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By R. Lanza, M. Hytros, N. Saka, I. Jureidini, J. H. Chun, D. Kim

"A novel method for delineating the solidification front in metal casting has been developed using the attenuation phenomenon of electromagnetic radiation (y-rays or x-rays) and computed tomography (CT). The densities of the liquid and solid phases that exist during metal casting may differ anywhere from 4 to 12 % depending on the metal. As in the medical imaging field, CT provides an excellent means of mapping this density variation in a solidifying casting into two-or three-dimensional images.In an effort to develop an industrial-scale sensor, laboratory-scale experiments have been conducted using a cobalt-60 (Co60) radioisotope and a sodium-iodide (Nal) scintillation detector. The CT image reconstruction was performed on a crucible containing pure tin in a two-phase state. Although the spatial resolution and data acquisition speed were not optimum, the CT images clearly differentiate the liquid and solid phases of the tin in the crucible. To maximize resolution and minimize data acquisition time, a linear accelerator (linac)-based CT sensor is being developed and tested for application in the continuous casting of steel and aluminum alloys.IntroductionIn all casting processes, the quality of a finished product and its production rate depend upon the shape and movement of the solidification front. From a quality perspective, it is well documented that solidification kinetics (heat and mass transfer, fluid flow, microstructure evolution) greatly influence the final properties of castings [l,2,3]. Product shortcomings, such as surface defects, cracks, macro-and microsegregation, and inclusions are directly controlled by the solidification process. By understanding the role the solidification front plays in the casting process, product quality may be dramatically increased through the reduction of defects."

Jan 1, 1997

By Philip Thompson

"Carefully planned laboratory test programs provide valuable data regarding the amenability of low grade gold ores to heap leaching. The most common laboratory test is the column leach test. The overwhelming problem associated with this type of test is the limit on the test column height. Most laboratories use a three (3) meter (10 foot) high column as a standard test due to building ceiling limitations, sample size limitations, etc. This paper presents a case study in which an ore sample was tested in a 1.5 meter, a three meter, and a six meter high column to determine the effect of column height on the test results. Other important factors such as sample preparation protocol, preliminary bottle roll testing to determine appropriate crush size, column diameter requirements, and leach solution analyses, are also discussed.IntroductionColumn leach testing has been used for years by many laboratories to determine the amenability of low grade precious metals bearing ores to heap leaching. However, the test work can be compromised by poor planning, misinterpretation of results, and extrapolation of data beyond the reasonable boundaries of the experiment. Preliminary test work should be performed prior to column testing. This preliminary work provides valuable information regarding the response of the ore to cyanidation and aids in the design of the column tests.The sample should be screened into various size fractions prior to testing. The fractions are assayed to determine the gold content of each size fraction and of the overall sample. The most valuable preliminary test is the bottle roll cyanidation test which is usually performed on five kilograms of coarse sample in a large rolling bottle which can accept material up to 50 millimeters top size. The residue from this test is screened at different sizes to determine the distribution of unleached gold in the residue. Comparison of the gold distribution in the leach residue with the distribution of gold in the feed at the same size intervals provides an indication of the appropriate crush size for the sample. The overall gold extraction from the sample at the crush size tested is also determined from these data. Lime and cyanide requirements can also be estimated from this test. The viscosity of the bottle roll pulp and the size distribution of the feed and leach residue can also suggest whether agglomeration of the ore will be required prior to column testing. Ores which contain significant amounts of clays (greater than 5 percent) will generally require agglomeration to prevent plugging of the test column."

Jan 1, 1997

By C. A. Silva

The kinetics of chlorination of titanium-bearing raw materials has been investigated. For comparison purposes pellets of controlled macro-porosity, made of analytical grade TiO2 and anatase concentrate (Brazil) , have been exposed to different combinations of gas composition - CO, CO2, C12 -, gas flowrate and temperature. A thermogravimetric technique and an adapted grain model have been used in order to assess the influence of the several experimental parameters upon the chlorination behavior.

Jan 1, 1997

By Andreas Nolte

This paper includes a comprehensive report about the metallurgical utilisation of reusable products from electronic scrap recycling, car shredding industry, used glasses an various waste products, such as slimes and flue dusts, generated in a secondary copper smelter. Depending on the copper content, the type of copper compounds and the characteristics of accompanying substances, the materials are treated by smelting in furnaces, operating under reducing or oxidizing conditions. HKs pyro- and hydrometallurgical processes, blast furnaces, converters anode furnaces, tin lead alloy plant and tankhouse will be outlined. The reusable products are categorized according to the origin of the materials and then presented in the form of quantity and quality balances. Processing methods, process able quantities and quality requirements of inputs are described. The utilization degree of the most important metals (copper, tin, lead and zinc) is described with graphics. The report is rounded by information on operating licence according to the environmental regulations of the Federal Republic of Germany and data concerning supply and contracts

Jan 1, 1997

By Karl A. Gschneidner

Magnetic refrigeration was first used in the mid-1920's and new developments seem to have taken place about every 20 years, and this is especially true for the mid-1990's. The active magnetic regenerator magnetic refrigerator has the promise to become the first practical machine utilizing the magnetocaloric effect for cooling (and also heating). The basic principles are briefly discussed. Since the temperature lift for the magnetocaloric effect spans about 50 K, one will need to utilize several ferromagnets with different magnetic ordering temperatures in order to reach temperatures below ~250 K. The basic properties, behaviors, limitations, and new phenomena and knowledge are discussed.

Jan 1, 1997

By I. Ohnaka

Although many works have been reported on the semisolid casting, the mold filling behavior of semi-solid alloys has not been so well understood. This paper compares the physical and numerical simulation results on the mold filling behavior. Physical simulation was performed by using solid-water mixture. The numerical simulation was made under the assumption of one phase flow with an effective viscosity. It was found that the solid particles stabilize the flow greatly if the kaction solid exceeds about 0.4, because viscosity increases greatly. The overall flow behavior can be estimated by the numerical simulation. Interesting flow behavior was also found which can not be observed in the case of one phase flow and which is difficult to simulate by the one phase flow assumption.

Jan 1, 1997

By Patrick R. Taylor

A novel method for Chemical Vapor Infiltration (CVI) using plasma technology is proposed, Plasma Enhanced CVI (PE-CVI). Due to the low rates at which CVI is currently performed, the use of plasma as a source of heat may be considered to be a faster and less expensive production method. Precursors fed in the hot region of the plasma gas are completely vaporized and forced by the same flow through a porous preform where it condenses as a new material. In this research, silica and methane where used as precursors to form SiC/on a / graphite felt (preform). To enhance the infiltration process, vacuum was used to increase the flow through the preform. Characterization of infiltrated graphite was perfontied using Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD). A uniform distribution of Sic was observed along the felt with only twenty minutes of infiltration process, yielding a 178% increment in weight.

Jan 1, 1997

By R. G. Reddy

The oxidation kinetics of A13Ti intermetallics have been studied at the temperature range of 850°C to 100O0C in pure dry oxygen. The oxygen diffusion rates were investigated using TGA method. Parabolic rate constants were calculated. The oxidation scales were analyzed using SEM, EDS and X-ray diffraction. A continuous A120, scales with a little TiO2(rutile) were formed on the intermetallic surface. The A13Ti intermetallic exhibited excellent oxidation resistance among the Ti-Al base intermetallics.

Jan 1, 1997

By G. Van Weert, A. van Sandwijk, O. W. J. S. Rutten

"Cathodic and anodic reactions in an acidic nitrate medium were studied in reference to the production of electrolytic manganese dioxide from pyrolusite' (Mn02) ores by reductive leaching. Two USA ores were investigated. The reductant for the pyrolusite ore is produced cathodically in an electrolytic cell and can either be nitrous acid (HN02) or nitric oxide gas (NO). In this work emphasis was placed on the nitrous acid leach. In a high-temperature leach in a nitrous/nitric acid medium, manganese and silver are solubilized and iron is not. Anodic electrowinning of manganese dioxide from the acidic manganese nitrate electrolyte yields flaky y-Mn02, similar to that produced from sulfate and chloride electrolytes. Cathodic regeneration of nitrorts acid was studied in a membrane cell in 1.0 M nitric acid and 0.0 to 0.1 M nitrous acid on a' platinized titanium cathode. At cathode potentials ranging from +950 to +700 mV (SHE), cathodic reduction to nitrous acid takes place, at cathode potentials < +700 mV, cathodic reduction of nitrous acid to nitric oxide takes place. A conceptual process is presented and discussed.IntroductionManganiferous-silver oresLarge reserves of manganiferous-silver ores are present in the Southwestern United States and Latin America. These ores are generally refractory to hydrometallurgical methods of treatment, due to the insolubility of the higher oxides of manganese (Mn 4+) in all common lixiviants such as cyanide solutions, dilute sulfuric acid, nitric acid, ammonia, salt solution, thiosulfates, etc. The silver is either bound by the insoluble manganese, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization.Higher oxides of manganese will dissolve if they are first reduced pyrometallurgically to manganous oxide (Mn2+). This is a widely used pretreatment for manganese dioxide ores and subsequent dissolution in sulfuric acid is common. In order to avoid the pyrometallurgical pretreatment with its large energy requirements and gaseous emissions, fully hydrometallurgical processes have been proposed. These processes are based on the presence of a reductant in solution, in order to reduce the insoluble higher oxides of manganese to soluble lower oxides. Aqueous S02 has been proposed and tested on industrial scale by the U.S. Bureau of Mines. After washing, silver could be extracted by cyanidation. The neutralization of the pulp prior to cyanidation however causes problems in filtration and the reagent consumptions are high [1]. More recently, acidified thiourea and bacteria were proposed for the solubilization of both manganese and silver in a single leach step. High extractions were obtained, but drawbacks of these methods are high reagent consumption or slow kinetics [2,3]. For the options of manganese recovery from the leach filtrate, precipitation with persulfate or ammonium carbonate and ion exchange have been proposed. The proposed options for silver reclaim are precipitation with either zinc or Na2S and adsorption onto activated carbon."

Jan 1, 1997

By H. Soto, J. Jara, F. Nava

A method has been developed to recover cyanide and copper from solutions containing copper complexes and thiocyanate. Copper is precipitated as copper thiocyanate or as copper cyanide depending on pH and the concentrations of thiocyanate and cyanide in the effluent. The copper precipitate assays over 50% copper and presents good dewatering characteristics. After settling it can be separated from the effluent by filtration. The solution containing the bulk of the cyanide is then oxidized with ozone to transform the remaining thiocyanate into cyanide. This results in a regenerated solution rich in free cyanide that can be recycled to the cyanidation process. Careful control of the pH of the solution is required. First, pH of the effluent is lowered to optimize the precipitation and oxidation stages, then the pH is restored to an alkaline value to regenerate the cyanide solution. Recoveries of over 96% copper and cyanide were obtained in laboratory tests using industrial solutions. With this procedure, cyanocidic gold/copper ores could be treated economically by heap leaching, since the cyanide consumed by the copper impurities could be regenerated at very low cost (most of the cost of cyanide regeneration would be compensated by the copper credits). In order to achieve this, a bleed of the barren solution could be treated by the proposed method, and then recycled to the leaching step. The volume of solution to be treated should be large enough to keep a cyanide/copper molar ratio higher than 3:1. This would assure that copper does not cause undue interferences in the leaching or the carbon adsorption stages. If the thiocyanate content is low, the oxidation stage can be avoided, and the solution can be recycled to the leaching stage directly after the solid-liquid separation stage.

Jan 1, 1997

By Guo Chang Jiang

In order to improve the IIAZ toughness of X-60 pipe steel, the intragranular ferrite plate (IFP) technology was used. The characteristics of IFP is claimed to be much fine ferrite plates appear inside the original austenite grains. By means of suitable Re, Zr, Ti additions in a bath with a higher initial oxygen potential, a good control of the peak temperature and the cooling rate during welding simulation, one can get a %IFP in volume over 50%, and the toughness gets up from 55 J to 160 J. It was found that the inclusions most effective in nucleating IFP are some deformable complex silicates which either entrap Re, Zr, Ti oxides or contain these elements. The greater the number of the evenly distributed and effectively nucleating inclusions, the more the %IFP in volume, and the finer the microstructure of the HAZ, so the better the relevant toughness. Generally, these silicates bahave as fine spheres along a line. The present authors revealed that these fine spheres result from the remelting of the shuttle- like silicates due to heating in the process of welding simulation. These silicates used to get a higher sulphur capacity, so MnS deposits might be observed on the periphery of the silicates. IFP was proved to be directly rooted in the [Mn] depleting zone which locates beside MnS deposits.

Jan 1, 1997

By Y. Kumagai, F. A. Souza

"Electroless plating process has been used in many fields such as automobile and electronic industries. Solutions used in these processes must be disposed or treated. Commonly, in these solutions metal ions, organic materials and others chemicals are in very high concentration. It is very difficult to keep the environmental regulations for disposal of these materials, and the cost of the plating process becomes higher.The objective of this study was to investigate the recovery of components of those baths in order to decrease the cost of the plating process as well as to meet the environmental regulation.In this study the recovery metal ions, sulfate ions, phosphite ions and organic compounds were investigated. Organic compounds used in electroless plating solutions are the organic acids. In this work the solvent extraction of the most used organic acids included citric, lactic, succinic, tartaric and malic was studied. The solvent phase considered in these studies was ethyl acetate.About 95% of the metal ion was recovered by chemical plating onto mica powder. The hypophosphite remained is oxidized to phosphite and with the sulfate ion, both are recovered as calcium salts by selective precipitation in pH 7 and 2 respectively. Organic acids were recovered by solvent extraction using ethyl acetate as solvent phase and the best results were for lactic acid and succinic acid.Along with this study, was developed the analytical parameters to perform wastewater analysis by using Ion Chromatography, High Performance Liquid Chromatography (HPLC), Fourrier Transform Infrared Spectroscopy (FTIR). Ion chromatography was used to perform analysis of sulfate and phosphite ions in liquid matrix, HPLC was used to perform analysis of organic acids in liquid matrix and FTIR was used for characterization of the solids obtained in the recovery processes."

Jan 1, 1997

By H. K. Lin

Pyrite oxidation in chloride solutions was investigated with cyclic voltammetry, ac impedance and potential step techniques. The pyrite oxidation in quiescent electrolytes is irreversible and controlled by diffusion. Depression of the semi-circle in the complex plane plot has been explained mathematically based on the concept of the equivalent circuit. When the semi-circle is depressed, the mathematical formula indicates that the reaction resistance should be obtained from the intersection of the semi-circle with Z-axis instead of the semi- circle diameter. The peak charging current densities at 1.10 and 0.90 V vs. SHE obtained from the equivalent circuit coupled with the ac impedance measurements match the peak current densities obtained with the potential step measurements.

Jan 1, 1997

By A. M. Alfantazi, M. Boissoneault, D. B. Dreisinger, J. Synnott

"The effects of five commercially available foaming reagents (range of 0 to 25 ppm) namely Dowfroth 250, Saponin, Yucca, Licorice and Meta-Para Cresol on acid mist control, current efficiency, polarization behavior, and deposit morphology and orientation were investigated. The deposition was carried out using a bench scale electrolysis apparatus (cell volume 3L) at 500 Nm-2 and 38°C for 3 hours from Kidd Creek zinc electrolyte. The acid mist control capability of the various reagents was studied and compared by characterizing the foam layer generated during actual electrowinning conditions and by direct quantitative measurements of acid mist levels on top of the electrowinning cells. Within the range considered, the addition of these reagents reduced the current efficiency, refined the grain size of the deposit, and changed to preferred orientation of most of the deposits. Among the reagents tested, acid mist measurements indicated that Licorice and Dowfroth 250 were the best acid mist suppressant at emissions of 0.30 mglm3 and 031 mg/m3 respectively while Yucca and MPC produced the most mist at 3.0 mg/m3 and 33 mg/m3 emission rates, respectively.IntroductionMost of the world's primary zinc is produced via a combined roast-Ieach-purificationelectrowinning process. Depending on the electrolysis conditions, several additives may be added to the electrolyte. Some (e.g. glue, antimony, sodium carbonate) are added to mainly counteract the detrimental effects caused by impurities while others (e.g. licorice, Saponin) are used as foaming reagents to prevent excessive acid mist formation. Acid mist emission is a problem in many electrolysis operations because it corrodes the equipment and is a health hazard to the workers in the tankhouse as well as it pollutes the environment. Due to recent trends towards more environmental protection and more stringent in-plant hygiene, there is an increasing need to minimize these aerosols. In order to eliminate or minimize these aerosols foaming agents are usually added to the electrolyte to produce a foam layer on top of the electrolyte, thus trapping most of the mist. The ideal foaming agent would trap all of the mist and would not interfere with the electrowinning process. It is also evident that the reagent toxicology, cost and availability are important factors that need to be considered.Review of the available literature clearly indicated that very little work has been done in the past on the subject of acid mist control in electrowinning operations particularly in the area of foaming and anti-misting properties of surfactants. Two papers [1,2] have reviewed briefly the existing technologies for acid mist control. Recently, most of the work in this area has focused on the development of special mechanical devices that could be attached to the electrodes and control the mist generation at the source before it is emitted to the cellhouse [2-5]. On the other hand, extensive body of literature exists that deals with the effects of anti-misting reagents on the electrowinning aspects [6-7]."

Jan 1, 1997

By A. Korbel

The progress in understanding the nature of strain localization in metallic materials and in particular the understanding of the role of external (deformation conditions) and internal (material substructure) factors in the development of the tendency toward concentration of plastic flow within transgranular shear bands was the background of the concept given in the title. Following this idea, the practical possibility of replacing the homogeneous in a micro scale mode of deformation by transgrasnular shear bands gives a chance to change the arrangement of the dislocation substructure in the material from that typical for homogeneous deformation into long wavelength (transgranular), pseudo-periodic dislocation walls. The presence or formation of such a substructure in a thermodynamically unstable matrix may result in the formation of the products of phase transformation along shear bands, giving rise to a composite-like structure. This work is aimed to provide a coherent justification to the concept of Natural-Metal-Matrix Composite and summarizes the results of experimental works in this area.

Jan 1, 1997

By Johan Sundström

Anhydrous DyC13 was prepared by dehydration of DyCl3?6H20 in a fluidized bed using both batch- wise and continuous feeding. A gas mixture with varied composition of argon and HCl was used. The productivity was high, reaching values of 0.25 mol H20/m2-st during the reaction step 6- 1 and 0.062 mol H2O/m2.s during the reaction step 1-0. The product was free from hydrolytic compounds, such as DyOCI, if control of inlet gas composition versus temperature was achieved. From the results of various experiments, some relations between HCI-concentration and temperature in order to avoid hydrolysis have been deduced. The fluidization process efficiency decreases drastically after the dehydration has proceeded down to about 10 mol% of remaining water. Therefore, in a final treatment the last traces of water were removed by slowly purging gas through a packed bed. The water content could thereby be reduced to less than 1 mol%.

Jan 1, 1997

By S. F. Cheng

Among the many extraordinary features of the rare earths are their magnetic and magnetoelastic properties. The rare earths, e.g. Tb, Dy, Nd, Sm, are known worldwide for their large magnetocrystalline anisotropy and magnetization, which has led to the importance of magnetic rare earths as vital ingredients of modem permanent magnets. In this paper, we focus on the strain dependence of these giant effects which gives rise to huge magnetostrictions, magnetomechanical couplings, and ?E effects. Magnetostrictions greater than 10-3 have been measured at temperatures as high as 500 K. At low temperatures magnetostrictions reaches -1%. ?E effects - 10. No other solid state material has matched these values. A proper balance of magnetic anisotropy and magnetostriction, plus a proper choice of crystal axes lead to alloys which can switch large quantities of energy between the internal (magnetic) and external (mechanical) states with the application of small triggering magnetic fields. In addition to the traditional use of these materials in transduction, they are particularly valuable for smart systems where reliability and robustness are needed such as active structure stiffening and active vibration control.

Jan 1, 1997

By Banqiu Wu

Zirconium carbide powder has been synthesized from zircon concentrate and methane using a high temperature plasma reactor, a non-transferred DC plasma torch was used as heat source. A high temperature filter consisting of graphite felt was designed, built and operated to separate the zirconium carbide from silicon carbide during the process. Characterization of the collected powders was done by wet chemical analysis using Atomic Absorption (AA), Scanning and Transmission Electron Microscopy (SEM and TEM) and by X-Ray Diffraction (XRD). It was found that the zirconium carbide purity was around 95% with silicon carbide being the primary impurity. The powders had particle sizes between 30 and 80 nm. The effect of several experimental variables are presented as well as temperature and velocity profiles calculated in the reactor.

Jan 1, 1997

By S. -H. Jeon, Y. -S. Choi

"The three dimensional current distribution on the rectangular cathode is predicted using a boundary element method with a linear element of trigonal type. The effect of cell geometry and anode shape on current distribution is simulated. Calculated results compare well with experimental results. The proper combination of anode size and distance between electrodes increase the current uniformity.The importance of electrodeposition as a fabrication technology in the electronics industry is large and growing. The main advantages of this wet processing method, in comparison to other dry processing methods, lie in its high yield, rapid processing and low cost. In nearly every application of electrodeposition the pursuit of deposit uniformity, especially thickness uniformity, has been technically imperative. The thickness uniformity of the deposit depends largely on the current distribution over the cathode. The current distribution is primarily determined by the geometrical characteristics of the electrodes and the cell. Also the polarization at the electrode surface and the mass transfer affect the current distribution.The current distribution is an important consideration for those involved in designing electrochemical systems and electroplating systems in particular. Although it is important, the common practice in industry is to use trial and error method to design the cell that optimize the uniformity of current distributions in electroplating. The purpose of this paper is to illustrate the useof boundary element method to predict three-dimensional current distribution in rectangular cell.The calculation of the current distribution is possible by various numerical techniques, which include the finite difference method (FDM)1, the finite element method (FEM)2, and the boundary element method (BEM)3,4. These methods of the numerical calculation have various problems, respectively, but the BEM is considered to be the most efficient. This is due to the fact that the BEM has the advantage of solving field equations only on the surface of a calculation domain. A good comparison between the BEM and the FEM for the secondary current distribution in a Hull cell was made by Matlosz et al.5The fundamentals on the theory of current distribution in electroplating are well-established in the literature by a number of authors.6, 7, 8 However, a small fraction of these works have been specially addressed to three-dimensional analysis, and, mostly thel·10 have focused on the problem qualitatively rather than quantitatively.Extending the previous work to three-dimension, we developed the program for the quantitative calculation of 3-dimensional current distribution using a boundary element method with a linear element of trigonal type. Integrals with singularity from the fundamental solution have been analytically computed and it is shown in detail in the Iiterature11. This paper deals with the three dimensional current distribution for the electrode position of copper in a cubic type cell and the effect of anode shape, size and the distance between electrodes on current distribution is studied."

Jan 1, 1997

By G. R. Adams, N. Y. Tang, N. Qiang

"Aluminum is the most important alloy addition to Zn baths for controlling the reaction kinetics between the steel substrate and molten Zn in continuous galvanizing operations. Due to the complexity of the Zn-Fe-Al ternary system, the measurement and control of effective bath Al remains a challenge for modem galvanizers. The successful development of Al sensors has made the real-time measurements of bath Al contents possible. To facilitate their application, a computer interface and a palm-size data logger have been developed by Cominco. Plant applications indicated that the sensor possessed sufficient accuracy for process monitoring and control. The working mechanism of the Al sensors and Cominco's development work is described, and the results of sensor applications are presented.IntroductionControl of bath Al content is critical in modem continuous galvanizing because it has a strong influence on coating structure and properties and the overall product quality. The control of effective bath Al content (Al in liquid solution) is particularly critical for galvannealing where a high bath Al content may lead to incomplete alloying during post annealing, and a low bath Al content may result in other operation problems, such as excessive bottom dross accumulation and difficulties in coating thickness control. The desirable accuracy of the Al control is within ±50 ppm of target levels. In principle, such an accuracy is achievable for modem chemical analysis facilities, such as atomic absorption photospectrometer (AAS) and induction-coupled plasma (ICP). However, a recent study carried out by the International Lead and Zinc Research Organization (ILZRO) indicated that such an accuracy is rarely achieved in the zinc and steel industries.(1)"

Jan 1, 1997