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By M. Friák, L. G. Wang, M. Šob, V. Vitek

"The paper gives an account of applications of quantum-mechanical (first-principles) electronic structure calculations to the problem of theoretical tensile strength in metals and intermetallics. First, we briefly describe the way of simulating the tensile test and the electronic structure calculational method. Our approach is then illustrated on calculations of theoretical tensile strength in W, NiAl and transition metal disilicides MoSi2 and WSi2 with C11b structure. In Wand NiAl, we consider uniaxial tension along [001] and [111] directions. Although tungsten is elastically nearly isotropic (C44 = C”), theoretical tensile strength exhibits a marked anisotropy (oth/001 = 29 GPa, o'th/111 = 40 GPa). Calculated results compare favorably with experimental value of 24.7±3.6 GPa obtained for tungsten whiskers grown along the [110] direction. Similarly, in NiAl, the 'hard' orientation [001] differs very significantly from the [ill] orientation (oth/001 = 46 GPa, oth/111 = 25 GPa). This anisotropy is explained in terms of higher-symmetry structures present or absent on the calculated deformation paths. In disilicides, the theoretical strength is calculated for [001] loading (oth/001 = 37 GPa and 38 GPa for MoSi2 and WSi2 , respectively). The role of relaxation of internal structure parameter is discussed and changes in bonding conditions during the tensile test are analyzed.IntroductionIn most engineering applications, the strength of materials is limited by the presence of internal defects. If there were no defects, then, for example, the tensile strength could be several orders of magnitude higher and its value would be comparable with that of shear modulus. Therefore, the strength of ideal (defect-free) crystal represents an upper limit of attainable stresses, which is called the ideal strength. While it may not be possible to achieve the ideal strength in practice, it is not possible to exceed it. However, the ideal strength is already approached in situations which are technologically relevant. These include the low-temperature deformation of inherently strong materials, such as diamond, Si, Ge and some of the transition-metal carbonitrides, deformation of whiskers, nanoindentation of materials with low defect densities, hardened thin films and coatings etc. The ideal strength sets the limits of elastic stability of a solid. Its knowledge is useful for estimation of the ideal work of fracture stresses needed for homogeneous nucleation of dislocations and for modelling of crack propagation."

Jan 1, 2001

By D. J. Senor

Closed chamber incineration (CCI) is a novel technique by which irradiated nuclear graphite may be destroyed without the risk of radioactive cation release into the environment. The process utilizes an enclosed combustion chamber coupled with molten carbonate fuel cells (MCFCs). The transport of cations is intrinsically suppressed by the MCFCs, such that only the combustion gases are conducted through for release to the environment. An example CCI design was developed which had as its goal the destruction of graphite fuel elements from the Fort St. Vrain reactor (FSVR). By employing CCI, the volume of high level waste from the FSVR will be reduced by approximately 87 percent. Additionally, the incineration process will convert the Sic coating on the FSVR fuel particles to SiO2, thus creating a form potentially suitable for direct incorporation in a vitrification process stream. The design is compact, efficient, and makes use of currently available technology.

Jan 1, 1994

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Hu Long

In this, the first systematic study of the oxidation of orpiment (As2S3) in sulfuric acid solution under oxygen pressure at temperatures above 170°C, the effects of retention time, temperature, particle size, oxygen partial pressure, the concentration of sulfuric acid and pulp density were evaluated. The effects of cupric and ferric ions on the oxidation rate of As(III) to As(V) were also examined. The products of oxidation are As(III), As(V), SO42- and elemental sulfur. At temperatures ranging from 170 to 230°C, most of the arsenic was found to be in the trivalent state, and oxidation to As(V) with oxygen was very slow. This was confirmed by attempting to oxidize a synthetic arsenious solution. However, the rate of oxidation of As(III) to As(V) is rapid in the presence of ferric ion. Elemental sulfur was found at all temperatures investigated, which can be further oxidized to sulfate at high temperature.

Jan 1, 1999

By Stephen W. Paff

The EPA has estimated that there are over 3,000 sites across the United States contaminated with lead. Techniques to remediate these sites include standard stabilization/disposal technologies, reclamation of lead using secondary lead smelters, soil washing, and biological removal technologies. In this paper, the current technologies used for lead remediation will be reviewed. Factors affecting the use of each technology, such as range of applicable concentrations, soil types, interferences from other contaminants, economics, and current technology status will be assessed. The paper will also focus on the results of a recent study completed by the Center for Hazardous Materials Research (CHMR), in conjunction with a major lead smelter, which demonstrates that secondary lead smelters may be used economically to reclaim lead from a wide range of lead-containing materials frequently found at Superfund sites. Such materials include battery case materials, lead dross, and debris containing between 3 and 70% lead. The results of development work completed by CHMR on the Acid Extraction Treatment System (AETS), which has been demonstrated to extract Lead from soils containing up to 30,000 mg/kg lead, will also be presented. The use of these technologies will be compared with other options for the remediation of sites.

Jan 1, 1994

By Ian Baker, Xavier Pierron

"Iron aluminides hold great promise for intermediate temperature applications (to ~ 600°C) because of their excellent oxidation and sulphidation resistance and good strength. However, they have poor low temperature ductility, a feature which is exacerbated by water-containing environments. This paper presents an overview of the effects of environment on the ductility of iron aluminides, including the effects of iron aluminum ratio; ternary alloying additions, particularly boron; strain rate; and temperature. The mechanisms involved in water-induced embrittlement are discussed.IntroductionOver the last few years, it has became increasingly evident that the ductility and fracture toughness of many intermetallic compounds, particularly aluminides, are reduced dramatically if they are mechanically tested in either air or in hydrogen-containing atmospheres (1-5). For FeAI and Fe3AI, it has been shown that water vapor, for example in air at room temperature, can form atomic hydrogen by reacting with the Al atoms (1, 2). As a result in iron aluminides, the environmental embrittlement process is quite similar to traditional hydrogen embrittlement. This can be easily demonstrated by either testing an iron aluminide in an environment free of the deleterious species or by testing at high strain rates, both of which result in greater ductility. The purpose of this paper is to review recent progress in understanding environmental embrittlement in FeAI and Fe3AI, and to consider possible environmental embrittlement mechanisms. Greater understanding of this phenomenon will lead ultimately to remedies to this problem which is a major reason for preventing the practical application of these materials. First, some background on the iron-rich aluminides."

Jan 1, 1996

By Francois Barthelat, Sam Goroshin, David Frost, Alexander Cappozi, Atefeh Nabavi

"In this study, a novel chromium–chromium sulfide cermet was produced by self-propagating high-temperature synthesis (SHS). Conventional techniques for manufacturing metal sulfides are complex, environmentally harmful, and not suitable for producing complex-shape articles. To overcome these disadvantages, a new method for the preparation of the metal-sulfur precursor charge is proposed, which can be described as reactive casting. The first cermet samples produced with the SHS process were found to be very porous, brittle, and have low mechanical strength. The possible sources for the generation of porosity were identified and analyzed and the process for manufacturing the cermet was modified. By improving the manufacturing process, the porosity inside the produced cermets was reduced from 70% to 12%.IntroductionMetal sulfide composites are in high demand in the chemical, metallurgical, and electrical industries because of their valuable characteristics such as hardness, semi-conductivity, electroluminescence, infrared transparency and catalytic properties. Current manufacturing methods for metal sulfides usually involve one of two different principal methods, including a complex multistage wet chemical process involving the precipitation of the corresponding salts from an aqueous solution with hydrogen sulfide, or hot sintering of the respective elemental reactant powders in a resistive furnace in a high-pressure inert or hydrogen-sulfide atmosphere [1, 2]. These conventional methods for synthesizing ceramic metal composites are complex, extremely time and energy consuming, environmentally harmful, and rarely able to manufacture articles with complex shapes. Therefore, in order to overcome these disadvantages, self-propagating high-temperature synthesis (SHS) was considered as an alternative method that offers significant improvements over the traditional cermet manufacturing methods [3]. SHS, which is a relatively new and attractive method for producing a wide range of advanced materials, is based on the self-sustaining feature of the highly exothermic reactions of the reactants. The SHS process results in high product purity, since the high temperatures generatedin the reaction cause any impurities to volatilize [4, 5]. SHS has low energy consumption and doesn’t require an external energy source and complex equipment, and it is self-contained [1, 5]. Since combustion synthesis has low power requirements, it is one of the few methods of materials synthesis that is feasible in outer space. Also, the process has a low cost and is capable of directly synthesizing articles with the desired shape, size and structure [5, 6]. The chemical reactions associated with SHS are typically completed in a few seconds leading to the formation of the condensed product. The high reaction rates and relatively rapid cooling in SHS reactions can avoid undesirable grain growth in products which often occurs with the conventional sintering method [3, 5, 7]. The traditional method for sample preparation in the SHS technique is to compact the reactant mixture powders in a steel die by a press to a typical density of about 80% of the theoretical maximum value, before igniting the mixture [8]. This method requires a large compression force to increase the green density and to minimize any pores in the green compact. To overcome these disadvantages, a new method for the preparation of the precursor charge in metal-sulfur by SHS is proposed which can be described as melt casting of a reactive mixture, or reactive casting in short."

Jan 1, 2012

By Zhucheng Huang, Ronghai ZHONG, Liangming Wen, Tao Jiang

The reduction roasting-magnetic separation and its strengthening of high silicon coal-containing mini-pellets by sodium additives were researched. The results show that the carbon gasification reaction and reduction of fine hematite in high silicon coal-containing mini-pellets with 3% sodium additives were enhanced. Comparing with no sodium additives, the gasification rate of carbon with 3% sodium additives reacting with CO2 for 40 minutes at 950 and the metallization rate of reduced pellets with 3% sodium additives after roasting for 35 minutes at 960 increased from 35.15% and 58.72% to 86.98% and 86.15%, respectively. The analysis of SEM equipped with EDS demonstrates that the inner pore of reduced pellets with 3% sodium additives was more developed and the iron grains size significantly enlarged, meanwhile, the iron grade of concentrate increased from 60.45% to 80.23% and the iron recovery rate decreased from 84.67% to 80.78% after grinding-magnetic separation.

Jan 1, 2016

By Katsuyoshi Tatenuma

"In order to mitigate the effect of global warming by preventing the accumulation of atmospheric CO2, a permanent fixation method of surplus CO2 as an insoluble mineral onto the sea bottom is proposed. As the proposed reduction method of atmospheric CO2, the concrete concept of this method is to form an insoluble carbonate mineral (CaCO3) by direct electrolysis of the seawater; Ca2++2HCO3 -+OH- ? ?CaCO3(insoluble)+CO3 2- (soluble)+H++H2O <not as coral reef reaction>, are directly disposed of itself onto the sea bottom. By this treatment, a concentration of carbonate is reduced in the section of superficial seawater, and therefore the absorption capacity of atmospheric CO2 increases depending upon the shift of chemical carbon equilibrium between the mass of superficial seawater and the atmosphere. As no additives are required, or no secondary waste are produced, the proposed method assuming as green-orientated, has possibility to resolve fundamentally the problem of global warming in a green orientate manner.IntroductionRecently, the amount of atmospheric CO2 has been exponentially increasing and it is a main greenhouse effect gas causing the global warming [1, 2]. The concentration of atmospheric CO2 has increased more than 30% (370ppm in 2001) during only last two centuries, therefore approximately 750 Gton-C of CO2 currently exist in the atmosphere, in which 180 Gton-C of CO2 are accounted for the increment during two centuries [1, 3, 4]. In order to avoid the progressive increase of CO2 global abundance, 3 Gton-C of the incrementing amount per year [4], have to be removed annually from the atmosphere."

Jan 1, 2008

By I. D. Reznik

On blowing nickel matte in a converter without quartz, first the oxidation of metallic iron and a part of FeS occurs without evolving sulfur dioxide, the formed FeO dissolves in a sulphide smelt and form a homogeneous oxysulphide smelt. On further increasing the FeO content, the oxysulphide separates into 2 layers. Based on the laboratory investigation of FeO-(FeS+Fe°) - (Ni3S2+Ni°) ternary phase diagram we have identified the separation region at 1250°C. The boundaries of the separation region have the form of an arc and the composition of the separated oxysulphide layers is defined by the canodes. In the nickel or copper-nickel matte - silicacalcium oxide slag system at 1250°C three layers, namely sulphide, oxysulphide, and slag may be formed. A high slag basicity due to the presence of CaO can serve to enhance the activity of FeO; a low nickel content in the matte corresponds to a high concentration of FeS therein; FeO from slag and FeS from the matte form a homogeneous FeO-FeS solution, i.e. an oxysulphide layer. The investigation on the "Camebaks" apparatus and by the nuclear gamma-ray resonance spectroscopy method of the phase composition in a slowly cooled oxysulphide layer has shown the presence of four phases: wustite, troilite, ferronickel grains, and calcium oxide-silica inclusions. Knowledge of regularities in the oxysulphides formation makes it possible to use them in pyrometallurgy of nickel and cobalt or preventing their formation.

Jan 1, 1997

By D. A. Robbins

The Resource Conservation and Recovery Act. of 1976 (RCRA) requires testing of waste materials as part of the determination of whether these materials are classified and managed as hazardous wastes. The adoption of one standard testing procedure and its application to all types of waste materials has stirred much controversy. In the center of this controversy is the appropriateness of this testing procedure in characterizing non-ferrous metal intermediates and slags. The authors have evaluated the relative availability of metals in several types of copper and lead slags as defined by various testing protocols. Also discussed is the relationship between the chemical character of the slag and the availability of metals to leaching and certain metallurgical practices that can influence metals availability.

Jan 1, 1983

By Kafui Nyavor

The indirect, and the direct contact mechanisms of bacteria oxidation of sulfides were studied using Thiobacillus ferrooxidans and pyrite. The aim was to determine which of the two generally aeeepted mechanisms played a dominant role, if any, during acid mine drainage (AMD) formation from the oxidation of sulfide minerals. The results show that at a pH of 4.5 where T. ferrooxidans are quite active, but where initial chemical oxidation of pyrite to Fe2+ is limited, the bacteria were unable to directly oxidize pyrite to any significant extent. Whereas, in the presence of Fe2+, T. ferrooxidallS assisted oxidation of pyrite by the indirect mechanism was observed and sustained over the pH and Eb range where the bacteria is active. The results lead to the conclusion that the direct contactmechanism of pyrite oxidition by T. ferrooxidans is insignificant. The predominant, and possibly the only, pathway involves the indirect bacteria oxidation of available Fe2+ to Fe3+, which in turn oxidizes FeS2 to generate additional Fe2+ and acidity in a cyclic process.

Jan 1, 1996

By David Cocke

Study of surface and subsurface interfacial chemistry of metallic and similar systems has its enormous technological importance. Copper, for example, is a common component of many alloys and bulk amorphous systems. It is being increasingly studied today because of its use for electronic interconnect systems where processing is done below 200 ºC. Since several types of copper oxides exist, and the degree of their formation is dependent on temperature, perhaps characterization by EDS-SEM depth profiling and EIS might delineate one type of oxide from another. In this paper, we described our work on transformation of copper oxides with temperature ranging from 70 to 350 °C and their characterization by SEM, EDS, and XRD. We also showed the use of the phase angle portion of the impedance as a means to identify the predominant structure and the transition through Cu3O2 between the predominant stable CuO and Cu2O.

Jan 1, 2009

By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015

By Takeshi Yoshikawa, Kazuki Morita, Kunitoshi Matsunaga

"In metallurgical grade silicon (MG-Si), most impurities mainly exist at the grain boundaries and distribute in silicon grains at extremely small contents. Grain boundary phases in MG-Si transform into liquid above the eutectic temperature, and migrate towards high temperature regions when heated under a temperature gradient. With the migration of all liquid phases in MG-Si to the surface, the impurity contents will be decreased less than their solubilities in principle.In the present work, the fundamental research was conducted to discuss the possibility for purification using the liquid phase migration technique. The purification limit was estimated by thermodynamic calculations, and metallic impurities were estimated to be effectively removed except for Fe and Al. The migration behavior of the liquid phase in the synthesized silicon substrate was investigated by unidirectional heating under infrared radiation at 1523-1548 K, and the proceeding of migration was confirmed. The migration velocity was 1.4--2.0xl0-7 mis, and found to be controlled by the liquid phase diffusion.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. To enable the widespread use of photovoltaics and for the photovoltaic electricity price to reach grid parity, a low-cost and abundant feedstock of solar grade silicon (SOG-Si) is essential. Recently, a modified Siemens process and a fluidized bed reactor process were developed to address the cost and energy issues associated with the conventional Siemens process. However, their cost reduction potential is limited because of the large energy consumption needed to convert silicon into gaseous compounds. Purification of silicon through metallurgical routes offers a promising way for producing SOG-Si from metallurgical grade silicon (MG-Si), because it enhances productivity and can also lower the process costs. Although several metallurgical processes such as directional solidification [l ], vacuum refining [2-4] and plasma oxidation [5-7], have been developed, processing times and refining efficiencies still have to be optimized."

Jan 1, 2013

Several processes are now available for the recovery of free and WAD cyanide from gold plant solutions and pulps. In the past, the incentive for evaluating cyanide recovery in gold plant flowsheets has been economic. In many cases, it has been possible to demonstrate (at least in the laboratory and on paper), an improvement in process economics by; (i) reducing the costs of tailings detoxification, (ii) recycling cyanide at lower cost than the purchase/delivery price of new cyanide, and (iii) generating additional revenue via by¬product sales. Despite these convincing arguments, few cyanide recovery plants have been built at operating gold mines. Also, there is arguably an even more compelling reason for mining companies to consider cyanide recycling. With the growing storm of negative public opinion that the use of cyanide in the mining industry is attracting - following several highly publicized spills over the last couple of years - the time has come for the gold industry to demonstrate environmental diligence and stewardship in the use of this commodity that is so vital for their industry. There is no doubt that the widespread implementation of cyanide recycling will reduce the impact of the cyanidation process on the environment, both by reducing the risk of spills (with less cyanide being transported from manufacturing plants to gold mines), and by reducing the loading of toxic and non-toxic metals and ions in the tailings. In this paper, the various processes that are available for cyanide recovery are discussed, along with the process chemistry. Results of several laboratory and pilot plant trials that have been conducted over the last few years are also presented.

Jan 1, 1998

By Ji-He Wei

Keywords: stainless steel, AOD refining, side and top combined blowing, mixing characteristics, water modeling The fluid mixing characteristics in the bath during the side and top combined blowing AOD (argon-oxygen decarburization) refining process of stainless steel have preliminarily been studied on a water model unit of a 120 t AOD converter. The geometric similarity ratio between the model and its prototype (including the side tuyeres and the top lances) was 1:4. On the basis of the theoretical calculations for the parameters of the gas streams in the side tuyeres and the top lances, the gas blowing rates used for the model have more reasonably been determined. The influence of the tuyere number and position arrangement, and the gas flow rates for side and top blowing on the characteristics has been examined. The results demonstrated that the liquid in the bath underwent vigorous circulatory motion during gas blowing, without obvious dead zone in the bath, resulting in a well mixing effectiveness. The gas flow rate of the main tuyere had a governing role on the characteristics, a suitable increase in the gas flow rate of the subtuyere could improve mixing efficiency, and the gas jet from top lance could make the mixing time prolong. Corresponding to the oxygen top blowing rate specified by the technology, a roughly equivalent and good mixing effectiveness could be reached by using six side tuyeres with an angle of 27° between each tuyere, and five side tuyeres with an angular separation of 22.5° or 27° between each tuyere. The relationships of the mixing time with the gas blowing rates of main-tuyeres and sub-tuyeres and top lance, the angle between each tuyere, and the tuyere number have been obtained.

Jan 1, 2005

By Adriana Gómez

White dross is a result of the aluminum oxidation during its primary production and is mainly composed of metallic aluminum, Al2O3, with minor amounts of AlN and some other oxides. Because of the great variety of phases, the quantitative characterization is complicated. This work shows a quantitative method to determine the main phases of white aluminum drosses by means of X-ray diffraction (the Rietveld method). Nowadays the Rietveld method is maybe the most useful method for obtaining quantitative phases information in multicomponent mixtures, this method permits relatively quick quantitative phase analysis by fitting the calculated X-ray diffraction profile with the observed one. The analysis were done using powder with a grain size less than 45 µm; to obtain the suitable material size the aluminum dross was grounded by ten minutes, several times. The grounded material was screened, and the material smaller than 45 µm was taken to quantitative XRD analysis. Keywords: Rietveld Method, Characterization, Aluminum dross.

Jan 1, 2005

By Jan Vrestal, Josef Tomiska, Pavel Broz

"Thermodynamic investigations on fcc solid ternary Fe-Ni-Cr alloys have been performed by means of the computer-aided Knudsen cell mass spectrometry. Ternary T.AP.-series (Thermodynamically adapted power series) are used for the algebraic representation of the thermodynamic excess properties. At 1650 K the molar excess Gibbs energy GE is negative over the whole field of stable fcc phase. The molar heat of mixing HE is exothermic in the predominant part of the fcc phase field. Only between the section with a constant ratio of mole fraction Xcr/XNi = 0.64 and the fcc phase field boundary the HE values are slightly endothermic. The results of this work can be used successfully for phase diagram calculations.IntroductionThermodynamic investigations on multicomponent alloy systems such as the Fe-Ni-Cr ternary system including the three binary boundary systems are very time-wasting and usually beset with considerable experimental difficulties. Additionally, the required experimental equipment is very expansive and the obtained results are not always satistying. Therefore it is understandable that many phase diagram calculations are based only on few experimental values of the molar excess free Gibbs energy GE. Consequently, Kundrat and Elliott [1] as well as Hillert and Qiu [2] used in their reassessments of the phase diagram of the Fe-Ni-Cr system thermodynamic data mainly assumed and/or optimized by means of various reasoning.Lee [3] reported recently, a revision of the used thermodynamic description of the Fe-Ni liquid phase is necessary to obtain a better agreement with the experimental data on the bcc/liquid or fcc/liquid tie lines and liquidus temperatures in the Fe-rich region of the Fe-Ni-Cr ternary system than in the previous assessments. This is 'in full agreement with mass spectrometric investigations of Fe-Ni alloys in the liquid and in the fcc solid phase, published earlier [4,5]. Indeed, phase diagram calculations based upon the molar excess free Gibbs energies GE obtained in these studies yield liquidus and solidus lines in excellent agreement with experimental phase diagram data [5]. Nevertheless, these experimental data have not been considered later on any more, not even in the revision by Lee [3]."

Jan 1, 1996