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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 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 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 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 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 T. Yegulalp, R. Farrauto, A. Belova, M. Castaldi

Calcium oxide, with its ability to capture and store carbon dioxide, is emerging to become an important tool in carbon management. Calcium oxide can be used reversibly to capture carbon dioxide in situ and then be regenerated to produce a pure stream of carbon dioxide ready for sequestration; the Zero Emission Coal Alliance technology utilizes this property of calcium oxide to generate emissions-free electric power from coal. The reaction of calcium oxide with carbon dioxide resulting in thermodynamically stable carbonate is well understood; however, the efficiency of this reaction is limited by the diffusion of gases through bulk calcium oxide and through a layer of carbonate formed on the surface. In addition, the regeneration of calcium oxide is an endothermic reaction and is favored at high temperatures. The purpose of this paper is twofold: first, to address the diffusion limitation, a thin layer of calcium oxide, supported on a high surface area material, is studied thermogravimetrically to demonstrate the physical adsorption of carbon dioxide on calcium oxide. The adsorption is to take place at temperatures lower than required to form calcium carbonate.

Jan 1, 2007

By Yongqi Sun, Zuotai Zhang

Our study investigated the influence of P2O5 and B2O3 on the viscosity and crystallization behavior of Ti-bearing blast furnace (Ti-BF) slags for the purpose of Ti extraction. The investigation of the crystallization behaviors were carried out using a single hot thermocouple technique (SHTT) and the viscosity was obtained by rotating cylinder method. For the viscosity, the results showed that P2O5 substantially increased the slag viscosity. P2O5 is a network-forming oxide, which increased the degree of polymerization of slags and accordingly increased the slag viscosity. However, both of slag viscosity and apparent activation energy for viscous flow remarkably decreased with B2O3 addition. As a typical network forming oxide, B2O3 was introduced into the network and existed dominantly as 2-D structure, BO3 triangular, which caused a simpler structure and a decreasing slag viscosity. As for the crystallization behaviors of Ti-BF slags, both P2O5 and B2O3 enhanced the crystallization trend of rod-shape rutile and suppressed the crystallization trend of dendrite CaTiO3. Therefore the added P2O5 and B2O3 caused the primary phase change from CaTiO3 to rutile. Additionally, it was found that the rod-shape rutile showed a 1-D growth, whereas the dendrite CaTiO3 showed a 3-D growth style.

Jan 1, 2015

By D R. L Vedoy, L Botha, S P. Gumfekar, J B. P Soares

Most of the known in-place reserves of oil sands are found in Canada. These oil sands ores are mined using various processes to extract bitumen. The by-product slurry resulting from the extraction process, known as tailings, is discharged into tailings ponds. Fine kaolin clays are an important ingredient of the tailings because they remain suspended in water for many years. Current polymeric flocculation/dewatering technologies use acrylamide-based polymers such as polyacrylamide (PAM), but sediments produced using PAM-based flocculants hold considerable amounts of water due to the formation of loosely-packed flocs. Anionic polymers are better flocculants due to bridging and the charge-neutralisation mechanism. In this paper, we will compare the synthesis of two flocculants: thermosensitive, anionic flocculants and thermosensitive, hydrophobically modified anionic flocculants. The first flocculant is a copolymer of acrylic acid (AA) and N-isopropyl acrylamide (NIPAM), in which AA is the anionic monomer. The second flocculant is a copolymer of NIPAM, AA and the hydrophobic monomer N-tert-butyl acrylamide. We evaluated the dewatering efficiency of 2 wt per cent kaolin using both flocculants by comparing settling rates at different flocculant dosages, charge neutralisation ability and supernatant clarity. To better understand floc formation, we measured the floc size formed by both flocculants at different flocculant dosages. We propose that the hydrophobic monomer in the terpolymer flocculant helps expel water out of flocs, ultimately decreasing the water content in the sediments.CITATION:Gumfekar, S P, Vedoy, D R L, Botha, L and Soares, J B P, 2015. Thermosensitive, hydrophobically modified anionic flocculants for dewatering kaolin clays, in Proceedings Tailings and Mine Waste Management for the 21st Century , pp 45–50 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Jul 27, 2015

By H. Wu, V. Izaxon

Intensive ventilation is required during the excavation of a mine opening and the subsequent exploitation of the mineral resources. The exchange of heat between the ventilation air and the rock mass has a major influence on the thermal regime of a mine, especially in the initial segment of the airway. In frozen ground, heat flow into the rock mass from the ventilation air can result in the eventual thawing of the permafrost, which can result in roof-rock instability. This paper presents a mathematical analysis of the dispersion process of ventilation-induced heat by thermosyphons placed on the surface of the mine. The principal uses of thermosyphons in the Arctic are to reduce the ground temperature to prevent potentially unstable permafrost from thawing and to increase the bearing strength of the material. The mathematical model of the physical problem, generally known as "the Stephan problem," takes into account the varying thermo-physical properties of air and the frozen and thawed rock mass, the thermal properties of the freeing fluid in the thermosyphons and the phase change of water. Finite-difference techniques were employed to determine the temperature isotherms around the thermosyphons. It was found that two rows of thermosyphons on a 10- x 10-m grid provide an acceptable design spacing for reducing the ground temperature around the mine airway.

Jan 1, 1997

By D. P. Patil, B. K. Parekh

Water is the mainstay for beneficiation of fine size coal and minerals; however, it is also the least desirable constituent in the final product. The basic concept of the novel process described in this paper is based on the differential surface heat conduction/ absorption capacity of individual particles, which differs for different species of minerals. When a mixture of fine material is exposed to a radiant energy source, the various solids present in the mixture will absorb heat energy depending on their heat-conducting properties and there will be a difference in the surface temperature of the particles. When this differentially heated solid mixture is placed on a moving belt, which is coated with a low temperature melting resin, the hotter component of the mixture will stick to the belt and relatively cooler particles will stay free on the belt and fall off at the end of the belt run. Experiments were conducted with pyrite, coal, and quartz of 6 × 18 mesh particle size. The goal of the test program was to find the optimum conditions at which there exists a required temperature difference between minerals and coal particles by controlling the operating system variables. Preliminary tests results showed that there is a potential for separating mineral matter from coal using the thermo-adhesive separation technique.

Jan 6, 2022

ABSTRACTFor the binary system copper-lead two relationsEquation 1andEquation 2have been derived for the activities of copper and lead at compositions and absolute temperatures within the liquid region of the phase diagram.These relations give, with greater accuracy than is given by previously published relations, the activity-composition temperature variations for all regions of the phase diagram of interest to metallurgists.These relations are essentially simple forms of the Margules equations but with linear temperature dependence applied to their coefficients. This has been done in such a manner that a phase diagram obtained from these relations agrees well with the data available for this system. The methods of obtaining the relations and constructing a phase diagram from them are both given in detail. The enthalpies and entropies of mixing are compared with those derived by other methods.

Jan 1, 1971

By V. L. Mitsopoulos

This paper provides a summary of tailings disposal techniques and the improvements that have been made through the introduction of thickened tailings disposal. The general properties and characteristics of thickened tailings are described, as is a design process for selecting appropriate technologies for thickening, pumping, transporting and storing tailings. The factors affecting the selection of an appropriate disposal site and operational considerations for the effective utilisation of tailings storage areas are also documented.

Jan 1, 2006

By T. Wisdom, D. Romo, G. Seale, R. Jansen

Thickening remains relatively misunderstood since it is typically near the end of the process and not directly involved in metal recovery. When operating well, thickeners are ignored and left to run independently, the ‘out of sight, out of mind’ phenomena. However, when operating poorly, there is a lack of basic understanding and remedial actions to solve issues are reactionary rather than proactively addressing shortcomings. This series of papers breaks down in sequential order the stepped phases required to gain an appreciation and thorough understanding of the science behind thickeners, and key thickener components, and basic troubleshooting skills. This second paper starts with identifying the different approaches to thickener test work including static and dynamic settling tests followed by high-rate versus paste thickening. Complimentary to test work, the mechanisms surrounding coagulation and flocculation are presented and explained. The basic mechanisms for coagulation and flocculation are discussed to support the different test work approaches and provide the reader with the basic background.

Mar 2, 2022