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By Kouji Mimura, Masahito Uchikoshi, Minoru Isshiki

"HfO2 is expected to be a gate dielectric used in ULSI alternatives to S1O2. Although the materials used in ULSI are required to be significantly pure, commercial Hf contains > 2 mass% Zr. It is important to establish a process for removing Zr from Hf. In the present study, anion-exchange separation using a multi-column method was employed. The separation tests were carried out at variety of temperatures and flow rates. The decrease in the flow rate of the mobile phase made the elution curves of both Hf(IV) and Zr(IV) broaden contrary to the case of Co(II), Cu(II), or Fe(III). This is caused by the difference in adsorption rate on the anion exchange resin. In addition, more than one column was connected in series in order to enhance the separation. As a result, the content of Zr(IV) was successfully reduced to 1/100 of that relative to the raw material.IntroductionHafnium is one of the most important materials in modem society. The main applications of Hf metal are as a control rod in a nuclear reactors because of its large neutron-capture cross-section and as an additive to various alloys because of its corrosion resistance [1]. In addition to those applications, attention has been recently paid to HfCh as a high-x"" dielectric used in ultra large scale integration, ULSI, as well as ZrCh, AI2O3 and La2C>3, which are expected to be alternatives to conventional S1O2 thin films [2].The materials used in ULSI are required to have a high purity in order to avoid unexpected errors due to impurities. Furthermore, high purity Hf is indispensable for investigating the intrinsic properties of Hf metal. Thus, it is significant to establish the purification process for Hf from both the industrial and academic perspectives."

Jan 1, 2012

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985

By Jafar Safarian

Bauxite is the main raw material used for the production of alumina (Al2O3) through the well-known commercial Bayer process. This process has significant challenges such as limitation in using low-grade bauxites as they contain significant amounts of impurities such as Fe, Si, Ti. The Bayer process residue, which is known as red mud, is also a global environmental challenge due to huge amount of this low value residue production. An alternative sustainable process with high potential to solve these problems and produce valuable and consumable by-products is a pyrometallurgical-hydrometallurgical process in which the low-grade bauxite ore is treated through a smelting-reduction process, yielding iron alloys and a calcium-aluminate slag. Alumina is then produced from the slag by hydrometallurgical treatment. In the present work, the reduction of pellets produced from different bauxite ores by hydrogen is studied and it is shown that complete iron oxides reduction is possible. Further smelting and smelting-aluminothermic reduction of the reduced pellets show that iron and silicon ferroalloys can be produced, in addition to a proper slag for alumina extraction.

By Kirsi M. Riihilahti

The oxidation characteristics of solid copper matte particles under simulated Kennecott-Outokumpu Flash Converting conditions are presented. The effects of feed matte grade, matte particle size, oxygen-to-matte mass ratio, oxygen content of the process gas and temperature on the particle oxidation rate, quality of conversion, particle size change and particle morphology were determined. The converting quality was highest (~68) with the 58% copper matte at 1100°C. At similar conditions, the 72% copper matte was more likely to produce copper oxides and leave unoxidized particles rather than directly produce sulfur dioxide at 1100°C, resulting in an average converting quality of 55. The quality of conversion was poorest for the 72% matte at 920°C (~45); the sulfur removal was extremely low even with a relatively high degree of oxidation. Fragmentation of the particles was significant in all cases with the 72% matte. A higher O2/matte .ratio and higher temperature, in general, resulted in increased fragmentation while oxygen enrichment had no significant effect. With the 58% matte, particle size was found to increase for the finest fractions rather than to decrease due to particle expansion.

Jan 1, 1998

By Emil B. Milosavljevic

The photochemical reactions of cyanide ion induced by light were investigated in the presence or absence of a titanium(IV) oxide semiconductor photocatalyst. The light sources employed were the sun and arrays of either mercury or fluorescent (cool white) lamps. The results obtained verify that cyanide decomposes much faster when TiO2 is present in the solution and that it is first oxidized to cyanate. However, contrary to the previous studies, it is established that cyanide is subsequently further oxidized via nitrite all the way to nitrate irrespective of the light source. As expected, the rates of the oxidation processes decrease with the illumination source utilized in the following order: Hg-lamps > sunlight > fluorescent lamps. As nitrate is a significantly less hazardous contaminant than cyanide, complete photocatalytic oxidation of cyanide to nitrate may be a viable method for decontamination of cyanide wastes. Contrary to previous claims, we find that cyanide is slowly photochemically decomposed even in the absence of TiO2. For example, with the mercury lamps as the light source, in two hours, cyanide concentration decreases to essentially zero; up to 7% was converted to cyanate and the remainder to unidentified products.

Jan 1, 1992

By A. Warczok

The heat transfer coefficient between liquid slags and solid surfaces is important for the design and operation of metallurgical reactors. An experimental technique developed for the purpose of measuring the heat transfer coefficient between liquid slags and solid metals is described. During the initial heating up of a Ni cylinder upon immersion in a liquid slag, a layer of frozen slag initially forms, then melts. The heat transfer coefficient measured during the initial rapid heat-up of the Ni cylinder, is approximately twice as high as the heat transfer coefficient measured during the final heat-up of the Ni cylinder subsequent of the liquidus temperature of the slag. The technique was tested in various melts i) NaNO3, ii) NaCl, iii) Na3AlF6 and iv) 2FeO*SiO2, giving consistent results. It was found that the heat transfer coefficient increases with increasing bath superheat and stirring. The heat transfer coefficient during the heating up following complete remelting of the frozen slag, is related to the slag superheat(AT) and the specific stirring energy(W) per kg of slag(E) as follows.

Jan 1, 1993

By Dietmar Eifler, Benjamin Jost, Marcus Klein

This paper focuses on the ductile cast iron EN-GJS-600 which is often used for components of combustion engines. Under service conditions, those components are mechanically loaded at different temperatures. Therefore, this investigation targets at the fatigue behavior of EN-GJS-600 at ambient and elevated temperatures. Light and scanning electron microscopic investigations were done to characterize the sphericity of the graphite as well as the ferrite, pearlite and graphite fraction. At elevated temperatures, the consideration of dynamic strain ageing effects is of major importance. In total strain increase, temperature increase and constant total strain amplitude tests, the plastic strain amplitude, the stress amplitude, the change in temperature and the change in electrical resistance were measured. The measured values depend on plastic deformation processes in the bulk of the specimens and at the interfaces between matrix and graphite. The fatigue behavior of EN-GJS-600 is dominated by cyclic hardening processes. The physically based fatigue life calculation “PHYBALSIT” (SIT = strain increase test) was developed for total strain controlled fatigue tests. Only one temperature increase test is necessary to determine the temperature interval of pronounced dynamic strain ageing effects

Jan 1, 2015

By J. V. Atwood

The U.S. Bureau of Mines has developed a novel Double Membrane Electrolytic Cell (DMEC) that exhibits unique features for recycling contaminated metals and metal alloys. The DMEC incorporates two anionic ion exchange membranes, separating anodic and cathodic regions of the cell. The ion exchange membranes prevent significant transport of unwanted cationic impurities to the catholyte from the impure anolyte while the anion/cation balance in cell compartments is maintained through the free movement of anions between compartments. The membrane barrier makes it possible to electro refine highly contaminated materials or to electrowin from solution while utilizing alternate anode reactions. Sinceanolyte and catholyte cross contamination has been eliminated, premium cathode products are produced. The DMEC has been tested at bench, pilot, and commercial scales. Configuration of the DMEC, cell operation, scale, up efforts, and significant design factors are discussed. Two separate recycling investigations utilizing DMEC technology are presented. The first investigation examines recovery of high purity cobalt and nickel from severely contaminated super aIloy scrap. The second involves? upgrading contaminated cobalt in the U.S. Government's National Defense Stockpile. Capital and operating costs for both potential applications are presented.

Jan 1, 1995

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen ternary 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, SbO1.5 and Sb2O3) in the PbO-SbO1.5 and PbO-Sb2O3 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 P. Mazumder

Numerical analysis is carried out to examine the effects of thermosolutal convection on the formation of complex patterns in directionally solidified binary alloys. A finite-difference analysis is used for dynamic modeling of a two-dimensional prototype of Vertical Bridgman system that takes into account heat transfer in the melt, crystal, and the ampoule; melt flow and solute transport. Actual temperature data from experimental measurements are used for accurately describing the thermal boundary conditions. A range of complex dynamical behavior is predicted in the melt flow due to flow transitions and this is found to be directly related to the spatial patterns observed experimentally in the solidified alloys. The model is applied to single phase solidification in the Al-Cu and Pb-Sn systems to characterize the effect of convection on the macroscopic shape of the interface. The application of the model to hyper-peritectic alloys in the Sn-Cd system shows that the presence of oscillating flow can give rise to a novel convection induced microstructure in which a tree-like primary phase in the center of the sample is embedded in the surrounding peritectic matrix.

Jan 1, 1999

By E. C. L. Cardoso

Hydrocarbon polymers, as PP, made from cheap petrochemical feedstock are important in many branches of industry. However, they have an undesirable influence on the environment and cause problems due to waste deposition and utilization. Polymeric materials composites account for an estimated from 20 to 30% of total volume of solid waste disposed. Thus, there is a tendency to substitute such polymers by those ones that undergo biodegradable processes. Polypropylene (PP) is a commodity, with high melting point, high chemical resistance, low density, with a balance between physical and mechanical properties and easy processing at low cost. Nevertheless, PP shows limitations for some special applications in automotive industry and civil construction. In order to minimize this deficiency, related to rheological behavior of polymer melt, especially referring to viscosity in processing temperature, a 50% mixture with HMSPP (High melt Strength Polypropylene) was used. PP/HMSPP was blended with 10, 15, 30 and 50% of natural (sugarcane bagasse) and synthetic polymers (PHB and PLA) aiming to partially biodegradable materials. The admixtures were subjected to gamma-irradiation at 50, 100, 150 and 200 kGy and then further assessed by mechanical tests in order to evaluate their degradability.

Jan 1, 2015

By Xin Li, Hai-Xing Fang, Bing Xie, Hong-Yi Li

Chromium-containing vanadium slag (V-Cr slag) was obtained by an industrial smelting process of Hongge Ore, which is valuable vanadium-titanium magnetite to extract V and Cr in China. Sodium roasting thermodynamics of V-Cr slag in presence of oxygen were calculated to evaluate the reactivity of chemical compounds. Results showed that the oxidation of FeV2O4 was intensified in presence of Na2CO3 while the oxidation tendency of FeCr2O4 was far lower than that of FeV2O4. It was probably that reactions of impurities including Al2O3, SiO2 and Fe2O3 with Na2CO3 happened and the products can promote the oxidation of vanadium or chromium compounds in lower valence. Based on thermodynamic analysis, a two-step selective extraction process of vanadium and chromium was proposed. Extraction rate of vanadium was 88.6% while 7.0% for chromium in the first extraction step; extraction rate of 90.7% and 95.4% for vanadium and chromium, respectively, were obtained in the second step.

Jan 1, 2014

By Richard L. Kerr

The U.S. aluminum recycling industry has experienced rapid growth in both its size and importance over the past two decades. Secondary recovery now makes up about one-third of total U.S .. aluminum supply compared with ]9 percent, of a much smaller total in the early 1970's. This growth has occurred in part because recycled metal performs as well as new aluminum in most applications, and because it provides major savings in production costs and natural resource utilization. In addition, the recycling industry has played a critical role in greatly expanded -production and reclamation of aluminum beverage cans. Recycled metal makes up over half of the content of aluminum sheet used: to manufacture beverage cans. In future years, both the-production and reclamation of aluminum cans are likely to rise in foreign markets, thus providing the industry with opportunities for further growth. Recyclers may also play a larger role in supplying auto producers who are using increasing amounts of aluminum in passenger cars and trucks. However, in order to take advantage of this growing market, an efficient infrastructure for collection of scrap and production of metal must be developed.

Jan 1, 1995

By Joel F. Flurnerfelt

Molten Al and Al alloys containing si, Mn, Ti, and y have been lanced with nitrogen-bearing gases. These lancing experiments provided the means for observing what phases form during exposure to nitrogen-bearing gases for finite periods of time, <2 minutes, at high temperatures, >1290oC. The experiments were conducted in sn induction heated drop tube furnace apparatus. The overall premise of these experiments was to select those Al alloys and gas compositions that show promise of forming secondary dispersoid phases, particularly AIN, in the Al matrix. The alloys selected will be atomized using gas atomization reaction synthesis (GARS) using the most favorable conditions. In this case, the chosen Al alloy will be atomized with a nitrogen-bearing gas, such that the Al and gaseous nitrogen species react to form a dispersoid phase within each powder particle. The powder particles that result from this "aggressive" GARS-process would be essentially Al metal-matrix composites within a uniform distribution of dispersoids. To date, only high-purity Al has been atomized using a mild GARS reaction. This work is funded by the Materials Science Division of DOE-BES under contract number W-7405-Eng-82.

Jan 1, 1996

By T. Xin

A vertical grain boundary intercepting a horizontal free surface forms a groove to reduce the combined surface energy of the system. We study grooving by surface diffusion with anisotropic surface energy. A recently developed delta-function model of facets is used to describe the surface energy with three or four fold symmetry. It is found that the groove grows following a similarity law. The self-similar groove profile is solved numerically by a shooting method. Even with strong anisotropy, the groove profile can be smooth if the exposed surface orientations do not include a facet orientation. The smooth self-similar groove shape is the same as an isotropic groove, but the size is reduced by a factor that depends on the degree of anisotropy. This induces a large error on the value of surface diffusivity if the isotropic model is used for an anisotropic system. In this talk. we will describe how to correct for this error.1 I Xin, T. and H. Wong, "Grain-Boundary Grooving by Surface Diffusion with Strong Surface Energy Anisotropy," Acta Materialia 51, 2305-2317 (2003). Keynotes: Grain growth, Surface Diffusion, Surface energy, Anisotropy

Jan 1, 2003

By Sergio Neves Monteiro, Nuã Simonassi, Helvio Pessanha Guimarães Santafé Jr.

"Thermoset polymers, like the polyester, become harder with increasing temperature owing to molecular crosslink formation, which is a thermal benefit for composite matrix applications. Natural lignocellulosic fibers, however, have low thermal resistance and tend to degrade with increasing temperature. Therefore, the combination of a lignocellulosic fiber, as reinforcement, with a thermoset polymer, as the matrix, results in a composite material with complex thermal behavior. In the present work, a thermal analysis was conducted on polyester composites with different amounts of coir fibers. Both TGA and DTG curves were analyzed to determine the effect of the coir fiber on the thermal resistance of the composites. It was found that the coir fiber sensibly affects the thermal behavior of the polyester matrix for fiber amounts above 10% in volume. This effect is associated with an increase in thermal degradation.IntroductionIn recent years, there has been an increase application of natural fibers as reinforcement of polymer matrix composites in several industrial sectors, with special participation in automobile components [1-3]. Figure 1 illustrates the different components of a modem BMW sedan that are fabricated with lignocellulosic reinforced polymer composites."

Jan 1, 2012

By Elizabeth M. Ho

Oxidants are added in uranium leaching in acid media to convert iron(II) in solution to iron(III). Iron(III) has an important role in the leaching of uranium by acting as an electron transfer agent for the oxidation of uranium(IV) to uranium(VI). The oxidation of iron(II) to iron(III) in sulfate solutions using sulfur dioxide/oxygen (SO2/O2) was carried out under typical uranium leaching conditions (pH 1-2, 20-50°C) to confirm literature trends and this work was then extended to the use of SO2/O2 in the leaching of uranium ore. The oxidation rate was found to be dependent on the initial SO2/O2 volumetric ratio and the oxygen mass transfer rate, but was independent of the initial iron(III) concentration above about 200 ppm at pH 2. The presence of 55 ppm organic extractant (Alamine 336) decreased the reaction rate. The oxygen mass transfer coefficient (kLa) for the mixing tank system was measured and was found to decrease with increasing solids density in a 1 g L-1 MgSO4.7H2O solution.

Jan 1, 2003

By Armando Valenzuela

Arsenic has been a common impurity in copper sulfide concentrates treated pyrometallurgically in Chile, which inevitably during the smelting-converting process reports in the final copper product affecting its properties, but also affecting environment as a very toxic occupational hazard. The enforcement of air quality standards, which regulate pollutants such as sulfur dioxide, particulate matter, and arsenic, has resulted in the implementation of pollution abatement plans and emission reduction schedules mainly by state-owned copper concentrate smelters. Investments associated with these plans incorporated gas-handling systems in order to capture polluting emissions. Electrostatic precipitators recover dusts containing mainly Cu and As which are leached to recover copper, while arsenic is disposed currently in the form of ferric arsenate. Gases containing high sulfur dioxide content are treated in plants to produce sulfuric acid, which is used in various classical and new hydrometallurgical processes. Additionally, smelters have effluents treatment plants for arsenic disposal either as ferric arsenate or calcium arsenate/arsenite. This paper reviews the environmental situation of the Chilean metallurgical industry, and the present trends for arsenic management are particularly emphasized since Chile is the world?s largest copper producer.

Jan 1, 2006

By Ahmet Geveci

[Generally accepted formula related to sulfur slag-metal distribution ratio is given by the following equation: [ ] According to the above equation it can be deduced that sulfur distribution between slag and metal is governed mainly by metal composition (?s term), slag composition (slag basicity and in turn sulfide capacity), oxygen potential of the system (ao¬¬ term) and temperature(related to equilibrium constant, K). In this study, the results of ladle furnace operations conducted in Erdemir-Iron and Steel Works Co. (Turkey) in relation to sulfur removal, have been given. Typical ladle furnace slag analyses of 4937K quality steel have been presented. Activity coefficient of FetO,?FetO, have been calculated with the relation obtained fromthe literature. Activity calculations have been performed with the program written in Mathcad. The changes in activity of aFetO in the slag phase,, have also been studied in relation to the sulfur removal: The relation between % Decrease aFetO and %DeS (measured)have been investigated for 4937K runs and someother types of steel produced in the Erdemir Plant. Related to ladle operations %desulfurization defined as [(%Sinitial-%Sfinal)/S%initial]*100 values have been presented for different steel qualities.]

Jan 1, 2006

By Kimio Itagaki

As a fundamental study for smelting the copper matte with high contents of arsenic and antimony in a strongly reducing condition, phase relations between the liquid matte and copper-rich alloy phases in the Cu-Fe-S-As or -Sb quaternary system and between the liquid matte and iron-rich alloy phases in the Cu-Fe-S-As or -Sb system saturated with carbon were determined at 1473 K by a quenching method. Activities of arsenic and antimony in these systems were also measured at 1473K by Knudsen cell-mass spectrometry. Furthermore, distribution ratios of silver, gold and platinum between the liquid matte and copper-rich or iron-rich alloy phases were determined in relation to the arsenic or antimony content in the systems. On the basis of these data, the elimination of arsenic and antimony from the matte to the iron-rich alloy (speiss) and the recovery of precious metals in reduction smelting of the copper matte were evaluated. It was suggested that the addition of pig iron to make a strongly reducing condition and form the iron-rich alloy, which is fluid at smelting temperatures, will be useful for fixing arsenic in the speiss.

Jan 1, 2006