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By Garrett May

We present a periodic technique for measuring the thermal conductivity of thin, disk-shaped samples. In samples of this type, temperature measurements must be made across the sample faces and are therefore subject to large error due to the interface resistance between the temperature sensor and the sample. The technique uses measurements of the amplitude and phase of the periodic temperature across both a reference sample and the unknown material at several different frequencies. Modeling of the heat flow in the sample allows the simultaneous determination of the thermal parameters of the sample as well as the interface resistance. The technique is demonstrated on nanocomposite samples less than 1.0 mm thick.

Jan 1, 2008

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 J. Phillip Mackey

The Peter Hayes Symposium on Pyrometallurgy, held as part of Extraction 2018, is an acknowledgement of his contributions to the basic science and principles underpinning modern pyrometallurgical processing. After completing his PhD at Strathclyde University, Scotland, in 1974, Peter took up a teaching position at The University of Queensland, Brisbane, Queensland, Australia in 1976. Peter Hayes’ research at the University since then has been focussed on: • The mechanisms and kinetics of heterogeneous solid/solid, gas/solid and liquid/ solid reactions, and • Experimental measurement of phase equilibria in complex high temperature metallurgical systems. This paper provides a brief biography of Dr. Peter Hayes and gives a full listing of Peter Hayes’ publications.

By V. G. Papangelakis

The implementation of a flow-through yttria-stabilized zirconia (YSZ) sensor for pH measurements in high temperature and concentrated electrolyte systems relevant to hydrometallurgical processing of nickeliferous laterites is discussed. Instrumentation involved the use of a custom made flow-through titanium electrochemical cell. Accuracy and validity of the pH measurements at temperatures up to 250C were assessed using concentrated sulphate process solutions ranging from synthetic binary sulphuric acid ? water solutions to progressively multicomponent metal ? sulphate solutions simulating laterite Pressure Acid Leach conditions. The measurements were also compared with theoretical models using recently obtained thermodynamic data. A difference of ±0.25 pH units was observed between measured and calculated pH values at temperatures. This is an acceptable difference given that these are the first direct high temperature pH measurements ever on the concentrated acidic sulphate solutions. This result is encouraging more research for the development of industrial electrochemical systems for direct pH measurements in autoclaves.

Jan 1, 2003

By Takahiko Okura, Satoshi Okano, Hiromichi Takebe

"Fine zinc concentrates tend to become sticky when roasted in a fluidized-bed reactor. The oxidation of high-purity ZnS powders and ZnS concentrates with different particle sizes were studied in terms of phase changes and particle morphologies. The sample materials were directly oxidized to ZnO in a roasting process performed over 700°C. Zinc oxide particles with diameters less than 0.5 ìðé formed at 700°C; the particle size increased by grain growth at 900°C. The coarse ZnS concentrate formed the oxysulfate ZnO2ZnS04 when roasted at 700°C; the sulfate transformed to ZnO at higher temperature.1. IntroductionRoasting is an important step in zinc extractive metallurgy because more than 80% of the world's zinc is produced from zinc sulfide concentrates using the roast-leach-electrowinning [1,2]. Currently, zinc concentrates with a finer particle size distribution are used to enhance recovery rate. However, the finer zinc concentrates tend to produce a sticky calcine in a fluidized-bed roaster [3].The factors that affect products in a fluidized-bed roaster include particle size, contaminant, O2 and SO2 partial pressures, and the feeding method of ore to the roaster. This study examined roasting behavior of high-purity ZnS powders and ZnS concentrates with different particle sizes. The phase changes and particle morphologies of the calcine samples producted from theZnS powders were studied."

Jan 1, 2012

By Xiaowen Liu

The DSC/TG, IR and XRD analysis were used to characterize the heating phase transformation of illite, which came from Ouhai deposit, China. It was discovered that the dehydration and de-hydroxylation of illite carried out stage by stage during heating. The adsorptive water and layer-inter water were dehydrated from room temperature to 500°C; and dehydroxylated in the range 500°C~800°C. In these stages of process, illite?s layer structure kept almost unchanged. After 800°Cillite began to change into disorder structure. At about 1100°C, the layer structure of illite had been destroyed, and amorphous SiO2 and mullite crystallite appeared. At about 1200°C the structure of illite completely destroyed and mullite crystal phase had become perfect..

Jan 1, 2006

By Jianhong Dong, Min Chen, Cuihuan Huang, Bo Li, Nan Wang

"Scale layer can be formed on the slab surface in the areas of secondary cooling and strand discharge during continuous casting process. From 1000 °C -1200 °C, the influence of steel composition on the stable oxide phases inside scale layer, particularly the types of alloying elements including aluminum, silicon and chromium, is investigated under different partial pressures of water vapor by the calculated predominance diagrams of iron oxide as well as its intermediate compounds formed with other metal oxides, and the stable oxide phase composition within scale layer under the working condition of secondary cooling is discussed. At lower partial pressure of water vapor, only a iron spinel (or ferrosilicate) phase is the stable phase with any alloying element contents in steel composition, whereas the stable phases are FeO and iron spine! (or ferrosilicate) inside the scale layer at higher partial pressures of water vapor .IntroductionOxide scale formation on the surface of cast and rolled products because of oxidation by the surrounding oxidizing atmosphere is a significant disturbance factor in steelmaking. The yield loss of iron because of scale formation is considerable during continuous casting and hot rolling process. Surface quality more often is impaired by scale property, which increasing the difficulty of quality assurance, dimensional accuracy and performance control. Furthermore, a potential source for subsequent surface cracking (hot shortness) can be caused by the enrichment of scrap residuals (Cu, As and Sn) at the steel substrate surface as a result of steel oxidation [1-2]. In flat products manufacture via thin slab casting technologies, these phenomena are particularly pronounced and require enhanced development efforts in descaling efficiency [3].Compared with the scale formation in continuous casting, the quantity of scale formed during hot rolling and reheating in the rolling mill is larger, and control of scale formation and descaling is a long-established task in hot rolling. Therefore, extensive research and development work have been carried out, including the effects of heating and rolling temperature on the thickness and microstructure of scale layer, heating time and furnace atmosphere, cooling mode, and steel composition on the scale formation, more attention has been given to the control of scale formation during reheating and hot-rolling process. On the other hand, hardly any specific efforts and countermeasures are taken in continuous casting, and very less research has been done despite the network-type crack on the as-cast strand surface caused by the subscale enrichment of scrap residuals [ 4-7]."

Jan 1, 2014

By Yoichi Takeda

The CaO-FeO,-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Yoichi Takeda

The CaO-FeOx-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By A. McLean, Y. Uchida, M. Iwase, M. Myochin, K. Wiikimoto

"Phase diagrams of FeO-containing ternary systems could be derived from experimental data for the activities of FeO. The systems investigated are CaO-CaF2-FeO, SrO-SrF2-FeO; BaO-BaF2-FeO, CaO-CaCl2-FeO, SrO-SrC12-FeO, BaO-BaC12-FeO, CaO-A12O3-FeO and BaO-SiO2-FeO.IntroductionThe importance of phase diagram cannot be overemphasized. In a book, ""Alloy Phase Equilibria""[l], the author, Professor A Prince, states, ""A metallurgist has been defined as a person who thinks in terms of phase diagram"". Whether one accepts this statement or not, it is self-evident that an ability to interpret phase equilibria is essential to the professional metallurgists.The physical chemistry studies of iron and steelmaking process often require phase diagrams of FeO-containing slags. Iso-thermal section of the phase· diagrams of such systems can be derived from experimental data for chemical potentials of FeO. Due to the recent developments in the area of solid state electrochemistry, rapid determinations of the FeO activities have become possible. The present paper is aimed at documenting the derivation of the phase diagrams of FeO containing slags.Experimental AspectsAn electrochemical method incorporating stabilized zirconia can be used for the measurements of the activities of FeO in various slags and fluxes[2]. For the details of the experimental technique, reference should be made to reference 2"

Jan 1, 2000

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and 1200°C. positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation Where negative deviations were observed.

Jan 1, 2003

By R. Hurman Eric

Within the Ag-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were re-established at 925°C by the equilibrium-quenching technique where samples were kept in evacuated and sealed silica capsules. Activities of Pb were measured by the dew-point method along the Ag-Pb binary at 925°C, 1100° and l200°C, positive deviations were observed and the results were modeled by the Krupkowski formalism. Activities of Ag, Pb, and S, along the ternary miscibility gap were calculated at 925°C by utilizing the boundaries binary thermodynamics, phase equilibria and tie-lines. Activities of PbS within the pseudobinary Ag2S-PbS mattes were also measured by the dew-point technique and the results were again modeled by the Krupkowski formation where negative deviations were observed.

Jan 1, 2003

By Stanko Nikolic

Ferrous calcium silicate slags are potentially important for future practice in copper converting operations and processes and can be described by the ?Cu2O?-FeO-Fe2O3-CaO-SiO2 system. Despite its industrial importance the phase equilibria in this system have not been fully investigated. Characterization of this slag system is necessary to improve the design and optimization parameters of new processes, including fluxing and operating temperatures. Experimental methods have been developed to investigate the phase equilibria of these slags at copper saturation and without copper. This technique involved equilibration of samples at a fixed oxygen partial pressure, rapid quenching, and analysis of the compositions of phases using electron probe x-ray microanalysis (EPMA). Liquidus and solidus data are reported for the primary phase fields of spinel, wollastonite and tridymite at 1250oC and an oxygen partial pressure of 10-6atm. The resulting data has been used to construct liquidus isotherms in the ?FeO?-CaO-SiO2 system both in equilibrium with and without molten copper. The experimental results were compared with the predictions of a thermodynamic computer package utilizing a self consistent thermodynamic database. The predictions of the model were in good agreement with the experimental isotherms when projected onto the FeO-CaO-SiO2 section, however the copper concentrations in the liquid phase at copper saturation were lower than predicted using the current database of the model.

Jan 1, 2006

By Chikabumi Yamauchi, Mitsuru Tanahashi, Tsuyoshi Taniguchi, Nobuo Furuta, Toshiharu Fujisawa

"It is essential to clarify the equilibrium relations among nonmetallic inclusions of the Mn0-SiO2-CrOx system and molten stainless steel in order to control non-metallic inclusions formed by the deoxidation of stainless steel with silicon. In the present study, the phase equilibria of the MnO-SiO2-CrOx system were measured by conducting the following experiments under controlled oxygen partial pressure, Po2, at 1873 K:1) Phase equilibria of the MnO-Cr20 3 binary system were measured for Po2 = 2 x 10-6 ~2 x 102 Pa.2) Phase equilibria of the MnO-SiO2-CrOx ternary system were measured for Po2 = 2 X 10-6 Pa.Based on the results, the phase diagram of this ternary system was established under the condition of the Si-deoxidation process of stainless steel (Po2 = 2 x 10-6 Pa and T = 1873 K).IntroductionAt the deoxidation stage in steelmaking process, generally multiple deoxidizers participate in deoxidation reactions, and the composition of deoxidation products ""non-metallic inclusions"" greatly varies depending on deoxidizing efoments and their contents. In order to control non-metallic inclusions formed by the refining process of steel, it is essential to clarify the equilibrium relations among non-metallic inclusions and molten steel.Especially, during the refining process of stainless steel, nonmetallic inclusions in molten steel seem to- change as follows. After the oxidation refining, Mn-chromite is formed in molten steel as non-metallic inclusion. By the deoxidation with silicon addition (mainly less than 1 mass%), Mn-chromite inclusions are changed their compositions to Mn-silicate. Segawa et al.[l] have reported the effect of amount of silicon addition on composition and mass ratio· of non-metallic inclusions during the Sideoxidation process of 18Cr-8Ni stainless steel at 1873 K, as shown in Figuri; L At higher silicon content than 0.5 mass%, only Mn-silicate was identified as non-metallic inclusion. On the other hand, at lower silicon content, both of Mn-chromite (MnO Cr2O 3) and Mn-silicate were identified. However, the thermodynamic and the kinetic analyses of the above-mentioned Sicdeoxidation process have not been made due to lack in the thermodynamic data for the non-metallic inclusions· of the MnO-SiO2-CrOx system, such as the phase diagrams, the activities of the components, and the free energy of intermediate compounds. In relation to the phase diagram of this system, those of the MnO-SiO2 [2] and the SiO2-Cr2O 3 [3] binary systems have been only reported"

Jan 1, 2000

By Wen-Ming Chien, Vamsi Krishna Kamisetty, Amrita Mishra, Ivan Gantan, Prathyusha Mekala, Dhanesh Chandra

"The phase equilibrium and characterization studies by using high temperature X-ray diffraction (XRD) and differential scanning calorimetric (DSC) methods have been performed for binary organic thermal energy storage materials. The organic thermal energy storage materials undergo a solid-solid state phase transition before melting which stores large amounts of thermal energy. Two materials [tris(hydroxymethyl)aminomethane(TRIS) and 2-Amino-2-methyl-l, 3- propanediol(AMPL)] were used for this study. Binary samples of AMPL-TRIS were prepared to perform high temperature XRD characterization and DSC studies and the binary AMPL-TRIS phase diagram was developed. The high temperature solid-state phases of AMPL and TRIS were characterized as a disordered BCC structure. It was found there is virtually no solubility of TRIS in AMPL or vice versa below -75 °C. The maximum solubility of TRIS in AMPL is 11% TRIS at 75 °C. The eutectoid transformation was shown at 19%TRIS-81%AMPL composition and at a temperature of 75°C. Lattice expansion calculations on single phase of TRIS and AMPL have been performed.IntroductionThermal energy storage materials can store a large amount of heat due to the presence of thermal transitions from the orientationally ordered to disordered phases occurring before melting. These molecules (such as amine and alcohol derivatives of neopentane) can reorient as a whole about the central carbon atom to form orientationally disordered crystals (ODIC) and their spherical shape makes them reorient relatively easier. Thermal energy storage materials are becoming increasingly important as a renewable energy resource. These molecules undergo large changes in enthalpies at solid-solid transitions. The presence of these compounds with large enthalpy changes are identified as potential thermal energy materials and some of die applications are solar cell systems [1-3]. Binary mixtures have been found as a way to adjust the transition properties in addition to pure compounds [4]. Tris(hydroxyrnethyl)aminomethane (TRIS, C(CH2OH)3NH2) and AMPL, CH3C(CH2OH)2NH2) are two important thermal energy storage materials."

Jan 1, 2012

By Hector M. Henao

To provide thermodynamic data for converting nickel matte to liquid nickel at high temperature, an experimental study was conducted on the phase equilibrium between the Ni-S alloy and the FeOX-SiO2, FeOx-CaO, and CaO-A12O3 base slag in a magnesia crucible and the CaO-Al2O3-MgO slag in an alumina crucible. All experiments were carried out at 1773 K under controlled pso2 of 0.1 atm and po2 in a range between 5x10- and 10-5 atm by using CO-CO2-SO2 gas mixtures. The dissolution of nickel in the slag was found to be minimum for the CaO-Al203¬-MgO slag with a molar ratio of NCaO/NA1203=1.7. The solubility of nickel in this slag at p02 of 6x10 atm (just before the precipitation of solid NiO) was 4 mass%. This result suggests that a CaO-A12O3 base slag could be used in converting Ni-S melt to nickel while minimizing nickel losses to the slag.

Jan 1, 2002

By K. Itagaki, H. Henao

"The experimental study on the phase equilibrium and distribution of minor elements such as chromium and copper between magnesia saturated FeOx-MgO-SiO2 slag and Fe-Ni alloy were carried out under controlled oxygen partial pressure between 10-6-5 and 10-10 using CO and CO2 mixed gas at 1773 and 1873 K.The effect of slag additives such as lime (CaO/SiO2 molar ratio: 1) and alumina (AlO1.5/SiO2 molar ratio: 0.1) on the distribution behavior of the minor elements was also investigated.The value of distribution ratio for chromium, defined by (%Cr in slag)/[%Cr in alloy], is larger than 70 at the pO2 region conducted in the present study for the MgO saturated FeOx-MgO-SiO2 slag at 1773K. These value are almost 4-order higher then that of nickel though the distribution ratio of copper shows similar values with nickel. Analysis of the data indicates that addition of lime in the slag and the increase of temperature reduce the dissolution of chromium into the slag and the addition of aluminum increases the dissolution of chromium into the slag while reduces the dissolution of copper and nickel.IntroductionChromium. is a minor element in a nickel oxide ore but a Japan major component in the secondary material of stainless steel and is also introduced in the Fe-Ni production process due to dissolving bricks of a furnace. Chromium is a concerned matter for the beneficial utilization and disposition of ·slag because Cr6+ is a harmful element. Considering Fe-Ni as an alloy component in steel making, and the demand of high purity nickel, chromium is an -undesirable element that has to be eliminated into slag prior to the steel making, or the production of high temperature refractory alloys. On · the other ·hand chromium is an element of steel alloy for many applications, thus Fe-Ni containing chromium in minor element is desirable in some stainless steel making."

Jan 1, 2000

By James A. Warren

The phase field method has been successfully employed as both a tool to model heterogeneous materials and as numerical method for calculating the motion of interfaces and phase boundaries without explicitly tracking those interfaces. The method has been used to model a diverse suite of problems describing the microstructural evolution in materials. These models are derived from thermodynamic arguments and symmetry principles, and usually guarantee positive local entropy production for systems out of equilibrium. Descriptions of how phase field methods can be applied to the problems of solidification, grain growth, and electroplating will be presented.

Jan 1, 2001

By Adam C. Powell

A new Cahn-Hilliard phase field model of transport-limited electrochemistry describes phase boundary motion due to oxidation and reduction reactions at metal-electrolyte interfaces. Benchmarks demonstrating the accuracy of the method include open circuit voltage and closed circuit current in metallothermic reduction, and linear stability theory in metal electrolysis, including a new stability criterion for reduction of liquid metal from liquid electrolyte. The model is applied here to understanding cathode interface stability in titanium electrolysis e.g. in the SOM process developed with Uday Pal, and to structure evolution in subhalide reduction of titanium dichloride by magnesium developed by Toru Okabe. Potential for application to new fuel cell and battery systems is also discussed.

Jan 1, 2006

By Dexter G. Mendoza

To analyze the behavior of minor elements in the copper smelting process, the phase relations and the activities of arsenic and antimony in the miscibility gap of Cu-Fe-S-X (X = As or Sb) system have been determined at 1473K by the quenching method and the double Knudsen cell- mass spectrometric method, respectively. The experiments have been conducted for the charges in the miscibility gap with different mass%Fe/mass%Cu ratios with varying arsenic or antimony content. The activity measurements indicate that the arsenic activities in both the metal and matte phases show extremely negative deviation from the ideal behavior. The Raoultian activity coefficients at infinite dilution in the metal and matte phases are found to be almost constant against the charges in the miscibility gap, and they are 4.3 x 10-3 and 5.5 x 10-2 for the metal and matte phases, respectively. Moreover, the activity measurements of antimony show an activity value larger than that of arsenic but it still deviates negatively from Raoult's law. The activity coefficients of antimony at infinite dilution are found to be 1.2 x and 2.2 x 10-1 for the metal and matte phases, respectively. The vapor pressures of the predominant As, AS2, AsS, Sb, Sb2, and SbS species in the gas phases of arsenic and antimony, respectively, equilibrated with the immiscible solutions have been calculated on the basis of the determined activity coefficients and they are very small at less than 1 Pa, even when their contents in the metal phase are increased up to 10 mass%.

Jan 1, 2002