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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 C. Basilio

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

Jan 1, 1985

By 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 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 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 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 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

By Charles A. Schacht

"Relining, lining maintenance, and ladle repair can represent a significant cost in steelmaking. Therefore, the objective of all steelmaking shops is to minimize this cost and to maximize the lining life. However, the thermomechanical behaviour of the ladle lining is highly complicated and sometimes misunderstood. The ladle design also has a significant influence on lining life. Other factors which have a direct influence on lining life are the shop lining installation practices and manner in which the ladle is used. The objective of this paper is to provide an understanding of the impact of these factors as related to improving the integrity of the lining and increasing lining life.Fundamentals of Steelmaking Ladle Lining Expansion ForcesNumerous studies have been conducted by the author on steelmaking ladles with molten metal capacities ranging from 110 ton s to 350 tons. The steelmaking ladle typically has a sidewall plate with a slight taper and for analytical purposes can be classified as a cylindrical vessel.A typical ladle is described in Figure I. The ladle sidewall lining usually consists of a working lining and a safety lining. Although the type of refractory used in the working lining varies based on the type of steel produced and other metallurgical requirements, the refractories typically used are: 70% alumina brick; direct bond mag-chrome brick; resin bond dolomite brick; and direct bond dolomite brick. Fireclay brick, high alumina brick, or a similar strength brick is used as the safety lining.Normally, the ladle lining is exposed to a through-thickness temperature gradient and restrained by the ladle sidewall plate, is described in Figure 2. The hot face side of the refractory lining develops a compressive thermal force and the ladle sidewall plate develops an equilibrating tensile force. The radial joints open on the cold side of the working lining as the lining joints have little or no tensile strength. A radial compressive load (P) develops between the working lining and the vessel shell due to the thermal restraint imposed on the lining by the shell. The radial compressive load is transferred from the working lining through the safety lining onto the ladle sidewall. Therefore, the safety lining must have the strength to accommodate the radial compressive load (P)."

Jan 1, 1991

By Paul F. Gnirk, Ralph A. Wagner, Joe L. Ratigan

This thermomechanical analysis used the finite element method to investigate the behavior of crushed salt backfill in a waste disposal room situated in a salt dome repository. The first of two objectives was to determine the transient temperature rise and degree of thermomechanical consolidation that occur in the backfill as a function of drillhole depths. The second objective involved the evaluation of closure due to salt creep of unlined emplacement drillholes and the determination of pressure on steel sleeve liners in the drillholes should liners become necessary for canister retrieval. The retrievability period was considered to extend for 25 years after waste emplacement. The canisters were assumed to contain ten-year old high level waste with a thermal output of 4.3 kW at the time of emplacement.

Jan 1, 1981