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By Robert G. Robins

Precipitation of ferric arsenate is an effective method for removing arsenic(v) from hydrometallurgical process solutions. The solubility and stability of this compound. FeAs04.2H20, has received some attention in recent years and the reported solubilities of amorphous and crystalline material have varied considerably. This paper reviews previous studies and reports some recent work with a consistent model to explain the variable results. Free energy data for ferric arsenate and its associated dissolved complexes are presented.

Jan 1, 1990

By S. q. Honingh, G. Van Weert

Currently produced zinc-enriched blast furnace dust is stored on site at CORUS IJmuiden. To end this practise, a research program was started in 1996. Four technologies were studied: oxidative autoclave leaching in a chloride medium, fluid bed pyrohydrochloridisation (pyrohydrolysis) to yield lead-zinc-free (hematite) calcine, EAF (plasma) smelting/zinc fuming, and incorporation of the dust in 'iron foundry cupola charges. All aim to remove zinc and lead, recycle the iron residue internally, and produce a saleable zinc-lead product.

Jan 1, 2000

A rotating-discelectrode system was used to evaluate the electrochemical behaviour of Eu(III) during its reduction in NaCl solutions. The solution pH and NaCl concentration have a great effect on the reduction kinetics. The thermodynamic modelling study also revealed that Eu(III) exists in various forms in NaCl solutions. At a low concentration of NaCl, the predominant species is the free Eu3+. Other Eu-chloro complexes become more predominant when the NaCl concentration increases.

Jan 1, 1992

By Alexandre Bonan

The paper reports on the results of a kinetic study on the oxidation reaction of aqueous free cyanide ions with H202, in the presence of Cu(2+) catalyst. The variables and respective ranges studied were the following: (CN) ° = 10 -100 mg/l pH = 10 -11 (H202/CN) mol ratio = 1 -3 (Cu/CN) mol ratio = 0 -0.25 The results lead to the development of a semi-empirical model whish incorporates both the useful oxidation reaction and the parallel alkaline decomposition of H202.

Jan 1, 1992

By J. L. Hill, M. A. R. Sharif, J. Lin

"A numerical algorithm has been developed to simulate the movement, breakup, and entrapment of the oxide film inclusions encountered during the mold-filling processes of aluminum castings. The flowfield is solved using the well-known Marker and Cell (MAC) method by a time marching process. The Volume of Fluid (VOF) method is used to track the free surface boundaries. A kinematic approach is employed to track the movement and breakup of the oxide films on the free surface or in the bulk liquid metal. The computer program based on the proposed algorithm is able to model the flow behavior and oxide film movement, breakup, and entrapment in mold cavities for aluminum castings.IntroductionMetallographic and fractographic studies of the aluminum castings show tangled networks of oxide films in the castings. These oxide films can form in the furnaces or during the mold filling processes. Green and Campbell [I] concluded that the oxide film defects dominate the strength of aluminum castings. The main cause of oxide film entrapment into the bulk molten metal during the casting processes is the surface turbulence. In film-forming alloys, if the surface breaks, due to a drop, a fountain, or a breaking wave, then the surface film is folded over and incorporated into the bulk liquid. The incorporation of surface films leads to cracks in the casting and other defects that are nucleated by the presence of the folded films, such as porosity and hot tears. Campbell [2] estimated that up to 80% of scrap in light-alloy casting is the result of surface turbulence."

Jan 1, 1999

By David R. Sadedin

The highly negative Gibbs free energies of hydrogen atom reactions suggest that refractory oxides such as titanium dioxide should be easily reduced by hydrogen atoms. These reactions appear to be most favourable at low temperatures; oxides should be reducible even at room temperature. Since hydrogen atoms are produced in plasmas containing hydrogen a number of investigators have used hydrogen plasmas of various sorts to test these possibilities for reducing refractory oxides, in particular TiO2. None of these attempts has succeeded, a small degree of reduction being achieved in only a thin layer near the surface. A deeper consideration shows that several factors complicate the reactions expected on the basis of the negative Gibbs free energy. One factor is that the back reaction by water molecules produces molecular hydrogen, not hydrogen atoms, and the metal atoms that have been reduced may be immediately re-oxidised. In plasmas there are complications due to diffusion, thermal and charge boundary layers and charged particle reactions. Interpreting the results of hydrogen atom reactions is difficult. Hydrogen is not detectable by electron dispersive spectroscopy and amorphous products are not determinable by x-ray diffraction. Another consideration is economics. The cost of producing hydrogen atoms has a large bearing on the metals for which hydrogen atom reduction may be competitive. In this paper these factors are discussed, some necessary basic studies are highlighted and the general principles of a laboratory reactor are given, together with the results of tests using ZnFe2O4, ZnO and TiO2 as test oxides.

Jan 1, 2006

By Nagy El-Kaddah, Thinium T. Natarajan

A modeling strategy is presented for computing the electromagnetic field and the shape of the molten metal in electromagnetic confinement systems. This strategy involves the use of a hybrid finite element/integral technique to calculate the electromagnetic field and force distribution in the melt. The free surface shape is determined from minimization of electromagnetic, gravitational and surface tension energies using the Lagrange method of multipliers. This approach was applied to model the electromagnetic levitation melting process. The model was found to accurately predict the measured shape of levitated droplets.

Jan 1, 2014

By Pandey H. D.

The paper describes a fluidised bed ion exchange method for simultaneous removal of phenols and cyanide from the effluent. Use of an eluant enables regeneration of the resin in the continuous operation mode. The breakthrough experiments conducted both on the laboratory scale and on a pilot plant scale have shown that while the level of phenol can be brought down from 462 ppm to about 6 ppm, the free cyanide is almost totally removed. An examination of data indicates that the method can serve the twin objectives of pollution control and phenolic compounds recovery.

Jan 1, 1992

By A. De, J. S. Zuback, T. Mukherjee, T. DebRoy

For successful commercial applications of additive manufacturing, metallic parts need to be defect free, structurally sound and reliable. However, additively manufactured metallic parts are susceptible to distortion, lack of fusion defects and compositional changes. Methods to measure susceptibilities of various alloys to these defects are needed but not currently available. Here we show that the necessary theories can be developed based on a well-tested numerical heat transfer and fluid flow model and decades of research in the field of welding. The proposed theories are validated with experimental results reported in the literature.

Jan 1, 2016

By Tim Robinson, Georges Houlachi, Michael Moats, Marco Ginatta, Michael Free, David Creber, Neale Neelameggham, George Holywell

"Electrolytic processing is used commercially to recover and/or refine metals such as aluminum, copper, magnesium, nickel, and zinc. There are also new and exciting opportunities to utilize electrometallurgy in the production of titanium, lead, and other metals. This paper reviews some of the main technologies that are used to produce and refine metals as well as some of the recent advances and future directions the electrometallurgy industry may implement to meet the challenges faced now as well as those that are likely to be faced in the future.IntroductionElectrolytic processing is used commercially to recover and/or refine metals that include large scale production for metals such as aluminum, copper, magnesium, nickel, and zinc as well as small scale production for metals such as gold and silver. There are also new and exciting opportunities to utilize electrometallurgy in the production of titanium, lead, and other metals. This paper will focus only on electrometallurgical processing of metals with relatively large production markets."

Jan 1, 2012

By Lifeng Zhang

The transport of fluid, heat ,and particles (bubbles and solid inclusions) in flowing molten steel is investigated in steel refining ladles, the continuous casting tundish, continuous casting mold and strand, and steel ingot casting processes. The two-equation k-?? model is used to simulate the turbulence. Multiphase fluid flow is numerically simulated with a Lagrangian-Eulerian approach, an Eularian-Eulerian approach and the Volume Of Fluid (VOF) method. The simulation can predict inclusion trajectories, inclusion removal fraction, free surface waves and other phenomena, which can be used to optimize these important metallurgical operations.

Jan 1, 2006

By C. Beckennann, C. Y. Wang

"Computer simulations of structural and compositional development in equiaxed dendritic alloy solidification are performed using a recently developed multi phase model. The model not only accounts for the transport phenomena occurring on the macroscopic (system) scale, but includes also the grain nucleation and growth mechanisms taking place at various microscopic length scales. In this paper, a numerical technique consisting of a fully implicit control-volume based finite difference method and a multiple time step scheme is developed for accurate and efficient simulations of both micro- and macro-phenomena. Sample numerical results are presented to reveal the effects of liquid now and crystal sedimentation on segregation and the final grain size distribution. In particular, the importance of the interplay between the dendrite microstructure and multiphase now patterns is shown.IntroductionIn recent years, modeling of equiaxed dendritic solidification without convection has experienced considerable progress (1,2]. Nucleation and growth kinetic laws have been coupled with transient heat conduction calculations to determine the solidification microstructure. However, modeling of equiaxed dendritic solidification with melt convection and solid movement has not been attempted so far, largely because of the complications associated with the transport of free equiaxed crystals in the melt. The gravity-induced transport of free crystals is fundamental to the development and extent of the equiaxed zone and also greatly affects the columnar to equiaxed transition. Another possible effect of crystal sedimentation or floatation is to cause severe macrosegregation as well as structural inhomogeneities. The only study available in the literature that accounts for both liquid convection and solid transport is by Ni and Beckermann (3], but deals with globulitic structures (as opposed to dendritic)"

Jan 1, 1994

By Willy Persson

A common feature of the kinds and amounts of impurities present most pyrometallurgical, processes is injection of oxygen to, remove various in the feed. The degree of success of a specific process step relies critically on control of the instantaneous oxygen potential/oxidation stage, throughout the step as well as upon termination of the step. This will, for instance, determine the distribution of impurities between metal and slag. As long as the operation is perturbation free -detailed analysis of all additions and application of advanced models often yield satisfactory control means However, a pyrometallurgical process is seldom free from disturbances, which reduces the accuracy of the static models and leads to inconsistencies in scheduled route might be uncontrollable changes in quality and quantity of feed, operator interventions and shift changes, timing of cranes, lining wear and accretions etc. The implementation of dynamic, control to correct for disturbances and, more generally for process optimization, requires continuous on-line information on, the actual status of the process. The implementation of sensors for continuous process monitoring, e.g., as regards the instantaneously prevailing oxygen potential or oxidation stage, has been hampered by the highly aggressive environment in smelters; This is. where remote-sensing techniques based on optics and spectroscopy, have proven to form invaluable, tools towards the realization of dynamic production control. Since about 15 years Semtch has developed and industrialized a remote-sensing technology, based on ,optics and spectroscopy, for continuous on-line process monitoring and production control of various pyrometallurgical processes. The presentation will discuss applicability aspects with examples and experiences from installations and tests in ferrous and non-ferrous industry. Keywords: Applied spectroscopy, Metallurgy, Process monitoring, Production. Control

Jan 1, 2003

By Upali Siriwardane, Tushar V. Kudale, Naidu V. Seetala

"Cellulose acetate (CA) membranes with 25% triethyl citrate (TEC) as plasticizer were prepared with varying thickness for CO2 gas separation from water-gas-shift (WGS) reaction products. The AFM analysis of the CA membrane showed that the uniform coating had fewer and smaller pores as the film thickness increased, and corroborated by gas permeability studies. The CO2 permeability has decreased faster than CO permeability with the CA/TEC membrane thickness, and findings support that the CA membrane could be used to entrap CO2. Several CA/TEC membranes were also staked to increase the separation efficiency. Positron Annihilation Lifetime Spectroscopy (PALS) was used to estimate the nano-porosity (pore size and concentration) changes of CA/TEC films. PALS results show a decrease in pore size with increasing CA-TEC concentration in acetone, while the pore concentration increases. The PALS results are correlated with the CO2/CO permeability variations as the CA-TEC concentration change.IntroductionHydrogen is one of the main energy sources available for the future advancement of clean fuel technologies especially for fuel cells. Generation of hydrogen and CO2 from Water Gas Shift (WGS) reaction mixtures of CO and H2O is of interest to many researchers since it allows a large scale production of hydrogen [1, 2]. Once hydrogen is produced using the WGS reaction, the output products contain mixture of CO, CO2, H2, and water vapor. Metallic membranes have been used as hydrogen separation membranes [3-6]. As H2 is separated from the mixture using the metal membranes, we need to separate CO2, and find ways of sequestration of CO2 to avoid environmental problems by greenhouse gasses. Polymeric Membranes have been used for CO2 separation [7]. Plasticizer can control the micro-structural properties such as pore size and concentration of polymer membranes [8], which influence the size/molecular weight dependent diffusion rates of the gas molecules. We have used cellulose acetate with triethyl citrate as plasticizer to separate CO2 from the WGS reaction products. Positron annihilation lifetime spectroscopy (PALS) is very sensitive and able to identify different kinds of defects and their agglomerates such as vacancies, vacancy loops, and voids [9, 10]. PALS has been successful in determining the free volume in polymers that influence the properties of the polymers [11, 12]. Microscopic properties of the free volume obtained from PALS have been correlated to macroscopic properties [13, 14]. We used PALS to study the nanoporosity (pore size and concentration) and fractional free volume changes of CA/TEC films, and used to understand the variations observed in the CO2/CO permeability as the CA-TEC concentration in the membranes change."

Jan 1, 2014

By Tsembel Darjaa, Toru H. Okabe, Yoshiaki Umetsu

"With the purpose of extracting molybdenum and rhenium from molybdenum sulfide concentrate; .electrolysis of slurry, solvent extraction and ·precipitation operations were carried out. The slurry of the concentrate in 10 mass% NaCl aqueous solution was continuously circulated into a vertical type 10 stack bipolar electrolytic cell consisted of carbon electrode disks, and, the concentrate was dissolved by electrochemically generated oxidizers at 313 K. The current efficiency for molybdenum dissolution was 73 % after 10 hours electrolysis, and the leach solution was found to contain 0.2 mol/l of molybdenum and 4x10-5 mol/l rhenium. This result shows the dissolution is more than 8 times faster than that obtained using a single cell. The leach solution from electro-oxidation was then subjected to a solvent extraction for rhenium which is then recovered as sulfides. After rhenium separation, molybdenum was precipitated by pH adjustment, and solid MoO3 (H2O)x crystals, free of sulfate, were obtained from the leach solution containing large amount of so42-.IntroductionIn the past, electro-oxidation using a bipolar cell was applied for leaching molybdenite concentrate and ores at U. S. Bureau of Mines [1-3] and also at Bhabha Atomic Research Center [4]. In· these previous studies, Moebious type bipolar cells, in which electrode plates were vertically inserted into the free surface of the electrolyte, were employed and its effectiveness was demonstrated.Recently, the present authors studied on leaching of Mongolian molybdenite concentrate, and the effectiveness of leaching of the concentrate by electro-oxidation in alkaline and acidic NaCl solutions was demonstrated [5]. The leaching reaction during the process can be explained by the 18 electron transfer reaction of molybdenite (MoS2) with the oxidizers produced in-situ by electrolysis of NaCl aqueous solution. Further investigation was made with respect to various process parameters for electrooxidation such as pH, pulp density and temperature of the slurry, and the dissolution behavior of minor elements such as iron, copper, and rhenium [6]. Solubilities of molybdenum in the leach solution at, various temperatures and pH .was · studied, and feasibility of molybdenum recovery by hydrolysis of molybdenum species was demonstrated. By adjusting the pH of the leach solution, molybdenum oxides or hydroxides free from sulfate were successfully obtained from the solution containing large amount of sulfate ion. Rhenium present in the concentrate at a level of several tens of mass ppm was found to dissolve into the leach solution, and co-precipitate with the molybdenum compounds. Rhenium in the leach solutions, therefore, has to be recovered before precipitation of molybdenum, otherwise it is lost in the precipitate."

Jan 1, 2000

By Donald R. Sadoway

The viability of treating certain forms of hazardous waste by direct electrolysis in molten oxides is under investigation. Secondary residue or waste mud produced in the course of chromate chemical production is the focus of attention in this study. The goal is to reduce the water soluble hexavalent chromium either to insoluble trivalent chromium or to chromium metal. Electrolysis tests have been conducted in a high temperature cell containing chromate sludge dissolved in an electrolyte composed of Al2O3, SiO2, CaO, and MgO. Oxygen production on a carbon-free anode has been confirmed.

Jan 1, 1992

By Sunil G. Warrier

A rapid infrared forming technique has been developed to fabricate titanium matrix composites. This technique applies infrared heating to infiltrate titanium alloys into carbon and silicon carbide prepregs. The entire process typically takes 1-2 minutes in an inert atmosphere. The advantages of this technique are that the process is fast, simple, does not require a vacuum or a high external pressure. The process is very economical both in energy conservation and operation costs. This technique has been used to produce void free composites with limited, well controlled fiber-matrix reactions and mechanical properties comparable to currently available titanium matrix composites.

Jan 1, 1993

By Shunsuke Yagi

A surface alloying technique was investigated using alternating pulsed electrolysis in an aqueous solution containing a single metal component for the formation of an Fe-Cr layer on an iron substrate. In the process, the iron substrate was dissolved during each anodic polarization of the pulsed electrolysis, providing iron ions in the vicinity of the substrate, while the Fe-Cr alloy was electrodeposited during subsequent cathodic polarizations. A bright, flat, and crack-free Fe-Cr layer with a composition gradient was obtained using a solution containing a trivalent chromium component and a complex forming agent together with some supporting or buffering salts.

Jan 1, 2006

By Forsén. O.

In this ?paper practical solidification of anodes containing nickel, arsenic, antimony and bismuth is compared with the equilibrium? diagrams and kinetic ?factors. In order to clarify the distribution of the impurity elements in the anode the structures were studied after the solidification and also after the electrolysis of anodes. This examination was carried out with optical microscope, scanning electron microscope and electrochemical measurements. All the nickel is remaining metallic in the copper matrix during the solidification and therefore nickel is dissolved in the electrolysis at all oxygen contents, when the nickel content is 0.25 wt-% or less in the anode. The practical .solidification mechanism of the anodes, when the nickel content exceeds 0.25 wt-%, proceeds by the crystallization of nickel oxides. In oxygen containing copper anodes nickel oxide is verified to crystallize together with antimony in certain conditions and to form a micaceous compound (3Cu2O?4NiO?Sb2O5), which may build up a very harmful floating slime in the electrolyte. Arsenic is strongly enriched along the phase boundaries in oxygen free copper anodes. An intermetallic compound Cu3As is formed when the amount of arsenic in the anode. exceeds 0.7 wt-%. This compound is more noble than the copper matrix. This means 'that a selective dissolution of copper-arsenic compounds takes place. The copper matrix dissolves more strongly than the grain boundaries. The solidification structures of oxygen free bismuth containing copper anodes show clearly the influence of bismuth. Thin bismuth films which are less .noble than the metallic copper matrix, are formed during the solid1ficatton process. As a result of this the?grain boundaries are dissolved faster than the copper matrix.

Jan 1, 1987

By J. P. Gu, C. Beckermann

"Melt convection and macrosegregation in casting of a large steel ingot is numerically simulated. The simulation is based on a previously developed model for multicomponent steel solidification with melt convection, and involves the solution of fully coupled conservation equations for the transport phenomena in the liquid, mush, and solid. Heat transfer in the mold and insulation materials, as well as the formation of a shrinkage cavity at the top are taken into account. The numerical results show the evolution of the temperature, melt velocity, and species concentration fields during solidification. The predicted variation of the macrosegregation of carbon and sulfur along the vertical centerline is compared with measurements from an industrial steel ingot that was sectioned and analyzed. Although generally good agreement is obtained, the neglect of sedimentation of free equiaxed grains prevents the prediction of the zone of negative macrosegregation observed in the lower part of the ingot. It is also shown that the inclusion of the shrinkage cavity at the top is important in obtaining good agreement between the predictions and measurements.IntroductionMacrosegregation in large steel ingots is one of the most well-known and now classical problems in the field of solidification and casting [1]. Commonly found macrosegregation patterns in steel ingots are a positively segregated zone at the top, negative segregation near the bottom in the equiaxed zone, inverse segregation near the ingot surface, V-segregates along the centerline, and A-segregates in the columnar zone [2, 3]. It is well established that the macroscopic transport of species leading to macrosegregation can occur by a variety of mechanisms, including thermally and solutally driven natural convection of the melt in the mushy zone, flow due to solidification contraction, and the sedimentation of free equiaxed crystals. Fredriksson and coworkers [ 4,5] provide recent overviews of the solidification transport phenomena and macrosegregation in ingot casting."

Jan 1, 1999