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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 ilie cell at temperatures between 800 and 1100 K was measured. Whilc the Emf of the cell at 900 K was measured to be 0.137 V, data discrepancies of ±0.03V were found. It was difficult to determine temperature dependence of ilie Emf. The Gibbs energy change for the reaction, 113 LbN (s) + 1/3 Mg3N2 (s) = LiMgN (s), at 900 K was determined to be tJ.Gor (LiMgN) -13.2 (±2.9) kJ/mol. Using thermodynamic information on ilie binary nitride from literature, the standard Gibbs energy of LiMgN was derived to be AGO 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 ilie stability region of the LiMgN phase. The diagram was found to be in good agreement with the isoiliermal phase diagram determined by ilie alloy equilibration meiliod. Although the obtained data includes large uncertainties, the results provide a better understanding of the iliermodynamic 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 Kazuki Morita

Dissolution mechanism and solubility of chlorine in the oxide melts, such as CaO-SiO2-Al2O3 (-Na2O), Na2O-SiO2-Al2O3 and CaO-SiO2-FeO systems, have been equilibrium technique was employed with controlled Po2 and PCl2, (Po2 = 10-6 -10 19 atm, PCl2 10-6 -10-13 atm at 1673-1748 K). The solubility of chlorine in the 40mass%CaO-40mass%SiO2- 20mass%Al2O3, slag was found to vary in proportion to Pb2/ w and pc/z/p' which proved that chlorine dissolved in the melts as C1 anion. Hence, the chloride capacity (CCI-), indicating the ability of molten oxide to absorb chlorine, has been defined as; The Ccl value was observed to increase with increasing slag basicity and temperature, and showed a reasonable relationship with that Of CS2-. Based on the result obtained in the present study, chlorine distribution during incineration with slags was predicted quantitatively.

Jan 1, 2003

By R. J. Mitchell

Results from investigations into impurity distributions over cathodes are presented with implications for various sampling methods, Selection of an optimum treatment procedure for the test sample is outlined. The impact of both these studies on the development of an in-house method for sampling Isa Process cathode is discussed. The economic compromise actually undertaken, satifying wants and needs to sustain confidence in high grade cathode purity is detailed.

Jan 1, 1987

By Garry W. Warren

The brass foundry industry produces a significant amount of waste sand containing Cu, Zn and Pb which is often classified as a hazardous waste due to Pb content. The potential application of a hydrometallurgical process to treat the sand by extracting metal values and thus detoxifying the material has been investigated. The process involves leaching of metal values followed by cementation. The emphasis of this investigation was on the leaching step, although some preliminary cementation experiments have been performed. In order for any alternative treatment scheme to be successful, the smaller size fractions of the sand must be addressed. Experiments have been performed on five individual size fractions using various lixiviants HCI, acetic acid and HCI/NaCI. Cu extraction was found to be slower than either Zn or Pb. Results obtained in this investigation indicate that copper is present in two forms, an oxide form which dissolves rapidly and is insensitive to the level of oxygen, and a less soluble form, probably metallic which dissolves more slowly and requires an oxidizing agent. The presence or absence of oxygen had no influence on the rate of Zn dissolution indicating that zinc is present mostly in oxide form. Toxicity Characteristic Leaching Procedure (TCLP) tests showed that residues could be produced which meet the toxicity limit for lead. Preliminary cementation experiments have also demonstrated the feasibility of Cu and Pb recovery.

Jan 1, 1991

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Y. Maeda

Non-ferrous smelting furnaces generally lnstal1 a gas cooling system for treatment of waste gas containing S02. From the point of view of corrosion resistance and recovery of waste heat, the high pressure boiler system Is the best way to cool gas, however this system requires high Initial investment and relatively higher operating costs. Because the feasibility of this boiler system greatly depends on the smelting process and scale, other lower temperature systems, e.g. water-cooled Jacket system, are more suitable If the smelting process does not produce enough steam nor generate enough electricity to compensate operating cost. In addition, the water-cooled Jacket system Is simple in structure and easy to operate. For those reasons, it is applied widely. A new smelting furnace. was planned tin our factory and It was necessary to install waste gas cooling equipment. In our case, a water-cooled Jacket system was mo11e feasible because of the low gas volume and high dust content. H was also expected to operate without maintenance for ten years. On the other hand, some leakage problems with the water-cool1ed Jacket had been experienced In the past. That is because S02 in the waste gas changed into sulfuric acid which corroded the Jacket material, As the first step, several data from actual usage were reviewed to throw light on the corrosion process, and an appropriate procedure to determine the operating temperature of cooling water was obtained. For the basis of this study, a water-cooled Jacket system was newly designed and tested for three months in a pilot plant. After this system's performance was confirmed, It was installed In a new furnace as a commercial pl.ant. After one year of operation, the initial thickness of carbon steel Jacket remains almost the same.

Jan 1, 1992

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

By D. W. Collins

The uptake of gold from halide solutions by activated carbon has been investigated using various techniques. Halide systems typically exhibit combined adsorption-reduction type behavior. In an attempt to gain more information about the nature of these processes, samples of synthetic highly-oriented pyrolytic graphite (HOPG) were contacted with aqueous solutions of gold-iodide. HOPG represents a model structure for activated carbon comprising of basal- plane sites, edge sites, and various defect sites. Two basic instrumental methods were used to examine the uptake of gold by HOPG. The first was standard X-ray photoelectron spectroscopy (XPS). The other involved several scanning probe techniques. XPS clearly indicated a preferred uptake of gold at edge sites. However, iodine appeared to be distributed on both basal-plane and edge sites. At low iodine additions, tapping mode AFM showed that clusters were concentrated along steps and surface defects. At high iodine concentrations, the HOPG surface was uniformly covered by iodine.

Jan 1, 1998

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 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 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 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