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By Toru H. Okabe

As part of a systematic study on the thermodynamic properties of complex nitrides, phase equilibria of the system Li-M-N (M Mg, AI, Ga) at 900 K were investigated. An attempt to determine the thermodynamic properties of complex nitrides was made by using the galvanic cell method, which utilizes LiMgN as an electrolyte under nitrogen atmosphere. The electromotive force (Emf) of the cell at temperatures between 800 and 1100 K was measured. While the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03 V were found. It was difficult to determine temperature dependence of the Emf. The Gibbs energy change for the reaction, 113 Li3N (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be !'J.Go, (LiMgN) = -13.2 (±2.9) kJ/mol. Using thermodynamic information on the binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be !'J.Go f (LiMgN)= - 121 kJ at 900 K. The thermodynamic stability range of nitride was discussed by constructing isothermal chemical potential diagrams that provide a better understanding of the stability region of the LiMgN phase. The diagram was found to be in good agreement with the isothermal phase diagram determined by the alloy equilibration method. Although the obtained data includes large uncertainties, the results provide a better understanding of the thermodynamic stability of nitrides. The potential application of this complex nitride to nitrogen chemical sensors or a medium for controlling nitrogen potential is also shown.

Jan 1, 2003

By Susumu Okabe

Top blowing lances are employed by the Mitsubishi Continuous Copper Converter for the continuous supply Of reaction gases into moken bath. In order to minimize the refractory wear caused by the interaction between the furnace lining and the melt splash. optimum furnace design and blowing condition are? required. An empirical equation obtained by the physical model study enables the estimation of the splashing rate on a vel1ical plane at a certain distance from the lance.

Jan 1, 1996

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Yoji Imai, Akio Watanabe, Masakazu Mukaida

"To clarify the feasibility of alkoxides and acetylacetonates as precursors for laser CVD of metal oxides, vapors of tantalum or titanium alkoxides and zirconium acetylacetonate were irradiated by KrF excimer laser and deposits were characterized by XRD and XPS measurements. As for tantalum and titanium, non-stoichiometric crystalline oxides grew nearly phototropically, however, zirconium oxides deposited showed only halo-pattern by XRD measurements. Electric conductivity measurements of tantalum oxides implied the improvement of the insulating properties by the addition of activated oxygen to the ambient.IntroductionThere has been renewed increasing attention to the metallic oxide thin films because ofits promising usefulness in many applications, such as high-Tc superconductors and ferroelectric devices. A variety of thin film preparation techniques have been studied such as sputtering, chemical liquid deposition (sol-gel and metalorganic decomposition), pulsed laser deposition and chemical vapor deposition (CVD). Among them, we think CVD is the most promising method because it offers a high controllability of morphology and good step coverage at relatively high growth rate. Preparation of oxide films by CVD can be achieved using a precursor containing metallic element and oxygen containing gas such as N20 at the same time. However, metalorganic (MO) compounds which contain both metallic element and oxygen, directly bonded to metallic element, seems to be more favorable because some of MO has a good properties for CVD such as a rather high vapor pressure, stability in ambient and low toxicity."

Jan 1, 1998

By Keiji Okumura, Hong Lan, Masamichi Sano

"Magnesium has been well known as one of the excellent agent of desulfurization, deoxidation, etc. in iron- and steelmaking because of its high reactivity. Since its production is energy nitensive, the price is very high. Thus magnesium has not widely been used as an agent in metal refining ·processes. In the present work, reduction of magnesia by carbon and aluminum is examined. Because the reaction is very sensitive to temperature, non-isothermal technique is applied to investigate the reaction kinetics. The effects of heating rate .and reaction interface area on the reaction kinetics .are studied. .A kinetic model is proposed based on the experimental results.IntroductionFor the metal refining processes, the production of high purity metal has been one of the most important research subject. In order to produce the high purity metal, the amount of the refining agent and the consumed energy is increasing. Therefore, if the future earth environment is taken into consideration, the further efficient and energy saving processes are required. Generally, Cao slag has mainly been used for desulfurization of molten iron as a desulfurization agent. However, environmental problems, such as recycling of disposal slags, are still unsolved. On the other hand, the deoxidation of molten steel is mainly performed by addition of aluminum. Therefore, the alumina inclusions· remain in. molten steel and the great efforts have been made to the removal of the inclusions. The affinity of magnesium with sulfur and oxygen is strong, and magnesium is well known as a powerful desulfurization and deoxidation agent. However, magnesium has been seldom used for the steel' refining process. The following reasons are considered. Generally, magnesium is expensive. And at iron- and steelmaking temperatures, the refining efficiency becomes low due to its abruptly .evaporation."

Jan 1, 2000

By N. Can

Kinetics and mechanism of the chemical interactions between Si3N4 and TiC were investigated by isothermally reacting samples under nitrogen and argon atmospheres at temperatures between 1600°C and 1700°C? The initial composition of the powder compact contained 20, 30 and 40 volume per cent TiC? Kinetic analysis were performed by measuring mass losses and composition of the titanium carbonitride (TiC1-xNx) at predetermined time intervals? It was found that in the Si3N4-TiC system the degree and rate of the reactions increased with increasing temperature and content of TiC in both nitrogen and argon atmospheres? Si3N4 in the presence of TiC was stable in nitrogen atmosphere and the reactions were confined to Si3N4/TiC and TiC/N2 interfaces? At both interfaces interchange reaction occurs by simultaneous diffusion of nitrogen towards the centre of the particle and desoprtion of carbon in the opposite direction resulting in formation of titanium carbonitrides with various compositions? Reaction products under nitrogen atmosphere were B-SiC, TiCl1-xNx and N2? The maximum "x" value in TiC1-xNx was found to be 0?67 under nitrogen atmosphere? Si3N4 was found to be unstable in argon atmosphere in the presence of TiC and dissociated into liquid silicon and nitrogen gas within approximately four hours of reaction time, depending on temperature? The reaction mechanism in the initial stages of the interaction between Si3N4 and TiC under argon atmosphere proceeds similar to reactions under nitrogen atmosphere? However, considerable amount of Si3N4 dissociates within the first half hour? Liquid silicon aggressively attack both TiC1-xNx and unreacted or partially reacted TiC particles through cracks and pores and diffuses into interier part of the particle forming liquid solutions? After this stage, reactions under argon atmosphere proceeded according to Si-Ti-C ternary system?

Jan 1, 1999

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 F. Sekula

Tetrahedrite and siderite are two main valuable minerals present in the silver Mária Bana deposit. The tetrahedrite concentrate prepared from it by flotation has certain specific properties from the metallurgical point of view. Siderite is concentrated in the flotation tailings. The paper presents results of the laboratory and pilot-plant testing of the combined hydrometallurgical and pyrometallurgical methods proposed for treatment of the tetrahedrite concentrate and siderite waste. The testing conditions were based on thermodynamic analysis of the reactions that proceed in the process. The proposed technology makes it possible to separate copper from sulphur, mercury and iron in a straightforward way. Copper, after its refining, can be subsequently treated in the finishing operations. At the same time it is a valuable source of precious and noble metals. The siderite-containing flotation tailings can be converted to iron of the technical purity and slag. The proposed method is a good starting point for the development of the closed-cycle technology.

Jan 1, 2006

By A. P. Paiva

With the aim of establishing a valuable alternative to the conventional methods, studies regarding the recovery of precious metals by solvent extraction have been increasing over the past few years. In this work, the selectivity of extraction presented by Cyanex 471X toward silver is investigated. Simulated chloride solutions considering contents of iron and copper usually present in actual leaching practice were used. The characterization of the aqueous solutions - in terms of the multiple equilibria established by the chlorocomplexes of the different metals and their relation to the total chloride concentration of the base-electrolyte - was successfully carried out by cyclic voltammetry. The results obtained support the important contribution of the electrochemical techniques for the understanding of the overall extraction phenomena.

Jan 1, 1994

By N. Moelans

A method using an ex-situ electrochemical measurement device was developed to determine the oxygen potential of non-ferrous metallurgical slags. The electrochemical cell consists of the molten slag sample, an inert Ir electrode, a stabilized Zr02 solid electrolyte and a NiINiO reference electrode. Different slags from non-ferrous pyrometallurgical processes were analysed at 1100 and 1200°C and pO2 values between 10-3 and 10.12 bar were obtained. The measurements were evaluated with? thermodynamic calculations and using processing considerations. It was found that the reproducibility and stability of the measurement was significantly improved by shielding the molten slag from the atmosphere by a thin layer of carbon, especially for slags with a low oxygen potential.

Jan 1, 2003

By J. S. Lee

A new high performance adsorbent is synthesized by the sol-gel method and applied to the removal of cadmium and mercury ions from aqueous solutions. Adsorbents based on metal oxides have been developed by immobilizing chelating molecules on the surface of the existing metal oxide networks and show ability for selective metal extraction from aqueous solutions. However, efficiencies of such adsorbents are limited due to low ligand density, and difficulty in pore accessibility. These difficulties are circumvented by synthesizing adsorbents using the sol-gel technique. In one example to be discussed, the sol-precursor possesses an organic moiety that binds cadmium, mercury, and copper ions. The capacities of 1.98mmol Cd(II-/gm and 6.40 mmol Hg/gm of this adsorbent are considerably higher than those of adsorbents prepared by the ligand immobilization technique. The scope of this paper is to discuss the development of the new adsorbent and its applications for cadmium and mercury removal from aqueous solutions.

Jan 1, 1999

"In this paper, a mobile heat treatment furnace from Akkermans Gloeitechniek, a Dutch company, was simulated with Computational Fluid Dynamics (CFD). The furnace is cylindrical with four oil burners, and large metal products such as dredging pumps and impellers can be flexibly heat treated to obtain required microstructure and mechanical properties through stress relief, annealing, hardening and tempering. The furnaces are exposed to the open air, and thus the heat loss becomes significant and varies from day to day and from season to season. Since the temperature of the metal products to be heat treated can only be measured on the surface, the temperature evolution inside the metal could not be tracked in practice. CFD simulation provides a useful tool to predict the temperature evolution within the metal pieces and within the combustion space of the furnace. Energy distribution and heat loss can be subsequently estimated. An overall energy balance through temperature measurement indicted relatively low energy efficiency. Especially during the soaking period, the high energy supplied is barely used to compensate the heat loss of the furnace to maintain a constant temperature of the metal piece. The current CFD modeling aims to give advice on how to modify the design and optimize the operation to reach higher energy efficiency and low heat loss. The CFD model consists of turbulent combustion model, radiation model in participating media, and conjugate heat transfer between the combustion space and solid metal. Temperature measurement was carried out to provide thermal boundary conditions and overall energy balance of the operation. After the model validation with temperature measurement within the combustion space and metal surfaces, furnace optimization will be conducted.IntroductionHeat treatment is a common practice in metal production and manufacturing industries. Through heat treatment at certain temperatures with special patterns, unique mechanical properties of the metals and the metallic products could be obtained. ""Akkermans Gloeitechniek"" is a company situated in K.inderdijk, at location of LHC-Holland (www.ihccaland.com), the Netherlands. Heat treatment of metals is its core business. Various type of heat treatment are applied, such as stress relieving, soft annealing and hardening (quenching), tempering, transformation and precipitation. At the company 6 furnaces are in operation and the 7th is being built"

Jan 1, 2004

By Kee Jeung Lee

In this study the characteristic factors and formation mechanisms for the hydrothermal preparation of a -quartz crystal powders were investigated to find the optimum synthetic conditions. The degree of Q -quartz crystal face development depended on the relative growth rate of a particular form that varies considerably with the degree of supersaturation, the reaction temperature, the concentration of mineralizers, and the presence of seed crystals in the feedstock. Alkali hydroxides and alkali halides were found to be effective in the reactions as mineralizers, which added in order to increase the solubility of the feedstock. The fine Q -quartz crystal powders were obtained in the temperature range of 250-450% and pressure range of 100-300atm. As the concentration of mineralizers increased, the particle size of crystalline powders became smaller at lower reaction temperatures. The fractional size distribution of synthetic crystal powders was depended on the hydrothermal conditions. As the reaction time and the amount of seed crystals increased, the width of particle size distribution became narrower. The weight mean particle size was in the range of 1 to 10m. The characterization of the products were carried out using XRD. SEM. PSA, FT-IR, Raman spectrometer.

Jan 1, 1997

By Gennadiy M. Poletayev, Mikhail D. Starostenkov, Alexandra S. Starostenkova

"The process of the combustion synthesis was modeled by computer simulation using the molecular dynamics method. The set of the critical parameters regulating the velocity of the reaction was found from these computer experiments. It was established that the character of structure-energetical transformations at the combustion synthesis in the systems Ni-Al and TiAl depended on the type of boundaries used for the phases delimitation in the bimetal thin films.IntroductionProducing new materials and products, based on the combustion synthesis (CS), is the objective of scientific investigations as one of the most perspective one for industrial applications. But there are several problems connected with theory and experiment. It allows us to forecast the properties of materials. First of all, the main problems are stipulated by structure-energetical transformations taking place at high velocities of the reaction and at high temperatures. It prevents the analyzing of the transformation mechanisms in materials, taking place at microscopic, atomic levels in details.It is evident, that computer simulation allows to decide some problems and to approach to more exact theoretical presentation of structure-energetical reactions taking place at CS. It is known, that the most typical systems, where CS is observed, are bimetals Ni-Al and Ti-Al. The investigation of interphase boundary stability in the systems of Ni-Al and Ni-Fe was made by the method of molecular dynamics in [1]. The bimetal thin film was presented by the packing of atoms in the plane (111) of FCC lattice. It was found that the discrepancy in the sizes of atoms A and B of bimetal was compensated by the formation of 60° top dislocations, set against interphase boundary in the absence of point defects and free volume. The density of top dislocations was proportional to the factor of size discrepancy of atomic components of the bimetal. Diffusional reconstruction of the interphase boundary and areas, situated near it, was observed only at definite concentration of point defects - vacancies, inculcated in the structure of the bimetal at the definite temperature. The atoms of the bimetal component of less size penetrated in the area of the second component with higher velocity. The clusters of intermetallic germs began to form. It led to the growth of the system temperature and acceleration of the process of the diffusional reconstruction of thin film. The following transformations were found: top dislocations splitted into single ones, which climbed from interphase boundary into the zone of more plastic component; the formation of sub grain structures took place."

Jan 1, 2001

By G. A. Brooks

Reactive ball milling has been proposed as a new route for producing carbides from oxides through carbothcrmic reduction. It is claimed that through milling oxide and graphite powders to the nanoscale, amorphous materials with very high reactivity are formed, that allows for easy transformation of the starting material to another in a subsequent thermal process. Thermodynamic analysis of this proposed process suggests that unless particle sizes are reduced to below 10nm, then reduction in size alone cannot explain a change in the stability of oxides. Even with nanometer scale powders, the products formed need to have a lower total surface energy than the reactants before a chemical change will occur. A model developed by Bhattacharya and Arzt for predicting localized temperature changes based on milling conditions suggest that temperarure rises less than 400 K will be achieved in laboratory conditions. The present calculations suggest that nanometer scale powders formed through high speed ball milling (>10 mls) may have undergone a process analogous to melting and quenching. Further work is required to fully distinguish these features.

Jan 1, 2003

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 dcsign 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 speetrometer.

Jan 1, 2003

By Stein Tore Johansen

Some ferro-silicon furnaces have heat-recovery equipment. Here, the recovery of electric energy from the off-gases can be increased by increasing the off-gas temperature. This is easily done by reducing the amount of air which usually is mixed into the?off?gas to cool the gas mixture. If the off-gas becomes too hot problems with severe fouling or clogging of the gas channels close to the furnace is observed. The result is irregular stops to clean the off-gas channels. The paper focuses on the nature of the clogging phenomena and some of the ways to avoid clogging. A detailed experimental study was carried out at the Elkem Thamshavn Plant. Theoretical studies were performed to understand the particle deposition, turbulent multiphase fluid flow and off gas combustion in the off-gas channels. The study has resulted in reduced clogging.

Jan 1, 1992

By B. C. Blakey

The economic feasibility of the sulphuric acid pressure leaching route for the extraction of nickel and cobalt values from limonitic ores is highly dependent upon the behavior of aqueous aluminium. This is primarily due to its precipitation as hydronium alunite ((H30)A13(S04)2(OH)6), which is one of the major scale-forming compounds found in autoclaves used for pressure leaching. As a result of renewed interest in the pressure leaching process, an investigation of the aqueous-solid eqilibria in the aluminium-sulphate-water system under acidic (< pH l), high temperature (230 to 270°C) conditions has been conducted. Pure hydronium alunite was synthesized in an autoclave by leaching boehmite (A100H) at elevated temperatures in sulphuric acid solutions initially 0.25 to 0.75 m H2S04 in concentration. Spontaneous, in situ precipitation of hydronium alunite followed. A high temperature solution speciation model was used for the analysis of the resulting solubility data in order to calculate equilibrium constants for the precipitation reaction.

Jan 1, 1994

Thallium is a very minor element found in lead ores. It&apos;s behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By C. D. Seybert, J. W. Evans

"The elimination of convection is essential in experimental investigations of diffusive transport (of heat and matter) during solidification. This paper describes an investigation of an approach whereby a magnetic field gradient is applied to a electrically non-conducting diamagnetic liquid. A magnetic body force then arises which is dependent on the volume susceptibility of the liquid and thereby on the density. With the field gradient aligned vertically and of correct magnitude, the variation of gravitational body forces due to density variations (arising from temperature variations, for example) can be counterbalanced by a variation in magnetic body force.Preparatory to a study of convection control in diamagnetic liquids, PN measurements have been made of the convection occurring during the solidification of water. A peculiar flow arises because of the density maximum at 4°C. Modeling of the flow the steady-state solidification of water in an extremely high field magnet at the NHMFL indicates that flow can be significantly reduced, but it is suggested that, due to field gradient variations within the cell, flow cannot be completely halted. INTRODUCTIONNatural convection is inherently a part of terrestrial solidification. Density-based convection during solidification, due to gradients of temperature and/or concentration, has a significant effect on a material's properties. The design of products with specific material characteristics has required the development of many processes to control convection (such as in the growth of semiconductor crystals, and electromagnetic stirring in steel casting). The expansion of fundamental knowledge about the process of solidification requires collecting data in the absence of density-based convection, while most of science's solidification data (and thus the equations that science has fitted to those data) have been obtained under the influence of gravity. Only relatively recently, through clever experimental design (e.g., drop towers, high altitude parabolic flights, and space laboratories), have investigators been able to study solidification in an environment with ""micro-gravity""."

Jan 1, 2001