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By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem's reduced chaotic temperature 'tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system's possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the 'tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

The results of laboratory, large-scale laboratory and commercial scale investigations regarding the process of slag melts cleaning by oxidizing-reduction gas mixtures with a wide range of Po2 and the use of matte of various compositions as an extracting phase are presented. The copper, nickel and cobalt behavior during the cleaning process has been studied based on SEM and x-ray Microprobe of the quenched slag melts. The general cleaning mechanisms have been found. On the basis of the obtained data the most efficient cleaning methods have been proposed.

Jan 1, 2003

By Jason M. Porter, Douglas L. Porter, David L. Olson, Travis W. Koenig, Van S. Blackwood, Brajendra Mishra, Robert D. Mariani

"Traditional alloy theory models have been applied relative to the three solid phases of uranium: alpha (orthorhombic), beta (tetragonal), and mainly gamma (body centered cubic)[l]. The Darken-Gurry and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer have been used to predict the behavior of four types of solutes: 1) Transition associated with alloying in and containment of the uranium fuel 2) Transuranic elements in the uranium 3) Rare earth fragmentation elements (lanthanides) 4) Transition metals and other fragmentation elements. Using these solute map criteria, elemental behavior have been predicted as highly soluble, marginally soluble, or immiscible (intermetallic phase formers) and have been used to compare solute effects during uranium phase transformations. The overlapping of these solute maps are convenient first approximation tools for predicting alloy behavior.IntroductionAn investigation is in progress to determine the role of various solute elements on size and shape of the 'Y phase field range for uranium to optimize the burning and material processing of nuclear fuel is in progress. Traditional alloy theory models based on correlations to elemental electronic and crystal properties are used to predict solubility and micro structural formation. The effectiveness of this model is based on microstructure property correlations. Darken and Gurry, and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer, models have been used to describe solute solubility with respect to uranium based the on correlation between elemental electronic structure and uranium phases. The alpha (orthorhombic), beta (tetragonal), and gamma (body centered cubic) phases have different solubilities for specific alloy additions as a function of temperature. Using the method of Waber, ellipse diagrams classified those solutes that should have broad solubility in the allotropes of uranium[2]. The predictive diagrams are made from four different correlations:"

Jan 1, 2012

By Gennady I. Gulyayev

A mathematical model of plastic deformation occurring in cold plug drawing of mother tubes with initial cross-sectional wall thickness variations (CSWTV) has been developed. The main provision of the model is that eccentricity em is of such value that projection of all forces acting upon the plug in the deformation zone along the axis perpendicular to the drawing axis equals to zero. Calculations have proven that with other conditions being equal increase in the die cone angle and the deformation cycle number reduces CSWTV. Theoretical findings were confirmed by practical results. Keywords: cold, drawing, plug, die cone, plastic deformation.

Jan 1, 2003

By Robert E. Moore

Synthetic spinel is proving to be a highly effective refractory for specific applications, but its cost limits applications. Formation of spinel from a raw material such as diaspore or bauxite could provide a suitable and less costly starting material. In the study reported here, finely ground (-325 mesh) diaspore from Missouri and bauxite from Guyana and China are combined with hardburned MgO (-325 mesh) in appropriate proportions to yield spinel and spinel with secondary phases. A classical sintering and creep study was completed, accompanied by a microstructure study to determine completeness of the reactions and morphologies of the reaction products.

Jan 1, 1991

Thallium is a very minor element found in lead ores. It's behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003

By D. D. Rodier

Most zinc concentrates contain some silver and varying amounts of such valuable trace elements as gold, indium, germanium and gallium. With increasing similarities in plant installations, the predominance of electrolyte process and the increasing environmental constraints on iron disposal, it is essential that zinc smelters optimize the recovery of any valuable elements in their feed stocks. The process options, to date, of smelting, flotation or leaching of silver-rich leach residues cannot be applied economically to all installations. It is therefore necessary that new innovative processes, to recover silver and other valuable metals from relatively low grade feeds, be developed. This paper attempts to place this strategy in the context of today's constraints and will also provide a simple evaluation tool for any process alternatives.

Jan 1, 1990

By P. A. Botha

Most sinter producers prefer to use a range of iron ores with the aim to optimize their sinter blends. ISCOR is however limited to the use of ore from two deposits, namely Sishen and Thabazimbi. Only sinter produced from Sishen ore is described in this report. The Sishen iron ore deposit provides high-grade hematite ore with a mean iron content of 65 per cent. Three major ore types are developed: massive, laminated and conglomeratic. The main ore mineral is hematite with minor to trace amounts of quartz, mica, phosphates and, in places, carbonates. A sinter product is characterized by its mineralogical composition and metallurgical properties. The production rate also plays an important role in the economic evaluation of sinter quality. Sinter-pot tests were conducted with varying basicities, given as the ratio of CaO to SiO:< and coke content. The results of these tests were characterized by mineralogical and metallurgical methods. Basicity of a sinter mix directly influences the mineralogical composition and metallurgical properties. The content of calcium ferrite and calcium silicate increases with increasing basicity, thereby increasing the reducibility and cold strength of the sinter product. Experiments performed during this study provided a model for the optimization of the sinter mix with respect to its mineralogical and metallurgical parameters.

Jan 1, 1991

By Noel A. Warner

Modern steelmaking is based on direct use of oxygen in high intensity batch reactors. A totally new approach is proposed in this paper, based on the view that pursuit of high intensity is unlikely to lead to successful coal-based continuous steelmaking. By substituting carbon dioxide and water vapor as the oxidants rather than using oxygen directly, the intensity is greatly reduced. Accordingly, subsurface formation of carbon monoxide bubbles can be avoided by careful manipulation of the three participating rate processes, gaseous diffusion, interfacial chemical kinetics and liquid phase mass transfer. Steelmaking can then be carried out without explosive ejection of molten droplets and the generation of micro-spray but rather in a controlled and fume less fashion. The vital component is the introduction of generic melt circulation technology. Three melt circulation loops in series are envisaged. Starting with a composite feed of iron ore fines, pulverized coal and lime flux, a metallized solid raft floating on molten iron is propelled out of the ironmaking loop onto the first of two downstream steelmaking loops. In the first, a liquid slag is formed, primary decarburization is undertaken not with oxygen but rather with CO2 and H2O and the melt is desulfurized. The semi-product stream enters the third melt circulation loop, where open-channel decarburization is effected along with dephosphorization to yield a low carbon steel product. Alternatively, the melt leaves the last loop to irrigate a packed tower countercurrent to argon at around 100 mbar to continuously produce ultra-low carbon (ULC) steel.

Jan 1, 2003

02, NaCI03, H202, Na0CI and Ce+4 have been examined as oxidants in an alkaline carbonate system for uranium in in situ leaching. The South Texas and New Mexico ores contained up to 2.6 meqJg of reducing compounds which consume oxidants in the leading operation. Leaching rates did not increase linearly with the oxidation potential of the oxidants. A mild oxidant can be used to maximize uranium oxidation selectively and oxidant efficiency. 02 can oxidize most of the uranium mineral with an adequate rate and high oxidant efficiency.

Jan 1, 1990

By Zhihong Liu

Monodisperse micron size nickel oxalate particles with rhombohedron morphology were prepared from condensed Ni(OH)2 suspension by a novel gel-sol process proposed by one of the authors. Firstly, condensed nickel hydroxide gel was formed by fast adding 1 mol dm-3 NaOH solution into 0.2 mol dm-3 nickel chloride solution, and then oxalic acid solution with a concentration of 0.25 mol dm-3 was dropped into the gel drop wise through a pump equiped with a pH controller under preset pH value, and in this process, Ni(OH)2 gel was converted gradually into monodisperse nickel oxalate sol. The formation of the nickel oxalate particles was found to proceed through a dissolution-recrystallization mechanism from the nickel hydroxide gel. The product particles exhibited rhombohedron like shape with micron size long axis and sub-micron size short axis. The effects of such factors, as temperature, surfactants, et al, were evaluated experimentally on the particles sizes and morphologies.

Jan 1, 2006

By D. Gregurek

In non-ferrous metal furnaces the installed magnesia-chromite refractory lining is exposed to several stresses, rather complex in their interaction. Therefore, a detailed investigation and understanding of wear mechanisms through “post mortem studies” is an important prerequisite for refractory producer. Additionally, in order to determine the most suitable refractory products and to improve the lining life of refractories, practical corrosion testing with processing slags is performed. For this purpose the test-facilities, such as induction furnace, rotary kiln but also cup test and drip slag test, allow the best possible understanding of chemothermal brick wear on pilot scale. Prior to testing a complete mineralogical investigation, thermo-chemical calculation via FactSageTM of the slag was carried out. Based on such research results, combined with specific process knowledge RHI Magnesita can recommend appropriate brick lining solutions for non-ferrous metal furnaces.

By Mark Tsirlin

Kinetics of the initial oxidation stages of diffusive silicide coatings on 8 molybdenum and niobium at 1100 - 1700 and under the pressure of 400 and 1330 Pa has been studied using methods of gravimetry and gas phase analysis of oxygen, as well as by SEK, XRD and EDMA methods. The first oxidation stage described by asymptotic equation in case of NbSi coating changed over to the stage described by parabolic equation. The asymptotic law was shown to depend on non - stationary conditions on the oxide layer boundaries. Interconnection between silicides and quartz structures, on the one hand, and peculiarities of oxidation kinetics, on the other, is [discussed. The possibility of estimation oxygen atom jump frequency in quartz and fractions of oxygen reacting with metal and with silicon proceeding from the analysis of the kinetic data was ascertained. Conditions of oxidation kine- tics transfer from asymptotic (or parabolic) stage to a non - protective "linear" stage, associated with volatile ~roduct formation, are also discussed.

Jan 1, 1995

By KNona C. Liddell

The ion interaction model Pitzer proposed twenty years ago is today the most widely used method for calculation of osmotic coefficients and electrolyte and single ion activity coefficients in aqueous solutions. This is due in part to the accuracy of the results that have been obtained for many concentrated electrolytes. An additional factor is that, compared to alternative activity coefficient models, there are many more parameter values available for the Pitzer equations. The important features of this model are reviewed. Published parameter values for Co, Ni, Cu, Zn and Fe are tabulated, and applications of interest in the aqueous processing of these metals are described.

Jan 1, 1993

By Chang Chia -Fu

The generic structure of our bimesogens is shown in and for a typical blue-phase mixture of the type we describe here. We use mixtures of the ratio 33.4% (n =2.6), 34.1% (n =6.57), 36.6% (n= 11.15) with of the high twisted power (HTP) agent BD H1381(available from Merck Chemicals and described in ref. We then studied the electric-field dependency of the selective reflection in BP I* at 20.7 °C by applying increasing and the decreasing pulsed alternating current (a.c.) electric fields (100 Hz).

Jan 1, 2006

By R. M. Taylor

Lime addition to acid mine drainage (AMD) leads to precipitation, predominantly of metal hydroxides and calcium sulfate, and is the benchmark for remediation by precipitation. Geo2 Limited of Melbourne, Australia has developed and patented a novel alternative precipitation scheme based on the formation of mixed valency, M(I1)-M(III), hydroxide sulfate salts. When the composition of AMD is appropriate, the Green Precipitate Process provides a useful and more effective alternative to conventional liming. The characteristics and utility of the Green Precipitate Process are described in terms of the underlying chemistry, and a case study where the Green Precipitate process outperforms conventional liming. A mobile pilot pipe reactor rig which was built by Geo2 to demonstrate the process, and used successfully in both Australia and the United States, is described.

Jan 1, 1998

By T. R. A. Davey

The technologies of lead, zinc and tin extraction have made varying degrees of progress over the past twenty years. Producers of all metals have faced increasing demands for reduction of pollution and environmental degradation, and the level of public concern is rising rather than abating. New processing techniques must therefore be not only economically feasible, but politically acceptable, even when the demands of "conservationists" and ?environmentalists? are unreasonable. A new generation of processing techniques has come into being, which do not rely on an expensive sintering stage, nor use metallurgical coke, which is difficult to make without serious pollution. They utilise intense reactors, conveying materials from one stage to the next preferably within an enclosed space, obviating fume emissions, and avoiding heat losses as far as possible. The acceptability of the new techniques? is increased if lowgrade or complex materials can be treated, along with a variety of returns and wastes. In addition, a good selling and servicing organisation seems to be as important as good process technology in determining the spread of the new processes. In the field of pyrometallurgical refining the need is for more general application of several recently developed techniques rather than a search for alternatives to the existing process technologies. However, there is a need for fundamental work investigating the phenomenon of oxygen anode overvoltage in the electrolytic zinc process, in order to make progress in the further reduction of energy consumption. There is also scope for further development and application of vacuum distillation to up-grade thermally produced zinc. This paper presents a personal view of processes which should be developed to overcome existing problems, as we approach the turn of the century,

Jan 1, 1990

By J. R. Goode

There are at least a dozen methods of selectively removing cerium from a mixture of the rare earth elements (REE) including separation techniques based on the oxidation of cerium to the quadrivalent state. Several of the oxidation processes have been operated on a commercial scale, others have been tested and in some cases are part of proposed flowsheets. In this paper, we describe and compare the various methods. We also present preliminary estimates of the costs of early Ce removal and discuss recovery and purity aspects of the options.

By Tetsuro Ohashi, Tooru Matsumiya, Yoshio Abe

"The three-dimensional deformation of a continuously cast slab was modeled into two-dimensional deformation by developing the solidified shell of the slab. The developed solidified shell was divided into rectangular elements. The thermal strain produced as the slab is wi thdrawn over one roll spacing in the casting direction was calculated from the temperature change during that time and the increment of the geometrical unbending strain during the time was calculated from the change in the radius of curvature of the slab by assuming that the neutral axis of bending is located at the mid-thickness of the slab and that the transverse section of the slab is kept in a plane during unbending. These strains were imparted to each element as initial strains. The interaction between the elements and the overall deformation of the solidified shell were analyzed by the finite element method.The analysis was performed on a slab being cast on a machine of the circular arc type with progressive unbending. The following findings were obtained as a result. The effect of unbending is spread in the upstream and downstream directions of the slab by the shear deformation of the narrow and wide faces. As the shear deformation increases, the strain in the unbending zone decreases and the strain outside of the unbending zone increases. The effects of secondary cooling conditions, slab size, radius of caster circular arc section, compression casting, etc., were also analyzed. IntroductionTo develop a method for preventing the internal cracking of continuously cast slabs, it is important to acurately analyze the deformation of the slab and this subject has been extensively investigated. Many researchers, including the present authors, have analyzed slab bulging. (1)- (11) Analysis has also been made of thermal deformation that assumes importance in continuous casting of small-section blooms.(12)-(18) However, unbending deformation, an extremely important subject for continuous casters of the circular arc type, has not been fully analyzed."

Jan 1, 1986

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure&apos; stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor&apos; afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996