Search Documents

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 Kenneth N. Han

Ammonia has been found to be an effective leaching reagent for gold, silver and platinum group metals in the presence of appropriate oxidants. Electrochemical and kinetic aspects of the dissolution of elemental gold in ammoniacal solutions have been investigated. The cathodic reaction of aurous di-ammine on the gold cathode has been investigated first. From this investigation, the standard electro-potential of the cathodic reaction .and hence. the Gibbs free energy of formation of the aurous di-ammine were established. The solubility of gold in ammoniacal solutions was also examined in relation to ammonia concentration, temperature and concentration of various oxidants. The anodic reaction of the gold disk in ammonia? in the presence? of various oxidants including oxygen, ozon, hypochlorite, hydrogen peroxide, cupric and cobaltic ammine, and iodine was also examined and the results have been discussed. Excellent dissolution yielding of gold and many other metals, typically better than 95% recovery in 1'-2 'hours of leaching at a temperature ranging 80°C to 190°C has been observed. Test results of the dissolution of gold from elemental state as well as other sources including sulfidic ores and scrap are presented.

Jan 1, 1998

By N. L. Piret, E. N. Mounsey

Ausmelt technology is successfully used to process primary and secondary materials to produce lead in large-scale commercial operations and to meet stringent environmental standards. The development and commercial data covering these applications and the results with respect to metallurgical, cost and environmental performance are reviewed in commercial operations. A new smelter is scheduled for commissioning in 2000 at Korea Zinc's Onsan site to process lead fume and other secondary materials to produce 50,000 tonnes per annum of lead bullion. The unique features of Ausmelt technology also allow for the efficient processing of polymetallic concentrates and secondary materials, particularly copper and lead, through the effective separation of these elements into metal, slag and fume species. This capability has been successfully demonstrated at a commercial scale and the results and implications for the industry are discussed.

Jan 1, 2000

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 R. M. Luna-Sánchez

Electrochemical studies, particularly Evans? diagrams, have been employed in hydrometallurgy to simulate and explain the redox phenomena that take place at mineral and metal surfaces during operations such as leaching and cementation. However, despite their utility, in some cases, the combination of the cathodic and anodic branches, determined separately, does not reproduce the chemical environment present when both processes occur simultaneously on a specific surface. In the present paper, limitations of Evans? diagrams are analyzed through two examples: silver sulfide cyanidation and gold cementation on zinc. In both cases, the surface kinetics are sensitive to the local pH and cyanide levels. When the electrochemical oxidation of silver sulfide or the reduction of gold are performed in the absence of its corresponding redox reaction, the local pH obtained does not simulate the real situation and the combined reaction kinetics may be very different from those determined from the Evans? diagrams.

Jan 1, 2003

By Viviane Tavares de Moraes, Denise Crocce Romano Espinosa, Jorge Alberto Soares Tenorio, Adriana Johanny Murcia Santanilla

"Increasing volumes of solid waste are generated worldwide, due to the continuous technological advances, the electronic scrap is part of these waste, requiring the study of recycling processes to stimulate this activity or the reuse of its components. The separation of nickel from sulphate leach solution, which also containing iron, zinc and aluminium was carried out using bis-(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272) as extractant, in order to determinate the effects of pH and temperature. The number of stages required for extraction was also assessed. The results showed that the metal extraction increased with increasing pH. On the other hand, increasing temperature was not favorable for all metals. However, under conditions used in this paper the purification of solution containing nickel was possible.IntroductionIncrease in the demand of metals in the world for use in industry causes a great exploration of natural resources. One outcome of this is increased investigations for the recovery of metals from industrial wastes. Nickel is found in wastes, such as batteries and electric and electronic devices, this kind of waste becomes a significant source for metals recovery. Since nickel is also present in printed circuit boards, which are associated with electric and electronic equipment, it can be recovered from this kind of waste through different techniques. It is important to highlight that iron is generally associated with this scrap [1] and for its removal chemical precipitation is often used. On the other hand, the solvent extraction process is widely used for treatment of leach liquors, because it can be produce high purity solutions [2, 3]. This technique is based on the purification of solution using contact between a liquor leaching and the immiscible organic solution, which contains an extractant that promotes the desired metal transfer [4]."

Jan 1, 2012

By Florian Kongoli

"Lime ferrite" slag with limited silica content has proven to be a valuable choice in the modem processes of copper smelting and converting due to several advantages that this slag offers compared to classical silicate slags. Nevertheless the liquidus surface of this slag has been experimentally measured only at low oxygen potentials such as in equilibrium with iron or hear it and in air. Although most of the smelting and converting processes that use this slag occur at intermediate oxygen potentials, the liquidus surface of this slag is not known at these conditions and the effect of oxygen potential and silica has not been correctly understood. This has brought some confusion in literature as well as in the industrial practice. In this work the liquidus surface of the calcium ferrite slags has been quantified by the means of a new thermophysicochemical model and a new type of liquidus surface diagrams which are very convenient for any industrial process that uses calcium ferrite slags. These diagrams can be easily used to select the lowest liquidus temperature of calcium ferrite slags at a minimum cost and can help design several fluxing strategies in copper smelting and converting processes. The effect of the oxygen potential and silica is also quantified and important industrially related conclusions are drawn.

Jan 1, 2003

By Jeffrey R. Taylor

The distribution of low concentrations of Cr, Mn, Rh, Co, Ni, Ag and Fe between copper matte and bullion phases has been measured at 1200oC. These results. together with values for nine other elements, have been used to develop a simple model to describe the distributions in terms of known thermodynamic properties?. The Temkin model for ionic melts was assumed to apply to the sulphide species in the Cu-S matte? phase and it is shown that the choice of sulphide species is particularly important for successful representation of the experimental .results?. In general, the lowest sulphlde (minimum sulphur :. metal ratio)? formed by the. metal is most suitable, although Ni, Co, Rh and Pd appear to associate with more sulphur in the melt than suggested by the? composition of their lowest sulphide. A correlation between the composition of the metal sulphide species formed in the ternary system and the? position of the minimum in the free energy of mixing curve in the metal-sulphur binary -system is? proposed.

Jan 1, 1983

By Kelly J. Driscoll

Impure zinc (98.5%) was electrorefined to high purity zinc (99.995%) using a fused salt electrolyte of molar composition 1: 1 : 1 :2 ZnCI2:KCl:NaCl:LiCl with a current efficiency of about 90% at 723 K. A recessed channel electrorefining cell was developed which achieved excellent mixing of both the metal and the electrolyte and by ensuring a very small anode to cathode spacing the voltage drop across the cell was 0.16 V and at a current density of 7kA m-2. The physical characteristics of the cell were observed using a low temperature model which showed the formation of droplets and rivulets which provided mixing. The application of this approach to the refining of other non-ferrous metals is discussed.

Jan 1, 1992

By Jin Yu, Fang-Qiu Zu, Yun Xi, Li-Na Mao

"According to the behaviors of resistivity-temperature of Cu-Sb70 melt, which suggests a partly reversible temperature-induced liquid structure transitions (LST) could occur in this alloy, in this paper, we investigated the dependence of solidification on the liquid state. Both resistivity and temperature were measured to track solidification process. The results show that the nucleating undercooling of the melt which experienced the LST increased and the solidified time decreased. Meanwhile, the solidified microstructures refined evidently, with the microscopic pattern of primary phase changes from disordered pillarlike dendrites into homotaxic ones. Moreover, it is verified that the microstructures would be different if the reversible part of the LST was restrained. The new phenomena and results reflected in this paper suggest that grasping the rules of melt structure change with temperature before material processing will give help for controlling the solidification more effectively and finally resulting in more ideal microstructures.IntroductionThe structure and quality of liquid alloys have a direct and important influence on the structure, performance and quality of the solidified ones. In recent years with in-depth study of liquid structure, researchers have found that some liquid structure transitions (LST) could occur on dependence of the temperature or pressure [1-5]. And the article [6] reported that a pressure-induced reversible LST was found in liquid triphenyl phosphite, which further confirmed the authenticity of the existence of the LST. Furthermore, in our earlier studies of Sn-based melts using resistivity method, some abnormal structure changes induced by temperature have been found at hundreds of degrees above liqiudus, and these LSTs are partly reversible[7]. This phenomenon has been discussed and it is suggested that the reversible LST in Sn-based melts are related to the short-range ordering (SRO) structures of Sn, which are tetrahedron structure with covalent bonding. However, does this reversible LST exist in other melts too?"

Jan 1, 2012

By M. D. Light

An intelligent control system (ICS) is being developed for ferrous iron oxidation by Thiobacillus ferroxitdans. The ICS provides computerized data acquisition and' control of process variables (temperature, Eh, pH, dissolved oxygen arid carbon dioxide concentrations and dilution rate) to maintain the ferrous iron oxidation at the highest possible rate. The ICS uses fuzzy logic for analysis of data inputs and implementation of control strategies. T:his paper provides preliminary information on the development of the ICS and? its operation.

Jan 1, 1991

By Byung-Young Choi

Nitrogenated carbon films were deposited on the high-frequency induction hardened steels by ion beam assisted deposition. X-ray photoeleetron. spectroscopy and scanning electron microscopy were used to analyze the chemical content and the morphology of the coated steels. Rolling contact fatigue tests were performed using Polymet RCF-1 machine with a constant supply of lubricant. It was found that CNx films adherent to the steels substrates were formed by ion beam assisted deposition. It was also found in the rolling contact fatigued specimens that non-propagating crack was initiated in the white etching area indicating the maximum shear stressed, region, leading to surface failure.

Jan 1, 2000

By C. Wieckert

Concentrated solar energy can be used as heat source for the production of metals. One of the most promising respective processes, the solar carbothermic production of Zn from ZnO, is investigated within the European research project SOLZINC, a cooperation of institutes and industries from France, Germany, Israel, Sweden and Switzerland. The solar produced Zn can be used as commodity or as an energy carrier for further processing on demand to electricity in Zn-air fuel cells/batteries or to generate hydrogen by reaction with steam. In both cases the Zn is oxidized to form ZnO, which can be recycled back to the solar plant. In these cyclic processes Zn acts as a means to store and eventually transport solar energy. Second product of the solar process step is a CO-rich offgas, which may e.g. drive a gas engine or may be shifted to hydrogen in a conventional reaction with steam. A pilot plant using 300kW concentrated solar power input has been constructed and operated successfully. 86mass-% of ZnO mixed with 14mass-% of charcoal are reacted to produce Zn and CO at a temperature of about 1200°C, yielding about 50 kg gaseous Zn per hour. Zn-dust with 95% purity is recovered from the offgas system that was designed to produce Zn for Zn-air fuel cells. Based on the results and findings from the pilot plant, a two tons Zn/h solar demonstration plant has been designed conceptually. Cost studies have been performed and scenarios for producing electricity or H2 via these ZnO/Zn-cyclic processes are evaluated.

Jan 1, 2006

By Junji Shibata

As one of the effective usages of various wastes discharged in non-ferrous metal industry, the synthesis of hydrotalcite was carried out using aluminum dross as a raw material. Hydrotalcite is one of the inorganic anion exchangers and has layered structure of complex hydroxide. The removal of toxic metal ions such as As(III), As(V), Cr(VI) and Se(IV) with the hydrotalcite was investigated, and the removal properties were compared from the viewpoint of the anion exchange amount and exchange rate. Hydrotalcite can be obtained by a co-precipitation method from the aluminum dross and the waste MgCl2 solution discharged in an aluminum regeneration process. Slight amounts of SiO2, Al2O3, Fe2O3 and so on remain in the reaction product as an impurity component. Interlayer distance of the obtained hydrotalcite is about 0.3nm. Hydrotalcite changes to Mg-Al oxide by the calcination at 773K for 3h, and then hydrotalcite is formed again by a rehydration operation after calcination. The toxic metal ions are removed from aqueous solution by the anion exchange reaction in the pH region where toxic metal ions exist as the anionic species like AsO2-, HAsO42-,CrO42-, and SeO32-. The exchange amount is considerably concerned with the valence of anionic species and the size of anionic species. The removal of toxic metal ions were investigated from the engineering aspects such as the low concentration limit to be removed, the amount of hydrotalcite to be used for the perfect removal of toxic metal ions and so on.

Jan 1, 2006

By Peter Hayes, Evgueni Jak, Ata Fallah Mehrjardi

Modern analytical tools, such as electron probe X-ray microanalysis (EPMA), are used in experimental characterization of phase equilibria and microstructures of complex slags. Integrated thermodynamic computer packages, such as FactSage, are used to provide more accurate descriptions of complex slag systems. These advanced methodologies have been applied to characterize dynamic steady state freeze linings in slag systems using submerged cold finger probes at controlled laboratory conditions, establishing the effects of bath chemistry, temperature, heat extraction rate and bulk fluid flow. It has been found that stationary freeze lining deposit interface temperatures at steady state conditions can be lower than the bulk slag liquidus temperature, and that stable operation below the liquidus is possible. A conceptual framework has been developed to explain the phenomenon and the range of interface temperatures that can be obtained in dynamic steady state conditions. These findings have important implications for the design of freeze linings and possible improvements to high-temperature metallurgical operations.

Jan 1, 2014

Acid mine drainage containing heavy metal ions is a large environmental problem facing the mining and mineral processing industry. The femte coprecipitation is a novel technique for removing heavy metal ions from waste water, recently applied to acid mine drainage. The fenite precipitation is usually performed at high temperature and therefore if applied in conventional manner, it becomes uneconomical to treat large quantities of acid mine drainage. In this paper the ferrite precipitation at ambient temperature-is &died. The possible mechanism of ferrite formation is discussed Experimental results from Noranda Tailing and Berkeley Pit water treated by this process are presented.

Jan 1, 1994

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

During electrowinning of nickel chloride, hydrochloric acid was regenerated instead of chlorine in a two membrane cell, by segregating the chloride catholyte with an anion exchange membrane, and the sulphate anolyte with a cation exchange membrane from the middle electrolyte (ampholyte) compartment. Successful operation of such a cell depends on controlling chloride leakage through the cation exchange membrane to the anolyte. Small amounts of chlorine gas could be detected in the oxygen evolved at the anode. In this paper, the chloride. leakage as a function of various types of cation exchange membrane and different composition of the anolyte is reported and discussed. Ag+ was added to the anolyte to eliminate chloride leakage to the anode. The cell voltage, electrode potential and voltage drop over the membrane as a function of current density has also been investigated.

Jan 1, 1996

By Bin Du

In recent years, concurrent product design and process is gaining popularity and will become a norm of the industry of the future. Forging has been a critical manufacturing process for production of components with superior tensile strength, toughness and grain flow. This paper describes an expen system which is being developed for forging die design and forging process analysis in concurrent engineering environment. Rules and guidelines pertaining to forgeability are formulated and incorporated into the knowledge-base in building the system. The system is built using an object-oriented paradigm. The object-oriented approach and hierarchical rule structure paradigm are briefly discussed. Finite element analysis packages (ALPID-2D) were incorporated into the program to give the simulation result of the forging process. The system can automatically produce a competent design and recommend a set of processing parameters for a given product. The designer can modify the design according to the result of the simulation.

Jan 1, 1992

By Baptiste Laubie

Agromining is a phytotechnology aiming at producing commercial metal compounds from low-grade ores thanks to hyperaccumulating plants. The fern Dichranopteris dichotoma is a rare earth element (REE) hyperaccumulator, which naturally grows on former mine tailings in China. It accumulates up to 0.35% of REEs in its aerial parts. Different hydrometallurgical processes are currently developed to recover these elements directly from the biomass or from ashes after combustion. The process presented here consists of a direct extraction by EDTA solution, followed by precipitation with acid oxalic. Optimal precipitation pH and influence of organic matter are determined by modelling and by experimental studies. The final solid contains 4.3% of REEs, with calcium as the main cationic impurity (0.45% of the precipitate). The recovery yield is similar for major REEs and is around 70%. After optimization, upscaling of the process will allow the agromining development to recover REEs from secondary resources with more environmentally friendly techniques.