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By Xiao Yang

Calcium oxide is one of the major fluxing agents used for steel refining. Because unreacted CaO remains in slag in most cases, discharged slag is difficult to be recycled smoothly. With the growth of environmental concerns, improving utilization efficiency of CaO is required to reduce the amount of discharged slag and energy consumption. The authors have reported a resource and energy-saving process by using multi-phase flux for dephosphorization. Reaction behavior of phosphorus in multi-phase CaO–FeOX–SiO2–P2O5 flux system was investigated. Formation mechanism of P2O5-rich phases was clarified at the interface between solid CaO or 2CaO, SiO2 and molten CaO–FeOx–SiO2–P2O5 slag. Phase relationship and thermodynamic properties of 2CaO, SiO2-3CaO, P2O5 solid solution were observed to confirm the condensation of P2O5 in solid phase. Based on these results, reduction of CaO consumption, discharged slag curtailment, and energy-saving effects in the novel refining process by using multi-phase flux were discussed.

By Mark R. Jolly, Jean-Christophe Gebelin, Aleksander Cendrowicz

"Injection of wax patterns is the first stage of the multi-stage process of investment casting. The quality of the final casting and its dimensional accuracy is highly dependent on this stage of the process. Pattern waxes used in the industry behave in a complex visco-elastic-plastic manner. The modelling of such material behaviour is therefore not simple.In this paper a number of configurations of die will be shown in which the injection of the wax has been carried out for a range of processing conditions. Some of the dies are transparent and the movements of wax front observed can be compared with those predicted by simulation. Surface defects in final components will also be shown and compared with the location predicted by simulation software. Some discussion will be presented on the limitations of the software used and the time-scales achieved for practical use as a design tool within the foundry environment. IntroductionThis paper presents the research activities carried out at the University of Birmingham on the modelling and prediction of the behaviour of industrial investment casting waxes during the injection of wax patterns. These research activities are done in the context of a more global study of the fundamental aspects of the investment casting process, the FOCAST project. Regarding the wax injection process, the aim of the project is to achieve a better understanding of the key factors that will lead to better castings. The filling of the die during the injection has been studied. Some other phenomena such as shrinkage/warpage or creep under residual stresses are also studied, but not presented here. Two commercial investment casting waxes have been characterised in order to model their behaviour and predict mould filling and subsequent defects.This paper will present the models that have been used in our work, the simulation packages used, the experiments carried out to validate the modelling and exhibit the defects due to bad filling, and finally the numerical simulation results."

Jan 1, 2001

By Robert E. Moore

Renewed interest in olivine refractories has led to efforts to characterize them employing modern techniques of experimentation and data analysis. Initial studies have focused on determination of physical and thermophysical properties. Special equipment for the determination of thermal shock resistance and creep behavior have been constructed. Optimal compositions for maximizing various properties are being identified using appropriate statistical techniques. The overall goal is to develop response surfaces for each of a selected group of engineering design and use properties. Development of ?olivine Refractories? in the United States The term "olivine refractories" is used here because it does appear that domestic deposits of this rock will be the focus of renewed interest and "olivinell is the preferred term in this country. There are extensive deposits of high quality olivines extending through parts of Georgia. North Carolina and in the state of Washington. The eastern olivines are much more localized and extensively altered compared to the western materials. The Washington olivines exist as massive rock deposits in the Twin Sisters mountain area northeast of Seattle and their inaccessi-bility has slowed efforts to develop them. The North Carolina olivines have been used in steel plant applications since the 1930's. Geologists use the term "olivine" to describe assemblages of ortho-silicates. 2RO.SiO2, wherein the RO may be MgO. FeO. MnO. etc. When the RO consists essentlally of MgO and FeO. the material is called dunite and. as such, is synonymous with "refractory olivine." Refractory olivines utilizing North Carolina materials were developed for brick products by Birch and Harvey in this country around the mid-1930's. (I) Their work was completely independent of that of V. M. Goldschmidt and co-workers who used massive dunites located in Denmark. (2) These deposits are currently being mined by A/S Olivine of Denmark for the manufacture of a rather complete line of brick shapes for use in steel-plant. glassplant. and cement kiln applications. Birch and Goldschmidt

Jan 1, 1982

By Thomas F. Nederpel

The production of zinc and zinc-aluminum coated strip can be reasonably accomplished on a single operating unit. However, if the hot dip coating line is equip d with only one mo 7 ten metal holding furnace, it is necessary to transfer liquid metal of different chemistries and reintroduce virgin material to obtain the 18" necessary balance of elements in the bath. Dofasco produces Galvanize and Galvalume on a coating line with a sin le liquid metal furnace and has developed not only an efficient liquid metal trans& system but also an effective means of reutilizing the zinc-aluminum mixtures without detrimental quality affects.

Jan 1, 1992

By Liya Bochkareva, David Hui, Sergey Eremeev, Maksim Kireitseu, Igor Nedavniy

The principal goal of the present paper is to demonstrate an application of modern software engineering tools for modeling virtual reality and molecular dynamics of novel nanocomposites. The main technical components of presented system are I) software and nanoengineering tools for modeling of virtual reality, molecular dynamic and 30 video images of novel diamcindscontaining nanocomposites and 2) Problem tracking system to be used during modeling of virtual reality. A computational scheme and software, which utilizes neural networks and/or Microsoft. Net technique was developed to predict properties of nano-structured materials and optimization and control of nano-devices. Developed software and IT nanoengineering tools can be used by both industrial and private single users. For commercial companies proposed technology may provide better cost-effective alternative to the existing solutions for nanoengineering and modeling their virtual realit. For private users (students, professors, and engineers) proposed technology and IT tools can provide simple and cost-effective solution for nanoengineering while studying, exploring virtual reality and modeling novel nanostructures and its properties leading to an innovation or a discovery. Because of using novel software and methodologies, users can easily operate proposed technologies by available computers and operating systems (Pentium III or IV). In addition, users can upgrade it by their own self-written models, if necessary. The proposed technologies could replace or be used along with technologies for modeling such as 30 max studio and others.

Jan 1, 2004

By J. M. Casas

This work presents the development of an ionic equilibrium model and its use to simulate the distribution and concentration of chemical species (speciation) in sulfuric acid - cupric sulfate solutions in the 0-2 pH range, 0.1-10 gpl copper concentration range and 15-45°C temperature range. The model consists of a set of equations which represent the equilibrium relationships for the ionic reactions and the mass balances for the components present in the system. The effect of ionic strength was taken into account by correcting the equilibrium constant in concentrated solutions. Several species can be formed at different pH and temperature values, the principal being: HSO-4, SO42-, CuSO4(aq), Cu2+, and H+ in order of increasing solution acidity. Simulations show that concentrations are highly dependent on pH. The sulfuric acid speciates mainly as bisulfate ion (HS0-4) and hydrogen ion (H+) at pH values lower than 1. The model presented in this work can be applied to predict and analyze the solution composition in electrolytic copper processes such as electrowinning, electrorefining and electrodialysis, as well as the purification of various industrial solutions.

Jan 1, 1999

By Von L. Richards

Rapid Freeze Prototyping (RFP) is a novel solid freeform fabrication technology that creates parts by depositing water droplets and freezing them rapidly to form layers. An investigation into the smallest thickness that can be achieved by the RFP process was conducted. The factors that could significantly affect the thickness of the part built by this process including substrate temperature, volumetric feed rate, table velocity, nozzle frequency, nozzle standoff distance, and head pressure were considered. A shell building technique for use with the RFP system has been developed. Thin wall ice patterns have been invested using production shell building techniques and an alcohol-based slurry. The finished shells were quantitatively evaluated by inspecting their total shell thickness, mold cavity dimensional reproducibility, and shell strength. Pattern loss is influenced by not only the alcohol / water interaction but also the starting thickness as it relates to thermal mass.

Jan 1, 2008

By D. M. Hausen

Multiple drill sections through many of the numerous breccia pipes in the American Eagle copper deposit at Copper Creek, Arizona, have been evaluated by means of alteration and geochemical data. Contoured plots indicate vertically plunging, concentric, cylindrical shells of alteration and mineralized rock that are similar in structure, geometry, magnitude and petrology to the San Manuel-Kalamazoo Deposit, located about 14 miles to the southwest. Both deposits are similar in dimension and consist of multiple, irregular, rod-shaped injections of porphyry into a granodiorite host. Analogous to the San Manuel-Kalamazoo Deposit, most of the porphyry plugs are oriented parallel to the cylindrical axis of the "ore shell". A continuously mineralized, elliptical shell, inferred from deep drilling, is capped by a flatter zone of copper mineralization. Above this flat zone, copper-bearing fluids were channeled upward along conduits that correspond with quartz-sericite "breccia pipes". At depth, zones of sericite and K-feldspar alteration products exhibit conformable relationships with the copper deposition. A "bullet-shaped" ore shell, with a nearly vertical axis, is proposed to explain the conformable zones of altered and mineralized rock. The "nose" or top of the "bullet" is 1800 to 2300 feet below the surface, and structurally controlled in part by steeply dipping Hi and ENE faults. If correct, this model suggests that the vertical ore shell may extend to great depth.

Jan 1, 1988

By Laurent Cohen

Since the 1970s, Solvent Extraction (SX) in hydrometallurgical processes has been a key enabling technology in the production of high-purity metals. Examples include copper, rare earth oxides, uranium, cobalt and nickel. Notwithstanding incremental improvements in extractant formulations, few breakthroughs can be recounted in this industry outside of the initial amine-, oxime- or phosphine-based reagent chemistries. However, the advent of lithium-ion batteries and their stringent requirements for critical materials (lithium, cobalt and nickel) offer new challenges and opportunities for SX. Solvay recently introduced a new extractant for lithium, CYANEX® 936, and developed unique modeling software capabilities in cobalt/nickel separation using CYANEX® 272, zinc SX using DEHPA® and rare earth separations using CYANEX® 572. This paper discusses trends in SX and provides insight on processing of critical materials essential to energy sources. It also summarizes the technical and economic benefits based on extractant selection and advances in modeling.

By Brian Cochran, C. Edward Eckert

"EXECUTIVE SUMMARYINTRODUCTIONThe commercial incentives for using molten aluminum in casting operations are numerous and substantial. Although these incentives apply broadly to both shape castings (foundry) operations and wrought alloy production, the merit of a particular motive is indeed downstream processing sensitive. Melting cost reduction is a universal incentive that impacts on essentially all aluminum products. At a natural gas burner cost of $4.50 per therm, for example, the reverberatory furnace energy cost is at least $0.01 per pound of aluminum melted, exclusive of melt loss, fixed costs, and other expenses. The Aluminum Statistical Review' cited 3.188 million metric tons of secondary aluminum that was recovered by the industry in 1995. This represents a re-melt energy cost of over $70 million. Other incentives to use molten secondary aluminum include throughput enhancement, metal chemistry assurances, environmental considerations, and the avoidance of an in-house scrap processing operation.A traditional disincentive to use molten secondary aluminum is metal quality. If a particular secondary processing operation was successful in achieving and preserving an acceptable metal quality level prior to shipment, the subsequent metal transfer and ladle delivery events would frequently obviate these efforts. For example, a metal superheat on the order of several hundred degrees is required for an unheated transfer ladle to travel 3 to 4 hours to a customer location. The rate of the y-alumina formation reaction approximately doubles for every 120°F increase in temperature, therefore, the effect of excess superheat on melt loss and metal quality is considerable. Linear oxidation reactions, such as magnesia formation in magnesium containing alloys, are influenced to an even greater extent by temperature.The typical quality detractor events are:"

Jan 1, 2000

By T. B. Braun

Cathode contamination is the principal factor affecting the quality of electrorefined copper. It is commonly accepted that annealability is unfavorably affected by the following elements, in decreasing order of adverse effect: tellurium, selenium, bismuth, antimony, and arsenic. Silver in cathodes has importance as it represents a nonrecoverable loss of silver to the refinery. Mechanisms for the contamination of cathodes by these elements are examined and the effect of operating variables on contamination, including anode composition, electrolyte composition, electrolyte temperature, addition agent practice, and electrolyte discard rate, are discussed.

Jan 1, 1976

By Kazusuke Sato, Takahiro Uno, Koji Hoshino

"A novel Ni coating technique of Ni(OH)2 powders was developed to improve the positive-electrode performance· of the Ni-MH batteries. It was found out that Ni(OH)2 powder was reduced by N2H4 without any catalysts in an alkaline - solution at high temperatures. In result of observation of pH and potential changes in the solution during the reaction, it was found that the reduced species was HNio2- ion dissociated from Ni(OH)2 in the alkaline solution. The molar fraction of reduced Ni of the Ni(OH)2 was increased in proportion to the amount of added N2H4. At the small Ni fraction, a porous Ni layer was formed on the surface of Ni(OH)2 powder. Open cell tests were carried out with the paste type electrodes made of either the Ni coated Ni(OH)2 powder or non-coat powder, and cell performances were compared. In result, it was found that the Ni coating technique is effective on improvement in the utilization of Ni(OH); as a positive-electrode active material under high current densities.IntroductionNi-MH rechargeable battery is generally used for the power source of portable machines and electric vehicles because of its good performance at high energy density and. long term cyclical life as well as cleanness and good safety. Cell component materials have been improved respectively, and as concerns ·the positive-electrode reducing 'the internal resistance is a principal problem to improve the discharging performance at higher current densities.In recent years, improved Ni(OH)2 powders coated with conductive materials as NI. or CoOOH have been developed for the· positive-electrode active materials in order to· reduce the internal resistance of the electrode1)· 2) The Ni coated Ni(OH)2, however, is costly because it is fabricated by .the -non-electrode plate technique which needs a expensive precious ·metal catalyst as PdC12We found that Ni(OH)2 powder was reduced by N2H4 without any cryatalysts in an alkaline solution at high temperatures. After the treatment, Ni(OH)2 powder become gray color like Ni powder from light-green color; and. turned into a magnetic. In this study, the mechanism of the -reducing reaction was investigated to apply the reactions .to a novel Ni coating technique of Ni(OH)2 powders, · and the performance of the Ni coated Ni(OH)2 powder obtained by the reducing process was evaluated as an -positive-electrode active material of Ni-MH batteries."

Jan 1, 2000

By Dongping Duan, Hongliang Han, Li Zhong, Siming Chen, E Zhou

In this study, physical, chemical and microscopic characteristics of Celestine were investigated firstly. Based on which, the thermodynamic analysis of Celestine reduction was discussed. And the experiments of Celestine carbon-containing pellets used in rotary hearth furnace process were studied. The results showed that it is feasible to deal with Celestine by rotary hearth furnace direct reduction process. When the temperature is 1200°C, C/O ratio is 0.8 and holding times is 20min, the conversion rate of SrSO4 in Celestine is above 95%, the utilization rate of Celestine is nearly 100%. This study can provide theoretical and technical basis on economical and rational use of Celestine.

Jan 1, 2016

By Alexandra Anderson

A computational fluid dynamic (CFD) model has been developed using ANSYS Fluent 17.0 to help identify areas of high wear within the refractory lining of a secondary lead reverberatory furnace. Once a base case simulation was validated using data from an operational furnace, areas of potentially high refractory wear were determined through the calculation of the temperature and velocity distributions within the furnace and on the hot face of the refractory lining. The CFD model was used to assess whether the predicted areas of high refractory wear could be minimized through changes burden geometry. The results showed that shape of the burden geometry greatly affected the overall flow patterns and heat transfer within the furnace.

By Ibrahim Yusufoglu, Ahmet Orkun Kalpakli, Cem Kahruman, Sedat Ilhan

"The effects of oxalic acid concentration, temperature, stirring rate and particle size on the dissolution rate of synthetically prepared calcium molybdate were investigated. Dissolution of calcium molybdate in oxalic acid solutions takes place as a series - parallel type reaction. In the first reaction step, which proceeds according to the ""Langmuir - Hinshelwood Mechanism"", calcium aqua oxalato molybdate is formed as a complex chelate intermediate product. In the second reaction step, molybdic acid is formed during the slow hydrolysis of calcium aqua oxalato molybdate, and it reacts rapidly with oxalic acid to form the polymeric hydrogen oxalate dimolybdate chelate as an end product. Activation energies were calculated as 41.4 and 49.9 kJ mol-1 for the first and zero order reactions. The fractional conversion versus time relationship can be given by the following equation.IntroductionMolybdenum is used widely in electric-electronic, metal working, aerospace and aeronautic, nuclear, glass and petrochemical industries because of its high melting temperature and resistance against chemical effects. However, the largest molybdenum consumers are the iron-steel and super alloy industries where molybdenum is used as an alloying element. Industrially important molybdenum minerals are limited to molybdenite (M0S2), powellite (CaMo04) and wulfenite (PbMo04), which are considered as primary molybdenum resources. Secondary molybdenum resources are spent catalysts and scrap [1-4].Molybdenum has been produced by pyrometallurgical processes in the past. Since it is possible to process low grade molybdenum ores and industrial wastes by hydrometallurgical processes, which are more environmentally friendly than pyrometallurgical processes, the importance of the use of hydrometallurgical processes has increased in the molybdenum production industry."

Jan 1, 2012

By Yeliz Demiraya, Onuralp Yucelb

"Production of strontium metal from its oxide was studied under the pressure of 1-5 mbar by methalothermic process. SrO with 99 % purity was used in the experiments. Effects of Al powder addition (100, 200, 300 % of stoichiometric ratio) and time were investigated on recovering of metallic strontium. Effects of BaO addition (100 %, 200 %, 300 %) was also investigated. The final residues were examined for their chemical composition. XRD, AAS and Flame Photometer were used for chemical analysis. More than 96 % of strontium metal recovery can be obtained.IntroductionStrontium is an element which is used in many advanced technology applications. Barium strontium titanat, strontium bismuth titanat, and strontium bismuth tantalat thin films are promising materials in ferroelectric and Schottky-based microelectronics technologies, especially for memory applications. Physical vapor deposition (PVD) techniques as magnetron sputtering, thermal evaporation and molecular beam epitaxy (MBE) are the most widely used methods for growth of these thin films [1-3]. In these techniques high-purity of Sr metal is used as evaporation sources and sputtering targets. Furthermore, metallic strontium is used as a ""getter"" in electron tubes, and as an alloying elements in aluminum alloys [4].The most used Sr compound is SrCO3 and widespread process used in production of SrCO3 is the hydrometallurgical carbonation of celestite. Although there are considerable amount of Selestite reserves, SrCO3 and strontinum metal are not being produced in Turkey, yet [5].Concentrated celestite (SrSO4) is conversed to SrCO3 in carbonate media. Black ash and direct conversion processes are currently used methods. There are many satisfactory studies about hydrometallurgical carbonation of celestite and decomposition of SrCO3 [6, 7]. Since strontium metal is produced from it’s oxide (SrO), SrCO3 needs to be decomposed to SrO."

Jan 1, 2011

By Shadia J. Ikhmayies

"Cadmium telluride (CdTe) is a very interesting material that has many applications. Thin films of p-type CdTe can be used as the absorber layer in the heterojunction CdS/CdTe thin film solar cells in which n-type cadmium sulfide (CdS) works as the window layer. A review of the photoluminescence (PL) spectra ofp-type CdTe thin films prepared by different techniques was performed. The presence of defects and impurities such as oxygen and chlorine influence the PL spectrum. Copper and other dopants change the PL spectra and enhance the defects band. Chemical-heat treatment especially with CdCh is known to improve the quality of CdTe thin films because it decreases the Cd vacancies and quenches deep traps, so it enhances the PL signal. A discussion of chemical-heat treatment especially with CdCh, the effect of the ambient atmosphere, and that of the measuring temperature is performed.IntroductionCadmium telluride (CdTe) is a II-VI compound semiconductor that has a cubic zincblende (sphalerite) structure with a lattice constant of 0 A4~11]. Other than all of II -VI semiconductors, CdTe can be made both n- and p-type. But due to self compensation it is not easy to get p-type CdTe films [2]. Polycrystalline CdTe thin films are interesting because they have a lot of applications. Most of the problems associated with the use of these films are attributed to inhomogeneity, self-compensation, and the difficulty of forming a stable and lowresistivity ohmic contact [3]. CdTe technology has been established for a large number of applications, including solar cells, optical and nuclear detectors, and thermal- and radiationimaging devices [3]. At present, the highest demonstrated conversion efficiency for a CdTe based heterojunction (ID), with CdS as a window layer, is 16.5% [4, 5]. CdTe thin films can be prepared by different experimental techniques, such as thermal evaporation [l], electrochemical deposition (ED) [3], close-spaced sublimation (CSS) [3, 4, 6], physical vapor deposition (PVD) [3], chemical molecular beam deposition (CMBD) [7], and close space vapor transport (CSVT) [8].The objective of this paper is to make a review of the photoluminescence (PL) spectra ofp-type CdTe thin films prepared by different techniques and discuss the factors that influence the PL spectra. The composition of the film is very interesting in determining its PL spectrum. Different kinds of defects, impurities and dopants have their finger prints in the PL spectrum. Deposition techniques and deposition parameters such as the deposition temperature and ambient atmosphere also have their influence. Heat and chemical treatments which are known to improve crystallization and reduce the defects change the PL spectrum."

Jan 1, 2013

By Eiichi Kuzuno, Atsushi Shibayama, Toyohisa Fujita, Kazuo Koike, Toshio Miyazaki, Hitoshi Masuda

"A solid sulfur is more useful to recover and store than a sulfuric acid as a by-product in the zinc hydrometallurgy. In this experiment a zin concentrate (sphalerite) was leached with ferric sulfate at about 373 K for 3 to 6 hours. Zinc was leached more than 95%. After a solid-liquid separation, the leached residue contained solid sulfur was obtained. The particles in the residue were dispersed by lignin and the solid sulfur of approximately 85% was recovered as float product by a flotation with frother in the pH 4. The dried float product was heated at 413K for 2 hours. The pure solid sulfur was recovered. On the other hand in the leached liquid a zinc oxide was ·added and ferrous .iron was oxidized to ferric iron by blowing oxygen. This ferric iron was returned to the zinc leached process after solid-liquid separation.IntroductionZinc concentrate is usually roasted as pretreatment in zinc hydrometallurgy and the produced S02 is changed to sulfuric acid. However, recently in Japan the utilization of sulfuric acid has been limited and it is more costly to store. Instead of producing sulfutic acid the solid sulfur recovery has been examined by direct leaching of zinc_ concentrate in this experiment.In the direct leaching, several kinds of effects have been studied for leaching of sphalerite in ferric sulfate solution. The addition of lignine siilfonate1 • 2) and fine· grinding3) increases the · speed arid leaching fraction of sphalerite. The leaching ratio depends on impurities in sphalerite ores4 • 5). Here, the zinc concentrate is leached ferric sulfate solution under atmospheric pressure at 373K. The solid sulfur in leached residue is separated as float products from other solids by sink-float separation and flotation. The sulfur in float products is purified by evaporation at 413K and recovered."

Jan 1, 2000

By Zhong Juya, Wang Yong, Guo Xueyi, Song Yu, Tian qinghua

"In this work, the flow of zinc in China, 2004, was traced within the STAF model, and the situation of production, consumption and recycling of zinc resources in China were introduced. The SFA is performed on zinc flows during its one year life cycle in detail. The result reveals that China produces and utilizes a large amount of zinc, while the efficiency of renewable zinc resources is still relatively lower. As one of the biggest producer and consumer of zinc in the world, China is facing a severe depletion of zinc resources. How to increase the resource efficiency is a significant issue for zinc industry of China. Based on the result, several advices were proposed in the paper, aiming to contribute important reference information for the industrial metabolism and resource management and recycling of zinc industry in China. IntroductionZinc is one of the important metals in national economic development in China; it has good conductivity and corrosion resistance, with high scalability when heated to 100 ~105_. Zinc is mainly used for galvanized zinc industry, as the coating of steel and various parts, and it has also been applied to the manufacture of brass, bronze and corrosion-resistant alloys, which are widely used in machinery manufacturing, printing, national defense and so on. In addition, zinc compounds are utilized in various fields, for example, ZnO is used for infiltration wood, paper, rubber, paints, etc.; ZnSO4 for leather, ceramics, textiles, medicine, etc.; ZnCl2 for infiltration wood; ZnS2O4 and Zn (HSO2 • CH2O) 2 for the paper and textile bleaching, etc. [1]. The extensive use and consumption of zinc in industrial production and social life promot the rapid development of zinc industry, which made zinc the third largest non-ferrous metals in the world."

Jan 1, 2008

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