in the wavelength range 400-1100 nm and used to produce the absorbance of the films. The first derivative of the absorbance was used to estimate the optical bandgap energy Eg by using the minima in the first derivative. The relation between the bandgap energy and the fraction x was found to fit with a parabola and bandgaps in the range 2.196: =Eg: =2.480 e V were obtained. Urbach tailing in the bandgap was also investigated.IntroductionPolycrystalline thin film CdS/CdTe solar cells are promising candidates for low cost and high efficiency photovoltaic applications. The fabrication process of these cells involves the deposition of a p-type CdTe absorber layer on top of an n-type CdS one which acts as a window. The efficiency of the solar cell is affected by the method of preparation of both layers [1, 2].Interdiffusion processes taking place at the CdS/CdTe interface have largely been realized to significantly affect the device performance [3] by changing the bandgap of both CdTe and CdS which modifies the spectral response of the solar cell [ 4]. The formation of a mixed crystal or a graded layer causes a reduction in the lattice mismatch at the CdS/CdTe junction [5] which is about 9% [ 6] and then a reduction in the number of interfacial states and recombination centers, thus enhancing the solar cell performance [7, 8]. A complete understanding of the properties of the intermixed layers CdSxTe1-x that usually constitutes the interfacial region in the CdS/CdTe solar cell is essential. According to our knowledge, a lot of research was devoted to the investigation of the diffusion of S into CdTe [3-5, 9]; but little on the direct investigation of the diffusion of Te into CdS [6]."

Jan 1, 2011

By Brajendra Mishra

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

Jan 1, 2003

By Jian-hua Ren, Guang-liang Wu

A lot of dust is produced in iron and steel enterprises, giving rise to serious environment pollution, with which all countries are trying to find methods to deal. The influence of relevant technological factors on dephosphorization was investigated in laboratory, and the effect laws of that were analyzed. The results demonstrate that, in the given conditions of the best slag-metal proportion for hot metal dephosphorization is 1:10, and the optimum temperature is 1350 , The phosphorus distribution ratio of dephosphorization agent containing converter dust of 30% has the maximal value, with dephosphorization rate reaching 85%. Under the optimal conditions, premelting dephosphorization agent can significantly improve the ability of dephosphorization, dephosphorization efficiency increasing to 92%. Therefore, the dust can substitute the oxidant and fixative of dephosphorization agent, be used in hot metal dephosphorization, to enhance the efficiency of utilization.

Jan 1, 2016

By Hylton McWhinney, Doanh Tran, Jewel Andrew Gomes, George Irwin, Sameer Pallavkar, Md Islam, David Cocke, Mohammad Rafiqul Islam

"High-performance nickel-based nanocrystalline zinc oxide adsorbents have been prepared adjusting Ni/Zn mol ratio of 1 :5 by thermal decomposition, coprecipitation and sol-gel method for selective adsorption of thiophene in liquid hydrocarbon fuels at ambient temperature and pressure. To understand the nature of reactive adsorption of thiophene (C4H4S) on Ni/ZnO, the effect of preparation techniques, morphological and textural structure on the desulfurization activity was investigated. A model fuel (20 mL) consisting of pentane (C5H12) and thiophene was prepared and adsorption experiments were performed by a batch method under ambient conditions. The physicochemical behaviors of the fresh adsorbents were obtained using X-ray diffraction (XRD) with EDAX, scanning electron microscopy (SEM). The sulfur concentration in the mixture was monitored by UV-vis spectrophotometry. The adsorption reaction confirmed that ZnO played a crucial role in taking up S element to convert it into ZnS. The deposition of nickel on ZnO is an innovative approach which takes advantage of the selectivity of Ni towards S-species and the high adsorptive capacity of ZnO support.IntroductionLow temperature deep desulfurization of fuels via selective adsorption of sulfur compounds keeping coexisting aromatic hydrocarbons and olefins intact is receiving increasing attention in the research community worldwide in order to satisfy the upcoming environmental regulations and fuel specifications. The sulfur compounds in the transportation fuels is a matter of concern when global crude oil slate is becoming heavier and sourer and environmental restrictions on both the refining process and the refined products are becoming more stringent. According to the current refinery technologies, the sulfur content in refinery fuel is typically around 300-500 ppm by weight (ppmw) [1-3]. Starting in 2006, sulfur limits in highway diesel and gasoline were set to 15 ppm and 30 ppm, respectively. During combustion sulfur in the fuel are converted to toxic sulfur oxide (SOx) and contributes to air pollution and acid rains [ 4]."

Jan 1, 2011

By Ian Baker, Xavier Pierron

"Iron aluminides hold great promise for intermediate temperature applications (to ~ 600°C) because of their excellent oxidation and sulphidation resistance and good strength. However, they have poor low temperature ductility, a feature which is exacerbated by water-containing environments. This paper presents an overview of the effects of environment on the ductility of iron aluminides, including the effects of iron aluminum ratio; ternary alloying additions, particularly boron; strain rate; and temperature. The mechanisms involved in water-induced embrittlement are discussed.IntroductionOver the last few years, it has became increasingly evident that the ductility and fracture toughness of many intermetallic compounds, particularly aluminides, are reduced dramatically if they are mechanically tested in either air or in hydrogen-containing atmospheres (1-5). For FeAI and Fe3AI, it has been shown that water vapor, for example in air at room temperature, can form atomic hydrogen by reacting with the Al atoms (1, 2). As a result in iron aluminides, the environmental embrittlement process is quite similar to traditional hydrogen embrittlement. This can be easily demonstrated by either testing an iron aluminide in an environment free of the deleterious species or by testing at high strain rates, both of which result in greater ductility. The purpose of this paper is to review recent progress in understanding environmental embrittlement in FeAI and Fe3AI, and to consider possible environmental embrittlement mechanisms. Greater understanding of this phenomenon will lead ultimately to remedies to this problem which is a major reason for preventing the practical application of these materials. First, some background on the iron-rich aluminides."

Jan 1, 1996

By John C. Carpenter

Solvent extraction is used to selectively recover copper from iron containing sulphate solutions. As chloride ions, which form series of complexes with transition metals, are now being used for leaching. Little is known of the effects of these ions, on solvent extraction behavior. It has been shown that commercial extractants of the L1X and Kelex series extract copper from chloride media: (1) at a lower pH than from sulphate solutions, (2) to similar loadings, and (3) except for L1X 63, without transferring chloride to the organic phase. A process for selective extraction of copper from chloride solutions should thus be compatible with standard stripping and electrowinning practice. Of several diluents, differing in aromaticity, kerosene gave enhanced extraction only with L1X reagents. A change in operating temperature had little effect on equilibrium metal distribution. All the extractants examined gave adequate separation of copper from iron. L1X 63 was found to extract chloro-complexes of copper and of iron and thus transfer chloride to the organic solution. Consequently this extractant and its mixtures are not preferred for use with chloride leaching systems.

Jan 1, 1976

By Hongbo Yang, Tongbo Zhang, Ting Huang, Jingshe Li, Fangfang Song

"Liquid core length is a very important parameter of the process of continuous casting, which directly reflects the cooling status in secondary cooling zone and solidification rate of the slab. In this paper, the billet caster in some steel plant in China was chosen as the prototype of simulating. A numerical simulating model for calculating the liquid core length of continuous casting billet was built by ProCAST software, which was verified reasonable and accurate by pin-shooting technique. Based on the model, the relationships between casting speed, casting temperature and liquid core length of casting billet were found, which was very practically useful for the workers on sit to improve casting billet quality. IntroductionContinuous casting process developed very rapidly because of the high metal yield, energy saving, and low-cost 111• And the quality requirements of continuous casting billet for customers became higher and higher with the fast development of economic121• Internal defect usually is the major quality problem for continuous casting billet[3•61 , which is influenced by the solidification process of casting billet, especially the solidification process of liquid core17•81 • So it is very important to study on the relationship between casting parameters and the liquid core length which means the distance between the crystallizer meniscus and the casting billet solidification end-point. In practical production process, the workers usually control the quality of casting billet according to the liquid core length."

Jan 1, 2013