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By Mansoor Barati, Leili Tafaghodi Khajavi

"This study involves employing solvent refining as a purification process in which silicon recrystallization takes place from an iron-silicon melt. It is believed that iron will act as the impurity “getter” and purified silicon crystals will grow from the alloy melt, while the impurities are segregated to the liquid alloy. Phosphorous is a problematic impurity to remove since its segregation coefficient in pure silicon is relatively large. To assess the feasibility and efficiency of phosphorous removal through solvent refining, it is critical to study its equilibrium distribution between solid Si and the Fe–Si alloy phase.The distribution of phosphorous between solid silicon and iron-silicon melt at 1210-1310 °C was measured to evaluate the impurity removal potential of each alloy. Interaction parameter between phosphorous and iron was calculated by varying the concentration of phosphorous in silicon.IntroductionAmong various semiconductor materials for manufacture of solar cells, silicon accounts for over 90 percent of today's PV materials [1, 2].The major challenge in producing solar silicon that operates efficiently is to meet purity level requirement through a cost efficient route. Silicon solar cells can play a significant role in answering the world's need for energy if cost reductions can be achieved through manufacturing process. Considerable effort has been made to replace the expensive, complex vapor-phase purification by a simpler and less costly process. One of the refining approaches that have attracted wide research interests is producing low-cost solar grade silicon by purification of metallurgical grade silicon. Since metallurgical processes are selective in removing impurities, a combination of various purification processes can be used to reduce the impurity level in silicon. Considering different thermodynamic characteristics of impurities, each refining step is responsible for lowering specific impurities."

Jan 1, 2012

By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

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 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 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 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 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 Sung Wng Kim

The binary antimonide compounds with the skutterudite structure have a potential for thermoelectric applications because of the high carrier mobility, high thermoelectric power, and relatively low thermal conductivity due to the complex crystal structure. However, the room temperature thermal conductivity of these skutterudite materials is as high as about IOW/mK with an estimated 80-90% contribution from the lattice thermal conductivity. Because the lattice thermal conductivity of related ternary skutterudite compounds can be substantially reduced due to the additional phonon scattering, a study of thermoelectric properties of these compounds is of interest. The binary IrSb3, ternary Ir1.xRuxSb3 and Ir(MxSb1.x)3(M=Ge, Sn) compounds were prepared by hot pressing of pre-reacted powders. We have measured the electrical resistivity, thermoelectric power, and thermal conductivity, in a temperature range from room temperature to 973K. The binary IrSb3 compound is found to have P-type electrical properties exhibiting a good Seebeck coefficient (up to 225µV/K around 773K), electrical resistivity(5x10-5Ohm M around 933K), and relatively low thermal conductivity(6W/mK around 950K). The lattice thermal conductivity, K[2] was calculated from the Wiedemann-Franz relationship.

Jan 1, 2002

By Paul Foote

SEEBECK discovered, in 1821, that if, in a closed circuit of two metals the two junctions are at different temperatures, an electric current will flow in the circuit. In the case of an iron and a copper wire, for example, current will flow from copper to iron at the hot junction, or from iron to copper at the cold junction. Two factors combine to cause the current. An electromotive force exists between the two metals, the magnitude of which, depends upon the temperature and upon the metals; this is called the Peltier e.m.f. If a single wire of homogeneous material is heated at one end, an electromotive force is developed between the ends of the wire, the magnitude of which depends upon the metal and upon the difference in temperature; this is known as the Thomson e.m.f: The total e.m.f. acting in the circuit is the sum of the Peltier e.m.f. at the two junctions and the Thomson e.m.f. in each wire, consideration being given, of course, to the algebraic signs of the four e.m.f.'s. The total electromotive force thus depends upon the difference in temperature of the two

Jan 9, 1919

By Qingyun Huang, Wei Lv, Junyi Xiang, Xuewei Lv, Chenguang Bai

The roasting is the key step for the extraction of vanadium from vanadium slag by calcification roasting–acid leaching process. In this study, thermogravimetric analysis and kinetic study of vanadium slag in the presence of calcium oxide was investigated. The maximum oxidation degree was slightly increased by increasing temperature from 700 to 900 °C then almost unchanged further increasing temperature to 1000 °C. The reaction mechanism was analyzed through both Sharp method and ln-ln method. Results showed that the mechanism the reaction in the a range of 0.1–0.8 corresponded to the random nucleation and subsequent growth, as represented as (G( a)=[ −ln(1−a)] 1/3 = kt. The apparent activation energy was calculated to be 3.5 kJ/mol according to Arrhenius equation.

Mar 1, 2018

By Qiang Zhong, Qian Li, Yongbin Yang, Tao Jiang

Thermogravimetric analysis (TGA) has been used to research the pyrolysis and combustion processes of coal used in rotary kiln of iron ore oxide pellet. Furthermore, the effects of air flow and oxygen concentration on the combustion behavior of coal were examined with TGA. The results showed that two individual stages can be distinguished for the pyrolysis of coal, the water evaporation stage and the de-volatilization stage. And the information on ignition and burnout characteristics can be obtained from the combustion process analyzed by TGA. Large air flow almost has no effect to the combustion process except that it enhances combustion intensity. However, the combustion process is further accelerated under oxygen-enriched conditions. With all experimental results, it could provide an attractive approach of analyzing coal for the rotary kiln process.

Jan 1, 2016

By Chengyi Ding, Yangyang Xie, Xuewei Lv, Senwei Xuan, Chenguang Bai, Kai Tang, Gang Li

Dicalcium ferrite (2CaOFe2O3, C2F) is one of the most significant bonding phase of fluxed sinters. Reduction of C2F was investigated via thermal kinetics analysis. The isothermal reduction behavior of C2F by 30% H2 and 70% N2 at 1123 K (850 °C), 1173 K (900 °C), and 1223 K (950 °C) were discussed by thermogravimetric analysis in this paper. The results revealed that the C2F reduction was typical one-step reaction. The apparent activation energy of the C2F reduction was 27.40 kJ/mol. The rate-determining steps of the C2F reduction were the first inner gas diffusion, then the inner gas diffusion and interface chemical reaction mixed controlling. The ln-ln analysis implied that the C2F reduction was described by the Avrami–Erofeev (A-E) equation, thus appeared as a 2D A-E equation kinetics reaction.

Mar 1, 2018

By M. J. Makhula, R. M. S. Falcon, S. O. Bada, L. M. Falcon

"SynopsisThe combustion and co-combustion behaviour of macadamia nut shell, high-ash coal, and anthracite, along with their blends was studied using thermogravimetry. The reactivities of all samples were analysed in air, oxygen, and CO2 atmospheres and at different heating rates from 10 to 40°C/min. Macadamia shell was found to have a lower ash content, 0.36%, than coal with 27.49% ash. The calorific values were similar, 19.64 MJ/kg and 19.44 MJ/kg respectively. The differential thermogravimetric results indicate that as the heating rates increase the ignition, peak, and burnout temperatures increase significantly, leading to high combustion rates. The interaction between the fuels was evaluated using the weighted average model, and the results indicated that there is more synergetic interaction between 20% macadamia plus 80% coal under oxygen than in air and CO2 atmospheres. The results of the investigation provide the combustion and co-combustion characteristics of various samples and their blends and indicate their combustion compatibilities. IntroductionThe global macadamia nut industry is developing at a very rapid rate. South Africa is currently the world’s third largest producer, with a production of about 35 000 t as of 2012 (Department of Agriculture, Forestry and Fisheries, 2013), compared to 840 t produced in 1996. The greatest numbers of the macadamia nut farms in South Africa can be found in Mpumalanga, Limpopo, and KwaZulu-Natal provinces, with Mpumalanga as the largest producing area. There are many factors influencing the increased demand for macadamia nuts, the most important factor perhaps being their nutritional value (California Dried Fruit and Nuts, 2011; MPC, 2014) and their suitability as a feedstock for manufacturing cosmetics, bakery products, nut paste, chocolates, sauces, and ice-cream. As a fuel, macadamia shell has a high heating value ‘as-fired’ of about 20.71 MJ/kg (Vhathvarothai et al., 2013), which could in turn be used in drying the nust, and the shell could also be milled and applied as a fertilizer."

Jan 1, 2015

By Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior of TiO2 nanoparticles was thermogravimetically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanoparticles, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500 °C at heating rate of 1O 'Cumin. The weight increase curve showed a maximum of ca 30 wt% at around 750 T and then gradually decreased to ca 12w% at 1000OC. This would be caused by the formation of TiS2 followed by the decomposition of TiS2 to lower sulfides, such as Til.08S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanpparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By Jhon Cuya

Titanium dioxide is the well-known catalyst for the photodecomposition of water in UV region and its nanoparticles show better performance than its bulk materials. Furthermore, partially sulfurized TiO2 is expected to be chemically stable and have an enhanced photocatalytic activity compared with TiO2. For this purpose, the sulfurization behavior ofTiO2 nanopartic1es was thermogravimetrically (TG) studied by a thermo-balance with a quartz spring using CS2. From the TG curve of TiO2 nanopartic1es, first, the weight decrease appeared down to around 8 wt% and then sulfurization reaction started at around 500°C at a heating rate of 1 C°/min. The weight increase curve showed a maximum of ca 30 wt% at around 750°?C and then gradually decreased to ca 12 wt% at 1000°C. This would be caused by the formation of TiS2 followed by the decomposition ofTiS2 to lower sulfides, such as Tit.0.8S2 and Ti3S4. From the comparison of the sulfurization of TiO2 nanoparticles with that of anatase, rutile and Ti(OH)4, it was found that TiO2 nanoparticles showed a similar behavior to that of Ti(OH)4.

Jan 1, 2003

By D J. McDougall

Due to changes in the solid-state conditions of minerals in the rocks surrounding hydrothermal, contact meta-somatic or metamorphosed ore deposits, positive or negative thermoluminescent anomalies may be found in their vicinity. Several types of equipment which can be used for both quantitative and semi-quantitative measurements of the emission are discussed and compared. Methods of selecting, preparing and testing samples to ensure reproducible results are outlined, along with the kind of data which can be obtained from different types of equipment. The normal thermoluminescence of rock-forming min~ erals in the common rock types is noted, and variations in the solid-state conditions in the wall rocks which will cause marked increases or decreases of true thermoluminescence are outlined, as well as the thermolum-nescence-like emissions which are present in the vicinity of ore deposits. Introduction T HERMOLUMINESCENCE occurs when certain crystalline materials are heated to temperatures ranging between 180' and 400°C. The light emission can be ascribed to the release of electrons metastably trapped within the crystal lattice, with peak emissions taking place at temperatures which are more or less specific for a particular set of traps; the area under

Jan 1, 1965