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.     

Thermodynamics of oxygen solutions in Fe-Mn melts

Oxygen solutions in Fe-Mn melts are analyzed thermodynamically. The composition of the oxide phase is determined, and the equilibrium oxygen concentrations in Fe-Mn melts are calculated over a wide composition range. The oxide phase mainly contains MnO: even at a molar fraction of manganese of 0.02 in the melt, the molar fraction of manganese oxide in the slag is more than 0.9. This is due to a much higher oxygen affinity of manganese as compared to iron; that is, manganese additives to iron considerably decrease the oxygen solubility. When the manganse content in the melt is 19.32%, the oxygen solubility curve has a minimum corresponding to an oxygen concentration of 5.136 × 10^?3%. However, a further increase in the managanese content results in an increase in the oxygen concentration in the melt. In liquid manganese, the oxygen saturation concentration at 1873 K is 0.0472%. The interaction parameter e _o(Mn) ^o (?0.207) and the activity coefficient γ _o(Mn) ^o (1.131 × 10^?4) have been calculated for the first time.     

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 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.     

Thermodynamics of carbon and oxygen solutions in manganese melts

The thermodynamics of carbon and oxygen solutions in manganese melts is studied. An equation for the temperature dependence of the activity coefficient of carbon in liquid manganese is obtained (γ _C(Mn) ⁰ = ?1.5966 + (1.0735 × 10^?3)T). The temperature dependence of the Gibbs energy of the reaction of carbon dissolved in liquid manganese with the oxygen of manganese oxide is shown to be described by the equation ΔG _T ⁰ = 375264 ? 184.66T(J/mol). This reaction can noticeably be developed depending on the carbon content at temperatures of 1700–1800°C. The deoxidation ability of carbon in manganese melts is shown to be much lower than that in iron and nickel melts due to the higher affinity of manganese to both oxygen and carbon. Although the deoxidation ability of carbon in manganese melts increases with temperature, the process develops at rather high carbon contents in all cases.     

Thermodynamics of the oxygen solutions in aluminum-containing Fe-Co melts

Thermodynamic analysis of aluminum-containing Fe-Co melts is performed. The equilibrium constants of the deoxidation of iron-cobalt melts with aluminum, the activity coefficients during infinite dilution, and the interaction parameters in melts with various compositions are determined. The oxygen solubility in the melts under study is studied as a function of the cobalt and aluminum contents. Aluminum is characterized by a very high affinity to oxygen in iron-cobalt melts. The deoxidizing capacity of aluminum substantially increases with the cobalt content in the melt. The curves of the oxygen solubility in aluminum-containing iron-cobalt melts have a minimum, whose position shifts to lower aluminum contents as the cobalt content in the melt increases. Further aluminum additions increase the oxygen concentration in the melt: the higher the cobalt content in the melt, the sharper the increase in the oxygen concentration after the minimum when aluminum is added to the melt. The aluminum contents at the minimum points in the oxygen solubility curves are determined, and the corresponding minimum oxygen concentrations are found.     

Thermodynamics of the oxygen solutions in manganese-containing Fe-Co melts

Thermodynamic analysis of the oxygen solutions in manganese-containing Fe-Co melts has been performed. The equilibrium constants of deoxidation reaction of iron-cobalt melts with manganese, the activity coefficients during infinity dilution, and the interaction parameters in various melts are found. During the deoxidation of manganese-containing Fe-Co melts, the oxide phase contains FeO and CoO along with MnO. The compositions of the oxide phase above Fe-Co-Mn-O melts are calculated. When the cobalt and manganese contents in the melts increase, the mole fraction of manganese oxide increases, and it approaches 1 in the case of pure cobalt. The dependences of the oxygen solubility in the melts on the cobalt and manganese contents are calculated. The deoxidizing capacity of manganese increases substantially with increasing cobalt content in the melt. The curves of oxygen solubility in Fe-Co melts have minima, whose values shift toward low manganese content in a melt. The manganese contents are determined at the minimum points in the oxygen solubility curves, and the corresponding minimum oxygen contents are found.     

Thermodynamics of the oxygen solutions in niobium-containing Fe-Ni melts

A thermodynamic analysis is performed for the oxygen solutions in niobium-containing Fe-Ni melts. The deoxidizing capacity of niobium in iron??nickel melts is shown to be low. It decreases slightly as the nickel content in a melt increases to 40% and then increases insignificantly as the nickel content increases to 60%; a further increase in the nickel content leads to a marked increase in the deoxidizing capacity. The solubility curves of oxygen in iron??nickel melts passes through a minimum, whose position shifts toward higher niobium concentrations with increasing nickel content. Subsequent niobium additions increase the oxygen concentration in the melt. The equilibrium constants of the reactions of niobium deoxidizing of iron??nickel melts, the activity coefficients, and the interaction parameters characterizing Fe-Ni-Nb-O melts are determined.     

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.     

Thermodynamics of oxygen solutions in the complex reduction of Fe-Co melts

Thermodynamic analysis of the complex reduction of metal melts is considered. The proposed analytical method identifies the influence of the weaker reducing agent in amplifying the effect of the stronger reagent. The curves of oxygen solubility pass through a minimum. Analysis of the extremal curves of oxygen concentration in the melt as a function of the content of reducing agents yields a formula for the content of the stronger reducing agent such that the oxygen concentration is minimal. Thermodynamic analysis of the combined influence of aluminum and silicon on the oxygen solubility in Fe-Co melts indicates that the reaction products may contain both mullite (3Al₂O₃ · 2SiO₂) and kyanite (Al₂O₃ · SiO₂). The presence of silicon in the melt intensifies the reducing action of aluminum: slightly when mullite is formed and significantly when kyanite is formed. When kyanite is formed, the curves of oxygen solubility pass through a minimum, whose position depends on the aluminum content in the melt but not on the silicon content. The aluminum content at the minimum declines slightly from iron to cobalt, as for Fe-Co-Al systems. Further addition of aluminum elevates the oxygen concentration. The formation of the compounds Al₂O₃, 3Al₂O₃ · 2SiO₂, Al₂O₃ · SiO₂, and SiO₂ is investigated as a function of the Al and Si content in the melt.     

Thermodynamics of titanium-based melts: II. Oxygen in liquid titanium

A method for the conversion of the thermodynamic characteristics of iron-based melts into those of titanium-based melts is used to calculate the change in the Gibbs free energy when oxygen dissolves in liquid titanium and when titanium is deoxidized by deoxidizing elements. It is established that beryllium is the most rational deoxidizer for structural, high-temperature, and functional titanium alloys and calcium is the most rational deoxidizer for foundry alloys. Free oxygen or volatile monoxides from liquid titanium cannot pass to a gaseous medium in vacuum, since it needs an unattainably low residual pressure.     

Influence of aluminum and chromium on the activity of oxygen in nickel based melts at 1600?C

The activity of oxygen in technically important nickel melts containing 15 wt pct cobalt and 5 wt pct molybdenum has been determined at 1600‡C for various concentrations of chromium ranging from 0 to 30 wt pct and aluminum varying from 0 to 15 wt pct. The activity of oxygen was measured by an electrochemical technique using yttria-doped thoria electrolyte cells. The results obtained are analyzed in terms of activity coefficients of oxygen as a function of aluminum and chromium contents in the melts. Clear positive deviations of the experimentally determined from the calculated activity coefficients of oxygen were found when aluminum was added to Ni-Co-Mo melts with or without chromium. From the results obtained in the range between 1 and 10 wt pct aluminum, the following equilibrium constants for the reaction 2 [Al] + 3 [O] ⇋ Al₂O₃ in the nickel based melts at 1600‡C were calculated: loga ₀ =-2/3 log [pct Al] - 3.94 for 0 pct Cr loga ₀ = -2/3 log [pct Al] - 4.21 for 10 pct Cr loga ₀ = -2/3 log [pct Al] - 4.81 for 20 pct Cr loga ₀ = -2/3 log [pct Al] - 5.06 for 30 pct Cr.     

Influence of aluminum and chromium on the activity of oxygen in nickel based melts at 1600‡C

Metallurgical and Materials Transactions B - The activity of oxygen in technically important nickel melts containing 15 wt pct cobalt and 5 wt pct molybdenum has been determined at 1600?C for...     

Thermodynamics of oxygen and nitrogen in liquid nickel equilibrated with CaO-TiO x and CaO-TiO x -Al2O3 melts

Equilibrium between CaO-TiO _x or CaO-TiO _x -Al₂O₃ slags and liquid nickel with respect to oxygen and nitrogen has been studied at 1873 K as a function of Ti (or Al) content in metal, using lime and alumina crucibles. The Al-O, Ti-O, and Ti-Al relations were obtained for liquid nickel equilibrated with these slags. Nitride capacity,_{C (N)}, defined by (mass pct N) · , was evaluated from nitrogen distribution ratios,L _N {= (mass pct N)/[mass pct N], coupled with oxygen content in liquid nickel. Activities of Al₂O₃ and activity coefficients of TiO₂ and TiO_1.5 were estimated either from the content of Al, Ti, and O, using the compiled data for the free energy of formation of oxide and the respective interaction parameters or from the values forL _N andC _(N).     

Thermodynamics of titanium-based melts: I. Thermodynamics of the dissolution of elements in liquid titanium

A method is described that involves the molar interaction parameters in liquid iron at a temperature of 1873 K, provides calculation of these parameters in liquid titanium at any temperature, and makes it possible to calculate the heats of dissolution of elements in liquid titanium and the activity coefficients of these elements. The changes in the Gibbs energy caused by the dissolution of some alloying and impurity elements in liquid titanium are calculated, and the activity coefficients of these elements are presented.     

Thermodynamics and phase relations in refractory metal solid solutions containing carbon,nitrogen, and oxygen

The refractory metals Nb, Ta, Mo, and W dissolve C, N, and O by forming interstitial solid solutions. The concentration of these components can be increased or decreased by annealing treatments, depending on the partial pressure of gases such as N₂, O₂, H₂O, CH₄, or CO and on the temperature of the specimen. New results in binary and ternary systems combined with those obtained in the last few years now provide most of the data needed for the thermochemical analysis of the solid solution phases and for the establishment of p-T-c phase diagrams. The mechanisms of the gas-metal reactions and the general feature of the constitution diagrams are similar for all refractory metals. However, marked differences exist between group Va metals niobium and tantalum and group VIa metals molybdenum and tungsten in the absolute values and temperature dependence of the equilibrium pressure of gaseous species and therefore also in the amount of gas absorbed. The data now available for the estimation of the final content of interstitials in solid solution after annealing treatments are compiled and discussed. On leave from the Max-Planck-Institut fur Metallforschung, Institut fur Sondermetalle, Stuttgart, Germany     

Thermodynamics of calcium and oxygen in molten titanium and titanium-aluminum alloy

The deoxidation equilibrium of molten titanium and titanium-aluminum alloys saturated with solid CaO has been measured in the temperature range from 1823 to 2023 K. The equilibrium constant of reaction CaO (s)=Ca (mass pct in Ti,Ti-Al)+O (mass pct in Ti,Ti-Al) and the interaction parameter between calcium and oxygen were determined for Ti, TiAl, and TiAl₃. The standard Gibbs energy of reaction for TiAl was obtained as follows: $$\Delta G^\circ = 279,000 - 103TJ/mol$$ The possibilities for the deoxidation of titanium and titanium-aluminum alloys by using calcium-based fluxes are discussed.     

Ignition of nickel in environments containing oxygen and chlorine

Metallurgical and Materials Transactions A - The mixed oxidation of nickel in gases containing both oxygen and chlorine has been investigated using the techniques of thermogravimetric analysis and...     

Ignition of nickel in environments containing oxygen and chlorine

The mixed oxidation of nickel in gases containing both oxygen and chlorine has been investigated using the techniques of thermogravimetric analysis and examination of the corrosion products by scanning electron microscopy. Two regimes of corrosion behavior have been detected: one in which a protective oxide film is present and the rate of corrosion is controlled by the transport of the volatile products of the reaction between the gas phase and the oxide, and one in which the protective film is penetrated and corrosion occurs rapidly enough to result in the ignition of the specimen. The oxide corrosion products on the specimens after corrosion have characteristic morphologies, with the products of volatilization type corrosion consisting of large grains and the products of ignition type attack consisting of fine spherical particles. Ignition is a serious hazard in environments containing 0.25 pct or more Cl₂ and 4 pct or more O₂ by volume at temperatures between 1000 K and 1100 K, but is not produced by exposures at higher temperatures. A model based on the stability of the protective film in steady state corrosion is presented which can be used to predict the transition from volatilization to ignition type attack.     

Ignition of nickel in environments containing oxygen and chlorine

The mixed oxidation of nickel in gases containing both oxygen and chlorine has been investigated using the techniques of thermogravimetric analysis and examination of the corrosion products by scanning electron microscopy. Two regimes of corrosion behavior have been detected: one in which a protective oxide film is present and the rate of corrosion is controlled by the transport of the volatile products of the reaction between the gas phase and the oxide, and one in which the protective film is penetrated and corrosion occurs rapidly enough to result in the ignition of the specimen. The oxide corrosion products on the specimens after corrosion have characteristic morphologies, with the products of volatilization type corrosion consisting of large grains and the products of ignition type attack consisting of fine spherical particles. Ignition is a serious hazard in environments containing 0.25 pct or more Cl₂ and 4 pct or more O₂ by volume at temperatures between 1000 K and 1100 K, but is not produced by exposures at higher temperatures. A model based on the stability of the protective film in steady state corrosion is presented which can be used to predict the transition from volatilization to ignition type attack.