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By G. L. Peralta

Geothermal energy is an important source of power in more than 12 countries and is a potential source in 50 countries. However, the exploration and use of geothermal resources generate residues such as scale and sludge. The scale is from the steam distribution pipes while the sludge is from cooling ponds. These solids contain significant levels of elements which are of environmental importance notably, arsenic, sulfur, copper, zinc and lead that require safe treatment and disposal. The compositions, phases, textures, morphologies and size of scale and sludge particles have been studied by laser particle size analysis, light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. In addition, their leachability was tested with protocol leaching procedures and sequential extractions. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how the scale and sludge are formed, their leaching behavior if disposed of in a landfill and in developing appropriate treatment strategies.

Jan 1, 1994

By D. C. Azubike

Wolframite (FeWO4) usually having cassiterite (SnO2) as a major impurity is a primary source of tungsten. Its direct reduction/carburisation with carbon in the temperature range 1000-1400°C, and with hydrogen at 600-900°C followed by carburisation with CO at 900°C are described. Depending on the conditions and reactants employed, Fe, Fe2W, B-Sn,WC, W2C, Fe3W3C and Fe6W6C are the products. Tin was found to inhibit the overall reduction and carburisation reactions significantly. The potential for either efficient separation of iron and tungsten or a one-stage production of an iron-based metal carbide composite is discussed.

Jan 1, 1992

By Li. Jiarong, Zuojian Liang, Qingyan Xu, Baicheng Liu, Shizhong Liu, Hailong Yuan

Single crystal solidification of turbine blades is a key technology for the production of reliable and high efficiency gas turbines. The solidification process of single crystal investment castings causes a number of problems that have to be solved such as the increase of casting defects and complexity of production process. Computer modeling and simulation is helpful to predict the defects and improve the process design. In the paper, a mathematical model for three dimensional simulation of solidification and single crystal growth of investment castings was developed based on CA, mechanism of crystal growth and basic transfer equations such as heat, mass transfer equations. Many factors including constitutional undercooling, curvature undercooling and anisotropy, which had vital influences on microstructure evolution, were considered in the model. Temperature, crystal growth interface and structure defects of investment castings of single crystal superalloy were investigated at withdrawal rates of 4.5mm/min and 7mm/min. Simulated results showed that microstructure evolution and structure defects were predicted reasonably and calculated results were coincident with experimental ones. The study indicated that three dimensional solidification simulation technique is a powerful tool for understanding the fundamental of solidification and the formation of structure defects in single crystal investment castings and finally for optimizing process design.

Jan 1, 2004

"Hematite pellets were electro-deoxidized to iron in molten sodium hydroxide to produce iron containing about 10-wt % oxygen. The anodic reaction was the evolution of oxygen on an inert nickel anode. Before the electrochemical reaction, there is a reaction between sodium hydroxide and ferric oxide to form sodium ferrite and, in order to compensate for the reduction in sodium oxide content, 1 wt % sodium oxide is added to the melt. In a laboratory cell, the cell voltage was 1.7 V with a current density of 5000 A m-2, a current efficiency of 90% and an energy consumption of 2.8 kWh kg-1.Introduction The iron and steel industry contributes about 2.3 bn tonnes/annum of the carbon dioxide to the atmosphere, which is about 10% of the total, and some believe that, in order to prevent a catastrophic rise in the earth’s temperature, carbon dioxide emissions must be reduced by 50% come 2050. However, by 2050, it is likely that the iron and steel industry would have grown significantly so that the production may have risen to 2 or 3 bn tonnes/year so in order to meet the 50 % reduction on today’s figure, the carbon dioxide may have to be reduced to 25% or less, which is a very demanding requirement. There are probably three ways of reducing the carbon dioxide output:1. By capture and sequestration, but this may be technically very demanding.2. Reduction using hydrogen in place of carbon."

Jan 1, 2009

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By P .. R. Ammann

A two-stage pyrometallurgical process has been developed for the recovery of copper (and other non-ferrous metals) from copper smelter slags. All types of slags, including highly oxidized, converter-type slags, are cleaned in an electric furnace which employs mechanical mixers to promote magnetite reduction and copper extraction at high rates. In a 10-ton pilot furnace, it has been demonstrated that slags can be cleaned to 0.2-0.3 per cent copper with economically acceptable usage of raw materials and energy; copper is recovered as a high-grade matte. Pilot plant data have been scaled up to a commercial furnace and engineering designs have been made for a furnace to treat 60 tons per hour of slag from a Noranda Reactor and the associated converters. Plans are being formulated for the construction of a prototype slag cleaning furnace.

Jan 1, 1976

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By Brajendra Mishra

Molten Salt electrolytic processes offer unique opportunities to extract and refine metals where gaseous or metallothermic reduction, hydro metallurgical extraction and aqueous electrolytic methods are thermodynamically constrained. Production of aluminum and magnesium by molten salt electrolysis are well known commercial processes. Several other reactive metals, such as lanthanides and actinides, as well as beryllium and calcium, make use of molten salt processing for extraction and refining. This presentation describes the science of molten salt chemistry and electrochemistry for winning and refining of several metals. In addition, recovery of metals from waste process salts by molten salt reduction as well as oxidation have been discussed. Material issues in design of molten salt reactors have been included. Various applications have been presented through case studies. Experimental data have been included to justify the suitability as well as limitations of these specific processes.

Jan 1, 2003

By Nagahiro Saito, Takashi Nishimura, Takamichi Ichikawa, Akio Fuwa

"Yttria-stabilized zircohia (YSZ) has high potential to be used as solid-oxide fuel cell (SOFC) electrolyte. However, the high efficiency of SOFC has not been yet achieved due to the high internal resistance of bulk electrolyte. The resistance becomes lower with the decrease in the electrolyte thickness. Thus, the decrease in electrolyte thickness leads to lower internal resistance. . The aim of this study is as follows: (a) to prepare the thin films of YSZ by inductively-coupled RF plasma-enhanced metal organic chemical vapor deposition (PEMOCVD) process using Zr(t-OC4H9)4,Y(DPMh and oxygeil, and (b) to reveal the relationship between the structural characterizations and the process parameters.1. IntroductionYttia-stabilized zirconia (YSZ) has, been widely used as not only heat-resistant materials but also the components in automotive oxygen sensors, electrolytes of solid-oxide fuel cell (SOFC)(1)(2) and the buffer layers for the high-temperature superconductor because of its low thermal conductivity, good mechanical properties and high ionic conductivity. However, it is said that the internal resistance of the bulk electrolyte is too high to be appropriate as a solid electrolyte for high-efficient SOFC. The authors believe that the thin YSZ electrolyte can give a high performance to characteristics SOFC, since the internal resistance becomes lower with the decrease of electrolyte thickness. Thus the process technology to prepare YSZ thin films is desirable and must be established.In recent years, the YSZ thin films have been reported by chemical vapor deposition (CVD), thermal CVD using metal chlorides (MC) of ZrCl4 and YC(3)(4), thermal CVD using metal organic compounds (MO)(5)(10) Zr(t-OC4H9)4 and Y(C11H19O2)(11) and plasma-enhanced (PE) CVD using MO. Here, these methods are called MCCVD, MOCVD and PEMOCVD. MCCVD has two disadvantages; a large quantity of chlorinated impurities in deposited films and high processing temperature (> 1273K). This high processing temperature leads to damage of substrates in particular, so the application of this technology is limited. On the other hands, the processing temperature by MOCVD becomes and is lower. Unfortunately, the accurate vapor pressures of these metal organic compounds have not been, known so: that it is difficult to control the composition and the film thickness by MOCVD method well. Moreover, the large amount of carbonic compounds in the films prepared by MOCVD method is produced. However, plasma-effect has been reported to decrease large amount of the carbonic impurities by PEMOCVD. However, PEMOCVD has many reaction parameters in plasma processing; the geometry of experimental apparatus, radio frequency, electronic power input and so on. Thus, the general understanding about the relationship among reaction parameters, the composition and crystal structure of thin deposit film by this method has not yet been established."

Jan 1, 2000

By M. Suzuki, M. Dobashi, M. Kahata, T. Yoshida

Almost 30% of steel in Japan is produced by electric arc furnace (EAF) treatment of iron scrap. EAF dust includes approximately 20 wt % of Zn and 3- 5 wt % of CI and is treated by the pyrometallurgical processes to recover Zn as Zn oxide. Direct hydrometallurgical processing is one of the most effective methods to recover high purity Zn. In this case, CI in the EAF dust is dissolved in the liquid phase by leaching, and the CI anion in electrolyte attacks anodes which are commonly made of a lead base alloy. Several processes have been proposed to remove CI anions from acidic sulfate solution. In this study, an electrolytic process was examined to eliminate CI anions from Zn sulfate electrolyte. From our study it can be said that the elimination rate of CI anion depends on the anode material ( i.e., the elimination rate is Pb-Ag alloy == Pb > DSE== Pt). In industrial Zn electrowinning process, the electrolyte contains Mn, which means the influence of Mn should be considered in the elimination of Cl. Mn dioxide deposition on an anode plate reduces the efficiency of CI removal. A periodical reverse current electrolytic system was examined to prevent this efficiency decrease, and deposited Mn dioxide could be removed very rapidly when the current is reversed. More than 95% of CI anion could be removed by this method in a shorter period than direct current method.

Jan 1, 1997

By Florian Kongoli

Non-ferrous smelting slags .can contain magnesia, which substantially increases the liquidus temperature. One option to counter this increase is to flux with calcia. In this work, experimental liquidus measurements including new measurements on industrial slags have been compared with a FACT-based thermodynamic model, which predicts the liquidus surface of multi-component iron silicate smelting slags containing both magnesia and calcia. The predictions, which agree well with experimental results, are summarized in both isothermal and non-isothermal diagrams to give a quantitative description of the liquidus surface.

Jan 1, 1998

By Kuniaki Murase

Cadmium telluride (CdTe) semiconductor has been well investigated as a CdS/CdTe heterojunction solar cell material since its band gap is suitable for energy conversion from sunlight into electricity. In this paper a new electrochemical processing of thin-layered CdTe using basic aqueous electrolytes is reviewed from the standpoint of thermodynamics using a potential-pH diagram. The cathodic electrodeposition of the stoichiometric CdTe with a flat surface morphology took place at more positive potentials than that of the Nernst potential for the bulk-Cd deposition and at more negative potentials than that for the hulk-To. In this potential region deviation from the stoichiometric composition of eleetrodeposited CdTe was controllable by the Cd(II)/Te(IV) concentration ratio, pH, or concentration of complexing agent for Cd2+ ions of the electrolytes, The deposition behaviors for ammoniacal media were well accounted for by the potential-pH diagram of the Cd-Te-NH3-H2O system devised by a combination of those of the Cd-NH3-H20 and the Te-H2O systems, Diagrams for other complexing agents, ethylenediamine and diethylenetriamine, were also constructed to investigate and discuss the electrodeposition conditions regarding the corresponding media.

Jan 1, 2003

By F. H. (Sam) Froes, C. Suryanarayana, K. C. Russell, C. M. Ward-Close

"Far from equilibrium synthesis allows development of novel crystal structures and microstructures, leading to achievement of enhanced physical and mechanical properties. A number of ""far from equilibrium"" techniques are reviewed with emphasis on the amount of departure from equilibrium. The ability of two such techniques, mechanical alloying (MAl, and physical vapor deposition (PVD) to develop novel structures are discussed in detail. For the MA process emphasis is placed on intermetallic compound compositions. Solubility extension, beyond rapid solidification (RS) levels, is found in terminal compositions but not for the intermetallics. Nanostructure-sized grains (< 100nm) form which can be retained after ""low temperature"" compaction. On continued milling in many cases the nanometer-sized grains transform to an amorphous structure. Ordering is destroyed by MA, except in those intermetallics with large negative enthalpies of formation. For the PVD process, a review of application to terminal light alloy compositions is presented. This includes a new high-temperature aluminum alloy, layered materials with nanometer spacing, corrosion-resistant magnesium alloys and low-density titanium compositions. IntroductionTo enhance the mechanical property combinations of advanced structural materials innovations in process/synthesis are required [1-6]. In this paper the capability of various ""far from equilibrium"" synthesis techniques [7,8] to produce novel constitutional and microstructural effects, and hence potentially enhanced physical and mechanical properties, in advanced materials is presented. The application of two such methods, mechanical alloying (MA) and physical vapor deposition (PVD) is discussed in detail. For the MA process emphasis is on intermetallic compositions with consideration given to solid solubility extension, microstructural refinement, amorphization, and formation of intermetallic compounds. For the PVD process application to terminal light alloy compositions is discussed."

Jan 1, 1994

By C. M. Iheagwara

An overview of the scope and ramifications of scrap recycling in the Nigerian metallurgical industries has been presented in this paper. The modern state-of-the-art processing techniques and the operational strategies employed in the recycling plants are discussed. Optimization techniques for cost effective recycling operations are highlighted. As new units within existing metallurgical plants and new metal working plants approach commercial operations, expansion of existing recycling plants and the emergence of new ones have been showing to hold the key to their profitability from the raw material standpoint. The present economic predicament of the entire industrial sub-sector, lack of sufficient foreign exchange to procure new machineries and the emergence of a maintenance culture have triggered a phenomenal increase in the number of spin-off industries which depend on metal recycling activities. This, it is argued, widens the horizon for scrap processing/recycling.

Jan 1, 1992

By John L. Hostetler

GALFAN, the Zn-5% Al-mischmetal hot-dip galvanizing alloy is coated onto steel sheet, wire, and tube using high-speed continuous galvanizing lines. Factors critical to producing high quality GALFAN are reviewed, The relationship between minimum mischmetal content in the GALFAN alloy and furnace dewpoint will be described. The relationship between peak annealing temperature and furnace dewpoint will also be shown. Typical suategies for operating multi-purpose hot-dip galvanizing lines including GALFAN will be described. A recent development has allowed preparation of steel smp for GALFAN coating using aqueous fluxes rather than high temperature annealing. This allows production of GALFAN-coated smp without over-ageing of the steel, and allows high steel strengths and hardnesses to be obtained. The principles of this process will be described.

Jan 1, 1992

By Edita Vircikova

The best demonstrated available technology (BOAT) for the removal of dissolved arsenic and some heavy metals as reported by USEPA (Contaminants and Remedial Options at Metal Sites, Draft Report, August 1993) (1) is still the chemical precipitation. Coprecipitation with the excess of iron is usually practised because of the availability of iron at low/no cost and also in order to meet the stringent regulatory discharge limits. The arsenic is usually removed with iron because of its common occurence in the mined orebodies and the excellent adsorptive property of the precipitated hydrous ferric oxide compounds. There has been controversy, however, over the long-term stability of the arsenic-bearing ferrihydrite which is produced.

Jan 1, 1995

By Tor Lindstad

Specific C02-emissions are given for the production of silicon-metal, ferrosilicon, ferromanganese and silicomanganese. Emissions taken into account come from reduction materials, from coke production and generation of electric energy. C02-emissions can be abated by direct and by indirect methods. A direct method is to replace fossil carbon as reduction material wholly or partially by endogenous carbon (biocarbon, charcoal). Another possibility is to produce metals by electrolysis instead of the present electric smelting furnace. Indirectly CO2-emissions can be reduced by energy recovery, thus saving coal, oil or natural gas for heat generation. Some reduction in global C02-emissions can be obtained by giving credit for the use of silica dust partially replacing cement in concrete. In addition to give an overview of possible methods, costs will be discussed.

Jan 1, 1999

By Noriaki Kurita, Norihiko Fulcatsu, Teruo Ohashi

"An electrochemical sensing device for hydrogen in molten metal has now been available owing to the development of the proton conducting solid electrolyte made of ceramics of metal oxide. The structure of the sensor and the theoretical limitations of its applications are discussed based on the electrochemical properties of the electrolyte used. The practical performance of the sensor is reviewed from the results of test measurements at the plants of aluminum and copper melting industries. The effectiveness of the sensor to the process control of continuous casting of copper is also discussed.IntroductionSince the in-line monitoring of the amount of oxygen dissolved in molten metal was realized by using the oxygen concentration cell based on zirconia solid electrolyte a similar method has been expected to be developed for sensing of hydrogen, which is a very important element of gas species in liquid metals, especially, in aluminum and copper. In 1981; Iwahara and coworkers found the dominant proton conduction at a high temperature in some perovskite-type oxide (1). Since then, the effort has been made to apply this proton conducting material as the electrolyte of the hydrogen concentration cell for high temperature use. The hydrogen sensor for liquid aluminum of this kind was first produced in 1991 (2) and released commercially from TYK Co., Ltd. Recently, we have developed the mother one usable at higher temperature such as copper and silver melting processes (3). In this note we discuss their structure, design and applicable limitations based on the electrochemical properties of this new type electrolyte. The performance of the sensor and benefit to use it to control the melting process is also discussed"

Jan 1, 2000

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983