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By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By A. R. Kiani-Rashid

Controlled graphitization has become known as a practical method for improvement of wear resistance and machining properties in steels. In this paper, the effect of heat treatment on microstructure of CK45 steel has been investigated. Austenitising was carried out at 920°C for 5 hours. Besides, isothermal transformation was conducted at 750°C in the time range of 1-20 hours. The microstructure of the steel considerably changes by this heat treatment process which exhibits the effects of temperature, appropriate austenitising duration and isothermal transformation. Conducted experiments show a suitable distribution of semi-spherical graphite particles especially on the surface of the steel. Also, analyses demonstrate that the amount of formed graphite in the austenitising temperature 920°C is more than graphite in single heat treatment temperature of 750°C.

Jan 1, 2010

By Jana Dobrovska

The paper deals with new approach for measurement and evaluation of chemical microheterogeneity of elements in polycomponent metallic systems (i. e. steels, Ni-alloys). The method is based on the original mathematical model for determination of distribution curves of dendritic segregation of selected elements and on the original mathematical model for determination of the effective partition coefficients of these elements in the structure of analyzed alloy. Application of the method at research of chemical heterogeneity of continuously cast steel slab is also presented. The original results of measurement of dendritic microheterogeneity of eight elements (Al, Si, P, S, Ti, Cr, Mn and Fe) in structure of nine zones of a transversal section of slab are given.

Jan 1, 2006

By Gábor Csicsovszki

We have developed a novel method - at the laboratory scale - comprising an ion-exchange separation and a membrane-electrolysis step for the purpose of zero-waste regeneration of spent HCl pickling liquors originating from hot-dip galvanizing of common steels. It is aimed at the parallel regeneration of HCl and iron. Experiments revealed that iron can be electrodeposited at high current efficiencies by maintaining the following conditions: 0.04-0.08 M HCl, 500-1000 A/m2, 20°C and stationary electrolyte in a conventional cell. Zinc in the solution did not disturb the deposition of iron, however it contaminated the product and it poisons the anion-exchange membrane required to tackle acidity during electrolysis. For a preliminary separation, anion-exchange tests were carried out to produce pure iron solutions. Beyond the equilibrium studies, column experiments were carried out showing that low flow rates of the loading solution and the ~1.5 M HCl eluent are essential for separation.

Jan 1, 2006

By S. Seetharaman, Du Siehen

"In the processing of molten metals, it is extremely important to monitor continuously the concentration levels of various minor elements. In the production of common metals like copper, iron and aluminium electrochemical sensors involving solid as well as liquid electrolytes are being increasingly used to measure the concentrations of minor elements. The present paper deals with the electrochemical principles underlying these measurements and the possible errors involved. One of the major difficulties in the case of the solid electrolytes is to correct for the consequences of the electronic contribution to the conduction of the electrolyte.The application of the electrochemical sensors for molten metals processing involves designing of these probes to withstand the industrial operating conditions. In this respect, significant achievements have been made with respect to the design of oxygen probes for liquid metals in general and liquid copper in particular. Some of the salient design features are discussed in the paper. The application of auxiliary electrodes for impurities in molten metals like phosphorus in copper and silicon in iron are taken up. The development of oxygen sensors for slags is given special attention. Recent developments in the field of sensor technology, as applied to metals processing are highlighted.1. IntroductionThe rapid technological advancement today require precise control of the process parameters and the impurity levels. Most of the molten metals processing in industrialized countries are often steered by suitable computer models, either phenomenological or simulations based on theoretical principles. These models often require that the process parameters are continuously monitored so that the progress is followed and modified suitably as and when required. It is common practice to measure temperatures by incorporating temperature sensors at the various strategic points of the reactor. In the case of monitoring the composition changes in the various phases, the method of sampling followed by routine chemical analysis involves a time lag as well as uncertainties in sampling and analysis. In this respect, electrochemical sensors have the advantage of generating accurate data when properly applied and increasing attention is being paid in the development of electrochemical sensors for various common species in molten metals processing. In the present paper, the developments in this area over the years are outlined and typical process applications are discussed. A greater emphasis will be laid on sensors based on oxygen conducting electrolytes and their application to the production of common metals like iron and copper."

Jan 1, 1996

By Young-Dae Kim, Dong-Sic Kim, Jong-Jin Pak, Kyung-Hyo Do

"Sulfur is one of the most harmful elements in stainless steel (SIS) products and the specification of sulfur content is getting more severe for high grade SIS. In order to accurately control the desulfurization reaction in high chromium containing SIS melts, it is important to know the thermodynamic interaction between chromium and sulfur in Fe-Cr melts over a wide range of chromium content. In this study, the equilibrium sulfur distribution, Ls, between a Ca0-Alz03 slag and Fe-Cr-C,.,-S melts were measured under CO atmosphere in the temperature range of 1823-1923 K. The specific effect of chromium on the activity coefficient of sulfur in the melts was determined with the consideration of carbon effect on sulfur. A separate experiment was carried to determine. Ls between a slag and FeCr- S melts (Cr: 0-30 mass%) at 1873K to check the validity of the thermodynamic parameter determined in the present study.IntroductionFerritic stainless steels containing chromium (Cr) up to 30 mass% have been developed for a good corrosion resistance and a high formability to replace austenitic SIS. Especially, Sulfur (S) causes a reduction of high-temperature strength and the hydrogen induced cracking (HlC) in stainless steel for line pipes. [l]Many studies on the desulfurization of hot metal and liquid steel have been carried out for several decades and they used HzS-H2 gas equilibrium technique for measuring the effects of many alloying elements on the activity coefficient of S in liquid iron. However, the study on desulfurization of Fe-Cr melts was very scarce.[2] In order to accurately control the desulfurization reaction of high Cr stainless steel, it is essential to know the thermodynamic relation between Cr and S in Fe-Cr melt over a wide range of Cr content and temperature.In the present study, the thermodynamic interaction between Cr and S in liquid iron was determined by measuring the equilibrium distribution ratios of S between Fe-Cr-C,.1-S melts containing a wide range of Cr up to 30 mass% and a 55 mass%Ca0-45 mass%Alz03 slag of which the sulfide capacity was pre-determined using Fe-C,a1-S melts in the temperature range of 1823-1923 K. The validity of thermodynamic parameter determined in the present study was checked by measuring the S distribution between a Ca0-Alz03-Mg0 slag of known sulfide capacity and liquid Fe-Cr-S alloy at 1873 K. Using Wagner's formalism, the results of experiment were thermodynamically considered to determine the effect of a specific concentration of Cr on the activity coefficient of S in liquid iron."

Jan 1, 2014

By Shijie Wang

Lifetime achievements of Professor Reddy ’s teaching, research and scholarship in the field of chemical and materials science and engineering are briefly described. He has devoted his entire career in the introduction and application of process engineering principles to the quantitative description of materials processing reactions, and industrial operations. He has formulated quantitative methodologies based on first principles of thermodynamics, phase equilibria and kinetics to: design of slags and fluxes for production and purification of metals and alloys; development of Reddy-Blander model for a priori prediction of impurities capacities of melts; development of novel ionic liquid electrolytes for materials processing; development of new theories for alloys and molten salts; design materials for fuel cells and capacitors; use of thermodynamic approaches to predict physical properties of materials; industrial energy waste separation and remediation; and thermal energy storage. He is a scholar and mentor, and has made numerous scientific and service contributions to the society and metallurgical and materials engineering education.

Mar 1, 2017

By Deming Wang, R. A. Overfelt

"The oscillating cup viscometer has become a dominant technique to measure the viscosities of high temperature molten metals. Unfortunately, the viscosity estimation model from the observed logarithmic decrement and period of the oscillation is very complicated. There are still large discrepancies of viscosity estimation values between using different measurement facilities and using different viscosity estimation models for a same molten metal. The purpose of the paper is to evaluate the accuracy of an oscillating cup viscometer in Auburn University. Two well known viscosity estimation models, Roscoe's and Torklep's equations, are compared and discussed. The theoretical literature for the fluid flow inside an oscillating cup is reviewed and a more accurate working equation for the Auburn oscillating cup viscometer is developed. Some design parameters of the oscillating cup viscometer, which directly affect the accuracy of viscosity estimation by using the working equation, are discussed. In addition, applications and experimental measuring data are presented in the paper for several different commercial alloys, such as aluminum alloys: A319, A356 and A201, nickel-base super alloys: In713 and In718, and casting irons, C40 Gray Iron and Ductile Iron.1 IntroductionThe oscillating cup viscometer is the most important and has been most frequently used in viscosity measurement for high temperature liquids [1-4]. The principal advantages of this technique over others are its mechanical simplicity and the ability to measure the time period and amplitude decay with great precision. In the viscometer, a high temperature liquid (such as a molten metal) is contained within a crucible suspended by a wire to form a torsional pendulum, which induces torsional oscillation motion. This motion is damped primarily by viscous dissipation within the viscous liquid inside the cup. The viscosity of the liquid can be calculated by an analytical or numerical solution ofthe equations of motion of the oscillating cup system."

Jan 1, 2001

By Anne Kvithyld

Silicon solar cells, that convert the energy of sunlight into electric energy, are attractive sources of energy. In the production line wafers of solar cells are sliced from a multicrystaline ingot solidified unidirectionally. Recycling scrap from top and sides of such ingots is addressed. SiC and Si3N4 inclusions are a major problem. Scrap from Scan Wafer ASA is melted in a high vacuum furnace at around 1500ºC. The filters, from commercial producers, are C and SiC with 10, 20 and 30 ppi. Characterisation of inclusions before and after filtration, and in the filter itself, is performed by microscopy. Dissolution of silicon in acid and counting of the un-dissolved inclusions is also carried out. In the filter Si3N4 needles and SiC inclusions were identified. The amount of these inclusions in the filtered silicon is much less than in the input. In conclusion, filtration using SiC and C filters in vacuum system in argon atmosphere removes SiC and Si3N4 inclusions from solar cell scrap. Flow of metal through the filters is not a problem. These results are promising with scale-up to industrial application in mind.

Jan 1, 2006

By Mingming Zhang, Marshall S. Coe, Marcelo W. Andrade

To supply iron units and flux burden in blast furnaces, sinter basicity is one of the vital parameters for sinter plants. The sinter basicity also plays an important role in sinter quality since it imparts the formation of different mineral phases in sinter. Pot-grate sintering tests were carried out with low and high basicity to investigate the effects of sinter basicity on sinter mineralogy, properties and productivity. It was found that with an increase in sinter basicity, both sinter productivity and reducibility (RI) increased. Tumbler index (TI) and low temperature degradation index (LTD) of high basicity sinter were comparable to low basicity sinter. Softening and melting tests showed that sinter with 3.5 C/S basicity had slightly higher softening temperature comparing to lower basicity sinter with C/S 2.6, acid and fluxed pellets. XRD analyses confirmed the formation of silico-ferrite of calcium and alumina (SFCA) and calcium ferrite (CF) in the tested sinter samples.

Jan 1, 2015

By M. Firdaus, M. A. H. Shuva, M. A. Rhamdhani, G. A. Brooks, S. Masood, M. A. Reuter

Declining grade of primary ores and resource efficiency have led us to process more alternative metal resources such as e-waste. One of the processing routes for extracting valuable metals from e-waste is through the black copper smelting. However, the underlying knowledge of the thermodynamics behaviour of the valuable metals contained in e-waste during smelting are limited which prevent us from developing an optimised process to recover all the metals. These different metals clearly will have different favourable conditions for their extraction. To illustrate this, the distribution behaviour of germanium (Ge) and palladium (Pd) between liquid copper and ferrous-calcium-silicate slag during black copper smelting was analysed. It was demonstrated that oxygen partial pressure and slag composition affect the partitioning of these metals to the copper phase and the favourable slag chemistry for recovering these metals is opposing. Considering the available thermodynamic data of these metals, an analysis for the optimum conditions is presented.

Mar 1, 2017

By Takeshi Yoshikawa, Kazuki Morita, Kunitoshi Matsunaga

"In metallurgical grade silicon (MG-Si), most impurities mainly exist at the grain boundaries and distribute in silicon grains at extremely small contents. Grain boundary phases in MG-Si transform into liquid above the eutectic temperature, and migrate towards high temperature regions when heated under a temperature gradient. With the migration of all liquid phases in MG-Si to the surface, the impurity contents will be decreased less than their solubilities in principle.In the present work, the fundamental research was conducted to discuss the possibility for purification using the liquid phase migration technique. The purification limit was estimated by thermodynamic calculations, and metallic impurities were estimated to be effectively removed except for Fe and Al. The migration behavior of the liquid phase in the synthesized silicon substrate was investigated by unidirectional heating under infrared radiation at 1523-1548 K, and the proceeding of migration was confirmed. The migration velocity was 1.4--2.0xl0-7 mis, and found to be controlled by the liquid phase diffusion.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. To enable the widespread use of photovoltaics and for the photovoltaic electricity price to reach grid parity, a low-cost and abundant feedstock of solar grade silicon (SOG-Si) is essential. Recently, a modified Siemens process and a fluidized bed reactor process were developed to address the cost and energy issues associated with the conventional Siemens process. However, their cost reduction potential is limited because of the large energy consumption needed to convert silicon into gaseous compounds. Purification of silicon through metallurgical routes offers a promising way for producing SOG-Si from metallurgical grade silicon (MG-Si), because it enhances productivity and can also lower the process costs. Although several metallurgical processes such as directional solidification [l ], vacuum refining [2-4] and plasma oxidation [5-7], have been developed, processing times and refining efficiencies still have to be optimized."

Jan 1, 2013

By Ross W. Smith

Microorganisms are increasingly finding use in mineral processing and hydrometallurgy both for the enhancement of mineral engineering operations and for the remediation of mineral industry wastes. Some of the applications, such as biologically assisted leaching of sulfide ores and biooxidation of refractory sulfide gold ores, are established commercial processes. Others, such as the use of organisms for the removal of heavy metal ions from dilute aqueous streams, are nearing commercial application. Other uses of microorganisms are potentially possible. These include use of microorganisms in leaching non-sulfide ores, the flocculation or flotation of minerals and remediation of toxic chemicals discharged from mineral engineering operations.

Jan 1, 1993

By Sergio N. Monteiro

Polymeric composites reinforced with natural fibers are increasingly been used in several engineering applications, from automotive parts to building construction elements. In addition to the relatively low cost, the natural fibers are also appraised by their renewable and biodegradable characteristics. Fibers extracted from the crust of coconut fruits, also known as coir fibers have been investigated for a possible use in composite materials. In the present work, the coirfiber/polyester matrix interfacial strength was evaluated by means of pullout tests. The variation of the pullout tensile stress vs. the embedded coir fiber length permitted to determine the critical fiber length and, thus, to calculate the interfacial strength. Observations by SEM complemented the results from pullout tests, indicating that coir fibers have a potential for application aspolymeric composites that could replace conventional materials such as wooden and gypsumpanels.

Jan 1, 2006

By W. Kunda

Silver nitrate solution is a very common product in hydrometallurgical processes involving the treatment of various silver bearing materials. Silver is recovered by electrolysis. The alternative method for the recovery of silver from aqueous solutions is the precipitation by hydrogen at elevated temperature and pressure. A previous study by the authors revealed the feasibility of this technique for the silver ammine sulfate system. Further study showed different behavior for silver in the silver ammine nitrate system and a systematic study was initiated to establish the optimum conditions for the process. The study showed that the process can be controlled by (1) composition of the feed solution, (2) temperature and (3) hydrogen pressure. The recovered silver product was in the form of very fine powder.

Jan 1, 1989

By Zhang Libo, Peng Jinhui, Zhang Zhengfu, Fu Mengbi, Han Yamei

In this paper, results of a novel synthesis method of carbon-coated LiNi113Mn113Co11302 cathode material for lithium-ion battery are reported. The carbon coating was produced from a precursor, glucose, by microwave-pyrolysis method. The structure, morphology and electrochemical performance of the bare and carbon-coated LiNi113Mn113Co11302 were characterized by X-ray diffraction, scanning electron microscopy and charge-discharge tests respectively. The L8(27) orthogonal experiments were carried out to optimize LiNi113Co113Mn1130z/C technological conditions. The conditions of the orthogonal experiments were that the glucose content were 1.5 % and 4 %, the holding time were 15min and 30min, the heating temperature were 400 °C and 500 °C and the solvent were H20 and CH3CH20H. The main experiment target include specific capacity at 0.1C and 0.2C, Capacity retention rate, medium voltage attenuation rate and The fifth discharge medium voltage. The data were analyzed by Minitab 14 statistics software. The results of analysis of variance indicated that the most influential factor was the glucose content despite of discharge rate. Secondly, the effect of the solvent was equivalent to the holding time.

Jan 1, 2013

By Thomas Boundy, PATRICK TAYLOR

Indium recovery from liquid crystal display (LCD) waste has been the subject of over 50 peer reviewed publications over the last decade; however, the first commercial recycling facilities are just beginning to be built. The low value of indium in the LCD screen material has posed a major challenge to would-be recyclers. Uncommon material combinations and geometries have further challenged development. A review of published literature regarding extraction of indium from LCDs will be presented and themes of advantageous processes will be highlighted. Barriers to rapid expansion of any recycling technology in the form of manufacturin gpractices, environmental regulations, and geographic constraints will be discussed.

Mar 1, 2018

By B. Q. Li, R. A. Mirshams

"A numerical algorithm is described for the simultaneous prediction of the thermomechanical behavior of the materials and microstructure evolption during metal forging. The numerical development is based on the finite element solution of the thermoviscoplastic deformation of metals coupled with the internal state variable model describing the microstructure evolution involving work hardening, recovery, recrystallization and grain size distribution. The finite element code for rigid viscoplastic deformation is developed based on the modification of the existing code for the thermal and fluid flow calculations. The code is tested against and compares well with the results reported in literature. The procedures for the integration of the · rnicrostructure model into the macro finite element model are described. Results are presented showing the characteristics of materials dynamics and mechanical deformation during simple metal forging processes.IntroductionIn industrial deformation processes such as hot rolling and forging, the workpiece undergoes both macroscopic plastic deformations and microstructural evolution. A computer model that allows to predict both materials dynamics and macroscopic deformation is obviously more useful for both fundamental understanding and deformation process optimization. For some industrial applications, especially those involving novel, light and high strength materials, such an integrated model is critical in that both materials and thermomechanical 'behavior during forging must be carefully controlled to obtain the products that meet the desired strength requirement [I]."

Jan 1, 2000

By R. V. Kumar

"The use of sensors to monitor gaseous species in industrial processes is discussed. All of the existing systems have disadvantages. Sensors, based upon solid electrolytes, which can be placed directly into the gas stream are attractive but many also respond to oxygen, need to be sealed at high temperatures and require a separate reference. This paper describes sensors, usually based upon two electrolytes, which do not respond to oxygen and do not require high temperature gas seals or separate references. The application of these sensors to the measurement of carbon dioxide, sulphur dioxide and trioxide and hydrogen chloride is described. These sensors can be placed directly into the gas stream at elevated temperatures.IntroductionOn-line gas sensing is becoming more important as concerns regarding the environment mount. There are many established techniques for monitoring gases in industrial processes, with applications in safety monitoring, chemical analysis or process and emission control. Flue gas analysis involves the greatest technical complexity, requiring several sophisticated capital-intensive spectroscopic instruments for different species as well as needing highly skilled operators. There are also several instruments, based upon aqueous electrochemistry, which are available for the analysis of the gases S03, S02, N02 but these require that the gases are sampled at high temperature and cooled, prior to analysis. These instruments cannot be considered as giving on-line measurements of the gas composition. Furthermore, the power requirement of these instruments frequently precludes battery operation for field and domestic use."

Jan 1, 1997

By S. Illendula, B. Q. Li, R. A. Mirshams

"An integrated mathematical model is developed to represent the thermomechanical behavior of the materials and microstructure evolution during metal forging. The model development is based on the finite element solution of the thermoviscoplastic deformation of metals coupled with the internal state variable model describing the microstructure evolution involving work hardening, recovery, recrystallization and grain size distribution. The procedures for the integration of the microstructure model into the macro finite element model are described. Computed results for both macro and micro phenomena during metal forging, such thermomechanical deformation such as velocity field and effective strain rate and materials characteristics such as distribution of grain size and recrystallization volume fraction, are presented.1. IntroductionThermomechanical behavior and material microstructural evolution are two critical, interrelated aspects associated with metal workpiece undergoing large plastic deformations such as encountered in forging processes. In much of the modeling work up to date, these two aspects have been addressed separately. Die designs and forging processes are investigated using finite element based thermomechanical models while material dynamics during forging is studied, more often than not, as a separate subject. For many industrial applications, especially those involving novel, light and high strength materials, it is critical to combine these two aspects into a single, integrated model so that materials dynamics and thermomechanical deformation during forging processes can be considered simultaneously [1], thereby providing required information for intelligent process design and optimal process control."

Jan 1, 1998