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By Dhanesh Chandra

Metal carbonyls are of great importance in chemical vapor deposition (CVD), composite materials fabrication, and other near-net shape technologies. Carbonyl CVD application applies to deposition of high-purity metallic/alloy coatings. Vapor pressures of solid Os3(CO)12,Rh6(CO)16, Ru3(CO)12, Ir4(CO)12, Re2(CO)10, Co2(CO)8, Cr(CO)12,, and W(CO)6carbonyls have been measured using gravimetric-torsion effusion system. The vapor pressure data is used for many low and high temperature CVD applications. Interesting decomposition/disproportionation vaporization behavior has been notedfor Rh6(CO)16, Ru3(CO)12 and Co2(CO)8. The vaporization studies of Rh6(CO)16 showed virtually complete decomposition to Rh metal and the measured molecular weight of the effusing gas from the solid Rh6(CO)16 was 27.75 g/mol, close to that of carbon monoxide as compared to 1065.56 g/mol for the value of solid Rh6(CO)16. Electron microscopic characterization, X-ray line broadening results for Rh carbonyl has been performed on the vaporization product. However, Ru3(CO)12, Co2(CO)8 showed very complex behavior. The molecular weights of the vaporizing species have been estimated and the numbers of vaporizing species are proposed. For example, there was partial decomposition of Ru3(CO)12to(approx. 52%) metallic Ru and CO gas during vaporization, as suggested by the difference in the molecular weight of the vaporizing species of 107.58 g/mol compared to the actual value of 639.33 g/mol. The dimer Co2(CO)8 partially disproportionates to tetramer Co4(CO)12, monomer Co(CO)4, and CO gas. Whereas, the Os3(CO)12, Cr(CO)12,, and W(CO)6have shown virtually no disproportionation. The total vapor pressures of all the above-motioned carbonyls, partial pressures of various species, average molecular weights of the effusing gases, equilibrium constants for the vaporization reactions, their enthalpies, entropies, and Gibbs energies will be presented.

Jan 1, 2006

By Marc Verhaege

The effluent under investigation results from a catalic oxidation unit in which paraxylene is oxydised to terephtalic acid. The solution contains cobalt and manganese as their acetates in a concentration range of 0,4 - 1,2 g/I of cobalt and 0,8 - 2,4 g/l of manganese. Before being fed into the main waste stream treatment unit of the plant it is advisable to apply a petreatment step in which both metals are eliminated to a great extent from this effluent. Conventional treatment is done by precipitation of both metals either through pH increment with a base or by adding a suitable reagent producing insoluble species. The aim of this study was to look for a treatment (elimination of both metal species) in which no sludge or precipitate is formed.

Jan 1, 1995

By S. Raghavan

The thermodynamic activities of MgO in the solid solutions that can exist in the system NiO-Mg0-Zn0 are determined by measuring the EMF of the cell: O2 (g), Pt / MgO, MgF2 // MgF2 // x MgO + yNiO + (1-x-y)ZnO / Pt, O2 (g) / MgF2 in the temperature range 1190-1237 K. Equilibrium phases were prepared along the quasi- binary lines MgO/NiO = 0.1765,0.3333, 1.0,3.0 and 5.667 with the ZnO contents being 0.1, 0.2, 0.25, 0.35, 0.5, 0.75 and 0.9. The crystal structures of the phases were identified by X-ray diffraction. Results obtained so far show that a single phase MgO-rich cubic solid solution exists upto 0.2 ZnO content and for compositions above 0.25 ZnO, a second ZnO rich wurtzite phase forms in addition. Activity measurements show that for low MgO and ZnO contents, the MgO activities exhibit ideal to slight positive deviation from ideality and at higher MgO contents, a negative deviation is shown. Further studies are in progress.

Jan 1, 1993

Electrocrystallization studies were conducted in a concentrated acid-copper electrolyte to determine the influence of chloride ions and glue on copper nucleation and on the structure of thin copper layers. Electrochemical experiments allied to SEM and XRD examination were performed to characterize the mechanism of nucleation in the presence of additives at 65°C. Results indicated that most of the copper nucleation from a 83 g dm-3 Cu2+ solution, with 140 g dm-3 of H2SO4 is achieved in a matter of milliseconds, Although the presence of chloride and glue, at the concentration levels tested, does not seem to substantially modify the nucleation mechanism, the morphology, nuclei density and the copper film structure and orientation are changed by the presence of additives and by electrolyte stirring.

Jan 1, 1999

By Carla Lupi

In this work, nickel-cobalt electrodeposition under galvanostatic conditions was investigated. Ni-Co alloy was electrowon from an acid sulphate bath containing 40 g/L Ni and2-8 g/L Co.. The effect of electrolyte composition, current density, temperature, solution pH and presence of buffers such as H3BO3 and (NH4)2SO4 on Co content of the binary alloy has been investigated. In particular, current densities ranging from 180 to 400 A/m2 and temperatures ranging from 27 to 60°C were tested. The composition of Ni-Co alloys may be diversified through the selection of process parameters. The experiments show that the highest cobalt content of the alloy is reached by using a buffer free electrolyte without solution pH control. Though, in these conditions, the most homogeneous, fine and regular deposit morphology is obtained, energy requirements are the highest in tests lasting just two hours.

Jan 1, 2003

By Yamei Han, Jiang Du, Jinhui Peng, Mengbi Fu, Libo Zhang, Zhengfu Zhang

"A continuously pilot synthesis by microwave-heating was used in preparing the cathode material LiNi113Co113Mn11302 for Li-ion battery, which used Ni1/3Co1/3Mn1/3(0H)2 and LizC03 as raw materials. Decomposition of the raw materials and synthesis of LixNi113Co113Mn11302 would be fmished in single roasting process. In addition, using microwave-heating would reduce the reacting time largely. Furthermore, the yield of LixNi1/3Co1/3Mn1/302 synthetized in single roasting process was 50 kg. Meanwhile, the effects of Li:(Ni+Co+Mn) molar radio (Li:(Ni+Co+Mn)=l.06, 1.075, 1.09, 1.15) was studied in this paper. XRD, SEM and EIS were used in characterizing the cathode material. The results showed that the best Li:(Ni+Co+Mn) molar radio was 1.075. It was found that the LiNi113Co113Mn11302 synthetized with Li:(Ni+Co+Mn)=l.075 had homogenous distribution of particles and ideal layered structure. The galvanostatic charge-discharge(O. l C, 2. 75-4.3V, vs. Lt /Li) tests showed that the initial discharge capacity of the LixNi113Co113Mn11302 was 159.5mAh·g-1, and the discharge capacity was 157.6mAh·g·1after10 cycles.IntroductionRecently, as the cobalt was expensive and the restriction of dynamic power, the commercial cathode Li2Co02 which was expensive, toxic, and high pollution had exposed its defects[1·2l. Since T.Ohzuku[3l first reported the layered LiNi113Co113Mn11302, this material had high reversible capacity and caused the attentions of researchers[4l. Its reversible capacity was l 60mAh/g and 200mAh/g in the voltage range of 2.75-4.3V[5-61. But for the present, preparing LiNiwCowMnw02 by traditional had lots of disadvantages, such as the long heating time, the high cost and the volatizing of lithium and so on[7-9l. According to these, traditional prepatation wasn't good for sustainable development and energy conservation."

Jan 1, 2013

By Shengfan Zhou, XUEWEN WANG, Changjun Jiang, Mingyu Wang

In the process of extracting vanadium from stone coal by sulfuric acid leaching - P204 solvent extraction, Fe(III) can accumulate in the organic phase which reduces the extraction of vanadium. In order to eliminate the effects of the accumulation of iron, oxalic acid was used as the stripping agent to strip the Fe(III). The effects of oxalic acid concentration, phase ratio O/A, stripping time and shake velocity on the stripping of Fe(III) were studied. The results showed that the Fe(III) stripping rate can reach beyond 96% at the room temperature with 70g/L oxalic acid using an O/A of 2 at 160 rpm shake velocity for 20min. After 2-stage stripping, the concentration of Fe(III) in organic phase was 0.008g/L.

Jan 1, 2016

By Juliana Gutiérrez-Paredes

Keywords: Slag, chromium oxide, recovery, stainless steel Experimental and theoretical work was performed to estimate the effect of slag basicity and amount of reducing agents on the reduction of chromium oxide from the slag which interacted with molten steel at 1600°C. The slag system contained CaO, MgO, SiO2, CaF2 and Cr2O3 together with Fe-alloys (Fe-Si and Fe-Si-Mg). The CaF2 and MgO contents in the slags were 10 mass % each; Cr2O3 was 25%. The amount of the ferroalloys ranged from 12.5 to 50 g per 100 g of slag. The (CaO+MgO)/SiO2 ratio was held at 1 and 2. The Cr yield was determined using both Fe-alloys as reducing agents. Some estimations were made to determine the theoretical effect of temperature, slag basicity, (CaO+MgO)/SiO2, and amount of reducing agents in the slag on the chromium recovery. The FACT (Facility for the Analysis of Chemical Thermodynamics) computational package is used to determine the equilibrium between the slag and molten steel.

Jan 1, 2005

By Hai-Peng Guo, Lu Jiang, Xiao-Man Yan, Bing Xie, Hong-Yi Li

Traditional, calcium compounds cannot be used in vanadium extraction processing due to the limitation of sodium roasting technology, which results in unsatisfied dephosphorization for vanadium-containing hot metal in converter and thus increasing the dephosphorization burden for subsequent steelmaking. The calcium roasting technology is an alternative for vanadium extraction and allows adding lime into vanadium slag in converter. In the present study, vanadium was leached by soda from roasted vanadium slag with high calcium content. Effects of roasting temperature and time, leaching temperature, Na2CO3 concentration andliquid to solid ratio on vanadium leaching rate were studied. The results show that 94% of vanadium was extracted by roasting the vanadium slag at 950℃ for 2.5h and then leaching in 160g/L Na2CO3 liquid at 95℃ for 1h with liquid to solid ratio of 10:1 ml/g. Impurities of Si and P reacted with calcium and formed insoluble Ca2SiO4 and Ca3(PO4)2 respectively.

Jan 1, 2015

By Jr. Loper, M. H. Kim, H. H. Jo, C. S. Kang, T. S. Song

"An investigation has been conducted to describe the effect of grain refiner (e.g.,Ti) or modifier (e.g., Sr) on the microstructure of an Al-11.3wt%Si alloy produced by the Ohno horizontal continuous casting process using a heated mold so as to obtain directional solidification at high cooling rate of 300 to 2000°C/s. Experimental results demonstrated that the directionality of the primary a grain was promoted by the addition of0.2 to 0.4%Ti or by the addition of0.02%Sr, whereas the addition of0.6%Ti suppressed this directionality. Feathery a grains were promoted by the addition of 0.2%Ti, while these feathery a grains were suppressed when over 0.4%Ti (grain refinement) or when 0.02%Sr was added. The addition of Ti also resulted in increased coarsening of the eutectic Si in these Al-1 l.3wt%Si alloys.IntroductionThe mechanical properties of conventionally cast Al-Si alloys can be enhanced through judicious control of the casting parameters, by the addition of grain refiners (e.g., Ti) and by the addition of eutectic modifiers (e.g., Sr).[1-3] The Ohno continuous casting process[4-5] uses a heated mold (maintained at a temperature above the alloy liquidus temperature) to produce a casting with a mirror surface free of shrinkage defects. The process is especially suitable for the production of high quality and non-deformable rods of small diameter. This study was conducted at investigate the effects of Ti and Sr on the microstructure of Al-1 l .3wt%Si rods cast by the 01).no process."

Jan 1, 1998

By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO Zn(g) + COl. This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction 2Fe2+ + ZnO = 2Fe3+ + Zn(g) or 2FeO + ZnO = Fe2O3 + Zn(g) does not occur at an appreciable rate, as is expected from thermodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide concentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By S. Gopalan, J. D. Milshtein, S. N. Basu

Production of syngas is proposed utilizing the W/W03 redox system and employing a solarpowered two-step thermochemical cycle. Three chemical reactions occur in two chambers. Assisted by a solar concentrator, a high temperature reaction reduces W03 powder to metallic tungsten in both chambers. Subsequently, the temperature in one of the chambers is lowered and H2(g) is produced via re-oxidation of the tungsten powder using steam. The temperature in the other chamber is simultaneously lowered to an intermediate temperature and CO(g) is produced via oxidation of the tungsten powder using C02(g)· The gas streams coming out of the two chambers result in the syngas production. A complete thermodynamic analysis of the system is described. The W/W03 redox cycle offers greater gravimetric fuel productivity compared to previously proposed systems, and the entire cycle can be operated below 1273K.

Jan 1, 2013

By Luciano R. G. Santos

Keywords: biosorption, cadmium, copper, biomass, spent zeolite. The majority of the industrial activities produce some kind of solid wastes. In this work two industrial residues (spent zeolite and wood sawdust) were chemically modified to increase their heavy metals sorption capacities. Manilkara longifolia (a Brazilian plant known as parajú) sawdust was first treated with NaOH and modified with different citric acid concentrations (0.6-1.2 mol/L) at 120°C, for 90 min. Infrared spectroscopy confirmed the presence of carboxylate groups in the wood structure as result of their mixing. Similarly, spent zeolites were also submitted to a chemical treatment (NaOH) to remove carbon deposited during oil cracking and to recover its sorption capacity. Batch experiments carried out at ambient temperature showed that both materials present sorption capacity for copper and cadmium comparable to weak acid ion exchange resins. A maximum of 78 mg-Cd/g and 59.7 mg-Cu/g as well as 29.9 mg-Cd/g and 14.6 mg-Cu/g were observed for the sawdust and the zeolite, respectively. The results were modeled according to the Freundlich and Langmuir equilibrium isotherms and compared with results of other studies.

Jan 1, 2005

By Chen Ya

Layered LiMn0.5Ni0.3Co0.2O2 was prepared from Mn(NO3)2, Ni(NO3)2, Co(NO3)2 and LiOH by co-precipitation and solid state reaction. XRD, C-V and galvanostatic charge-discharge methods were used to examine the structural and electrochemical characteristics. The LiMn0.5Ni0.3Co0.2O2 delivered a high discharge capacity of 167 mAh/g between 2.5 and 4.3 V with excellent cycling stability.

Jan 1, 2006

By Xiang-yang Zhou

Keywords: Low-Grade Dolomite, Low CaO Content, High Specific Surface Area, MgO. A low energy consumption preparation technology of magnesium oxide with low calcium oxide content and high specific surface area from low-grade dolomite has been investigated. The optimum technical conditions for the preparation of magnesium oxide are the followings: dolomite is partially calcined at 750-800° for 2 h; the optimum solid-liquid ratio range in calcined dolomite slurry is 20-30 g?l?1; carbonation temperature, carbon dioxide pressure and end point pH value of carbonation are less than 40°, 0.4-0.6 MPa and 7 respectively during carbonation process; decomposition temperature of Mg(HCO3)2 solution is near 100°; calcination temperature of the precursor (i.e. precipitated basic magnesium carbonate) is less than 850°. More than 90% of magnesium can be extracted by the technology. The MgO product (CaO < 0.38%) with a specific surface area of near 50 m2?g?1 also can be obtained by the technology.

Jan 1, 2005

By Koji Matsubara, Yoshiaki Iguchi, Shoji Hayashi

Iron ore particles of a limonite iron ore were reduced completely with H2 at 1023K to 1273K in a fluidized bed. Then, at 973K, the formed iron was exposed to HrH2S mixtures (sulfur activity, as=0.5) for 3.6ks and carbidized with CO-H2-H2S· mixtures at 0.1 MPa. During the carbidization, the particles of about 150mg were sampled at every 600s interval. The sampled particles were analyzed by XRD and chemical analysis for C and S to evaluate the content of Fe3C, Fe5C2, Fe and free carbon. The reaction extent is defined as fo=Xfc3C +xFc5c2; x is the molar fraction of Fe in Fe3C. The carbidization curves can be fitted very well to -ln(l-f0)=g(pb T)t; g(p; T) is the carbidization rate, i.e. the carburization rate on the pore surface of reduced iron. The rate is found to be nearly proportional to the specific surface area of reduced iron, a P 0 , which decreases with increasing the reduction temperature. The value of a P 0 does not change by the carbidization and the stability of the iron carbide product in the atmosphere increases with the temperature.

Jan 1, 2000

By Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

By Atsushi Shibayama

The aim of this research was to develop a copper recovery process from mine tailings (0.34%Cu) using flotation followed by high-pressure oxidative leaching (HPOL) and solvent extraction. The results of HPOL using the concentrate of mine tailings obtained by flotation under the optimal conditions of the previous study shown that an efficient copper dissolution of 94.4% was achieved in an H2O media, while the copper concentration of PLS reached to be 2.9 g/L. The solvent extraction of PLS obtained from the optimal HPOL showed that 91.3% copper was recovered in stripped solution under the determined optimum conditions, in which the copper concentration achieved to be 44.8 g/L. Finally, a proposed copper recovery process from the concentrate of mine tailings was developed by combination of HPOL and solvent extraction, while a total copper recovery of 86% was achieved.

By Alwin Frei, Aldo Steinfeld, Peter G. Loutzenhiser, Enrico Guglielmini

"Using concentrated solar radiation as the energy source of high-temperature process heat, the carbothermal reductions of Al2O3 to Al and SiO2 to Si were examined thermodynamically and demonstrated experimentally at vacuum pressures. Reducing the system pressure favors Al(g) and Si(g) formation, enabling their vacuum distillation and avoiding contamination by carbides and/or oxycarbides. Exploratory experimentation in a solar reactor was performed with mixtures of charcoal with alumina and silica in the ranges of 1300-2000 K and 1997–2263 K, respectively, at 10-3 bar by direct exposure to concentrated thermal radiation. Distilled samples contained up to 19 wt% of Al in Al-Al2O3 mixtures and 79 wt% of Si in Si-SiO2 mixtures. When the reducing agent is derived from a biomass source, the solar-driven carbothermal processes are CO2 neutral.IntroductionMetallurgical extractive processes for producing Al1-2 from Al2O3 and Si3-6 from SiO2 are characterized by their high specific energy consumption and concomitant emissions. Alternatively, concentrated solar energy can be used as a high-temperature heat source to drive the carbothermal reductions and, thus, avoid greenhouse gas emissions and other pollutants derived from fossil-fuel-based processes7-12. When the reducing agent is biomass charcoal, the solar-driven carbothermal reduction is CO2 neutral. The carbothermal reductions of Al2O3 and SiO2 are represented by the simplified overall stoichiometric reactions:"

Jan 1, 2011