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By Fabiola Alvarez, Ana E. Bote, Daniel Pasquevich

"The oxidation of aluminum and its alloys was extensively studied for improving the corrosion resistance in structural materials having high specific strengths. But this reaction involves the formation of a very thin barrier layer on the metallic pieces. Furthermore, the ·recent development of the directed melt oxidation process for producing metal-ceramic; composites has renewed the interest in the study of interaction between gases and metals. Oxidation experiments in the presence of different chlorine partial pressures and at different temperatures were performed in ·a thermogravimetric balance, and microstructures were analyzed by electronic microscopy and X-ray diffraction. The oxy-chlorination kinetics was determined and the oxide formed W(IS amorphous at temperatures below 600 °C and crystalline .at higher temperatures. The appropriate experimental conditions for the fastest completed oxidation was further determined.IntroductionThe use of fine powders for the manufacture of ceramic components has significant advantages. They include excellent sinterability; low sintering temperature and better microstructure leading to improved mechanical properties. The conventional method of producing fine oxide powders involves controlled precipitation and pirolysis of suitable salts. The main limitation of the high temperature decomposition route is the evolution of environmentally unacceptable and corrosive gases. Controlled precipitation of hydroxides from solutions of salts, followed by thermal treatment involves large volumes of solutions and the calcination step that can induce grain growth (1).Direct oxidation of aluminum metal for producing alumina powder requires high temperatures for the direct oxidation of molten Al alloys by a vapor phase oxidant process (2, 3) or high technological process like thermal plasma reactor ( 4).Oxidation of high purity aluminum (5, 6) below the melting temperature· is initially characterized by a nearly linear reaction rate, followed by a rate which decreases rapidly with further weight gain. However, the oxidation rate of an aluminummagnesium alloy is much faster and it does not conform to any common oxidation law, but it is nearly parabolic at temperatures between 200 and 400 °C, an nearly linear· above 400 °C."

Jan 1, 2000

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would be reduced at the new smelter to about a half of the sum of those from previous two 1 smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive offgases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By Metehan Erdogan, Furkan Özdemir, Ishak Karakaya, Mustafa Elmadaglı

Tungsten is mainly produced by H2 reduction of WO3 which makes its production difficult and costly. A promising method was recently reported for direct electrochemical production of tungsten from CaWO4 (scheelite) which is estimated as the seventy percent of the all tungsten reserves of the world. This paper investigates the application of pulse current in the electrochemical reduction of CaWO4 pellets attached to a current collector. The electrolyte was composed of calcium chloride and sodium chloride salts at eutectic composition (48 pct mol NaCl at 873 K). The reduced samples were cleaned with dilute hydrochloric acid solutions and characterized by X-ray diffraction and scanning electron microscopy. Examination of the results revealed that metallic tungsten was obtained by pulse current reduction.

Jan 1, 2016

By Akira Yazawa

The similarities and differences in copper, nickel and lead smelting processes are discussed based on the sulfur-oxygen chemical potential diagrams and the free energy minimization assessments using a thermodynamic software. The prominent features of copper smelting are ascribable to the fact that copper has a strong affinity for sulfur but weak for oxygen and the liquid phase immiscibility between Cu and Cu2S. During the oxidation of sulfides, nickel metal is not stable except at temperatures higher than 1500°C, well miscible with its sulfide, and is oxidized more easily than copper. Metallic lead looks as stable as copper during the oxidation of the concentrate but Pb and PbS. are much more miscible with each other and the vaporization loss is considerable. In the reductive smelting of oxides, the effects of oxygen potential and temperature on the copper contents in slag are not significant due to the monovalent character of copper and the reduction of copper content in slag is not easy in practice. The effect of the slag compositions on the oxidic metal contents of slag is much more significant for lead than either copper or nickel. Due to the immiscible nature between Pb and Fe, high grade lead bullion is easily obtained and lead is more tolerant to impurities.

Jan 1, 1998

By W. Kasprzak

Modern light metals processing technologies are very complex and involve a diverse set of variables that must be quantitatively evaluated. The most effective way to design new casting processes that deliver specified metallurgical and mechanical properties is to develop a method of simulating the "real-time" process within a test sample of sufficient size. The results can then be analyzed and the required optimizations can be performed. This paper presents a novel method of simulating the industrial casting processes in a laboratory environment using an experimental apparatus based on the principle of high frequency induction heating. The applicability and accuracy of the proposed analytical method is demonstrated, for example, by simulation of the solidification and heat treatment of a test sample composed of two dissimilar materials. The simulation can be used to develop a stress model for an engine block made from an aluminum based alloy with iron cylinder liner inserts.

Jan 1, 2002

By Jiayan Li, Yi Tan, Yao Liu, Yaqiong Li, Shenrui Wu

"A metallurgical grade silicon (MG-Si) refining concept process was presented. Under vacuum conditions, silicon was selectively oxidized by high purity silicon dioxide to form gaseous silicon monoxide while impurities with low vapor pressure in MG-Si were rejected in residue; Then high purity silicon was obtained from the disproportionation of condensed silicon monoxide; and by-produced silicon dioxide was recycled for the oxidation step. Thermodynamics on boron rejection during the oxidation were studied in this work. In the temperature range of 1200-1800K, the saturated vapor pressure of boron, and the Gibbs free energy changes, the equilibrium partial pressures of silicon monoxide and boron oxides of potential reactions were calculated. And the effect of boron activity in MG-Si was also discussed. The results indicated that boron in MG-Si can be rejected during the oxidation and it showed the potential for the further development of the new refining process.IntroductionAs global energy consumption growing dramatically, higher prices of energy and global warming problem have attracted more and more attention [1]. As a clean and renewable energy industry, the photovoltaic (PV) industry converts solar energy to electricity using solar cell device and has a growth rate of about 30% in recent years. It has caused a shortage of silicon feedstock due to that about 90% of solar cells are made of crystalline silicon. And high energy consumption during the production of silicon material, i.e. solar grade silicon (SoG-Si), is main obstacle for its mass production."

Jan 1, 2012

By A. Tsubouchi, F. Noguchi, T. Takasu

"A high current density operation is desired to improve the productivity in copper electrorefining. However, a lot of problems still remain such as passivation at anode, dendritic deposition at cathode and impurity behavior during the electro refining.Effects of the current densitY on the morphology of copper deposition on the cathode, and passivation at the anode were investigated at various fluid velocity of electrolyte in the present study.Although a granular appearance of the copper deposition was obtained with increasing high current density, it was depressed by an increase of the fluid velocity of the electrolyte. A uniform deposition on the cathode was also observed when the fluid velocity of the electrolyte become higher. It was ascertained that passivation at the anode was suppressed by circulating electrolyte during electrolysis. INTRODUCTIONIt is desirable to operate at high current density in copper electrorefining in order to improve plant productivity without enlarging the size of electrodes(1). However, there are many problems in copper electrorefining at high current density with the usual commercial practice, for example, anode passivation, dendritic deposition and an increase of impurities in the cathode.In general, it is effective to agitate the electrolyte in order to suppress these problems(2). Smith et a1.(3) have performed electro refining experiments at various current densities in the range of 8 to 32 Aldm2 and at electrolyte fluid velocities in the range of 40 to 120 mlmin, and they obtained well consolidated, void free copper even at high current density in a high electrolyte velocity. However, they did not discuss the recovery ratio and the passivation behaviour at the anode. Walsh et a1.(4)(5)(6) experimented with the rotating cylinder electrode, and ascertained that electrolysis can be carried out at high current densities under the condition of pure electrolyte.With regards to anode passivation, there are several papers by previous workers(7)(8). Our group ascertained the process of producing anode slime during electrolysis(9). However, these experiments were carried out without forced circulation of electrolyte. Therefore, in the present study, to solve these problems, we electrolyzed at current densities in the range of 4 to 50 Aldm2 with circulating electrolyte in the range of 0 to 48 mlrnin. The effect of electrolyte fluid velocity on the surface morphology of deposited copper at cathode and passivation at anode were investigated when electrolysis were carried out with circulating electrolyte at high fluid velocity and at high current density."

Jan 1, 1997

By Eren Hüseyin Obuz

In this study, the leaching kinetics of rare-earth elements were investigated using HCl and HNO3 solutions. A standard crushed complex ore was utilized as raw material. The complex ore (particle size of under 54 μm) contains REE (Ce, La, Nd, Pr, etc.). Different leaching durations were selected for the kinetic studies. The highest leaching efficiency was obtained in HCl solution, and the leaching mechanism was identified to diffusion through a product layer. The rate constants of Ce, La, Nd, and Pr were calculated as 1.08 × 10−2, 0.86 × 10−2, 1.87 × 10−2, and 1.34 × 10−2 h−1, respectively.

By Esperidiana A. B. Moura, Célio H. Wataya, Roberta A. Lima, Rene R. Oliveira

The purpose of this study was to investigate the mechanical, morphological and thermal properties of biodegradable composites based on aliphatic-aromatic copolyester/polylatic acid blends (PBAT/PLA blends) reinforced by açaí seed fibers, an abundant byproduct of the açaí fruit agro industry. The biodegradable polymeric composites were prepared by melting extrusion process using a twin-screw extruder machine. The fibers removed from the açaí seed were used as the reinforcement and PBAT/PLA blends as the matrix. The influence of the açaí seed fibers addition on properties of composites was investigated by tensile and impact tests, SEM, DSC, and XRD analysis. Correlation between properties was discussed. In addition, açaí seed fibers characterization by SEM, XRD and WDXRF have also been carried out. The addition of açaí seed fibers on biodegradable PBAT/PLA blends showed that it is possible to get interesting property gains in biodegradable polymer by using waste from renewable sources.

Jan 1, 2015

By ZHANG Ting

In view of the high consumption and contamination of traditional vanadium extraction technology, a new process of leaching the converter vanadium slag without roasting with titanium dioxide waste was proposed. Extraction mechanism of P204 in the leaching solution had been researched and single factor experiments show that after a prereduction of Fe, and under conditions: ambient temperature，leaching solution original pH=2.5, phase ratio (A/O)=1:3, shaking time 8min, the extraction rate of V is more than 98.62% meanwhile the separation rate between V and Fe is up to 135.3 in the 20%P204-10%TBP-Sulfonated kerosene extraction system.

Jan 1, 2015

In low carbon TRIP steels, the formation of carbide-free bainitic ferrite is crucial for the stabilization of austenite. Based on experimental investigations modeling the bainite reaction is examined adopting diffusional and displacive mechanisms, as well as the semi-empirical JMAK approach. Transformation tests were carried out to study the isothermal austenite decomposition into bainitic ferrite for a model steel containing 0.6wt%C, 1.5wt%Mm and 1.5wt%Si which replicates the composition of remaining austenite at the start of the bainite reaction in a classical C-Mn-Si TRIP steel. In the diffusional approach, classical nucleation theory is employed and subsequent growth of bainite plates is modeled using the Zener-Hillert theory. In the displacive approach, the autocatalytic nucleation of bairtite plates is assumed to be rate controlling. The predictive capability of all models is evaluated for temperature ranges where different morphologies of bainitic ferrite have been detected, The shortcomings and inherent challenges associated with either of these modeling approaches will be delineated.

Jan 1, 2003

By M. Opler

Presently, only a few large copper refineries are able to produce Grade A cathodes from copper scrap. Today's technology needs large plants for smelting, converting or refining the main impurities and casting the anodes for electrolytic refining. A new ECUPREX® PROCESS, by-passes all pyrometallurgical operations and produces directly copper cathodes starting from copper scrap with high lead and tin contamination. Copper scrap from chopped cables, copper cements and electronic scrap are suitable feed for ECUPREX® PROCESS. This process uses a non-conventional electrolyte and produces a surprisingly high quality, smooth cathode assaying only few ppms of total metallic impurities. Bench-scale work followed by a successful mini-pilot plant run, has led to the construction of an operating pilot plant equipped with a 1,000 Ampere cell. The results of the operations of this pilot plant are presented and described in this paper.

Jan 1, 1995

By V. A. Luganav

The behavior of arsenopyrite under heating has been studied by many scientists. It has been already established that under heating at more than 650°c and without air access the arsenopyrite dissociates with the formation of one atom arsenic. Under vacuum the dissociation process begins at 5500C with the formation of elemental arsenic. The residue of dissociation process contains pyrrhotite and throilite. In the presence of pyrite, arsenopyrite dissociates under lower temperature and with a higher velocity than without it. The industrial realization of fool scale processing of arsenic bearing raw materials is possible only by the use of standard equipment and oxygen containing blast. In this view the paper presents the results of the study on the effect of oxygen in the gaseous phase and its addition into the charge of pyrite in the process of arsenopyrite decomposition. Thermodynamic analyses showed that under thermal processing of arsenopyrite in the presence of pyrite and limited quantities of oxygen in the gaseous phase the formation of arsenic sulfides is possible according to the following reactions:

Jan 1, 2003

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000

The effect of change in slag composition upon metal losses to the slag and the relationship between slag composition and slag matte separation was investigated at 1400°C. The synthetic slags containing CaO, MgO, SiO2,, A1,0, and FeO were similar to those employed in the electric furnace smelting of sulphide Cu-Ni concentrates containing PGM (Precious Group Metals) from the Merensky Reef of South Africa. The matte with a grade of 9.3% Cu and 16.0% Ni was a typical electric furnace product. The results indicated that the Cu and Ni solubility in the slag increases with the increase of the basicity ratio and CaO and MgO contents of the slag. At constant CaO/MgO ratios the rise in basicity decreases the metal losses. When FeO and SiO2 contents of the slag are kept constant, the substitution of MgO with CaO decreases the metal losses. The relationship between slag composition and matte-slag separation was found to depend primarily on the basicity ratio and the FeO content of the slag. The net effect comes from a strong interaction of the two in such a way that increasing basicity and decreasing FeO contents deteriorate the clean separation of the two phases.

Jan 1, 1994

By Chan. C. L., Zehr. R., M. M. Chen, J. Mazumder

"Two three-dimensional models of a surface tension gradient driven flow during laser surface heating are developed. The first model is based on a perturbation solution. The basic solution corresponds to the stationary axisynwnetric case and perturbation is based on a small scanning velocity. The advantage of seeking a perturbation solution, as it turns out, is that the three-dimensional flow is modeled by two sets of two-dimensional equations which are presumably much more tractable than the original three-dimensional equations. Numerical solutions are obtained and discussed. The second model is a full three-dimensional numerical solution of the Navier-Stokes equations, using a point-by-point partially vectorized iteration scheme. Surface shape is also determined in a self-consistent manner. The effect of the presence of convection on pool geometry, cooling rate and solute redistribution is presented and discussed.IntroductionThe existence of fluid flow and convection and their effects were first reported in the fifties (1,2). The role of convection in controlling pool geometry such as pool shape, undercut and ripples, and defects such as variable penetration, porosity and lack of fusion and weld properties such as weld homogeneity and bead formation is studied by a number of researchers and is reviewed by the authors in a recent paper (3).Recently, surface tension gradient driven flow has been identified as one of the forces responsible for convection within the molten pool (4,5). It is postulated that surface tension gradient driven flow is responsible for the surface ripple formation in the weld pool (6-8). Oreper, et al. (9) developed a two-dimensional convection model. Buoyancy, electromagnetic and surface tension gradient forces were considered. The formulation was based on a specified pool profile. It was found that the surface tension gradient is the dominant force in most cases. However, the solid-liquid interface is not known a priori. In fact, the solid-liquid interface, i.e. the pool shape, is a piece of information that the model should be able to predict. A two-dimensional transient self-consistent (i.e. the solid-liquid interface is solved as part of the solution] model for laser surface melted pool was first developed by Chan, Mazumder, and Chen (3)). This model predicted a non-uniform cooling rate, hence non-uniform microstructure. Depending on the Prandtl number (i.e. material) and surface tension number, the shape of the molten region as well as the cooling rate changes. It was also predicted that the recirculating velocity is of one or two order of magnitude higher than that of the scanning velocity. This model provides the detail of the flow field and heat transfer on a plane perpendicular to the scanning direction. However, the front-to-back motion and its effect on heat transfer also play important roles in the physical process, especially for the fact that the recirculating velocity is so much higher than the scanning velocity. Such a motion cannot be obtained from two-dimensional models."

Jan 1, 1986

By Tetsuro Ohashi, Tooru Matsumiya, Yoshio Abe

"The three-dimensional deformation of a continuously cast slab was modeled into two-dimensional deformation by developing the solidified shell of the slab. The developed solidified shell was divided into rectangular elements. The thermal strain produced as the slab is wi thdrawn over one roll spacing in the casting direction was calculated from the temperature change during that time and the increment of the geometrical unbending strain during the time was calculated from the change in the radius of curvature of the slab by assuming that the neutral axis of bending is located at the mid-thickness of the slab and that the transverse section of the slab is kept in a plane during unbending. These strains were imparted to each element as initial strains. The interaction between the elements and the overall deformation of the solidified shell were analyzed by the finite element method.The analysis was performed on a slab being cast on a machine of the circular arc type with progressive unbending. The following findings were obtained as a result. The effect of unbending is spread in the upstream and downstream directions of the slab by the shear deformation of the narrow and wide faces. As the shear deformation increases, the strain in the unbending zone decreases and the strain outside of the unbending zone increases. The effects of secondary cooling conditions, slab size, radius of caster circular arc section, compression casting, etc., were also analyzed. IntroductionTo develop a method for preventing the internal cracking of continuously cast slabs, it is important to acurately analyze the deformation of the slab and this subject has been extensively investigated. Many researchers, including the present authors, have analyzed slab bulging. (1)- (11) Analysis has also been made of thermal deformation that assumes importance in continuous casting of small-section blooms.(12)-(18) However, unbending deformation, an extremely important subject for continuous casters of the circular arc type, has not been fully analyzed."

Jan 1, 1986

By Jay S. Gunasekera

Metal parts are traditionally processed by either filly-liquid (e.g., casting) or filly-solid (e.g., forging) state. Semi-solid metal forming incorporates elements of both casting and forging. In 1991, Gunasekera(5) developed a model illustrating the influence of flow stress by the liquid fraction. The result fits Kiuchi's (1979)(7) experimental data quite well. This model assumed the liquid part is surrounded by solid as small pockets inside the material, which is opposite to the real practical situation. Since the melting usually first happens at the grain boundary, it is better to treat the semi-solid material as small metal crystal surrounded by liquid.

Jan 1, 1997

By Zhang Libo, Li Wei, Peng Jinhui, Guo Shenghui, L. Jing

Partially stabilized zirconia ceramics (PSZ) were prepared by microwave sintering using natural baddeleyite which was obtained by flotation of baddeleyite ore as starting materials. Because of using natural baddeleyite as raw and the process producing no waste, it realized shorter process, energy savmg, environmentally-friendly and non-damage processing. In this work natural baddeleyite stabilized with 3.8wt.% CaO were sintered at 1300°C for 60min in a multi-mode 2.45GHz microwave furnace. Microwave sintering could fast heating and sintering. Besides that, microwave sintering could heat materials wholly, low the sintering temperature, improve the materials properties and save energy. X-ray spectrum displayed the product composed by the tetragonal phase and monoclinic phase that also showed the product was PSZ. Fine and uniform microstructures were observed in the product through scanning electron microscopy. PSZ which was with high density was confirmed by the method of the Archimedes technique.

Jan 1, 2011

By Min Chen, Lei Xu

Sintering behavior and performance of high alumina refractory based on the ternary subsystem MgAl2O4-CaAl4O7-CaAl12O19 were investigated using ZrO2 as an additive up to 8 wt.% by solid state reaction sintering. It was found that the added ZrO2 could dissolve in the CA6 grains in the form of a solid solution, which enhanced the isotropic growth of CA6 grains and then improved the sintering. As a result, the densification process was improved and areas with enrichment of ZrO2 showed a more compact structure. With further increase of ZrO2 addition, tetragonal ZrO2 were found to locate in the grain boundaries for exceeding the solid solubility limit, which enhanced the thermal shock resistance, indicating that addition of ZrO2 exhibited a positive effect on sintering behavior and performance of this refractory. In addition, it is considered that the optimal amount of ZrO2 addition was about 4% considering the performance together with the cost.

Jan 1, 2015