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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 Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By Helfried Nafe

"For about a century thermodynamically absurd facts have been propagated in conjunction with the iron-carbon phase diagram. These facts concern fundamental relationships of chemical thermodynamics. Attention is turned here to the discussion of only one of the relevant aspects of the subject, i.e. the definition of the thermodynamic activity of the solute and its implications for the iron-carbon solution.IntroductionThe view on the iron-carbon solution is characterized by the assumption that the solute may appear in two different forms, i.e. graphite and cementite. Accordingly, two carbon solubilities are differentiated, on the one hand for graphite and, on the other hand, for cementite. As a consequence, two versions of the phase diagram exist simultaneously, the application of which depends on the prevailing conditions, (i) the so-called stable phase diagram with graphite as solute and (ii) the metastable one that is based on the cementite-in-iron solution. These diagrams are joined together in the double phase diagram that originates from Heyn [l ], with the first ideas mainly going back to Stansfield [2] and Charpy [3].Thermodynamically, the most inadequate implication of the Fe-C double phase diagram is that the carbon activity may take values larger than unity. With the standard state of the activity being that of the pure substance, i.e. the Raoultian one, such a value implies the nonsensical existence ofa state purer than pure. The explanation of this physical state, ifthere is any, vaguely refers to supersaturation and, in the wider sense, to the physico-chemical phenomenon of metastability. Other aspects of chemical thermodynamics are likewise involved. Therefore, the comprehensive investigation into the present subject requires more topics to be considered than only one separate issue. Not only should the criticism of the present view be in the focus but also the discussion of new ideas capable of reconciling the experimental facts, known about the F e-C system, with the fundaments of chemical thermodynamics. All this, however, cannot be provided here because of the limited space available. As a consequence, in what follows only a part of the whole problem is under scrutiny, i.e. the definition of the thermodynamic activity and its role for the interpretation ofrelevant experimental facts."

Jan 1, 2014

By Malti Goel

"The cost-effective capture of carbon dioxide (CO2) from the point sources for its reduction the atmosphere offers many challenges in materials science. Novel CO2 capturing approaches using chemical, physical and biological methods are in the research stage and are aimed to minimize the cost. Appropriate materials development , which can withstand required temperature or pressure as the case may be for CO2 emanating from coal gas or industrial waste gases form the minimum condition. Other requirements are reclyclability of material and cost of separation. Nano-material composites can be more effective in selective capture of CO2 and can offer solutions for large-scale separation process. Nano-porous material catalysis can enhance the reaction rate of CO2 with other chemicals and thus help in capture of CO2 and convert it into value added products. This paper reviews recent industrial scale developments. In the Indian context, R&D priority areas in CO2 capture process development with a focus on energy industry are presented.IntroductionScience of Climate Change is growing at an enormous pace. With the ultimate goal of stabilization of greenhouse gases in the atmosphere, new scientific approaches are being researched worldwide. A shift in policies from low carbon and no carbon energy sources to fossil fuel sources with capture of carbon and its permanent storage is taking place. The process of carbon capture is both energy and materials intensive and the cost of power generation may increase up to 40% when carbon capture and storage (CCS) technology is implemented. Development of cost effective R&D technology therefore remains the greatest challenge before the scientific community."

Jan 1, 2009

By Shengqin Zhang, Yousef Mohassab, Feng Chen, Hong Yong Sohn, Mohamed Elzohiery, Amr Abdelghany

A novel ironmaking process is under development at the University of Utah aimed at producing iron directly from iron oxide concentrate in a flash reactor. This process will reduce hazardous emissions and save energy. The kinetics of magnetite reduction with hydrogen was previously investigated in our laboratory in the temperature range 1150 to 1400 oC at large temperature increments (~100 oC increments). Due to the significant melting that occurs above 1350 oC, the reduction kinetics was measured and analyzed in two distinct temperature ranges of 1150 to 1350 oC and 1350 to 1600 oC (~50 oC increments). Experiments were performed using magnetite concentrate particles of different sizes under various hydrogen partial pressures and residence times. Reduction degrees of more than 90 % were achieved in a few seconds at temperatures as low as 1250 ºC. Different rate expressions were needed to obtain reliable agreement with experimental data.

Jan 1, 2016

By Daniel K. Kim

The charge for the copper refinery is a mixture of anodes produced at San Manuel from BHP source concentrate and copper purchased from external sources. Control of unwanted impurities in the tankhouse - is very important and beneficial. Currently available removal/recovery technologies were reviewed for the control of bismuth and antimony levels in the electrolyte. Recent studies have focused on solvent extraction (SX) technology and generated successful results for the removal and subsequent recovery of bismuth and antimony. The SX system employs the reagent, ACORGA SBX-50, in conjunction with a patented high chloride stripping system. The latter enables recycle of the eluant, avoiding the high costs associated with conventional systems, such as regeneration of resin. Concerns over potential transfer of organics and chloride ion to the electrolyte were readily addressed, solved and demonstrated using conventional, established technology. This paper describes the benefits of electrolyte purification, the flexibility afforded by the SX system, the operational practices necessary for maintaining adequate control of bismuth and antimony impurities in the electrorefining environment and possibilities for future development /exploitation of the Zeneca SX system at the San Manuel refinery.

Jan 1, 1998

By William J. Pardee, Michael A. Shaff

"Deeper materials science knowledge from mathematical models and in situ material property sensors will be exploited in next generation factory process controllers to improve productivity and quality. These intelligent control systems will accelerate productivity growth and materials science application through the ease with which they can be modified to accept new materials knowledge and sensors. Carbonization of resin matrix carbon fiber composites, specifically, is a violent solid state chemical reaction with large stresses due to gas pressure, matrix shrinkage, and differences in thermal expansion. The matrix strength falls sharply, then rises again during the process. At least two competing reaction paths are important; the first cleaves methylene bonds, reduces toughness, density and stiffness; the second reforms those bonds, ultimately resulting in aromatic ring condensation that increases density, strength, and modulus. Since these reactions have different temperature dependencies, one can expect to shift the process towards the second path by changing the heating rate, but that change must be accomplished without producing macroscopic interlaminar crack growth. To accomplish this, we employ gas sensors to infer matrix chemical state and acoustic emission to identify microstructural changes and to recognize brittle fracture. The latter does not prevent delamination, but is important in testing models for the causes of delamination and in improving the processing cycle. This paper describes a control strategy to accelerate the process while still lowering the risk of failure.IntroductionDeeper materials science knowledge from mathematical models and in situ material property sensors will be exploited in next generation factory process controllers to improve productivity and quality. These intelligent control systems will be more easily modified to accept new materials knowledge and sensors, thus accelerating productivity growth. Such a control strategy for carbonization control is described below.Carbon-carbon composites are time consuming and costly to manufacture. Processing methods have been developed empirically and are usually very conservative because the process often fails when any change is made. Apparently minor changes in materials or geometry can produce failures that are difficult to diagnose and correct. We will describe below several essentially unavoidable sources of variability. These are best dealt with by applying materials science to adapt (i.e., closed loop control on materials properties) the process in real time to reduce the effect of unavoidable model idealizations, material variability and environmental noise. The most critical issue in control of the carbonization process control is avoiding catastrophic delamination. The strategy developed below makes use of a priori materials knowledge and real time sensors to accelerate the now very slow process without destroying the material, and without requiring unreasonable resources to determine the statistical properties of the material."

Jan 1, 1988

By J. M. Tannenbaum

A depth-sensing micro-indentation technique is developed for evaluating mechanical properties of materials at elevated temperatures (to 1200°C). System description and design considerations of the test apparatus are described. Based on Hertzian spherical indentation approach, the micro-indentation test apparatus is capable of determining Young?s modulus and creep strength of test materials with flat, tubular, or curved architectures from room to 1200°C under either air or controlled gaseous environments. Calibration tests were conducted on a H13 Tool Steel coupon from 22°C to 500°C and single crystal Haynes 230 alloy at 1000°C with excellent agreement to the literature values. Indentation creep tests of Haynes 230 alloy were carried out at 1200°C with preliminary results showing good correlation to creep exponents. Further system refinements will be investigated, and additional testing will be conducted.

Jan 1, 2010

By R. Nilsson

In the present work, an assessment of the sulphide capacities of a number of binary and ternary slag systems have been carried out in the light of a sulphide capacity model. The model is based on the expression: {CS- exp (-A G °/R T) ? ao2 / fs2-} where AGO is the standard Gibbs energy change for the above reaction, ao2 is the activity of oxygen ions and f, is the activity coefficient of the sulphide ion in the slag. In the present model, the ratio (ao2/fs2) is optimized for the experimental data available in literature. The systems assessed are the binaries MnO-SiO2, CaO-SiO2, Al2O3-CaO, as well as the ternaries CaO-Al2O3-SiO2 and CaO-MnO-SiO2. In the case of all these systems, the experimental data available in literature were complemented by measurements carried out at the Division of Theoretical Metallurgy. The sulphide capacities of some FeO- containing binary, ternary and quaternary slags are also examined. The potentiality of the model to estimate the sulphide capacities of complex slag systems from binary and ternary data is demonstrated.

Jan 1, 1996

By I. M. Ritchie

Cyanide owes its great success as a lixivant for gold to the great strength of the Au-CN bond. A replacement for cyanide must similarly be a strong complexant for gold (I) or gold (III). The various alternatives are briefly considered and it is concluded that only thiosulfate has a reasonable chance of replacing cyanide as a relatively non-toxic lixivant at the present time. However, there are considerable technical problems to be overcome before thiosulfate can be considered to be a realistic alternative to cyanide. Firstly, the leaching of gold using aerated ammoniacal thiosulfate with copper as a catalyst is a complex process which needs to be understood and controlled carefully in order to achieve maximum recoveries with minimum reagent losses. Secondly, there needs to be an option similar to the CIP process for recovering and concentrating the dissolved gold thiosulfate complex from pulps produced in the processing of low grade gold ores. The prospects for overcoming these technical' challenges are evaluated and discussed.

Jan 1, 1998

By Mahesh C. Meyer Jha

AMAX has developed a chloride refining process to produce pure nickel and cobalt metals from mixed sulfide .precipitates, Metal chloride solutions, generated in a hydrochloric acid leaching step and purified in a solvent extraction circuit, are converted to metal oxides .and HCI gas by pyrohydrolysis. A pilot plant consisting of a 30-inch diameter fluidized bed reactor and other ancillary units was designed, constructed, and operated for over one year. Process design was aimed at minimizing energy consumption, maximizing conversion efficiency, and achieving simplicity of operation and control. The operation provided valuable information on process scale up parameters, process control strategies, and materials of construction., Several process variables such as bed temperature, solution composition, solution feeding system, bed particle size distribution, and fines recycle system were investigated to determine their effects on process efficiency and the physical and chemical characteristics of the product.

Jan 1, 1985

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Robert A. Reiley

Under the traditional environmental paradigm, industry, stakeholders, and government impact the environment through production, consumption, and regulation. For more than twenty years, this paradigm has survived more or less unchallenged. Environmental action has followed a typical pattern: industry pollutes, the public clamors, government enacts legislation, and industry expenditures for pollution-control equipment soar. In the 1990's, many groups realize that command-and-control techniques may not be the most effective method of dealing with environmental issues in the new millennium. The need for regulatory reform became apparent in the 1980's after an accident at the Union Carbide plant in Bhopal, India. In addition, the prospects of an integrated European market and increased global trade sparked a need for common standards regarding the production of goods and services, which led to the adoption of the International Standards Organization (ISO) 9000 Quality Standards. These factors, and others, triggered the development of the Environmental Management System (EMS). Over the past decade, country-and industry- specific EMSs were developed. However, the IS0 realized the need for a single, internationally recognized standard that would be workable for any type organization. The goal of this standard is to promote economic competitiveness, remove trade barriers, and promote environmental protection. To this end, the IS0 14000 Standards were developed to provide business with a structure for managing environmental impacts. This article argues that a new paradigm has begun to transcend the old. Protection of the environment if shifting from "government drivers" to "market drivers". This shift means that industry and stakeholders, instead of government, are taking the lead to develop ways to protect the environment. This article also argues that government can use this new paradigm, in a time of declining budgets and regulatory reform, to continue to protect the environment through increased compliance monitoring and rigorous enforcement. Specifically, the IS0 14000 Standards can allow the government to reduce compliance costs, streamline permit and reporting requirements, and provide business with regulatory flexibility. Finally, this article argues that IS0 14000 will be central to the regulatory reform effort, because it can be internally implemented with little need for legislative intervention.

Jan 1, 1999

By Rolf R. von Oppenfeld

Onsite hazardous waste processors often find obtaining a Treatment Storage and Disposal (TSD) permit one of their first major challenges. Some processors may spend the time and money required by the permitting process, only to find out later that a permit was not necessary. This paper will present and analyze four strategies that processors may use to avoid obtaining a TSD permit. Some facilities will be able to remove their waste streams from RCRA's oversight by ensuring the material is not "hazardous" waste. Parties that treat waste while it is in process may be able to avoid generating "waste" altogether. Certain treatment facilities have been specifically exempted by EPA. Finally, treatment of waste while it is in generator storage tanks may be allowed without a RCRA TSD permit. Hazardous waste point of generation, an important determination relating to these strategies, will also be discussed. Generators and processors will find this paper useful when evaluating their permit exemption potential

Jan 1, 1996

By S. Seetharaman

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 oldie 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.

Jan 1, 1996

By Patrick R. Taylor

Keywords: Thermal Plasma, Electroreduction, Electrolysis, Transition metals, Waste treatment, Molten oxides, Chromium oxide. An innovative process to treat transition metal oxide waste materials from diverse sources is presented. This technology involves using reverse-polarity DC plasma driven electrolysis in molten oxides. The process results in the recovery of the transition metal and other heavy metals from waste. By-products generated throughout the processing was converted to environmentally acceptable slag. The significance of this technology is that the treatment of the waste is accomplished in one step which in turn lowers the cost of remediation. Moreover, this process uses high temperature properties of thermal plasmas, which makes it possible to use molten oxides instead of halides as electrolytes. Chromium was successfully reduced from chromium oxide through the plasma driven electro-reduction process. It was shown that the selection of the appropriate ionic conducting oxides was critical for the formation of a slag that would enhance the reduction of chromium oxide.

Jan 1, 2004

By Yutaka Shiraishi

Two methods were developed to measure the viscosity of the slag from the glassy to the liquid states in an ascending temperature process. The first method employs rotating parallel plates within which is placed a solid cylindrical sample in line with a sphere. The second method uses a tube which is pushed into a sample held in a rotating crucible. Both methods were tested using standard glasses, including boron trioxide and NBS standard glass #711. The main difference between these two methods is in sample preparation. Comparative measurements between two methods were performed using a sodium boro-disilicate glass containing 5%mol of alumina. The results showed good agreement in the mid-range of glassy viscosities, 105 to 107 Pa.s. In the liquid state, there were no significant differences between the two methods.

Jan 1, 2003

By Yutaka Shiraishi

Two methods were developed to measure the viscosity of the slag from the glassy to the liquid states in an ascending temperature process. The first method employs rotating parallel plates within which is placed a solid cylindrical sample in line with a sphere. The second method uses a tube which is pushed into a sample held in a rotating crucible. Both methods were tested using standard glasses, including boron trioxide and NBS standard glass #711. The main difference between these two methods is in sample preparation. Comparative measurements between two methods were performed using a sodium boro-disilicate glass containing 5%mol of alumina. The results showed good agreement in the mid-range of glassy viscosities, 105 to to7 Pa.s. In the liquid state, there were no significant differences between the two methods.

Jan 1, 2003

By Grant E. Casley

Since 1970 Mount Isa fines Limited has made a significant increase in blister copper production from approximately 100,000 to 155,000 mt per annum and in fact 161,040 mt were produced in the calendar year 1974. Flowsheet developments including fluidised bed roasting and converter slag flotation are discussed, particularly their contributions to minimising major equipment changes in smelting and converting. The use of model- ling and simulation techniques for such an exercise is mentioned. The paper reports the alterations made to both equipment and operating techniques in the reverberatory furnace and converter sections to achieve the regular production of 250 mt of blister per converter day from a 41% Cu matte grade. The effects of flux composition on converting performance are highlighted. The air quality control programme is discussed in relation to its restriction of blister copper production.

Jan 1, 1976

By David Melgaard

A significant emerging recycling, waste minimization problem stems from legacy waste from the nuclear weapons program and from production of power using nuclear fuel. Premium quality metals used in nuclear plants become contaminated, making them unsuitable for reuse. Consequently, decontamination studies were conducted to evaluate the decontamination capacity and partitioning effeetiveness of Electroslag Remelting (ESR). Eight laboratory melts were conducted to evaluate the efficacy of using ESR to transport radionuclides from the liquid metal phase to the liquid flux or slag phase. To determine the decontamination effectiveness, several surrogate compounds for uranium, plutonium and other fission products were added to the melts. During the melts, the melting rate was varied, typical slag additives were used, and two different slag compositions were evaluated. The resultant post-test ingots and slag were then analyzed to determine the partitioning of the surrogates. ESR generally proved very effective in removing contaminates from the metal with a few noted exceptions. -

Jan 1, 2003