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By Steven Wright, Sharif Jahanshahi, Shouyi Sun

"While there is a large industry based on recovering platinum group metals (PGM) from complex sulphide ores containing Cu and Ni, there is little information on the thermodynamics of the matte phase formed on smelting the ore and in particular the behaviour of Pt in the matte.The equilibrium between metallic platinum and industrial mattes was studied in a series of experiments where a small quantity of matte (5g) and platinum foil of 150 µm thickness (0.5 g) were equilibrated in magnesia crucibles at 1400°C under conditions where the oxygen and sulphur partial pressures were controlled.The chemistries of the phases were determined from EDS analysis using a scanning electron microscope. Line scans were initially used to confirm that the foils had attained a uniform composition across their thickness. The composition of the matte was determined from analysis of an area of matte including the small metallic droplets and dendrites.The distribution of Pt in Cu-Fe-Ni mattes (Pt: 1.5 – 3%) and solid Pt alloys (Pt: 54 – 72%) was studied. For a matte of base composition 45%Fe, 11%Ni, 8% Cu, at a base temperature 1400°C, the following behaviour was observed for the Pt distribution ratio:Under the range of sulphur and oxygen pressure of this study (log pO2 from -15 to –12.2, log pS2 from – 4.6 to –2.2), the distribution ratio of Pt between matte and alloy was independent of the sulphur and oxygen pressure, having a value of 0.04.The Pt distribution ratio increased from 0.02 to 0.08 with temperature from 1340 to 1450 oC.For mattes where the proportions of Cu and Ni were kept constant, a slight decreasing trend was shown for the distribution ratio of Pt versus the iron content (37 to 53%) in the matte but was not confirmed because of experimental uncertainty."

Jan 1, 2003

By Steven Wright, Sharif Jahanshahi, Shouyi Sun

"While there is a large industry based on recovering platinum group metals (PGM) from complex sulphide ores containing Cu and Ni, there is little information on the thermodynamics of the matte phase formed on smelting the ore and in particular the behaviour of Pt in the matte.The equilibrium between metallic platinum and industrial mattes was studied in a series of experiments where a small quantity of matte (5g) and platinum foil of 150 µm thickness (0.5 g) were equilibrated in magnesia crucibles at 1400°C under conditions where the oxygen and sulphur partial pressures were fixed.The chemical composition of the phases was determined from EDS analysis using a scanning electron microscope. Line scans were initially used to confirm that the foils had attained a uniform composition across their thickness. The composition of the matte was determined from analysis of an area of matte including the small metallic droplets and dendrites.The results of the equilibrium study are presented in terms of how the oxygen and the sulphur pressure affect the distribution of Pt, between the matte and the alloy foil (Lmatte/alloy). Other variables investigated were matte chemistry, i.e., the Fe content and the temperature. The activities of platinum in the mattes were calculated using a regular solution model describing the activity-composition relationship in the alloy."

Jan 1, 2003

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore. there has been a growing interest in the removal of handful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp clements and satisfying the environmental regulations. In this paper, the available thennodynamic data of the residual tramp elements in the molten steel are summarized and the possibility of the removal of residual tramp elements from the molten steel is thcnnodynamieally estimated.

Jan 1, 2003

By Jongmin Jeong, Jaehong Shin, Joo Hyun Park, Chul-Woo Nam, Kyung-Ho Park

Because sulfur and phosphorus are very harmful in steel products, there are increasing requirements for refining these elements from ferroalloys industries. Hence, in the present study, simultaneous desulfurization (de-S) and reducing dephosphorization (Rde-P) from silicomanganese (SiMn) alloy were investigated using metal-slag equilibration method under highly reducing condition at 1773 K. Experiments were carried out by equilibration between SiMn alloy and MnO-based slag in graphite crucible under p(O2) = 10−18 atm. Slag composition was designed by changing basicity (CaO/SiO2) and MnO content at fixed Al2O3 (=20%) and MgO (=5%) contents. De-S ratio increased with increasing basicity until C/S = 1.5 whereas Rde-P ratio was not significantly affected by slag basicity. This was because thermodynamic driving force of de-S reaction was greater than that of Rde-P reaction under present experimental conditions. The de-S and Rde-P ratios commonly increased with decreasing oxygen partial pressure.

Mar 1, 2017

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985

By Steven Wright

BHP Billiton?s Olympic Dam copper flash smelter employs the direct to blister process for smelting high grade copper concentrates. SO2 evolution during tapping gives rise to safety concerns. A thermodynamic model for the blister copper (Cu-Fe-S-O) was used to predict the volumes of SO2 evolved. The Multiple Phase Equilibria Model (MPE) was used to evaluate the slag chemistry inside the furnace. The blister copper model was used to explore the relationship between %S and %O in the copper and the amount of SO2 evolved on cooling. The volume of SO2 evolved was sensitive to the O content with reduction to levels below 0.2 ? 0.15% likely to suppress SO2evolution on cooling. Concentrations of S and O in copper samples from trials generally lay above the equilibrium line calculated for an average temperature of 1275C and a partial pressure of SO2 of 1 atm. Consequently there is a thermodynamic driving force for SO2evolution when cooling to this temperature during tapping. A number of potential process options to suppress SO2 evolution on tapping were investigated thermodynamically. Some of the options require treatment of the blister in a forehearth or separate furnace, while others impact on current practises in the flash furnace with slag present. The opportunities that these options present are discussed.

Jan 1, 2006

By S. E. Olsen, K. Tang

Slag-metal and slag-metal-gas heterogeneous equilibria involving MnO-containing slags have been simulated using recently developed Mn-based alloy and IRSID oxide thermochemical databases. A large number of experimental equilibrium data have been used to verify the calculation results. The experimental slag-metal and slag-metal-gas equilibria in MnO-SiO2binary, MnO-SiO2-CaO and MnO-SiO2-Al2O3ternary, MnO-SiO2-CaO-Al2O3quaternary andMnO-SiO2-CaO-Al2O3-MgO higher-order system can be reproduced within experimental uncertainties. The influence of temperature, CO partial pressure and slag chemistry on the Mn-and Si-distribution equilibria have been quantitatively evaluated. This leads to a sound basis for optimizing the manganese ferroalloy production processes. Key words: MnO-containing slag, manganese ferroalloy, equilibrium simulation, thermochemical database

Jan 1, 2004

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 Shahab Alizadeh, Ahmad Khodadadi Darban, Mehdi Mohseni, Mahmoud Abdollahy

This study probed the selective separation of lanthanum and yttrium in a nitrate medium in the presence of aluminum and calcium impurities using di-(2-ethylhexyl) phosphoric acid (D2EHPA). The factors studied in a central composite design (CCD) included extractant concentration, pH, concentration ratio of total impurities to rare earth elements, and interaction of these three factors. The extraction mechanism and types of extracted metal-containing species were delineated by the slope analysis method. The obtained thermodynamic data showed that lanthanum and yttrium extraction by the D2EHPA extractant was exothermic. The extraction of both rare earth elements was accompanied by an entropy reduction. The negative magnitude of ΔS in yttrium extraction reaction suggests stronger D2EHPA-Y(III) complexation relative to La(III). As entropy decreased and enthalpy increased, the extraction process became unspontaneous. Using the proposed flowsheet, lanthanum and yttrium products with > 90% purity were obtained.

Aug 10, 2021

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996

By Jong-Oh Jo1

Thermodynamics of Ti, N and O in liquid iron was studied in order to establish a data base for the prediction of TiN and TiOx formation in liquid stainless steels containing various alloying elements including Cr, Ni and Si as a function of temperature. The interaction parameters of these elements on Ti and N were determined using the metal-nitride-gas equilibration technique. The TiN stability diagram for a commercial stainless steel grade was constructed from the measured thermodynamic parameters, and its validity was confirmed experimentally. The interaction parameters between Ti and O, and the equilibrium constants for Ti deoxidation reactions for the formation of Ti2O3 and Ti3O5 were also determined by the equilibration of the melts with those oxides identified by the XRD and the EPMA analyses.

Jan 1, 2006

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By Jiayan Li, Yi Tan, Yao Liu, Yaqiong Li, Shenrui Wu

"A metallurgical grade silicon (MG-Si) refining concept process was presented. Under vacuum conditions, silicon was selectively oxidized by high purity silicon dioxide to form gaseous silicon monoxide while impurities with low vapor pressure in MG-Si were rejected in residue; Then high purity silicon was obtained from the disproportionation of condensed silicon monoxide; and by-produced silicon dioxide was recycled for the oxidation step. Thermodynamics on boron rejection during the oxidation were studied in this work. In the temperature range of 1200-1800K, the saturated vapor pressure of boron, and the Gibbs free energy changes, the equilibrium partial pressures of silicon monoxide and boron oxides of potential reactions were calculated. And the effect of boron activity in MG-Si was also discussed. The results indicated that boron in MG-Si can be rejected during the oxidation and it showed the potential for the further development of the new refining process.IntroductionAs global energy consumption growing dramatically, higher prices of energy and global warming problem have attracted more and more attention [1]. As a clean and renewable energy industry, the photovoltaic (PV) industry converts solar energy to electricity using solar cell device and has a growth rate of about 30% in recent years. It has caused a shortage of silicon feedstock due to that about 90% of solar cells are made of crystalline silicon. And high energy consumption during the production of silicon material, i.e. solar grade silicon (SoG-Si), is main obstacle for its mass production."

Jan 1, 2012

By J. H. E. Jeffes, K. T. Jacob

The activity coefficients of oxygen in liquid Pb-Sn alloys have been measured between 550 and 1100°C by use of solid oxide galvanic cells: Pt, Ni-NiO | Zr02 Solid electrolyte | O (Pb + Sn), Cermet, Pt; and Pt, Fe-FeO | Zr02 Solid electrolyte | 0(Pb + Sn), Cermet, Pt. Alcock and Richardson's quasi-chemical equation, with the coordination number of atoms set to 2, is found to predict successfully the activity coefficients of oxygen in these alloys. The relative partial molar enthalpy and entropy of oxygen at 1 atom per cent in the alloys have been calculated from the variation of the activity coefficient with temperature. The addition of Sn to an unsaturated solution of O in Pb is shown to decrease significantly both the partial molar enthalpy and entropy of O. As the measurements were restricted to a narrow range between 750 and 1100°C in Pb-rich alloys, however, the pronounced variation of the partial molar enthalpy of O with temperature at constant alloy composition predicted by the quasi-chemical model could not be verified.

Dec 1, 1971

By Zhang-Guang Gao, Ming-Mei Zhu, Rui-Rui Zhao, Chao Jiang

This paper focuses on the CaO-SiO2-FeO-MgO-MnO-P2O5 slag system that represents the major components of dephosphorization slag in BOF. Phosphorus distribution between 2CaOSiO2-3CaOP2O5 Solid Solution and Liquid Slag were analyzed by FactSage. The effects of slag content, basicity on the distribution ratio of P between the solid solution phase and the liquid phase (LP) and the percentage content of P in solid solution phase and liquid phase have been discussed. The results show that, with the increase of basicity, LP (wt%) decreases until the basicity reaches 1.9, then it turns to increase. LP (wt%) increases gradually with the increasing amount of FeO or P2O5.

Mar 1, 2017

By C. Basilio

Thermodynamic calculations based on a rigorous mass balance technique have been carried out for the chalcocite-potassium ethyl xanthate (KEX) system. The results of the calculations are used to: i) construct Eh-pH diagrams for KEX additions ranging from 0 to 10-4 M, ii) determine the amounts of cupric ions and copper xanthate formed at different Eh and pH values to make three-dimensional diagrams, and iii) determine the minimum KEX addition required to form CuX and CuX2.. This allows prediction of the optimum conditions for flotation and comparison of this with microflotation test data. In addition, voltammetry experiments have been conducted on chalcocite electrodes at pH 9.2 and pH 6.8 in order to gain information on the role of metastable species in flotation. On the basis of these experiments, possible reaction mechanisms are discussed and comparisons are made with what is expected on the basis of thermodynamics.

Jan 1, 1985

By Kobayashi M

Particulate chalcopyrite samples (78 ~ 98 mole per cent chalcopyrite, screen size fraction from 710 to 250 µm) were prepared by crushing and sieving lump ore samples from 12 locations in the Mt Isa Mine. Measurements of thennoelectric power (which does not involve the passage of a current) were made using a packed bed that was compressed by loading with a weight and placed in a temperature gradienL Details of the apparatus are described.The effect of particle size was investigated by preparing 12 fractions, with mean particle sizes ranging from 605 to 2.2 µm, from one of the ore samples. Values of thennoelectric power decreased with both increasing particle size and loading pressure; however it remained fairly constant for particle sizes above 80 µm, when loading pressure exceeded 3.3 MPa.Measurements of the chalcopyrite samples gave an average value of -260 JlV/K (-248 ~ -268 µV/K) for nine samples and about -290 µV/K for three samples, showing that these samples were all n-type semi-eonductors.

Jan 1, 1990

By Takao Mori

Novel rare earth boron icosahedral compounds are investigated as potential high temperature thermoelectric materials. REB50-type compounds and REB22C2N compounds were synthesized and the thermoelectric properties measured. Seebeck coefficients in excess of 200 V/K are observed at temperatures above 1000 K for the REB50-type compounds. Strikingly, n-type behavior was observed for REB22C2N. Up to now, non-doped B12 icosahedral compounds have all been p-type. The discovery of an n-type compound is extremely important in terms of the potential development of this class of compounds as viable thermoelectric materials. Low thermal conductivities of < 0.03 W/cm/K at room temperature was observed for these rare earth boron cluster compounds.

Jan 1, 2006