Internal-oxide-band formation during oxidation of Ag-Mg alloys

Ag-3a/oMg was oxidized in air over the range of 400–900°C. Internal-oxide bands of MgO formed approximately parallel to the surface, the first band appearing at some finite, but irregular depth below the surface. The region between the surface and the first band appeared to be free of precipitates, but TEM showed that very small clusters, about 50 Å in diameter, formed in the PFZ, causing significant hardness (greater than 300 VHN). The clusters contain more oxygen than that corresponding to stoichiometric MgO. The hardness between oxide bands was also high, but not as high as in the PFZ. The kinetics of thickening of the internal-band region followed the parabolic rate law between 400 and 700° C, with departures from the parabolic law occurring at higher temperatures. The activation energy for the parabolic rate constants was 19.4 Kcal/mol, a value less than the total for oxygen diffusion and oxygen dissolution. The reaction front was planar and parallel to the surface prior to band formation at temperatures of 400–600° C. Nucleation of the first band resulted in nonplanar and nonparallel oxide. Little or no correlation existed between grain boundaries and oxide formation. Nodules of virtually pure silver formed on the surface initially at grain boundaries and subsequently within grains. Nodule formation is attributed to stress-enhanced (resulting from strains associated with precipitation) diffusion of silver to the surface via dislocation pipes. Internal-band formation is discussed in terms of prior data in the literature and various models. It is thought that stress effects (induced by precipitation), nucleation, and clustering of oxygen with Mg play significant roles in causing internal-band formation.     

The transient state in the oxidation of binary alloys forming the most-stable oxide: A numerical solution

The initial transient high-temperature oxidation stage for binary alloys forming the most-stable oxide has been examined by means of a numerical procedure based on the finite-difference method. At variance with previous models, the present treatment takes into account the effect of the rate of the reaction at the scale/gas interface over the corrosion kinetics. The calculations concerning the transient stage are developed either using the general parabolic rate law to represent the overall scaling kinetics or using the rate law of the reaction at the scale/gas interface as a boundary condition without imposing any particular rate law to the overall process. A correct analysis of the oxidation behavior of binary alloys during the transient stage must take into account the kinetics effect of the rate of the surface reaction. The concentration of the most-reactive element at the alloy/scale interface changes regularly with time, decreasing gradually from the initial bulk value to its final steady-state value. The present results are in good agreement with those obtained by means of an approximate analytical model developed previously.     

High-temperature sulfidation of Fe-30Mo alloys containing ternary additions of Al

Fe-30Mo alloys containing up to 9.1 wt% Al were sulfidized at 0.01 atm sulfur vapor over the temperature range of 700–900°C. The sulfidation kinetics followed the parabolic rate law for all alloys at all temperatures. For alloys containing small and intermediate amounts of Al (<4.8 wt.%), a duplex sulfide scale formed. The outer layers of the scales were found to be relatively compact FeS in all cases; whereas the inner layers were composed of the layered compound MoS ₂ (intercalated with iron), the Chevrel compound Fe _x Mo ₆ S ₈,a spinel double sulfide Al _x Mo ₂ S ₄,depending on the Al content of the alloy and the sulfidation temperature. Extremely thin scales were found on the alloys with higher Al contents. Accordingly, extremely slow sulfidation rates were observed—even slower than the sulfidation rate of pure Mo. The transition of the sulfidation kinetics from a high-rate active mode to a low-rate passive mode requires both a critical Al content in the alloy and a critical Mo content. Because of the two-phase nature of the alloys, the latter requirement implies a critical volume fraction of the intermetallic second-phase in the alloy, which has been known as the multiphase effect. Interestingly, the multiphase effect in these alloys was also a function of the Al content in the alloys.     

The relation between the parabolic rate constants for the internal oxidation of binary alloys in terms of weight gain or thickness

A calculation of the parabolic rate law for internal oxidation in binary alloys expressed in terms of weight gain shows that its dependence on the concentration of the most-reactive component is different from that predicted by the classical Wagner treatment for the rate constant expressed in terms of thickness of the internal oxidation zone. It is shown that the ratio between the two rate constants for a given system is a very sensitive function of the concentration of the reactive element in the alloy.     

The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.     

The Internal Oxidation of Ternary Alloys II: The Coupled Internal Oxidation of the Two Most-Reactive Components Under Intermediate Oxidant Pressures

The kinetics of the coupled internal oxidation of the two most-reactive components in the scaling of ternary alloys under oxidant pressures below the stability of the oxide of the most noble component are examined using a number of simplifying conditions which allow to develop an approximate analytical treatment. The precipitation of the two oxides may occur either at a single front or at two different fronts of internal oxidation. The former case corresponds to a unique solution for all the parameters involved in the process. On the contrary, the existence of two fronts of internal oxidation yields a finite range of possible solutions for the oxidation kinetics as well as for all the other relevant parameters. Even though the present treatment does not allow to predict which solution will be adopted by a real system, it is possible to set limits to the values of the parameters yielding physically-acceptable solutions. After considering a general case, the treatment is applied to a real system already examined experimentally.     

The Internal Oxidation of Ternary Alloys I: The Single Oxidation of the Most-Reactive Component Under Low Oxidant Pressures

The internal oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant is examined assuming a gas-phase oxidant pressure below the stability of the oxides of the other two components. The precipitation of the most-stable oxide leaves behind a matrix composed of a binary alloy of the two less-reactive components, whose composition affects the solubility and diffusivity of the oxidant within the region of internal oxidation, with an effect on the reaction kinetics. Approximate relations between these properties are proposed and used to predict the kinetics of internal oxidation of C under the assumption of parabolic rate law. The results obtained for the ternary alloys are compared with the behavior of binary A–C and B–C alloys with the same C content. A new important factor in establishing the difference between the internal oxidation in ternary A–B–C alloys and in binary A–C and B–C alloys under a fixed gas-phase oxygen pressure and C content is the ratio between the concentrations of A and B in the bulk ternary alloy.     

The corrosion of Co-Nb alloys in reducing/oxidizing-sulfidizing gases at 600–800°C

The corrosion of the two pure metals and of two alloys containing 15 and 30 wt% Nb has been studied at 600–800°C in H₂-H₂S-CO₂ gas mixtures providing 10⁻⁸ atm S₂ at all temperatures and 10⁻²⁴ atm O₂ at 600°C and 10⁻²⁰ atm O₂ at 700 and 800°C. The corrosion kinetics were rather complex, being sometimes parabolic and in other cases nearly linear. Under a constant temperature the addition of niobium generally reduced the corrosion rate, except at 700°C when pure cobalt corroded more slowly than the two alloys. The corrosion rates for the same material decreased with an increase in temperature under the same sulfur pressure. Except at 800°C under 10⁻⁸ atm S₂, which is below the dissociation pressure of cobalt sulfide, the scales presented an outer layer of pure cobalt sulfide and an inner layer of complex composition containing a mixture of double sulfide, niobium oxide and in some cases of unreacted metallic cobalt particles. The addition of niobium was generally beneficial, the effect increasing with its concentration in the alloy, but the corrosion rates of the alloys were still much higher than that of pure niobium, mainly as a result of the lack of formation of a protective layer of niobium sulfide. The corrosion behavior is examined with special reference to the consequences of the low solubility of niobium in cobalt and to the relation between the microstructure of the alloys and the scales.     

An analysis of the internal oxidation of binary M-Nb alloys under low oxygen pressures at 600–800°C

The corrosion of M–Nb alloys based on iron, cobalt, and nickel and containing 15 and 30 wt% Nb has been studied at 600–800°C under low oxygen pressures (10^–24 atm at 600°C and 10^–20 atm at 700–800°C). Except for the Co–Nb and Ni–Nb alloys corroded at 800°C, which formed external scales of niobium oxides, corrosion under low O₂ pressures produced an internal oxidation of niobium. This attack was much faster than expected on the basis of the classical theory. Furthermore, the distribution of the internal oxide in the alloys containing two metal phases was very close to that of the Nb-rich phase in the original alloys. These kinetic, microstructural, and thermodynamic aspects are examined by taking into account the effects of the limited solubility of niobium in the various base metals and of the two-phase nature of the alloys.     

The oxidation of two Fe−Nb alloys under low oxygen pressures at 600–800°C

The oxidation of two Fe–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800°C under low oxygen pressures, similar to those prevailing in environments of the coal-gasification type. The reaction produced only an internal oxidation of niobium to form two niobium oxides (NbO₂ and Nb₂O₅) and in some cases a double Fe–Nb oxide. The kinetics of this reaction were very slow at 600°C but rather fast at 700 and 800°C. A peculiar feature of the internal oxidation of these alloys is that the distribution of the internal oxides follows closely that of the Nb-rich phase in the original two-phase alloys. This behavior, as well as the lack of formation of external scales of niobium oxides, is mainly a result of the limited solubility of niobium in iron and of the consequent presence of two metal phases in the alloys.