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By Hidekazu Nakagawa

We investigated the anodic dissolution behavior of titanium in TMHA-Tf2N molten salt, which has a wide electrochemical window of about 5 V, in order to develop an electrodeposition method for titanium. By etching a titanium electrode in HF?HNO3?H3PO4 solution, the titanium electrode became electrochemically active, and a redox reaction was observed at around -0.15 V vs. I-/I3- in (TMHA-Tf2N)?HTf2N solution. We identified the redox reaction consists of the reduction of the proton and the oxidation of hydrogen. The diffusion coefficient of the proton in TMHA-Tf2N was calculated to be 6.9 10-8 cm2 s-1 at 50 °C from the cathodic peak current in the cyclic voltammogram. Anodic decomposition of the molten salt was not observed up to 6.0 V vs. I-/I3- on titanium electrode, while it was observed at around 2.0 V vs. I-/I3- on platinum and glassy carbon electrodes. Cathodic decomposition of the molten salt was observed at around -3.0 V on the titanium electrode, as well as on the platinum and glassy carbon electrode.

Jan 1, 2006

By Prakash Venkatesan, Yongxiang Yang, Seshadri Seetharaman, Aida Abbasalizadeh, Jilt Sietsma

Electrolytic production of metallic neodymium is carried out in fused fluoride salts containing neodymium oxide. Two major challenges pertaining to neodymium production are (a) low oxide solubility and (b) possible fluorine gas evolution. A novel iron-based reactive anode is proposed and tested to overcome fluorine gas evolution during electrolysis of neodymium oxide in molten fluoride salts.

Mar 1, 2017

By Moelans. N.

A method using an ex-situ electrochemical measurement device was developed to determine the oxygen potential of non-ferrous metallurgical slags. The electrochemical cell consists of the molten slag sample, an inert Ir electrode, a stabilized Zr02 solid electrolyte and a NilNiO reference electrode. Different slags from non-ferrous pyrometallurgical processes were analysed at I 100 and 1200 °C and pO2values between 10-3 and 10-12 bar were obtained. The measurements were evaluated with thermodynamic calculations and using processing considerations. It was found that the reproducibility and stability of the measurement was significantly improved by shielding the molten slag from the atmosphere by a thin layer of carbon, especially for slags with a low oxygen potential.

Jan 1, 2003

A novel, low-pressure adaptation of Praxair?s coherent jet technology utilizing CoJet lances was developed for application at Inco&apos;s Copper Cliff Smelter where oxygen is available in large tonnage quantities but only at relatively low supply pressures (< 193 kPa header pressure). The project objectives were to evaluate the effect of coherent jet technology on controlling oxygen lance accretion (?horn?) formation and to increase oxygen efficiency in the Inco Oxygen Top-Blowing Nitrogen Bottom Stirring (TBBS) MK Reactor used for converting nickel- contaminated chalcocite to semi-blister copper. This paper describes the development and subsequent implementation and testing of two CoJet lances in this application.

Jan 1, 2005

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander model for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2, MgO-SiO2, FeO-CaO-SiO2, FeO-FeO1.5-CuOo.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-MgO and FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte (L s/m as), and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5-CaO-MgO slag and liquid copper (L s/Cu as) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte-metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for prediction in multi-component slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes.

Jan 1, 2003

By Alfonso Nájera

Turbulent flow of liquid steel and its control is studied using different geometries of turbulence inhibitors. Four designs of turbulence inhibitors were characterized through experiments of tracer injection I a water model and mathematical simulations using the Reynolds Stress Model (RSM) of turbulence. Geometries included octagonal-regular, octagonal-irregular, pentagonal and squared. A layer of oil was used to model the behaviour of tundish flux during steel flow. Fluid flows in a tundish using these geometries were compared with that in a bare tundish. Experimental and simulation results indicate that the flow in the bare tundish and a tundish using turbulence inhibitors open large areas of oil due to strong shear stresses at the water-oil interface but the squared inhibitor. These phenomena are explained by the high gradient of the dissipation rate of the turbulent kinetic energy using the squared inhibitor. Using this device the kinetic energy reports a high gradient from the tundish floor to the free bath surface as compared with other geometries.

Jan 1, 2006

By John Dasher

One of our War Plants processed Bolivian concentrates as low as 17% Sn by the Arnhem process (pressure leach with HCL) and sent the waste acid down a ditch to Galveston Bay where the chlorides, mostly iron, hydrolyzed. Oyster men, and Texas, demandedimpoundment until a disposal process could be developed. A recycle process found by lab work was recommended, piloted and a plant built. This involved cementation of As Sb, Cu, Bi and Ag on light moving scrap iron and of Sn & Pb on Al turnings (then not recyclable), evaporation and crystallization of hydrous FeCl2, roasting crystals in a muffle furnace and absorbing HCI for reuse. The residue from leaching the low grade concentrates was floated to remove undissolved sulfides, classified and passed over sand and slimes tables to get a smeltable concentrate, a discardable sand tail and a slimes tail worth treating After desliming at 2 micro meters cassiterite, oxide flotation gave good, lab results; but commercial equipment wasn&apos;t adequate then. Chloride volatilization, with or without smelting gave high recoveries of Sn as SnCl2, whose marketing was questionable. I have heard this was finally fluxed and smelted.

Jan 1, 1992

By Carole Read

Hydrogen is under consideration by several countries for its potential as an energy carrier for transportation applications. In order to compete with vehicles in use today, hydrogen-powered vehicles will require a driving range of greater than 300-miles in order to meet customer needs and expectations. For the overall vehicular light-duty fleet, this dictates that a range of 5 to 13 kg of hydrogen be stored on-board (assuming a fuel cell power plant) within stringent system weight, volume, and cost constraints. Vehicular hydrogen storage thus constitutes a major scientific and technological challenge. To meet this challenge, the U.S. Department of Energy (DOE) initiated a ?National Hydrogen Storage Project? with roughly 40 universities, 15 companies and 10 federal laboratories, actively engaged in hydrogen storage research. Centers of Excellence in metal hydrides, chemical hydrides, and carbon-based materials have been established, as well as independent university and industry projects in the areas of new concepts/materials, hydrogen storage testing, and storage system analysis. Recent technical progress in each of these areas is discussed, as well as collaborative hydrogen storage activities under the recently established International Partnership for the Hydrogen Economy (IPHE).

Jan 1, 2006

By Masao Miyake, Eiichiro Matsubara, Tetsuji Hirato, Yasuhiro Awakura

"Zn-Cr alloy coating with around 15 wt% Cr has been found to have much higher chemical corrosion-resistance to steel than conventional zinc plating, while· its structure has not been clarified. The Zn-Cr alloy plating is performed at high current densities around 1 A cm-2 and for 10 to 20 sec using acidic aqueous sulfate solutions with some additives in the iron-steel industry. Due to the high current densities, it seems reasonable to consider that the Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings have a non-equilibrium phase and have a structure change in the .direction of thickness. In this research, the crystal structure of the Zn-Cr alloy coating electrodeposited at high current densities and change of the structure in the direction of thickness were examined by X-ray diffraction. The coatings containing under 20 and 35-40 wt% Cr had hcp and bee structure, respectively, while the coatings containing 20-35 wt% Cr comprised two phases with the hcp and the bee structure. The structure of the coating varied in the direction of thickness; both the hcp and bcc phases coexisted in the vicinity of the substrate, while the hcp phase became predominant with increasing distance from the substrate.IntroductionRecently it has been reported that Zn-Cr alloy coating containing around 15 wt% Cr has much higher corrosion-resistance to steel than conventional zinc plating.1-3) The corrosion-resistanc·e of Zn-Cr alloy plated steel sheet with a plating amount of 20 g m·2 is, for example, superior to that of Zn plated steel with a plating amount in the range 60 to 90 g m·2 , which is widely used for automotive bodies today.4l The Zn-Cr alloy plating is obtained by electrodeposition at current densities over 0.5 A cm·2 from a sulfate solution containing zinc and trivalent chromium ions and some additives.5•6) The deposition current densities mentioned above are much higher than those for usual electroplating processes, e.g., Zn, Cu and Ni plating, carried out about 0.05 A cm·2 • Therefore, the time required for plating is very short; around 10-20 sec. Due to the high current densities, it seems reasonable to consider that the· Zn-Cr alloy plating proceeds under an unsteady-state condition and that the resulting coatings do not have a phase expected from equilibrium diagrams; no phase diagram of the Zn-Cr system with a full composition range has been available. 7). In other words, the alloy phase plated would be a non-equilibrium phase with unknown structures."

Jan 1, 2000

By Norihiko Fukatsu, Takashi Iwamoto, Noriaki Kurita, Koji Katahira, Kunihiro Koide, Teruo Ohashi

"The galvanic cell-type hydrogen sensor employing CaZro.9Ino.t03-a. as the solid electrolyte was designed for the measurement of hydrogen activities in molten copper under industrial .conditions. The sensor probe consists of the cap-shaped solid electrolyte with porous platinum electrode on the inside and alumina refractory tube. The gas mixture of the composition 4%H2-0.5%02-Ar was made to flow on the inside electrode. The hydrogen sensor probe was inserted directly into molten copper and the melt was used as the outer electrode. The effect of oxygen activity gradient to EMF was eliminated theoretically by measuring the oxygen activity in the melt simultaneously with an oxygen sensor. The high stability of output and excellent response to the change of hydrogen activity were obtained over the wide range of industrial copper melting conditions.IntroductionIn the metal casting process, hydrogen easily dissolves in molten metals from water vapor in the surrounding atmosphere. Owing to the large difference in hydrogen solubility between liquid and solid metal, dissolved hydrogen becomes a cause of the defects of blowholes in castings or ingots. It is necessary to control the hydrogen content in the molten metals [l]. Using proton-conducting ceramics as a solid electrolyte, high temperature-type hydrogen sensor can be constructed [2]. SrCe03- and BaCe03-based perovskite-type oxides exhibit appreciable proton conduction under hydrogen containing atmosphere at high temperature [3-5]. A hydrogen sensor for molten aluminum using CaZro.91no.103-a. has been developed and widely used in the ·process control in the aluminum melting industry [6,7]. The same type of hydrogen sensor has also been expected in the copper melting industry. .. However, CaZro.91no.103-a shows ·not only proton but also oxide ion conduction in the high temperature and at low oxygen activies like the copper melting· conditions. Then we studied the oxide ion conduction in CaZro.91no.103-a. iit · detail [8]. From the consideration on the EMF of the galvanic cell employing this material as electrolyte, it was shown that the unknown hydrogen activity may be precisely determined from cell potential which is corrected for the effect of oxygen potential gradient And the hydrogen sensor based in this principle was constructed and tested in laboratory-scale [9,10]. We repeated the similar tests in factory-scale and developed the sensor system for practical uses [11, 12]. In this report, the structure and system of the hydrogen sensor for molten copper will be introduced first. The reliability of the sensor will then be demonstrated from the results of experiments for sensor probes carried out in TYK's laboratory."

Jan 1, 2000

By Suleyman Tekeli, Serdar Salman, Bulent Aktas

"The effect of La2O3 content up to 15 wt% on phase stability, sintering and microstructure of cubic zirconia (8YSZ) was investigated. XRD results showed that the specimens containing up to 15 wt% La2O3 were composed of only cubic structure. Also, the specimens doped up to 5 wt% La2O3 revealed no La2O3 peaks, indicating that La2O3 was completely solubilized in the cubic structure. However, when> 5 wt% La2O3 was added, the peak of La2Zr2O7 compound emerged, showing that the overdoped La2O3 was not solubilized in the 8YSZ matrix. The lattice parameter of the 8YSZ slightly decreased with the increasing La2O3 content up to 1 wt% but further increase in the La203 amount resulted in an increased lattice parameter. The comparison of grain size of the 8YSZ specimens with various La2O3 content showed that grain size slightly increased with the increasing La2O3 content up to 1 wt% but further increase in the La2O3 amount resulted in a decreased grain size.IntroductionAt atmospheric pressures, three polymorphic forms of Zr02 are stable at different temperatures i.e. monoclinic, tetragonal and cubic. A high-pressure orthorhombic form of Zr02 has also been reported[l]. The successful production of pure Zr02 bodies is not possible all the time due to the large volume expansion associated with the martensitic tetragonal-monoclinic transformation. This fact restricts the applications of zirconia, in spite of its excellent mechanical and thermal properties. However, the stabilization of the high temperature polymorphs at room temperature as stable phases is made possible by addition of suitable dopants. Fully stabilized cubic Zr02 and partially stabilized tetragonal Zr02 show interesting properties and are widely used as ionic conductors, coatings and gas sensors in solid oxide fuel cells and structural applications[2]. Most frequently used dopants include Y203, CaO, MgO and Ce02, although other oxides, such as those of rare earth elements, can also act as stabilizers of the high temperature structures. The incorporation of aliovalent cations to the lattice, forming substitutional solid solutions, allows to control the concentration of anionic vacancies in the structure. This aspect is particularly important in designing ionic conductors[3], and is also determinant in the stabilization process[ 4]. The process of stabilization with larger ionic radii dopants is rationalized by the crystal chemistry model[ 5], that describes the dopant cations as typical stabilizer when they have larger ionic size, lower charged state and higher ionicity than Zr4+ The ionic radius of Zr4+ is 0.84 Å and that for La3+ is 1.016 Å [6]."

Jan 1, 2012

By Shize Jin

Effect of four polyols, namely ethylene glycol (EGL), glycerol (GCL), propanediol (PDL), butanediol (BDL) and three organic acids, namely oxalic acid (OA), malonic acid (MA) and succinic acid (SA) on the current efficiency (CE) and the cell voltage during zinc electrowinning was studied. Galvanostatic polarization was conducted in a supporting electrolyte (SE) containing 180 g dm-³ H2SO4, 60 g dm-³ Zn2+ and 8 g dm-³ Mn2+ at 38°C with magnetic stirring. The imposed current density was 50 mA cm-². The anodes were made of a Pb-Ag alloy and the cathodes were made of an aluminum alloy. The results showed that all the polyols tested in this study decreased the current efficiency and the cell voltage, but the decrease of the cell voltage was not important. Oxalic and succinic acids decreased the current efficiency to a less extent than the polyols, but did not decrease the cell voltage much. The only compound that increased the current efficiency was malonic acid, and its capacity of decreasing the cell voltage was the highest within the seven tested organic compounds.

Jan 1, 2003

By E. Allaine

Carbochlorination kinetics of pure MoO3, Nb2O5, Ta2O5 and V2O5, by Cl2+CO+N2 gas mixtures was investigated between 380 and 1000 °C. Standard free energy of carhochlorination reactions and phase stability diagrams of these refractory metal compounds were calculated. The influence of total gas flow rate, temperature, reactants partial pressures on the reactivity of these oxides were investigated. The apparent activation energies were found to be about 83, 75, 110 and 100 kJ/mole below 650°C for MoO3, Nb2O5, Ta2O5 and V2O5, respectively. Above this temperature, the Arrhenius plots exhibit a rate anomaly attributed to thermal decomposition of COCl2 and/or structural changes of these refractory metal oxides. The apparent reaction order of carbochlorination of these oxides with respect to Cl2+CO was determined. For these refractory metal oxides, the reaction rate was maximum for a Cl2/CO ratio of about 1 in the chlorinating gas mixture. Results of carbochlorination of these oxides are compared and discussed.

Jan 1, 1995

By T. V. Swaminathan

Monazite sand is normally processed by, the caustic soda route to produce mixed rare earths chloride, thorium hydroxide and trisodium phosphate. Bulk of the mixed rare earths chloride is used for the preparation of FC catalysts. Recently some of the catalyst producers have shown preference to cerium depleted (lanthanum enriched) rare earths chloride rather than the natural rare earths chloride obtained from monazite. Therefore, a process for producing cerium depleted rare earths chloride, cerium p thorium and uranium from Rare earths + thorium hydroxide obtained by treating monazite based on stepwise hydrochloric acid extraction, was developed in our laboratory. The process involves drying of the mixed rare earths-thorium hydroxide cake obtained by monazite-caustic soda process followed by stepwise extraction of the dried cake with hydrochloric acid under specified conditions.

Jan 1, 1989

By Guozhu Ye

Hydrometallurgical zinc recovery from EAF dust has several advantages compared to pyrometallurgical alternatives in terms of low temperature operation, lower energy consumption and higher flexibility. Many hydrometallurgical processes have been suggested and tested over the years without success. The main reasons are: -Low leaching yield of zinc due to the fact that a high fraction of ZnO in the EAF dust exists in the zinc ferrite structure which makes selective leaching of ZnO not possible -Many of the proposals could not handle the halide in the EAF dust To eliminate these two disadvantages, two zinc ferrite elimination concepts have been tested and developed in the REZIN project of the EU 5th Framework Programme. The two concepts for zinc ferrite elimination could be shortly described by the following chemical reactions: A. ZnOFe2O3 + 2CaO = Ca2Fe2O5 + ZnOfree B. ZnOFe2O3 + C = Femet + CO/CO2 + ZnOfree These two concepts were investigated in details in combination with a subsequent leaching step using the novel EZINC process for recovery of zinc from EAF dust. Leaching of pretreated samples has shown great increases of a zinc recovery yield. A zinc recovery of over 90 % could be reached, as compared to about 50 % for no-pretreated samples. This paper will describe the two concepts in details.

Jan 1, 2006

By Luiz R. P. De Andrade Lima

This paper presents a mathematical model for the oxide copper ore heap leaching process. The data used in the model include physical-chemical, .geometrical and operational data, as: leachable metals ore contents, .flow rate and acid concentration, parameters of passivity, ore size distribution, the average residence time of the solution in the heap, height, irrigated area and weight of ore in the heap. In this model the heap is divided into horizontal and plane layers of constant area. The flow of the liquid in the heap is considered unidirectional and the solid-fluid reaction model is considered under diffusive control. The average residence time of the solution into the heap and the apparent effective diffusivity of the acid through the ore particles have .a significant influence on the rate of the copper extraction and its concentration in the pregnant solution; therefore these parameters are used in the model calibration. When this algorithm was applied to a laboratory test, the results showed that the model is adequate to predict the process performance.

Jan 1, 1999

By M. J. Perpich

Electrochemical and chemical leaching tests were carried out on chalcocite, covellite and chalcopyrite in acidified iron sulfate solutions sparged with a mixture of O2 - SO2. The gas mixture catalyzed the ferrous to ferric oxidation reaction in situ and, therefore, increased the redox potential and oxidizing strength of the solution. Anodic polarization curves in dilute sulfuric acid on copper sulfide electrodes showed that chalcopyrite passivates and dissolves at current densities orders of magnitude less than chalcocite and covellite. The addition of a depassivating agent (Ag+) increased the passive current density of chalcopyrite and caused breakdown near 0.625 V (SCE). The depassivating effect was also observed during the leaching of chalcopyrite particulate samples as small amounts of Ag+ added to acidified iron sulfate solutions in the presence of O2 - SO2 mixtures greatly increased the leaching rate and the total amount of Cu oxidized (> 90%). Passivation was prevented in the absence of Ag+ by decreasing the initial oxidizing power of the solution and by pretreating the sample in a reductive leach. Both of these methods resulted in transformation of the chalcopyrite surface from its characteristic greenish-gold into deep black. Increased concentrations of Fe+++ due to 02 - S02 sparging were then able to oxidize the transformation product.

Jan 1, 1999

By G. Cifuentes

It&apos;s know that the cathodic purity and the electrolyte treatment is affect for the solid present in the electrolyte. Anodic slimes properties (f.e.: chemical composition, crystalline composition, sedimentation) was studied in copper electrorefining, this properties were modify through by anodic composition and current density. In this paper will be present only the preliminary anodic slimes relationship at different lead anodic composition. The anodic material was doped during the poured process with lead at different composition. It&apos;s confirm the apparition of the (Bindheimitte) SMbz07. The specific gravity of this specie is approximately 7.3 - 7.5, with this values is biggest the probability of sedimentation and smaller the slimes not sedimentabel.

Jan 1, 1999

By Anna Wasilkowska

The study concentrates on the effects exerted by microstructure, deformation history and uniaxial stress conditions (temperature, stress state, strain rate) on the mechanical properties offerritic TRIP-aided steels for automotive applications. In low-alloyed TRIP-steels it is quite difficult to separate the effect of the austenite to martensite phase transformation from the influence of the ferritic matrix contributing to the yield stress and uniform elongation. Investigation of transformation kinetics of retained austenite as a function of the deformation temperature show that using the parameter k to characterize the retained austenite stability allows to identify regious of different temperature sensitivity separated by a transition temperature of 10±5°C. The observed low strain-rate sensitivity of the flow stress is an intrinsic property of the ferritix matrix and points to defomtation governed by slip. The ultimate tensile strength is much stronger affected by temperature than the yield stress. The influence of the temperature on the elongation is complex, because of the heating of the specimens by 60-l20°C at moderate and high strain rates. The increase of the total strain can be understood in terms of thermal softening of the ferrite. On the other hand, the steep increase of the stress during dynamic testing is an effect of accommodated elastic and plastic strains in the matrix. The strain- hardening exponent is dependent on the conditions imposed during testing. The martensite transfomtation rate is lower and the critical stress for martensite nucleation is much higher under compression compared to tensile loading. In secondary tensile tests, the yield stress increases steeply, and the ultimate tensile strength and the total elongation depend linearly on the amount of pre-straining. The results confirm that in the range of 8=10-4 s-l the TRIP-effect governs room temperature plasticity. Keywords: TRIP-steels, mechanical properties, strain rate sensitivity, temperature sensitivity, austenite stability

Jan 1, 2003

By Yuri Gelfgat

"This paper presents some results of the investigation of the steady magnetic field influence on hydrodynamics and heat/mass transfer in processes of semiconductor single crystal growth (Si, Ge, InSn). The investigation employed mathematical and physical simulation techniques of relevant processes and full-scale experiments on growth facilities. A number of additional MHD phenomena have been found generated in the melt due to the rearrangement of flow pattern, the formation of specific convective cells, and the origin of MHD boundary and shift layer.IntroductionMagnetohydrodynamic (MHD) means of creating forces by contact-free methods in liquid conducting media have been widely used in the production of volume semiconducting single crystals. The goal of this method is to control convective transfer processes in the melt volume and on the crystallization front [1-3]. This is due to the sufficiently high conductivity of semiconductor melts (s = 104 /106 O1m-1 ) and an obvious relationship between the hydrodynamics in the melt and at interfaces and the conditions of formation of single crystals and their quality [ 1].All types of MHD effects rest upon the generation of volume electromagnetic forces in the melt by various means as well as on the possibility to direct them arbitrary in space and to adjust easily their absolute values. Fig. l presents different means how to implement MHD phenomena during single crystal growth. It should be emphasized that in all the modifications given in Fig. l additional energy introduced into the melt cannot influence directly the crystallization process since it is incomparable to the energy of molecular forces. Both the influence and efficiency of MHD means are determined solely by the change of motion, heat and mass transfer characteristics."

Jan 1, 1998