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By V. E. Antonov

Hydrides of iron and iron-based alloys are thermodynamically stable only at hydrogen pressures in the gigapascal range and rapidly loose hydrogen under ambient conditions. At low temperatures, however, these hydrides can be retained in a metastable state at atmospheric pressure after being cooled under the high pressure to liquid nitrogen temperature. This review will discuss the current state of studies on phase transformations in the Fe-H and related systems and also on the composition, crystal structure and physical properties of the hydrides, both under high hydrogen pressures and in the "quenched" metastable state at ambient pressure. The studies at ambient pressure include magnetization measurements, X-ray and neutron diffraction, Mossbauer spectroscopy and inelastic neutron scattering. In the sections on Mossbauer and structural investigations of hydrides of Fe-Cr and Ni-Fe alloys new experimental results will be presented.

Jan 1, 2002

By Katri Avarmaa

Aluminum and copper are large volume metals in electronic appliances, while tin and indium exist as common minor elements. All of these non-ferrous metals are aimed to be separated and recycled from the end-of-life electronics into non-ferrous scrap fraction(s), and further through pyrometallurgical and/or hydrometallurgical processes to pure metals. Depending on the mechanical pre-treatment processes, aluminum and copper liberation from each other varies. This study focuses on the influence of alumina on indium and tin distributions between copper alloy and iron silicate slags with 0, 9 and ∼16 wt% of Al2O3. The experiments were executed with an equilibration-quenching-EPMA technique in an oxygen pressure range of 10−10–10−5 atm at 1300 °C. The metal-slag distribution coefficient of indium remains constant as a function of alumina in slag, while that of tin increases. Therefore, aluminum in feed or alumina addition to the slag improves the recovery of tin into copper. Nevertheless, oxygen pressure has clearly more significant influence on the behavior of both the metals in the smelting conditions.

By W. K. Choi

Stainless steel exposed to wet environments at ambient temperature is subject to the formation of a surface biofilm. Depending upon the prevailing environmental conditions (dissolved oxygen, pH, Eh, concentration of cationic/anionic species), the biofilm may stimulate corrosion through formation of differential aeration zones and concentration cells. Corrosion significantly impacts the United States economy, since on a yearly basis, corrosion induced losses are estimated to be over $200 billion. A large portion of this corrosion is imputable to bacterial activity, and basic information is needed for a better understanding and control of the biocorrosion phenomenon. The present study has investigated the influence of Thiobacillus ferrooxidans in the corrosion of American Iron and Steel Institute (AISI) 304, 316 and 416 stainless steel samples. The formation of biofilm and microstructural changes on the surface of stainless steel samples and their weldments were assessed by microscopic examination, and the changes in the mechanical properties by stress-strain measurements. The significance of the results will be discussed.

Jan 1, 1993

By Sang Han Son

The vapor pressures of FeCI2 and ZnC12 in the FeCl2-ZnCl2 system were measured by the transpiration method at 873K and 917K. The vapor pressure data were interpreted to indicate the formation of complex ions in the FeCl2-ZnCl2 melts. It is presumed that the complex molecule FeZnCl4 as well as FeCI2 and ZnCI2 exists in the vapors in equilibrium with molten FeCl2-ZnCl2 mixtures. The activities in the FeCl2-ZnCI2 system are shown a negative deviation from Raoult's law. These results suggest the formation of complex ions such as ZnCl42- in molten FeCI2-ZnCI2 mixtures.

Jan 1, 2003

By Hiroyuki Sano, Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa, Shin-ya Iwahori

"Pyrometallurgical process using Cu2O-based slag was proposed as a recycling process for copper scrap. However, it is difficult to remove nickel from copper by oxidative refining. Therefore, it is necessary to reduce the concentration of nickel in copper before the oxidative refining. In the present work, the copper enrichment stage in this recycling process, where copper scrap melt is separated into the Fe-C-Cu melt and the molten copper, was taken up and the compositions of both melts were measured. Based on the above results, the distribution ratios of nickel between the Fe-C-Cu melt and the molten copper were calculated. Furthermore, the optimum condition of copper enrichment stage was discussed from the viewpoint of nickel removal and copper recovery. The possibility of recovering 4N-purity copper by using this recycling process was confirmed.IntroductionRecycling is well known as a method for saving resources and reducing environmental damage. More than 99% of copper is used in metallic form - as metal or copper alloys[l]. High-grade copper scrap is directly re-melted and reused, while low-grade copper scrap is transported to copper smelters to be pyrorefined and electrorefined. Nevertheless, a great amount of copper is being stockpiled in the cities and should be recycled in the near future. At that time, the current recycling process will face new problems due to the increases in the recycling rate to the smelters. This includes insufficient combustion heat to melt copper scrap and ·almost no benefit in electrorefining because the scrap does not contain gold and silver. Thus, an alternative pyrometallurgical method for copper scrap refining will be required."

Jan 1, 2000

By J. H. Ahn, J. K. Yoon, Jung-Eui Lee

"A concentration change during grade transition operation in steel thin slab casting is predicted with computer simulation, water model and plant trial. Fluid flow and mixing patterns in various tundish levels and flow rates were analyzed through three-dimensional mathematical modeling. Comparing with water model experiments, a simple, efficient and accurate computational model has been suggested to predict the concentration profile at outlet of tundish. Based on the model, mixing in/below the mold was analyzed considering EMBR. The predicted concentration profiles show good agreements with the measured values. It is found that the lower vortices in the mold are suppressed by the electromagnetic field and the plug-like flow region develops which decreases the intermixing of two different grades of steel and shortens the length of transition region.1. IntroductionContinuous casting is the primary mode of production of semifinished steel products as it offers tremendous advantages in terms of energy savings, increased yield and higher productivity over the traditional ingot casting process. Efforts have to be made constantly to improve the quality of the cast product, reduce costs and thus increase the competitiveness of the steel manufacturer. One way of reducing costs is to reduce the amount of intermixed steel during the grade transition operation.Several different procedures exist to handle the casting of dissimilar grades for the conventional slab casting. Each procedure has its own merits and demerits. In order to choose the best method for a particular operation, there are a lot of researches. In the case of present continuous thin slab casting of POSCO mini mill, the only possible method is to change ladle during the grade transition. Due to the high casting speed (3.8m/min-4.4m/min) it is impossible to change the tundish and due to the thin thickness of slab it is also impossible to insert grade separator."

Jan 1, 2000

By Ann E. Visser

Aqueous Biphasic Systems (ABS) form upon the admixture of certain water-soluble polymers or polymers and salts above critical concentrations, and thus represent liquid/liquid extraction systems whose nature is entirely aqueous. We are currently investigating the utility of ABS (and its solid phase analogs) as "green" alternatives to the use of volatile organic diluents in separations of metal ions. Chaotropic (water-destructuring) metal ions with small negative AGhyd (e.g., Tc04) tend to partition quantitatively to the PEG-rich phase of an ABS, but even hydrated metal cations can be partitioned to the PEG-rich phase if a suitable extractant (e.g., halide, dye, crown ether, etc.) is used to produce a more chaotropic ion-complex.

Jan 1, 1999

By Kenneth N. Han

Thermodynamic and kinetic aspects of nickel and cobalt leaching from metals. minerals and ores in various media have been reviewed and discussed in this paper. A kinetic model developed to delineate the leaching mechanisms for these metals has been discussed in view of experimental observations. The current review also includes the dissolution behavior of nickel and cobalt from various minerals such as oxides, sulrides. ocean floor manganese nodules, and laterites. A particular emphasis has been extended to similarities and differences of the dissolution behavior of these two metals in various media. The leaching of nickel as well as cobalt metal in acidic solutions and arnmoniacal solutions exhibits in most part mass transfer controlling. although at some pH's, chemical controlling or mixed controlling mechanisms seem to prevail. The leaching of nickel and cobalt from oxides in acids and ammoniacal solutions. on the other hand, can be described best by chemical controlling mechanisms.

Jan 1, 1993

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By Marco Antônio Siqueira Rodrigues

The possibilities for treating rinse waters fiom chromating bath by electrodialysis are discussed together with the possibilities of optimizing the treatment process for waste reduction and reuse of water and chemical products. An industrial effluent with 4600 ppm of Cr(VI), besides other metallic contamination, was used as work solution. This solution has been recirculated on an electrodialysis cell of three compartments, using exchange membranes Selemiom AMT and CMT. A migration of dichromate ions into the anodic compartment was obtained, so that an extraction of circa 99.9 % of Cr(VI) present on the solution was observed, resulting in water with a Cr(V[) concentration of 4 rnd. These results show that electrodialysis can be used to treat these effluents, and this water could be reused as rinse water. The solution of the anodic compartment, consisting at the beginning of the experiment of H2S04, 0.1 N, reached 7200 mg/l of Cr(VI). This concentrate could be reused on the chromating bath itself.

Jan 1, 1999

By Fei Ruan, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"Viscosity is an important physical parameter of slag in metallurgical processes. Most studies of aluminosilicate and aluminate systems assume that aluminum occurs in tetrahedral coordination. In this case, the O/Al value was utilized to describe the slag structure in terms of the network character of aluminosilicate and aluminate systems. Composition and viscosity data from the literature and the trends were analyzed according to the O/Al value and temperature. It is shown that the O/Al value explains the trends in more than ten systems, containing more than 200 data points. In aluminosilicate system, the trend that viscosity value changed with the O/Al value which implies that alumina works as network modifier such as basic oxides or works as network former. In aluminate system, irrespective of the system and temperature, viscosity decreased steadily when O/Al value increased.IntroductionMetallurgical slags, which are made of oxides and many also contain fluorides, play an important role in metallurgical processes such as iron making, steel making and secondary refining processes. Aluminosilicate slags are applied in a wide range in metallurgical processes. A polymerizing effect of the addition of aluminum and an association of aluminum with low-field strength cations is further supported by the physical variations in aluminosilicate and aluminate systems. The behavior of alumina in silicate melts has been studied by various authors [1-6]. It is generally accepted that Al2O3 is amphoteric [7] because Al3+ ions can behave in profoundly different ways in a silicate melt. When added to a pure silica melt, Al2O3 acted as a network modifier, breaking the bridging oxygen of the pure silica network, thereby decreasing the viscosity in a similar manner to other network modifiers, such as CaO, MgO etc. to form [1/2Ca (AlO4)]4- complexes. However, when added with alkali or alkali-earth metal oxides, some of the Al3+ ions assumed tetrahedral coordination and replaced Si in the liquid network, the missing charge was compensated by Me+ or Me2+ ions. Therefore Al2O3 acted as network former [8, 9]."

Jan 1, 2011

By Yichi Lu, Haydn N. G. Wadley, Douglas T. Queheillalt

"Using a 3-D ray tracing methodology combined with laser ultrasonically measured elastic constant data near the melting point, ultrasonic propagation in cylindrical single crystal bodies containing either a convex or a concave solid-liquid interface have been simulated and used to design new sensing concepts. Ray paths, wavefronts and time-of-flight (TOF) of rays that travel from a source to an arbitrarily positioned receiver have been calculated. Experimentally measured TOF data have been collected using laser generated/detected ultrasound on model systems with independently known interface shapes. Both numerically simulated data and experimental results have shown that the solidification (interfacial) region can be identified from ultrasonic transmission TOF data. Since convex and concave solid-liquid interfaces result in distinctively different TOF data. When TOF data collected in the diametral plane are used in a nonlinear least squares algorithm, the interface curvature has been successfully reconstructed and ultrasonic velocities of both the solid and liquid obtained. The reconstruction errors were found to be less than 5%.IntroductionMany of today's single crystal semiconductors are grown by variants of a vertical Bridgman technique in which a cylindrical ampoule of a molten semiconductor is translated through a thermal gradient, resulting in directional solidification and the growth of a single crystal, Fig. 1.1 It has long been recognized that during crystal growth the velocity and the shape of the solid-liquid interface, together with the local temperature gradient, control the mechanism of solidification (i.e. planar, cellular or dendritic), the likelihood of secondary grain nucleation/ twin formation (i.e. the loss of single crystallinity), solute (dopant) segregation, dislocation generation, etc. They thus determine the crystals' resulting quality.2-4 The solidification rate and the solid-liquid interface shape are also sensitive functions of the internal temperature gradient (both axial and radial) during solidification.5•6 This in turn is governed by the heat flux distribution incident upon the ampoule, the latent heat release at the interface, and heat transport (by a combination of conduction, buoyancy and surface tension driven convection, and radiation) within the ampoule. The solid-liquid interface's instantaneous position, velocity and shape during crystal growth are therefore difficult to predict and uncontrolled during growth, especially for those semiconductor materials with low thermal conductivity (e.g. CdTe).4-6 The development of technologies to non-invasively sense the interface position and shape throughout the vertical Bridgman crystal growth process has therefore become a key step toward developing a better understanding of the growth process, for enabling sensor-based process control, and thus ultimately for improving the yield and quality of difficult to grow semiconductor materials like CdTe."

Jan 1, 1997

By P. D. Lee

The effect of strontium on porosity formation in aluminum-silicon alloys is not well understood and there is no consensus upon the cause of the effects observed. This paper describes a series of experiments where the effect of adding strontium on pore formation was observed directly with combination of a traditional temperature gradient stage and real time micro-focus radiography. These in situ observations provide a new insight into the effect of strontium on the nucleation and growth kinetics of porosity. The addition of strontium was found to have a minor effect on the growth of the pores in the mushy zone. However, strontium appeared to alter the nucleation and stability of hydrogen bubbles within the melt. The interaction of strontium with titanium-boride grain refiners produced an even stronger change in the nucleation and stability of the bubbles formed.

Jan 1, 2002

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as 'burning' of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

First, a classification of the various primary sources of feed materials for the production of cobalt is presented from a mineralogical point of view : sulfides, arsenides, sulfo-arsenides and oxide minerals. Each of these cate- gories will be characterized by its behaviour towards concentration methods, taking account of the presence of the associated minerals of other metals and of the nature of the gangue minerals. Then, for each category of cobalt bea- ring ores, typical flowsheets of treatment will be presented and discussed and the characteristics of the cobalt concentrates produced will be under- lined having in view their subsequent processing by pyro - and (or) hydrome- tallurgical methods.

Jan 1, 1988

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014

By S. Seetharaman

The present paper presents. the concept of micro-models and illustrates the application of the same in the simulations metallurgical processes. Development of micromodels requires access to accurate thermodynamic, thermophysicaland kinetic information for the relevant systems with suitable models to extrapolate the data as functions of temperature and composition. Experimental measurements and modelling of the thermodynamic properties, sulphide capacities and viscosities of oxide melts carried out in the department are presented. The incorporation of these models in process models, with special reference to ladle refining of steel is illustrated. Typical example of micro-modelling of solid-gas reactions is also presented.

Jan 1, 1999

By N. L. Piret

Reprocessing of low zinc-bearing residuals with a zinc content of less than 10%, originating from the iron and steel industry, has been given more and more attention in the last few years, due to the potential landfill liability and the increasing cost of disposal by dumping. Whereas, recycling of hazardous electric arc furnace dust is already being performed commercially on a large scale in the U.S., Japan and Western Europe, almost no reprocessing takes place in the case of these low grade zinc-bearing materials. In blast furnaces and basic oxygen furnaces dusts and / or sludges are generated at a rate of 1 to 2 % of the respective production. The technologies for the retreatment of these types of materials, either commercially available or still being developed are briefly described hereafter. They involve internal recycling, upgrading by physical separation methods, separate hydrometallurgical processing and pyrometallurgical treatment. Their scope and limitations are critically assessed in terms of technological applicability, economic feasibility and environmental compatibility. Since, the possibtlity of achieving economic profitability is unlikely with this type of material, the main criteria for acceptability of the treatment process are: generation of a iron-rich material, suitable for treatment by the iron/steel industry, acceptance of the non--ferrous metal-bearing sub-product by zinc smelters, generation of non-hazardous waste materials.

Jan 1, 1992