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By J. M. Casas

This work presents the development of an ionic equilibrium model and its use to simulate the distribution and concentration of chemical species (speciation) in sulfuric acid - cupric sulfate solutions in the 0-2 pH range, 0.1-10 gpl copper concentration range and 15-45°C temperature range. The model consists of a set of equations which represent the equilibrium relationships for the ionic reactions and the mass balances for the components present in the system. The effect of ionic strength was taken into account by correcting the equilibrium constant in concentrated solutions. Several species can be formed at different pH and temperature values, the principal being: HSO-4, SO42-, CuSO4(aq), Cu2+, and H+ in order of increasing solution acidity. Simulations show that concentrations are highly dependent on pH. The sulfuric acid speciates mainly as bisulfate ion (HS0-4) and hydrogen ion (H+) at pH values lower than 1. The model presented in this work can be applied to predict and analyze the solution composition in electrolytic copper processes such as electrowinning, electrorefining and electrodialysis, as well as the purification of various industrial solutions.

Jan 1, 1999

By James A. Voigt

The efficient separation of metal species from aqueous streams by precipitation techniques requires 'a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems: The effects of solution chemistry, precipitator design, and solvent choice are considered.

Jan 1, 1996

By Oliver Zach

To know as much as possible about the condition of the refractory material (lining thickness, slag layer, build ups, ...) in an high temperature furnace is very important due to the safety and economic impacts. The new CONSCAN system offers the possibility to measure the inner surface of an furnace, and based on this results to calculate the thickness of the refractory lining, slag layer, build ups,.... The CONSCAN System provides this results as figures and graphics. This system is also working under hot conditions so it is not necessary to cool down the furnace. Based on these results the process control and the refractory lining concept could be optimized for maximum campaign life of the furnace.

Jan 1, 2006

By B. R. Westphal

The Integral Fast Reactor (IFR) concept being developed by Argonne National Laboratory is based on the pyrometallurgical processing of spent nuclear metallic fuel with subsequent fabrication into new reactor fuel by an injection casting process. During fabrication, a dilute scrap stream containing uranium alloy fines and broken quartz (Vycor) molds is produced. Waste characterization of this stream, developed by using present operating data and chemical analysis, was used to evaluate different uranium recovery methods and possible process variations for the return of the recovered metal. Two methods, comminution with size separation and electrostatic separation, have been tested and can successfully recover over 94% of the metal. Recycling the recovered metal to the injection casting process was evaluated for the different economic and process impacts. The physical waste parameters and the important separation process variables are discussed relative to their effects on the viability of recycling the material. A discussion of the criteria that is being used to establish the acceptable operating limits is also presented.

Jan 1, 1992

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By Yufeng Guo

Mineralogy and physico-chemical characteristics of a nickel hydrometallurgical residue and recovery of iron-bearing minerals by flocculation-magnetic separation were studied. The results show that the nickel residue is super-fine and fraction less than 0.045mm reaches 85.4%. Ferrous minerals are chiefly magnetite and ferruginous glass. Magnetite accounts for 31.7% and exists as free magnetite. Ferruginous glass is of multicomponent amorphous substances with low-iron grade but strong magnetism, and accounts for 39.9% of total iron minerals. Addition of flocculants increases granularity and magnetic force of fine iron-bearing particles and improves iron grade and recovery. The tests with flocculation separation show that a concentrate assaying 56.68% Fe with 81.72% recovery was obtained in a magnetic tube. A concentrate with 56.92% iron grade and 67.96% recovery was obtained by flocculation-magnetic separation with a magnetic cylinder.

Jan 1, 2006

By Martin Brueggemann

The Tyrone copper solution extraction and electrowinning plant was the first such facility built by Phelps Dodge Mining Company in 1984. Over the next 20 years, the aqueous flow rate capacity of the plant has been expanded from the original design of 12,000 gallons per minute (gpm) to 34,000 gpm to meet production goals in the face of declining copper grades in the leach solutions. The ability to process higher aqueous flow rates through existing equipment comes at the expense of increased organic loss through entrainment to raffinate. These losses of organic (diluent and extraction reagents) can account for up to 10 percent of the plant?s total operating costs. With the recent dramatic price increase of petroleum-based products, these operating costs due to losses are sure to increase. This paper will discuss recent improvements at the Tyrone SXEW plant that have resulted in a 40 percent reduction of organic losses. These improvements include picket fence modifications, new fence materials, organic recovery systems, and operational practices within the solution extraction process.

Jan 1, 2006

By S. Sundarraj

The morphological transition between columnar and equiaxed structures is an important solidification phenomenon frequently observed in castings, especially complex parts with varying cross-section, The mechanical properties and the occurrence of defects such as hot tears are strongly dependent on the structure formed in the casting. Hence, it is important to understand the conditions leading to columnar or equiaxed structures. Although extensive work has been done in modeling solidification systems, almost all of the existing models are based on the assumption that the structure formed in the casting is either purely columnar or purely equiaxed. Prediction of the columnar-equiaxed transition (CET) requires a solidification model which accounts for the formation of both columnar and equiaxed structures, along with related microscopic and macroscopic solidification phenomena. In this paper a CET model is presented which: (i) takes account of both columnar and equiaxed structures, (ii) accounts for macroscopic heat transfer coupled with microscopic phenomena such as nucleation, growth and microsegregation, (iii) satisfies solute conservation, and (iv) is easy to implement in commercial finite element and finite difference software. The proposed model predictions of CET have been validated with available experimental results for a uni-directional solidification of an aluminum-copper alloy. A sensitivity analysis has also been carried out to determine the effects of various parameters on the CET model predictions. The model is being extended to other alloy systems and more complex geometries. This work will be published in due course.

Jan 1, 1996

By Singareddy R. Reddy, Ramana G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. An expression for the activity coefficient of a dilute solute, 2(oxygen), in a binary solvent 1-3 is derived. It is used to calculate the logarithmic activity coefficient of oxygen in Pb-O-Gu, Pb-O-Bi, AgO- Sn, Pb-O-Sn and Ag-O-Pb metallic systems. Self interaction parameter of the solute is derived from the partial Gibbs energy of solute using constant compositional path. The derived equation is used successfully to deduce the self interaction parameter of oxygen in Pb-O-Gu and Pb-O-Bi metallic systems. The predicted thermodynamic parameter data i.e activity coefficient and self-interaction parameters are in an excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionThe nature of solute interactions such as oxygen, nitrogen and sulfur with the metallic solutions are important for a number of chemical and metallurgical processes. Several theories [1-23] have been developed to evaluate fundamental thermodynamic properties of solutes constituting two elements. The activity of solutes has been calculated using statisticalor quasi- chemical approach.Wagner's [4] Ideal Solvent Model is based on one energy parameter to describe the compositional dependencies of the activity coefficient of nonmetallic solutes such as oxygen in binary metallic solutions. This model depends on a constant energy of interaction for the exchange of atoms from the coordination shell of an oxygen atom to the shell of an interstitial site and cannot account for properties of strongly interacting systems [4]. Therefore, several attempts have been made to improve the Wagner's model for the strongly interacting systems. [10-16]."

Jan 1, 1996

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By Akira Yazawa

Oxidic dissolution loss of metal in slag is discussed thermodynamically in terms of oxygen potential, activity coefficient and equilibrium constant. To understand basic principle, regular solution model is applied for model calculation of the activity behaviour of metal oxide in FeO-SiO2-CaO slag, and effects of slag composition, temperature, and basicity of oxide on dissolution loss are demonstrated. As: a simplified but practical conclusion, the dissolved metal loss in slag is inversely proportional to activity coefficient of metal oxide, and also to FeO content in slag when amount of slag is taken account.

Jan 1, 1994

By M. El Ganaoui, P. Bontoux

"A computational model to investigate solid/liquid phase change transitions for binary alloy under directional solidification is presented. Conservation equations are developed by using an homogeneous formulation. A second order accuracy method of time and space based on finite volume approximation has been evaluated by comparing results to spectral solution for time-dependent solutal convection developping in a melted alloy. For extended model to solid/liquid interface effects time amplification of solutal perturbation injected near the interface is described before considering solutal convection is melt.IntroductionThe enthalpy method gives a front fixing approach for energy equation without introducing coordinate transformation. The interfare position is recovered a posteriori [1]. A number of authors have extended this approach so as to include the convection phenomena within the two phase 'mushy region' [2, 3, 4, 5, 6].We have developed a time-dependent enthalpy-porosity formulation for directional solidification [4, 6, 8]. The interaction between solid and liquid phases is modelised by a Darcien type force in the phase change area. The behaviour of the melt is similar with the flow of an incompressible fluid in a porous medium. This force is proportional to the relative phase velocity. It corresponds to a damping force depending on the anisotropic permeability of the 'mushy zone'. The permeability depends on the liquid fraction and on the size of·solidification microstructures. An informative discussion of a new slant on the general approach of continuum mechanics needed to analyze the formation of mushy zone is given in [12]. The method is extended to the presence of species diffusion: the solutal Stefan condition which expresses the solute incorporation or rejection across the interface is accounted implicitly in a species equation valid in all the domain [14, 15]."

Jan 1, 2001

By Mike Trovant, Stavros A. Argyropoulos

"A fixed grid numerical model for phase change problems is proposed. The model solves for heat transfer and fluid flow, via the coupled solution of the energy, continuity and momentum equations. In addition, the numerical scheme accounts for temperature varying thermophysical properties and determines the shrinkage profile resulting from phase and density change. Simulations are run to determine the effect of varying model parameters and wall cooling rates on the location and shape of the shrinkage void formation in cylindrical casts. Results are shown for both aluminum and magnesium.IntroductionThe mathematical modeling of phase change processes (be they solidification or melting problems) entails solving for many interrelated phenomena. A comprehensive numerical simulation of the casting of a metal, for example, would have to account for: (a) heat transfer in both the solid and liquid portions of the metal and in the mold, (b) the release of latent heat during phase change, (c) fluid flow behavior in the liquid portion of the metal, (d) temperature induced shrinkage caused by liquid contraction and solidification contraction, and (e) the development of thermal stresses with accompanying shrinkage in the solid portion of the cast and mold. A schematic of the relationships that exist between the coupled equations which govern solidification is shown in Figure 1."

Jan 1, 1994

By Raymond E. Healy

Mercurian e1ectrum (Au-Ag-Hg alloy) is the principal Au-bearing phase in the massive sulphide ores at Trout Lake, Manitoba. The average composition of this phase (in wt %) is 49.2 % Ag. 38.7 % Au and 11.0 % Hg, with ranges of 17.34 to 76.47 % Ag, 1.62 to 79.86 % Au and 1.29 to 30.87 % Hg. Compositional variation reflects solid solution in the a-phase of the Ag-Au-Hg system. Backscatter electron imagery reveals systematic zoning and suggests a general crystallization sequence from metamorphic pore fluids of progressively Ag-rich compositions. Investigation of the occurrence of gold in mill products demonstrates that mercurian electrum accounts for over 90 % of the Au in Trout Lake ore. I Invisible" gold in pyrite (x = 0.72 ppm Au) and arsenopyrite (x 30.2 ppm Au) is confirmed by SIMS analyses, and accounts for 7-10 % of the Au in the ore, and 35 % of the Au lost to the tailings. The remaining 65 % of the Au lost to the tailings consists principally of mercurian electrum locked with pyrite. No significant losses of mercurian electrum in the size range amenable to flotation and/or regrinding is indicated.

Jan 1, 1989

By Murat Baydogan

Effect of retrogression and reaging treatment on hardness and stress corrosion cracking resistance of 7075 aluminum alloy was investigated. As received 7075 alloys in T6 temper condition were retrogressed at 170, 220, 240 and 380°C for different durations between 15 s and 60 min. Subsequent reaging was made at the T6 aging condition. Treated materials exhibited higher hardness and better stress corrosion cracking resistance than T6 temper in a wide range of retrogression temperature and time. The highest hardness was obtained after retrogression at 170°C for 210 s followed by reaging, corresponding to 20% hardness improvement. Improvement in stress corrosion cracking resistance of the alloy by as much as 85% was also observed. In this paper, improvements in hardness and stress corrosion cracking resistance are discussed on the basis of the microstructural changes during retrogression and reaging treatment.

Jan 1, 2006

By Vaughan R. Voller

"The wide range of length and time scales found in solidification processes are outlined and discussed. Methods for Direct Microstructure Simulation (DMS) are introduced. Key features in sharp interface and phase field models are presented. Concepts in micro-macro solidification modeling are covered. Basic details of microstructure and segregation models are provided. A description of a recent segregation micro-macro model is presented in detail.IntroductionA solidification process involves the containment of a liquid region, which, due to cooling, transforms over time to form a fully solid product. The development of the solid microstructure and the segregation of solute components during this transformation are controlled by phenomena that occur across a wide range of length and time scales. A ""successful"" model of a given solidification process needs to account for these phenomena. Standard models of solidification employ a discrete grid of node points and associated volume elements in the special domain, with a discrete time step to track the transient changes of nodal values, describing the composition and microstructure. Through the use of such models significant progress has been made towards a complete understanding of solidification process and phenomena (see the conference proceedings in Refs [1-9]). As solidification models become more sophisticated, however, they all run into the problem of resolving the full range of disparate space and time scales.Two approaches can deal with this problem1. Direct Microstructure Simulation (DMS) where the grid size and time step are chosen to scale with the smallest length and time scales of the given problem.2. Micro-macro modeling where the grid size and time step scale with the macroscopic process scale and phenomena at smaller scales are accounted for via sub-grid modeling and volume averaging.Currently full DMS of solidification is beyond the reach of available computer power and the application and development of micro-macro models is an important and critical research area."

Jan 1, 2001

By Sarah Beutner Mavrogenes

The mineralogy of three slags from a domestic secondary copper refinery were studied by applied mineralogical techniques to determine the: 1) phases present, 2) phase chemistry, 3) phase abundance, 4) associations, 5) crystalline habit, 6) grain size, 7)microtextures, and 8) causes for certain metallurgical problems, such as metal losses to the slags. The slags were produced by skimming the bath prior to melt-down to allow heat from the flame to reach the bath. The first slag is highly viscous and all three slags contain a large amount of copper. The "first slag", which is skimmed prior to treatment of the bath with fluxes, contains metallic copper, cuprite, delafossite, magnetite, Mg-hercynite, common spinel-chromite solid solution, picrochromite-chromite solid solution, common spinel-picrochromite solid soiution, gahnite, cassiterite, silica-rich glass, and corundum. Its abundant solid refractory phases make the slag difficult to skim. The "soda-rich slag", skimmed after the treatment of the bath with sodium carbonate flux, contains cuprite, delafossite, magnetite, cassiterite, Na-Al-silicate, and Na-Al-Ca-silicate. It contains less metallic copper than the first slag and lacks the refractory minerals. The "phosphorus-rich slag", skimmed after treatment of the bath with a copper phosphide flUX, contains metallic copper, cuprite, delafossite, berlinite, cassiterite, silica, apatite, Cu-Fe-rich apatite, copper phosphate, Cu-Fe-phosphate, and a Pb-phosphate. In contrast to the above three copper-rich slags, recent charges have produced a silver-copper-rich slag. The "silver-rich slag", skimmed after the treatment of the bath with a copper phosphor ide-borax flux, contains, cassiterite, delafossite, cuprite, a Na-Al-silicate, magnetite, metallic copper, MgO, common spinel-chromite solid solution, and wollastonite. Silver ranging from 0.05 to 2.02% was found by atomic absorption and inductively coupled plasma spectrometry analyses in the metallic copper phase.

Jan 1, 1989

By Jewel A. G. Gomes

Electrocoagulation (EC) has been performed with Al-Fe electrode system with changing polarity for the removal of arsenic from water. The removal process has been studied using ICP-AES and Anodic Stripping Voltammetry with a wide range of arsenic concentration (1-1000 ppm) at various pH (4-10) and residence times (1-60 min). Electrochemically generated by-products have been analyzed using XRD, FTIR, XPS, SEM/EDS and Mössbauer Spectroscopy. Results revealed expected crystalline iron oxides (magnetite (Fe3O4), lepidocrocite (FeO(OH)), iron oxide (FeO)) and aluminum oxides (bayerite (Al(OH)3), diaspore (AlO(OH)), mansfieldite (AlAsO4?2(H2O)), as well as some interaction between the phases. The amorphous or ultra-fine particular phase was also found in the floc. The substitution of Fe3+ ions by Al3+ ions in the solid surface has been observed, indicating an alternative removal mechanism of arsenic in these metal hydroxides and oxyhydroxides by providing larger surface area for arsenic adsorption via retarding the crystalline formation of iron oxides.

Jan 1, 2006

By John J. Jonas, Sang-Hyun Cho, Ki-Bong Kang

"The recrystallization behavior of Nb micro alloyed steels containing Cr, Mo, Ni and Ti. was studied using hot torsion testing with the aim of modeling the recrystallization processes and the mean flow stress taking into account the microstructural behavior during hot rolling. The kinetics of static and metadynamic recrystallization were characterized and appropriate expressions were formulated for the recrystallization kinetics. These are shown that the recrystallization kinetics depend on steel composition and the processing conditions. The stress-strain curves were determined in order to derive new equations for the peak stress, peak strain, mean flow stress and softening kinetics. The peak strain is influenced by the presence of alloying elements; their addition, which has a solute drag effect, retards the rate of grain boundary motion, shifting the peak to the right. The addition of Nb to the steel results in a significant increment in the activation energy for hot deformation, and Mo has smaller effect than Nb, but Cr has the opposite effect. It was also found that the deformation activation energy in these steels was not altered by the addition of Ni. The rate of metadynamic recrystallization increases with strain rate and temperature and is observed to be independent of strain, in contrast to the observations for static recrystallization.The mean flow stress (MFS) calculations, based on the Sims analysis, are then compared with the predictions of a model based on an improved Misaka mean flow stress equation in which solute effects, strain accumulation, as well as the kinetics of static and metadynamic recrystallization are accounted for. Good agreement between the measured mean flow stresses, which is obtained from the mill logs of POSCO Kwangyang #3 HSM (hot strip mill), and 'predicted ones is obtained over the whole range of rolling temperatures. The results demonstrate that dynamic recrystallization followed by metadynamic recrystallization, supported by the unexpected load drops, sometimes occurs for the rolling schedules studied in the present analysis."

Jan 1, 2001