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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

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

By A Vickerfält, J Huss, J Martinsson

The European Union has listed vanadium (V) as one of the critical raw materials for the transition to a future green society, as stated in the Critical Raw Material Act, written by Grohol and Veeh (2023). In the steelmaking industry based on V-containing iron ore, V is a possible by-product from the slag. A requirement for slags to be suitable for V extraction is a V content preferably above 8 wt per cent as V2O3 and a phosphorus (P) content below 0.1 wt per cent as P2O5. Hence, it is important to keep V in the slag phase while the P is moved to the metal phase during the steelmaking process.

Aug 21, 2024

By Y. A. Chang

The objective of the present study is to evaluate and compile the relevant phase equilibria and thermodynamic data reported in the literature for the ternary system Cu-Fe-S. It is hoped that the results presented here will be useful to practising engineers and scientists in industry who are attempting to improve continually the existing processes of copper extraction and refining. At the same time, the present work will undoubtedly reveal the lack of some basic data which are important for the improvement of our existing extractive processes. Lastly, this work will also show that the development of theoretical models for the alloy phases in the Cu-Fe-S system is essential before complete consistency between the phase equilibria and the thermodynamic data can be achieved.

Jan 1, 1976

By Baozhong Ma, Qian Li, Yonggang Wei, Shiwei Zhou, Bo Li, Chengyan Wang, Hua Wang

The magnesium-rich nickel oxide ore (w (Ni) =1.09 %, w (MgO)=29.08 %) mixed with 6 % and 8 % anthracite were roasted at different temperatures. XRD and SEM/EDS techniques were utilized to characterize the phase and microstructure transformation of the ores. The results show that lizardite and chrysotile of raw ore were converted into forsterite and enstatite during reduction roasting process. Simultaneously, iron and nickel oxide were reduced and migrated from the initial magnesium silicate. Fe3Si were formed when the roasting temperature went up to 1300 ℃ and 1350 ℃, and a small amount of Ni was observed in it. Temperatures got too high were not benefit to the polymerization of ferronickel.

Jan 1, 2015

By Bowen Li

Andalusite is an excellent raw material for refractory applications due to its high aluminum oxide content and phase transformation to mullite at high temperature. Granular andalusite in particle sizes of about 1 to 2 mm was traditionally utilized for the manufacturing of refractory brick. However, if powder andalusite in micron particle size is utilized in high-alumina refractory products, reinforcement on the refractory brick can be obtained and the sintering temperature can be decreased. The phase transformation of powder andalusite plays a key role for the difference.

Jan 1, 2006

By Yingbao Yang, Jinyue Liu, Yonggang Wei, Bo Li

Due to the depletion of copper ore with high-grade and low impurity contents, the raw materials for copper smelting exhibit low copper contents and high impurities. High-impurity elements lead to the poor performance of the final copper product; thus, the removal of impurity elements during the oxygen-enriched copper smelting process is crucial. In this study, based on the production of high-grade matte, the occurrence states of impurity elements (such as As, Pb, and Zn) are analyzed in the input and output materials of the oxygen-enriched smelting process, and the phase transformation mechanisms of impurity elements are revealed during the oxygen-enriched smelting process. The effects of temperature, Fe/SiO2 ratio and oxygen concentration on the distribution behaviors of impurity elements in dust, slag and matte and the removal rates of impurity elements in matte are clarified. The results show that the impurity elements mainly exist as As4, As4S4, As2O3, Pb, PbS, PbO, Zn and ZnS in dust, as FeAsO4, As2O3, FeAsS, PbSiO3, Zn2SiO4 and ZnFe2O4 in slag, and as As, FeAsS, PbS, PbO and ZnS in matte. High smelting temperature, low Fe/SiO2 ratio and low oxygen concentration are beneficial for improving the matte grade and the removal rates of impurity elements Pb and Zn in matte. Low smelting temperature, low Fe/SiO2 ratio and high oxygen concentration are beneficial for removing impurity element As in matte.

Aug 8, 2023

By Yuanbing Ling

Keywords: Calcium sulfate, Sulfuric acid, Phase transformations, Thermodynamic analysis As part of a boarder research project, seeking the development of a cost-effective process for direct production of the high value material, -calcium sulfate hemihydrate, from sulfuric acid at atmospheric as opposed to elevated pressure conditions, the fundamental work presented here has been undertaken. This includes experimental monitoring of phase transformation reactions and thermodynamic analysis of the relationships among the various phases, namely, calcium sulfate dihydrate, hemihydrate and anhydrite in aqueous sulfuric acid solution at temperatures ranging from 20oC to boiling point.

Jan 1, 2004

By N. Hanief

This research involves the investigation of phase transformations in the platinum-chromium coated system. Single-layer 0.1 µm platinum coatings were deposited via electron beam deposition on 99.98 percent pure chromium substrates. Specimens were subjected to systematic heat treatment in a vacuum furnace at 900°C for up to 20 hours. Phase formation and the changes in surface morphology were investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM).Both CrPt and Cr3Pt phases are formed during heat treatment for different times at 900°C. Significant changes in the morphology of this coated system were detected after heat treatment at 900°C for 20 hours.

Jan 1, 2012