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By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By K. B. Shedd

Questions regarding possible adverse health effects from exposure to zeolites arose when the inhabitants of two villages in Turkey were found to have high incidences of mesothelioma, a disease generally identified with exposure to asbestos. No asbestos deposits are known in the area, but some fibrous zeolites have been found. Further investigations have resulted in conflicting opinions as to whether fibrous zeolites are related to the high incidence of mesothelioma in Turkey. The U.S. Department of the Interior, Bureau of Mines examined the habits of domestic zeolites by scanning and transmission electron microscopy. Only erionite and mordenite particles possessed acicular to fibrous habits. With the exception of a rarely occurring woolly erionite sample, the fibrous zeolites were not dimensionally equivalent to asbestos.

Jan 1, 1982

By Jack S. McPartland

Historically, research on thiosulfate leaching of precious metals ores has been focused on processing of difficult to treat ores. Thiosulfate leaching of ores and concentrates containing sulfide minerals, copper, manganese and preg-robbing carbon constituents has been evaluated. Cyanide leaching is generally considered an efficient, environmentally acceptable means for processing of non-refractory precious metal ores, Consequently, commercial processing of finely disseminated, oxidized precious metal ores is normally accomplished using alkaline cyanide leaching. Recent changes in regulatory climate have, however, called into question the acceptability of cyanide leaching in a number of locations worldwide. In some cases where the use of cyanide is being questioned, thiosulfate leaching may provide an acceptable alternative. Developments in thiosulfate leaching of precious metal ores are reviewed in this paper.

Jan 1, 1999

By Michael S. Moats, Daniel Kim, Shijie Wang

"The behavior and deportment of lead, arsenic, antimony and bismuth are critical in producing high quality cathode by copper electrorefining. A critical review of research related to these elements is presented along with a comparison to industrial data, where appropriate. These elements exist predominantly in the anode as complex oxides along die grain boundaries. Upon dissolution, Group 15 elements report both to the electrolyte and slimes while lead essentially enters the slimes. The deportment of the Group 15 elements appears to be influenced by several chemical interactions which are discussed. The effect of these elements on floating slimes and anode passivation is reviewed. Under normal electrorefining conditions, lead, antimony and bismuth are thought to enter the cathode through the encapsulation of slime particles. The literature indicates that arsenic enters the cathode predominately by electrolyte entrainment. Finally, areas for future research regarding these elements are presented.IntroductionControlling lead, arsenic, antimony and bismuth is critically important for the production of high quality cathode in copper electrorefining. The reasons for this are twofold. First, ASTM Grade 1 Cathode specifications [1] for these elements are low, as listed in Table 1. Second, they can affect the efficiency of the electrorefining process (e.g., through passivation, current efficiency, slime processing)."

Jan 1, 2012

A novel process is being developed for metal recovery from waste electrical and electronic equipment involving a leach reactor coupled to an electrochemical reactor. Metals such as Ag, Au, Cu, Pb, Pd, Sn etc. are dissolved from shredded electronic scrap in an acidic aqueous chloride electrolyte by oxidising them with aqueous dissolved chlorine species. In the electrochemical reactor: (i) chlorine is generated at the anode for use as the oxidant in the leach reactor, and, simultaneously, (ii) at the cathode, the dissolved metals are electrodeposited from the leach solution. The extended Butler-Volmer equation was used to provide predictions of the electrode potential dependences of partial current densities and, hence, total current densities, current efficiencies and alloy compositions for acidic aqueous chloride electrolytes containing Ag(I), Au(III), Cu(II), Pb(II), Pd(IV) and Sn(IV) species, together with dissolved chlorine. With judicious choice of kinetic parameters, the predicted total current density ? electrode potential behaviour of such solutions was in good agreement with experimental data for a rotating Pt disc electrode. Reduction of dissolved chlorine at a Pt rotating disc electrode exhibited mass transport controlled behaviour, in agreement with Levich?s equation over the potential range 0.3-0.9 V (SHE). This could form the basis of a linear sensor, possibly using a microelectrode for measurement and control of the dissolved chlorine concentration in the efflux of leach reactors and inlet to electrowinning reactors in the envisaged process.

Jan 1, 2003

By Daniel Kim, Justin McAllister, Shijie Wang

"At the Kennecott Utah Copper Refinery, impurities in the electrolyte are being precipitated in the circulation system and form a hard scale in the piping. This scale must be removed periodically for proper electrolyte flow. Distinct layers of differing composition form as the operating conditions of the tank house change. Scale samples from the inlet and outlet pipes were analyzed to discover the nature of the precipitates. Each sample was sectioned and examined under optical microscopy and SEM. The composition of the scale was analyzed using ICP, XRD, and SEM/EDX mapping. The rate of deposition was determined by measuring the amount deposited on new pipes after elapsed time intervals. In order to determine how to minimize the formation of the scale, the mechanism was studied and the results are presented in this paper.IntroductionIn copper electrorefining, impure copper anodes are refined into pure copper cathodes. The impurities from the anodes are either insoluble and report to the slimes or soluble and dissolve concentrating in the electrolyte. These impurities are controlled by bleeding electrolyte from the system. Over time, the impurities combine to precipitate a hard scale on the surfaces contacted by the electrolyte. The scale causes problems with tank house circulation systems. In order for the refinery to operate properly, the scale must be removed periodically from the walls of the pipes. The first step to control the buildup of scale on the pipes is to understand the composition and the phases that are present in the scale."

Jan 1, 2012

By Corby G. Anderson

For over a century, the Sunshine Mine in Idaho has been a major producer of silver. An estimated 335,000,000 troy ounces of silver has been mined. This has established the Sunshine Mine as the largest single source of silver in the world. Because the dominant silver containing mineral is tetrahedrite, a copper and antimony sulfide, normal metallurgical treatments to recover the precious metal are not practical. Thus, over the course of the company's history, novel, hydrometallurgical technologies have been developed on-site to handle complex, precious metal containing materials. Recently, the use of Sunshine technology has been extended to the recycle of secondary materials. As well, the use of Sunshine technology by other organizations for treatment of both primary and secondary feedstocks containing precious and base metals is an area of growing interest. This paper will provide an overview of Sunshine hydrometallurgical technologies including the applicability of Sunshine technology to the recycling of precious and base metals.

Jan 1, 1995

By Marc Verhaege

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

Jan 1, 1995

By Honggang Zhong, Xin Cao, Qijie Zhai, Hongmei Song, Congsen Wu, Cheng Zhang, Jingzheng Ye

"The influence of superheat on the solidification structure and ferrite/austenite phase transformation of a novel lean duplex stainless steel (DSS) was investigated on a setup, which designed to thermally simulate the continuous casting process. The results showed that the macrostructure of the samples all exhibited chill zone, columnar zone and equiaxed zone. The distance from chill zone to position of columnar to equiaxed transition (CET) moved from 51.0 mm to 39.8 mm with an decrease of superheat from 70 °C to 10 °C, and that the grains in the chill zone tended to be finer. In equiaxed zone, the fme and uniform grains were observed when superheat higher than 40 °C; while, coarse grains were found in samples poured at low superheat. Generally, the volume fraction of ferrite increased along the dendritic growth direction, and stabilized in equiaxed zone. The high superheat decreased the volume fraction of ferrite in equiaxed zone, while it had indistinctive influence on chill zone and columnar zone.IntroductionDuplex stainless steel with approximately equal volume of ferrite and austenite, offering an attractive combination of corrosion resistance and mechanical properties. [ l]. The production of DSS, worldwide application in structural engineering[2] and petrochemical industry[3], have increase by more than 100% in the latest decade[4]. But due to the sharp prices increase of nickel and chromium, lean duplex stainless steels which have lower contents of alloy elements were developed. They perform well in both mechanical and corrosion resistance[S, 6] and even have TRlP(Transformation Induced Plasticity) effect[?]. Nonetheless , the mechanical properties of DSS was affected greatly by the solidification structure, such as columnar to equiaxed transition (CET), grain size and phase content[8]. So, the solidification behavior of stainless steel was investigated widely"

Jan 1, 2014

By R. C. Chaturvedi, S. B. Padwal

"Padwal and Chaturvedi have developed the model based on M-K theory, considering Hosford's yield criterion and critical thickness strain criterion"" to predict the sheet metal forming limits under simple (constant) strain ratio paths. This analysis has been extended in this paper to predict the sheet metal forming limits under complex strain paths. The effects of exponent ""a"" in Hosford's yield criterion and strain paths on the forming limits under complex strain paths are studied using this analysis. The predictions of the present analysis are compared, both for simple and complex strain paths, with experimental results of Ishigaki for A.K. steel and also with the predictions of Rao and Chaturvedi's model. The quantitative analysis of the error in predicting the forming limits has also been carried out using a method suggested by the authors earlier.1. INTRODUCTIONThe constant strain ratio condition has been assumed in the theories developed for prediction of forming limit diagrams (FLO). In actual forming operation, this condition is seldom satisfied. Even in the case of simple single stage press formed components, the strain path becomes curved and non-linear. In the case of pressings with complex shapes, or multiple stages of forming, the changes in strain path are more pronounced and even abrupt.Experimental study of the forming limits, under two stage strain paths, by Ishigaki [1], has shown that the forming limits are path dependent. It has been observed that the forming limits lower than that under simple strain paths, may be obtained under certain strain paths (when the first stage strain path is either equibiaxial tension or uniaxial tension, followed by the second stage strain path as plane strain). Rasmussen's work [2J, on the theoretical study of forming limits under curvilinear strains paths, has shown that a large drop in formability can result from very small changes in strain path. Thus if a deformation process gives rise to failures due to plastic instability, the failure is not necessarily due to insufficient formability of the material. In such cases, FLOs based on constant strain ratio path should not be used directly in predicting the success or failure of the forming operation. Thus the knowledge of forming limits under complex strain paths is of great importance to the interpretation of press-shop problems."

Jan 1, 1994

Acid generation from reactive sulphide mineral tailings has become a major environmental problem in the mining industry. Initiation of chemical and biochemical oxidation reactions of the sulphide mineral leads to acid generation. A novel concept of safe disposal and utilization of reactive fine mill tailings is presented in this paper. The paper also presents the results of a preliminary laboratory experimental .study of the concept. The tailings are agglomerated using portland cement as a binder. The cold bonded agglomerates are encapsulated with other chemical additives to act as acid neutralizers, oxygen and ironoxidizing bactericides., The primary. factors influencing the choice of bacterfoides to inhibit the acid generating bacteria are their costs, toxicity and environmental friendliness. The paper discusses the utilization of agglomerated' products as aggregates for underground backfill, or as gravel for surface land cover.

Jan 1, 1991

Gas flow and heat transfer phenomena in two industrial-scale waste-heat boilers of the Outokumpu copper flash smelting process were analyzed with a commercial computational fluid-dynamics (CFD) package Phoenics. Various operating conditions were simulated for the first boiler and particularly for the second boiler. The gas flow pattern was compared qualitatively with the physical laboratory models, and the general flow pattern was consistent with the laboratory visualization. The heat transfer simulation was validated with, temperature measurements for both boilers, and good agreement was reached between the computed temperature profiles and the measured data. The computational results indicate that gas flow in both boilers is of three-dimensional and recirculating nature. The numerical tracer experiments indicate that some dead volume is present in both boilers, and the boiler modification reduced the dead volume from 38% to 15% under basic operating conditions. Radiative heat transfer accounts for 65-90% of the total 'heat transported in the radiation sections of both boilers under different operating conditions. The modified boiler is very efficient for cooling the off-gases at almost doubled volume flow rate. The CFD modeling proved to be a useful tool for numerical experiments and analysis of boiler performance for process: optimization.

Jan 1, 1998

By James Wang

In July 2003, The Office of Hydrogen, Fuel Cells and Infrastructure Technologies of the Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy solicited Grand Challenge Proposals to establish three Centers of Excellence in hydrogen storage developments for reversible metal hydrides, non-reversible chemical hydrides and carbon storage materials, respectively. The program mission is to research and develop cost-effective, on-board hydrogen storage systems that enable a minimum range of 300 miles within the weight and volume constraints of the vehicle. Currently, no hydrogen storage technology available can meet the DOE cost and performance targets. In April 2004, Sandia National Laboratories was selected by DOE to lead the Metal Hydride Center of Excellence with partners from 5 other national laboratories. We will present the organization and recent accomplishments of the Metal Hydride Center which is confident to accomplish DOE/FreedomCAR and Fuels Partnership objectives for 2010 in hydrogen storage for vehicular transportation applications.

Jan 1, 2006

By Masafumi Maeda

Our aim in this project was to develop a new copper refining technology utilizing pyrometallurgical treatment and a raw materials preparation technique. In the recycling process; raw material is not an idealized concentrate of copper sulfide but is composed of various types of scrap, industrial wastes such as sludge, ash and slag, and municipal wastes. Since we cannot expect oxidation heat in this process as in sulfide smelting, organic materials are viewed as an alternative energy source. Quality of the copper produced is targeted as 99.99% and an intermediate grade will also be marketable. To benefit the plant, rare metals and other nonferrous metals will also be recovered The overall system is described in this paper, specific topics outlined and preliminary research presented. Current Japanese technology for recycling copper based materials is briefly reviewed.

Jan 1, 1995

By Tianzu Yang, Weifeng Liu, Lin Chen, Wei Chen, DUCHAO ZHANG, HUI XIAO

Oxygen-rich side blow bath smelting (OSBS) technology was developed in 2000 based on Vanyukov process. This technology exceeds the traditional pyrometallurgical methods by its great processing capability, high metal recovery and environmental-friendly property. In the past 15 years, OSBS technology extended its application area from lead industry to bismuth, antimony and waste recycling industries, etc. This paper introduces the history and new developments of OSBS technology. The typical industrial applications examples of the OSBS technology in China, including high lead slag reduction, low grade bismuth-lead concentrate smelting and metallurgical waste recycling, are reviewed. Especially, the unique furnace properties and technical parameters are compared. Finally, the potential research directions of OSBS technology are summarized.

Jan 1, 2016

By Robert G. Robins

Precipitation of ferric arsenate is an effective method for removing arsenic(v) from hydrometallurgical process solutions. The solubility and stability of this compound. FeAs04.2H20, has received some attention in recent years and the reported solubilities of amorphous and crystalline material have varied considerably. This paper reviews previous studies and reports some recent work with a consistent model to explain the variable results. Free energy data for ferric arsenate and its associated dissolved complexes are presented.

Jan 1, 1990

By Takafumi Kondo, Satoshi Yamashita, Noboru Masuko

"Aqueous oxidation of phosphite ions to phosphate ions with dissolved oxygen was examined at 80° C and pH 4.5 mainly from the stichiometric point of view. Dissolved oxygen alone can not oxidize sodilim phosphite in aqueous solution, but when sulfur dioxide is coexistent, cooperative oxidation for both sulfite and phosphite can occur in aqueous solution. Sulfur dioxide itself is well known as a reducing agent, but it also reacts as an oxidation-promoting agent for other species under a certain condition. So sulfur dioxide is· a promising cheap reagent for waste phosphite processing.IntroductionIn a liquid-phase oxidation reaction using the dissolved oxygen gas, the eoexistence of a copper salt is required generally. Recently, it was reported that the oxidation reaction progressed by using mixed gas of sulfur dioxide and oxygen without the copper catalysis, and the attention has been collected1·3). The present authors also noticed the phenomenon since the early time and have been studying on the reaction mechanism of sulfur dioxide in liquid phase oxidation 4l. It was found that; by using the SO2-O2 mixed gas, the oxidation of phosphite ions to phosphate ions proceeded efficiently in sulfuric acid solutions. In the present report, the applicability of SO2-O2 mixed gas as a cheap oxidizing agent to the industrial processing of the waste solution of electroless nickel· plating is investigated. It is well known that the sulfur oxide dissolved in aqueous solution is oxidized ·by the oxygen in the air to sulfuric acid according to the following equation"

Jan 1, 2000

By Moto Goto

Today, Pierce-Smith converters, coupled together with various types of smelting units, are used in most of the world's smelters, However, due to the "batch" processing nature, and problems associated with fugitive emissions during the transfer of melt and blowing stages, this arrangement will unlikely be adopted in future smelters. Modern day alternative processes include the Mitsubishi Process, Outokumpu Flash Smelting and Flash Converting Process, the Noranda Process, and the Ausmelt Process, but only the Mitsubishi Process is a "truly continuous" smelting and converting operation, producing a constant flow of blister without tapping, and is economically proven by long term commercial operations. This paper reviews recent advances in modern continuous converting technologies, with a special section devoted to operation of the "first standalone Mitsubishi C-furnace" coupled together with a Noranda Reactor, at Port Kembla Copper Pty, Ltd. in Australia.

Jan 1, 2003

By R. David Prengaman

During the past several years a new insoluble lead anode has been developed for copper electrowinning. The new anode consists of a rolled lead-calcium-tin alloy sheet attached to a slotted copper bus bar by a soldering process which produces a complete metallurgical bond between bar and sheet. The metallurgical bond greatly reduces the resistance between the bus bar and the lead sheet and the high conductivity does not deteriorate during the life of the anode. The rolled anode thins uniformly and does not suffer preferential grain boundary or internal corrosion commonly seen in cast anodes. The lead-calcium alloy containing a high tin content corrodes slowly because the rolling process produces a uniform, fine grained structure. The wrought product is very strong and ductile; and contains no internal defects, segregation, cracks, or pores which can reduce the life of the anode. Because the anodes corrode uniformly, a high percentage of the anode thickness can be utilized thus extending the life of the wrought anodes. The anode alloy composition which is stable only in wrought form, produces exceptional resistance to passivation during current interruptions. First introduced into liberator cells, the new electrowinning anodes have been specified as the anodes of choice for every new SX-EW tankhouse constructed in the last two years. This paper describes the new anode, its method of construction, service history, and how it differs from present copper electrowinning anodes.

Jan 1, 1987

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