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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 Antti Roine

Sulfidic zinc concentrates are usually roasted in a fluidized bed furnace into sulfur-free oxide form. Metallic zinc is produced from this oxidic calcine using hydrometallurgical leaching, solution purification and electrowinning stages. The roasting step is necessary because zinc oxides are easier to dissolve using traditional leaching methods than zinc sulfides. The Kokkola Zinc smelter uses various types of zinc concentrates and secondary materials as feed mixture. This makes it difficult to find optimum process parameters for the roaster when the composition and particle size distribution of the feed mixture varies even on a daily basis. Certain conditions may even cause difficult accretion problems or increase the amount of calcine in the process off-gas line excessively. A thermochemical heat and material balance model was developed for process advisor, in order to estimate the effects of different process parameters (temperature, process air coefficient, concentrate feed, oxygen enrichment, water feed, etc.) on the heat balance, roasting temperature and calcine composition. This model was constructed using the heat balance module of HSC Chemistry 4.0 software. The prevailing chemical compounds in the concentrate and calcine were verified using mineralogical analyses and equilibrium calculations. The roasting process seems to operate near chemical equilibrium conditions, if the behavior of the main components is considered. This paper describes briefly the basic principles of the calculation model and outlines the results with several diagrams and discussion. The calculated results were in reasonable agreement with the recent process air oxygen enrichment and water feed test campaigns carried out at Kokkola in 1999.

Jan 1, 2000

By Vinod K. Namilakonda

In situ synthesis of discontinuously reinforced aluminum alloy metal matrix composites was investigated. Aluminum alloy (A356: Al-7 wt% Si) was reinforced with dispersed AlN particles. Thermodynamic calculations were made for the composition determination of various phases formed during bubbling of NH3 gas into the Al alloy melts in the temperature range 1173-1473 K. Experiments were carried out for in situ production of AlN particles with the reaction between Al melt and NH3 gas in high temperature resistance furnace at 1473 K. The products were characterized using SEM, EDS and XRD. Effect of bubbling time of NH3 gas on the AlN formed in the composites was studied. The amount of AlN reinforcement in the Al alloy composites was observed to be in the range of 5 to 35 wt%. Good agreement was observed between the experimental and thermodynamic calculated data on the composition of AlN in Al alloy composites.

Jan 1, 2006

By Jasper Kwong

The recycling of MgO-C refractories as a slag conditioner in EAF (electrical arc furnace) foaming slags have been evaluated by the Albany Research Center. The amount of MgO in the slags is critical for the foaming quality. Good foaming slags provide the benefits of high energy efficiency and low refractory consumption and require saturation with MgO. A computer model predicting the chemistry of MgO saturated foaming slags was designed to predict suitable amounts of MgO additives from MgO-C spent refractories. This model can also help to reduce the amount of slags and to improve the economics of producing steel. The implementation of this recycling program is underway at steel plants and the experience of recycling spent refractories will be discussed.

Jan 1, 2002

By H. Sieber

Multilayer samples of tantalum and aluminum with the composition of Al-25Ta were prepared by cold rolling of elemental foils. The microstructure and phases were characterized by XRD, SEM and TEMISAED and the reactive phase formation was examined by DSC and DTA measurements in multilayer foils rolled for different deformation levels. The rolling procedure yields a decrease of the Ta particle size in the Al matrix and also results in the formation of a multilayer structure with a thickness of the elemental foils down to 200 nm in average. No phase formation is observed during the cold rolling procedure. While XRD and DSC measurements show no phase formation up to the melting of aluminum for samples rolled up to 40 F&R (fold and rolling) passes, in samples rolled for 50 or more F&R passes a first phase formation reaction yield an interfacial layer of TaAl3. Contrary to former studies in the investigated cold rolled Al- 25Ta multilayers the reaction starts at temperatures as low as about 340°C. The first stages of the reaction are associated with two exothermic maxima, that increase in amplitude and shift to lower temperatures with increasing number of F&R passes. At higher temperature the TaA13 reaction layer thickens very sluggishly and yields a third exothermic maxima at about 600°C. Isothermal DSC scans show the reaction is not finished for samples containing elemental particles larger than 1 pm after annealing at 550°C for 5h. In all the investigated samples no Al- Ta phase other than Tad3 was observed to grow for heat treatments up to 800°C. Multilayer samples heated up to 1400°C show a morphology consisting of small AITa2 particles embedded in a single phase TaA13 matrix. The multilayer microstructure and reaction product morphology are characterized by SEM and TEM investigations in cross-section and plan view geometry.

Jan 1, 1998

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By Jiangtao Li, Zhongwei Zhao, Xingyu Chen, Xuheng Liu

In tungsten ion-exchange process, excessive sodium impurity enters into ammonium tungstate solution. However, the Na content of the final ammonium paratungstate (APT) product must be strictly controlled. Consequently, it is necessary to remove Na from the ammonium tungstate solution during processing in order to obtain the required purity of APT. In this study, porous Na specific absorbent, Na1+xAlxTi2−x(PO4)3, is used to remove Na from the ammonium tungstate solution. Through experiments, the effect of reagent concentration of Na1+xAlxTi2−x(PO4)3, reaction time, reaction temperature and Na concentration on the Na removal were investigated. The results showed that under optimal reaction conditions of reagent amount of NATP 1.0 times of theoretical amount, reaction temperature 25 °C and reaction time 15 min, the Na removal from commercial (NH4)2WO4 solution can reach 98%. Na1+xAlxTi2−x(PO4)3 has a good applicability to different Na+ concentrations. The obtained APT product reaches the national standard purity of zero level.

Jan 1, 2014

By Miroslav Raudensky, Kallol Bera, Jaroslav Horsky, Jee G. Chang, Ampere A. Tseng

"A combined experimental and finite element approach to study the local heat transfer coefficient is presented in this paper. The heat transfer coefficients at different cooling regimes in a roll are quantified by an inverse heat conduction technique; the heat transfer phenomena involved are then discussed. A discussion of the application of the heat transfer information found in the present study for better design of a roll cooling system is also included. Finally, an identification of areas where further work is needed is presented.IntroductionIn metal rolling processes, the roll is used as a tool to deform the workpiece at very high speeds. As shown in Fig. 1, the heat transfer phenomena involved in the process are complicated by the interaction between the roll and the strip, mainly including 1) the heat transferred from the workpiece to rolls in the contact regions, 2) the heat created in the interface due to the deformation of the workpiece and the friction between the workpiece and roll, and 3) the heat removed by watercooling as well as the ambient air. All of these transport phenomena occur at extremely high pressure, high speed, and high heat flux; these make the control of the roll temperatures an extremely challenging problem.In hot rolling, proper cooling of rolls can lead not only to improve the roll shape quality by controlling the thermal crown of the roll, but also to extend the roll life by minimizing the thermally induced stresses [1,2]. Also, knowledge of roll temperatures can contribute to insights about the roll/workpiece interfacellubricant behavior, and lead to the desired surface condition of the workpiece. Therefore, adequate roll cooling or control of roll temperatures is of critical concern to mill designers and process engineers. In order to have proper operation of the process, a good understanding of the influence of cooling practices on the roll is essential [3]."

Jan 1, 1994

By H. Y. Sohn, S. PalDey

"Fine particles of nickel aluminides and Ni4Mo were synthesized by reducing mixtures of, respectively, A1Cl3 + NiC12 and NiC12 + MoC12 vapors with hydrogen. Though thermodynamically favorable, the coreduction of NiC12 and A1Cl3 by H2 to form Ni3Al did not readily happen experimentally. The addition of a small amount of aluminum vapor was needed to initiate the coreduction reaction. The product particles as observed by TEM were very fine but usually agglomerated. The electron diffraction pattern of particles identified NiAl and NiA13 along with Ni3Al and metallic Ni. The content of Ni3Al was maximized at 52 mol% at 1050°C under the partial pressures ofH2, A1Cl3, and NiC12 at 57, 1.4, and 0.5 kPa, respectively. When a mixture of NiC12 + MoC15 was reduced by hydrogen, Ni4Mo particles with some Ni or Mo particles were obtained, the maximum content of Ni4Mo obtained being 93 mol % . The particle size was in the range of 100 to 200 nm. An Ni4Mo coating of 700 nm thickness on an Ni substrate was also prepared.IntroductionThe search for new high-temperature structural materials has stimulated much research on intermetallic compounds. Nickel aluminides have low densities, relatively high melting points, and good high-temperature strength properties. They show an increase, rather than a decrease, in yield strength with increasing temperature (1). Ni4Mo is also of interest as a high-temperature structural material. The major shortcomings of these intermetallics are their inherent brittleness at room temperature when they are in polycrystalline form. For much the same reason, the conventional casting of intermetallics is difficult. Ingot metallurgy and powder metallurgy are two other processing techniques. The first technique is quite energy consuming. In powder metallurgy, the powders of metals and alloys are consolidated in near net shape and then subjected to secondary processing. It would, therefore, be advantageous if intermetallic compounds can be produced in fine powder form from inexpensive raw materials, using less energy."

Jan 1, 1998

By G. L. Fredrickson, T. A. Johnson, B. R. Westphal, J. C. Wass, S. X. Li, D. Vaden

"Recovery of uranium from the Mk-IV and Mk-V electrorefiner vessels containing a LiCl/KCl eutectic salt has been on-going during the pyrometallurgical processing of used nuclear fuel for 14 and 12 years, respectively. Although austenitic stainless steels are typically utilized for LiCl/KCl salt systems, the presence of cadmium in the Mk-IV electrorefiner dictates an alternate material. A 2.25Cr-1Mo alloy (ASME SA-387) was chosen due to the absence of nickel in the alloy which has a considerable solubility in cadmium. Using the transition metal impurities (iron, chromium, nickel, molybdenum, and manganese) in the electrorefined uranium products, an algorithm was developed to derive values for the contribution of the transition metals from the various input sources. Weight loss and corrosion rate data for the Mk-V electrorefiner vessel were then generated based on the transition metal impurities in the uranium products. To date, the corrosion rate of the 2.25Cr-1Mo alloy in LiCl/KCl eutectic is ""outstanding"" assuming uniform (i.e. non-localized) conditions.IntroductionLow-enriched uranium products are being recovered from the Experimental Breeder Reactor-II (EBR-II) and Fast Flux Test Facility (FFTF) used nuclear fuels by a pyrometallurgical treatment process at the Idaho National Laboratory (INL). The treatment process comprises a set of operations designed to neutralize bond sodium, recover uranium from radioactive fission products, and place the fission products into acceptable waste forms [1-2]. Reactive sodium metal, essential for heat transfer purposes during reactor operations, is readily converted to chloride during the process. Electrorefined uranium products are currently being stored pending a final disposition decision. Treatment of the EBR-II used driver fuel was initiated in June 1996 while blanket fuel processing started in September 1998. These treatment processes continue on the balance of the used fuels."

Jan 1, 2011

By Hong Ouyang

A unified computational model has been developed for the Bridgman growth processes of B-NiAI and CdTe crystals. To handle the geometrical and physical complexities, a two-level approach has been developed. At the gtobatlevel, conjugate heat transfer, phase change dynamics, and variable material properties along with the realistic geometries and thermal boundary conditions are accounted for inside the entire crystal growth system. Refined calculations are then made within the ampoule, with the boundary conditions supplied by the global simulations. This model can optimize the use of computational source, help understand solidification behaviors, and improve designs of crystal growth system.

Jan 1, 1996

By Yuanbo Zhang, Zhixiong You, Li Qin, Guanghui Li, Tao Jiang

Low-grade manganese oxide ore is generally characterized by high iron content. In this work, sulfidation roasting of an iron-rich manganese oxide ore with elemental sulfur was characterized. The experimental results indicated that manganese dioxide can be selectively reduced over iron oxide by using elemental sulfur. The manganese phases in roasted product included low-valence manganese oxide, manganese sulfide and manganese sulfate, while those of iron mainly depended on the sulfur addition. Iron oxide would only be reduced or sulfidized at larger sulfur additions. The effect of roasting temperature and S/Mn mole ratio on the phase transformations was also investigated; extractions of Mn/Fe by sulfuric acid were evaluated. An extraction of Mn greater than 95% was obtained while that of Fe was controlled less than 10% under the optimal conditions.

Jan 1, 2016

By C. E. Hunt

Since the turn of the century, copper-nickel sulphide ores have been processed at the Sudbury, Ontario operations of INCO Limited, currently the largest integrated mining, milling, smelting and refining complex in the free world. Through the years operational, ecomomic, social and legislative changes have dictated the need for research and development directed at mitigating the impact of existing operations on the surrounding natural environment and also the reclamation of areas affected by earlier mining activities. Approximately one hundred years of mining history and the current annual processing of some 12 million tons of ore presents significant challenges with respect to waste disposal, liquid effluent treatment and land reclamation, particularly in light of rapidly evolving environmental regulations' and controls within the Province of Ontario.

Jan 1, 1992

By Kenneth C. Mills

Interfacial phenomena can have a dramatic effect on the separation of phases. Furthermore, since they involve surface-active materials, concentrations at ppm levels are enough to cause dramatic effects on separation processes. The effects of (i) emulsification, (ii) contact angle and wettability and (iii) Marangoni flows on phase separation are reviewed.

Jan 1, 1999

By D. Y. Wang, G. Y. Sha, X. L. Shen, D. R. Gu

The study of the volatilization kinetics of zinc and lead in pellets made of zinc-leadbearing dust mixed with coal powder, in a nitrogen atmosphere and at a temperature range between 1100 °C and 1300 °C, shows that the reduction temperature has a significant effect on the volatilization rates of zinc and lead, and that both the particle size of the coal powder and the extra carbon content has no effect on the volatilization rates. The obtained activation energies for the volatilization of zinc and lead are 79.42kJ/mol and 88.74kJ/mol respectively. The volatilization rate of zinc is controlled by the reaction between the zinc oxide and carbon monoxide while that of lead is controlled by the lead evaporation reaction, and the diffusion of gaseous lead through the gas boundary layer covering the surface of the reduced liquid lead.

Jan 1, 2000

By M. Soltanieh

The liquidus surface? and tie-lines in the nickel-cobalt-sulphur ternary system have been determined between 1<273-1573 K. The experiments were conducted by equlibrating the liquid sulphide with the metallic alloy phase. The liquid sulphide phase was sampled and chemically analyzed. The alloy was analyzed by electrol} microprobe. Combining the present results with the.avai1abl~ literature data, the thermodynamic properties of this system were calculated.

Jan 1, 1998

By Desmond Cook, Cynthia P. Dogan, Dale Govier, Gary Korth, James C. Rawers

"The microstructural and mechanical properties of iron powders processed in an attrition mill are highly dependent upon the processing environment. Extended high-energy ball milling in argon resulted in nanocrystalline bcc-Fe microstructure, while processing in nitrogen or alloying with carbon resulted in both nanocrystalline bcc-Fe and bct-Fe microstructures. In this U.S. Bureau of Mines study, both X-ray diffraction and Mössbauer analysis were used to show that the infused carbon and nitrogen concentrations were predominantly on the grain boundaries. Explosive consolidation resulted in a fully dense product with microstructure similar to the microstructure of the mechanically processed powder. Hardness values of the compacts correlated highly with grain size, independent of the processing conditions.IntroductionNanocrystalline materials have been theorized and shown to have unique properties that make them interesting for material scientists and promising for material engineering applications. Several conferences have been devoted solely to the techniques of preparing nanostructured materials have been held(l,2,3.). To date, most techniques used to generate nanocrystalline materials produce only a few grams of particles(1). High-energy ball-milling, however, is an efficient and effective technique that can produce substantial quantities of nanocrystalline materials with homogenous chemical composition that cannot be produced by conventional processing techniques(3).Applications and material evaluations of nanocrystalline materials require several grams of solid samples. Because nanocrystalline microstructures' are thermodynamically unstable, producing consolidated macro structures of nanocrystalline material has proved to be very difficult(2,3). In particular, retention of the nanocrystalline microstructure during consolidation of nanocrystalline particles has proven to be a problem. In contrast to many consolidation techniques that require elevated temperatures, explosive compaction uses a shock wave for consolidation( 4,5)."

Jan 1, 1994

By Martin B. Schranz

Copper sulfate pentahydrate is recovered from the spent etchant waste stream of a printed circuit board manufacturing facility by cooling crystallization. The fluidized bed crystallizer contains submerged cooling surfaces which are bathed in a stream of air. The air bubbles provide agitation which improve heat transfer, reduce fouling and maintain crystals in suspension. The recently patented apparatus (US 5,523,064) has advantages when compared to a conventional surface cooled crystallizer including capital cost, ease of operation and production of larger more uniform crystals

Jan 1, 1997

By L. Sh. Tsemekhman

The results of laboratory, large-scale laboratory and commercial scale investigations regarding the process of slag melts cleaning by oxidizing-reduction gas mixtures with a wide range of Po2 and the use of matte of various compositions as an extracting phase are presented. The copper, nickel and cobalt behavior during the cleaning process has been studied based on SEM and x-ray Microprobe of the quenched slag melts. The general cleaning mechanisms have been found. On the basis of the obtained data the most efficient cleaning methods have been proposed.

Jan 1, 2003

By Chuanhong Li, Zuohua Lin, Zhancheng Guo

"Catalytic mechanism of CeO2 in combustion of coals was investigated in this paper. Catalytic combustion of four kinds of coals with different metamorphic grades by CeO2 was examined, suggesting that catalytic function of CeO2 increases with increase of metamorphic grade of the coals. One important reason for CeO2 promoting combustion of the coals is that pyrolysis of anthracite is advanced by CeO2, which not only raises the pyrolysis rate and pyrolysis conversion ratio, but increases contents of light components in pyrolysis gas; and both pore space and specific surface area of the pyrolysis char are enlarged by CeO2, which is another reason. In order to realize in situ catalysis for reducing catalyst consumption, it is crucial to increase catalyst particle number and enhance the bonding force between catalyst and coal. In addition, remarkable energy saving effect was observed when a nanometer calcium-based rare earth catalyst obtained by hydro-thermal synthesis was applied to catalytic combustion of coal injection into blast furnace.Introduction Coal combustion is acknowledged as one of the most important coal applications. Since addition of catalysts could reduce the ignition temperature of pulverized coal and accelerate the coal combustion, catalytic combustion is generally accepted as an effective measure to realize fast combustion of coal. Furthermore, different catalysts added may produce different effects on ignition temperature of coal. It is reported activity of catalysts with the same cation follows this order: OH->CO3 2->Cl->SO4 2-; while that of the catalysts which have the same anion follows: Cs+>Rb+>K+>Na+>Ba2+>Li+>Sr2+>Ca2+>Mg2+>Be2+ [1-4] .Due to the special physical and chemical structure, CeO2 plays an important role in the catalysis field. Many literatures point out that CeO2 not only has great catalytic effect on energy conversion, succeeded in catalyzing combustion of gaseous fuels such as CH4, CO, etc. but also can catalyze combustion of some liquid and solid fuels such as JP-10, black carbon, carbon deposit in the automobile exhausts and so on [5-9].Pyrolysis, the first step of combustion, directly influences ignition temperature and combustion rate of coals. So a great variety of catalysts were applied to catalyze pyrolysis of coals. And plenty of studies suggest that the alkali and alkaline-earth metal compounds inherent in the coals show apparent catalytic effect on coal pyrolysis. Meanwhile, addition of alkali and alkaline-earth metals into coal combustion process also indicates obvious catalysis effect, accelerating coal pyrolysis, improving pyrolysis conversion ratio, increasing contents of pyrolysis gases and changing composition of the pyrolysis gases [10-15].Although alkali and alkaline-earth metal compounds have good catalysis effect on coal combustion, their application in the catalysis field was limited because of their erosive attack to the combustion equipments. In contrast, CeO2, as a substitution of the traditional coal catalysts, presents widely potential application due to its good catalysis ability, non-corrosive and nontoxic. However, investigation on CeO2 catalyzing coal combustion is rarely reported. In this work, catalytic mechanism of CeO2 in coal combustion was studied, in an attempt to provide theoretical foundation for developing new catalysis technologies."

Jan 1, 2009