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By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By Hannu Johto

Boliden Harjavalta has operated a flash smelter for nickel sulphide concentrates in Finland since late 1959. The original nickel flash smelting process was modified in 1995 to a novel nickel matte smelting (DON) with semi-low iron where the batchwise operated converting became obsolete. Since that, the process has been applied to multiple chemically variable nickel sulphide concentrates with high environmental performance. In this paper, the status of the current smelter operations is described together with the recent modernizations of the nickel flash smelting furnace and the slag cleaning furnaces.

By Zuomei Jin

The Mineralogical form of Silver in a Ag-rich complex ore was determined. In the complex sulfide ore, acidic thiourea leaching resulted in 35% extraction of silver directly. In the same complex sulfide ore, under the effect of ultrasonic treatment, 65% of silver can be ex¬tracted. After the above ore had been roasted and acidically leached of Zn and Cu, the silver extracted from this Pb-Ag residue was 96.8%. The effets of temperature, thiourea and ferric ion concentrations and partical size were examined. The leaching rate of silver from the Pb-Ag residue was diffusion controlled. The activation energy was calculated to be 10. 49%KJ/mole. The kinetic model for the thiourea leaching of silver from Pb-Ag residue was obtained and is given by, The kinetics of silver cementation by aluminium in thiourea solutions was also investigated. The activation energy was calculated to be 65. 13KJ/mole, which is reasonable fora rate-limiting surface reaction.

Jan 1, 1995

By S. R. Reddy

Thennodynamic properties of several quaternary systems are calculated using our recently modified Margules equations. The modified Margules equations are expressed up to infinite order in the vicinity of solvent. Quaternary system of one solvent and three,solute partials are derived. First order interaction coefficients of binary, ternary and cross -interaction parameters of quaternary system are used to'evaluate the partial functions. In the original fonn of Margules equations,derived partial functions are convergent and same 'as Unified ,Interaction Parameter Fonnalism. But considering up to infinite order of the Margules coefficients, the functions are divergent, in order to overcome this restriction, Margules equations are modified to get consistent equations. Derived partial functions are thennodynamica Hy consistent with Maxwell and Gibbs Duhem relations. The derived logarithmic activity coefficient of the solvent and solutes are consistent with the ternary systems. The calculated data, ie., activity coefficient values of nitrogen and interaction coefficients are in good agreement with the data of Fe-Cr-V -N. Fe-Ni-V -N, Fe-Cr-Ta-N and Fe-Ni-Ta-N systems.

Jan 1, 1999

By Afshin Sadri

Acousto Ultrasonic-Echo (AU-E) is a technique developed to provide accurate measurements of the refractory lining wear in operating smelters based on the principles of stress wave propagation. The objective of the system is to provide feedback for the continuous optimization of the overall smelter operation. In some cases, the AU-E refractory lining measurements have allowed clients to extend their smelter campaigns and operate safely for several years beyond their planned reline schedule. In other cases, AU-E results inform clients of serious issues within their furnace allowing them to shut down their smelters ahead of predicted failures and possible disasters. This paper presents the results of several smelter AU-E inspections of the hearth and sidewall. These case studies demonstrate how the AU-E results were used to positively affect the smelter operation.

By Jianhui Wu, Jing Zhan, Chuanfu Zhang, Zhijian Wang, Chu-ping Xia

"A novel technology about interactive roast of complex bismuth sulfide ore with low grade and Pyrolusite was put forward using the low-grade bismuth sulfide ore and pyrolusite as raw materials. The predominance diagram of Bi-Mn-S-O system was drawn by thermodynamic calculations. Stable coexistence area ofBizO3 and MnSO4 and its control condition was obtained. The interactive roast conditions including roasting temperature, roasting time, the ratio of n(MnO2)/n(S), ventilation rate and so on are investigated systematically. The results show that the sulfur-retained ratio reaches about 98%, in which formation rate of MnSO4 was 94.04%, most of the residual sulfur in the ore exist in the form of BhsO32(SO4)10 in the roasting products The optimum roasting conditions were as follows: roasting temperature of 650°C, roasting time of2h, 1.4 for n(MnO2)/n(S) and 140L/h for ventilation rate.IntroductionBismuth is a ""green"" rare metal with the characteristics of safe, nontoxic and low melting point[l].The use of bismuth and its oxides is extending from traditional fields such as pigment, fusible alloy, bismuth class of drugs and metallurgical additives to the high-tech fields such as semiconductor, high-temperature superconducting materials and nuclear power and so on. Bismuth is one of the precious advantageous resources in China which owns the most abundant bismuth resources in the world. Bismuth metallurgical process is divided into the pyrometallurgy and hydrometallurgy [2-4]. Hydrometallurgy for bismuth is mainly used for the processing oflow-grade complex bismuth ore, whose key steps are oxidative leaching process of the bismuth sulfide ore by strong oxidants(FeCb, Clz, HNO2 etc) in hydrochloric acid system. Therefore, the corrosion of strong oxidants, high demand for equipments and poor operating environment are its inherent disadvantages. Pyrometallurgy for bismuth is mainly used for the processing of high-grade bismuth raw materials or concentrate, which is the main method for bismuth metallurgy at present."

Jan 1, 2013

By Takayuki Watanabe, Yoshiki Shimizu, Yusuke Moriyoshi

"B-C-N nanotubes prepared by a flush evaporation method using a de arc plasma were mainly characterized by transmission electron microscopy (TEM) and electron energy· loss spectroscopy (EELS). The nanotubes obtained· were divided into three types such as carbon boron nitride and carbon or carbon nanotubes surrounded with boron nitride nanotubes. These types of nanotubes were obtained at higher temperatures than about 3000 K, however, these were not formed at lower temperatures than about 3000K. On the other hand, 11anocapsules were· formed at all the experimental temperatures and nanocapsules with a homogeneous phase were obtained at lower temperatures than about 3000 K. The effect of additives on the formation of B-C-N nanotubes was not clear. Based on these experimental data depending on temperatures and corresponding microstructures, the formation mechanisms of both nanotubes and nanocapsules were briefly .discussed 1 Introduction As reported previously, nano tubes have unique electrical properties1, 3) The preparations of nallotupes have been usually carried out by flush evaporation methods using either a de arc plasma or a laser4 -5) By these methods the reaction rate is so rarid that we have no data of intermediate products between initial raw materials and. final products of nanotubes 6-9). So, the formation mechanisms of nanotubes have been mainly speculated only from the microstructures of resultant nanoiubes. In order to have more reliable formation mechanisms, it is particularly important to have the information of intermediate products at the corresponding temperatures. From the viewpoints, we have studied about the effects of temperatures on the preparation of nanolubes. Here we report mi firstly some problems on the preparation of B-C-N nanotubes 10), secondly the effects of temperatures on the preparation of B-C-N nanotubes, and finally the formation mechanisms of nanotubes."

Jan 1, 2000

By I. D. Reznik

Regularities of cobalt and nickel distribution between slag and matte, slag and metallic alloy on the base of concepts on exchange reaction equilibrium are considered. It is shown that the distribution of cobalt and nickel in industrial processes approaches to equilibrium one. Oxysulphiae influence on the bahaviour of cobalt, nickel and sulphur is shown. The recommendations on conduction of the processes of smelting, converting and slag cleaning based on the analysis of the methods or" non : ferrous metal separation from iron are given.

Jan 1, 1993

By Niels Verbaan, Ralph Fitch, Charlotte Forstner, David Dreisinger

A process has been developed to extract gold, silver, indium, gallium, lead, copper, zinc, and other metals from a large resource using an oxidizing acid chloride heap leaching technology. The ore is crushed and/or ground to improve reactivity and then contacted with a solution containing NaCl-HCl-NaOCl. The value metals are leached into solution as chloro-complexes. The leachate is treated in a series of separation and recovery processes to produce separate saleable or disposable products. The paper will provide a summary of process development and application to a silver-indium ore from Bolivia. The possible application of the process to other ore types will be presented for discussion.

Jan 1, 2015

By William Petrul

Image analysis studies were performed on mill products from laboratory flotation tests of the Zn-Pb ore from the Faro deposit in Yukon, Canada, to determine mineral liberations at specific grinds and to predict recoveries at optimum flotation conditions. The minimum and optimum grinds for liberating sphalerite and galena were predicted from size analysis data for the minerals in large ore pieces, and determined by image analysis studies of the mill products. The determined optimum grinds are about 2 Tyler mesh sizes larger than predicted because sane of the fine grained sphalerite and galena occurs in interstices between coarser grained pyrite and is liberated when the pyrite grains are broken apart. Materials balance calculations were performed on the analyzed values for the liberated and unliberated sphalerite and galenaa to determine their distributions in the mill products. The laboratory flotation tests recovered 74% of the sphalerite and 83% of the galena in Zn and Pb concentrates respectively. The mineral evaluation study indicates that the optimum recovery for sphalerite and galena are 85 and 83% respectively. The company is currently recovering 80% 'of the sphalerite and 82% of the galena.

Jan 1, 1989

By W. L. Dalmijn, J. M. Krowinkel

A recycling concept of end-of-life televisions starting with shredding will produce a complex material mixture, very heterogeneous in size, shape and degree of liberation. Basically all materials in television scrap are valuable, which means that recovery is important for either economic, environmental or sustainability reasons. However glass, plastics and metals are the materials with the highest potential for recovery. Non-magnetic materials from shredded television sets can be separated into three characteristic size fractions that need further separation for a high value-added recycling of the materials. This study investigated the potential of physical separation of these size fractions into valuable material streams using polyseparator, tlrldy current separator, dry and wet shaking tables and electrostatic separator. An overall mass balance of the mechanically processed televisions was calculated. Evaluation of the produced material fractions showed that heterogeneity in particle shape and size together with the presence of unliberated materials caused sever difficulties in separation when exclusively based on mechanical techniques. The results indicate that a certain degree of dismantling is necessary to achieve products of appropriate quality in physical separation. In order to improve recycling of electronic scrap through design for recycling cooperation between the electronics industry, the manufacturers and the recyclers of electronic goods is necessary.

Jan 1, 2000

By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander model for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2, MgO-SiO2, FeO-CaO-SiO2, FeO-FeO1.5-CuOo.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-MgO and FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte (L s/m as), and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5-CaO-MgO slag and liquid copper (L s/Cu as) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte-metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for prediction in multi-component slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes.

Jan 1, 2003

By ZhiLong ZHAO, Lin Lin, Zhancheng Guo, Jingtao GAO, Huiqing Tang

Grain sticking often occurs in the fluidized bed reduction of f ine iron ore, which is closely related to the precipitation morphology of metallic iron on the surface of ore particles. In this work, simulating the gas-solid reduction process of iron ore, in situ observations were carried out to investigate effects of doping mineral oxides on the precipitation morphology evolution of metallic iron during reduction of iron oxides with CO. Results indicate that the precipitation morphology of metallic iron is related to the quantity of doped mineral oxides. The minimum mole fraction of doped oxide ( xyOA N ) that can inhibit the growth of iron whiskers is related to its cation radius ( Ax r ), extranuclear electronic layers ( Ax n ) and valence electrons ( Ax q ). Their relation can be expressed as:

Jan 1, 2016

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By George Kazonich

The high costs and environmental problems associated with making iron and steel in the United States is driving the development of new technologies to replace the blast furnace. A prototype reactor incorporating rocket technology was designed and built. This rapid rate reactor was operated successfully and consistently made iron metal. Minus 325-mesh magnetite particles could be reduced to iron metal in less than 50 ms in a high temperature flow through reactor. Iron product was recovered inside the reactor and in a downstream cyclonic separator. The results of typical operation and how parametric changes affected the reduction of iron ore concentrates are discussed.

Jan 1, 1993

By Versiane Albis Leão

This work aims at the selection of an appropriate eluant for cyanide recycling using ion exchange resins. Based on a literature review as well as on experimental results, the elution of resins loaded with copper and minor amounts of iron and nickel is discussed. The resins Imac HP 555s, Amberlite IRA 900 (Rohm&Hass) and Purolite A860S (Purolite Co) were eluted using either NaCI, zinc and nickel cyanides, hydrochloric acid, sulfuric acid or acid thiourea solutions. The results indicate that saline solutions are effective only with polyacrylic resins (Purolite A860S), failing to desorb the metals, specially the nickel cyanocomplex, loaded on polystyrene-based resins. Cyanide solutions of both zinc and nickel are capable of eluting over 90% of the loaded metals. In contact with pure acid' solutions, iron precipitates onto the resin beads, as Cu(II) ferrous cyanideCu2Fe(CN)6.xH20. Thiourea is able to elute all the three metal cyanocomplexes owing to the increased solubility of copper cyanocomplexes in the presence of this complexing agent. The results demonstrate that a universal eluant is not available and the selection of the most appropriate resin-elution procedure should be based on the specific features of the system under consideration

Jan 1, 1998

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By Rikiya Kamezawa, Rudiono, Manabu Takeuchi

"Schottky type solar cells based on phthalocyanine (Pc) thin films were fabricated, and their photovoltaic performance was investigated in various ambient atmospheres. Most of cells prepared in this study showed a good rectification and photovoltaic effects in the visible wavelength region. The introduction ofN02 gas into the measuring chamber was confirmed to increase the current both in dark and under light illumination. However, chemical reaction between the Al electrode and N02 formed some oxide and deteriorated the Schottky barrier, resulting in an increase in cell resistivity. SF 6 gas also showed similar effects on the cell performance.IntroductionPhthalocyanine is one of the typical organic semiconductors, which shows high photoconductive sensitivity in the visible to infrared region. Today, several kinds of metal phthalocyanines are used in electrophotographic photoreceptors. In addition, application of phthalocyanines to solar cells have also been trying by many workers [1, 2]. Many efforts have been made for improving performance of phthalocyanine solar cells by modification of device structure [3, 4], doping by dye or pigment [5, 6] and incorporation of metal clusters [7]. It is known that electrical conductivity in phthalocyanine is increased by adsorption ofNO2 [8, 9]. We tried to improve photovoltaic performance ofphthalocyanine solar cell by adsorption ofNO2. This paper describes the influence of N02 adsorption on the photovoltaic behavior of phthalocyanine solar cells."

Jan 1, 2000