Internal oxidation of ternary alloys. Part I: Kinetics in the absence of an external scale

A treatment of the kinetics of internal oxidation of ternary alloys in the absence of an external scale is presented. The analysis involves simultaneous internal oxidation of the two solutes in the ternary alloys. A comparison with measurements on Ni-4 at.% Al-1 at.% Si alloys at 800°C reveals a good agreement between theory and experiment.     

Oxidation of γ-Ni−Al−Si alloys at 1073 K

The formation and development of oxides in Ni–4Al and Ni–4Al–xSi (at.%, x=1, 3, 5) alloys at 5–9×10^–6 and 1 atm oxygen pressure at 1073 K have been studied. The oxidation rate increased with an increase of silicon content in the alloy at the early stage of oxidation, but decreased after longer time exposure due to formation of an intermediate layer composed of NiO and spinel (NiAl₂O₄ and Ni₂SiO₄) between the top NiO layer and the internal-oxidation zone. This intermediate layer became a barrier for releasing stress, generated by the volume expansion associated with oxidation of solute atoms, resulting in high dislocation density and severe distortion in the internal-oxidation zone for the Ni–Al–Si alloys. In Ni–4Al alloy where no complete intermediate-layer formation occurred, stress was easily released by an enhanced vacancy gradient, and therefore an enhanced vacancy-injection rate into the alloy, resulting in a higher oxidation rate than the situation where a sample was oxidized at an oxygen pressure associated with the dissociation of NiO.     

Transition from internal to external oxidation for binary alloys in the presence of an outer scale

The critical concentration required for the transition from internal to external oxidation of the most reactive component B of a binary A-B alloy for the case of simultaneous formation of an outer AO scale is calculated by extending Wagner's original analysis, which excluded the presence of an AO oxide. It is shown that the formation of an outer AO scale tends to produce an increase in the critical concentration of B, essentially as a result of a decrease of the enrichment of B in the internal oxidized region. Examples of the calculation of some parameters are presented to examine the effect of the different factors on the properties of internal oxidation and on its transition to the formation of an external scale of the oxide of the less noble component.     

Internal oxidation of dilute silver alloys

Internal oxidation of dilute silver alloys containing Al, Mg, Zn, Cu, and Sn was studied in air at temperatures between 573 K and 1173 K. Electrical resistivity, gravimetric, and gas-extraction measurements were made. The general trend of the resistivity is that it increases upon oxidation at lower temperatures and the resistivity decreases at higher temperatures in all of these alloys except Ag-Mg, in which it increases even at 1173 K. The increase in resistivity is considered to be related to the formation of clusters having excess oxygen. A detailed investigation was performed on Ag-Al alloys. The O/Al ratio in the clusters in Ag-2.2 at.% Al is much higher on oxidation at 773 K than for stoichiometric Al₂O₃ at 1173 K. The clusters release the excess oxygen on subsequent annealing at high temperatures, and decompose to stable Al₂O₃ at 1173 K.     

Oxygen solubility and a criterion for the transition from internal to external oxidation of ternary alloys

Smith's model is expanded in order to derive expressions to quantitatively describe the oxygen-solubility behavior in ternary alloys as a function of alloy composition. Multicomponent-diffusion theory is used to establish a criterion for the onset of internal oxidation beneath the external scale when oxidizing conditions favor formation of the oxide of the least-noble metal in a ternary alloy. The oxygen-solubility model and the criterion are applied to the oxidation of Ni–Cr–Al alloys in 76 torr of oxygen at 1100 and 1200°C, predicting the minimum Al concentrations required to form a protective Al₂O₃ scale. It shows that sufficient Cr additions would significantly reduce the oxygen solubility and also alter the oxygen distribution in the ternary alloys, avoiding the oxygen supersaturation necessary for the onset of internal oxidation. These two factors make it easier to establish the protective Al₂O₃ scale.     

The internal oxidation of two-phase binary alloys beneath an external scale of the less-stable oxide

The internal oxidation of two phase binary A-B alloys by a single oxidant at high temperatures, under partial pressures sufficient to also form external scales of the less-stable oxide, is examined by means of quantitative models and compared with the corresponding behavior of single-phase alloys. It is shown that, depending on various factors, particularly on the solubility and diffusivity of the most-reactive component B in the most-noble component A, this process may or may not involve a diffusion process of the alloy components, leading to different scale morphologies. It is also concluded that even when the solubility and diffusivity of B in A are sufficiently high, so that the internal oxidation of the common type occurs, the restriction to the diffusion of B in the alloy due to its limited solubility affects the kinetics of internal oxidation, producing an increase of the rate of internal oxidation and of the critical concentration of B in the alloy required for the transition to the external oxidation of B with respect to single-phase alloys under the same values of all the relevant parameters. The lower the solubility of B in A, the larger these effects.     

Contribution to the understanding of the parabolic oxidation mechanism of dilute alloys. Part I: Oxides with metal excess or oxygen deficit

Concerning the parabolic oxidation of alloys with a low content of a different valence element, we show that the Wagner-Hauffe valence approach contains some inaccuracies. This paper is devoted to the growth of an oxide MO with metal excess or oxygen deficit. The analytical processing consists in solving the differential equation connecting the point defect flux to the oxygen pressure. This equation has been solved analytically in the case where the foreign-element concentration is very high compared to that of the point defects in the pure oxide. On this assumption with a lower-valence dopant, as long as the oxide conductivity remains essentially electronic, the oxidation is limited only by the transport of ionic defects across the scale under the electric-potential gradient. Moreover, an increase of the dopant concentration may lead to an oxide exhibiting partial ionic conductivity. Consequently, the parabolic constant variations as a function of the dopant concentration is not monotonic, contrary to results published before. With a higher-valence dopant, the conductivity always remains electronic, and this result agrees with predictions based on the Wagner Hauffe approach, though the demonstrations are fundamentally different.     

The oxidation of Ni-Nb alloys at low-oxygen pressures at 600–800°C

The oxidation of two Ni–Nb alloys containing 15 and 30 wt.% Nb has been studied at 600–800° C in H₂–CO₂ mixtures providing an oxygen pressure of 10^–24 atm at 600° C and 10^–20 atm O₂ at 700 and 800° C, these pressures being less than the dissociation pressure of nickel oxide. The scales formed on both alloys at 600 and 700° C show only a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both the metal phases present, i.e., Ni₈Nb and Ni₃Nb. Only small, or even no, Nb depletion was observed in the alloys close to the interface with the zone of internal oxidation at these temperatures. On the contrary, samples of both alloys corroded at 800° C produced a continuous external scale of niobium oxides without internal oxidation. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in nickel.     

Enhanced Oxygen Diffusion Along Internal Oxide–Metal Matrix Interfaces in Ni–Al Alloys During Internal Oxidation

A study of the internal oxidation of dilute Ni–Al alloys in an NiO/Ni Rhines pack was performed at 800, 1000, and 1100°C. Considerable deviations from the classical internal oxidation model have been observed. The rate of internal oxidation depends not only on the concentration of the alloying element but also on its nature, which contributes to determining the size, shape, orientation and distribution of the internal oxide precipitates. For instance, the precipitates in the Ni–Al alloys are continuous rods, arranged in a cone-shaped configuration that extends from the surface to the internal oxide front. The observed depths of internal oxidation for the various concentrations of aluminum are discussed and related to the morphologies of the internal oxide precipitates. The apparent N^(s) _oD_o values determined from internal oxide penetrations increase with increasing solute content in the alloy. It is postulated that diffusivity of oxygen is enhanced along the internal oxide–metal matrix interface compared with that in the metal matrix.     

The Internal Oxidation of Ternary Alloys. III: The Coupled Internal Oxidation of the Two Most-Reactive Components under High Oxidant Pressures

The kinetics of the simultaneous internal oxidation of the two most-reactive components B and C in ternary A–B–C alloys, where A is the most-noble and C the most-reactive component, in the presence of an external layer of the A oxide, AO, (high oxidant pressures) are examined assuming the existence of either a single or a double front of internal oxidation. For a single front a unique solution is obtained for the parabolic rate constant of internal oxidation under assigned values of all the parameters involved. When the front is double, a finite range of solutions is allowed with an upper limit equal to the single-front solution and a lower limit equal to the rate constant for the growth of external AO scales. In the case of a single front of internal oxidation, an increase of the rate constant for the growth of the external scales produces an increase of the rate constant for the internal oxidation but a decrease of the degrees of enrichment of the components being oxidized internally within the region of internal oxidation. The behavior in the case of a double front is more complex because it depends also on the actual value of the ratio between the rate constants of internal oxidation for the two fronts.     

The Internal Oxidation of Ternary Alloys. VIII: The Transition from the Internal to the External Oxidation of the Two Most-Reactive Components Under High-Oxidant Pressures

Ternary A–B–C alloys, where A is the most-noble and C the most-reactive component, exposed to oxygen pressures above the stability of the least stable oxide AO (high-oxidant pressures) may present two different types of internal oxidation, i.e. either a coupled internal oxidation of both B and C beneath an external AO scale or a single internal oxidation of C beneath an external scale of the oxide of B. This paper examines the conditions required to avoid the coupled internal oxidation of B plus C beneath external AO scales, considering both the case of formation of a single and a double front of internal oxidation. The analysis, based on an extension to ternary alloys of the criterion defined by Wagner for the transition between the internal and external oxidation of the most-reactive component of binary alloys, shows that the addition of B to binary A–C alloys is very effective in reducing the C content needed for this transition in comparison with binary A–C alloys. This results provides a basis for a possible explanation of the third-element effect. However, the actual possibility of its occurrence depends also on the ability to avoid other oxidation modes, not examined here.     

Internal oxidation of Ag-in alloys: Stress relief and the influence of imposed strain

The kinetics of internal oxidation of silver-indium alloys containing 3.5, 5.9, and 9.8 at.% In in air at temperatures 773 to 973 K were established by TGA with no load applied to the specimens. Silver nodules free of oxide particles were observed to form at the surface during internal oxidation. The volume of these silver nodules was comparable to the total volume increase caused by internal oxidation. The alloys were also creep tested during oxidation in air at creep rates varying from 10^–7 to 5×10^–5 s^–1 at 773, 873, and 973 K. The parabolic rate constants k_p for the internal oxidation of the solute were determined from the measured widths of the internal oxidation zones. A small increase in k_p was observed with increased strain rate. The large volume change associated with internal oxide formation resulted in a stress gradient between the stress-free surface and the internal oxidation front which is under a high compressive stress. Stress relief occurred by transport of silver to the surface. A Nabarro-Herring creep type mechanism based on lattice diffusion of Ag cannot account for the high rate of silver transport to the surface. Pipe-diffusion controlled creep is proposed as the mechanism of stress accommodation by silver diffusion.     

Phase stability,oxidation, and interdiffusion of a novel Ni−Cr−Al−Ti−Si bond-coating alloy between 900 and 1100°C

A novel, low-expansion experimental Ni–Cr–Al–Ti–Si bond-coating alloy was investigated in the as-cast state concerning its phase stability, oxidation resistance in air, and interdiffusion with single-crystal IN-100 at 900, 1000, and 1100°C. Isothermal oxidative thermogravimetry was employed up to 500 hr. Interdiffusion was compared to a commercial Ni–Co–Cr–Al–Y alloy on IN-100. Oxidized Ni–Cr–Al–Ti–Si specimens and diffusion couples were characterized by metallography, SEM, EDX, XRD, and XRF. The Ni–Cr–Al–Ti–Si alloy provides good oxidation resistance in air at least up to 1000°C. The alloy is an alumina former. Due to its coarse microstructure, other oxides (e.g., rutile) may form and considerably dominate the oxidation behavior. The kinetics of oxidation were correlated with temperature, formation of phases, and morphology of oxides. Interdiffusion fluxes between Ni–Cr–Al–Ti–Si and IN-100 were mainly directed to the superalloy. They were faster than in Ni–Co–Cr–Al–Y/IN-100 diffusion couples.     

The Internal Oxidation of Ternary Alloys. V: The Transition from Internal to External Oxidation of the Most-Reactive Component under Low Oxidant Pressures

This paper examines the conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys by a single oxidant under gas-phase oxidant activities below the stability of the oxide of the two most-reactive components using Wagners criterion. For this, approximate relations between the solubility and diffusivity of oxygen and the composition of the binary A–B alloy matrix in the zone of internal oxidation, already developed previously, are used. The critical C content needed for the transition in ternary alloys is calculated as a function of the many parameters involved. At variance with the behavior of binary alloys, for ternary alloys this critical C content depends also on the ratio between the concentrations of A and B in the bulk alloy. The results calculated for ternary alloys are compared with those obtained for binary A–C and B–C alloys under the same values of all the relevant parameters. Finally, complete oxidation maps for ternary alloys under low oxidant pressures,including the condition for the stability of external scales of the C oxide, are also presented.     

铁在双相Fe—Cu合金中的内—外氧化

三处Ｆｅ－Ｃｕ合金在氧分压低于氧化铜平衡分解压条件下的高温氧化结果表明,合金中同时发生了活泼组元铁的内氧化和外氧化,外氧化膜为单一铁的氧化物,内氧化区中氧化铁和金属铜继承了原始合金中两相的分布。内氧化区前沿的合金中未发现铁的贫化。这种氧化膜结构的单相合金中罕见而在双相合金中较为普遍,被认为是双相合金中两组元间有限地互溶度使得氧在合金中的过饱和程度比在固溶体合金中更强烈的结果。     

High-temperature oxidation of Fe-Cr-Al-Si alloys extruded into honeycomb structures

The oxidation behavior of Fe–20Cr–5Al–(0.5–5)Si and Fe–(12–20)Cr–(5–7)Al–(1–2)Si alloys extruded into honeycomb structures has been investigated at 1150°C in air for up to 500 hr. The oxidation weight gains decrease with increasing Si and Cr contents in the 5-Al alloys. Si additions are more efficient than Cr additions to reduce the weight gain. Increasing Si content in the 5-Al alloys suppresses the formation of an iron-chromium complex oxide, forming mullite and vitreous silica in the scale, although the location is not clearly indicated. The 5-Si alloy shows anisotropy in elongation of the honeycomb specimen during oxidation in the Fe–20Cr–5Al–xSi alloys, whereas alloying with Si and Cr does not improve the oxidation resistance of the 7-Al alloys significantly. These results are explained by Wagner's theory of a secondary getter. However, we point out additionally that the difference between Si and Cr in the Pilling-Bedworth ratio and the solubility of their oxides in the Al₂O₃ scale may contribute to the significant effect of Si additions. Finally, this paper demonstrates that the selected Fe–Cr–Al–Si honeycombs having walls 200 m thick show excellent oxidation resistance over 500 hr at 1150°C in air. The time to catastrophic oxidation is roughly proportional to the wall thickness in extruded honeycombs.     

The Internal Oxidation of Ternary Alloys. VII: The Transition from the Internal to the External Oxidation of the Two Most-Reactive Components Under Intermediate Oxidant Pressures

The conditions for the transition between the coupled internal oxidation of two most-reactive components and the formation of external scales in the scaling of ternary alloys under oxidant pressures below the stability of the oxide of the most-noble component, denoted as a situation of intermediate oxidant pressures, are examined under a number of simplifying conditions which allow to develop an approximate analytical treatment. If the precipitation of the two oxides occurs at the same front of internal oxidation, the kinetics of internal oxidation as well as the critical B and C contents needed for the transition have a single solution under fixed conditions of all the parameters involved. On the contrary, in the presence of two different fronts, when the most-stable oxide forms at the innermost front, a whole range of possible solutions is predicted. In both cases, the critical-C content needed to avoid the simultaneous internal oxidation of B plus C is progressively reduced by the addition of B. This behavior provides the basis for a possible interpretation of the “third-element effect”. However, the existence and the magnitude of this effect are complicated by the occurrence of other modes of oxidation for these systems. Thus, a general treatment of the third-element effect under intermediate oxidant pressures requires an exhaustive analysis of all the oxidation modes permitted for ternary alloys under these conditions.     

Hot-Corrosion Resistance of Ni–Cr–Al–Y and Ni–18% Si Alloys in Sulfate Eutectic and Sulfate Plus Vanadate Melts at 973 K

The hot-corrosion resistance of Ni–Cr–Al–Y and Ni–17.8 wt.% Si was examined in sulfate and sulfate plus vanadate melts at 973 K. Two salt-deposit compositions were considered: (a) sodium sulfate+50 mole% magnesium-sulfate eutectic and (b) sodium sulfate plus 20 mole% sodium meta-vanadate. Both types of deposit were molten at the test temperature. Cyclic hot-corrosion tests were conducted in a gas mixture consisting of oxygen, sulfur dioxide, and 0.0240 vol.% sulfur trioxide. The hot-corrosion kinetics were evaluated using weight change and the corrosion mechanism deduced from post-test metallography. The results indicate that the nickel–silicon alloy had much better hot corrosion resistance than Ni–Cr–Al–Y under all test conditions considered. The sample preparation process is outlined, the test procedure summarized, and the experimental results are presented and discussed.     

The Internal Oxidation of Ternary Alloys. VI: The Transition from Internal to External Oxidation of the Most-Reactive Component under Intermediate Oxidant Pressures

The conditions for the transition from internal to external oxidation of the most-reactive component C of ternary A–B–C alloys are examined, assuming the presence of external scales of the oxide of the component of intermediate reactivity B. For this, approximate expressions for the diffusion coefficient of oxygen and for the concentration of oxygen dissolved in the binary A–B alloy matrix within the zone of internal oxidation as functions of the composition of the metal matrix within the zone of internal oxidation are used. Numerical calculations of the critical content of C needed for this transition are carried out for different combinations of values of the various parameters involved. The results obtained for the ternary alloys are compared with the corresponding data calculated for the binary A–C and B–C alloys under oxygen pressures insufficient to oxidize the most-noble alloy component. This allows to predict the possibility of existence of a third-element effect under intermediate oxidant pressures.     

The Internal Oxidation of Ternary Alloys. IV: The Internal Oxidation of the Most-Reactive Component Beneath External Scales of the Component Having Intermediate Reactivity

The kinetics of internal oxidation of the most-reactive component C of ternary A–B–C alloys in the presence of external scales of the oxide of the component of intermediate reactivity B, BO, are examined using convenient approximations. The precipitation of the most-stable oxide leaves behind a matrix composed of a mixture of the two most-noble components, A and B, whose composition changes with depth due to the consumption of B to form the external scale. For the calculation of the parabolic rate constant use is made of approximate expressions for the concentration of oxygen dissolved in the binary A–B metal matrix within the zone of internal oxidation and for the diffusion coefficient of oxygen as functions of the alloy composition. Numerical calculations of the parabolic rate constant of internal oxidation are carried out for different combinations of values of the various parameters involved. The results obtained for the ternary alloys are compared with the corresponding data calculated for the binary A–C and B–C alloys under the same conditions.