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By D. Bessinger, J. M. A. Geldenhuis

High titania slag is produced from the smelting of ilmenite. These slags contain approximately 85 per cent TiO2 and consist mainly of a M3O5 solid-solution phase. During cooling the slag can decrepitate to a fine particulate material, which decreases the value of the product. Based on X-ray diffraction analyses of the decrepitated slag after cooling, it was found that the M3O5 phase had almost disappeared. The disappearance of the M3O5 phase was linked to oxidation of the slag. A M6O11 phase formed in the decrepitated slag. It is postulated that decrepitation of high titania slag is caused by volume changes due to the oxidation of the M3O5 phase in the slag.

Jan 1, 2005

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 M. A. Vasina, I. A. Matveeva, E. A. Naumova, V. V. Doroshenko, N. A. Belov

"Using the calculated (Thermo-Calc software) and experimental methods (SEM, TEM, EMPA, DSC, XRD, etc.) the phase composition, structure and hardening of aluminium alloys of the Al-Ca-Zn-Mg system were studied in the following range: 2. 5%Mg, up to 10% Ca, and up to 14% Zn (wt%). Fragments of this quaternary phase diagram in the aluminium corner were constructed, including the liquidus surface, as well as some vertical sections. It was shown that the relatively large amount of zinc enters in the Ca-containing phase, which formula can be described as (Al,Zn)4Ca. An increase of Zn content leads to formation of Al4Ca primary crystals at lower concentrations of calcium. The eutectic (Al)+(Al,Zn)4Ca has a fine structure and aluminide particles are capable to spheroidization during the heat treatment at temperature 500 C. The maximal level of hardness observed on calcium containing alloys was higher than 200 HV, what gives the reason to expect good strength properties. With an example of an Al-9% Zn-2,5%Mg-3,5% Ca model experimental alloy based on the (Al)+(Al,Zn)4Ca eutectic, a principal possibility of manufacturing thin rolled sheets was demonstrated.INTRODUCTION Aluminum alloyed with calcium was first studied in 1970-80s by such authors as Piatti (1976), Moore (1978, 1980), Il'enko (1985), Swaminathan (1990), and Perez-Prado (1997) as superplastic materials. In particular, the alloy systems Al-Ca-Zn were studied (Il'enko, 1985, Swaminathan, 1990, Perez-Prado, 1997). For some time there was no new published works concerning the aluminum-calcium alloys. During the last years many works were published dedicated to the calcium alloying of magnesium alloys (Kim, 2011; Xu, 2011; Aljarrah, 2008; Bakhsheshi, 2014). This urged the authors (Belov, Naumova & Akopyan, 2016) to start studying cast and wrought aluminum-calcium alloys for construction (2008–2014). There is almost no information in the literature concerning triple and more complex diagrams of the aluminum-based system states with calcium and other elements. In recent work, parts of the state diagrams are plotted for the aluminum angle zone: Al-Ca-Mg-Sc (Belov, Naumova & Bazlova, 2016), Al-Ca-Ni-Sc (Belov, Naumova & Bazlova, 2017), Al-Ca-Si-Sc (Belov, Naumova & Akopyan, 2017) and others. Special attention was paid to the study of the system Al-Ca-Zn-Mg (Naumova, 2017). Based on this system creation of advanced extra-high tensile alloys is planned. Wrought extra-high tensile alloys series 7??? based on the system Al-Zn-Mg-Cu are well studied."

Jan 1, 2018

By Q Shu, T Deng, B Yan, B Song, D Wang

In view of the lack of phase equilibria data of vanadium-bearing oxide system and the desirability of them for design or optimisation of vanadium extraction process, the phase equilibria relationships of V2O3-FeO-SiO2-CaO(15 mass per cent) system were determined experimentally and then an isothermal section phase diagram of this system was constructed. Totally, 81 samples of different composition were equilibrated at 1623 K for 48 hours in iron crucible under Ar atmosphere. The equilibrated samples were quenched quickly in cold water, and then the phase constituents of all the samples were identified by X-ray diffraction (XRD) combined with electron probe microanalysis (EPMA) measurements.

Aug 21, 2024

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 J Bang, I-H Jung

Ti is an important constituent for steels and superalloys. During the continuous casting process and ElectroSlag Remelting process (ESR), Ti in molten steel and superalloy can have chemical reactions with casting flux and ESR slag containing CaO and CaF2. In order to investigate such exchange reactions, the understanding of the (Ca,Ti//O,F) reciprocal slag system is prerequisite. In the present study, a coupled phase diagram experiment and thermodynamic modelling of the (Ca,Ti//O,F) reciprocal system was performed. In particular, the phase diagram of the CaF2-TiO2 system was experimentally investigated by Differential Thermal Analysis (DTA) experiment and quenching experiments followed by Electron Probe MicroAnalysis (EPMA) phase analysis. The Gibbs energy functions of all solid and liquid phases in the (Ca,Ti//O,F) reciprocal system were optimised to reproduce the present data and all available reliable experimental data in literature.

Jun 19, 2024

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 Z. Z. Öztürk, N. Sarica, A. H. Üçisik, C. Bindal

"Titanium oxide films were fabricated on commercially pure titanium surfaces via anodization procedure. Anodization parameters, anodization time and voltage were altered, whereas temperature and chemical composition of anodization bath were kept constant. The main idea in this study is to obtain rough titanium-oxide surfaces. The type and feature of titanium oxide formed were observed via SEM and EDX analyses. What was revealed from SEM and EDX analyses were combined with Ti-O phase diagram in order to make judgment on the type of phases obtained, e.g. solid solution and/or compounds. Studies on the different regions of each sample showed that surfaces consist of different titanium oxide compounds with various O/Ti ratios in nano level and solid solutions varying in terms of chemistry on the same sample. Thus together rough surfaces and inhomogeneous distribution of "titanium oxides" were obtained. It was also found that when anodization time and voltage were increased, more granular surface with higher O/Ti atomic ratio was obtained."

Jan 1, 2015

By O. F. Oxtoby, J. E. Olsen, M. W. Erwee, Q. G. Reynolds

"The extraction of molten products and wastes through smelting furnace tap-holes during the tapping process is a complex procedure involving many coupled thermophysical effects. Insight into the fluid flow behaviour in such systems can be gained by using computational mechanics tools to build highfidelity models of the fluid flow and other relevant physics. Previous work using such models indicates that the nature of the flow in the tap-hole, as well as operational parameters such as the tapping flow rate, depends strongly on the properties of the material being tapped and the geometry of the tap-hole channel. Additional complications arise when multiple fluid phases (for example, slag and metal) are present simultaneously, when porous coke beds hinder flow to the tap-hole entrance, and when the geometry of the tap-hole changes over time due to cycles of wear and repair. In the present work, challenges with the coupling of phenomena such as multiphase flow and porosity into computational fluid dynamics methods for tap-hole modelling are discussed in the context of electric furnaces used for ferromanganese production. Qualitative and quantitative results of computational models of flow through tap-holes are presented and compared as a function of material parameters to determine sensitivity effects, and in response to operational parameters to determine typical process behaviour over the duration of a tap. IntroductionPyrometallurgical production using electric furnaces accounts for substantial portion of the world supply of ferroalloys and other strategic materials (Degel et al., 2015). A range of different furnace designs may be used depending on the metallurgical process, with circular three-electrode submerged arc furnaces (SAFs) powered by alternating current being the most common for commodities such as ferromanganese and silicomanganese (Olsen, Tangstad, and Lindstad, 2007).As shown in Figure 1, manganese furnaces typically operate with a deep charge consisting of an upper layer of loose burden (onto the upper surface of which is fed solid raw material), a molten slag layer partially or completely filled with unreacted carbonaceous reductant (generally metallurgical coke), and a molten metal layer which settles to the bottom of the furnace due to its high density. The solid particles present in the slag and burden layers form porous beds which hinder the fluid flow of molten process material and gases inside the furnace (Olsen, Tangstad, and Lindstad, 2007).In order to remove material from the furnace during normal operations, a single tap-hole is built into the sidewall of the vessel near to the level of the hearth. Tapping involves removing both slag and metal phases through the same tap-hole channel, which makes tap-hole design, operation, and maintenance particularly complex. In the case of processes such as ferromanganese, which operate with no external gas injection or open arcs present at the furnace electrodes, flow of material out of the tap-hole is driven primarily by the hydrostatic pressure generated by the weight of the solid and liquid phases above the tap-hole."

Jun 1, 2019

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

Phase equilibria have been determined experimentally for pseudo-ternary sections of the form ?MnO?-(CaO+MgO)-(SiO2+Al2O3) with a fixed Al2O3/SiO2 weight ratio of 0.17 and MgO/CaO weight ratios of 0.25 and 0.17 respectively for temperatures in the range 1473-1673 K. The primary phase fields present for the MgO/CaO weight ratio of 0.17 include manganosite (Mn,Mg,Ca)O; dicalcium silicate a-2(Ca,Mg,Mn)O?SiO2; merwinite 3CaO·(Mg,Mn)O·2SiO2; wollastonite [(Ca,Mg,Mn)O?SiO2]; diopside [(CaO,MgO,MnO,Al2O3)?SiO2]; tridymite (SiO2); tephroite [2(Mn,Mg)O?SiO2]; rhodonite [(Mn,Mg)O?SiO2] and melilite [2CaO?(MgO,MnO,Al2O3)?2(SiO2,Al2O3)]. For the section with MgO/CaO weight ratio of 0.25 the anorthite phase (CaO·Al2O3·2SiO2) is also present. The liquidus temperatures of ferro- and silico-manganese smelting slags have been determined. The liquidus temperatures at low MnO concentrations are shown to be principally dependent on the modified basicity weight ratio (CaO+MgO)/(SiO2+Al2O3).

Jan 1, 2004

By S. Ganguly

Slag samples taken from adjacent to the furnace wall of a submerged arc ferromanganese smelting furnace have been found to contain high concentrations of K2O. To characterize the phase equilibria relevant to these slags experimental studies have been carried out to determine pseudo-ternary sections of the form ?MnO?-CaO-(SiO2+Al2O3) with a fixed Al2O3/SiO2 weight ratio of 0.65 and 6.0 wt% K2O for temperatures in the range 1523-1673 K. In the pseudo-ternary section investigated the primary phase fields are found to be mullite, 3Al2O3?2SiO2; corundum, Al2O3; spinel, MnO?Al2O3; manganosite solid solution, (Mn,Ca)O; dicalcium silicate,2CaO?SiO2; gehlenite 2CaO?Al2O3?SiO2; anorthite CaO?Al2O3?2SiO2; kalsilite KAlSiO4 and leuciteKAlSi2O6. It was found that the presence of K2O in the slag decreases liquidus temperature in the anorthite and gehlenite primary phase fields. The manganosite primary phase field is expanded in the direction of increased (Al2O3+SiO2) and the liquidus temperatures in the manganosite primary phase field are increased significantly with the presence of K2O in the slag.

Jan 1, 2007

By R. Hansson

Zincite and spinel phases are present in the complex slag systems encountered in zinc/lead sintering and zinc smelting processes. These phases form extensive solid solutions and are stable over a wide range of compositions, temperatures and oxygen partial pressures. Accurate information on the stability of these phases is required in order to develop thermodynamic models of these slag systems. Phase equilibria in the Fe-Zn-O system have been experimentally studied for a range of conditions, between 900 and 1580°C and oxygen partial pressures (pO2) between air and metallic iron saturation, using equilibration and quenching techniques. The compositions of the phases were measured using Electron Probe X-ray Microanalysis (EPMA). The ferrous and ferric bulk iron concentrations were determined using a specially developed wet-chemical analysis procedure based on the use of ammonium metavanadate. XRD was used to confirm phase identification. A procedure was developed to overcome the problems associated with evaporation of zinc at lowpO2s and to ensure the achievement of equilibria. An isothermal section of the system FeO-Fe2O3-ZnO at high ZnO concentrations at 1200°C was constructed. The maximum solubilities of iron and zinc in zincite and spinel phases in equilibrium were determined at pO2=1*10-6atm at 1200and 1300°C. The morphology of the zincite crystals sharply changes in air between 1200 and 1300°C from rounded to plate-like. This is shown to be associated with significant increase in total iron concentration, the additional iron being principally in the form of ferric iron. Calculations performed by Fact Sage with a thermodynamically optimized database have been compared with the experimental results. Keywords: Phase Equilibria, Fe-Zn-O, Quenching, Wet-Chemistry, EPMA, XRD, ISP.

Jan 1, 2004

By E. Haccuria

Due to the growing share of electrical cars, the use of lithium ion batteries significantly increased. Recycling of these batteries is essential to safely dispose hazardous materials as well as to recover valuables (Cu, Ni, Co, etc.). In order to optimise the recycling process, accurate information is required on the slag phase equilibria for battery smelting. The slag is a multi-component system containing alumina from the battery cases, silica and lime from fluxes, and manganese and lithium from the electrode materials. The present study accurately determined the phase equilibria in the "MnO"-Al2O3-SiO2 sub-ternary system at metal alloy saturation. Particular attention was given to the accuracy and reliability of the final results by highlighting the different reaction pathways, mass transfer- and reaction mechanisms taking place in the system during experiments. This attention enabled improved experimental methodology and measurements. Based on the present study, further measurements will be undertaken in the quaternary "MnO"-Al2O3-CaO-SiO2 system at low "MnO" concentrations, which closely represents the future recycling industrial slags.

Jan 1, 2014

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 X Ling, M Barati, E Moosavi-Khoonsari

In the pyrometallurgical process of secondary lead recycling, a desulfurising agent, such as Na2CO3 is added to minimise the emissions of sulfur into the atmosphere, while silica is introduced into the smelter as a fluxing material. Subsequently, a significant amount of Na2O and SiO2 remains in the downstream reverberatory furnace and blast furnace slags. However, there is limited understanding of the thermodynamic behaviour of silicate-based lead slags rich in Na2O, posing challenges in accurately determining the optimal condition for targeted metal recovery and final slag composition. In this work, the equilibrium phase relations of the PbO-Na2O-SiO2 system in the primary phase field of Na2SiO3 are studied from 800 to 1000°C via equilibration-quenching method. Samples with different compositions were prepared and held in platinum capsules in air at these temperatures to reach equilibrium. The equilibrated samples were subsequently quenched and the phase compositions were measured by electron probe microanalysis (EPMA). The results were then compared to those of previous studies and any discrepancies were resolved.

Jun 19, 2024

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 L. Voisin, K. Yamaguchi, D. G. Mendoza, K. Ltagaki

The behavior of arsenic and antimony in the Cu-0 system was thermodynamically investigated to understand their elimination during a blister-making stage in copper smelting. Firstly, the phase relations in a miscibility gap composed of the liquid slag and copper phases in the Cu-0-As and Cu-0-Sb systems at 1523 K were established by a quenching technique. It was found that arsenic and antimony distributed preferentially into the slag phase in the miscibility gap. Secondly, the activities of arsenic and antimony in the miscibility gap of these systems were determined at 1523 K by using a double Knudsen cell - mass spectrometer method. It was clarified that the activity of arsenic in the copper and slag phases showed the negative deviation from ideality while that of antimony in the copper phase a slightly positive deviation. These data obtained in this study suggest a possibility to eliminate arsenic and antimony by means of over-blowing in a converter after discharging the slag.

Jan 1, 2007