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By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,12, 7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 3 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

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

By M. Timucin

High-temperature phase relations in the Pb-PbS system were established by the quenching of samples equilibrated in evacuated and sealed silica capsules. The liquid-miscibility gap seen in some previously published phase diagrams was not observed. The thermodynamic activities of PbS in liquid solutions of this system were derived at 1473 K from the isopiestic equilibration of samples belonging to this solution series with Cu2S-PbS melts of known PbS activities. The behaviour of Pb-PbS melts was found to be compatible with a subregular solution model. This model also made it possible to obtain an analytical liquidus for PbS that was in excelent agreement with the experimental determination.

Jan 1, 1988

By P Hayes, B Zhao

A range of materials are treated in zinc fuming processes to recover metal values and produce benign slag waste products. The selection of the optimum process conditions in these various technologies can be greatly assisted by the use of a chemical thermodynamic model of the system. In this paper the effects of slag chemistry on the liquidus temperatures, subliquidus phase equilibria and thermodynamic properties are described by a FACT model of the ZnO-PbO-FeO-Fe2O3-CaO-SiO2 system. In addition new experimental data on the effect of Al2O3 on the liquidus are presented. The implications of these findings for plant practice are discussed.

Jan 1, 2000

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

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 W Y. Kim, Y B. Kang, Y J. Park

The phase equilibria in the Al2O3–TiOx system were investigated in wide ranges of temperature and oxygen partial pressure: 1300~1600°C and 10-16.6~10-8 atm, respectively. The equilibrium phases and their compositions were identified using X-ray diffraction (XRD) and electron probe microanalysis (EPMA), respectively. Most noticeably, a wide range of pseudobrookite solid solution was found in equilibrium with almost pure alumina. At each temperature, the cationic ratio expressed as RTi = nTi/(nAl + nTi)) of the pseudobrookite solid solution showed a noteworthy dependency on the oxygen partial pressure. This resulted in the formation of a broad range of pseudobrookite solid solutions, ranging from Al2TiO5 (RTi = 1/3) to Ti3O5 (RTi = 1.0). Complete miscibility within the pseudobrookite solid solution was observed at 1600°C, with only a minor miscibility gap becoming evident below 1500°C. Based on the results obtained in the present study, the behaviours of Al2TiO5 pseudobrookite have implications in two key domains: (1) understanding changes in the physical properties of the materials, and (2) elucidating the evolution of Al–Ti complex oxide inclusions in liquid steel which can deteriorate the steel cleanliness.

Aug 21, 2024

By Zhibao Li, Lanmu Zeng

The behavior of dicalcium silicate in NaOH-NaAl(OH)4-Na2CO3 solution is of significance for controlling the silica level in the production of alumina via the sintering process. Dicalcium silicate samples were obtained through a twostep approach: coprecipitation of calcium and silicate from CaCl2-Na2SiO3-NaOH solutions; and calcination of the hydrated precursor at 1200°C for 4 hours. The optimization of the synthesis parameters including temperature, solution concentrations and aging time was also investigated. Xray diffraction (XRD) and chemical analysis show that the calcined solids include dicalcium silicate with trace amounts of wollastonite. The solubility of the synthesized dicalcium silicate in HCl, NaOH, mixed NaOH-NaAl(OH)4 and NaOH-NaAl(OH)4-Na2CO3 solutions was determined. It was found that the solubility increases with increasing HCl and NaOH concentration. The effect of temperature on the solubility in HCl solutions is limited, but the solubility decreases with increasing temperature in NaOH solutions. The solubility of dicalcium silicate in NaOH-NaAl(OH)4 and NaOH-NaAl(OH)4-Na2CO3 solutions was shown to increase with increased temperature, Al(OH)3 and Na2CO3 concentration. The BromleyZemaitis model for the aqueous electrolyte system was selected to predict the solubility of dicalcium silicate. The model’s predictions yielded certain success compared with experimental solubility data.

Jan 1, 2014

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

Phase equilibria studies have been carried out on the "FeO"-Si02-MgO-A120rCr203 system in equilibrium with iron in the range of compositions and temperatures directly relevant to the nickel laterite deposits being investigated by Xstrata Nickel within the Araguaia belt in Para State, Brazil. Liquidus temperatures and primary phase fields have been measured as a function of composition using equilibration, quenching and electron probe X-ray microanalysis measurements. The results are presented in the form of pseudo-ternary sections. It was found that in the composition range investigated, olivine (Mg,Fe)2Si04 and pyroxene (Mg,Fe)Si03 are major primary phases. In addition, tridymite Si02 and spinel (Mg,Fe2+)O?(Al,Cr,Fe3+h03 are also present in the higher Si02 and lower Si02 regions respectively. The results of the phase equilibria studies were validated in a subsequent pilot smelting test.

Jan 1, 2009