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By Peter Fischer

A demonstration plant for QSL technology with a continuous through-put of up to 10 t/h concentrate has been in operation at the Berzelius smelter, Duisburg, Germany since early 1981. In the QSL-process, both oxidation and reduction steps are performed in a single horizontal long cylindrical reactor. In the present demo-reacior, 2.5 M diameter by 22 M long, these steps are separated by a low partition wall with an underflow opening, to prevent backmixing of slag. -Tests on a variety of concentrates, including high-lead Missouri-type material and lower grades, have shown recoveries and consumables indicating very attractive economics. Investment cost estimates further enhance the economic attractiveness. Environmental protection afforded by the QSL system is a major advantage. The process has proven its reliability and versatility and is now ready for commercialization. Continued test work, including smelting secondary lead materials, is planned.

Jan 1, 1983

By T. Kamata, S. Takemoto, H. Takeuchi, M. Takayanagi, Y. Akahori, I. Jimbo

"A cooperative research work on the silver recycling process is underway between Matsuda Sangyo Co., Ltd. and Tokai University in Japan. Silver wastes treated here are mainly from photograph industries where the concentration of minor element is steadily increasing in the recent years. The waste materials are concentrated and the impurities are removed by evaporation and slagging. In this paper, the industrial practice of wastes treatment is introduced and the result of the laboratory studies on the removal of antimony and tin from the binary and ternary alloys will be discussed. Characteristics in the behavior of antimony and tin during the process are also discussed with the observation of practical operation.1. IntroductionPrecious metals such as gold and silver primarily come from mining practice and the byproduct in copper smelting. However, the recycled amount of these precious metals have been increased 1 along with the environmental restriction and the widely accepted idea of saving resources on the earth in the recent years.· Though the recycle process of precious metals are comparatively simple from other metals refining, the process has been getting more complicated as wastes treatment has to deal with more impurity elements which are intentionally added to the products. Among these additives, antimony is used in the film materials in the photography industries to suppress its inflammability. Tin is another concern ,that is also coming from photography wastes; These minor elements have become problematic during the recycle.The removal of these minor elements has been in operation at Matsuda through a traditional oxidation refinement process using a reverberatory furnace. However, the complexity of the charge makes the recycle process more tedious and troublesome. In order to investigate the minor element behavior in the complicated materials system during the silver recycling processes, a cooperative research work is undertaken between Matsuda Sangyo Co., Ltd. and Takai University in Japan. Silver wastes treated here are mainly discharged from photograph industries where the minor element contents such as antimony, tin and bismuth in those wastes are steadily increasing in the recent years. The liquid wastes containing silver are concentrated and then treated pyrometallurgically with solid wastes from other sources, where the impurities are removed ·by evaporation and slagging. The purpose of this study is to investigate detailed behavior of impurity elements in the silver. containing systems."

Jan 1, 2000

By G. Upadhya

Considerable success has been achieved recently in modeling microstructural evolution during solidification of castings bthrough the coupling of macroscopic heat transfer with microscopic solidification kinetics models. However, a complete model for simulation of solidification in complex shaped castings involves: (i) the description of fluid flow, during and after mold filling, coupled with (ii) heat transfer to the mold and surroundings by use of a macro model, followed by (iii) a description of subsequent solidification of liquid metal by use of a micro model for solidification of the alloy under consideration. This paper describes the coupling of solidification kinetics model to a 3D, transient, fully coupled fluid flow and heat transfer model. Coupling between the macremicro models is achieved by using the latent heat method. Micro models for the eutectics of gray, white and ductile iron are discussed. This coupled code has been used for predicting the thermal history and microstructural data for shaped castings. Various applications of the model, including prediction of shrinkage defects, grain density contours, and graylwhite transition region in the casting, are presented for a relatively complex casting geometry.

Jan 1, 1992

By Toshiharu Hayashi

We prepared the water dispersed with Au particles ranging from 10 to 20 nm size by a novel wet chemical synthesis; generating seeds of Au cluster by adding a borane dimethylamine complex into chloroaureic acid (gold salt) solution, and then growing simultaneously with aminoalcohol included in the solution. As-prepared Au nano-particles with chemical surface modification were found to have some attractive performances, i.e., showing a high dispersiveness in an aqueous solution in a long time, sintering nano-particles at low temperature, and having low resistivity in the film prepared from nano-particles. In the case that smaller Au nano-particles were removed from as-prepared colloid, especially, Au thin film formed on the surface of Si plate showed the excellent value of 7.0x10-6ohm cm (reference peculiar resistance: 2.35x10-6 ohm cm).The sintering temperature was dependent on the elimination of 2-aminoethanol that modified on the surface of Au nano-particles.

Jan 1, 2006

By Huanyu Zhang, Zhancheng Guo, Liqiang Fan, Huiqing Tang

"In this study, a simple process has been developed for zinc oxide recovery from RHF (rotary hearth furnace) secondary dust. The results have shown that a high dissolution efficiency of soluble zinc was achieved with water leach at ambient temperature with a liquid/solid ratio of 10/1 in 30min while 20% of the dust was left as solid residue. The rate of dissolution increased slowly after the dissolution efficiency reached 90%. The leaching process was found to be controlled by external diffusion. After separation, zinc was precipitated in leached liquor by introducing a precipitation agent of potassium hydroxide. The resulting solid was purified and dried at 393K. Zinc powder in the form of ZnO with purity of 98.5 mass% was obtained with an average size of 12.4µm.IntroductionThe RHF (rotary hearth furnace) direct reduction process is widely used in many iron and steel enterprises to deal with various metallurgical dusts [l]. The basic principle of this process is that first various metallurgical dusts (BF dust, EAF dust and so on) are pelletized with a coal reductant, and they are then subjected to a fast reduction using RHF after being dried. Highly metallic pellets are produced and at the same time, nonferrous elements such as Zn, Pb, K and Na are evaporated into the RHF flu gas as secondary dust. Zinc is listed by the Enviromnental Protection Agency as one of the 129 priority pollutants. Therefore, recovering zinc from the industrial wastes is important in terms of enviromnental protection [2-3]. On the other hand, nowadays China is in shortage of zinc resource and the annual output from metal recycle only accounts for some 13% of the total zinc resource. There are many ways proposed to recover zinc from various wastes [ 4-7]. The aim of this paper is to recover zinc oxide from RHF secondary dust by a method with water leach followed by caustic precipitation. This work investigated the influence of the leaching temperature and leaching liquid/solid ratio on the zinc recovery efficiency. The process consisted of three stages: (1) leaching with water; (2) liquor/residue separation; and (3) zinc precipitation in caustic milieu."

Jan 1, 2014

By Chikabumi Yamauchi, Mitsuru Tanahashi, Jutaro Miura, Takaharu Iwadachi, Toshiharu Fujisawa

"Tue oxidation behavior of molten Cu-Be alloys was investigated by exposing· the molten Cu-Be alloys to various Ar-O2 atmospheres to control the oxygen partial pressure, PO2 = 10 ~105 Pa at 1423 K. The following results were obtained:• The oxygen · partial pressure in gas phase affects the morphology of the oxide formed on the surface of the alloy and · the oxidation rate of beryllium.• At lower oxygen partial pressure, a molten Cu-Be alloy is covered with a homogeneous and compact internal layer of BeO. Thus, the beryllium oxidation rate can be minimized.• By adding a small amount of calcium or zirconium into the molten Cu-0.5 mass% Be alloy, a protective BeO layer is formed even at higher oxygen partial pressure. Thus, the beryllium oxidation rate can be reduced.IntroductionCopper-beryllium (Cu-Be) alloys are well recognized for their unique properties, such as high electrical conductivity, high strength, high fatigue strength, excellent properties at elevated temperatures, good formability and good corrosion resistance. .This extraordinary collection of properties are the reasons why Cu-Be alloys are expected to be ""Key-materials"", which are necessary to further advance science and technology and to be applied in.various fields such as electronic devices, machine parts, repeater housings of undersea optical fiber communication cables, etc.However, a large amount of beryllium is oxidized to BeO in melting stage of the current Cu-Be alloy production process, because beryllium is a highly reactive element. This is one of the ·main factors that negatively affect the production yield and th_e product quality."

Jan 1, 2000

By J. Shibata

The recovery process of valuable metals, such as Ll, Mn, Ni and Cr from a waste lithium battery was developed n this study. Lithium and Mn are selectively leached from the battery by using dilute mineral acid. Main part of the battery comprises stainless steel, and Fe, Ni and Cr are easily leached by the mixture of dilute HCl and HNO3 Lithium and Mn are precipitated as metal carbonates from the? individual leached solution with sodium carbonate solution. The solution containing Fe,Ni and Cr Is treated by solvent extraction to separate NI and Cr from the leached solution. The experiments are carried out for leaching and separation steps. According to the experimental results, the flow. sheet for a recovery process of valuable metals from a waste lithium battery has been established.

Jan 1, 1995

By B. Q. Li, S. P. Song

"Numerical models are developed to represent complex electromagnetic, free surface deformation and fluid flow phenomena in floating zone refining processes with radio frequency inductive heating. The computational methodology is based on the coupled finite/boundary element method for the electromagnetic field distribution and the Galerkin finite element method for magnetically driven fluid flow and free surface profiles of the molten zone. With the models, the complex transport and free surface phenomena in a floating zone system can be studied as a function of various operating conditions including applied current, frequency, inductor position and shape, surface tension, floating zone diameter and height. Results show that the equilibrium shape is sensitive to the height of the molten zone and that the free surface shapes can have a significant effect on the melt flow in the molten zone. Our extensive simulations also suggest that to ensure accurate results, the same mesh should be used, whenever possible, for both the electromagnetic forces and fluid flow calculations.1. IntroductionThe floating zone processes have been widely used in the materials industry to grow ultra-pure rare earth metal or semiconductor single crystals for sensor or electronic applications that have a tough demand on purity. Developed based on the principle of magnetic melting/levitation, the processes possess a main advantage that the molten zone is supported in air by the electromagnetic forces generated by the coil (see Figure 1), and therefore is free from contamination from a container. Consequently, the final products made from the floating zone processes have higher inherent purity than those by other techniques [1-4].Complex physical phenomena occur in the floating zone processing of materials. These include free surface deformation, magnetically-driven melt flow, which may be turbulent or mildly turbulent [5] depending on the applied conditions, and solidification. Thermal stresses also develop in the single crystals, which are affected by the flow and temperature field and which can have direct implications to qualities of single crystals [6]. An understanding of the fundamentals governing these physical phenomena can be of critical value in elucidating the physics that controls the properties of the metal or semiconductor crystals being produced, thereby providing a rational basis for process improvement and quality control."

Jan 1, 1997

By G. Brooks, J. Naser, M. A. Sattar

CFD models have been developed and numerical simulations have been carried out to predict the formation of foam in oxygen steelmaking. Foam was considered as a separate phase comprising a mixture of gas and liquid. Bubble break up and coalescence models have also been incorporated in a CFD model to predict the number density of individual bubble classes. A population balance equation was used to track the number density of each bubble class. Decarburization with heat generation from chemical reactions was integrated in the process. User subroutines were written in FORTRAN to incorporate the foam formation, the bubble break up and coalescence rate and decarburisation in the main program. The model predicted the foam height, bubble number density, velocity of phases, decarburization, and turbulence. The result from the model has been compared with available data from literature and found to be in reasonable agreement with the experimental and plant data.

Jan 1, 2014

By K. Krishnapisharody

A mathematical model has been developed to predict the interface dynamics and droplet generation of the buoyant phase in a two-fluid system. The model employs the well-known SIMPLE algorithm for obtaining flow fields and the Volume of Fluid (VOF) method, for interface tracking. The implementation of the model in water-oil systems, where the oil layer is placed above a recirculating water bath, is discussed. The evolution of the water-oil interface leading to the formation of oil droplets is computed realistically.

Jan 1, 2008

By Luis Hoyos-Reyes, Jesus Gonzalez-Trejo, Adriana Cervantes-Clemente, Marco Gutierrez-Villegas, Manuel Palomar-Pardave, Cesar Real-Ramirez

Recent improvements on Peirce-Smith Converters (PSC) have combined numerical and physical simulations. However, most of the physical simulations have been carried out in cold-water models with only one tuyere. Several authors have proved that 2D numerical simulations do not reproduce the hydrodynamic behavior observed in physical simulations. On the other hand, most of the 3D numerical models have used a PSC thin slice with only one tuyere, but symmetric boundary conditions on the virtual walls have been imposed in order to reproduce the behavior of the whole converter. Therefore, there is no coincidence with the rigid walls of the physical models. The aim of this work is to quantify the effect of the virtual walls boundary conditions of a PSC thin slice and to determine the minimum number of tuyeres to characterize the fluid flow behavior of the entire converter.

Jan 1, 2009

By Christine Wenzl, Andreas Filzwieser, Stefan Konetschnik

"The METTOP-BRX-Technology is a novel manifold electrolyte inlet, which allows improved productivity and production in new and existing tankhouses by achieving higher current efficiency and cathode quality, as well as using current densities higher than 400 A/m2. Two installation examples are shown: Montanwerke Brixlegg AG, Brixlegg, Austria (upgrade of existing tankhouse) and Xiangguang Copper, Yanggu, China (new tank house). Montanwerke Brixlegg AG has been using the METTOP-BRX-Technology since 2005, and converted half of the whole tankhouse to METTOP-BRX in 2011 in order to use a current density of more than 400 A/m2. Xiangguang Copper started up their second tankhouse in May 2011. This tankhouse was constructed in the same way as the existing tankhouse, but was designed for 292,000 t/a cathode copper (existing tankhouse: 200,000 t/a) by using the METTOP-BRX-Technology. This production increase is a consequence of a much higher current density, namely 410 A/m2, compared to 280 A/m2 in the old tankhouse.IntroductionCopper electrorefining has been practised for more than hundred years, the last big change being the implementation of stainless steel cathodes in the 1980s [1], In 2005, the METTOP-BRXTechnology was first introduced. This technology was developed jointly by METTOP and Montanwerke Brixlegg, Austria, and allows improvements in productivity and production in new and existing tankhouses in an economic way. The METTOP-BRX-Technology is a novel manifold inlet that allows improved tankhouse productivity by increasing current density and/or current efficiency while maintaining or improving cathode quality [2]."

Jan 1, 2012

By De-qing Zhu, Jian Pan, Tie-jun Chun, Dong Chen, Yu Cui

"A study of processing pyrite cinder and metallurgical slag using “one step” technology in strand grate - rotary kiln is presented, which aims to efficiently recover the valuable metals of iron, lead, zinc and copper. The effect of chloridizing roasting parameters including roasting time and temperature on the removal rates of nonferrous metals was investigated. It is shown that copper and zinc are difficult to remove and lead is removed more easily. The preheated pellets were reduced in a rotary kiln, where zinc and lead can be removed easily and high iron grade and good metallurgical performance prereduced pellets can be obtained. Furthermore, the chlorination and the reduction mechanisms of copper, lead and zinc are discussed. It is revealed that the phases of copper, lead and zinc in slag are complex and ferrite and silicate of metals are difficult to remove.IntroductionAs two kinds of significant secondary resources, metallurgical slag and pyrite cinder contain not only abundant iron but also considerable copper, lead, zinc and so on. Several tens of millions of tons of metallurgical slag and pyrite cinder are discharged in nonferrous metal and chemical industries annually in China [1, 2]. In addition, the accumulated waste slag in storage is more than one hundred million tons, which not only occupies much land but also pollutes the environment [3]. However, because the metallurgical slag and pyrite cinder are treated by high temperature processing, the properties are distinctly different from the properties of natural ores, and iron is in close association with copper, lead and zinc. So, metallurgical slag and pyrite cinder are difficult to efficiently utilize and only a small amount is used as additives in cement, paving, brickmaking and auxiliary additives [4-7]."

Jan 1, 2011

By E. Salinas-Rodriguez, J. Hernández-Ávila, E. O. Ávila-Dávila, A. Romero-Serrano, M. Perez-Labra, G. Juárez-López

"Single phase rubidium jarosite was synthesized by precipitation from aqueous solution. X-ray diffraction and SEM-EDS analyses showed that the synthetic rubidium jarosite formed in subspherical particles with an average particle size of about 35 µm. The chemical analysis showed an approximate composition of Rbo9432Fe3(SO4)2 1245(OH)6. The decomposition behaviour of the jarosite in terms of solution pH was thermodynamically modeled using FACTSage by constructing the potential-pH diagram at 298.15 K. The E-pH diagram showed that the decomposition of jarosite leads to goethite (FeOOH) together with Rb+ and SO42- ions. The experimental decomposition of the Rb-jarosite was carried out in alkaline solutions with five different Ca(OH)2 concentrations. The decomposition process showed an ""induction period"" followed y a progressive conversion period where the Rb+ and SO42- ions formed in the aqueous solution. In contrast, calcium was incorporated in the solid residue and iron was transformed into amorphous ferrihydrite. The kinetic analysis showed that this process can be represented by the unreacted-core chemically controlled model. The reaction order with respect to Ca(OH)2 is 0.4342 and the calculated activation energy is 98.70 kJ mol-1. IntroductionJarosite type compounds are hydrous sulfate minerals containing alkalis and ferric ions, MFe3(SO4)2(OH)6, where M can be H3O+· Na+, K+, Rb+, Ag+, NH4 +, Tl+, ½ Pb2+ or ½ Hg2+. Jarosite-type compounds were formed by the natural ""in situ"" oxidation of pyritic ores leading to the replacement of the original iron sulfides and iron oxides (Dutrizac and Kaiman) [1]. The great interest in jarosites is due to its ability to eliminate or diminish the iron concentration of the acid leach solutions produced in the hydrometallurgical zinc process, with relatively low losses of divalent metals such as Zn2+, Cd2+, Cu2+ or Co . However, the losses of the metal values demand a careful study of the conditions under which the jarosite compounds are formed together with their chemical properties."

Jan 1, 2012

By F. M. Nakla

Various methods of Applied Mineralogy were used for determining the nature and composition of products yielded by flotation tests for Maghara coal beneficiation. Coal samples obtained from the Sa fa mine in Northern Sinai, Egypt, were crushed, sieved, &apos;and <32 mesh size fraction was cleaned by froth flotation. Experiments were conducted to determine the effect of certain parameters on beneficiation of Maghara coal by flotation. The investigated factors included nature of frothing and/or collecting reagents, pH value of the medium, particle size distribution in the head sample, and pulp density of the coal slurry. The quality of head samples, coal concentrates, and tailing products were determined by chemical analysis, microscopic study, x-ray diffraction analysis, and occasionally by infrared (IR) absorption spectroscopy.

Jan 1, 1989

By Rashmi Kumar, Amit Chatterjee, Sanjay Chandra

The practice of adding alloying materials to a molten bath is an integral feature of many pyrometallurgical operations. However, very little is known about the dissolution rate and solution mechanisms of solid additives in liquid melts. In foundries where large tonnages of liquid metals are handled, there is considerable interest in achieving optimum metal quality at minimum cost. This objective is influenced by several factors and the solution is often plant specific. Though the amount, sequence and mode of ferroalloy addition vary from plant to plant, various fundamental factors determine how quickly these additions dissolve in the bath. At the Ingot Mould Foundry (IMF) in TATA STEEL blast furnace hot metal is used to cast ingot moulds. The composition of hot metal desired for making ingot moulds demands addition of 20 kg each of Ferromanganese and Ferrosilicon in the 12 T transfer ladles into which the blast furnace metal is poured at the IMF. Owing to low temperature of hot metal at the IMF, casting commences immediately and complete dissolution of the ferroalloys is often not possible. To study this aspect in detail and to evolve suitable corrective measures, a mathematical model for the melting of a solid particle in a liquid metal bath was developed at TATA STEEL. The model was validated using the data available in literature. In keeping with published work, two separate dissolution periods were identified - a "shell period" and a "free dissolution period". The maximum thickness of the crust formed around a spherical particle shortly after immersion, can be obtained by using the mathematical model which has been developed. The model can also be used to investigate the effect of various parameters such as superheat of the bath, size of the particle, etc., on the maximum crust thickness and the particle melting time. On the basis of this study, the addition of ferromanganese and ferrosilicon was optimized at the IMF in Tata Steel.

Jan 1, 1996

By Milton Manrique, Edgar E. Vidal, Patrick R. Taylor

"Ultrafine zirconium carbide powder has been synthesized using zircon concentrate and methane in a thermal plasma reactor. The effect of several experimental variables, such as power used and zircon particle size, on the conversion has been studied. A thermodynamic analysis of the possible reactions and stable compounds was performed. A mathematical model that describes the in-flight decomposition of zircon particles was developed based on a description of the temperature and velocity profiles calculated in the reactor. It was shown that the formation of zirconium carbide from zircon and methane is thermodynamically possible. Complete 'vaporization of zircon in the reactor is predicted when the particle size is below 45flm and the effective power entering the reactor is 15 kW. The powders were collected and characterized by XRD, SEM, TEM and chemical analysis using ICP. Results of the product analysis indicated the presence of zirconium carbide, zirconium oxide, silicon carbide and silicon oxide.IntroductionIn recent years there has been an increased interest in the production of nanometric sized powders of ceramic materials for use in advanced materials applications. One possible method to produce these powders is with a thermal plasma reactor, which offers high temperatures and fast quenching rates. This technology has been called - Thermal Plasma Synthesis - [1].Zirconium Carbide (ZrCx) has typical properties of transition metal carbides: elevated hardness - between alumina and diamond - a high melting temperature of 3420°C and high chemical stability at room temperature [2]. ZrCx has a Bl crystal structure with deficiencies in the number of carbon atoms in the cell with x between 0.6 and 1 [3]. Different methods have been used to produce ZrC, one method is by direct reaction of zirconium hydride or halide with carbon. Other methods used are direct reduction and carburization of zirconium oxide (Zr02) and reaction of metallic zirconium with a caburizing gas such as acetylene [3]. Recently small films of ZrC have been obtained using a sputtering device [4,5]. ZrC has been used in nuclear plants as a low neutron absorbing and high mechanical resistant refractory material and also as a constituent in cathodes made of UC-ZrC [6]. It is also used in the form of tubes, boats and crucibles to handle molten metals and as part of electronic devices used for thermoionic transducers. Recently ZrC has been used along with zirconium diboride (ZrB2) to produce composite materials [7,8]."

Jan 1, 1996

By A. E. Clark

Rare earth compounds are widely known as possessing many extraordinary magnetic properties. In this paper, we focus on the huge magnetically induced displacements (magnetostrictions) which characterize the compounds of terbium with iron (Terfenol). Materials prepared commercially by both free-standing-zone (FSZ) and modified Bridgman (MB) techniques have now become available in large sizes and shapes. Prior to the development of the Terfenol alloys, it was possible to achieve giant magnetostrictions only at cryogenic temperatures. In the cubic Laves phase TbFe2 compound, saturation strains exceed 3000 x 10-6 at room temperature and above. Large magnetization &apos;jumps&apos; can occur, causing huge spontaneous magnetostrictions with small triggering magnetic fields.

Jan 1, 1992

By Yue Tian, Shengqian Wang, Lifeng Zhang

This paper is to discuss the removal of non-metallic inclusions from molten steel using a high frequency magnetic field. In experiments, a certain amount of aluminum was added to the molten steel in a crucible to generate aluminum inclusions. A layer of aluminum clusters were observed close to the wall of the crucible after the electromagnetic (EM) field was imposed. Three dimensional EM field and fluid flow simulation were performed and showed that over 91% inclusions transported to the skin depth (2.31 mm) of the molten steel. The calculation of inclusion removal agreed well with the experimental observation. The separation mechanisms of inclusions from the molten steel by the high frequency EM field were discussed.

Jan 1, 2014

By Takahiro Miki

Soldering material widely used is Sn-Pb alloy, which have low melting point and excellent electrical, strength properties and wettability. However, Pb is one of the toxic elements, which is undesirable due to environmental and safety reasons, thus Pb-free alternative alloy is preferred for new soldering material. Sn-Ag and Sn-Zn based alloys have been viewed as very promising candidates, among many potential substitutes. Addition of third element to these alloys will decrease melting point of the alloys. Hence, Sn-Ag-In and Sn-Zn-Mg alloys are expected to be suitable for replacing Sn-Pb solder alloy. In order to design new Pb-free soldering materials, it is crucial to understand precise thermodynamic properties and phase diagrams of alloy systems. In the present work, ion current ratios of Ag to In and Mg to Zn were measured for Sn-Ag-In and Sn-Zn-Mg alloys by mass spectrometry, respectively. Also, the authors reviewed the thermodynamic properties of terminal binary alloys determined by other researchers and evaluated a thermodynamic functions to express the excess Gibbs free energy of each binary alloy. Thermodynamic functions to express the excess Gibbs free energy of liquid Sn-Ag-In and Sn-Zn-Mg ternary alloys were determined, utilizing the assessed Gibbs free energy of terminal binary alloys with the measured ion current ratios using mass spectrometer.

Jan 1, 2003