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By P. Schloth, H. van Swygenhoven, N. Chobaut, J-M. Drezet

"In the current trend toward thicker aluminium plates, a major concern is the stress build-up during quenching which causes distortions during machining. Indeed, cooling rates are not high enough, especially at the core of such thick plates, to prevent any precipitation and quench induced precipitates lower the hardening potential. Multi-scale modelling is required when predicting macro-scale stresses after quenching for thick heat treatable aluminium components. The reason is the instantaneous strong coupling between phase precipitation at the nano-scale and material hardening due to precipitation or softening owing to solute depletion at the microscale. For thick parts, quenching intensities decrease when going from the skin to the core of the component, thus introducing a gradient of nanostructure and consequently a gradient of mechanical properties. In addition, large thermally induced deformations lead to high macroscale residual stresses although part of them is relaxed by plastic deformation. These stresses have been measured in water quenched thick plates of 7040 and 7449 aluminium alloys using neutron diffraction and layer removal techniques and the results when compared with a thermomechanical finite element model of quenching highlight the influence of precipitation.IntroductionIn the processing route of heat-treatable aluminium alloys (AA), a critical step is quenching from the solutionizing temperature. High cooling rates are desired, as they avoid formation of coarse precipitates, which reduce mechanical properties. Fast quenching, however, cannot be achieved in the centre of thick components, where the quenching rate can be more than one order of magnitude lower than at the surface. The existence of a thermal gradient between core and surface leads to a differential thermal deformation which is accommodated by elastic and plastic deformation to comply with the compatibility of deformation. Whenever the material yields, especially at high temperature when the yield strength is low, residual stress remains after quenching due to the irreversibility of plastic deformation. After quenching, the plates are in a state of residual stress that causes unacceptable distortions during machining and may reduce service life drastically. Since stress relaxation is negligible during ageing treatments [1 ], agehardened aluminium parts are usually stress relieved prior to ageing. This is typically achieved by applying plastic deformation: stretching from 1.5 to 3 % in the rolling direction (L) can reduce the internal stresses by a factor of approximately 10 [2, 3]. However, complex geometries or thicker components like thick sheets require other approaches. Reducing the quenching rate by using boiling water for instance leads to lower residual stresses [1, 4]."

Jan 1, 2013

By Milton Manrique, Edgar E. Vidal, Patrick R. Taylor

"Ultrafine zirconium carbide powder has been synthesized using zircon concentrate and methane in a thermal plasma reactor. The effect of several experimental variables, such as power used and zircon particle size, on the conversion has been studied. A thermodynamic analysis of the possible reactions and stable compounds was performed. A mathematical model that describes the in-flight decomposition of zircon particles was developed based on a description of the temperature and velocity profiles calculated in the reactor. It was shown that the formation of zirconium carbide from zircon and methane is thermodynamically possible. Complete 'vaporization of zircon in the reactor is predicted when the particle size is below 45flm and the effective power entering the reactor is 15 kW. The powders were collected and characterized by XRD, SEM, TEM and chemical analysis using ICP. Results of the product analysis indicated the presence of zirconium carbide, zirconium oxide, silicon carbide and silicon oxide.IntroductionIn recent years there has been an increased interest in the production of nanometric sized powders of ceramic materials for use in advanced materials applications. One possible method to produce these powders is with a thermal plasma reactor, which offers high temperatures and fast quenching rates. This technology has been called - Thermal Plasma Synthesis - [1].Zirconium Carbide (ZrCx) has typical properties of transition metal carbides: elevated hardness - between alumina and diamond - a high melting temperature of 3420°C and high chemical stability at room temperature [2]. ZrCx has a Bl crystal structure with deficiencies in the number of carbon atoms in the cell with x between 0.6 and 1 [3]. Different methods have been used to produce ZrC, one method is by direct reaction of zirconium hydride or halide with carbon. Other methods used are direct reduction and carburization of zirconium oxide (Zr02) and reaction of metallic zirconium with a caburizing gas such as acetylene [3]. Recently small films of ZrC have been obtained using a sputtering device [4,5]. ZrC has been used in nuclear plants as a low neutron absorbing and high mechanical resistant refractory material and also as a constituent in cathodes made of UC-ZrC [6]. It is also used in the form of tubes, boats and crucibles to handle molten metals and as part of electronic devices used for thermoionic transducers. Recently ZrC has been used along with zirconium diboride (ZrB2) to produce composite materials [7,8]."

Jan 1, 1996

By S. Ozbilen

"Al-Li binary alloys with nominal Li contents of0.15, 1.1and2.8 (in wt%) were aged naturally at room temperature for two months, aged at low temperatures ( 65 and 1 OOEC) for up to 2 months and aged artificially at 190EC for 4 days after water quenching to 25EC following solutionizing at 530EC for 20 minutes. Ageing behavior of these binary alloys were studied by Vicker's Hardness measurements and DSC thermal analysis. Thermal analysis results indicate the formation of GP zones of Al-Li system in Al-2.8wt%Li binary alloy. In the same alloy, rapid quenching from one phase region (a) gives rise to precipitation of small o' particles in a matrix (a) with still high supersaturation. During ageing of this alloy below lOOEC an additional transformation, i.e., GP zone formation occurs proceeding at a very high rate which is described on the basis of the theoretical analysis for the quenched Al-Li system proposed by Khachaturyan et al [6]. Ageing at temperatures below 11 OEC takes place slowly by the formation of small d' particles of lower thermal stability than the quenched-in d precipitates in addition to GP zones resulting in an increase in hardness compared to water quenched samples. During artificial ageing, GP zones transform by dissolution to d' precipitates while d' particles already in the microstructure coarsen during under aged condition at which hardness increases with time till peak aged condition.IntroductionIn binary Al-Li alloys the d' (Al3Li) fully coherent internally ordered inetastable phase of Li2 structure with a=0.4038d [1-5] forms homogeneously between 120 and 190EC before the formation of stable d' (A!Li) phase and cause the superior mechanical properties. This is due to an appreciable age hardening effect resulting because of the d' precipitation during ageing [1]. The response of d' to decomposition and its formation kinetics have been studied previously and it is believed that the decomposition of the a-supersaturated solid solution occurs in a two stage process; i.e., a 6 d' (Al3Li) 6 d(A!Li). Khachturyan et al [6] theoretically investigated precipitation of the d' phase and gave an interpretation of the transformation paths of the quenched Al-Li alloys. They predict that the disordered supersaturated solid solution congruently orders, and then the uniformly ordered solution decomposes into ordered regions that differ in Li-content. Finally, ordered d' phase forms in the disordered matrix."

Jan 1, 1998

By M. Bhattacharya, A. Dutta, P. Barat

"Pinning of dislocations at nanosized obstacles like precipitates, voids and bubbles, is a crucial mechanism in the context of phenomena like hardening and creep. The interaction between such an obstacle and a dislocation is often explored at fundamental level by means of analytical tools, atomistic simulations and finite element methods. Nevertheless, such studies fail to predict the effect on the overall plasticity on account of insufficient information about the underlying statistics of this process comprising a large number of dislocations and obstacles in a system. Here we propose a new statistical approach, where the statistics of pinning at idealized spherical obstacles is explored by taking into account the generalized size distribution of the obstacle along with the dislocation density within a three-dimensional framework. The application of this approach has been demonstrated for dislocation pinning at nanovoids in neutron irradiated type 316-stainless steel.IntroductionPresence of nanoscale obstacles like precipitates, voids and bubbles play a crucial role in determining the deformation behavior of a crystalline solid on account of the interactions between the line defects and such localized obstacles. In the context of the glide motion of dislocations, the obstacles can offer resistance to a moving dislocation, thereby causing a hardening effect [l-3]. In some other cases, inclusions like voids and bubbles can affect the rate of dislocation climb through diffusive [4] and non-diffusive [5] mechanisms. Over the last few decades, numerous studies have been performed to gain an insight of the dislocation-obstacle interactions at a fundamental level. These include the interactions responsible for the hardening effect, in addition to those pertaining to the non-conservative motion of dislocations.Although the elementary mechanisms of the various dislocation-obstacle interactions have been vastly explored and understood by means of analytical theory and numerical simulations, it remains difficult to quantitatively understand their effects on the macroscopic deformation behavior. This is due to the fact that their influence on the gross plastic deformation of a bulk sample would be the collective outcome of a large ensemble of such interactions. As a result, it becomes infeasible to predict the bulk deformation behavior of a material until the statistics of pinning of the dislocations at the localized obstacles is available. In the context of precipitate hardening, some well known attempts to extract the pinning-statistics were made by Friedel-Fleischer [6] and Mott [7] by analytical means, which were later tested through simplified 2-dimensional in-silica modeling [8]."

Jan 1, 2014

By A. Tsubouchi, F. Noguchi, T. Takasu

"A high current density operation is desired to improve the productivity in copper electrorefining. However, a lot of problems still remain such as passivation at anode, dendritic deposition at cathode and impurity behavior during the electro refining.Effects of the current densitY on the morphology of copper deposition on the cathode, and passivation at the anode were investigated at various fluid velocity of electrolyte in the present study.Although a granular appearance of the copper deposition was obtained with increasing high current density, it was depressed by an increase of the fluid velocity of the electrolyte. A uniform deposition on the cathode was also observed when the fluid velocity of the electrolyte become higher. It was ascertained that passivation at the anode was suppressed by circulating electrolyte during electrolysis. INTRODUCTIONIt is desirable to operate at high current density in copper electrorefining in order to improve plant productivity without enlarging the size of electrodes(1). However, there are many problems in copper electrorefining at high current density with the usual commercial practice, for example, anode passivation, dendritic deposition and an increase of impurities in the cathode.In general, it is effective to agitate the electrolyte in order to suppress these problems(2). Smith et a1.(3) have performed electro refining experiments at various current densities in the range of 8 to 32 Aldm2 and at electrolyte fluid velocities in the range of 40 to 120 mlmin, and they obtained well consolidated, void free copper even at high current density in a high electrolyte velocity. However, they did not discuss the recovery ratio and the passivation behaviour at the anode. Walsh et a1.(4)(5)(6) experimented with the rotating cylinder electrode, and ascertained that electrolysis can be carried out at high current densities under the condition of pure electrolyte.With regards to anode passivation, there are several papers by previous workers(7)(8). Our group ascertained the process of producing anode slime during electrolysis(9). However, these experiments were carried out without forced circulation of electrolyte. Therefore, in the present study, to solve these problems, we electrolyzed at current densities in the range of 4 to 50 Aldm2 with circulating electrolyte in the range of 0 to 48 mlrnin. The effect of electrolyte fluid velocity on the surface morphology of deposited copper at cathode and passivation at anode were investigated when electrolysis were carried out with circulating electrolyte at high fluid velocity and at high current density."

Jan 1, 1997

By Liangying Wen, Feng Xia, Chenguang Bai

"The situation of the Ti-V-Magnetite samples reduced with microwave has been investigated in laboratory. Firstly, the paper focuses on the heating behaviors of vanadium-titanium magnetite and characteristics of carbothermic reduction of V-Ti-magnetite in the microwave field. The effect of concentrate's size, quality on heating behaviors and reduction processes were researched. Results show that microwave heating may be a new heating resource replace of carbonic combustion reaction in reducing reaction. When the allocation of carbon is (16.7-30)%, carbothermic reduction of V-Ti-magnetite in the microwave field can proceed; with the increasing of carbon mixed, the metallization rate increases; and Fe, V can be reduced from their oxides in the microwave field; Titanic low oxide can be reduced from TiO2.1. IntroductionThe resource of Ti-V-Magnetite is abundant in the western area of Panzhihua in China, so far a mineral deposit of 4.64 billion tons have been proved up, it contains 14.75 million tons of V2O S which accounted for 87% of the vanadium and 5.93 hundred million tons of TiO2 accounted for 94% of the titanium resource respectively in China. The previous study proved that the major composition of mineral of the Ti-V-magnetite are Ti-magnetite, limonite, iron spinel, magnesium spinel etc, and the main elements of the Ti-V-magnetite in this area are Fe, Ti, V, Cr, Co, Ni, Ga, Sc etc[1] Due to the restrict of the BF-BOF process technical, during the smelting of the iron, the level of extracting the vanadium, titanium as well as other metal elements is limited. This results serious wasting of resources. To develop a new reduction process of Ti-V-magnetite is on the agenda, the microwave assistant reduction could meets this need, based on its characteristic of easy controlling of heating rate. To make use of the microwave energy to substitute the released heat sources of carbon combustion with air, use the solid phase state reduction at a relative lower temperature, make the beneficial element in Ti-V-magnetite transferred into the metal phase, then separated from the impurity. It is well worth to point out that once the microwave based reduction method has its industrial scale, it will take an outstanding position by its less release of carbon dioxide. This new environment-friendly process will play a vital role in the development of social industry and economy."

Jan 1, 2008

By Nagy El-Kaddah

"One of the emerging technologies for the production of ultra-clean metals is electromagnetic filtration. The theory and the mechanism of electromagnetic separation of inclusions from molten metal are briefly reviewed along with basic electromagnetic separation systems. This paper focuses on inclusion removal in the induced current separators, with specific reference to a new separator developed at the University of Alabama. A simple analytical model is presented for the analysis of particle separation in such a system. The role of the applied magnetic field on inclusion removal will be discussed. It is shown that particle velocity increases exponentially with increasing magnetic field strength. At moderate field strengths, the velocity of 50 to 100 u. inclusions· are an order of magnitude larger than those achieved by buoyancy. The separator developed at the University of Alabama is described together with experimental results of laboratory and large scale experiments on purification of molten aluminum. These results demonstrate the capability of the system for producing super-clean metals.IntroductionThe nature of extraction, refining and processing of metals is such that oxides and other non-metallic particles will always be present. This is due to the highly reactive nature of metals with oxygen and other non-metallic elements. The presence of these type inclusions in metals, even in minute amounts, can seriously flaw the reliability and performance of the final product. They not only reduce the strength and the stiffness of the metal/1/, they are the reason behind many of manufacturing defects such as porosity in castings, surface and internal cracks in continuously cast ingots and rolled products, etc., which act to cause premature failure of manufactured parts. In fact, for critical applications such as turbine blades, there is virtually no tolerance for inclusions above ten microns in size /2/. Therefore, removal of inclusions from the liquid metal is an essential processing step.The demand for cleaner metals has brought major changes in the technology and practice of metal refining and casting. Inclusion removal from the melt is currently achieved by passing the melt through a series of melt treatment systems, including induction stirring furnaces, argon-stirred ladle, and ceramic foam and deep-bed filters /3,4/. These systems are generally capable of removing all inclusion particles above 50 microns in diameter, which meets current cleanliness requirements for most applications. However, they may not be able to meet the projected cleanliness levels for critical applications due to kinetic and operational limitations of these systems in removing smaller particles /5/."

Jan 1, 1996

By R. A. Masumura, C. S. Pande, D. Agassi

"Grain size has a different effects on the critical current density (Jc) of high and low transition temperature (Tc) superconductors. In high Tc superconductors, the critical current density Jc across grain boundaries depends sensitively on the misorientation 8. It was pointed out by Pande that this dependence is directly related to dislocation structure of the grain boundaries i.e., it is due to dislocation cores and stresses. These ideas are developed further in this paper leading to a relation between Jc and 8. The analytical result is compared with the experimental results on bicrystals and used to explain the difference in behavior between high and low Tc superconductors.IntroductionThe grain size distribution and its evolution with time and temperature is important in determining the properties of high and low transition temperature (T c) superconductors. The distribution is a convenient function to characterize the processing of a high Tc material during sintering. For example, it is known that the maximum density of ceramic materials is obtained when the grain growth is reduced but grain boundaries are still mobile. For practical superconductors, the processing parameters are selected to achieve optimum properties: highest possible T c and maximum critical current (Jc). In terms of an average grain size, the requirements for optimum T c and Jc are sometime in conflict. In A15 type superconductors and even in NbTi, larger Jc have been measured in smaller rather than larger grain sized material. Conversely, in a high Tc materials like YBa2Cu307, higher Jc have been found in larger grain sized or single crystal specimens.Extended defects such as grain boundaries in low T c superconductors can be effective pinning agents for magnetic flux lines, thereby increasing the transport critical current density of these materials [1]. On the other hand, the transport critical currents in polycrystals of high Tc superconductors such as YBa2Cu307 is found to be relatively small (much smaller than those in single crystals of the same material) [2]. It is now known that grain boundaries in high Tc polycrystals can in many cases form ""weak links"" reducing the critical current density across them. This phenomenon can be studied more precisely by experiments on bicrystals, where there is only one grain boundary. It is found that the critical current density is quite sensitive to the misorientation angle of the bicrystal [3,4]. Although the original experiments were conducted on YBa2Cu307, other Tc superconductors have been shown to give the same result [5]."

Jan 1, 1994

By Alexander I. Raitchenko

"Although one takes into account only thermal expansion usually at analysis of convection onset, the essential factors include magnetic and electric fields. If Lorentz-force originating from intercrossed electric and magnetic fields' action is directed downwards its effect strengthens gravitational action, and value of critical Rayleigh number (limit value for convection onset) must decrease; increasing of critical Rayleigh number should be observed in case of Lorentz-force directed upwards. Extent of such an influence is determined by relation of Lorentz-force to hydrostatic head in gravitational field. Competition between electromagnetic force due to nonuniformity of electroconductivity (on account of its temperature dependence) and electromagnetic buoyancy force may have ambiguous effect: both increase or decrease of critical Rayleigh numbers. Proposed conception is applicable to analysis of situations in liquid conductors and conductive gases.IntroductionStatic or dynamic situations in fluid media are determined besides properties of these media by a variety of external influences. However one correlate~ the onset of the convection and its development with influences of the minimum quantity of external causes frequently. Most known and usual factors are the gravitational and temperature fields. The number of processes includes heat generation in media volume, and theoretical analysis in these cases takes into account this interior heating together with boundary temperature conditions. But explanation of many natural and technical events is not complete and cogent within limits of thermo-gravitational terms. The whole complex of acting factors which influence convective processes in techniques and nature is greater in many cases. In particular the action of · electromagnetic nature often has not less importance than gravitation one. Stability or instability of a current layer in the plasma must be determined by non-uniformity of electroconductivity owing to non-uniformity of temperature [1]. The presence of Joule dissipation in the plasma through which the electric current flows stipulates initiation of origin of overheated instability [2]. It is known that electroconductivity of arc in the boundary zone changes sharply with radial distance [3], and this must influence its stability essentially. If the intercrossed electric current and magnetic field begin to act on an electroconductive fluid besides the non-uniform temperature field and the gravity, the conditions for the onset of the convection change radi- . cally: both the temperature field and their solutions have to be changed also. The analysis of equilibrium single-time correlation functions of fluctuations must be employed for situations with enlarged number of factors as this was in case for the Rayleigh-Benard problem where the object is a horizontal layer of liquid. This can be carried out by taking into account the detached forces' correlations [ 4, 5]"

Jan 1, 1999

By Erich Hovestädt, Hans-Jürgen Odenthal, Christian Wuppermann, Herbert Pfeifer, Antje Rückert

"During the argon oxygen decarburization (AOD) process high-chromium steel melts are decarburized by oxygen and inert gas injection through sidewall nozzles and a top-lance. Due to the large amount of the injected processing gas, low frequency oscillations of the vessel can be observed. It is suspected that these oscillations can influence the converter's structure. The exchange of forces between fluid and the surrounding vessel is the focus of this study. An oscillation model was developed and tested, one objective being to limit the computational effort which is necessary for fully coupled and time resolved CFD and FEM simulations. Experimental results obtained from water-model studies as well as from on-sight measurements are available and were used in order to validate the numerical results. The authors' intention is a contribution towards a more in depth understanding of the factors influencing vessel vibration during the AOD process.IntroductionDuring the last four decades the AOD process has been established as a reliable and efficient refining process in stainless steel making. The injection of process gases (O2, N2, Ar) through sidewall nozzles shows advantages in mixing effectiveness compared to other injection geometries e.g. bottom blowing [1]. Stainless steel grades contain usually more than 10% chromium. With decreasing carbon content during the decarburization periods the tendency of chromium oxidation increases according to the varying chemical equilibrium which depends on the partial pressure of carbon-monoxide (CO) in the gas phase. That's why oxygen is gradually replaced by inert gases, usually argon or nitrogen, in order to lower the CO partial pressure and thus to minimize chromium oxidation. Despite the high injection velocity of approximately Ma = 1, the kinetic energy of the gas jets is consumed within a short distance from the nozzle exits due to the large density ratio between gas and melt of approximately 1:8000. With increasing distance to the nozzle exit, the initial horizontal velocity of the gas jet decreases and due to buoyancy force motion of the detached bubbles turns into a vertical direction. Subsequently a gas plume develops with its typical conical shape described by various authors [1-4]. Due to the drag force between gas bubbles and melt also the liquid phase is forced into a vertical motion. Near the free surface and the wall regions the melt flow is deflected in different directions. Subsequently, the typical flow pattern in the AOD vessel arises, as sketched in Figure 1 and described in literature [5-9]."

Jan 1, 2012

By A. Dell’Era, M. Pasquali, C. Lupi

"An electrochemical cell has been designed to treat very diluted cobalt solutions, i.e. those deriving from recycling processes of lithium-ion batteries. A reticulated vitreous carbon sponge was used as cathode and a Pt-coated Ti net as anode. A controlled potential electrolysis has been carried out in a solution flowing in the cell and maintained at a constant pH of 6.5. Considering the cathode dimensions (10.0 cm * 10.0 cm * 1.25 cm), rather high volumes of solution (>1 litre) can be treated with flow rates up to 1.6 l/min. The process yield is obviously related to the solution concentration; it has been observed that, starting with a solution containing 200 ppm of Co2+, the yield is initially ~35-40%, but it decreases to ~20% when 80% of the initial cobalt content has been electrowon. The yield increases up to ~50% if the carbon electrode is coated by cobalt. The conditions allowing a fast and complete removal of cobalt are outlined. Introduction Industrial liquid effluents containing heavy metal ions arise not only during hydrometallurgical processing, but also in many sector of chemical industries utilizing metal catalysts and process reagents. These waste solutions containing low quantities of metallic ions can be treated by chemical precipitation, solvent extraction, ion exchange, etc. before final discharge. All these techniques could be efficient for complying the aqueous effluents with the severe rules related to the environmental impact, but they can not directly produce metals. Particularly the chemical precipitation presents two main drawbacks, huge amount of sludge prodction and reagent costs to produce this useless and sometime dangerous sludge that have to be considered. Electrochemical technologies can be used for the treatment of effluents polluted by metal ions, showing the following advantages in comparison with other processes: 1. recovering of the polluting substances in metallic forms, with subsequent reusing; 2. absence of process slag, which should be subsequently disposed of. In this work an electrochemical reactor with a reticulated vitreous carbon cathode and a platinated titanium net anode has been designed and utilized for removal Co from waste aqueous solutions. Porous materials have been used as electrodes for this cell, as their high specific surface area favours the treatment of these low metal content solutions (1-7). This kind of electrodic material presents very interesting chemical-physical characteristics such as: low density, low thermal expansion and high electrical and thermal conductivities; particularly the reticulated vitreous carbon (RVC) presents a very elevated void volume, rigid structure, good resistance to temperatures in non-oxidizing environments and very low resistance to fluid flow."

Jan 1, 2008

By Carla Lupi, Mauro Pasquali

"Photographic technology is based on light sensitivity of silver halides that, because of silver properties, are capable of forming photographic images. Photographic laboratories and hospital departments because of digital photographic systems less use this technology today. Nevertheless recovery of silver is still advantageous because environmental problems related to Ag ions danger to biological system. Many processes have been studied to treat silver containing photographic bath: cementation, chemical precipitation and electrowinning. In this work, after preliminary voltammetric tests, a batch electrometallurgical process has been studied to completely deplete the silver containing photographic fixing baths. The effect, of silver concentration in the electrolyte, varying over the range 0,2-1 g/L, bath stirring and current density ranging from 10 to 500 A/m2 on process yield and deposit quality, has been investigated. Introduction Photographic wastes, electronic scrap and spent catalysts constitute the main sources of materials for silver recycling. Among those silver secondary sources, the photographic discharged material could be still important and useful, even if photographic laboratories and hospital departments, because of digital photographic systems, less use photographic technology. Several processes have been developped in order to recover silver used in the field of photography from both photographic solutions and scrap film paper[1-5]. Fixing solutions are very complex baths but, because of silver position in the electromotive series, electrolysis could represent an advantageous method for silver recovery. Electrolysis produces high purity silver without generating new pollutants, while the fixer can be reused: obviously it is necessary to purge off a portion of this solution in order to avoid the excessive build up of other deleterious compounds into solution. A tested recovery method was constituted by the dissolution of silver from X-ray films with concentrated nitric acid. Internal electrolysis and external electrolysis methods were carried out using a steel electrode as cathode and a copper electrode as anode [6]. Silver recovery from photographic chemical solutions has been also performed in a special cell [7]: the solution is supplied to the bottom of a non-agitated cell having a vertically elongated form and including a central anode enclosed by a cathode. An other study discloses the use of an electrolytic cell comprising at least one anodic compartment and one cathodic compartment: the solution is treated in the cathodic compartment and then recycled in the anodic one [8]. A more recent work proposes the use of zirconium cathode for the recovery of silver from photographic fixing solution [9]: studies carried out by cyclic voltammetry showed that about 98% of total Ag can be recovered with an electrical efficiency close to 92%."

Jan 1, 2008

By Jinqian Zhao, Jiarong Li, Shizhong Liu

"Creep cavitation of in single crystal (SX) superalloy was investigated. The constant load creep tests, in single crystal superalloys DD6, were conducted at the conditions of 800°C/700MPa, 850°C/550MPa and 900°C/450MPa, respectively. It was found that there were square facets on the stress fracture surface, and microscopic cavities in the ruptured specimens in the vicinity of the fracture surface. Both the square facets on the fracture surface and microscopic cavities in the section of the ruptured specimens show the morphology of the same thing at the different views, namely creep cavities, which are take the form of flatten cuboid. In fact, creep cavities are the longitudinally tensiled creep cracks slowly growing during the stress tensiling. The factors of creep cracks nucleation and growth conditions include: (a) enough high temperature to activate diffusion (b) casting pores as nucleation origination (c) high strains and strain rates. Eventually, the instantaneous fracture mechanism of creep specimen is cleavage fracture.IntroductionFor the materials used in elevated temperature service, creep behavior has to be accounted for. It is well recognized that creep rupture in polycrystalline materials at high temperature occurs principally by the nucleation and growth of microscopic cavities at grain boundaries, followed by microscopic cavities linkage to form micro- and eventually macro-intergranular cracks[l,2]. Without the usual grain boundaries, SX superalloys have superior capabilities at high temperatures to polycrystalline superalloys, and have become an established feature of gas turbine technology where they are commonly employed in the manufacture of high performance blades[3]. A considerable amount of work has been done over the past tens of years, and many models for nucleation and growth of creep cavities have been proposed, however, those are mainly for polycrystalline materials.In order to improve creep resistance that single crystal superalloys, in which grain boundaries are removed, have been developed. Because there don't exist grain boundaries in SX superalloy, the mechanism of nucleation and growth of creep cavities must be different from that in polycrystalline materials.Understanding the formation and characteristics of creep cavitation is crucial to model the lives of single crystal superalloys.M. Marchionni and L.G. Zhao et al. found that there were square facets on the stress fracture surface [4,5]. Roger C. Reed pointed out creep cavities lie in the necked region[6]. In this paper, the effects on the formation of creep cavities are discussed, as well as the morphology of creep cavities and fracture mechanism of SX superalloys."

Jan 1, 2013

By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Jian Li, S. Penttilä, P. Liu, W. Zheng, C. Bibby

"The materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. The current Canadian pressure-tube supercritical water (SCW) concept design requires core outlet temperature of 650 °C at 25 MPa with peak cladding temperature reaching as high as 850 °C. Aside from oilier challenges, there is currently very limited data on candidate stainless steels' corrosion resistance under this operating condition. Austenite stainless steels that include 316L, 304H, AL6XN and 3 l0S that cover a wide range of Cr contents are promising candidates for either direct in core applications or as base coating materials. However, their corrosion resistance has not been tested systematically under this stringent condition. In this study, these types of stainless steels are tested, and their corrosion resistances are compared.IntroductionThe Canadian pressure-tube supercritical water (SCW) concept will operate at a core outlet temperature of 650 °C at a pressure of 25 MPa, with potential peak cladding temperature reaching as high as 850 °C. High-temperature corrosion resistance is one of the key design requirements for fuel cladding components. As summarized by Allen [1 ], most testing to date has been carried out at temperatures below 730 °C. To date, SCW corrosion data above 600 °C is very limited. Even at relatively low temperature exposure to SCW (e.g. 500 °C), F/M steels develop a thick oxide layer rapidly, while some austenitic stainless steels develop thinner surface oxide. Ni based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of intermetallic precipitates [2-5]. Dissolution of major alloying components from all of these alloys could also pose significant problems for downstream piping [6]. Kaneda et al. [7] suggested some modified stainless steels provide better SCW general corrosion resistance, with no sign of SCC under the slow-strain rate test.Cho [8] suggested that as the Cr content increase, general corrosion resistance improved at 510 °C and 25 MPa. However, similar to Cho's work, most of the SCW corrosion resistance assessments were based on weight change measurement. This can be unreliable due to potential exfoliation of thick oxide film. Besides, there have been no systematic SCW corrosion resistance tests for candidate stainless steels under higher temperatures. SCW corrosion rate increase dramatically for alloys tested at 600 °C [1]. It is also important to understand the role of major alloying elements under this stringent operating condition, not only for fuel cladding components' materials selection, but also for coating materials development."

Jan 1, 2013

By Masatsugu Morimitsu, Tian Zhang

"This paper presents a novel anode for oxygen evolution in acidic aqueous solutions to produce non-ferrous metals by electrowinning. The method to prepare the anode was thermal decomposition of a precursor solution, and the obtained anode consisted of Ru02-based oxide catalytic layers formed on a titanium substrate, in which the catalytic layer contains nano-oxide particles as the active component. The oxygen evolution potential was lower than amorphous lr02-Ta20s coated titanium anodes so that the cell voltage of electrowinning was further reduced with the amorphous Ru02-based electrode.IntroductionElectrowinning (EW) is used to produce high purity of non-ferrous metals, and the primary metal production of copper, zinc, nickel, and cobalt by EW consumes huge electric energy worldwide, which tends to increase with increasing demand of such metals. The reduction of electric energy consumption is a significant issue for electrowinning industry, which means that the cell voltage reduction is needed to realize more energy-efficient EW processes. Another issue is also indicated from environmental perspectives; i.e., an improvement in EW plant environment by eliminating hazardous byproducts and wastes. Such byproducts and wastes include lead oxide, manganese oxide, and acid mist.We have been developing the anodes for energy-efficient and environmentally friendly electrowinning processes [ 1-11]. The development has been successfully done with the invention of the smart anode, MSA TM (Morimitsu Smart Anode) [ 1-5], which has low polarization for the main reaction and high polarization for the side reaction, in which the main reaction is oxygen or chlorine evolution, while the side reaction is the anodic deposition of each or both of lead oxide, manganese oxide, and cobalt oxide. The anode consists of a valve metal substrate coated with amorphous or less crystalline oxide catalytic layers. One of the typical examples of such oxides is amorphous lr02-Ta20s, and the substrate is normally titanium plate or mesh. The most important point of the oxide is that the amorphization or less crystallinity induce the increase in the active surface area only to the main reaction, not to the side reaction, thereby the polarization of the main reaction being reduced.In this paper, we present the smart anode consisting of RuO2-based catalyst formed on titanium substrates for oxygen evolution in electrowinning. The preparation, characterization, and polarization behaviors of the anodes are shown, and the cell voltage data for zinc or copper electrowinning using the anodes are also presented."

Jan 1, 2012

By Jeffrey Shepherd, Scott R. Smith, Eduard Guerra

"Electrochemical and spectroscopic evidence for the dissolution of a Au electrode by meso-2,3- dimercaptosuccinic acid (DMSA) from an acidic LiCl04 electrolyte is presented. Near the potential of zero charge, DMSA was determined to form a stable layer on the metal surface but at more anodic polarizations, DMSA was displaced from the metal through an oxidative process. The anodic displacement of the layer from the electrode resulted in a small amount of Au that was detected in the electrolyte using atomic absorption analysis. The extent of Au dissolution, was monitored while holding the potential of the electrode for 24 hours at the thermodynamic Eo/H,O in LiCl04 electrolytes containing 10 mM DMSA. This routine resulted in detectable quantities of a soluble Au-DMSA complex in the electrolyte and the greatest leaching was observed at a pH = 2.0. At room temperature, the leaching rate was stable at 10.9 µg cm·2 hr·' however, upon increasing the temperature to 50.0°C, the rate of Au dissolution increased yielding an average rate of extraction of 40.1 µg cm·2 hr- 1. Interestingly, after the first 12 hours of leaching at 50.0°C, the leaching current decreased dramatically suggesting surface passivation which prevented further Au extraction. The implications of this process in the industrial leaching of Au will be discussed.IntroductionThe use of cyanide in the industrial process of leaching Au from ores has raised concerns regarding both operational safety and environmental issues surrounding the disposal of spent leaching eftluents in tailings ponds. Depending on the chemical nature of the processed ore, the spent solutions that are released into the tailings ponds can contain toxic cyanide, either dissolved or complexed with different metals and may pose serious risk to wildlife as well as freshwater contamination to nearby water systems. Because of these issues, some recent studies have focused on the exploration of more environmentally-friendly molecules to selectively leach Au with appropriate kinetics. However, to effectively leach Au into an aqueous solution, a suitable ligand that reacts to form a stable chemical bond with Au is needed to form soluble Au complexes that can be later recovered [I]. Recently several sulfur bearing alternatives have been shown to leach significant quantities of Au in aqueous solutions. These include thiourea [2], thiocyanate [3], and thiosulphate [4]. However, alkylthiols are also known to quickly form a stable covalent Au-S bond [5], but have been relatively understudied in term of their ability to leach Au in solution, even though some short chain thiols are water soluble and relatively nontoxic."

Jan 1, 2012

By Jie Li, Liangxing Jiang, Yexiang Liu, Junfeng Gui, Bo Hong, Xiaocong Zhong, Yanqing Lai, Xiaoying Yu

"Pb-based alloys with Pr and Ag were prepared in vacuum electromagnetic induction furnace. The tensile strength, corrosion rate and anodic potential in sulfate solution were measured, and the experimental data were analyzed according to the metallographic phases of alloys, the micromorphology and composition of their oxide films. The results show that, with the addition of Pr, the ultimate tensile strength and corrosion rate of pure lead were increased, and the anodic potential decreased. The extra addition of Ag can improve the properties of alloy further. Comparing with Pb-Ag0.8 alloy which is widely used in zinc electrowinning industry, the ultimate tensile strength of Pb-Ag0.6-Pr2.0 alloy was increased by 31.75%, the anodic potential under 50mA/cm2 was decreased by 30m V.IntroductionIn zinc electrowinning industry, the Pb-Ag (0.5-1.0 wt.%, 0.8wt.% normally) anode is widely used as an insoluble anode['l. It can meet the basic requirements, but still has several problems such as high oxygen evolution over-potential (about 860mV), unsatisfactory corrosion resistance, lead contamination of the cathode product and high consumption of Ag etc.In order to reduce the energy consumption, enhance the corrosion resistance, improve the product quality and reduce the consumption of Ag (or even dispense with it), much research has been done, mainly focusing on Pb-based alloy anodes and Ti-based coated anodes. Detailed investigations have already been carried out on binary alloys (Pb-Ca and Pb-Co), ternary alloys (Pb-Ag-Ca, Pb-Ag-Ti, Pb-Ag-Sn, Pb-Sr-Sn, and Pb-Ca-Sn) and quaternary alloys (Pb-Ca-Sr-Ag, Pb-Ca-Ce-Ag, and Pb-Ag-Sn-Co)[Z-4l, Although these anodes can effectively reduce the consumption of Ag, only the Pb-Co and Pb-Ag-Sn-Co anodes perform well with regard to reducing the anodic potential. However, their complicated manufacturing conditions restrict further commercial use.Besides its application in nonferrous metal electro-winning industry, Pb-based alloy is also used as grid alloy for lead-acid battery, serving as active materials supporter and current collector. In order to enhance the corrosion resistance and deep-cycling performance, reduce the impedance of the corrosion film, the addition of appropriate rare earth elements into anodic grid alloys has become a research focus. Studies proved that RE can enhance the mechanical strength of grids, inhibit the formation of anodic Pb(II) film on the surface of grids and then reduce the impedance of the film[ 10-12l."

Jan 1, 2013

By Gaifeng Xue, Lei Zhang, Xia Liu, Lina Wang, Pu Liu, Benquan Fu

"Experiments were conducted to investigate the behavior of the integrated process with a three-dimensional electrode reactor combined with Fenton process for coking wastewater treatment. Effects of initial pH value, reaction time, H20 2 dosage, Fe2+ dosage on Total organic carbon (f OC) removal rate were investigated. The kinetics of degradation of TOC from coking wastewater by three-dimensional fluid bed electrode reactor combined with Fenton process was also studied. Experimental results shows that three-dimensional fluid bed electrode reactor combined with Fenton process had better synergic effect, average 17.4% TOC removal rate was improved within an hour. It was found that TOC degradation in coking wastewater followed a pseudo-first-order reaction kinetic model. The optimum degradation efficiencies of TOC were up to 60% as pH3.4, 3.5 mM ofFe2+ andl.2-1.8ml/L H20 2 in 90min reaction period. Furthermore, the integrated process showed a rapid reaction performance at a low temperature within a short reaction time and remained high efficiencies for TOC removal. Overall, the integrated process was proved feasible for coking wastewater treatment in practical applications.IntroductionCoking wastewater is generated from coal coking, coal gas purification, and by-product recovery processes of coking, which is composed of phenolic compounds, heterocyclic compounds, polycyclic aromatic hydrocarbons, ammonia, cyanide, polycyclic nitrogen-containing aromatics, acyclic compounds, etc. Most of these constituents are refractory, poor biodegradability, toxic and carcinogenic['-31. Currently, coking wastewater is usually treated by different forms of A/O biological nitrogen removal process as the primary treatment process, but the aforementioned processes are not efficient enough to meet the requirements from the National Discharge Standard in China (GB13456-1992). According to the continuous requirement on improving environmental protection for coking industry (revised 2008), increasing wastewater utilization ratio and reducing discharge of effluent in the coke industry has to be implemented for cleaner production and sustainable development. Therefore, advanced technologies need to be developed to treat coking wastewater and reutilize the product as industrial cooling water, which would be one of the best choices to achieve zero discharge of wastewater and reduce water consumption per ton of steel [4-51 . In this study, three-dimensional fluidized bed electrode reactor combined with Fenton process was adopted to advanced treatment of coking wastewater, and the effects of operating conditions, including H2O 2 dosage, Fe2+ dosage, initial pH, and reaction time on TOC removal rate, were investigated. Meantime, study of kinetics of reaction was estimated."

Jan 1, 2013

By E. A. Chavarriaga, L. J. Jaramillo, O. J. Restrepo

"This paper presents the results of the manufacturing ceramic pigments with spinel structure, using methods of synthesis of low temperature. In this work we obtained spinel structures type by the methods of Self-combustion, Coprecipitation, Microemulsion, Gel citrate and Pechini. These methods become an attractive alternative to traditional method (ceramic method), since we can work at a lower temperature, reducing manufacturing costs, lower fuel consumption, less wear on equipment and other environmental and economic implications. Also it is possible to have control over features such as stoichiometry, morphology of the products, reaction times and structures. The products obtained by these routes will be used in the manufacture of ceramic pigments and characterized using different techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-VIS spectrophotometry.IntroductionSpinels are ternary oxides AB204, where A and B are cations occupying tetrahedral and octahedral positions respectively. These oxides exhibit interesting electrical, magnetic and catalytic properties [1-4], depending on its nature, charging and intrinsic distribution of ions [5].The most widely used method to prepare spinels has been through solid state reaction, which consists of mixed oxides at high temperatures [6, 7]. In the last years, there have been a strong tendency to use chemical routes for the synthesis of crystalline ceramic particles at low temperatures [8,9]. Unconventional methods currently employed for the synthesis of complex oxides are Gel citrate method, Pechini, Spontaneous combustion, Microemulsion and Coprecipitation. Pechini method [10, 11], based on polymeric precursors, does not require high temperatures and allows stoichiometric control for greater reproducibility. This method involves the formation of a polymeric resin between a metal quelate and polyhydroxy acid of alcohol by polyestirification.Coprecipitation is important for many environmental problems related to water resources, including acid mine drainage, migration of radionuclides in waste repositories dirty, transport of contaminant metals in the industry, metal concentrations in aqueous systems and the technology of wastewater treatment. The coprecipitation process can vary in each case; the partition in the solid phase can be carried out by surface adsorption, ion exchange, surface precipitation, occlusion and formation of solid solution. The formation of solid solution is the result of structural incorporation of the marker in structural support sites resulting in a minor component in the solid solution with the host phase that has a very low solubility of pure solid [12]. Synthesis by gel citrate method allows the use of a route to obtain ceramic pigments from a very simple experimental system in which the stoichiometric control, the size and shape of the particles and the purity of the phases obtained can be controlled more accurately [13]."

Jan 1, 2012