Thermodynamics of oxygen solutions in Fe-Ni-V melts

The oxygen solutions in Fe-Ni melts with up to 5% V are analyzed thermodynamically. The results of the works in which the fields of the vanadium-deoxidized oxide phases in iron and nickel were determined are generalized. The thermodynamic model developed for the calculation of the deoxidation of iron-nickel alloys with vanadium is shown to be adequate. The deoxidizing capacity of vanadium decreases insignificantly as the nickel content in the melt increases to 20% and increases substantially as the nickel content increases further. The oxygen solubility curves pass through a minimum, whose position changes from 2.3192% V for pure iron to 0.7669% V for pure nickel. We determined the equilibrium point [V]* between the (Fe, Ni)V₂O₄ and V₂O₃ oxide phases for alloys of six compositions at 1873 K. In nickel, [V]* is almost 200 times lower than in iron. The deoxidation of the Fe-40% Ni melt with vanadium is studied experimentally, and the experimental results agree satisfactorily with the calculated data.     

Effect of zirconium on the oxygen solubility in liquid nickel and Ni–Fe melts

The oxygen solubility in liquid nickel containing zirconium is studied experimentally for the first time at 1873 K. The equilibrium constants of the reaction of interaction between zirconium and oxygen dissolved in liquid nickel, the interaction parameters characterizing these solutions, and the zirconium activity coefficient in nickel at infinite dilution are found. The equilibrium constants of the reaction of interaction between zirconium and oxygen dissolved in the melt, the Gibbs energy of the reaction of interaction between zirconium and oxygen, and the interaction parameters characterizing these solutions are calculated at 1873 K for a wide composition range of Ni–Fe alloys. The oxygen solubility in various Ni–Fe melts containing zirconium is found at 1873 K. The deoxidizing capacity of zirconium increases as the iron content increases to 30% and decreases at higher iron content in the melt. This can be explained by the fact that an increase in the iron content lead to, on the one hand, a strengthening of the bonding forces of oxygen atoms in a melt and, on the other hand, to a significant weakening of the bonding forces of zirconium atoms with the base metal.     

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.     

Surface tension and wettability studies of liquid Fe-Ni-O alloys

Surface tensions of iron-nickel alloys were measured as a function of oxygen potential at 1550 °C using the sessile drop technique. The surface tension of pure liquid nickel and iron-nickel alloys was measured at a total pressure of 1 atmosphere under varying CO₂/CO ratios. An increase in the oxygen potential in the gas phase was found to correspond to a decrease in surface tension of pure nickel and iron-nickel alloys, indicating that oxygen is surface active in both liquid nickel and iron-nickel alloys. At low oxygen potentials, nickel additions to liquid iron were found to cause small decreases in alloy surface tensions; however, at higher oxygen potentials, the surface tension of the alloy exhibited a minimum value as nickel was added to iron. The adsorption coefficients of oxygen in liquid iron-nickel alloys and pure liquid nickel were determined from the surface-tension data using Belton’s analysis, and were found to be similar to those calculated from kinetic studies. Wettability of iron-nickel alloys on an alumina substrate was studied through contact-angle measurements. At a constant alloy nickel content, the contact angle between the alloy and alumina decreased with increased oxygen potential in the gas phase.     

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 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.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron alloys containing nickel and aluminum

The solubility of nitrogen in liquid iron-base Fe-Ni-Al alloys has been measured up to the solubility limit for formation of aluminum nitride using the Sieverts’ method. Measurements were conducted over the temperature range from 1843 to 2023 K and aluminum concentration range from 1.5 to 3.0 wt pct Al. The effect of nickel additions was determined at 2, 5 and 10 wt pct Ni. The cross interaction parameter describing the effect of nickel and aluminum on the activity coefficient of nitrogen in iron was determined. The first and second order effects of nickel on the activity coefficient of aluminum also were determined. The solubility product of aluminum nitride increases with increasing aluminum content and increasing temperature. Addition of nickel decreases the solubility products of aluminum nitride in lower aluminum content alloys. However, the effect of the cross interaction terme _Al ^NiAl becomes significant with increasing aluminum content and compensates for the effects of the first and second order nickel-nitrogen and nickelaluminum interaction terms. Therefore the effect of nickel additions show little effect on the solubility products of aluminum nitride in higher aluminum alloys.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron, Fe-Cr, Fe-Cr-Ni, and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG‡ = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

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 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.     

Thermodynamic assessment of Mg deoxidation reaction of liquid iron and equilibria of [Mg]‐[Al]‐[O] and [Mg]‐[S]‐[O]

The deoxidation reaction of magnesium was investigated thermodynamically employing the equilibrium system between magnesium vapour and liquid iron in the molybdenum chamber sealed with an iron cover at 1873 K as a fundamental study to address the clean steel production technology in the steelmaking process. The previously reported thermodynamic data for magnesium deoxidation reaction are limitedly in good agreement with only their respective specific Mg concentration range, but fail to explain the thermodynamic equilibria generally over the wider range of magnesium concentration beyond the limited range. Therefore, the equilibrium constant, K_Mg for the magnesium deoxidation reaction as well as the first and second‐order interaction parameters between magnesium and oxygen were determined over the extensive magnesium mass content range covering up to 0.04 %. Furthermore, the phase stability diagram based on the equilibria of [Mg]‐[Al]‐[O] in liquid iron for the purpose of controlling the oxide inclusions in the steelmaking process was accomplished using the determined thermodynamic parameters. The equilibria of [Mg]‐[S]‐[O] were also discussed in order to evaluate the utilisation of Mg as a desulphurizing agent as well as deoxidizer in the production process of low carbon steels.     

Nitrogen solubility and aluminum nitride precipitation in liquid iron,Fe-Cr,Fe-Cr-Ni,and Fe-Cr-Ni-Mo alloys

The nitrogen solubility and aluminum nitride formation in liquid Fe-Al, Fe-Cr-Al, Fe-18 pct Cr-8 pct Ni-Al and Fe-18 pct Cr-8 pct Ni-Mo-Al alloys were measured by the Sieverts' method. The temperature range extended from 1823 to 2073 K, and the aluminum contents from 1.01 to 3.85 wt pct Al. Increasing aluminum content increases the nitrogen solubility. The effect of molybdenum additions was determined for 2, 4 and 8 wt pct Mo levels. The first and second order effects of chromium, nickel, molybdenum and aluminum on the activity coefficient of nitrogen in iron were determined. The first and second order effects of chromium, nickel and molybdenum on the activity coefficient of aluminum also were determined. The nitride precipitates were identified as stoichiometric aluminum nitride, AIN, by X-ray diffraction analysis. The lattice spacing was in good agreement with the ASTM standard patterns for AIN in both higher and lower Al content solutions. The solubility product of AIN increases with increasing aluminum concentration and with temperature in liquid iron and the iron alloys studied. However, the magnitudes of the solubility products of AIN in those alloys are different because of the effects of chromium and nickel additions. Additions of molybdenum show little effect on the solubility product of AIN. The standard free energy of formation of AIN in liquid iron is: δG? = -245,990 + 107.59 \T J/g-molAIN, based on the standard state of the infinitely dilute solution in liquid iron for aluminum and nitrogen, referred to a hypothetical one wt pct solution, and on the pure compound for A1N.     

高纯度Ca-Al系列合金研制及其应用基础

在高温（2700—2800K）下,通过熔融还原特制的活性氧化物（CaO、BaO、MgO）制得了高纯度Ca—Al系列合金,其中含有多种化合物,它们在熔化和气化状态下不分解。理论分析和实践证明：用Ca—Al系列合金对钢液进行脱氧、脱硫时,能提高合金中组元的利用率,将[O]、[S]含量降低到很低值,脱氧产物为易于上浮排除的、变性的各种铝酸盐（CaO（BaO,MgO））x（Al2O3）y（x：y=1.0-1.5）。Ca-Al系列合金是良好的终脱氧剂和精炼剂,是“纯Al粉＋纯Ca粉＋Fe粉”机械混合物的替代产品。     

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.     

Spinel deoxidation equilibria in the Fe—Mn—Al—O system – experiment and computation

The concentration and chemical potential of oxygen in liquid Fe—Mn alloys equilibrated with the spinel solid solution, (Fe, Mn)Al_2+2xO_4+3x, and α-Al₂O₃ have been determined at 1873 K as a function of manganese concentration. The composition of the spinel phase has been determined using electron probe microanalysis. The results are compared with data reported in the literature. The deoxidation equilibrium has been computed using data on free energy of solution of oxygen in liquid iron, free energies of formation of hercynite and galaxite, and interaction parameters reported in the literature. The activity-composition relationship in spinel solid solution was derived from a cation distribution model. The model is in excellent agreement with the experimental data on oxygen concentration and potential and the composition of the spinel phase.     

Thermodynamic assessment of the Al deoxidation reaction in liquid iron

The deoxidation reaction of aluminum in liquid iron has been investigated thermodynamically using Al₂O₃ crucible at 1873 K under Ar atmosphere as a fundamental study for the accurate control of inclusions in the ladle refining process. In addition to the equilibrium constant log K_A1 for the aluminum deoxidation reaction, the first-order and second-order interaction parameters between aluminum and oxygen were experimentally determined in the concentration range of aluminum up to 1 %. The temperature dependence of the equilibrium constant and the first-order interaction parameter e^A1 was also obtained: log K_A1 = 12.32 - 47400/T, e^A1 = 15.57 - 36500/T. The equilibrium relation between aluminum and oxygen contents in the aluminum deoxidized iron by applying interaction parameters and the equilibrium constant determined in this work satisfies fairly well the equilibrium data over the whole concentration range of aluminum considered.     

Diffusion in β2 Fe-Ni-Al alloys

Diffusion in the β(bcc) phase field of the Fe-Ni-Al system was investigated at 1004°C with solid-solid diffusion couples assembled with β₂ alloys of selected composition. Experimental diffusion paths were determined for all couples and interdiffusion coefficients calculated at composition points corresponding to intersections of diffusion paths and maxima and minima of concentration profiles. The dependence of interdiffusion coefficients on composition was most clearly presented in terms of the parameter Fe/(Fe + Ni). The diffusive interactions between aluminum and nickel as represented by the cross coefficients were either positive or negative depending on the ternary composition. The Fe/(Fe + Ni) ratio appeared to be a significant parameter since iron and nickel atoms behave differently in affecting the degree of ordering in nonstoichiometric (Fe, Ni)Al alloys with less than 50 at. pct aluminum.     

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.