Thermodynamics of the oxygen solutions in Fe-Ni-Ti melts

The oxygen solutions in Fe-Ni melts containing up to 3% titanium are analyzed thermodynamically. The results of the works that determined the fields of the oxide phases in iron and nickel deoxidized by titanium are generalized. The proposed calculation model is shown to adequately describe the titanium deoxidation of iron-nickel alloys. The deoxidizing capacity of titanium decreases as the nickel content in the melt increases to 40% and, then, increases sharply as the nickel content increases further. The oxygen solubility curves pass through a minimum, whose position changes from 0.5644% Ti for pure iron to 0.6332% Ti for pure nickel. The points of equilibrium between the TiO₂, Ti₃O₅, and Ti₂O₃ oxide phases are determined for six alloy compositions at 1873 K. The titanium deoxidation of Fe-40% Ni melts is experimentally studied, and the calculated and experimental results are in good agreement.     

Aluminum deoxidation equilibrium in liquid Ni-Fe alloys equilibrated with CaO-Al2O3 slags

The deoxidation equilibrium for Al in Ni-Fe alloys was studied in the equilibrium experiments between CaO-Al₂O₃ slags and Fe-30, 50 and 70 % Ni alloys at 1873 K. By using the values for the first and second order interaction parameters between oxygen and nickel in liquid iron and those between oxygen and iron in liquid nickel, the effect of Ni on the activity coefficient of Al in liquid iron and that of Fe on the activity coefficient of Al in liquid nickel were determined in the whole composition range of Ni-Fe alloys. The oxygen contents in Ni-Fe alloys calculated by the iterative method based on pure iron were in good agreement with those based on pure nickel in the range of [% Al] < 0.03. From this fact, it was found that the Wagner's approximation relating to the multi-component solution was applicable to the deoxidation equilibrium in the whole composition range of Ni-Fe alloys in the restricted concentration of a deoxidizer.     

Thermodynamics of Oxygen Solution in Fe–Ni Melts Containing Boron

Fe–Ni alloys are widely used in engineering today. They are sometimes alloyed with boron. Oxygen is a harmful impurity in Fe–Ni alloys. It may be present in dissolved form or as nonmetallic inclusions. The presence of oxygen in Fe–Ni alloys impairs their performance. Research on the thermodynamics of oxygen solutions in Fe–Ni melts containing boron is of considerable interest in order to improve alloy production. The present work offers a thermodynamic analysis of solutions of oxygen in Fe–Ni melts containing boron. The equilibrium constant of the reaction between boron and oxygen dissolved in the melt in such systems is determined. The activity coefficients at infinite dilution and the interaction parameters in melts of different composition are also calculated. When boron reacts with oxygen in Fe–Ni melts, the oxide phase contains not only B₂O₃ but also FeO and NiO. The mole fractions of B₂O₃, FeO, and NiO in the oxide phase are calculated for different boron concentrations in Fe–Ni melts at 1873 K. For iron melts with low boron content, the mole fraction of boron oxide is ~0.1. With increase in the nickel and boron content in the melts, the boron-oxide content in the oxide phase increases. Its mole fraction is close to one for pure nickel. The solubility of oxygen in Fe–Ni melts is calculated as a function of the nickel and boron content. The deoxidizing ability of the boron improve significantly with increase in nickel content in the melt. The curves of oxygen solubility in Fe?Ni melts containing boron pass through a minimum, which is shifted to higher boron content with increase in nickel content in the melt. The boron content at the minima on the curves of oxygen solubility are determined, as well as the corresponding minimum oxygen concentrations.     

Thermodynamics of the oxygen solutions in iron-nickel melts

The oxygen solutions in Fe-Ni melts containing chromium, manganese, vanadium, carbon, silicon, titanium, or aluminum are studied thermodynamically. The equilibrium constants of the deoxidation of the melts by these elements are determined, and the activity coefficients for infinite dilution and the interaction parameters in alloys of various compositions are found. The oxygen solubilities in the alloys are calculated as a function of the nickel and deoxidizer contents. The deoxidizer contents at the minima in the oxygen solubility curves for the melts are determined, and the corresponding minimum oxygen concentrations are calculated. As the nickel content in the system increases, the deoxidizing capacities of chromium, manganese, and silicon are shown to increase substantially, and the deoxidizing capacity of carbon increases most strongly. As the nickel content in the melt increases, the deoxidizing capacities of vanadium and titanium first decrease insignificantly and then increase substantially. As the nickel content in the melt increases to 50%, the deoxidizing capacity of aluminum first decreases and then increases; in pure nickel, it is identical to that in pure iron.     

Thermodynamics of the oxygen solutions in zirconium-containing iron-nickel melts

Thermodynamic analysis of the oxygen solutions in zirconium-containing iron-nickel melts is carried out. The equilibrium deoxidation constants of the melts by zirconium, the activity coefficients at infinite dilution, and the interaction parameters in melts of various compositions are determined. The dependences of the oxygen solubility in the melts on the nickel or zirconium content are calculated. Zirconium is shown to possess a very high deoxidizing capacity in iron-nickel alloys. The zirconium contents at the minima in oxygen solubility curves and the corresponding minimum oxygen concentrations are determined. As the nickel content in a melt increases to ∼45%, the deoxidizing capacity of zirconium decreases and, then, increases. The deoxidizing capacity of zirconium in pure nickel is noticeably higher than that in pure iron.     

Transfer of iron to Cu–Ni alloys from the lining of the vacuum induction furnace

In Ni–Cu alloys, iron must be excluded in many cases. Iron may enter the alloy from the batch or the furnace lining. Since the Fe₂O₃ content in refractories may be as much as 2.5%, it is important to assess the increase in iron content in alloys on account of interaction with the furnace lining. In the present work, the influence of the Fe₂O₃ content in the crucible and the volume of the crucible on the iron content in the final alloy is studied. Thermodynamic analysis and experimental data indicate that the nickel and copper in Ni–Cu alloys may reduce iron that is present in the lining. When using low-iron batch, iron from the crucible is transferred almost completely to the melt. The increase in iron content in Ni–Cu alloys is investigated as a function of the capacity of the vacuum induction furnace and the Fe₂O₃ content in the periclase crucibles, with complete transfer of the iron from the lining to the melt. With increase in furnace capacity, less iron enters the melt from the crucible. With more than 200 kg of metal, the increase in iron concentration mainly depends not on the furnace capacity but on the Fe₂O₃ content in the refractory. In order to produce Ni–Cu alloys with <0.01% Fe, refractories with Fe₂O₃ content no higher than 0.5% must be used. To produce Ni?Cu alloys with <0.05% Fe, the use of lining refractories with Fe₂O₃ content no higher than 2.5% is recommended.     

Absorption of gaseous oxygen by liquid cobalt,copper, iron and nickel

An experimental investigation of the rates of oxygen solution in molten cobalt, copper, iron and nickel was carried out using pure oxygen and a constant-volume Sieverts’ method. It was found that the volume of gaseous oxygen which initially reacted with the inductively stirred metals was strongly dependent on the physical nature of the oxide film which formed during the first stage of reaction. The initial temperature of the molten iron, cobalt, and nickel was 1600°C, and for copper was 1250°C. For initial oxygen pressures above the melt of about one atmosphere both molten iron and copper, which formed liquid surface oxides, initially absorbed nearly 20 cm³ (STP) O₂/cm² of melt surface area, while molten cobalt and nickel, which formed solid oxides, absorbed about 6 cm³ (STP) O₂/cm² under the same experimental conditions. For approximately 30 s after the initial reaction between these liquid metals and gaseous oxygen, the oxygen absorption rate was proportional to the square root of the oxygen pressure above the melt, and proportional to the melt surface area, but independent of melt volume. The rate-limiting step for oxygen absorption by liquid iron, cobalt and copper can be described by dissociative adsorption of oxygen molecules at the gas/oxide interface. After 30 s of reaction, the rate of oxygen absorption became less dependent on the oxygen pressure above the melt. This indicated that the rate-controlling step was changing from a surface reaction to growth of the oxide layer by cationic diffusion in the bulk oxide. The oxidation rate of liquid nickel appears to be too complex to be described by models for dissociative adsorption of oxygen molecules at the gas/oxide interface and parabolic growth of the oxide layer. The formation of a thin layer of nickel oxide which allows oxygen to migrate through cracks or grain boundaries may be responsible for the relatively high oxygen absorption rate compared to that of liquid cobalt. R. H. RADZILOWSKI, formerly a Graduate Studient at The University of Michigan     

Activities in liquid Fe-V-O and Fe-B-O alloys

The activities in liquid Fe-V-0 and Fe-B-O alloys have been determined using the following galvanic cells Cr-Cr₂O₃(s) | ZrO₂(CaO) | Fe-V-O (l, saturated with oxide) Cr-Cr₂O₃(s) | ThO₂(Y₂O₃) | Fe-V-O (l, saturated with oxide) Cr-Cr₂O₃(s) | ZrO₂(CaO) | Fe-B-O (l, B₂O₃ saturated with Al₂O₃) The solubility of oxygen in Fe-V alloys at 1600°C decreases with increasing vanadium content to a minimum of about 180 ppm at 3 wt pct V, and then increases to over 4000 ppm at 36.3 wt pct V. Vanadium was found to decrease the activity coefficient of oxygen and the value of the interaction coefficient e_o ^V at infinite dilution of vanadium is -0.14. The activity of vanadium was calculated from the measured electromotive force, and log γ_v was found to be represented well by the quadratic formalism for N_v < 0.4: log γ_V = -0.70N ² _Fe -0.30 At 1550°C boron decreases the solubility of oxygen down to about 80 ppm at 0.67 wt pct B in Fe-B melts in equilibrium with B₂O₃ saturated with A1₂O₃ (N_{Al 2} O₃ = 0.087). The boron deoxidation product, ’K′ = (wt pct B)²(wt pct 0)³ at infinite dilution of boron is 4.4 × 10_-9 and 1.5 × 10^-8 at 1550° and 1600°C, respectively. Boron decreases the activity coefficient of oxygen in liquid iron, and the value of the interaction coefficient e_o ^B is -2.6 at infinite dilution of boron. The activity coefficient of boron at infinite dilution (γ^° _B) is 0.083 at 1550°C relative to solid boron.     

Oxygen activities in Cr-containing Fe and Ni-based melts

Plug-type, ZrO₂-based oxygen sensors have been used for long-term measurements of oxygen activity in Fe–O–Cr and Ni–O–Cr melts. In these melts, equilibrated with chromium oxide, oxygen activities a_O were determined as a function of Cr content. From the experimental results, data were derived for activity coefficients f_O and of 1st and 2nd order interaction parameters e_O^Cr and r_O^Cr. Cr₂O₃ has been identified as the oxide phase in equilibrium with the metal melt at ≥ 5 wt.% Cr in the case of iron and at ≥ 0.2 wt.% Cr in the case of nickel. Oxygen activities and oxygen contents in Cr-containing iron melts are lowered with increasing additions of nickel. Further investigations were directed to a_O determination in Fe–O–Cr–C and Fe–O–Cr–Al melts.     

Solubility of oxygen in carbon-bearing Fe-Ni melts

Oxygen solutions in carbon-bearing Fe-Ni melts are analyzed thermodynamically. The equilibrium oxygen concentrations in Fe-Ni alloys in the presence of carbon have been determined for the first time over a wide composition range and a wide range of the partial pressures of carbon mono-and dioxides. As the carbon concentration increases, the oxygen concentration decreases in melts of all compositions. As the nickel content in the melt increases, the equilibrium oxygen concentration decreases at the same carbon concentration. The difference in the oxygen concentrations in iron and nickel at the same carbon concentration is almost two orders of magnitude, which can be explained by the substantial weakening of the bonding forces of oxygen in the melt and the less pronounced weakening of the bonding forces of carbon atoms with increasing nickel content. The oxygen solubility curves pass through a minimum, whose position changes with the nickel content from 2.443% C for pure iron to 2.842% C for pure nickel. The solubility of oxygen in a Fe-40% Ni melt is experimentally studied at various carbon contents. The experimental results agree well with the calculated data.     

Thermodynamics of oxygen behaviour in cobalt-nickel alloys

In this study the concentration and chemical potential of oxygen in liquid Co-Ni alloys equilibrated with cobalt-nickel aluminate spinel solid solutions and alumina have been determined at 1773, 1823 and 1873K as a function of nickel concentration. The oxygen content of the melt has been measured by suction sampling and inert gas fusion analysis. The corresponding oxygen potential has been determined with the following solid state cell: Mo, Mo+MoO₂ | (MgO)ZrO₂ | (Co, Ni) melt + AI₂O₃ + (Co, Ni)O·(1+x)Al₂O₃, Mo. The effect of nickel on the activity coefficient of oxygen in Co-Ni alloys has been determined. The results for the activity coefficient have been modelled with Wagner's interaction parameters and also the more recent exponential method of St. Pierre et al. at the three temperatures.     

Absorption of gaseous oxygen by liquid cobalt, copper, iron and nickel

An experimental investigation of the rates of oxygen solution in molten cobalt, copper, iron and nickel was carried out using pure oxygen and a constant-volume Sieverts' method. It was found that the volume of gaseous oxygen which initially reacted with the inductively stirred metals was strongly dependent on the physical nature of the oxide film which formed during the first stage of reaction. The initial temperature of the molten iron, cobalt, and nickel was 1600‡C, and for copper was 1250‡C. For initial oxygen pres-sures above the melt of about one atmosphere both molten iron and copper, which formed liquid surface oxides, initially absorbed nearly 20 cm³ (STP) O₂/cm² of melt surface area, while molten cobalt and nickel, which formed solid oxides, absorbed about 6 cm³ (STP) 0₂/cm² under the same experimental conditions. For approximately 30 s after the initial reaction between these liquid metals and gaseous oxygen, the oxygen absorption rate was proportional to the square root of the oxygen pressure above the melt, and pro-portional to the melt surface area, but independent of melt volume. The rate-limiting step for oxygen absorption by liquid iron, cobalt and copper can be described by dissocia-tive adsorption of oxygen molecules at the gasJoxide interface. After 30 s of reaction, the rate of oxygen absorption became less dependent on the oxygen pressure above the melt. This indicated that the rate-controlling step was changing from a surface reaction to growth of the oxide layer by cationic diffusion in the bulk oxide. The oxidation rate of liquid nickel appears to be too complex to be described by models for dissociative ad-sorption of oxygen molecules at the gasJoxide interface and parabolic growth of the oxide layer. The formation of a thin layer of nickel oxide which allows oxygen to migrate through cracks or grain boundaries may be responsible for the relatively high oxygen ab-sorption rate compared to that of liquid cobalt. Formerly a Graduate Student at The University of Michigan     

The relationship between relative oxide ion content of Na2SO4, the presence of liquid metal oxides and sulfidation attack

According to the “oxide ion” theory, sulfidation attack does not occur until oxide ions present in the fused Na₂SO₄ melt react with the normally protective oxide scale. It has already been shown that chromia reacts with and decreases the oxide ion content of sodium sulfate and inhibits sulfidation attack. Based upon the results reported herein, the reduction of the oxide ion content of sodium sulfate is a necessary but not sufficient condition for sulfidation inhibition. It is shown that the oxides of molybdenum as well as vanadium react with and decrease the oxide ion content of Na₂SO₄. It is shown that the addition of either Mo or V to nickel imparts sulfidation resistance. However, it is also shown that whereas the addition of Cr₂O₃ to Na₂SO₄-coated nickel-base superalloys prevents or inhibits sulfidation attack, no beneficial effects are noted when either MoO₃ or V₂O₅ are codeposited with Na₂SO₄ onto nickel-base superalloy substrates. The reactions between V₂O₅ with metal oxides were also studied. V₂O₅ readily fluxes Al₂O₃ and slowly reacts with Na₂SO₄. The relationship between accelerated oxidation, oxide ion content of a fused melt and the fluxing of the normally protective oxide scale by liquid metal oxides is discussed.     

Formation of metallic phase on reducing-gas injection in multicomponent oxide melt. Part 2. Density and surface properties

The density and surface tension of melts of ferronickel (0–100% Ni) and oxidized nickel ore are measured by the sessile-drop method, as well as the interface tension at their boundary in the temperature range 1550–1750°C. The composition of the nickel ore is as follows: 14.8 wt % Fetot, 7.1 wt % FeO, 13.2 wt % Fe₂O₃, 1.4 wt % CaO, 16.2 wt % MgO, 54.5 wt % SiO₂, 4.8 wt % Al₂O₃, 1.5 wt % NiO, and 1.2 wt % Cr₂O₃. In the given temperature range, the density of the alloys varies from 7700 to 6900 kg/m³; the surface tension from 1770 to 1570 mJ/m²; the interface tension from 1650 to 1450 mJ/m², the density of the oxide melt from 2250 to 1750 kg/m³; and its surface tension from 310 to 290 mJ/m². The results are in good agreement with literature data. Functional relationships of the density, surface tension, and interphase tension with the melt temperature and composition are derived. The dependence of the alloy density on the temperature and nickel content corresponds to a first-order equation. The temperature dependence of the surface tension and interphase tension is similar, whereas the dependence on the nickel content corresponds to a second-order equation. The density and surface tension of the oxide melt depend linearly on the temperature. The results may be used to describe the formation of metallic phase when carbon monoxide is bubbled into oxide melt.     

Solubility of oxygen in Fe–Co melts containing titanium

Solutions of oxygen in Fe–Co melts containing titanium are subjected to thermodynamic analysis. The first step is to determine the equilibrium reaction constants of titanium and oxygen, the activity coefficients at infinite dilution, and the interaction parameters in melts of different composition at 1873 K. With increase in cobalt content, the equilibrium reaction constants of titanium and oxygen decline from iron (logK(FeO · TiO₂) =–7.194; logK(TiO₂) =–6.125; logK(Ti₃O₅) =–16.793; logK(Ti₂O₃) =–10.224) to cobalt (logK(CoO · TiO₂) =–8.580; logK(TiO₅) =–7.625; logK(Ti₃O₅) =–20.073; logK(Ti₂O₃) =–12.005). The titanium concentrations at the equilibrium points between the oxide phases (Fe, Co)O · TiO₂, TiO₂, Ti₃O₅, and Ti₂O₃ are determined. The titanium content at the equilibrium point (Fe, Co)O · TiO₂ ? TiO₂ decreases from 1.0 × 10^–4% Ti in iron to 1.9 × 10^–6% Ti in cobalt. The titanium content at the equilibrium point TiO₂?Ti₃O₅ increases from 0.0011% Ti in iron to 0.0095% Ti in cobalt. The titanium content at the equilibrium point Ti₃O₅ ? Ti₂O₃ decreases from 0.181%Ti in iron to 1.570% Ti in cobalt. The solubility of oxygen in the given melts is calculated as a function of the cobalt and titanium content. The deoxidizing ability of titanium decline with increase in Co content to 20% and then rise at higher Co content. In iron and its alloys with 20% and 40% Co, the deoxidizing ability of titanium are practically the same. The solubility curves of oxygen in iron-cobalt melts containing titanium pass through a minimum, whose position shifts to lower Ti content with increase in the Co content. Further addition of titanium increases the oxygen content in the melt. With higher Co content in the melt, the oxygen content in the melt increases more sharply beyond the minimum, as further titanium is added.     

Distribution of nickel between copper-nickel and alumina saturated iron silicate slags

The solubility of nickel in slag was determined by equilibrating copper-nickel alloys with alumina-saturated iron silicate slags in an alumina crucible at 1573 K. The experiments were carried out under controlled oxygen partial pressures in the range of 10^-10 to 10^-8 atm by use of suitable CO-CO₂ gas mixtures, and at Fe/SiO₂ ratio 1.34. The results showed that nickel dissolves in slag both as Ni²⁺ (nickel oxide) and Ni‡ (nickel metal), and the relation obtained was: (Wt pct Ni in slag) = (ie33-01) The activity coefficient of nickel oxide (γ^dgNio) and distribution coefficient of nickel (A_Ni) is calculated to be 0.375 and 233.3, respectively. γ^dgNio and A_Ni are found to be independent of oxygen partial pressures. The presence of alumina increases the solubility of nickel in slags.     

Thermodynamics of iron alumino-chromite spinel inclusions in steel

The effect of chromium on the oxygen concentration of iron melts in equilibrium with various spinel reaction products has been determined. Alumina crucibles were used and experiments were performed at 1550, 1600, and 1650°C. Thermodynamic relationships between the equilibrium concentrations of chromium and oxygen in the iron melts have been established for chromium concentrations ranging up to 20 wt pct. Results from X-ray and electron microprobe analyses for the composition of the deoxidation products, together with solute activity relationships, indicate that the composition of the equilibrium spinel phase changes progressively from iron aluminate in the absence of chromium, through a series of aluminate-chromite solid solutions, FeO (Al _x Cr_1−x )₂O₃, (<0.5 pct chromium), to a complex chromite spinel, Fe₂Cr₇O₁₂, (0.5 to 3 pct chromium), and finally chromium oxide, Cr₃O₄ (>3 pct chromium). Deoxidation diagrams have been constructed and the effects of small amounts of alloying elements on the deoxidation behavior of aluminum interpreted in terms of buffered reactions which maintain oxygen concentrations in the melt at levels in excess of those normally associated with aluminum killed steel in equilibrium with alumina alone.     

Study on Microstructures of Al-4 wt pct V Master Alloys

Aluminum (Al)-V master alloys have attracted attention, because they can potentially be efficient grain refiners for wrought aluminum alloys. In this paper, the microstructure and factors affecting the microstructure of Al-4 wt pct V master alloys were investigated by means of controlled melting and casting processes followed by structure examination. The results showed that the type and morphology of the V-containing phases in Al-V master alloys were strongly affected by the temperature of the melt, concentration of vanadium in solution in the melt and the cooling conditions. Two main V-containing phases, Al₃V and Al₁₀V, which have different shapes, were found in the alloys prepared by rapid solidification. The Al₃V phase formed when there were both a high temperature (1273 K to 1673 K (1000 °C to 1400 °C)) and a relatively high vanadium content of 3 to 4 wt pct, while the Al₁₀V phase formed at a low temperature (<1373 K (1100 °C)) or a low vanadium content in the range of 1 to 3 wt pct. The results also showed that the type of V-containing phase that formed in the Al-4 wt pct V master alloy was determined by the instantaneous vanadium content.     

Thermodynamic properties of solid alloys of chromium with nickel and iron

The thermodynamic properties of chromium have been determined in the Ni-Cr and Fe-Cr binary systems and in the Fe-corner of the Fe-Ni-Cr system. These properties are based on experimental measurements using solid oxide electrolyte cells of the type: Cr, Cr₂O₃ I ThO₂-Y₂O₃Cr (alloy), Cr₂O₃. In the Ni-Cr system, between 900 and 1300°, the activity of chromium exhibits negative deviation from ideality up to about 25 at. pct chromium. For alloys higher in chromium content, the activity of chromium exhibits positive deviation from ideality. In the Fe-Cr system, between 900 and 1200°, and 0 and 63 at. pct Cr, the chromium activity when referred to solid pure chromium exhibits positive deviation from ideality in both the γ and α phases, approaching ideality with increasing temperature. The nickel and iron activities in these two respective binary systems were calculated by a Gibbs-Duhem integration. The activity of chromium, referred to solid pure chromium, was measured between 900 and 1200° in solid Fe-Ni-Cr alloys with chromium concentrations of 9, 20, and 30 at. pct and Ni concentrations of 8, 18, and 30 at. pct. Additions of nickel to Fe-Cr alloys in the above concentration range are found to increase the chromium activity. The effect of nickel in increasing the chromium activity is greater at both greater chromium contents and lower temperatures. Formerly Graduate Student at The University of Michigan, is Staff Associate, Gulf Energy and Environmental Systems, LaJolla, California. This paper is based on a portion of a thesis submitted by F. N. MAZANDARANY in partial fulfillment of the requirements for the degree Doctor of Philosophy at The University of Michigan.     

On the Formation of non-metallic inclusions in fe-50 pct Ni type alloys by deoxidation with Mn,Si, and Al

This investigation deals with deoxidation experiments in 30 g lab melts of Fe-50 pct Ni alloys. After deoxidation with different amounts of Mn, Si and Al and their combinations the samples were quenched into water at different times. Metallographic studies comprising light microscopy, scanning electron microscopy, electron microprobe and image analysis were performed. Classical nucleation theory was used for computation of the different supersaturation with oxygen or the deoxidant necessary for homogeneous nucleation. The different deoxidation reactions and the transformation of inclusions due to diffusion of oxygen, or the deoxidant, from or into the inclusions was treated for the different cases of deoxidation. Most deoxidation reactions take place within some seconds. The experimental results were to be used to estimate the pertinent interfacial tensions between the oxides and the melt and the values obtained for the different oxides seemed to be reasonable. The diffusional computations were successfully used for predicting the different transformations taking place. For example, in deoxidation with 0.03 pct Si the oxygen solubility is controlled by the equilibrium with liquid FeO ⋅ SiO₂. The time taken to reach equilibrium is determined by the number of inclusions and the particle size. In deoxidation with 0.1 pct Si or more, the equilibrium is controlled by SiO₂ inclusions and the time taken to reach equilibrium, less than 1 s, is much shorter compared to the samples with 0.03 pct Si. The deoxidation reactions with aluminum were treated in the same way, and it was shown that the number of particles determined the time elapsing before equilibrium with respect to the formation of FeOAl₂O₃ or A1₂O₃. It was further shown that transformation of primary liquid FeOAl₂O₃ with high contents of FeO into solid FeOAl₂O₃ was expected to occur within one second. However, the experiments showed that it took somewhat longer, due to formation of solid FeOAl₂O₃ around the liquid FeOAl₂O₃ inclusions, thereby preventing the diffusion of aluminum into the particles.