Search Documents

By Yoshinao Kobayashi

he removal of oxygen from titanium and zirconium is important for use in application because it significantly affects the mechanical and physical properties such as ductility and toughness. However, thermodynamic properties of oxygen in molten titanium and zirconium have not been clarified and the effective deoxidation process of molten titanium and zirconium has not been established. In this study, the standard Gibbs energy of reaction of oxygen and yttrium in molten titanium and zirconium have been measured by a chemical equilibrium technique. Molten titanium, zirconium, and their alloys with aluminum were equilibrated with a Y2O3, A12O3, or Zr02 pellet in a cold crucible. The results are summarized as follows:

Jan 1, 2000

By Yun Soon Han, Joo Hyun Park

Indium (In) solubility in the FeO-SiO2-Al2O3-5%CaO slag was measured under p(O2)=10¯¹¹ atm at 1573 K to clarify the dissolution mechanism of In in FeO-bearing metallurgical slag. The In solubility increased with increasing oxygen partial pressure, whereas it decreased by increasing the activity of basic oxide, viz. FeO. Thus, a dissolution mechanism of In in the FeO-SiO2- Al2O3-5%CaO slag was described by the following equation. In(s)+1/4O2(g)=(In+)+1/2(o2-) The enthalpy change of the In dissolution reaction was negative, indicating that the dissolution reaction was an exothermic reaction. This is consistent with the above reaction mechanism.

Jan 1, 2014

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

Cospidie (3CaO*2SiO2*CaFe2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel, The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiO2-CaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been deterimed by an electromotive force methods using CaF2 as solid electrolyte and a transpiration method as follows: ^fG° (cuspidine) /kjmol-1 = 5198 + 0.825T (+12) (1313<T/K<1329): EMF method ^fG° (cuspidine) /kjmol-1 = 5178 + 0.813T (+8) (1221<T/K<1469): Transpiration method The chemical potential diagram and constituent activities for the CaO-SiO2-CaF2 System have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

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 (CuOQs) increased with increasing slag basicity, defined by Xcao /XSiO, The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

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 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 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