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By Hsin H. Huang

Equilibrium calculational software programs can be effectively utilized to model the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation on extraction and recovery processes. Illustrative examples using the calculational program ST ABCAL for the creation of diagrams such as EwpH, activity or concentration-pH, and activity or concentration-EH are presented to demonstrate the fundamental characteristics of real hydrometallurgical mercury dissolution and recovery processes. An industrial application will include leaching of mercury from K 106 mercury sulfide waste and solution purification by iron cementation.

Jan 1, 2003

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By D. A. R. Kay

Phase stability diagrams are used to predict the abilities of lanthanum and cerium oxides to desulfurize coal gasification products in the temperature range 800-1000 C. Results of desulfurization studies in laboratory fixed bed reactors illustrate the effects of i) sorbent preparation, ii) input gas quality and iii) temperature, on the desulfurization reaction. 2CeO(2-x)(s) + H2S(g) + (1-2x)H2 = Ce2O2S(s) + 2(1x)H2O(g) The results of desulfurization/oxidation regeneration cycles are also reported.

Jan 1, 1989

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 Roberto Parra

The selective reduction smelting of Cu2O in Cu2O-FeOx-SiO2 melts has been studied at laboratory level, using as a feed a dead roasted calcine from a copper concentrate. The purpose of the study was to evaluate the kinetic and mechanisms of the indirect reduction with CO and the direct reduction with graphite from 1260°C to 1350°C. The reduction rate by CO was found to be 10-2 to 10-1 mole Cu2O m-2s-1. The graphite reduction macrokinetics for FeO and. Fe2O3 containing melts, was found to be a first order reaction with respect to the Cu2O concentration, with a kinetic constant of 104 to 10-3 s-1. The reduction rate was not sensitive to temperature nor to stirring, in the range studied. The measured reduction rate is almost one order of magnitude larger than the observed rate for the direct reduction of FeO.

Jan 1, 1999

By Alicia Esther Ares

This study was conducted to investigate the directional solidification of Zn-20%A1 and Zn20% A1-1O%Si-3o/oCu alloys under different conditions of heat transfer at the metal/mould interface. The type of structure obtained in both cases was analyzed and related to the solidification thermal parameters such as cooling rate, growth rate, thermal gradient and recalescence which were determined from the temperature versus time curves. These parameters were correlated with the structure-like length of columnar grains and size of equiaxed grains. The metallographic analyses were done performing quantitative metallography and composition analysis of the different alloying elements along the cast samples by SEM (Scanning Electron Microscopy) and EDXA (Energy Dispersive X-Ray Analysis). Correlations between properties, structures and thermal parameters were found.

Jan 1, 2008

By Jaeheon Lee

Gold-copper alloys are shown to form during the cementation of gold on copper in a solution containing 0.25M [S2O32-] at 25oC. The alloy composition is strongly dependent on the initial Cu:Au ratio in solution and ranges from Au3Cu to AuCu3. XPS results for Au, Cu, S, and O are reported as a function of depth through an entire deposited film with an initial solution containing 20 ppm [Au] and 30 ppm [Cu]. The deposit contained about 20 atomic % gold and was predominantly Cu3Au. Underpotential deposition (UPD) theory is discussed as a mechanism for explaining the formation of these alloys. Several other systems that produce alloys during contact reduction/cementation are also discussed.

Jan 1, 2003

By C. Hennesmann, D. Maijer, S. L. Cockcroft, P. Yo

"Die cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. As part of a collaborative research agreement between researchers at the University of British Columbia and Canadian Auto Parts Toyota Incorporated, work has been underway to predict heat transport and porosity formation in die cast A356 wheels. The basic heat transfer equations have been solved using the commercial finite element package ABAQUS to which specialized routines have been added to predict porosity. Preliminary work on predicting porosity formation focused on using the Niyama parameter as a measure of the probability of porosity. The latest version of the model incorporates a new fundamentally based porosity criterion, which takes into account the effect of hydrogen concentration. The development of this model together with its application to a series of cylindrical test castings as well as a production cast wheel are presented.I. IntroductionDie cast aluminum wheels are one of the most difficult automotive castings to produce because of stringent cast surface and internal quality requirements. Microporosity, in particular, is a common defect that can adversely affect wheel quality. The mechanism of microporosity formation in aluminum alloys is complex owing to its dependence on the interaction of a number of phenomena occurring during solidification including the decrease in hydrogen solubility, the decrease in volume, the development of the solidification structure, and the increase in difficulty in interdendritic feeding [1]. As a result, the amount, size, and distribution of microporosity is affected by a large number of casting parameters including thermal variables, melt composition, grain structure, modification, and inclusion content, making optimization by trial-and-error methodologies difficult.The use of criteria functions, based on thermal conditions during casting, offers a relatively simple approach to predicting microporosity. In practical terms, they are useful because they provide a straightforward method of assessing the impact of varying casting parameters on porosity through various thermal parametersl21 such as thermal gradient, cooling rate, solidification time, and solidus velocity. Drawbacks of criteria functions include insensitivity to varying hydrogen concentration and the limitation to qualitative predictions. Consequently, in aluminum alloys, attempts have been made to develop models incorporating the effects of hydrogen gas and microstructure evolution. However, these types of models represent a significant increase in complexity and sacrifice the simplicity and ease of application of the thermally based criteria functions."

Jan 1, 2001

By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By Qiang Yu

This paper reports on a research project supported by NSF, which aims at developing a multi-scale methodology for systematic microstructure prediction in thermo-mechanical processing of metals. This methodology is based on combining mesoscopic microstructure models with macroscopic process formulations and involves the following three main steps: (I) based on the given global processing conditions, the gross deformation patternof the entire workpiece is modeled using a continuum-based algorithm, (2) the resulting parameters are then extracted from the continuum-based simulation, post-processed and passed on to the mesoscopic numerical module, and (3) the microstructural changes are finally modeled at the mesoscopic scale. This approach is expected to overcome the disadvantages of current microstructure prediction practice employing empirical relationships between microstructural features and processing parameters. Keywords: Thermo-mechanical processing, Microstructure, Grain growth; Recrystallization; Mesoscopic models; Finite Element Method

Jan 1, 2003

By Chao Zhang, Jian Guo, Chaoquan Yao, Leige Xia, Xinyu Li, Jianliang Zhang

In this research, analytical reagents were used for the sintering experiments. And the sinters were using X-ray diffraction, scanning electron microscope and mineralogical microscope analysis to study the effect mechanism of manganese on the silico-ferrite of calcium and aluminum (SFCA) bonding phase formation during the sintering process. The results indicated that the increasing content of manganese would greatly reduce the content of SFCA, and promote the formation of calcium aluminum silicate and the amount of pores and cracks. The existence of manganese inhibited the silicon form into the SFCA and a great deal of Fe2O3 was participated in the crystal transition to Fe3O4. When the ratio of the added manganese was less than 3% in the mixing, the calcium ferrite was in substantially interleaving corrosion with hematite and magnetite. Both the porosity and silicate glass phase content were low simultaneously, which contributed to the sintering production.

Jan 1, 2015

By P. A. Botha

Most sinter producers prefer to use a range of iron ores with the aim to optimize their sinter blends. ISCOR is however limited to the use of ore from two deposits, namely Sishen and Thabazimbi. Only sinter produced from Sishen ore is described in this report. The Sishen iron ore deposit provides high-grade hematite ore with a mean iron content of 65 per cent. Three major ore types are developed: massive, laminated and conglomeratic. The main ore mineral is hematite with minor to trace amounts of quartz, mica, phosphates and, in places, carbonates. A sinter product is characterized by its mineralogical composition and metallurgical properties. The production rate also plays an important role in the economic evaluation of sinter quality. Sinter-pot tests were conducted with varying basicities, given as the ratio of CaO to SiO:< and coke content. The results of these tests were characterized by mineralogical and metallurgical methods. Basicity of a sinter mix directly influences the mineralogical composition and metallurgical properties. The content of calcium ferrite and calcium silicate increases with increasing basicity, thereby increasing the reducibility and cold strength of the sinter product. Experiments performed during this study provided a model for the optimization of the sinter mix with respect to its mineralogical and metallurgical parameters.

Jan 1, 1991

By Soumendra Basu, Uday Pal, Yang Yu, Srikanth Gopalan, Karl Ludwig, Deniz Cetin, Jacob Davis

"A limiting factor for Solid Oxide Fuel Cell (SOFC) performance is the oxygen reduction reaction (ORR) at the cathode surface. Changes in the surface composition and structure on annealing at 800°C has been studied, since these can influence the ORR. Idealized single crystals of cathode materials La0.8Sr0.2MnO3 (LSM) and La1-xSrxCoyFe1-yO3 (LSCF) were grown as heteroepitaxial thin films on lattice matched single crystal substrates. Changes upon heating the films to operating temperature and pressures were characterized using various synchrotron x-ray techniques. Total Reflection X-ray Fluorescence (TXRF) measurements, which probe compositional changes, were made at high temperature in real time. The LSM surfaces were found to develop manganese enrichment when heated. Highly strontium doped LSCF were found to develop strontium-rich surfaces. HArd X-ray PhotoElectron Spectroscopy (HAXPES) was used to investigate the electronic structure of the materials. Highly strontium doped LSCF precipitates a surface strontium phase that contains both oxide and carbonate contributions.IntroductionSolid oxide fuel cells (SOFCs) are chemical to electrical energy conversion devices that could potentially reshape how energy demands are fulfilled. SOFCs have a potential efficiency over 70%, fuel flexibility, low emissions, and low degradation over long time scales. Commonly, SOFCs are operated at high temperatures (above 800°C). At these temperatures expensive housing is needed to contain an operating stack as well as coatings to contain the oxidation of the metallic interconnects. Lowering the temperature of an operating device would allow for more conventional materials to be used, thus lowering overall cost. Understanding the reaction kinetics of the oxygen reduction reaction at the surface of the cathode is vital to designing a system that will perform well at lower temperatures. A commercialization goal is to reduce operating temperatures without sacrificing performance.In order to exploit the advantages of SOFCs, an understanding is needed of the surface chemical states of cations on the surface of the cathode and how this relates to the oxygen reduction reaction (ORR):"

Jan 1, 2014

By Wang Zhi

High-Mg-content concentrates are usually treated in Jinchuan flash smelting Furnace. Because the viscosities of high-Mg-content slag is very high, the operation of flash smelting becomes very difficult. To solve this problem, the viscosities of the semi-synthesized FeO-MgO-Si02 slag of different compositions were measured. The results showed that when in the slag the weight percentage of MgO [m(Mgo)] is 6-10%, the ratio of the weight percentage of iron to that of Si02, m(Fe)/m(SiO2) is 1.1-1.4 and the temperatures are within 1473?1773K, the slag viscosities increased with the increase of m(Mgo) and m(Fe)/m(sio,). When m(Mgo)<6%, the smelting temperature should be controlled at I 300°C in order to to keep the smooth operation. When m(Mgo» 10%, the temperature should be kept above 1633K. When the content of MgO is higher, a lower viscosity slag ean be produced by decreasing the ratio of m(Fe)/m(sio,). The appropriate ratio of m(Fe)/m(sio,) for Jinchuan flash smelting furnace is about 1.2.

Jan 1, 2003

By F. Kongoli

Viscosity is an important parameter of copper smelting and converting processes. It affects the settling of matte or metal droplets in the slag, distribution of elements etc, Despite this importance, confusion exists on the viscosity of copper smelting slags as a result of disagreements found among the measured viscosity data of several authors especially in the slags of high ferric iron content and close to magnetite precipitation. In this work a critical review of the existing data on the viscosity of copper smelting slags has been first carried out and the effect of oxygen potential on the viscosity of copper smelting slags has been clarified through a coupled quantification of viscosity and liquidus temperature. The confusion in the literature has been clarified and the importance of the relation between the viscosity and the liquidus temperature is discussed,

Jan 1, 2003

By T. V. Jayaraman, D. Das, B. Mallesham, A. R. James

The PNN-PZT xPb(Ni0.3Nb0.67)03-(1-x)Pb(Zr0.31 Ti0 69)03 (0.2=x=0.6) based relaxor-ferroelectric material was synthesized by colurnbite precursor (NiNb206) method via conventional solid state reaction. Homogeneous mixture of required oxides and precursor was calcined at 850°C for 4 hrs to obtain phase pure perovskite. Pellets of PNN-PZT ceramics were sintered at 1100oC for 4 hrs. Phase pure perovskite structure was confirmed by the X-ray diffraction analysis. From the X-ray diffraction analysis it is also confirmed that there is a structural transformation from the rhombohedral to tetragonal with increase in PZT content and existence of morphotrophic phase boundary (MPB) at x = 0.5 composition. The morphology and microstructure of the sintered pellets were observed using the scanning electron microscope. P-E loop measurement shows the high remnant polarization (19.12 µC/cm2) and low coercive field (6.89 kV/cm) at MPB compared to all other compositions. The electromechanical planar coupling coefficient (kp) was measured through the resonance and anti-resonance method using the LCR meter. The piezoelectric strain coefficient (d33) measured directly using the d33-meter. At x = 0.5 composition the highest value of d33 = 398 pC/N is obtained.

Jan 1, 2012

By K. Mansfield

Spent Pot Lining (SPL) is an unavoidable waste product of the electrolytic process in the smelting of aluminium. SPL is considered to be a hazardous waste in various countries because it contains significant quantities of absorbed fluorides along with traces of cyanide. In 1995, Portland Aluminium undertook the investment of AUD$26,400,000 to construct a Research and Development processing facility at Portland, Victoria, Australia, to treat SPL. Extensive research, development and design were carried out over 5 years prior to the investment decision. This study led Portland Aluminium to install an Ausmelt pyrometallurgical furnace to combust and melt the SPL producing a hydrogen fluoride (HF) laden gas, which was cooled and then converted to aluminium fluoride (AlF3). Both the cooling and AIF3 manufacture were processes developed by Portland Aluminium. Many commissioning, equipment reliability and process problems have been encountered that had not been experienced in the trials at Ausmelt or in the developmental process for the treatment of the furnace offgases to form AlF3. Designs based on anticipated process expectations have had to be re-engineered by the SPL team to ensure plant and operational success. In June 2001, the installation of the final major component - a slag granulation process - was completed. This has produced a vitrified (glassy) slag that is expected to have leachability qualities acceptable to the Victorian Environment Protection Authority (EPA) to allow commercial end uses of the slag material to be developed. Today (September 2001), the smelter has successfully used the fluoride product, namely 65- 70% AIF3, in aluminium production and the SPL plant has significantly increased throughput with expectations to be at annual design rates of 12,000 tonne of SPL in early 2002. "The Alcoa Portland SPL Process" has been technically developed and is a proven process for the treatment and recovery of valuable components from SPL materials.

Jan 1, 2002

By C. J. Parradies

During injection into a die, semi-solid metal alloys exhibit a shear-rate, history-dependent flow response. Simulating the injection of a thixotropic material requires that empirically determined boundary conditions and viscosity are specified as a function of both temperature and shear rate history. Experiments were performed using an industrial die casting machine that was instrumented with sensors to measure the pressure and temperature during the injection of a semi-solid aluminum alloy through a tube. This benchmark experiment was used to develop a simulation of the die casting process that could then be applied to more complex die geometries. The results of the experiments were analyzed using the exact, steady state solution for a power law fluid and simulations accounting for slipping at the boundary between the semi-solid metal and the die. Results indicated that the no-slip condition cannot be used to simulate the velocity boundary condition, because the measured pressure is much lower than that predicted by the models. An estimated apparent slip coefficient was introduced to account for the reduced pressure. During some of the experiments, a sudden drop in the measured pressured, prior to decreasing the ram velocity, coincided with observations of segregation in the form of concentric rings visible on the polished surface of cross-sections cut from material remaining in the tube.

Jan 1, 1997

By Shusen Cheng, Dongdong Zhou

The high temperature distribution in ironmaking and steelmaking industry is very important to control the smelting process. Although equipment is available to measure the temperature in the smelting process, in general it could just measure one certain point or only at discrete times. The real time temperature distribution in ironmaking and steelmaking is important because it could reflect reaction information and help to control the operation parameters. In this paper, a new method to detect the temperature distribution in ironmaking and steelmaking through the application of digital imaging system based on the color CCD was studied. In addition, the two-color method and partial least square method were used in the calculation model to improve the accuracy. The results agreed well with the measured temperature.

Mar 1, 2017

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014