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By Katsunori Yamaguchi

A new technique for the removal of tramp-elements from steel scrap has been required from the viewpoint of saving energy and protection of environment. In order to obtain fundamental information on the removal of copper, tin and zinc from molten iron, the extraction method by using of phase separation in the liquid Fe-Pb-C system was investigated at 1453K A mixture of iron, lead and carbon melted in a carbon crucible separates into two phases of lead and iron containing carbon. The compositions on the miscibility gap in' the Fe-Pb-C system are 95A%Fe-4.5%C-0.l %Pb and 99.9%Pb-0.1 %Fe. The distribution ratios of copper, tin and zinc between the lead and the iron phases, Lx=[masso/uX in molten Pb]/(masso/uX in molten Fe), are 2.2, 2.2 and lA, respectively. Seventy percent of copper and tin from iron scrap can be eliminated with comparable lead addition. Gold, silver and palladium are enriched in the lead rich phase, on the contrary platinum and rhodium are more distributed to the iron rich phase than to the lead phase.

Jan 1, 2003

By G. Barbery

The models for particle composition prediction that have been put forward are limited to simple textures and lead to an independance of grade with respect to particle size in broken ore. A presentation is made of a modification in texture description; binary textures, in which each subeonstituent has its own breakage characteristics are introduced. The calibration of the textural model can be made using heavy liquid separation results. The application to the case of coal is presented. Coal washability data present spe¬cial difficulty due to the distribution in the specific gravity of coal, which must be taken into account. Coal s.g. distribution is taken as a generalized exponential distribution. Model calibration is then possible and is shown to be in good agreement with experimental data.

Jan 1, 1987

By Jing Lin, Yuan Xu, Qingcai Liu, Dengfu Cheng

"Smelting reduction technology has been developed greatly in recent years. But one of the key problems for this technology is about the refractory that used as lining material in the molten bath. Investigation and test shown that corrosion rate of refractory was much higher and the corrosion mechanism was much more complexity in the molten bath of smelting reduction with iron bath than that of the blast furnace and rotary furnace technology [l-5]. The corrosion behavior and corrosion rate of Al2OrC-ZrO2 series refractory in the melt of smelting reduction with iron bath have been studied by rotary immersion and quasi-static immersion test in this paper. The major factors that affect the interaction between the melt and refractory were investigated. The test results shown that the corrosion rate of AI2O 3-C-ZrO2 series refractory decreased with the ZrO2 increasing when ZrO2 content was from 3% to 10%. Ferrous oxides content, relative moving speed between the melt and refractory and temperature of the molten bath were the important factors that affect the corrosion rate. But the ferrous oxides concentration was the most important one. The corrosion rate was increased as a linear relation with the rising of ferrous oxides content of the melt. The corrosion rate in the quasi-static immersion was much less than that of the dynamic immersion (rotary immersion) for the Al2O 3-CZrO2 series refractory in the same testing condition. The corrosion mechanism of Al2OrC-ZrO2 series refractory is: graphite oxidized in advance, then interaction between the constituents of refractory and melt taken place and deteriorate layer of refractory and new compounds were formed, the properties of refractory was changed.IntroductionSmelting reduction with iron bath is a typical technology [3, 4, 6]. The obvious features of the melt for smelting reduction technology with iron bath are much higher ferrous oxides and much more complexity melt composition and structure than that of the blast furnace technology [2, 5-8]. The properties of the melt were changed dynamicilly and constantly in reduction process. On the other hand, the behavior of the melt depends on the activity and the reduction rate of ferrous oxides in the molten bath[9]. Because of the high concentration of ferrous oxides in slag and high reduction rate in the molten bath, the corrosion behavior and corrosion mechanism of the refractory lining by melt are an important factor in development of the technology of smelting reduction with iron bath. Up to now, improving refractory quality to anti-corrosion of melt and developing high quality and long term refractory used as the lining refractory materials in the molten bath of the final reduction furnace are also the most important questions for developing smelting reduction technology."

Jan 1, 2000

By Xiao-hui Fan, Xu-ling Chen, Zhi-yuan Yu1, Guanghui Li, Min Gan, Yun-song Huang, Tao Jiang

Compared with the traditional de-NOx processes by cleaning the waste gas, a new approach for reducing the formation of NOx during sintering process is proposed. Since more than 90vol% of NOx comes from the fuel combustion, the influence of sintering coke breeze pretreated by CO(NH2)2 additive on the NOx emission is researched. As adding CO(NH2)2, the reduction agents (NHi) are generated during the pyrolysis of CO(NH2)2, which reinforce the NOx reduction, And the appropriate content of CO(NH2)2 is 1.0 mass% of coke breeze.

Jan 1, 2015

Reduction of titania and ilmenite ores by Cf4-H2-Ar gas mixture was investigated in a laboratory fixed bed reactor. Titania was reduced to titanium oxycarbide in the temperature range of 12OO-1500°C. At 1400-15000C, the extent of reduction of titania to titanium oxycarbide achieved more than 85% in 90 min. Optimum conditions for titanium oxycarbide synthesis by reduction of titania include temperature in the range of 1300-1450°C, methane content 8 vol% and hydrogen content above 35 vol%. Ilmenite ore was reduced by Cf4-HrAr gas mixture to metallic iron and titanium oxycarbide. Metallic iron catalyzed methane cracking and solid carbon deposition. Titanium oxycarbide formed at temperatures as low as 950°C. The optimum temperature for reduction of ilmenite is 1200°C and the optimum methane content is 8 vol%. Increase in hydrogen content increased both rate and extent of reduction. With 5 vol% CH4-75 vol% Hr20 vol% Ar gas mixture, the reduction of ilmenite completed in 60 min. Reduction of titanium oxides to oxycarbide with following chlorination may be an efficient alternative technology for processing of titanium minerals.

Jan 1, 2001

By J. Jakumelt

The coupled simulation of mold filling and solidification for an investment casting process presents difficult. This is due to the complexity of the carious physical process and the geometry, To achieve this task in a precise way, the CFD program FLUENT and the casting simulation tool CASTS were closely coupled. Any physical quantity, such as velocities or temperatures, can be exchanged via files after each time step of the simulation. The communication and operating sequence of the programs is controlled by PERL-scripts. This enables the expertise of FLU ENT for flow simulation and the strength of CASTS, for casting simulation to be combined. The coupled simulation was successful applied to an aerospace investment casting. Several physical models were tested for correct treatment of the casting filters, the porosity of the mold and the viscosity of the liquid metal. The results demonstrate that even complex investment casting geometries can be investigated using CASTS-FLUENT.

Jan 1, 2003

By Peter Ehren

Global Geoscience is developing a Rhyolite Ridge project, a shallow boron-lithium resource deposit, located in Nevada about 25 km from Albermarle’s Silver Peak operation. The main minerals of interest are the boron mineral searlesite (40%wt) and lithium containing clay minerals. These minerals are found among principally calcite, feldspar, muscovite, dolomite, and quartz. The equivalent commercial value is about 7–9% boric acid (H3BO3) and 0.8–1.0% lithium carbonate (Li2CO3) equivalents. Selective agitated leach tests at SGS Lakefield laboratory showed that searlesite can be acid leached between 20 and 75 °C and at a pH lower than 4. On the other hand, lithium can be leached between 20 and 75 °C and at a pH lower than 1. In other words, lithium can be recovered at low temperatures if sufficient free acid is available, which gave the motivation to investigate heap leaching of the mineral. The PLS contains boric acid, magnesium, sodium, lithium, potassium aluminium, and iron sulfates.

By M. E. Coleman, G. Money

"Clyde Materials Handling is an established customer-driven solutions provider, which utilizes its knowledge, expertise and technologies to transform the production processes of its customers, who operate in the ferrous and non-ferrous metals industries.With over 30 years experience in the process improvement industry, Clyde Materials Handling has helped their global customer base transform the way in which they operate their processes, which has enabled them to generate sustainable economic benefit and maintain their positions as leaders in their respective markets.Clyde Materials Handling has supported operators within the metals market by developing and deploying pneumatic conveying and pneumatic injection technologies. These environmentally supportive and sustainable solutions have been used to transport raw materials within operating facilities, from storage to silo, as well as injecting these materials directly into the heart of production processes.Clyde Materials Handling has worked closely with their customers, such as Codelco in Chile, where their pneumatic solutions have been used to inject a consistent, pulseless and accurate flow of copper concentrate into a bath smelter, which has helped to fuel the operational capacity, availability and productivity.This paper will discuss and highlight the ways in which pneumatic injection technologies, created by Clyde Materials Handling, and applied in partnership with their customers, have helped to improve the operational performance of the production processes of operators across the non-ferrous metals markets with specific reference to applications in the Peirce Smith Converter.Clyde Materials Handling has applications injecting Electronic Scraps, Dusts, Reverts, and other additives to the Peirce Smith Converter. They also have experience of modified PS Units used for Slag Cleaning. There experience with the Codelco Teniente Converter is also directly related to this area of operation."

Jan 1, 2009

By R. Leiby

Prior to March 1992, the only component of the lead acid battery that was not recycled by East Penn Manufacturing Company was the sulfuric acid electrolyte. This acid was unusable in new batteries because the iron level was found to exceed new product specifications. The development of a liquid ion exchange process to remove the iron from the acid allows East Penn to currently recover over three million gallons of sulfuric acid annually. The process is based upon the use of an iron selective liquid ion exchange material or solvent to extract iron from the sulfuric acid electrolyte followed by regeneration of the solvent. Equilibrium and kinetic data for the extraction and regeneration steps were collected in order to scale up the process to commercial scale. An electrochemical process for the treatment of the acid used in the regeneration step was, also developed which significantly reduces the volume of strip acid required in the process.

Jan 1, 1995

By N. Pradhan, B. K. Mishra, B. D. Nayak, B. K. Mohapatra, R. K. Mohapatra

"Present study is about use of a group of Iron[Fe(III)] Reducing Bacteria (IRB) to convert the goethite (a-FeOOH) present in the original lateritic Nickel ore to magnetite under an anaerobic condition and subsequently release the bound Co(III) and Ni(II) through leaching. The lateritic Nickel ore contains 0.8% Ni, 0.049% Co, 1.92% Cr, 0.32% Mn and 50.2% Fe. An anaerobic dissimilatory Fe(III) reducing bacterial consortium capable of using acetate as carbon source (electron donor) and lateritic ore as terminal electron acceptor, changes the initial light brown color of the ore to dark brown. The change in color is due to the conversion of goethite to magnetite, which was confirmed by XRD. When the IRB treated sample was subjected to both bioleaching and acid leaching, it shows a greater recovery of Nickel and Cobalt values as compared to untreated original lateritic Ni ore. Further a magnetic separation method was used to separate the magnetic part of the treated lateritic ore and subjected to acid- and bio-leaching for better recovery of Nickel and Cobalt.IntroductionIt has been known that micro-organisms have the potential to reduce metals but more recent observations have shown that a diversity of specialist bacteria and archaea can use such activities to conserve energy for growth under anaerobic conditions [12]. Natural Fe(III) oxides are high in surface area and are reactive [1]. Fe (III) oxides adsorb a wide range of metal cations and anions by complexation to surface hydroxyl groups [17], and function as the primary redox buffering solid phase in many sediments and subsurface materials [5].Recently a number of bacteria have been isolated based on their ability to use metal ions, including Fe(III), as electron acceptor under anaerobic conditions. These are capable of producing energy by coupling the oxidation of organic compounds to reduction of Fe(III). Iron[Fe(III)]-Reducing Bacteria (IRB) have been isolated and identified from a wide variety of environments including freshwater and marine aquatic sediments and submerged soil [8]. The biogeochemical cycle of iron is linked to those of the trace metals, as many trace metals coassociate with Fe(III) oxides or reduced iron phases (e.g., magnetite, siderite, or iron sulfide). IRB can utilize Fe(III) oxides as terminal electron acceptors for respiration [18]; thereby reducing all or a fraction of the solid. The reductive portion of the iron biogeochemical cycle in non-phototropic environments (e.g., sediments and subsurface materials) is driven by the direct enzymatic reduction of Fe(III) oxides to Fe(II) by dissimilatory iron reducing bacteria [13,14]."

Jan 1, 2009

By Ravi S. Bellur-Ramaswamy, Daniel A. Tortorelli, Robert Haber, Nahil A. Sobh

We optimize continuous quench process parameters to produce functionally graded aluminum alloy extrudates. To perform this task, an optimization problem is defined and solved using a standard nonlinear programming algorithm. Ingredients of this algorithm include 1) the process parameters to be optimized, 2) a cost function: the weighted average of the precipitate number density distribution, 3) constraint functions to limit the temperature gradient (and hence distortion and residual stress) and exit temperature, and 4) their sensitivities with respect to the process parameters. The cost and constraint functions are dependent on the temperature and precipitate size which are obtained by balancing energy to determine the temperature distribution and by using a reaction-rate theory to determine the precipitate particle sizes and their distributions. Both the temperature and the precipitate models are solved via the discontinuous Galerkin finite element method. The energy balance incorporates nonlinear boundary conditions and material properties. The temperature field is then used in the reaction rate model which has as many as 105 degrees of- freedom per finite element node. After computing the temperature and precipitate size distributions we must compute their sensitivities. This seemingly intractable computational task is resolved thanks to the discontinuous Galerkin finite element formulation and the direct differentiation sensitivity method. A three-dimension example is provided to demonstrate the algorithm.

Jan 1, 2001

By Jan Petter Maehlen

Solid H-absorbing materials are in focus of ongoing R&D to offer viable solutions for the hydrogen storage and supply systems aimed on use of hydrogen as energy carrier for automotive transportation. Low operating pressures, combined with high gravimetric and volumetric efficiencies, together with fast kinetics of hydrogen release at ambient temperatures (providing conditions for a low energy loss due to decomposition), are the most important features of the ?ideal? H storage material. Hydrides of the light elements are the only possible candidates to build systems with an overall efficiency similar to those accommodating liquid or compressed (700 bar) hydrogen. One promising material from this point of view is aluminium trihydride, alane AlH3 with a gravimetric storage capacity of 10 wt.% H. This work was focused on studies of the crystal structure and thermal decomposition of alane by application of powder synchrotron X-Ray diffraction.

Jan 1, 2006

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus. The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn304) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6.7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn304 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10-5 m2/s range. The pore size was mainly between 0.1 and 10 um.

Jan 1, 2003

By Hector M. Henao

The FeOX-CaO-SiO2 base slag at intermediate oxygen partial pressures is very often used in non-ferrous smelting processes. This slag would also contain Al2O3 and MgO because these compounds are normal components in the ore and the refractory of a furnace. The objective of the present work is to determine the effect of Al2O3 or MgO addition on the liquidus temperatures of the plain FeOX-CaO-SiO2 slags in the atmosphere between intermediate pO2 of 10-6 and that of iron saturation at 1250 and 1300 °C. The experiments were carried out at given mass%CaO/(mass%CaO+mass%SiO2) ratios ranging from 0 to 1 and at spinel-tridimite double saturation. The experimental results show that the effect of Al2O3 or MgO addition on the plain FeOX-SiO2-CaO slag is not uniform and depends on the content of Al2O3 or MgO, the oxygen partial pressure and the mass% CaO/mass% SiO2 ratio. It is apparent that Al2O3 or MgO addition enlarges the spinel or wustite saturation area at almost all the oxygen partial pressures and temperatures of this research. The obtained phase diagrams will be useful in the metallurgical industry to assist in the selection of slag chemistry, operation condition and development of new processes.

Jan 1, 2006

By Qinghai Pang

"With the increasing proportion of bituminous coal in blend coal, the safety of blend coal during pulverization and transportation is gradually being paid more and more attention. Therefore, the explosivity of bituminous pulverized coal (PC) with different volatile content from 25 to 38% was studied by measuring the combustion flame length after its injection into a glass pipe with the heat source installed in the center. The results indicated that high volatile content bituminous PC is apt to have higher explosivity. By blending different bituminous PC with 10% anthracite, the explosivity of bituminous PC showed a positive correlation with the proportion –OH radical. However, different bituminous PC seemed to have the same explosivity when the addition of anthracite increased to 20%. With the further increasing proportion of anthracite to 30%, the explosivity of bituminous PC with high –OH proportion became negligible while a weak explosivity of high –CH3 proportion bituminous PC still remained.IntroductionWith the increasing iron ore prices and decreasing steel prices, it has become critical for iron and steel enterprises to control the cost in ironmaking and steelmaking process. Blast furnaces (BF) are the main consumer in ironmaking process, which occupies 70% fuel consumption of total steelmaking process [1]. In this circumstance, any means necessary is taken by BF operators to lower the cost of iron in production. Coke and iron ore are the main expense in this process, who takes up a very high proportion in total cost. Pulverized coal injection (PCI) is the most efficient way to reduce coke ratio, which replace coke with relatively cheaper PC.At present, most of BF is injected with blend coal in the consideration of decent combustion property and quantity of heat. Simultaneously, bituminite and anthracite blending is an effective method to obtain blend coals with required composition and performance, such as volatile and ash content, etc. Nevertheless, a very huge gap was found between the price of bituminous coal and anthracite in some regions of China, in which the price of bituminite can be just 70% of the price of anthracite. Thus, iron enterprises in these regions attempt to possibly amplify the proportion of bituminite in blend coal. Increasing proportion of bituminite results in higher volatile content in blend coal, by which the safety of blend coal during pulverization or transportation was deteriorated.Relatively, coals with higher volatile content usually possess stronger explosivity, which means that volatile and explosivity may related to some extent. However, the relationship between volatile and explosivity is not of certainty for some PC with high volatile content around 40% was found to be inexplosive in comparison to the coals with lower volatile content. With the increasing proportion of bituminous coal in blend coal, investigations on the factors of PC explosivity have become more and more important. Therefore, bituminous coals with different volatile content were selected. The explosivity of blend coal and its relationship between volatile content and functionality was investigated in this research."

Jan 1, 2014

By H. Y. Sohn, Joshua E. Ramos, Moo Eob Choi

"A new technology for ironmaking based on direct gaseous reduction of iron ore concentrate is under development. This technology would drastically lower CO2 emission and reduce energy consumption by nearly 38% of the blast furnace requirements. Experiments were performed using iron oxide concentrate at 1150oC in a bench-scale facility, which was the highest temperature that could be reached in the facility. The reduction extent was determined at residence times of 3.5 - 5.5 seconds in which the reduction extent approached 43% with 0% excess H2 and 95% with 860% excess H2. Separate kinetics measurements showed that the rate is much faster at 1200 - 1400 oC. Experiments were also carried out using syngas (mixtures of H2 + CO). About 90% reduction in 3.5 seconds with 860% excess hydrogen contained in the syngas demonstrated sufficiently fast reduction for a suspension process and the feasibility of usingsyngas instead of pure hydrogen.IntroductionDespite the improvements in the modern blast furnace (BF) process, it suffers from many drawbacks. The process requires the feed in the form of sinters or pellets and high-grade coking coal. Thus, BF iron production is projected to decrease gradually [1]. The main factors for this are the environmental regulations [2] and the high capital investment cost.A large number of new ironmaking technologies have been developed or are under development [3]. Most of these processes, however, are not sufficiently intensive to replace the blast furnace because they cannot be operated at high temperatures due to the sticking and fusion of particles. Therefore, a new technology is under development for producing iron directly from fine concentrates by a gas-solid suspension technology, which would reduce energy consumption by about 38% of the amount required by the blast furnace and drastically lower environmental pollution, especially CO2 emission, from the steel industry."

Jan 1, 2009

By Wenya Du, Qingbo Yu, Peng Li, Qin Qin

"A new heat recovery system is proposed. This system uses the endothermic heat of gasification reaction instead of sensible heat to recover the energy of molten blast furnace slag. The gasification technological parameter in molten blast furnace was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer. The results showed that, according to different gasification agent, this system can produce syngas with different C-H ratio. The exergy efficiency of this system is high and its internal exergy loss rate is about 11%. This method can bring huge economic and environmental benefits which are important to the survival and sustainable development of iron-steel enterprises. The molten BF slag acts as not only thermal media but also good catalyst. The kinetic parameters on gasification reaction with different types of coal used differ from each other.IntroductionEnergy consumption in the iron-making process is about 50%~60% of the total energy input. The blast furnace is very important in the iron & steel process. So energy conservation and emission reduction about blast furnace is very important. In recent years, in order to recovery energy, many new technologies such as TRT (Top gas pressure Recovery Turbine) and CCPP (Combined Cycle Power Plant) were used in iron-making. But the energy of molten blast furnace (BF) slag has only been used limitedly so far.Molten BF (Blast Furnace) slag is the byproduct of iron-making at the high temperatures range from 1723 to 1923K, and has a large amount of sensible heat remaining. The yield of molten BF slag is about 300 kg per ton of pig iron. In conventional processes, molten BF slag is quenched rapidly using a large amount of water to produce a glassy-granulated slag. The quenching slag must be dried before it can be used in cement manufacture. During the process, a large amount of water was consumed and the energy of molten slag can not be recovered. At the same time, it causes environmental pollution problems. So the critical problems of the process are not only energy recovery of molten slag and reducing emission of H2S and SO2, but also guaranteeing the subsequent use value of slag. For this propose, many new technologies were investigated to recover the thermal energy of molten slag. The promising methods are dry granulation [1-4] and reforming of methane [5-9]. The method, utilization of reaction heat instead of latent heat and sensible heat, is quite attractive from viewpoints of energy storage without heat loss, and makes a connection to other industry. But both of them are in laboratory. In this paper, coal gasification in molten BF slag was used to recover the energy of molten BF slag. The gasification technological parameter in molten BF was calculated and the exergy of the system was analyzed. The gasification reactions were studied kinetically by the isothermal thermogravimetry using STA409PC thermal analyzer."

Jan 1, 2011

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006

By M. Potesser

In the primary and secondary copper industry the anode furnace is the most important process step in the refining procedure to reach an enhancement in value and quality of the copper by a selective oxidation and reduction. By combining the advantages of the conventional tilting hearth anode furnace and the benefits of the drum type anode furnace a new aggregate was developed and patented. The cross-section of the furnace is elliptical and the whole unit is tiltable. During the melting period, the contact surface between the burners and the bath or the scarp is enlarged - an increased energy input is the consequence. For the refining period the furnace is rotated, whereby a high bath level is guaranteed. Due to the longer residence time of the gas in the copper melt, not only the gas consumption is reduced but also the efficiency/quality of the refining process is improved. This investigation shows a metallurgical comparison between the new anode furnace concept with the elliptical profile/cross section and the conventional, tiltable hearth anode furnace as well as the drum type anode furnace. The CFD modeling of the currents in these different furnaces delivered helpful data to compare the geometry of the different furnaces. The investigation covered the refining of blister copper from primary metallurgy, from secondary metallurgy as well as from a mixture of both copper melts. The paper underlines the possibilities for a reduction of the tap-to-tap time and for an increase in production capacity, which can be achieved by applying the new furnace concept in comparison to the conventional furnaces.

Jan 1, 2006

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