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"Silver is traditionally recovered in base metal smelters (lead and copper), or as a by-product of other precious metals (gold and/or PGM's). This paper presents the results of non-conventional techniques to recover silver from complex materials. The PLATSOL® process has been developed to recover, in one step and without the use of cyanide, base metals (copper, cobalt, nickel) and precious metals (gold, PGM's) from sulphide concentrates too low in grade to enter the mainstream extraction processes. Silver is only partially recovered in solution with gold and the PGM's during the PLATSOL® process. However, the silver minerals are transformed into silver chloride, which can then be recovered from the PLATSOL® residue using conventional techniques. Some South American silver concentrates contain levels of impurity (mostly arsenic) so elevated that the penalties incurred significantly affect the process economics. The present results have shown that a low temperature calcination process transforms the concentrate into a product well suited for traditional recovery treatments. Metallurgical details will be provided, as well as the results of mineralogical studies that helped clarify the process mechanisms.IntroductionSilver occurrences in nature are very diversified, and, therefore, primary silver is produced as a by-product of many base metal and precious metal operations [1], as well as a co-product of most gold ores. However, difficulties can arise when high temperature processes are used for refractory gold ores or copper concentrates, or when the silver concentrate contains impurity elements such as arsenic that trigger high penalties."

Jan 1, 2012

By Roger Wilmoth

Exposed, open pit mine highwalls contribute significantly to the production of acid mine drainage (AMD) thus causing environmental concerns upon closure of an operating mine. Four innovative technologies were evaluated under the U.S. Environmental Protection Agency?s, Mine Waste Technology (MWTP), Prevention of AMD Generation from Open-Pit Highwalls Demonstration Project. This project is funded by the U.S. Environmental Protection Agency (EPA) and jointly administered by the EPA and the U.S. Department of Energy (DOE) through an Interagency Agreement. The objective of the field demonstration was to evaluate the technologies ability to decrease or eliminate acid generation from treated areas of the highwall in comparison an untreated highwall area. The field demonstration was performed at the Golden Sunlight Mine (GSM) a subsidiary of Placer Dome U.S., located near Whitehall, Montana. GSM is an operating gold mine. The highwall at GSM was divided into five plots measuring 15.24 by 15.24 metres (m) and each technology was assigned a plot with the fifth plot being used for comparison as a background control plot. The four technologies were spray-applied. The applied insitu treatment technologies included: 1) A modified, furfuryl alcohol resin sealant, utilizing wood and agricultural by-products to coat the rock surface. 2) EcobondTMARD, a phosphate based process that forms a stable, insoluble compound, coating the rock surface. 3) Two ARD passivation technologies, magnesium oxide and the Dupont technology developed to create an inert layer/coating on the pyrite, preventing oxidation. The technologies were evaluated using the following methods: 1) ASTM D 5744-96, Accelerated Weathering of Solid Materials using a Modified Humidity Cells, 2) mine wall residual wall rinse sampling, 3) microscopy, and 4) core drilling followed by water injection testing.

Jan 1, 2003

By Douglas Robinson

This paper describes technical work done to develop a Spouted Bed Electrode Cell into a commercially viable Electrowinning Cell; (a previous paper has been presented at the ECS meeting in Paris in May of this year, with a more general overview of the cell, [1]). The studies have included hydrodynamic tests to understand the criteria for the circulating flow of metallic beads in the cell, particularly in the region at the entrance to the draft tube, and electrochemical tests to find a suitable diaphragm for extended time electrolysis. Various patent pending features were developed including a double nozzle to allow for automatic stopping and restarting of the bed, an arrowhead shaped draft tube to control the flow of beads into the entrance to the draft tube, a roof-top shaped device to control the flow of beads out of the top of the draft tube, an overflow weir to allow the continuous recovery of beads from the cell, and a family of diaphragm fabrics for extended operation. Prior to the identification of the diaphragm material, short circuits would develop within a few hours. A pilot scale cell was operated for three days, with continuous operator attention, and then for ten days with operator attention only on day shift. The cell is currently advancing to the next stage of development which will involve continuous testing in a commercial copper electrowinning facility.

Jan 1, 2003

By David Dreisinger

The pressure oxidation of pyrite is an important hydrometallurgical technology, especially in the total oxidation of refractory gold ores and concentrates (gold is locked in the pyrite structure preventing direct cyanide recovery). It has been noticed in some commercial applications and benchscale studies that the leaching of pyrite may be slow and apparently can be inhibited by the presence of molten elemental sulfur in the leach pulp. The purpose of this study was to determine whether Ortho-Phenylene-Diamine (OPD) could be used as a surfactant or dispersant for sulfur in the pressure oxidation of pyrite. OPD has previously been shown to be useful for pressure leaching of zinc and copper sulfides at 150 C.In this work, the interfacial chemistry of sulfur was studied at temperatures of up to 190 C in the presence and absence of OPD and other surfactants. The contact angle between molten sulfur and pyrite was also measured. Finally, the impact of OPD on the kinetics of pyrite oxidation was measured in bench-scale pressure oxidation experiments. The essential finding of this study was that OPD lowers the interfacial tension between molten sulfur and acid solutions and increases the contact angle (reduces wetting) between molten sulfur and pyrite. The work of adhesion between sulfur and pyrite was reduced by more than an order of magnitude in the presence of OPD. In bench scale tests, addition of OPD was found to significantly accelerate the rate of oxidation of pyrite. Conveniently, it was found that OPD was also fully degraded during high temperature oxidation processes. No residual OPD was detected in solution or solid samples from the leach testing. OPD is recommended as a sulfur dispersant in the pressure oxidation of pyrite and/or elemental sulfur containing feeds.

Jan 1, 2003

By P. Chris Pistorius

Calcium treatment of alumina inclusions, to convert the alumina to molten or partially molten calcium aluminates, is a well-established treatment for steel, to improve the castability of aluminium-killed steel. However, the role of magnesium in calcium-treated steel is not fully clear, nor is the origin of the several percent of magnesium oxide that is often present in calcium-treated inclusions. To study this, steel was sampled after calcium treatment at an industrial steel plant, and the inclusions identified by energy-dispersive X-ray microanalysis (EDX) on polished sections of the samples (analysing the samples in a scanning electron microscope). The predicted fraction liquid in the inclusion was estimated from the ternary alumina-magnesia-lime phase diagram. Inclusions with higher CaO contents generally had lower MgO contents, indicating that the calcium wire is not the origin of the magnesium in the inclusions; this was also confirmed by wet chemical analysis of the calcium wire. Instead, it appears that magnesium-alumina spinel inclusions form during extended ladle contact after aluminium killing and before calcium treatment. While such spinels have been stated to cause poor castability (clogging the submerged-entry nozzle), it is clear that calcium treatment successfully modifies the spinel inclusions to mixed alumina-lime-magnesia inclusions, where the magnesia content contributes substantially to liquefaction of the inclusions: for typical MgO contents of around 10%, the range of Ca:O ratios which yield liquid (or partially liquid) inclusions is extended substantially to lower Ca:O ratios.

Jan 1, 2006

By Bruno Lebon, Koulis Pericleous, Georgi Djambazov, Mayur Patel

"High speed compressible jets are used in a number of steel-making applications. In the case of the BOF, a compressible oxygen jet reacts with a carbon-rich iron bath to reduce carbon levels and produce steel. The intensity of the process is governed by the speed of the jet and by the size and shape of the depression created in the metal and slag by the force of the jet, i.e. by the corresponding free surface. This is a difficult CFD problem, since there are compressible and incompressible regions in the flow domain, which need to be handled differently in a finite-volume (FV) pressure-correction scheme. Also, standard turbulence models do not account for compressibility, or the large difference in density between the cold oxygen jet and the hot reacting surroundings. Corrections are introduced to the k-E model to remedy this deficiency and the results are validated against experimental data. The compressible/incompressible boundary is handled through a transition region, based on Mach number.IntroductionThe deformation of a free surface by a compressible high speed jet is of paramount engineering interest, particularly for understanding the physical processes within a Basic Oxygen Furnace (BOF). In a BOF, a supersonic oxygen jet impinges on a molten iron surface, thereby creating a cavity. Oxygen penetrates the bath and removes carbon, resulting in low carbon steel [1].The challenges in modelling such a process lie in coupling a solution domain with distinct compressible and incompressible regions and in dealing with large density differences between the modelled gas and liquid. The modelling of compressibility within the jet is crucial, since the correct velocity profile in the jet is required to determine the cavity depth with accuracy."

Jan 1, 2012

By Bo Yan, Jiaquan Zhang, Haibo Sun

"Based on the validation of steady-state isothermal mathematical model by a 0.4-scale water model for the single-strand slab casting tundish, the effect of varying pouring temperature on the flow, temperature field, and residence time distribution(RTD) of the liquid steel was studied by a transient hydrodynamic model. Due to the decreasing temperature of ladle stream over a casting period of 50 min, the direction of vortex flow at the downstream side of dam changes to clockwise from the anticlockwise at 4 min after the new teeming, and reverts to anticlockwise direction again at 43 min. Meanwhile, the melt flow state in the dam hole is also varying with time. For conventional isothermal water modeling, the RTD parameters obtained are much different as compared with the non-isothermal ones. For the flow control devices(FCD) design, however, the identical optimal scheme can be concluded from the point of view of isothermal modeling.IntroductionOriginally, tundish was adopted as a buffer and distributor to hold and allocate molten steel for sequence casting upon ladle exchange and to provide a desired steel flow rate to the mould below. With the increasing demand to strand quality, the tundish has become a critical metallurgical reactor to enhance inclusions removal, avoid reoxidation of molten steel, and prevent slag entrapment. The general trends to obtain these metallurgical effects are to optimize steel flow pattern and to extend the residence time of molten steel in the tundish through increasing the volume of tundish and/or using FCDs in the interior of the tundish."

Jan 1, 2012

By Tiruttani Munikamal, Suresh Sundarraj

"A numerical model of the induction hardening process of steel cranks has been developed and the predicted results of temperature and phase distribution during this solid state phase transformation process are verified with experimental data from the literature. This heat treatment process involves heating the crank to the austenitic temperature range followed by rapid quenching in water to harden the surface of the crank. The model has been developed using ABAQUS, commercial FEA software. The formation of martensite, pearlite, and retained austenite phases are modeled and implemented through a user defined function in ABAQUS. A sensitivity study on the various process parameters affecting the amount of phase distribution has been carried out.IntroductionThe type of surface and sub-surface microstructure as well as the residual stresses that are present in a component after manufacturing, significantly affects it fatigue performance. The wear resistance of the automotive components such as crankshaft, gears, camshaft and bearings depends on the surface hardness. In order to achieve the surface hardness, these steel components are subjected to a type of quench hardening heat treatment process. There are several heat treatment processes available for the industrial application to improve the mechanical properties of the final part. Case hardening using induction heating is one of the widely used industrial techniques for improving the surface microstructure of a steel component. It consists of two stages i.e. induction heating cycle, followed by quenching in a fluid medium (usually water or oil)"

Jan 1, 2012

By Alex Moyano

Due to very demanding environmental rules, and to the incrementing impurities contents in the processed concentrates, Codelco Norte smelter permanently faces new demands for planning the production program with the present fulfillment of the environmental regulation. Accordingly, the CN smelter along with IM2, developed an impurity distribution simulation model, M-DICE, which predicts the impurities behavior for each of the process units of the smelter under different process configurations and concentrates quality. The development of the M-DICE included the gathering of operational data for the process units of the CN smelter, including temperature, oxygen enriched air, matte grade, etc. Then based on a mass balance for each of the process units involved in the smelter a thermodynamic evaluation was done to derive the arsenic fractional distribution among the condensed (matte/white metal/copper/slag) and gas phases. Then, the validated M-DICE was able to predict the arsenic behavior in the Teniente converter processing complex concentrates with high arsenic content, among others. At present, M-DICE is in its last stage of development, and is expected to be a suitable environmental and process management?s tool for the Codelco-Chile?s smelters.

Jan 1, 2006

By Cam T. Nhan

The potential use of coal fly ash as a construction material has been recognized for many years,. In this work, an admixture of the ash residue is investigated for use as a landfill liner. In particular, its performance as a chemical barrier to the leachate from the municipal solid waste (MSW,) is determined. The test specimens are a water compacted admixture of class F fly ash, low in calcium content, which is blended with lime dust and calcium bentonite. MSW is passed through the compacted fly ash specimens under a gravitational head. The. diffusion of elements in the leachate through this material is monitored as a function of time. The distribution profiles of the retained elements in the compacted admixture provide prediction of the long term performance of the compacted admixture directly affect the leachate diffusion rate, hence, the mobilities of the retained elements.

Jan 1, 1992

By Laurentiu Nastac

"This paper describes the development and validation of a comprehensive multiscale modeling approach capable of predicting at the mesoscopic scale level the ingot solidification structure and solidification-related defects commonly occurring during the vacuum arc remelting (VAR) process. The approach consists of a coupling between a fully transient macroscopic code and a mesoscopic solidification structure code. The predictions from the multiscale model, including grain morphology and size, primary and secondary dendrite arm spacings, Laves and NbC phases, tendency for freckling and columnar-to-equiaxed transition, were validated against experimental measurements for a 20-inch diameter VAR alloy 718 ingots. The validated model was then used to investigate the effects of melting rate and ingot diameter on the solidification structure of VAR processed 718 ingots.IntroductionThe objective of this work was to develop a fully transient multiscale modeling approach to get an insight into the effect of processing parameters on the cast micro- and macro-structure during VAR processing. The developed model assists in achieving better control of the ingot solidification structure and to determine trends in the macrosegregation in these ingots. Another objective of this work was to analyze the transient effects of production rate and ingot size on the resultant ingot microstructures. This objective was met by first understanding the effects of the full range of processing parameters typically used in the VAR process. Processing parameters such as power input and heat extraction rate significantly influence the ingot liquid pool size and shape as well as the ingot structure, which in turn will greatly impacts the final ingot quality."

Jan 1, 2012

By Carlos Schvezov, Eliana Agaliotis, Alicia E. Ares, Mario Rosenberger

"The interaction between a solidification front and a spherical particle was modeled and simulated in order to study the phenomenon of ""pushing"". Finite element methods were employed in axisymetric domains. The drag force is calculated from the calculated fluid flow field and the repulsion force is the Lifshitz-Van der Waal force. The thermal field is decoupled from the force field. The model is applied to a metallic matrix containing particles with similar, lower or higher thermal conductivities than the matrix, resulting in planar, convex and concave interface shapes, respectively.The results show that the critical velocities for pushing for concave and convex interfaces are about one order of magnitude larger and one order of magnitude lower than the critical velocity for flat interfaces, respectively. The simulated results were in very good agreement with reported experimental results.IntroductionThe solidification interface of materials containing spherical particles in some cases can push the particle ahead the interface. This phenomenon generally occurs during the solidification of different materials such as, metallic alloys containing native particles, metal matrix composites containing particles or fibers as reinforcements and crystallization of semiconductor, optical, optoelectronic or biological materials. In all cases the interaction strongly determines the distribution of particles and the resulting physical and physic-chemical properties of the resulting material. The phenomenon has been investigated for many years both experimentally and by mathematical modeling [1-21]. The process is complex due to the variety of phenomena involved during pushing. In all cases, the physical problem depends on the properties, nature, and morphology of the interacting media; the particle, melt and solid; and external fields such as gravity, thermal and electromagnetic fields."

Jan 1, 2012

By Mari Naess, Jan Erik Olsen, Gabriella Tranell

"Fume, also known as dust, is produced during metal refining. Exposure to fume is damaging to the health of plant operators. A mathematical model has been developed to study the different factors governing the fuming mechanism. It is shown that natural convection is the main driving force of the phenomenon, and that the fuming rate is highly sensitive to the area of the exposed metal surface. A new feature introduced in the modeling concept is the ability to include a gas flux of unconsumed process gas flowing up through the metal surface. This reduces the fuming rate, and should normally not be neglected.IntroductionFormation of fume from the ladle in which metal is refined into its final specifications is an environmental issue of importance for the working environment in the production plant. In layman-term fume is often known as dust. It is formed when metal reacts with oxygen. As an example of a fuming process, we will focus on ladle refining of silicon. Note that many of the principles and conclusions will apply to other metal refining processes. For silicon production, silica fume (S1O2) is produced when silicon metal (Si) reacts with oxygen (O2).Silicon is produced in a submerged arc furnace. The metal is tapped from the furnace into a ladle for refining. The refining is conducted by injecting a mixture of air and pure oxygen at the bottom of the ladle. The oxygen reacts with the metal and the impurities, and the amount of impurities is reduced according to product specification. At the ladle surface, metal also reacts with oxygen present in the air surrounding the ladle. This reaction produces silica fume as illustrated in Figure 1."

Jan 1, 2012

By M. S. Moats

A considerable amount of research has been conducted to determine the causes of anode passivation. Chemical and electrochemical reactions that occur after passivation have received little attention. Chronopotentiometry, linear sweep voltammetry, cyclic voltammetry, and impedance spectroscopy have been used to elucidate three reactions that occur after passivation of commercial copper anodes. These involve the dissolution of silver and subsequent cementation and transformation of selenides, the oxidation of lead sulfate to lead oxide, and oxygen evolution. The amount of silver dissolution depends on the silver content of the anode, the time to passivation, and the molar ratio of Ag/(Se+Te). The oxidation of lead from PbSO4 to PbOx explains a potential plateau of oxygen evolution. Silver affects the duration of oxygen evolution on the PbOx. Anodes containing kupferglimmer display a characteristic oxygen evolution potential. It is believed that kupferglimmer provides a lower overpotential for oxygen evolution than the other slime phases or passivated surface.

Jan 1, 1999

By Heinz Böni, Christian Ludwig, Bernhard Steubing, Uca Silva

"Chile will soon have to find solutions for dealing with rapidly growing quantities of Waste Electrical and Electronic Equipment (WEEE) due to its strong economy and fast increase of internet and communications technology usage. To support this process, the state of the Chilean recycling infrastructure as well as government, industry and consumer efforts to deal with ewaste were analyzed. Current e-waste quantities were assessed and future flows were predicted using a material flow analysis model. In this model computer hardware was used as tracer equipment for WEEE. Best available numbers indicate that today’s formal recycling infrastructure receives less than 3% of the annual quantities of computer waste. This study represents the most comprehensive analysis regarding e-waste in Chile, identifying relevant streams of e-waste and providing a basis for authorities and producers of electronic goods in order to take the necessary actions to establish an adequate recycling system.IntroductionSince 1991, Chile has experienced a period of strong economic growth. It is amongst the countries with the fastest development in the sector of Information and Communication Technologies (ICT) in Latin America and the number of people with access to ICT has been growing rapidly. The high growth rates of the computer market over the last years are representative for the ICT sector with the consequence that the generated quantities of electronic waste are increasing rapidly [1, 2].Waste Electrical and Electronic Equipment (WEEE) or e-waste is “any appliance using an electric power supply that has reached its end-of-life” as defined by the OECD [3]. Even though the overall waste management in Chile has improved much over the last decade, the issue of ewaste was hardly addressed. Due to the value of the materials contained in computer waste - such as precious metals, basic metals as copper or plastics - it may be assumed that an important quantity is already being recovered. This usually takes place on the informal market under questionable conditions for human health and the environment [1, 2, 4]."

Jan 1, 2008

By Masanori Harata

A fundamental study was conducted on a new process for producing scandium (Sc) metal or aluminum-scandium (Al-Sc) alloy by the calciothermic reduction of scandium oxide (Sc2O3). In this study, aluminum (Al) and calcium chloride (CaCl2) were used as the collector metal and flux for the reduction, respectively. A mixture of Sc2O3, Al, and CaCl2 in a tantalum crucible was placed inside a stainless steel reaction container, and the feed mixture was reacted with calcium (Ca) vapor at 1273 K for 6 h. After the reduction experiment, the reaction product (CaO), CaCl2 flux, and excess Ca reductant were removed from the obtained alloy sample by leaching with an aqueous solution. The formation of Al3Sc in the Al matrix phase of the alloy was confirmed by X-ray diffraction (XRD) and electron microprobe analysis (EPMA). This result indicates that Sc2O3 was successfully reduced to metallic Sc and alloyed in situ to form liquid Al-Sc alloy during the reduction. When Al was not used in the reduction experiment, a complex oxide (CaSc2O4) was formed, and the reduction was incomplete. This study demonstrates that the Al-Sc alloy can be directly produced by calciothermic reduction using CaCl2 flux and Al collector metal.

Jan 1, 2006

By J. H. de. Visser

The transfer of molten metal in smelting or refining operations is typically performed in open trough-type launders that are constructed of either water-cooled copper troughs or refractory lined steel jackets. This transfer can be either continuous or batch. Batch operations transfer metal through an open launder. The uncovered launder has many operational and environmental drawbacks. In order to improve workplace hygiene, designs have evolved toward ventilated launder covers that .are connected to secondary exhaust systems that use negative pressure under the cover removing fume and hot gases to secondary fume control devices. In smelting operations, a variety of covers have been employed which insulate the launder and contain the fumes and also provide additional heat along the length of the launder through a series of premix or inspiration-type burners that add combustion products to the normal fume load in the launder. Cover designs have proven to be inadequate in that hinged unventilated covers hinder convenient access while heated ventilated covers are costly to maintain. Covers that employ refractory bricks and overhead enclosure-type exhaust hoods have been somewhat successful, but restrict operator movement and require large volumes of exhaust air. An example is given of a cover and off-gas system for launders that is designed to provide superior insulation and heating capabilities, as well: as better control of the fume gases-and ease of maintenance. The cover system must maintain the balance between maintaining launder heat and fume removal. The construction of the covers must be able to withstand high internal temperatures and maintain its structural properties.

Jan 1, 1999

By Florian Kongoli

While calcium ferrite slags have been successfully used in continuous copper converting for the last 30 years, ferrous calcium silicate slag was proposed about 8 years ago as an additional alternative for copper smelting. Although both slags are normal extensions of each other their phase relations have not been completely clarified. In this paper the liquidus relations of both slags have been quantified at various areas that cover both of them. The existing experimental data have been first reviewed and discussed in relation to the solidification procedure. An original physical model is then used to predict various diagrams of the liquidus surface of both slags. It is shown that the ternary liquidus diagrams normally used for FeOx-SiO2-CaO system are not suitable for industrial slags. The new model diagrams of Fe/CaO versus SiO2 and Fe/SiO2 versus CaO as well as Fe/CaO versus Temperature and Fe/SiO2 versus temperature are proven to be much more convenient for ferrite and ferrous calcium silicate slags. Based on these diagrams the effect of SiO2 and CaO on the melting temperature is quantified. The effect of Cu2O is also quantified through the model. Some Fe/CaO versus Cu2O and Fe/SiO2versus CaO at various copper contents are predicted and the results show good agreement with the experimental data. It is also shown that in the presence of liquid copper, Cu2O is dissolved in the slag depending on the oxidation degree of the system and might lower the liquidus temperature. Some discussions are also presented taking into account plant observations and important conclusions are drawn for copper smelting and converting

Jan 1, 2006

By Yukihito Sasaki

Sumitomo Metal Mining Co. Ltd. planned an expansion program for the Toyo smelter and refinery in order to increase the production capacity of electrolytic copper to 450,000 tpy in 2007. Regarding the flash smelting furnace, a drastic increase in the average concentrate smelting capacity from 2,300 tpd to 3,950 tpd was required to achieve the plan. It was necessary to examine the performance of the Sumitomo concentrate burner when the feed rate was considerably increased. The authors developed a mathematical model to describe the combustion phenomena in the Toyo flash smelting furnace. This model was developed incorporating the fluid flow, heat and mass transfer, and chemical reactions of the copper concentrate and ancillary fuel. The copper concentrate was considered to mainly comprise chalcopyrite (CuFeS2). The reaction of CuFeS2 was assumed to consist of two steps, namely, the decomposition of CuFeS2 and the oxidation of the resulting pyrrhotite (FeS) and sulfur (S). The combustion phenomena in the furnace at the increased feed rate were predicted using this model. It was found that the Sumitomo burner was capable of enhancing the smelting capacity. This is attributed to the wide dispersion of the concentrate particles caused by an increase in the particle mass and a long residence time in the reaction shaft; this is due to the low temperature of the reaction air. However nonuniformity of the reaction in the reaction shaft was enhanced with the increased feed rate. In order to improve the nonuniformity of the reaction, an increase in oil-burner oxygen and an enlargement of the diameter of the dispersing cone were useful. By combining the expertise of the Toyo smelter staff and the calculation results, the concentrate smelting capacity of the Toyo smelter has been stably increased to 3,600 tpd thus far, and further improvements of the smelting performance are still being carried out.

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