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By D. Neuschiltz, M. Witthaut, R. Cremer

"Metastable (Ti,Al)N coatings with fee structure have been shown to exhibit superior performance as compared to TiN under conditions of wear at elevated temperatures due to their better oxidation resistance and hardness. The oxidation resistance of these coatings increases significantly with increasing Al-content. However, the deposition of (Ti,Al)N films with Ti/ Al ratios below about 30/70 leads to a hexagonal structure which is not suitable for tribological coatings. Only little is known about the location of the cubic to hexagonal phase transition and hence about the optimum composition of (Ti,Al)N hard coatings.To determine the position of this transition, Tii-xAlxN films with different Ti/Al ratios were deposited on high speed steel at substrate temperatures between 100 and 700 °C by means of reactive MSIP. The composition of the films was determined by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS), the crystallographic structure by thin film X-ray diffraction (XRD).It could be shown that in case of deposition temperatures of 300-700 °C a two-phase region exists in the metastable TiN-AlN phase diagram, which expands with increasing temperature, wheras at 100 °C substrate temperature no two-phase region was observed. But in opposition to the phase diagram known from literature, which is based on thermodynamic estimations, the detected two-phase region is narrow for typical PVD temperatures, thus allowing the deposition of cubic single-phase Al-rich (Ti,Al)N hardcoatings for tribological applications. Based on these results, a new Ti1-xAlxN film with x = 0.62 has been developed, which showed an increase of oxidation resistance by a factor of 4."

Jan 1, 1998

By Y. A. Chang, J. Woodford, C. R. Kao

Reactive diffusion studies between NbC and Si were carried out at 1300 °C under a vacuum of 10-5 torr and a uniaxial pressure of 1 MPa. The annealing time ranged from 8 to 100 hours. The Si used was single crystal silicon; the NbC was hot-pressed powder compact. A NbSi2+SiC two-phase reaction layer formed with NbSi2 as the matrix and SiC as discontinuous particles. The microstructure of the reaction product is homogeneous, dense, and fine. The NbSi2 grain size and SiC particle size are in the micron range. The growth of the reaction products follows parabolic kinetics. Extrapolation of the data to zero thickness suggests an apparent incubation time of 3.5 hours. However, for short annealing time «60 hours), the thickness data can be approximated by linear kinetics with an initial growth rate of about 2 11m/hr. Based on these experimental observations, a growth mechanism for the reactive diffusion between Si single crystal and NbC powder compact is proposed. We propose that the nucleation sites for the SiC particles are at the voids of the NbC powder compact. This proposed nucleation mechanism offers a potential way of controlling the SiC particle size by changing the void size and void density of the NbC powder compact. This hypothesis, if proven to be true, will allow us to control mechanical properties of the composites by tailoring the SiC particles formed. It is also pointed out that the microstructure requires Si to be the dominant diffusing species and to diffuse through the reaction layer, while Nb and Conly have to undergo local rearrangement.

Jan 1, 1996

By Marcelo A. Martorano, Moyses L. Lima, João B. F. Neto

"Directional solidification is an essential refining step to obtain solar grade silicon from metallurgical silicon. This step can be carried out in a Bridgman furnace, where nearly constant temperature gradients and solidification velocities are imposed on the solid-liquid interface. In the present work, this directional solidification was conducted in a static furnace, in which large temperature gradients and low solidification velocities were enforced to increase macrosegregation. The resulting ingots were analyzed regarding their macrostructures, microstructures and chemical composition. Using measured cooling curves in the ingot as boundary conditions, a mathematical model based on the concept of a stagnant liquid layer at the solid-liquid interface was implemented to predict the macrosegregation profiles. The chemical analyses of the ingots show macrosegregation of several impurities to the ingots top. The mathematical model indicates that liquid convection plays an important role in stabilizing the planar solid-liquid interface, increasing the macrosegregation of impurities.IntroductionMost of silicon used for photovoltaic (PV) energy production is obtained by chemical processes, such as, Siemens and its derivations [1]. However, these chemical processes have drawbacks related to relatively high energy consumption and investment costs, and to safety and environmental problems. In order to overcome these difficulties and to fulfill the silicon demand for PV applications, several metallurgical routes are under development [2] to produce silicon of enough purity to PV applications (SoG-Si) from metallurgical grade silicon (MG-Si).Metallurgical routes involve different steps among which the directional solidification is pointed out as a fundamental one [1]. Directional solidification can cause macrosegregation of impurities to the last part of the ingot to solidify. The impurity segregation during solidification is related to the low solute partition coefficient (k0) between liquid and solid silicon. Most of the impurities in MG-Si have k0 << 1, except for boron, phosphorus and oxygen, which require specific steps of the metallurgical routes to be eliminated. The equilibrium partition coefficient and the solubility limits for the most important impurities in MG-Si are shown in table 1"

Jan 1, 2014

By Chen Song

Cobalt basic carbonate particles were precipitated from 1.0mol cobalt nitrate or cobalt sulfate solution with ammonia carbonate. By controlling the zeta-potential of the particles and the ionic strength of the solution, the uniform particles with ellipsoid or rod shapes were obtained. During the precipitation process, the interface tension was diminished to the minimum and therefore the Ostwald ripening and secondary nucleation were both inhibited. The morphology and the size control by zeta-potential seem to be the result of thermodynamics rather than classical crystalline kinetics. The particle sizes were in the range of 0.4-0.6, 0.3-0.4 micrometer. After thermolysis, the spinel-type C0304 particles were produced. The morphologies of C0304 particles were similar to that of their precursors.

Jan 1, 2003

By Zhijing Zhang, Ramana G. Reddy

"The viscosity of molten oxides is one of the important physical properties since viscosity has a decisive influence on fluid flow. The knowledge of the viscosity of molten oxides is essential for modeling and controlling of metallurgical process. In the present study, viscosities of high basic Na2O-B2O3 and Na2O-SiO2 binary melts and viscosities of Na2O-SiO2-B2O3 ternary melts were measured as a function of temperature and composition. Experiments were carried out using rotary viscometer and graphite components. Our experimental results were compared with those in literature. Based on the current experimental data, the previously developed viscosity model was modified. The characteristic features of viscosities of these melts have been discussed. The predicted viscosity results are in excellent agreement with the present experimental data in the temperature range with molten state samples. IntroductionThe viscosity of molten oxides is one of the important physical properties since this property has a decisive influence on fluid flow, and is one of key factors to be taken into consideration in process modeling. The manufacturing operations require the viscosity of molten oxides to be within certain ranges. Although, some viscosity measurements on borosilicate systems have been carried out [1-4], the viscosity data in literature are available only for a few temperatures and cover small composition ranges. The agreement between the results of these works is not satisfactory [I-4]. Even the viscosities of binary systems Na2O-B2O 3 and Na2O-SiO2 generally are well studied, the available viscosity data in literature are only found in the composition range of O to 0.333 mole fraction ofNa2O. The aim of the present study is to provide a base with accurate experimental data for reliable model extrapolation."

Jan 1, 1999

By C. O. Bounds

Management of emission control dust from electric? arc furnace (EAF) steelmaking as an RCRA-EPA listed hazardous waste places economic and environmental pressures on the steelmaking industry. Horsehead Resource Development Company, Inc. (HRD) serves the industry by recovering nonferrous metals from the dust in rotary kiln plants in Palmerton, PA and Chicago, IL, and has demonstrated the commercial viability of its patented coal-fired FLAME REACTOR Process. However, because of location and/or regulation, many steelmakers could be more economically served via on-site processing of its dust. Therefore, in 198-7, through a contract with the Gas Research Institute, HRD embarked on a program to develop a gas-fired reactor and test a prototype unit. The development program has successfully proven the environmental, technical and economic performance of the concept. Consistently high zinc, lead and cadmium recovery to an oxide concentrate as well as production of a nonhazardous, delistable slag have routinely been achieved. The gas-fired FLAME REACTOR field experiment results and the economic performance of on-site or smaller regional plants will be highlighted.

Jan 1, 1990

By Elliot Schwartz, Julian Szekely

"In this paper we describe an experiment that was recently performed on the IML-2 Space Shuttle mission in which the thermophysical properties of molten metals were measured using electromagnetic levitation. In the planning of these experiments calculations had to be performed to predict the levitation and stirring forces, heating rates, sample deformation, and internal flows within the sample. These predictive calculations were essential for both the planning of the experiments and for the re-planning of experimental runs during the actual Space Shuttle mission.Introduction""Materials Processing in the Computer Age"" involves the use of mathematical modeling to obtain a quantitative understanding of the phenomena that govern materials processing operations. Microgravity, or space shuttle experimentation represents a specific case in point here; the very high cost of the space shuttle flights, the very limited flight opportunities that are available, and the tight resources aboard a shuttle clearly mandate that these experiments be very precisely planned and that all possible opportunities for mathematical modeling be fully exploited.The purpose of this paper is to present the results of calculations performed for the planning of a space shuttle experiment involving electromagnetic levitation and wherever possible present a comparison of the computational predictions with both experimental measurements and asymptotic analyses. Finally we shall seek to discuss the practical implications of both the computational methodologies and the potential experimental findings."

Jan 1, 1994

By W. K. Collins

Engineered Scavenger Compounds (ESCs), developed by the U.S. Bureau of Mines, are a novel class of compounds that can selectively recover a desired element from a solid or molten alloy. Lithium titanate (Li2Ti3O7 or L&apos;20-3T&apos;02) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (Al-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both are metastable, the hexagonal phase that forms during the scavenging of Li from Al-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electrodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li2Ti3O7 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1993

By M. Nilmani, H. Pham

"A mathematical model was developed for the dissolution of particles in gas-stirred liquid baths, linking the hydrodynamic flow field of the bath, the average particle trajectory and liquid-side mass transfer controlled dissolution kinetics. The model was validated by comparison with experimental data for the dissolution rates of urea particles in gas-stirred aqueous CaCl2 solutions measured during this study. The dissolution rates of urea. particles were measured using an image analysis system.The effects of operating conditions on the dissolution rates of urea particles were investigated. It was found that the key operating parameters influencing the utilisation efficiency of particles were the gas flowrate, particle diameter and lance submergence. An optimisation of the operating conditions for the model urea-aqueous CaCl2 system indicated that the utilisation efficiency increased with decreasing gas flowrate and decreasing particle size for a given lance submergence.IntroductionThe utilisation solid reagents in molten baths varies from one process to another, depending upon the rates and mechanisms of the reactions between the particles and melts, as well as the trajectory and residence time of the particles in the melts. Previous studies have not attempted to predict the utilisation efficiency of injected solids by coupling the motion of the particle with its dissolution rate. Instead, the particles have usually been assumed to remain suspended in the bath until completely dissolved, and the mass transfer coefficients were based on the average specific mechanical energy dissipation rates in the bath. Investigations of this nature relevant to the present study have been undertaken by Apelian et al. [1], Brucato et al. [2] and Langberg and Nilmani[3]. The objective of the present study was to develop a mathematical model, incorporating both the reaction kinetics between the particles and liquid and the particle motion simultaneously, to predict the dissolution rates and times of the particles. The mathematical model was validated by comparison with experimental dissolution rates of a cold model analogue system measured using an image analysis technique, and then applied to optimise the operating conditions in the model system."

Jan 1, 1996

By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from &apos;a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20&apos; 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

By R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l &apos; d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young&apos;s equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By Jose Bengoa

Low metal prices and environmental restrictions are always a challenge for copper smelters operation and its productivity. Thus, in order to reduce production costs and control gas emissions, improvements of the Teniente Converter (CT) operation were made at 110 Smelter Plant of Southern Peru Copper Co" 110, Peru, and the main objective was to increase its capacity for smelting copper concentrates without affecting normal operation, The present work eorresponds to a recent study conducted during the normal industrial operation of the Teniente Converter in this plant and, it shows the effect of increasing air oxygen enrichment from 28 to 34% on its productivity. The results show an increasing of concentrate smelting rate from 800 to 1370 tpd and hence a notorious improving in copper production, and practically no effect on the refractory consumption. The increment of the concentrate throughput, increases also the SO2 concentration and the sulfuric acid production, showing the effort done by this operation in order to accomplish the environmental Peruvian regulation,

Jan 1, 2003

By Eun Duck Park

The gold catalyst supported on iron oxide was prepared from gold dissolved in aqua regia by a deposition-precipitation method and applied to CO oxidation in the absence and presence of hydrogen. Some characterization methods such as X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), temperature programmed reduction (TPR), temperature programmed oxidation (TPO), and the pulsed CO chemisorption with temperature programmed desorption (TPD) were conducted to explain different catalytic activities of Au/Fe2O3 catalyst pretreated at different conditions. The particle size of gold was about 10 nm for Au/Fe2O3 calcined in air at 373 and 573 K. For complete CO oxidation, the decreasing CO conversion with a reaction time was observed at low temperatures but its initial catalytic activity can be restored by a heat treatment at high temperatures. This catalyst was quite active for the selective CO oxidation in the presence of hydrogen especially at low temperatures. In the presence of hydrogen, the deactivation was significantly diminished.

Jan 1, 2006

By R. Hurman Eric

The electrode in a slag-resistance electric furnace is the central factor in the design and operation of the furnace by its role of conveying the smelting power, i.e. heat needed for the operation. The control parameters are the size and positioning in the slag bath which are defined by slag resistivity, furnace resistance, cell constant and power input sequence all of which are closely interrelated. The flow of heat generated by the electrode current determines the energy distributions and thus the furnace dimensions. Heat flow models concerning vertical, horizontal and combined two-dimensional flows are discussed. All these considerations are based on the experimentally determined slag properties such as its resistivity.

Jan 1, 1995

By D. P. Cook, Jr. Jones, J. W. Evans

"It is well understood that the flow of liquid metal in the mold region of the caster can have a notable effect on the overall solidification behavior in aluminum casting. Previously our group has characterized the flow in this region in a water model, using particle imaging velocimetry. The flow is significantly effected by the specifics of the metal delivery system, i.e. size, geometry, used during the cast. Recently, a time-averaged 3D numerical model of the nozzle, combo bag and sump region has been developed and its validity has been tested against experimental data. Cases were run for different sized combo bags as well as bags that have been blocked. The results show satisfactory agreement between the physical and mathematical models.IntroductionFluid flow in the head of an electromagnetic (EM) and direct chill (DC) ingots has been shown to effect many important operational parameters in casting such as superheat removal, macrosegregation, and hot cracking. In most cases, the momentum from the nozzle is diverted through a delivery system, termed a bag, before entering the mold region. The specific geometries of the bags vary widely from operator to operator suggesting that there is still some question as to the optimum design. Several studies [1-4] have been carried out to understand the influence of the bag design on the solidification behavior in aluminum casters. However, few studies have included numerical prediction with experimental verification. Unfortunately, many simulations performed today still do not accurately account for flow in such devices.Recently, a significant amount of research into the flow resulting from the metal delivery systems has been performed [5-8]. The thrust of this research has been characterizing the flow patterns by a measurement technique called particle imaging velocimetry. The data suggest that the method of delivering the liquid metal into the mold region has a significant effect on the nature of the flow. With a detailed set of quantitative data from a water model, a numerical model can be built and tested to ensure a proper description of the flow field. The computational model used in these simulations is designed to represent a laboratory scale model of a caster in which ""combo"" bags were simulated. Such bags are mostly of a densely woven glass fiber material with low permeability to aluminum. ""Windows"", of a more open weave, permit aluminum to flow from the bag, see Fig. I. Two different sized combo bags were modeled, each subject to two different outflow window configurations. Furthermore, experimental measurements [9] were used to validate the model results."

Jan 1, 1999

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By Dimitrios Fillippou

Magnesium hydroxide is used in a number of industrial applications, from the neutralisation of acid effluents to the production of pharmaceuticals. High-quality magnesium hydroxide powders can be produced by hydrating slow-reacting magnesia in dilute magnesium acetate solutions. The process of magnesia hydration shows many similarities with a typical hydrometallurgical leaching operation; however, its kinetics are crucial not only for process design and control, but also for the production of powders with a desirable particle morphology. This article shows the results of an experimental work whereby industrial heavily-burned magnesia powders were hydrated in 0.01 to 0.1 mol/L magnesium acetate solutions at temperatures ranging between 333 and 363 K. Examination of the magnesium hydroxide produced and the analysis of the kinetic data suggest that the hydration of heavily-burned magnesia in magnesium acetate solutions is a dissolution-precipitation process controlled by the dissolution of magnesia particles. The activation energy was estimated to be 60 kJ/mol, while the reaction order with respect to magnesium acetate concentration was found to be about one.

Jan 1, 1999

By Dandan Jian, Christian Karcher

Information of liquid steel flow patterns inside the mold may be obtained from the velocity at the free surface (meniscus). This meniscus flow may be measured using the contactless electromagnetic technique termed Lorentz force velocimetry (LFV). It is based on the measurement of Lorentz forces acting on a magnet system when an electrically conducting metal melt interacts with the field lines stretched by the magnet system. Force sensor and the magnet system form a so-called Lorentz force flowmeter. In this paper we present a series of model experiments that demonstrate the feasibility of using two identical flowmeters that are arranged in a certain distance one behind the other. In this case, surface velocity may be determined by just cross-correlating the two force signals recorded by the two sensors. This technique is called time-of-flight LFV. A special prototype of a respective measuring device, called meniscus velocity sensor (MVS), has been developed to measure local free-surface velocity. In the present paper we describe experimental results of respective measurements in the model test stand LiMeSCo (liquid metal surface velocity correlation). To check the potential of the time-of-flight technique, in a first step we measure surface velocities during solid-body rotation of metallic substances. We observe that small modulations in the signals that are due to the natural unevenness of the solid body can be used to determine surface velocities. In a second step we apply the time-of-flight technique to liquid metal free-surface flow. Here we use the low-melting eutectic alloy GaInSn as a test melt. In this case we observe that the cross-correlations between the signals are much rarer and much weaker than in the solid-body experiments. We conclude that the presence of the localized magnetic fields, produced by the permanent magnets of the flowmeter, give rise to intense deformation of the free surface and the creation of surface waves. The field acts as a magnetic obstacle. We observe that the flow velocity is decreased right underneath the magnetic field and is accelerated in the side regions. This magnetic obstacle effect may restrict the determination of the local surface velocity in application.

Jan 1, 2012

By M. Shevchenko

Integrated experimental and modelling research program on the phase equilibria and development of thermodynamic databases of the lead and copper metallurgical gas/ slag-matte-metal-solids systems (PbO-“Cu2O”-FeO-Fe2O3- ZnO-CaO-SiO2) is being undertaken to support improvements in the pyrometallurgical smelting and recycling processes. This is the first systematic investigation of phase equilibria of slag systems in equilibrium with Pb metal, providing information for systems in which copper coexists in slag with lead or zinc as major components. The experimental studies involve high-temperature equilibration of synthetic samples, rapid quenching, and measurement of the compositions of equilibrium phases using electron probe X-ray microanalysis (EPMA). FactSage-based thermodynamic database development is integrated with experimental research. Initial thermodynamic assessments are used to identify priority compositions and conditions for experiments, which are planned to provide specific data to assist thermodynamic optimisation. Significant improvement in the accuracy of the phase equilibria description is achieved. Continuous database improvement and extension to include new elements are targeted. Example of industrial application is given.

By A. J. van der Zeeuw

The use of SME 529 in the extraction of copper from acidic liquors and of copper and nickel from ammoniacal solutions, is illustrated with results of laboratory and bench scale mixer/settler experiments. Special features of SME 529 are its high loading capacity and the ability to keep the complexes dissolved in the organic phase up to quite high concentrations.

Jan 1, 1976