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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 Satoshi Yamashita, Noboru Masuko

"Newly prepared bipolar membrane is promising to become a key material of an electrolyser for a production process of strong reducing solvent. This research is basic research for using bipolar membranes as electrolysers of reducing agents, Cr(II), TI(III) and V (II) on the laboratory scale. In this report, a bipolar membrane was tried with an electrolyser, reducing chromic chloride to chromous chloride. An analysis of mass balance demonstrates advantages of it over the former electrolyser equipped with an anion and/or. cation exchange membrane. The effects of current density and concentration of Cr(lll) on the reduction rate of Cr(II) and the current efficiency were examined No deterioration of the bipolar membrane resulted from the electrolytic reduction of Cr(III). IntroductionRecently, bipolar membrane that was the development subject for a long time in the industry of ion exchange membranes has met the stage of the practical application at last [l]. The expectation of the application to the hydrometallurgy field increases. We took up the manufacturing of the strong reducibility solvent as part of the application of bipolar membrane to hydrometallurgy technology. This laboratory has much experience in the electrolytic reduction of Cr (II) aqueous .solution such as chromous sulfateusing bipolar membrane were compared in theory to chromous chloride aqueous solution manufacturing of the strong reducibility solvent. The advantage of applying bipolar membrane by substituting ion exchange membrane is described, and the experimental result is reported."

Jan 1, 2000

By Adam Powell, Soobhankar Pati

"Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.IntroductionSolid Oxide Membrane (SOM) Electrolysis is a variation on the Hall-Héroult process for molten salt electrolysis of oxides which promises to solve many of the problems of its predecessors. Magnesium in particular is both soluble in molten salts and highly reactive, such that it migrates to the anode and reacts with the oxygen or C02 anode product, reducing current efficiency to as low as 10-20%. But a zirconia solid electrolyte between the molten salt and anode blocks this reaction, boosting current efficiency to at least 90%. Separating the anode from the molten salt also opens up anode material selection to liquid metals and SOFC cathode materials such as Lai.xSrxMn03 (LSM) and YCr03. And zirconia's selectivity makes the oxygen by-product very pure."

Jan 1, 2012

By Shadia J. Ikhmayies

"Cadmium sulfide (CdS) in the form of thin films is an interesting material because it has a large variety of applications ranging from photovoltaic to luminescent devices. N-type CdS is usually used as a window layer in the heterojunction CdS/CdTe thin film solar cells. A review of the photoluminescence (PL) spectra ofn-type CdS thin films prepared by different techniques was performed. The effects of different dopants and impurities and the effects of temperature and deposition parameters on the PL spectra were discussed. Annealing in different atmospheres causes the changes in material structure and phase change from cubic to hexagonal phase which can be detected through the variations in the PL spectra. CdCh heat treatment improves the cystallinity of the films and enhances the exciton peaks and the green band in the PL spectra.IntroductionThin CdS films deserve attention because their expected gap emission lies very close to the highest sensitivity of the human eye. Thus, one might assume that thin CdS films are an appealing host for photonic devices [ l]. They have been used in a lot of applications including electronic and optoelectronic devices [2]. Thin films ofn-type CdS are widely used as a window layer in heterojunction solar cells such as CdS/CdTe solar cells. Doped and undoped CdS thin films can be obtained by different techniques such as; spray pyrolysis (SP) [3], chemical bath deposition (CBD) [2, 4], pulsed laser deposition [5, 6, 7], laser ablation [l], thermal evaporation [8].Several experimental techniques have been used in order to study semiconductor defects. In particular, photoluminescence (PL) has been shown as a powerful and sensitive tool in examining the crystal quality of polycrystalline thin films. PL can be used in the detection of defects which are radiative active. These defects can also act as traps in the transport of carriers [9]. The photoluminescence (PL) of thin film CdS is strongly influenced by the unbalanced stoichiometry, which is typical for CdS and is in general evoked by a Cd surplus. With increasing Cd content, the emission spectra move far below the gap to the red spectral range. Besides stoichiometry problems, independent of the material deposited, the PL properties of thin films depend on surface features and the influence of the interface between the film material and the substrate [10]."

Jan 1, 2013

By Toshihiro Tanaka

The information on viscosity and surface tension of molten slag is indispensable to design new refining procedures in ferrous and non-ferrous processes. For example, the authors have tried to develop "Capillary Refining" to remove impurities in liquid metals by applying capillary absorption of molten slag with those impurities into solid fluxes which have a lot of small capillary tubes. It is necessary to adjust the above physico-chemical properties to adequate conditions on the capillary penetration. In the present paper, we discuss our recent trial to predict surface tension and viscosity of molten slag in multi-component systems. We have derived a thermodynamic model to predict the surface tension of molten slag by using ionic size, molar volume and surface tension of pure components. In addition, we have applied neural network computation to evaluate the viscosity of molten slag. We found good agreement of the calculated results with experimental values of the surface tension as well as the viscosity in various slag systems.

Jan 1, 2006

By Jonathan M. Berkoe

Design engineers and metallurgists have long recognized the need for better methods to calculate a wide range of fluid dynamic effects in smelters and hydro- metallurgical facilities. Examples can range from the capture of fume in the secondary hoods of a copper converter, to controlling the thermal effects of heat transfer resulting from metal and slag flows within a furnace. With the advent of relatively low-cost, high- speed computers and user-friendly, commercially available computerized fluid dynamic (CFD) programs, these calculations can now be made. Use of CFD increased the understanding of both hot gas and molten flows in smelter facilities and has already led to design improvements in converter fume control hoods as well as improved management of heat transfer in electric furnaces. This paper will present two representative CFD applications to metals industry facilities. To date, Bechtel has implemented CFD results on four continents.

Jan 1, 1999

By Atsushi Shibayama

The aim of this research was to develop a copper recovery process from mine tailings (0.34%Cu) using flotation followed by high-pressure oxidative leaching (HPOL) and solvent extraction. The results of HPOL using the concentrate of mine tailings obtained by flotation under the optimal conditions of the previous study shown that an efficient copper dissolution of 94.4% was achieved in an H2O media, while the copper concentration of PLS reached to be 2.9 g/L. The solvent extraction of PLS obtained from the optimal HPOL showed that 91.3% copper was recovered in stripped solution under the determined optimum conditions, in which the copper concentration achieved to be 44.8 g/L. Finally, a proposed copper recovery process from the concentrate of mine tailings was developed by combination of HPOL and solvent extraction, while a total copper recovery of 86% was achieved.

By Alain Jardy, Valerio De Felice, Jean-Pierre Bellot, Ismael Lis Alves Daoud, Stephane Hans

"Gas-stirring ladle treatment of liquid metal has been pointed out for a long time as the processing stage mainly responsible for the inclusion population of specialty steels. A steel ladle is a complex three-phase reactor, where strongly dispersed inclusions are transported by the turbulent liquid metal / bubbles flow. We have coupled a population balance model with CFD in order to simulate the mechanisms of transport, aggregation, flotation and surface entrapment of inclusions. The simulation results, when applied to an industrial gas-stirring ladle operation, show the efficiency of this modelling approach and allow us to compare the respective roles of these mechanisms on the inclusion removal rate.IntroductionThe reduction of the weight of high performance materials together with the improvement of mechanical properties and the increase of the recycling of used metal are new challenges which emphasize the importance of metal cleanliness. Ladle treatment of specialty steels has long been described as the secondary metallurgical process mainly responsible for the non-metallic inclusion derived from the deoxidation process. The treatment is accomplished by blowing argon through one or more porous plugs for the purposes of desulphurization, minor composition adjustments, and inclusion removal. Gas injection is applied on routine basis to achieve both the stirring of the liquid bath (thermal and chemical homogenization) and the entrapment of the inclusions by the bubbles (flotation). Furthermore, the turbulence produced in bubble swarms enhances the probability of inclusion collisions and makes aggregation the first mechanism for particle removal. The physical processes involved in gas stirred ladles are numerous and complex owing to the three dimensional and multiphase (metal-gas and inclusions) nature of the reactor. Despite these difficulties, the population balance equations can be implemented in CFD code11'21 and combined CFD-PBM (computational fluid dynamics - population balance method) models are investigated for steel ladle processes13'41 and produce very promising results in terms of inclusion removal efficiency."

Jan 1, 2012

By W. G. Davenport

Chapter 11 determined the combinations of industrial oxygen, oil and blast preheat that will steadily produce 65% Cu matte from pure chalcopyrite concentrate. It showed that the . combinations are described by a flat plane. It also showed that the minimum energy requirement for making 65% Cu matte occurs with maximum oxygen enrichment, zero oil and zero blast preheat. This chapter examines the, effect of matte grade on industrial oxygen, oil and preheat requirements.

Jan 1, 2001

By Keiji Okumura, Hong Lan, Masamichi Sano

"Magnesium has been well known as one of the excellent agent of desulfurization, deoxidation, etc. in iron- and steelmaking because of its high reactivity. Since its production is energy nitensive, the price is very high. Thus magnesium has not widely been used as an agent in metal refining ·processes. In the present work, reduction of magnesia by carbon and aluminum is examined. Because the reaction is very sensitive to temperature, non-isothermal technique is applied to investigate the reaction kinetics. The effects of heating rate .and reaction interface area on the reaction kinetics .are studied. .A kinetic model is proposed based on the experimental results.IntroductionFor the metal refining processes, the production of high purity metal has been one of the most important research subject. In order to produce the high purity metal, the amount of the refining agent and the consumed energy is increasing. Therefore, if the future earth environment is taken into consideration, the further efficient and energy saving processes are required. Generally, Cao slag has mainly been used for desulfurization of molten iron as a desulfurization agent. However, environmental problems, such as recycling of disposal slags, are still unsolved. On the other hand, the deoxidation of molten steel is mainly performed by addition of aluminum. Therefore, the alumina inclusions· remain in. molten steel and the great efforts have been made to the removal of the inclusions. The affinity of magnesium with sulfur and oxygen is strong, and magnesium is well known as a powerful desulfurization and deoxidation agent. However, magnesium has been seldom used for the steel' refining process. The following reasons are considered. Generally, magnesium is expensive. And at iron- and steelmaking temperatures, the refining efficiency becomes low due to its abruptly .evaporation."

Jan 1, 2000

By Ulrich E. Klotz, Gemot Pottlacher, Shahid Mehmood

"Platinum alloys are frequently used in technical applications and in jewellery. Their thermophysical properties such as density, heat capacity, thermal conductivity and surface tension play an important role in casting processes and are required as input data for casting simulation. Scope of this work was to investigate these properties by different methods. Platinum and four alloys namely, Pt96Cu4, Pt68Cu32, Pt50Cu50 and Pt25Cu75 were investigated. Melting range and thermal expansion was measured at fem by DSC and dilatometry, respectively.At TU Graz wire shaped samples were investigated by an ohmic pulse heating technique. This technique allows the calculation of specific heat capacity and the temperature dependencies of electrical resistivity, enthalpy, and density of these alloys in the solid and liquid phase. Experimental results were compared with available literature and data from thermodynamic calculation using the SNOBl database and ThermoCalc.IntroductionPlatinum is a precious element and its alloys are commonly used in jewellery. But Platinum is much more difficult to cast then other jewellery elements like silver or gold, because of its high melting temperature, large shrinkage during freezing, low thermal conductivity, high surface tension, and high viscosity. As a result there arise problems during casting. Hence to resolve these difficulties a detailed study of thermophysical properties of solid and liquid platinum and its alloys is necessary for simulation and casting. The Platinum alloy samples were prepared by vacuum induction melting and casting into copper molds. Rods of 3 mm in diameter and a length of 80 mm were prepared and drawn to wires of 0.5 mm in diameter."

Jan 1, 2011

By Gary K. Elliott

Many industrial processes generate hot waste gases which contain particulate pollutants. Conventional clean-up techniques suffer limitations either because collection efficiency is low or because the gas must be cooled before treatment. thereby increasing costs and preventing energy recovery. The application of increasingly stringent environmental legislation to the non- ferrous metallurgical industry Is presently illustrating these conventional technology limitations. Low density ceramic media allow filtration to take place at high temperatures and are now rapidly becoming accepted in many industries. This paper reviews experiences with a proprietary low density ceramic filter element, Cerafill. It includes consideration of the structure, composition. typical operating and case studies with particular reference to non-ferrous metallurgical furnace applications.

Jan 1, 1992

By Brad Wahlquist

An ex-situ biological treatment system was implemented at a gold mine site in South Dakota. The system removes selenium and nitrate from a mixture of groundwater and surface water runoff at ambient water temperatures. The Applied Biosciences? system replaced a denitrification system that did not perform consistently, did not treat for selenium and required heating of the influent water. Installation was completed in phases starting with the selenium circuit being brought into operation in February, 2002 and the nitrate circuit in March, 2002. System design can accommodate average flows of 380 L/min (100 gallons/minute) and a maximum flow of 1,136 L/min (300 gallons/min). Four cells were designed to remove nitrate from approximately 30 mg/L to below 10 mg/L and two cells were designed to remove selenium from 0.01 mg/L and higher, to below 0.005 mg/L. No pretreatment is required to operate the system at ambient temperatures, which can fall as low as -12C in the winter, and treat water at temperatures ranging between 8C to 16C. Nutrient requirements are met using a sugar based nutrient mixture that includes a balanced C:N:P:S ratio, trace elements and vitamins. Since start up, the system has consistently been in compliance for nitrate and selenium, treating water to below detection limits for both contaminants. This paper discusses laboratory biotreatability testing of a system designed to remove selenium, arsenic, and nitrate and full-scale implementation and optimization of a system to remove nitrate and selenium.

Jan 1, 2003

By J. B. Cocanour

Pioneering work at the U.S. Bureau of Mines (USBM) has produced a personal computer (PC)-based, software-driven video photometric color sensor for real time process control of metallurgical streams. The video photometer is an inexpensive optical sensor which operates in the visual area of the electromagnetic spectrum and collects color information through plastic optical fiber. The red, green, and blue (R/G/B) voltage components of the color video signal are digitized and characterized through software and then presented as the control variable for software-based proportional-integral-differential (PID) control. This sensor has been successfully employed in the control of a laboratory copper electrolytic circuit. With this sensor, copper solutions were analyzed on-line without the need for sample removal, dilution, mixing or reagent addition, thereby allowing for the real time control of the circuit.

Jan 1, 1994

By Yong Hack Lee

Nonferrous smelting processes have been through a rapid transformation since the beginning of 1980. The copper smelting technology has changed from the conventional Blast Furnace process to the Flash Smelting and MIB process. In the field of lead smelting, the technology has changed from the Blast Furnace Smelting to the Direct Smelting such as QSL and KIVCET. In 1992, Onsan Refinery successfully commissioned Direct Smelting QSL technology for lead. The QSL could produce more than 160,000 ton per year of lead bullion from lead concentrate and various residues. Moreover, since the year 2000, the TSL (Top Submerged Lance) Technology utilizing the same Direct Smelting process has been successfully commissioned to treat lead concentrate as well as lead sulfate residue produced from a hydrometallurgical zinc plant. This paper presents and compares the energy flows of lead smelting processes such as a conventional process and the Direct Smelting Processes plotted on the Pb-O-S phase diagram. The oxygen potential diagram suggests how to control the oxygen potential in the furnace. Also, it describes the recent operational experience in the TSL plant of Onsan Refinery with necessary mass balance of key elements.

Jan 1, 2003

By M. S. Lee

A cold model study on the effects of various operating conditions on the dispersed-phase holdup in a liquid-liquid emulsion generated by bottom gas injection has been performed using water and kerosene. Dimensional analysis was used to correlate the holdup with the operating conditions and the sampling locations. The holdup increased with gas velocity, and decreased with axial and radial distances. The radial distribution of holdup follows a Gaussian function. The holdup increased with increasing ratio of the heavy phase to light phase volumes and decreased with the total height of the heavy phase. The combined effects of various operating conditions can be represented by the Froude number. The variation of the holdup within the plume was correlated by a single equation involving a set of dimensionless numbers.

Jan 1, 1995

By Leonard J. Friedman

Modern smelting systems using continuous, flash and/or oxygen smelting processes have a significant effect on the choice of sulfur dioxide control processes and system arrangements. Based on gases from an enriched air or oxygen smelting furnace and copper converters the paper reviews and analyzes alternate processes and system arrangements for recovery of sulfur dioxide. The work indicates the choice system to include a conventional sulfuric acid plant for converter gas and a liquid SO2 plant to handle the high strength smelting fur¬nace gas. The liquid SO2 plant would be used as a fly-wheel to damper the flow and SO2 concentration variations of the con-verter acid plant. Potential energy recovery alternates and product flexibility are also reviewed.

Jan 1, 1983

By A. V. Tarasov

Based on the data available in the literature and the practical experience of new metallurgical plants, a method has been proposed and relevant studies conducted for metallurgical processing of zinc sulfide concentrates. Process conditions and parameters have been identified, which ensure high levels of recovery of zinc into solution. This is achieved by leaching concentrates under the normal pressure at a temperature of >90°C in the presence of ferric iron ions. Sulfide sulfur is converted to elemental sulfur in this process. To produce elemental sulfur it is necessary to maintain oxidizing conditions in the system, characterized by a positive Eh value. In order to eliminate the interfering effect of elemental sulfur formed in the process, it is possible to add surfactants into the concentrate pulp. The proposed technology has certain advantages as compared with the high-temperature pressure leaching and is considered as a basic technology to be applied to increase zinc production at one of the Russian zinc plants.

Jan 1, 2006

By Riyad N. Ahmad-Bitar, Shadia J. Lkhmayies

"CdSi-xTex thin films were prepared by first producing CdS:In thin films by the spray pyrolysis (SP) technique and then annealing the films in the presence of Te vapor in nitrogen atmosphere. X-Ray diffraction (XRD) measurements showed that the films are polycrystalline with the wurtzite structure. Transmittance measurements were recorded at room temperature in the wavelength range 400-900 nm and used to deduce the absorbance. The first derivative of the absorbance was calculated and used to find the values of the bandgap energy, where more than one bandgap was obtained for each film. These results show that the films are inhomogeneous or the composition differs with location. The photoluminescence (PL) was recorded at T = 60 K and a deconvolution peak fit was performed for each spectrum. The results of the PL spectra are consistent with those obtained from the first derivative and confirm the inhomogeneity of the films.IntroductionPolycrystalline thin film CdS/CdTe solar cells are promising candidates for low cost and high efficiency photovoltaic applications. The CdS/CdTe interface plays an active role and a detailed knowledge of its properties is crucial for thorough understanding of the device. High efficiency devices have been obtained in spite of the large lattice mismatch (9. 7%) between hexagonal CdS and cubic CdTe. Interdiffusion at the CdS/CdTe interface is considered to affect the performance of the devices [1]. The formation of a mixed crystal or a graded layer at the interface causes a reduction in the lattice mismatch at the CdS/CdTe junction [2] and then a reduction in the number of interfacial states and recombination centers, thus enhancing the solar cell performance [3, 4].The objective of this work is to investigate the transmittance, photoluminescence (PL) and structure of CdSi-xTex thin films prepared by annealing the spray-deposited CdS:In thin films in the presence of tellurium vapor. X-ray diffraction (XRD) was used for exploring the structure. Transmittance is used to deduce the absorbance where its first derivative was used to find the bandgap energy which varies with composition. The evolution of the PL spectra as functions of tellurium concentration was evident and it confirmed the inhomogeneities of the films."

Jan 1, 2011

By Kazuyuki Kakegawa

"Sintered body of lead zirconate titanate (PZT) was prepared through the spark plasma sintering (SPS) technique. When the mixture of raw materials was calcined at 800°C and sintered at 900°C for 10 min. with SPS technique, the sintered body had almost theoretical density but was a mixture of lead titanate (PT) and PZT. When a calcining temperature of 1100°C was employed, sintered body had a single PZT phase but a lower density. High dielectric constant was obtained for a sample calcined at 800°C, sintered with SPS tecbriique and fired again in the air at 1100°C.IntroductionSpark plasma sintering (SPS) is a recently developed technique for sintering metals and ceramics1. The scheme of SPS is shown in Fig. 1. Sample is put in a graphite die in a vacuum chamber. It is pressed and pulse voltage is applied. The electric current heats the die. It is said that the pulse causes a spark-plasma between particles in the sample. Because of the spark- plasma, sample can be sintered at temperatures lower than that in the ordinary sintering by several hundred degrees of Celsius. The sintering period is also very short2Low sintering temperature and short sintering period in SPS technique cause low reaction rate. It is both disadvantage and advantage. In some cases, the reaction cannot be completed under the SPS conditions. If a mixture of several compositions having different properties can be sintered without a compositional change by the diffusion during the sintering, combination of properties, and therefore a design of property will be possible3. The low reaction rate of SPS may enable such combination."

Jan 1, 2000