Search Documents

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuO0.5) increased with increasing slag basicity, defined by XCao/Xsio2 The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

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 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 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 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 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 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

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 Douglas M. Matson, Rongbiao Gu, Christopher San Marchi, Anil Saigal

"Hydrogen embrittles most structural metals, although the form and magnitude of embrittlement depends on the source of the hydrogen as well as the stress in the metal. Hydrogen fuel cell systems typically store gaseous hydrogen fuel at high-pressure, which provides both a source of hydrogen and high stresses in the containment materials. Understanding and measuring the effects of hydrogen on the mechanical properties of common structural metals, especially fatigue properties, is important for safe, long-term operation of such systems. This work explores the use of thermography to efficiently and quantitatively evaluate hydrogen-assisted fatigue of type 304 austenitic stainless steel. In particular, thermographic analysis was used with rotating-beam fatigue testing and shown to provide repeatable results which are in general independent of test cycle frequency while reducing test times by several orders of magnitude. The effects of hydrogen were studied by thermally precharging fatigue test specimens in gaseous hydrogen prior to thermography-assisted fatigue testing and then compared to testing of non-charged specimens. Hydrogen-precharging increased the strength of this type 304 austenitic stainless steel and increased the fatigue life by a factor of about 50-100.IntroductionThe world is facing a severe energy and environmental challenge: how to provide competitive and clean energy for its citizens in light of an escalating global energy demand and concerns over energy supply security, climate change and local air pollution. As a carbon-free energy carrier, hydrogen provides a promising vector for storing and distributing renewable energy. Hydrogen is an important industrial gas that is used extensively in many industries. However, with growing demand for clean energy, hydrogen fuel cell systems are being developed for use in consumer products, such as fuel cell vehicles, which changes the landscape for safe design of high-pressure gaseous hydrogen systems."

Jan 1, 2012

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 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 &apos;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 J. F. Elliott

The thermodynamic behavior of sulfur and oxygen in copper matte has been measured by equilibration of the melt 00 a gas consisting of CO, SO2 and Ar. The oxygen potential ranges from 10-9 to 10-7 and that for sulfur from 10-4 to 10-2 atm. The work is a continuation of the earlier study by Luraschi and Elliott in our laboratory. A model has been developed that permits extra-polation of the results to ascertain compositions of the matte that are saturated with various oxides of iron.

Jan 1, 1983