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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

By Kimio Itagaki

As a fundamental study for smelting the copper matte with high contents of arsenic and antimony in a strongly reducing condition, phase relations between the liquid matte and copper-rich alloy phases in the Cu-Fe-S-As or -Sb quaternary system and between the liquid matte and iron-rich alloy phases in the Cu-Fe-S-As or -Sb system saturated with carbon were determined at 1473 K by a quenching method. Activities of arsenic and antimony in these systems were also measured at 1473K by Knudsen cell-mass spectrometry. Furthermore, distribution ratios of silver, gold and platinum between the liquid matte and copper-rich or iron-rich alloy phases were determined in relation to the arsenic or antimony content in the systems. On the basis of these data, the elimination of arsenic and antimony from the matte to the iron-rich alloy (speiss) and the recovery of precious metals in reduction smelting of the copper matte were evaluated. It was suggested that the addition of pig iron to make a strongly reducing condition and form the iron-rich alloy, which is fluid at smelting temperatures, will be useful for fixing arsenic in the speiss.

Jan 1, 2006

By Hector M. Henao

In order to provide the thermochemical data regarding the slag system, which are of importance for sulfide smelting and metallurgical processes but still lacking, an experimental study was carried out on the phase relations and activity of iron oxide in the FeOX-CaO-SiO2 system at temperatures between 1300 and 1400 °C and partial pressures of oxygen between 10-9 and 10-4atm. First, the solubility of CaO and SiO2 in the solid FeO were obtained and the tie lines connecting between the solid wustite (FeO) or magnetite (Fe3O4) phase and the liquid phase were determined. Secondly, iso-activity lines for FeO in the homogeneous liquid region were determined, based on the activity of iron in the Pt-crucible used in the equilibrium experiments. The activity coefficient of FeO in this region was also derived from the composition of FeO and FeO1.5 in the liquid region. Finally, the effect of (CaO/SiO2) ratio in the system and partial pressure of oxygen on these thermochemical quantities is discussed.

Jan 1, 2006

By Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinler should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified, In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By Florian Kongoli

The production of a homogeneous self-fluxing sinter is an important step in iron making processes. A good sinter should have good permeability and reducibility and has to keep those characteristics for a certain time. An early melt down of the sinter in the blast furnace, where its solid state reduction is essential, would cause many problems such as low permeability and reductibility. Nevertheless, the important factors that influence these characteristics, such as the chemistry of the sinter and the fluxing effect during sintering and sinter reduction conditions have not yet been clarified. In today's new reality where many new minor components such as Al2O3 and MgO enter to the sinter through raw materials, the quantification of the fluxing effects during sintering becomes even more important. In this work, the liquidus surface and phase relations of the sinter primary melts in the CaO-FeO-Fe203-Si02 system at sintering conditions have been quantified. The fluxing effect of oxygen potential, Al2O3 and MgO has also been quantified by the means of some practical diagrams that can directly help the optimization of the sintering processes.

Jan 1, 2003

By Shoukun Wei, Cong Wang, Lin Cheng, Zhiyu Qiao, Jingkui Liang, Weidong Zhuang

"The subsolidus phase relations in the Sm2O3-CeO2-CuO ternary system sintered at 1000°C in air have been investigated by X-ray powder diffraction. The system can be divided into two ternary phase regions and three binary phase regions. Solid solution Sm2-xCexCuO4-y is the only ternary phase in the system. The maximum solid solubility was confirmed to be x = 0.2. The crystal structure, oxygen content and superconductivity of the solid solution Sm2-xCexCuO4-y have been investigated.I. INTRODUCTIONAfter the first discovery of the superconducting ceramic system La-Ba -Cu-O[l] with Tc = 30 to 40K, other families of cuprate-based ceramics have been synthesized with higher critical temperature. These oxides include the R-Ba-Cu-O (R: rare earth) systems (Tc=90K or so)[2,3], the Pb-Sr-(R,Ca)-Cu-O systems (T c = 50 to 100K), the Bi-Sr-Ca-Cu-O systems (Tc=80 to 105K)[4], the T1-Ba-Ca-Cu-O systems (Tc=85 to 125K)[5], the Hg-Ba-Ca-Cu-O systems (Tc=90 to 150K)[6,7], and some others. The improvement of Tc is very rapid. The measurement of the Hall and Seebeck coefficients shows that they all are p-type superconductors. In 1989, Tokura et al.[8] discovered the superconductors R2_XCexCU04_y(R = Nd, Pr, Sm) with Tc=20 to 24K (onset) and found that the charge carrier is electron in contrast to their hole doped counterparts. This discovery increases the fundamental understanding of the cuprate-based superconductors by comparing their characteristics and mechanisms to those of the p-type superconductors.One of the outstanding features of these n-type superconductors is the difficulty in obtaining samples in good charactors, such as the difficulty in obtaining zero resistivity state in single crystal or bulk samples; the semi-conductivity of bulk samples in ordinary state (opposite to the superconducting state) and a reducing reaction involved before the superconductivity has been found[9]. Therefore, it is necessary to optimize the sample preparation of the n-type superconductors. All the n-type superconductors have been found· considerable solid solubility. The compositional variations play a governing role in the carrier doping of the superconducting phases. Also, it is vital to the ceramic processing of superconductors to identify the compatible phases in the phase diagram. Finally, there is always the possibility of finding additional compounds, both superconducting and non-superconducting, in an unexplored system."

Jan 1, 1996