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By Dinabandhu Ghosh

The stability diagram of the ternary system Ti-C-O is drawn in the present work for four temperatures, 1473 K, 1573 K, 1673 K and 1873 K, showing the stability fields of TiC, Ti, TiO, Ti2O3 and TiO2. An analysis of the system reveals that it is not possible to produce Ti in a carbon-saturated system; instead, the stable product is TiC. However, Ti can be an equilibrium product in a carbon-unsaturated system at prohibitively low values of pCO and pCO2; for example, at 1873 K, these limiting values are: pCO = 10-6.76 atm and pCO2 = 10-13.36 atm, which, when exceeded, produce TiC and TiO respectively. The magnesiothermic reduction is examined through the stability diagram (log pO2 vs. 1/T) of the system Ti-Mg-O, drawn for a number of pMg values, presenting the pairwise stability fields such as Mg(l) + Ti(s), Mg(v) + Ti(s), MgO(s) + Ti(s), etc. The diagram shows that magnesium reduction of TiO to Ti is possible only at T < 1641 K with pMg = 1 atm and only at T < 1569 K with pMg = 0.5 atm. An experimental scheme for Mg vapor reduction of TiO2 is proposed in which an argon stream is passed over a Mg(liquid) evaporator at temperature T1 (say, 1234 K); the resulting Ar-Mg mixture at 1 atm is subsequently flown over a bed of TiO2 at temperature T2. A thermodynamic analysis establishes that complete reduction to Ti is possible and that the best results are obtained when T1 = T2.

Jan 1, 2006

By A. Niedbalska

A technique was developed for low pressure diamond synthesis using a specially prepared glassy carbon. The glassy carbon is produced in the form of solid plates by slow carbonization process of phenol formaldehyde resin interrupted at temperatures of 1273° K, 1073° K, and 923° K. The diamond synthesis is performed using cobalt plates as a catalyst-solvent. Synthesis was carried out at applied pressures of 6.0 and 3.8 GPa and a temperature of 1970° K and 2170° K. The products were analyzed by the x-ray powder dyffraction method and by microprobe to identify the diamond crystallites. The samples were taken from the place of contact between the glassy carbon and the cobalt catalyst. They were separated from the charge by a chemical method. Diamonds of the best form and the largest size were obtained at pressures that were much lower than those used in the traditional graphite method of diamond synthesis.

Jan 1, 1989

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure&apos; stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor&apos; afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Byung-Su Kim

The reaction between calcium sulfate and hydrogen is of interest both as a means of regenerating calcium sulfide as a reductant of sulhr dioxide to elemental sulhr and for producing elemental sulhr from gypsum. This reaction was investigated using a thermogravimetric analysis technique in the absence and presence of nickel catalyst. The reaction temperature was varied between 973 and 1153 K, while the hydrogen partial pressures of 12.9 - 86.1 kPa were utilized. At 1073 K and a hydrogen partial pressure of 86.1 kPa, 60 % of the original calcium sulfate in the absence, and 95 % in the presence, of the nickel catalyst was converted to calcium sulfide in one hour.

Jan 1, 1999

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of the cell at temperatures between 800 and 1100 K was measured. While the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03 V were found. It was difficult to determine temperature dependence of the Emf. The Gibbs energy change for the reaction, 113 Li3N (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be !&apos;J.Go, (LiMgN) = -13.2 (±2.9) kJ/mol. Using thermodynamic information on the binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be !&apos;J.Go f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of the stability region of the LiMgN phase. The diagram was found to be in good agreement with the isothermal phase diagram determined by the alloy equilibration method. Although the obtained data includes large uncertainties, the results provide a better understanding of the thermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By Ramana. G. Reddy, Haoxing Yang

The electrodeposition of zinc from zinc oxide using urea and choline chloride mixture in a molar ratio 2:1 is investigated in different experimental variables, namely, the concentration of added [BMIM]HSO4, temperature, and applied cell voltage. The additive, [BMIM]HSO4, was determined to have beneficial effect on the current efficiency, energy consumed in the process and surface morphology of the deposits. The highest current efficiency (92.6%) and lowest energy consumption (2.92kWh/kg) was obtained for solution with 20mg/mL [BMIM]HSO4. The morphology showed the formation of absorbed additive layer on the cathode at higher concentration of additives. Experiments were conducted at different temperatures between 343K and 388K and at various applied cell voltages between 2.7V to 3.6V to determine the best experimental conditions. By varying temperature, highest current efficiency (91.3%) and lowest energy consumption (2.69 kWh/kg) was obtained at 373K. The electrodeposition process is enhanced between the applied voltage 3.0-3.3V by achieving lower energy consumption (2.75~3.06kWh/kg) and higher current efficiency (88.4~89.7%). SEM images showed grain size is significantly increased in higher applied voltages. While at higher temperatures, it seemed to generate particle growth as clusters at the outer deposit layer.

Jan 1, 2014

By Sumantra Mandal

The hot deformed microstructure of the 15Cr-15Ni-2.2Mo-Ti modified austenitic stainless steel (commonly known as alloy D9) was investigated employing electron backscatter diffraction (EBSD). Hot compression tests were conducted in a Gleeble thermo-mechanical simulator at temperatures of 1173K-1373K (in steps of 100K) with a strain rate of 10 and 100 s-1 to different strains. Various kinds of deformation patterns were observed inside the deformed grains. These were inferred as the development of geometrically necessary boundaries or formation of parallel set of micro-bands. Recrystallized grains were partitioned from the deformed grains employing grain orientation spread approach. Extent of dynamic recrystallization (DRX) was found to be minimal at 1173K. DRX was predominantly found to happen at and above 1273K which increases with increase in strain. DRX nucleation and development mechanisms were discussed with respect to bulging of the parent grains and sub-grain rotation. Special emphasize is given on the role of annealing twins on DRX nucleation and subsequent expansion.

Jan 1, 2009

By Xiaodi Huang, Matthew Andriese, Zheng Zhang, Jiann-Yang Hwang, Zhiwei Peng

"The thermal decomposition and regeneration behaviors of wüstite were investigated by in situ high temperature X-ray diffraction (HT-XRD) under non-isothermal condition at heating rate of 4 K min-1 in vacuum ranging from 294 K to 973 K. Wüstite on heating decomposes to magnetite and iron up to 823 K, above which it exhibits marked tendency to regenerate. Investigation of thermal stability of the reaction system shows that the decomposition proceeds under kinetic reaction control while the regeneration is under thermodynamic control. Kinetics study based on the Coats-Redfern integral approximation method indicates that the decomposition reaction follows a Komatsu-Uemura model-based diffusion-controlled kinetics with activation energy of 32.860 kJ mol-1. The thermodynamics analysis of regeneration reaction demonstrates that wüstite regenerates at lower temperature than stoichiometric ferrous oxide.IntroductionOwing to its importance in preparing various magnetic ceramic/metal nanocompostites or nanocrystals with high values of coercivity for the application as recording media, wüstite (non-stoichiometric ferrous oxide) has been attracting the attention of scientists over a long period [1-6]. The thermal behavior of wüstite was investigated by several researchers and phase transformations due to thermal decomposition and regeneration of wüstite during the heating in a specific temperature range was observed [7-9]. In spite of wüstite being found to dissociate to magnetite and iron at temperatures lower than 848 K and then regenerates at higher temperature, a clear understanding of the reaction mechanisms is clearly lacking [9]."

Jan 1, 2012

By Zhigan Deng

Cooling crystallization was used to separate iron (III) and nickel (II) from acidic sulfate solution produced by leaching of molybdenum-nickel black shale. The effect of K2SO4 concentration, crystallization temperature, solution pH and crystallization time on recovery of nickel (II) and precipitation of iron (III) was investigated, in order to obtain effective separation of nickel and iron. The optimum parameters determined were as follows: 200 g/L K2SO4, 10 °C crystallization temperature, solution pH of 0.5 and 24 h crystallization. Under these conditions, 97.6% nickel (II) was recovered as K2Ni(SO4)2, 6H2O crystals and only 2.0% of the total iron (III) was precipitated. Recrystallization yielded K2Ni(SO4)2, 6H2O crystals with a purity of 98.4%.

By Nobuaki Sato

The electrical conductivity, k, of pure and sodium doped sulfur melts was measured with and without ultrasonic waves at temperatures ranging from 140 to 340&apos;C by the two probe method using an ultra high resistance meter. The k value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it mouutuniocally increased from 10-5 to10-4 A&apos; 1 cm-1 with an increase of the temperature. The addition of the sodium metal to the sulfur melt was found to cause a larger jumping in the K value. The k value increased with the increase of Na proportion in the melt. For a 10mol% Na doped sulfur melt it was as high as max ~30 A 1cm -1 above 180 C under the irradiation of of ultrasconics.

Jan 1, 2003

By J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994

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 Liu Zhonghua

Hydrogen reduction of cobalt sulfide (Co9S8) was experimentally investigated in the temperature range 813-1053 K. The results revealed that the reaction kinetics can be described by the shrinking core mod¬el in chemical control regime at low temperatures, it is of first order with respect to hydrogen concentration, and the reaction activation energy is 67.4 kJ/mol. The SEM second electron images of the samples before and after experiments showed that the swelling of the sample above 973 K is due to the formation of metallic cobalt whiskers.

Jan 1, 1992

By Anjali Talekar

Low temperature heat capacities of pentaerythritol [PE: C(CH2OH)4], pentaglycerine [PG: (CH3)C(CH2OH)3], and 2-amino-2-methyl-1,3-propanediol [AMPL: (NH2)(CH3)C(CH2OH)2]have been determined by adiabatic calorimetry from 3 K to 300 K. To the best of our knowledge, this is the first reported heat capacity measurement below 280 K for PE and AMPL. The Debye temperatures for these organic crystals have also been determined and compared with other alcohol derivatives of neopentane.

Jan 1, 2006

By R. Padilla

A thermogravimetric study has been conducted to follow the decomposition and volatilization of arsenic from enargite concentrate in nitrogen and slightly oxidizing atmospheres. Temperature has a large effect on the rate of volatilization of arsenic. Fractional volatilization of arsenic as high as 98% were obtained in less than 60 min at 650°C in nitrogen atmosphere, while in slightly oxidizing atmosphere the same volatilization could be achieved in 30 min. It was found that arsenic volatilizes as sulfide in nitrogen atmosphere and as 4xture of sulfide and oxide in atmospheres containing 1% oxygen. By using the pore blocking and the first order kinetic models, apparent activation energies of 213 and 200 kJ/mol for the temperature range of 780 - 900 K and 205 and 184 kJ/mol for the temperature range of 900 - 985 K were determined for enargite and copper concentrate, respectively.

Jan 1, 1997

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By Byung-Su Kim

The recovery of elemental sulfur from sulfur dioxide has important implications for coal- burning power plants and nonferrous metal smelters. The thermodynamic analyses showed calcium sulfide to be suitable for recovering elemental sulfur from sulfur dioxide. At the temperatures of 1023 to 1153 K under the sulfur dioxide partial pressures of 5.0 - 60.1 kPa, elemental sulfur from sulfur dioxide was recovered by its reaction with calcium sulfide. The kinetics of this reaction were measured at the same conditions using a thermogravimetric analysis technique. This reaction scheme would be attractive if the coproduct calcium sulfate can be reduced to regenerate calcium sulfide. This is the topic of another paper. At 1073 K under the sulfur dioxide partial pressure of 25.8 kPa, 48 % of the original calcium sulfide was converted to calcium sulfate in an hour. Under the same conditions, 55 % of the regenerated calcium sulfide were converted to calcium sulfate in an hour even after third regeneration.

Jan 1, 1999

By Jie Li, Shu Yang, Zhongliang Tian, Xun Hu, Yanqing Lai, Shaolong Ye

The electrolyte with high solubility for Sc2O3 is very important to realize the preparation of Al-Sc master alloy by the molten salt electrolysis. The solubility of Sc2O3 in K3AlF6- Na3AlF6-AlF3 melts is determined with an isothermal saturation method. The effects of KR (ratio of K3AlF6 to K3AlF6+Na3AlF6), the concentration of Al2O3 and the temperature on the solubility of Sc2O3 are also investigated. The results indicate that the solubility of Sc2O3 in K3AlF6-Na3AlF6-AlF3 melts increases and then decreases with KR increasing. The solubility of Sc2O3 is 8.698 wt.% in (K3AlF6-Na3AlF6)(KR25%)-18 wt.%AlF3 melts at 940℃. The effect of temperature on the solubility is little, and the values are 8.575 wt.% and 8.762 wt.% respectively when the temperatures are 930℃ and 960℃. The solubility decreases from 8.809 wt.% to 7.058 wt.% as the concentration of Al2O3 increases from 1.5 wt.% to 5.0 wt.% at 950℃.

Jan 1, 2015

By Yang Cui

The partition ratios of lead and antimony between liquid copper and MgO saturated Cu2O-CaO-SiO2 flux and their removal rate by using CuCl-based flux were measured between 1423 K and 1573 K. For Cu2O-CaO-MgOsatd. system, the partition ratio of Pb was not affected by the CaO content at 1573 K, while that of Sb increased with increasing CaO content. The maximum value was 160 at the CaO content of 15.4 mass%. For Cu2O-CaO-SiO2-MgOsatd. system, two liquid phases of calcium silicate rich phase and Cu2O rich phase were observed at 1573 K. The partition ratios of Pb and Sb between calcium silicate phase and liquid copper depended on the (mass%CaO)/(mass%SiO2) ratio. When the (mass%CaO)/(mass%SiO2) ratio increased, the partition ratio of Pb decreased and that of Sb increased. For CuCl flux, the removal of Pb from liquid copper at 1473 K was possible, and a relatively low concentration could be reached. Moreover, most of lead as metal chloride vaporized from flux. For the removal of antimony from liquid copper at 1423 K, it was difficult by CuCl flux, and the removal ratio was approximately 20% for 75 minutes. However, the addition of CaO or Na2CO3 to CuCl flux was relatively effective to remove antimony, and the concentration of antimony reached a relatively low value after 15 minutes by using CuCl-CaO or CuCl-Na2CO3fluxes. Moreover, a small part of antimony as chloride vaporized from flux.

Jan 1, 2006