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By Takashi Nagai, Hideaki Sasaki, Masafumi Maeda

"The production of solar cells is increasing dramatically and the shortage of polycrystalline silicon for these cells has become a serious problem, making development of a low-cost production process for solar grade silicon essential. An electron beam melting technique is known to be effective for the removal of phosphorus from molten silicon. Although the phosphorus is removed by preferential evaporation in this process, the rate of removal is not sufficient, and its improvement requires thermodynamic information on phosphorus in the molten silicon. In this research, the vapor pressure of phosphorus in equilibrium with a siliconphosphorus alloy was measured by double Knudsen cell mass spectrometry with a system blowing gas into the Knudsen cell. The activity of phosphorus in silicon, the Gibbs energy change of the dissolution of phosphorus in silicon, and other factors were estimated from the results. Using these data, we provided guidelines on how this process can be improved.IntroductionSolar energy is in great demand since it is inexhaustible and cleaner than that from conventional energy resources. Silicon is the material most widely used to convert solar energy into electricity. Figure 1 shows the recent production of solar cells. High purity silicon for solar cells, namely solar grade silicon (SOG-Si), has been commercially supplied mainly from off-grade high purity silicon in the semiconductor industry. However, production of solar cells has increased rapidly in recent years, and the shortage of SOG-Si has become a serious problem, so that a new processes which can produce SOG-Si economically are required.Directional solidification was applied to remove transition metal elements such as Fe or Ti by segregating them from the remaining melt. However, such solidification is useless for phosphorus because the segregation coefficient of phosphorus is nearly unity. Numerous approaches have been made in an attempt to produce a resource of low cost SOG-Si from metallurgical-grade silicon (MG-Si). [1,2]"

Jan 1, 2012

By V. L. Stolyarova

As part of an effort to develop the fluoride electrolysis route for the production of rare earth metals and alloys, a study of the thermodynamic properties of DyF3 has been carried out by Knudsen cell mass spectrometry. A quadrupole mass spectrometer QMS 420 was used in conjunction with the Knudsen cell arrangement. The experiments were carried out in the temperature range 1280-1440 K. Vaporization was carried out from platinum, molybdenum and tantalum cells. The Dy*, DyF+, DyF2+ fragment ions and the DyF3 parent ion were identified in the mass spectrum of the DyF3 vapour. The DyF, vapour pressure was obtained by the complete isothermal vaporizadon method as well as the ion current comparison method, and the enthalpy of sublimation of DyF3 was evaluated. From the DyF3 vapour pressure data obtained at different temperatures, the enthalpies of formation of DyF3 in the gaseous as well as condensed phases have been evaluated. The experimental data are compared with the thermodynamic information available in literature.

Jan 1, 1995

By Kevin Trumble, David Johnson, Kyungjean Min

The electrolytic manganese dioxide (EMD) production through electrodeposition from manganese nodules by reduction leaching in H2SO4 medium using sucrose as reductant followed by purification through 2-stage precipitation methods is described. The purified leach liquor was the starting solution for electrodeposition. Influence of in situ addition of a cationic surfactant Cetyltri-methylammonium bromide (CTAB) (0–500 mg dm −3) on the surface morphology and electrochemical properties of the EMD was examined. The XRD patterns of the deposited material were indexed to the c-MnO2 phase. FESEM results demonstrated that in the presence of CTAB uniform nanofibrous type grains were formed. Higher concentration of CTAB in the electrolytic bath however, drastically decreased the current efficiency (CE) and increased the energy consumption (EC) during electrodeposition. Under the optimum CTAB concentration of 100 mg dm −3 the obtained CE and EC values were 87.64% and 1.70 kWh/Kg respectively.

Mar 1, 2018

By Katsunori Yamaguchi

Secondary materials, that contain relatively high concentrations of platinum group metals, (PGMs) are treated in copper smelting process. The PGMs lost in the slag is increasing with increasing quantities of scrap treated amount. To determine the portion of the PGMs chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. An experimental study was carried out to determine the distribution of palladium between the FeOx–SiO2 slag and the liquid Cu2S–FeS matte at 1573 K and a fixed partial pressure of SO2 of 0.1 atm. It was found that the distribution ratios are around 10−3 for platinum and palladium. The distribution ratios show a tendency to increase when the grade of matte is increased above 60 mass% Cu. In addition, the solubility of platinum in FeOx–SiO2 slag equilibrated with a pure palladium and the Pd-Cu alloy was determined at 1573 K and the range of oxygen partial pressure from 10−9 to 10−7 atm. The solubility of palladium in the slag tends to increase with increasing oxygen partial pressure and activity of CuO0.5 in the slag.

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Kazuaki Mita

There are various intermetallic compounds in the Zn-Fe system. We synthesized them at about 673K. A specimen was examined chemically and X-ray diffraction was applied to ensure the formation of intermetallic compounds. Material containing two phases was placed in a Knudsen type effusion cell and the mass spectrum studied to evaluate the vapor pressure of zinc. The thermodynamic properties of intermetallics was then evaluated through measured intensity.

Jan 1, 1999

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen ternary system, which is of fundamental importance for discussing the' recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, SbO1.5 and Sb2O3) in the PbO-SbO1.5 and PbO-Sb2O3 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Wei-Tong Du, Yu Wang, Gang Wen

Carbon dioxide (CO2), a major component of the greenhouse gases, could be comprehensive utilized as a valuable resource to oxidize vanadium during the converter vanadium extraction process. The thermodynamic software, FactSage, was utilized to study the oxidation ability and theoretical cooling ability of using weak oxidant CO2 as coolant in vanadium-containing hot metal. Besides, experimental research on vanadium extraction in CO2 and O2 mixed blowing extracting process had been undertaken. The results indicated that the elements C, Si, V, Mn etc. could be oxidized by weak oxidant CO2, and the content of V2O3 in slag was approached to pure O2 blowing. Furthermore, CO2 had a remarkable cooling ability and the molten bath temperature kept on decreasing as CO2 blowing rate increases. This research has proved that CO2 and O2 mixed blowing in vanadium extraction process are effective.

Jan 1, 2015

This report presents overview of the authors' results of thermodynamical investigation of some important metallurgical processes and phenomena. Among them: carbo thermal reduction of silica, and boron oxide, silicon carbide obtaining from different precursors, investigations on copper and manganese ores processing, investigations on pollution from different sources. Special attention is paid-to thermodynamical approach to investigation and estimation of multi component multi element compositions stability, developed by the authors. Also are discussed some auxiliary but' important for the thermodynamical investigations issues.

Jan 1, 1997

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By Jing Zhan, Gui Li, Wei-feng Li, Li-Hua Jiang, Chuan-fu Zhang, Jian-yang Hwang

Thermodynamics analysis for processing the charge with lead concentrate and lead sulfate-containing materials in bottom blowing smelting furnace was conducted. The results show that the technology of large-scale processing PbSO4- containing materials with PbS concentrate in bottom blowing furnace under the condition of using high-iron slag type, batch heat supplement, high temperature and rich oxygen is thermodynamically feasible. The exploration test and industrial experiment confirm the results. When S content in mixed ore is 16~17% with coke foam content of about 5%, the lead paste amount can be increased up to 40%.

Jan 1, 2015

By Huang Chao

The thermodynamics analysis on reducing-matting smelting of sulfide ore of lead, antimony and bismuth which use ferric oxide as sulfur fixed agent is first analyzed. Due to the analysis of reaction mechanism, ferric oxide is first reduced to ferrous oxide, then ferrous oxide produce reducing-matting reaction with sulfide ore and reducing agent as reaction equation: MeS+FeO+CO=Me+FeS+CO2. The reaction thermodynamic calculation shows that the reducing-matting reactions of lead sulfide, antimony sulfide, Jamesonite, and bismuth sulfide are feasible, but is infeasible for zinc sulfide. These conclusion provide a feasible method for solve the pollution which produced in the smelting of sulfide ore of lead, antimony and bismuth.

Jan 1, 2006

By Zhihe Dou, Guozhi Lyu, Liping Liu, Yi Luo, Ting-an ZHANG, Xijuan Pan, Zhuolin Liu

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (Mf'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f'), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By I. Barin

The thermodynamics of cyclone smelting of sulphidic copper ores is described using as example the production of copper matte with 75 wt % Cu. Equilibrium calcualtions and material and energy balances show that an increase in process temperature from 1600 K to 1900 K results in the extensive transfer of minor elements such as As, Sb, Bi, Pb, Zn,.... to the gas phase. A pilot plant for carrying out the cyclone smelting process is described. Calculations of material and heat transfer for the reaction of ZnS show that the smelting reactions of sulphides in the cyclone take place very rapidly at high temperatures. The dissociation of the sulphides with subsequent oxidation reactions in the gas phase plays an important part in. the process and is mainly controlled by heat transfer.

Jan 1, 1983

By A. Mikula, S. Karlhuber

"Unique physical and mechanical properties made the Pb-Sn solders attractive for low temperature joining of electronic parts. But since lead in solder materials has become a great enviromental problem and health concern, lead will be slowly replaced by other materials in soft solders. Some of these materials which are currently under investigation are ternary tin alloys. Many different physical properties like wetting behavior, electrical and thermal conductivity and surface tension are measured on these alloys, but on the thennodynamic properties and the phase diagram of the alloys under discussion there is only little information available. We investigated the (Ag, Au, Cu)-Sn-Zn systems and determined the thermodynamic properties over the whole composition range by emf-measurements. From these measurements we also got some information on the liquidus. In the Sn-rich corner the phase diagrams are still under investigation.IntroductionSoldering is technically defined as the joining of two base materials, mostly metals or metal coated nonmetallic substrates, with a third metal. The melting temperature of the third metal or metal alloy should be well below those of the substrates. Solder alloys can be categorized in soft and hard solders. Soft solder alloys usually contain lead, tin, bismuth, indium or cadmium and hard solders gold, zinc, aluminium or silicon. The difference between soft and hard solders is the melting temperature of the soldering material. This temperature is around 350°C.An interesting brief history of solders is given by Vianco and Frear [1]. They report, that in 4000 B.C. solders were already used in Mesopotamia. From archaeoligical evidence those solders were gold-based hard solders.Tin-lead soft solders and their use are not easily found, because in course of time tin has been reduced to stannic acid, making the identification quite difficult. Well preserved soft solder artifacts were discovered in King Tut's tomb dating from 1350 B.C. In ancient time Pb-Sn solders were used primarily for the manufacture and repair of cooking utensils and metal tools. The Romans used lead-tin solders extensively in the construction of the aqueducts."

Jan 1, 1996

By R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l ' d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young's equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By Do-Hyeong Kim, Tae-Jung Kim, Seung-Yeon Won, Jong-Jin Pak, Min-Kyu Paek

Liquid iron alloys containing V, Mo, and Ni can be produced by the carbothermic reduction of spent catalysts used in petrochemical industry. Thermodynamics of carbon in these alloy melts is important for refining these alloys. In the present study, the carbon solubility in Fe-V, Fe-Mo, Fe-Ni, Fe-V-Mo, Fe-V-Ni, Fe-Mo-Ni and Fe-V-Mo-Ni alloy melts of various compositions was measured at 1873 K. The temperature dependency of vanadium effect on carbon solubility in liquid iron was also measured in the temperature range from 1823K to 1923K. The additions of vanadium and molybdenum significantly increased the carbon solubility in liquid iron alloys while nickel decreased the solubility. The experimental results were thermodynamically analyzed using Lupis’ relation at constant activity to determine the first- and the second-order interaction parameters of vanadium, nickel and molybdenum on carbon at carbon saturated condition. Using thermodynamic parameters determined in the present study, the carbon solubility in Fe-V-Mo-Ni alloy melts of various composition were accurately predicted and verified experimentally at 1873 K.

Jan 1, 2014