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By Junhong Noh, Kug Sun Hong, Jung-Kun Lee, Bo Ding

"The photocatalytic splitting of water into H2 and O2 by oxide nanoparticles has received much attention. However, the full potential of photo-catalysts for efficient hydrogen generation out of water has not been fully realized yet due to unresolved limitations including the low electrical conductivity and ineffective carrier extraction. Here, we report composite oxide materials consisting of 1-dimensional (1-D) transparent conducting oxide (TCO) core and TiO2 shell. Highly conductive ITO nanowires were grown on a flexible SUS mesh as a core component. The photoelectrodes consisting of these 1-D nanocomposites have increased carrier mobility due to the TCO core, while the TiO2 shell provides the photocatalytic functionalities. In addition, the built-in-potential at the interface between TCO core and the TiO2 shell improves the collection of charge carriers from TiO2 to TCO. These factors altogether contribute to increasing the photocurrent of the device under light.I. IntroductionPhotocatalytic behavior of semicondcutors has been extensively explored since it was discovered in TiO2 in 197Os. When TiO2 is exposed to UV light, the light is absorbed and electron/hole pairs are generated in the conduction and valeence bands. Holes in valence band will oxide/mineralize pollutant target directly or indirectly (via mediator hydroxyl radical). If the adsorbed A is O 2, O 2 will react with electron from conduction band to generate hydroxyl radical as described in the second set ofreactions. The photocatalytic reaction is schematically explained in Figure 1.Photoelectrochemical (PEC) cells using the photocatalytic reaction have attracted emerging interest as a potential route to convert solar radiation into useful forms of energy by reaction such as water splitting to generate hydrogen1 or the reduction of carbon dioxide.2 Another application ofphotocatalysis is water splitting and CO2 reduction, both of which utilize the electrons that are optically excited to the conduction band. 3•4 For this purpose, the conduction level of the semiconductor should be higher than hydrogen production level (EHZ1HZO) while the valence band should be lower than water oxidation level (Eo21112O). Electrons and holes will be generated on the semiconductor site, and holes generate O 2 at semiconductor site, while electrons will migrate to counter electrode to execute reduction forming H2. In addition to that, materials should be chemically stable to resist photocorrosion and have long lifetime of electron/hole pairs. TiO2 is a suitable material from the viewpoint of band arrangement and chemical stability requirement"

Jan 1, 2012

By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO = Zn(g) + CO2 This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction does not occur at an appreciable rate, as is expected from thennodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide coneentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By Nobuaki Sato

The electrical conductivity, k, of pure and sodium doped sulfur melts was measured with and without ultrasonic waves at temperatures ranging from 140 to 340° C by the two probe method using an ultra high resistance meter. The II: value of the pure sulfur melt with irradiation jumped at around 170°C by an order of 102 after which it monotonically increased from 10-5 to 10-4 (omega) 1cm-4 with an increase of the temperature. The addition of the sodium metal to the sulfur melt was found to cause a larger jumping in the II: value. The II: value increased with the increase of Na proportion in the melt. For a 10 mol% Na doped sulfur melt it was as high as max. ~30 (omega) 1cm-1 above 180°C under the irradiation of ultrasonics.

Jan 1, 2003

By D. G. C. Robertson

The thermodynamics and kinetics of the reactions involved in fuming zinc from oxide slags using coal or coke were first studied in 1955 and have been the subject of many investigations since that time. The key reaction is ZnO(in slag) + CO Zn(g) + COl. This paper will review the some of the recent work, and will add new insights obtained in experiments carried out by the authors. In the first series of experiments it was shown that the reaction 2Fe2+ + ZnO = 2Fe3+ + Zn(g) or 2FeO + ZnO = Fe2O3 + Zn(g) does not occur at an appreciable rate, as is expected from thermodynamic considerations. In the second series of experiments it was shown that zinc does not fume from the slag at a significant rate unless a reductant has been added. This again is in accord with thermodynamic considerations, but is in contradiction to some of the experimental results reported in the literature. A third series of experiments was carried out with excess coke being present, so that the rate of supply of reductant was not in any way controlling the rate. The kinetics of zinc oxide reaction were then found to be independent of the zinc oxide concentration, but increased with increasing basicity, and temperature. The presence of high concentrations of FeO in the slag also improves the kinetics. At low zinc oxide concentrations iron oxide reduction occurred in parallel with zinc oxide reduction. We propose that (under the conditions of this work) the kinetics were controlled by a chemical step, namely the rate of desorption of an adsorbed CO2 species. This is the same mechanism as reported by Belton and co-workers for the kinetics of the reduction of FeO. This explains why the reduction of metal oxides in slags by hydrogen is often faster than by CO.

Jan 1, 2003

By R. Moreau, V. Uspenski, K. Messadek, Y. Delannoy

Experiments and numerical simulations have been carried out to investigate the properties of quasi-2D turbulence. A new mercury model experiment has been built and tested in a uniform magnetic field up to 6T, (Ha~ 1000), ensuring a better two-dimensional behaviour than earlier versions (Alboussiere et al., 1997), limited to 0.2T. The quality of the experimental results has been improved in order to get wave number spectra (instead of frequency spectra) and higher signal over noise ratio (due to the higher magnetic fields). In parallel, some two-dimensional "direct" numerical simulations were performed using a commercially available code to solve a 2-D motion equation involving a source term to model the Hartmann layer. This term is derived from the condition of closure of the electric current, which allows to transfer the Hartmann effect into the 2D-core flow without simulating the layer itself (Sommeria & Moreau, 1982). No subgrid scale modelling is needed in such a two-dimensional situation where most of the energy is carried by the large scales.

Jan 1, 1999

By Vadim J. Jabotinski

This paper describes several areas of application for electron beam processing of materials. The technology and use of electron beam systems in gas phase synthesis reactions are described. Gas phase reactions may be used to generate ultra- fine metal or ceramic powder that are very pure and crystalline. Among the examples presented are: the generation of nanometer sized metal powders and the gas phase synthesis of silicon carbide for silica and methane. The experimental system is described and future theoretical and experimental objectives are identified.

Jan 1, 1998

By KAGAN BENZESIK, Onuralp Yücel, Mehmet Bugdaycı, Ahmet Turan

ZrB2 and B4C are one of the most significant advanced ceramics. They are being used in various industrial areas from space technology to nuclear industry owing to their physical properties such as high melting point, high thermal/electrical conductivity and low density. Present study was conducted in two main stages: Self-propagating high-temperature synthesis (SHS) reactions and leaching. ZrO2, Carbon black, B2O3 were used as starting material to produce ZrB2-B4C powders by SHS. Also Mg powder was used as the reductant. The reaction mixtures (approximately 100 g) were mixed thoroughly 15 minutes in a turbula mixer and charged into Cu crucible and compacted. W (tungsten) wire was placed at the top of copper crucible and the reaction realized by passing current through the wire. After initiation, a highly exothermic reaction became in a self-sustaining mode and propagated throughout the SHS mixture. The samples were characterized by using AAS and X-Ray Diffraction.

Jan 1, 2016

By J. M. D. Wilson

An analytical program using a combination of SEM-based image analysis techniques is developed for automated modal analysis of ores containing silicate and other gangue minerals. Previous knowledge, gathered by means of either optical microscopy, X-ray diffraction, SEM, or electron microprobe analysis is used to establish discrimination criteria in the image analysis program. The program initially discriminates minerals on the basis of their relative grey values in a backscattered electron image. For those minerals which have overlapping grey levels the minerals are identified by the program using energy dispersive X-ray spectrometry with X-ray counting for twelve or more elements. This technique is useful to quantify ores in which the gangue minerals are numerous. Two cases of application are presented.

Jan 1, 1999

By Joseph C. Milbourne

Tetra Technologies CCIX? (continuous countercurrent ion exchange) system has been involved in a wide range of uranium concentration, separation and purification applications over the past 40 years. Uranium ion exchange applications have ranged from the treatment of copper heap leach solution containing 5 parts per million of uranium to the treatment of high strength sulfuric acid solutions containing several thousand parts per million of uranium. The flexibility and the countercurrent mode of operation and other unique features of the CCIX? have resulted in successful uranium recovery from these solutions and many others.

Jan 1, 1995

By Entov Vladimir M., Gilmer R. Burgos, Andreas N. Alexandrou

"Processing of metal alloys in their mushy state represents a new trend in metal processing. As part of this process, known also as thixocasting, a specially prepared slurry at a temperature in the mushy region is injected into a die. Parts produced using this technology offer better mechanical properties than those produced by casting, and comparable to those of forged alloys.In thixocasting, semisolid slurries are highly concentrated suspensions of rounded rosette-like crystals in eutectic liquid. The mechanical behavior of the slurry is determined by the structure and properties of the skeleton formed by the alpha phase particles. The skeleton structure is almost never at equilibrium, and its evolution is, governed by a number of kinetic phenomena of different c11'aracteristic time-scales. Therefore, the skeleton structure depends on the mechanical and thermal history of the material. As a result of these kinetic processes, the rheological properties of the material, such as effective viscosity and yield stress, decrease with structure breakdown, and increase with its development. In the present investigation, the behavior of semisolid slurries during processing is modeled using the conservation equations, and a Herschel-Bulkley fluid model. The rheological parameters are assumed to be functions of the solid volume fraction, and of a structural parameter that changes with processing history. The evolution of the structural parameter is described by a first order kinetic differential equation that relates the rate of build-up and break-down of the solid"

Jan 1, 2000

By R. C. Hubli

Copper (II) chloride has proven to be an efficient lixiviant for copper sulphide ores and secondary sources of copper such as scrap. Nickel sulphides are generally associated with copper ores and copper-nickel matte is an intermediate product of processing mixed sulphides. While the copper species in aqueous chloride media are present as chlorocomplexes, the presence of nickel as Ni++ offers effective separation between the two by solvent extraction techniques. Oxidation of millerite by cupric chloride in sodium chloride solutions has been studied as a function of rate of agitation, leaching time, temperature, acid concentration and total initial cupric concentration. The reaction has a 1/2 order of dependence on initial cupric concentration in the range of 0.0 to 0.5M. The activation energy for the temperature range 333 -363 K has been found to be 59.2 kJ/mol with chemical reaction at the unreacted mineral surface as the rate controlling step. The rate expression, according to the shrinking-core model, for initial cupric concentrations between 0.0 to O.5M, is evaluated as

Jan 1, 1996

By J. E. Klein

Bench scale tests using a stack of ten whole SAES St909 pellets, 6 grams, to crack methane have been completed with pure methane feed. Test conditions ranged from 600 to 800°C at 101 kPa (760 ton) with a methane feed rate of ten sccm. Methane reformation tests, test where hydrogen was passed through a St909 bed after cracking methane, were performed to determine if and how much methane can be generated under "reformation" conditions. Phase structure determinations of St909, composed of a ZrMnFe alloy with aluminum used as a pellet binder, after methane cracking were complicated by the number of materials that can be formed by the elements in the St909 and the carbon from methane cracking. It was determined that the aluminum not only alloys with the Zr, Mn, and Fe in the St909 alloy, but also forms aluminum transition metal carbides in addition to ZrC as the carbon content and the temperature of the St909 increases. Some A14C3 was also found in some pellets. Passing hydrogen over St909 pellets after methane cracking formed methane at various rates in the temperature range of 600 to 800°C. Temperatures of 800°C gave the best methane cracking performance and efficiencies decreased rapidly with temperature.

Jan 1, 2002

By R. F. Hammen

Copper is one of the most widely used metals in industrial processes and is also present in most mining operations. Extraction of copper from solutions often proves difficult due to the presence of complexing agents. ChromatoChem, Inc. has developed a Solid Phase Extraction (SPE) support (HiPAC) for removal and recovery of metals from wastewater. The HiPAC SPE support employs chelating agents covalently coupled to a long linker molecule. Several solutions containing copper and complexing agents were tested including 1) copper and carbonate, pH 9.8, 2) mixed metals and anions with copper and cyanide, pH 11, and 3) copper and the chelating agent EDTA, pH 11. The copper was extracted from solutions one and two at high pH, but the EDTA containing solution needed the pH lowered to make the copper available for capture. In each example, the copper concentration was significantly reduced by HiPAC SPE treatment.

Jan 1, 1994

By Neeraj Saxena, Madhu Huggahalli, Jerry Bednarski, Ken Grieshaber, David Stoffel

"The use of oxy-fuel burners in secondary aluminum melting applications offers several advantages over air-fuel burners including reduced fuel consumption, faster charge to tap times and lower NOx emissions. Their successful, safe and economical use in a furnace depends on several factors and considerations such as burner and flue placement, metal circulation, charge practices and the type of refractory used in the furnace.These factors required in the successful conversion of furnaces from air-fuel to oxy-fuel based burners are discussed in this paper. Critical parameters are identified and examined using computational fluid dynamics (CFD) simulations. Parameters are estimated via laboratory testing and validated through trials performed at commercial installations. Guidelines and a simplified approach to estimate a priori the economic impact of converting from air-fuel to oxy-fuel are presentedThe final products of this research are simplified and validated tools for modeling aluminum furnaces. These include improved heat and energy balance models and parameterized CFD solutions which provide rapid customization to individual furnace configurations. These tools provide field engineers with immediate and accurate predictions of performance, allowing for repeated precise scenario analyses."

Jan 1, 2001

By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

By K. Kalgraf

The motion and stability of the metal/electrolyte interface is determined by Navier-Stokes equation. The equation may be decomposed into two independent equations by taking the divergence and curl of Navier-Stokes equation. The divergence determines the motion and stability of magneto-gravitational waves. The curl of Navier-Stokes equation gives an equation containing only velocity and magnetic field, and states that the magnetic field is driving a circulation pattern in the cell, and this magneto-flow has its own stability conditions. The waves are called Alfven waves, and their stability properties are related only to magnetic field and geometry.

Jan 1, 2001

By Helena Byrdziak

KGHM Polska Miedz SA, in existence since nineteen seventies, operates three underground mines and three smelters with total production of over 400 000 mtpy of electrolytic copper. Its impact on the environment, very serious in the past, has been gradually reduced. While in general emissions into the air and water have been brought under control, attention recently has shifted to the disposal of wastes and residues. The main streams of wastes are flotation tailings, slags and dust captured from the dedusting systems. Much effort has already been expended and is still being spent to utilize this waste for by-products production or to dispose of it within the process by recycling. The most effective measures taken up thus far, as well as present activities directed at tailings disposal, are presented.

Jan 1, 1997

By M. C. Ruiz

This work outlines the results of leaching studies on a copper concentrate containing chalcocite (Cu2S) and digenite (Cu9S5) with an acid saline solution of cupric chloride oxygenated at ambient pressure. The variables studied included the stirring speed, concentration of cupric ions, concentration of HCI, concentration of chloride ions, oxygen flow rate, temperature and time. The leaching system was found to be very effective for the dissolution of the concentrate. Over 95% of the copper was dissolved in 30 minutes with negligible dissolution of iron. The dissolution of copper increased with the stirring speed up to about 400 rpm and depended little on the total chloride concentration. The oxygen flow rate affected the dissolution of copper only below 0.1 1/min. The concentration of HC1 did not influence the dissolution providing its was sufficient to avoid the precipitation of copper oxychloride. The study of the effect of the temperature showed a maximum in copper dissolution around 90 "C

Jan 1, 1997

By S. W. Ip

Over the years, the importance of surface and interfacial phenomena has been neglected by the copper-nickel industry. As a result, little data on the surface and interfacial tension of the Ni matte and slag system are available in the literature. In view of the scarcity of information in this area, the surface tensions of the Ni-Fe-S system together with the Ni-Fe-S and fayalite type slag system were measured using the sessile drop technique. Drop images were obtained by X-ray radiography. For the Ni-Fe-S system, the results showed that the surface tension of the matte increases with matte grade. The surface tension behavior with changing matte grade showed a slight negative deviation from ideality. This indicated that FeS is slightly surface active in the nickel matte system. Results also indicated that small increase in sulphur content in the matte can decrease the surface tension quite significantly. The measured surface tension of the Ni-Cu-S system showed a linear relationship with the Cu2S content in the matte. The surface tension decreased with Cu2S content. Interfacial tension measurements showed a similar trend. That is, interfacial tension increased with increasing matte grade. The presence of MgO (-1.5%) and A12O3 (-6%) in the slag does not affect the interfacial tension value. Effects of matte surface tension on phenomena such as entrainment of matte in slag and infiltration of matte into refractory pores are discussed. The calculated flotation coefficients indicated that flotation of nickel mattes cannot be avoided by changing the matte grade. Filming of matte on bubbles can occur below a matte grade of about 19% Ni3S2. As for infiltration, refractory bricks containing high Cr2O3 will be easily wetted by matte regardless of matte grade. Therefore, bricks containing high Cr2O3 can easily be infiltrated by liquid matte.

Jan 1, 1993

By Stavros A. Argyropoulos, Henry H. Hu

"The assimilation of exothermic additions in liquid metals exhibit an array of unique coupled heat, mass and momentum transport phenomena. These phenomena are further complicated by the presence of a moving boundary.This paper describes a) A mathematical model which simulates the complex phenomena, and b) An extensive verification of the mathematical model. The SIMPLER algorithm was employed to solve numerically the pertinent partial differential equations. The computational results indicated that the exothermic heat of mixing led to a rapid increase in temperature around the moving boundary, which produced an enhanced convective flow in the liquid phase. The intensification of fluid flow around the moving boundary resulted in an acceleration of the melting process.Verification of the model was carried out in two contexts. The first was, in a low temperature physical model consisting of ice immersion in different sulfuric acid solutions. In this physical model, both temperature and velocity measurements were carried out. The model results were compared with experimental measurements and they were found to be in excellent agreement. The second context employed high temperatures, involving the assimilation of silicon in high carbon liquid iron. The model was also applied to predict fluid flow, heat and mass transfer for these high temperature experiments and a good agreement was obtained.In addition new dimensionless heat transfer correlations that quantify these complex phenomena will be presented."

Jan 1, 2001