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By Dhanesh Chandra

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

Jan 1, 2006

By Hongmin Zhu, Kai Huang, Shuqiang Jiao

"Garlic peel was used as the raw material to synthesize the biosorbent for the selective recovery of precious metals from the acid chloride solution. Garlic peel is rich in carboxyl-, amino- and thiol-groups, has the potential of exhibiting high affinity to Au(III) when appropriate chemical modification process was employed. Here in the present study, the biosorbent was prepared by cross-linking garlic peel particles with concentrated sulfuric acid. Adsorption tests for mixing different metal ions such as Au(III), Fe(III), Cu(II), Ni(II) and Zn(II) from various concentrations of hydrochloric acid media indicated that Au(III) was selectively adsorbed on the cross-linked garlic peel gel over the other coexisting base metal ions investigated. The crosslinking mechanism and selective adsorption of Au(III) were also investigated briefly.IntroductionPrecious metals are quite popularly applied in the modern industries such as jewelry, electronics and electrical devices, catalysts in chemical industry, etc. While their high values, limited deposit and quite large demand in industry makes its recovery from the industrial wastes, typically e-wastes, quite necessary. Actually, many techniques have been developed to recycle and recover the precious metals from various industrial wastes effectively in last decades, but the cleaning and ecofriendly processes are still seriously scarce [1]. Taking into account of the typical recovery processes using cyanide lixiviant in the alkaline media, or aqua regia, followed by the further recovery process using activated carbon adsorption or cementation with zinc, iron or aluminum plate or powder, though they both are quite effective recovery processes, if considering the special requirements on safety and ecofriendliness for the modern hydrometallurgical processes, various improved or novel extraction processes are greatly demanded [2]. Recently, the biosorption technology applied to the recover precious metals in the hydrometallurgical process has become a concern [3,4]. Inoue’s research group made great progress in the recovery of precious metals such as gold, palladium and platinum from the e-wastes such as spent mobile phone by using biosorption from the hydrochloric acid media [5,6]. This new hydrometallurgical process exhibits the prominent advantages of being cost-effective for its short process, easy operation and near-zero emission. In the above recycling process for e-wastes treatment, the preparation of biosorbents is the key and backbone of the whole recovery process. For this purpose, they developed a series of suitable sorbents for precious metals recovery by using the tanning-based or cellulose-based biomass such as persimmon peel, grape peel, orange juicing residue, waste cotton, waste paper through the crosslinking process with concentrated sulfuric acid and relative chemical modification processes [7-10]. In the present study, we also applied this technique to prepare the biosorbent of precious metal uptaking by using garlic peels as the raw materials, and investigated the adsorption properties of such-obtained gel in the hydrochloric acid media."

Jan 1, 2012

By F. K. Letowski

Leaching in froth is a particular case of a three phase (liquid-solid-gaseous) process which combines flotation with leaching by using a reactive gaseous reagent as a flotation carrier and a leaching solution as the reactive liquid medium to fonn the foam (froth) in' which the solid particles are suspended. Some physico-chemical and engineering aspects of leaching in froth are discussed and illustrated by its application for cleaning the mineral graphite. Leaching of the graphite concentrate containing 4L4% of the elemental carbon and 3.16% of the sulphidic 'sulphur was canied out in the froth fonned by: (a) a concentrated chloride solution, with a small addition of nitric acid, in the foam state; (b) a mixture of gaseous O2, NO., and H20 encapsulated in the foam; and (c) notable particles of graphite suspended in the foam. The laboratory experiments werecanied out in a "flotation column"-type reactor ala temperature from 80 to !08°C and under total pressure of 100 to 200kPa. In the 3-stage leaching-flotation process, the non-flotable fraction of particles was separated three times from the notable fraction. The concentration of carbon and elemental sulphur in the final flotable fraction was 96% C and 0.38% S respectively. The expected advantages and possible application in hydrometallurgy are suggested.

Jan 1, 1995

By S. Fitzel

The Betts process for electrorefining of lead has been in operation since 1902 in the Trail Operations Metallurgical complex. The Betts process allows production of high purity lead in a single electrochemical step. Process improvements and plant expansions have taken place over the many decades of operation of this process which has proven to be robust, flexible, and capable of successfully treating a large range of anode bullion compositions. This paper reviews the history of the Betts lead electrorefining process, the innovations and quick industrial adoption of new discoveries that took place at the end of the nineteenth century. The process was first implemented in Trail Operations and integrated very well with metallurgical needs then and now.

By Mitsuhiro Ito

"To allow various wastes containing high levels of chlorine to be used as alternative raw materials for Portland cement, two practical methods of chlorine removal were developed. In the first method, chlorine is extracted from the wastes during the cement manufacturing process. In the second, ash-dust waste with high chlorine content is first washed and then dehydrated to cake before being introduced to the cement manufacturing process. This cake can be used as an alternative for some cement raw materials. By combining the two methods, various wastes previously considered unsuitable for recycling due to their chlorine content can often now be used in cement manufacturing plants. As such, these methods represent a major contribution to environmental protection as well as a solution to problems relating to the diffusion of heavy metals and dioxins from cement plants.1. IntroductionWaste generation levels have risen rapidly in recent years. in both the consumer and industrial sectors and today, the need for effective, efficient waste management is one of the most pressing and serious problem of today's society.The Japanese cement industry has reacted to the increase in waste generation by using certain materials as alternative raw inputs or fuels for cement production, in an effort to contribute to society and conserve energy resources.These wastes often contain non-negligible levels of chlorine and heavy metals, however, both of which are unsuitable for cement production. Depending on the element content, Heavy metals have a particularly negative effect -on cement quality; in addition, they can be released into the environment. Chlorine, on the other hand, is contained in large amounts in incinerated ash from household wastes as well as in certain plastics. Both substances are considered impediments in cement-production, not only because they reduce the quality of the cement produced but also because they impair operating safety on cement production lines.To address this problem, two practical technologies have been established for separation and recovery of chlorine components during cement pre-processing and production. This paper introduces the application of these technologies with a special focus on incinerated ash from urban wastes, a representative form of waste material having notably high concentrations of chlorine, heavy metals, and dioxins. We also outline the technologies enabling this material to be used as an alternative input to cement production."

Jan 1, 2000

By Jamil M. Khalifeh, Shadia J. Ikhmayies, Bothina A. Hamad

"We computed the optical properties of the cubic niobium nitride (o-NbN) compound using the full potential linearized augmented plane wave (FL-LAPW) method within density functional theory (DFT). The complex dielectric function and optical constants, such as optical absorption coefficient, refractive index, extinction coefficient, energy-loss spectrum, and reflectivity, are all calculated and compared with experimental results. The behavior of the computed quantities is similar to that obtained experimentally, but the optical positions are shifted to lower energies. This shift was related to the strong interband transitions, which are located at energies higher than 5 eV for NbN- as they are for IV B transition-metal mononitrides- and they appear in the computed spectra and not in the experimental spectra. These interband transitions simply shift the position of the reflectivity edge or the screened plasma frequency to the longer wavelength side.IntroductionIn recent years, NbN, as a transition metal nitride, has become a very popular material due to its high hardness, melting point, wear resistance, chemical inertness and temperature stability, which makes it suitable for use as emission cathodes in microelectronics and sensors, optical films and micro-mechanics etc [l]. Niobium nitride has long been known as highly polymorphic material, for which several crystalline structures have been reported in the literature [2]. These structures include the well known super-conducting rock-salt (Fm-3m, or Bl) structure (o-NbN), the hexagonal structure with space group p63/mmc and prototype Fe2N (18fuN), the hexagonalstructure with space group p63/mmc and prototype NiAs ~-NbN) and others.There has been a lot of computational studies for the structural and electronic properties ofNbN [3, 4-7], but according to our knowledge there is not any computational work that has been devoted to study the optical properties of this transition metal compound. At the same time a number of authors had performed experimental work in this direction. For example, Xin-kang et. al [l] studied the microstructure and optical properties of magnetron sputtered NbN thin films. Torche et. al [8] studied the composition, structure, electrical and optical properties of nonstoichiometric niobium nitrides. Newport et. al [9] investigated the reflection and transmission spectra of cubic niobium nitride films, and Tanabe et. al [10] had investigated the optical parameters and reflectivity of reactively sputtered NbN thin films by using in situ ellipsometry."

Jan 1, 2013

By D. H. H. Quon

Results of a study conducted to determine the properties of iron ore pellets made from Mount Wright and Carol Lake ore concentrate fines with partial and full substitution of bentonite by several organic binders are presented. Carboxy methyl celluloses 7H and 6TL, hydroxy ethyl cellulose (natrosol) and modified guar gum all produce pellets of acceptable wet, green and dry strength. However, when fully substituted, an inorganic binder such as calcium carbonate is required for satisfactory strength development after induration. Mixing the Carol Lake ore with Mount Wright ore in a 50-50 ratio also achieves the same result. The failure of the Carol Lake ore in the pelletization process is attributed to the low hematite content of the ore. The results are very similar to those from the extrusion studies reported earlier (8).

Jan 1, 1989

By Gabriel Plascencia

Copper was oxidized in the temperature range from 300 to 1000 GC under different pressures of oxygen. In the range from 300 to 500°C, copper oxidizes following the logarithmic rate law; while in the range from 600 to 1000°C oxidation follows the parabolic rate law. Transition from logarithmic to parabolic growth occurs at about 525°C. X-ray diffraction was performed on oxide scales to account for the CuO/Cu2O ratio at different temperatures. Activation energies found in this work are in good agreement with reported values.

Jan 1, 2003

By Yasuhiko Ito

"This talk is concentrated on the topics of compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate. As a typical example, electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film is described. Another example is the formation of various kinds of intermetallic compound films including Ni2Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail.IntroductionGenerally speaking, surface film formation by molten salt electrochemical process can be divided into the following three categories:(i) single element film formation on the electrode by electrodeposition,(ii) compound film formation on the electrode by electrocodepostion of more than two elements, and(iii) compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate.This talk is .concentrated on the topics of category (iii), especially on the electrochemical implantation. Typical example can be seen in the electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film. Another example is the formation of various kinds of intermetallic compound films including Ni2 Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail with examples above as well as other experimental results also obtained very recently in the author's laboratory."

Jan 1, 2000

By Luben Savov

This paper presents recent research works on the removal of the tramp elements Cu, Sn, Zn and Pb from steel. The evaporation of Cu and Sn in iron-based melts treated at reduced pressure of the gas phase was studied in a vacuum induction melting furnace. The effect of chamber pressure, temperature and melt composition was investigated. Since the main source of contamination of steel with Sn and Zn is the recycling of tinplate and zinc coated steel, respectively, possibilities for the removal of meta1ic coatings in a scrap pre-treatment stage were studied, too. Tin was removed in the temperature range 400-5S0°C by treatment with reactive gases featuring high sulphur potential. Zinc can be removed by evaporation or by a combination of thermal and mechanical treatment. The paper discusses the thermodynamics of Pb in carbon-saturated iron melts, too.

Jan 1, 2001

By Lv Guozhi, Ren Xiaodong, Liu Yan, Dou Zhihe

"This paper investigated a new desulfurizer, dolomite and ferrosilicon. Magnesium vapor produced by silicothermic reduction of dolomite and ferrosilicon in an immersion tube of molten iron was injected into the molten iron by carrier gas through the underpunch of the tube and desulfurization reaction occurred. In order to explore the desulfurization process of molten iron by the new desulfurizer, the thermodynamics, and experiments of magnesium vapor production and desulfurization have been studied. Through thermodynamic calculation, the reaction temperature of magnesium vapor production by 75ferrosilicon and light-burned dolomite is 1838K in the standard state and decreased with the decreasing partial pressure of magnesium vapor, PMg· When PMg=25kPa, the reaction happens at 1673K. From experiments of magnesium vapor production, reduction efficiency of Mg vapor is about 60 % in 15 minutes at 1673K. From hot metal experiments, the desulfurization efficiency is 89.35%, and the lowest sulfur concentration after desulfurization is 46ppm.IntroductionPretreatment desulfurization of hot metal has become a necessary step in modem optimizing steelmaking process for its cheap cost, which can not only liberate of blast furnace productivity and reduce the burden of produce steel, but also effectively improve overall economic efficiency of the iron and steel system[l-ZJ_ At present, injection magnesium particle is one of the two main methods of desulphurization in hot metal owing to its strong affinity for sulphur, low amount of slag produced, low iron loss in slag skimming and low equipment investment[3l. However, there are still some insufficiencies on the hot iron pretreatment with magnesium particles at present[4-5l"

Jan 1, 2013

By P. C. Chaubal

The overall kinetics of oxidation of single partic1es of chalcopyrite have been studied for temperatures up to 1273 K. The experiments were conducted in a stationary bed reactor using a non-isothermal technique. Any mass and heat transfer effects on the kinetics of oxidation were eliminated by using a high-enough gas flowrate. Up to temperatures of 873 K, pore-bl1ocking kinetics were applicable, whereas above 873 K, power-law kinetics gave a satisfactory fit of the data. The activation energy was 215 kJ/mol below 754 Kand 23.7 kJ/mol above 1,060 K. Predominance area diagrams were constructed at various temperatures and used in conjunction with X-ray analyses of partially oxidized samples to determine the intermediate phases formed during the reaction. The analysi1s also provides a justification for the kinetic models used. The results indicate that the reaction rate is first order with respect to oxygen concentration and inversely proportional to the square of the particle size throughout the ranges of temperature studied.

Jan 1, 1985

A rotating-discelectrode system was used to evaluate the electrochemical behaviour of Eu(III) during its reduction in NaCl solutions. The solution pH and NaCl concentration have a great effect on the reduction kinetics. The thermodynamic modelling study also revealed that Eu(III) exists in various forms in NaCl solutions. At a low concentration of NaCl, the predominant species is the free Eu3+. Other Eu-chloro complexes become more predominant when the NaCl concentration increases.

Jan 1, 1992

By D. G. C. Robertson

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

Jan 1, 2003

By Akira Nishikawa

During the twentieth century, the copper smelting industry achieved dramatic expansion corresponding to the vast growth of global economy. This was largely due to innovations in pyro-metallurgical processes, such as autogenous smelting and continuous smelting and converting technologies. However, as copper production capacity increased, its impact on the environment also could not be ignored, and thus with increasing global environmental awareness, many smelting operations either had to renew or rebuild their facilities. In addition to these changes, in places like Japan and Europe, with scarce primary resources, the treatment and recovery of metals from a variety of items such as car shredder dust, used electrical appliances and electronic devices, on top of scraps traditionally treated, is having a profound effect on the reduction of waste and the preservation of primary resources. Thus compared to the days when copper smelting focused on the environmental control in order to break with "Smoke Stack Industry", copper smelting today is making an important contribution to the sustainable development of human society.

Jan 1, 2003

By Ray Y. Lin

Chemical vapor deposition of tungsten carbide on the surface of steel has been investigated at temperatures between 400 and 550C in an atmosphere containing tungsten hexafluoride, hydrogen and benzene. The tungsten fluoride flow rate was maintained at 20 ml/min. The hydrogen flow rate was at 100 ml/min. The benzene concentration varied from 1.15 to 5.56% in the reaction gas. It was observed that the higher the temperature, the faster the deposition rate for tungsten carbide. But the dependence of the deposition rate on the benzene concentration was not systematic. From the x-ray diffraction analysis, it was observed that W, W2C and WC are all presented in the coating. The amount of each phase presented in the coating depends on the temperature and, to a less extent, on the benzene concentration. The microhardness measurement has also been done for all CVD carbide coatings obtained in this study.

Jan 1, 1992

By André L. de Vegt

Soil and groundwater beneath a zinc production plant in The Netherlands are contaminated with metals and sulfate. To avoid contamination of nearby drinking water aquifers, a hydro-geological containment system and a biological treatment plant for the extracted ground water have been installed. Currently about 5000 m3/day of groundwater is extracted from a combination of 12 shallow and deep wells. Heavy metals and sulfate have to be removed from the extracted water before it can be discharged into a river. Several water treatment methods have been studied and pilot tested at the site. The preferred and selected process is based on the activity of sulfate reducing bacteria (SRB) and combines sulfate removal and heavy metal removal in one single installation. Anaerobic bacteria reduce sulfate to sulfide resulting in the precipitation of metal sulfides. Excess sulfide Is biologically converted to elemental sulfur. A full scale biological treatment system was started up in May 1992. Design, start-up, commissioning and operational experiences are reported in this paper. Concentrations of metals and sulfate in the SRB water treatment plant effluent are well within the limits set by the Dutch Authorities for discharge to surface water.

Jan 1, 1995

By Tim Robinson, Georges Houlachi, Michael Moats, Marco Ginatta, Michael Free, David Creber, Neale Neelameggham, George Holywell

"Electrolytic processing is used commercially to recover and/or refine metals such as aluminum, copper, magnesium, nickel, and zinc. There are also new and exciting opportunities to utilize electrometallurgy in the production of titanium, lead, and other metals. This paper reviews some of the main technologies that are used to produce and refine metals as well as some of the recent advances and future directions the electrometallurgy industry may implement to meet the challenges faced now as well as those that are likely to be faced in the future.IntroductionElectrolytic processing is used commercially to recover and/or refine metals that include large scale production for metals such as aluminum, copper, magnesium, nickel, and zinc as well as small scale production for metals such as gold and silver. There are also new and exciting opportunities to utilize electrometallurgy in the production of titanium, lead, and other metals. This paper will focus only on electrometallurgical processing of metals with relatively large production markets."

Jan 1, 2012

By Zuoren Huang

The flowsheet of the hyd.rametallurgical zinc plant which is in use at Zhuzhou Smelters is described. The principal features of the process are fluid bed roasting, continuous calcine leaching, solution purification, zinc electrolysis, electrolyte cooling, and finally, the melting and casting of zinc forms. The Zhuzhou process for the flotation of silver from the leach residue collected on the Moor filters is described. The technical details of the process are outlined and the operating data are analyzed. The flotation facilities are described in detail and concentrate grades and recoveries are presented. The waelz process is used to concentrate In, Ge and Ga remaining in the leach residue after silver flotation. These elements subsequently are recovered by selective leaching in sulphuric acid, and details of this operation also are presented.

Jan 1, 1990

By Enrico Cerilli, Bryan Salt

Xstrata Nickel’s Sudbury Smelter has systematically developed its converting aisle from a single stage to a counter current multi stage converting process. This has required the development of two unique converters; the Slag Cleaning Vessel (SCV) and the Slag Make Converter (SMC). This has resulted in a unique three stage converting process that enables treatment of secondary materials and producing a slag that can be discharged without further treatment. The paper will also discuss future changes currently being considered to further improve environmental, plant hygiene and productivity performance.

Jan 1, 2009