The nature of the third-element effect in the oxidation of Fe-xCr-3 at.% Al alloys in 1 atm O2 at 1000 °C

The oxidation of an Fe-Al alloy containing 3 at.% Al and of four ternary Fe-Cr-Al alloys with the same Al content plus 2, 3, 5 or 10 at.% Cr has been studied in 1 atm O₂ at 1000 °C. Both Fe-3Al and Fe-2Cr-3Al formed external iron-rich scales associated with an internal oxidation of Al or of Cr+Al. The addition of 3 at.% Cr to Fe-3Al was able to stop the internal oxidation of Al only on a fraction of the alloy surface covered by scales containing mixtures of the oxides of the three alloy components, but not beneath the iron-rich oxide nodules which covered the remaining alloy surface. Fe-5Cr-3Al formed very irregular external scales where areas covered by a thin protective oxide layer alternated with others covered by thick scales containing mixtures of the oxides of the three alloy components, undergrown by a thin layer rich in Cr and Al, while internal oxidation was completely absent. Conversely, Fe-10Cr-3Al formed very thin, slowly-growing external Al₂O₃scales, providing an example of third-element effect (TEE). However, the TEE due to the Cr addition to Fe-3Al was not directly associated with a prevention of the internal oxidation of Al, but rather with the inhibition of the growth of external scales containing iron oxides. This behavior has been interpreted on the basis of a qualitative oxidation map for ternary Fe-Cr-Al alloys taking into account the existence of a complete solid solubility between Cr₂O₃ and Al₂O₃.     

Effects of aluminum on the oxidation of 25Cr-35Ni cast steels

The oxidation kinetics and morphological development during reaction of two cast austenitic steels at 1000°C in pure dry oxygen at 20 kPa are reported. Both steels contained approximately 25 wt.% Cr and 35 wt.% Ni and, in addition, one steel contained 3.3 wt. %. Both steels oxidized to form external scales consisting mainly of Cr₂O₃ with a thin outer layer of manganese rich spinel. Scale growth kinetics were parabolic, and somewhat faster rates were observed for the aluminum bearing steel. In both steels, deep internal oxidation occurred at the site of primary (interdendritic) carbides. The kinetics of this process were parabolic, and rate control was attributed to oxygen diffusion along the interface between internal oxide and matrix metal. In the aluminum-free steel, interdendritic carbides were converted to chromium rich oxide, but when aluminum was present, a sheath of aluminum rich oxide formed around the carbides. In this latter case, the rate of interdendritic penetration was somewhat slower. The aluminum bearing steel also formed large numbers of rod-shaped Al₂O₃ precipitates within the austenitic dendrites. Deepening of the Al₂O₃ precipitate zone also proceeded according to parabolic kinetics at a rate consistent with rate control by diffusion of oxygen along the oxide-alloy interfaces.     

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 corrosion of two NiNb alloys under 1 atm O2 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 pure oxygen under 1 atm O₂ at 600–800 °C. The scales formed on both alloys under all conditions show an external scale, generally duplex, containing an outermost layer of nearly pure NiO and an innermost region of NiO mixed with the double NiNb oxide NiNb₂O₆. Moreover, the samples corroded at all temperatures also show a region of internal oxidation composed of a mixture of alpha nickel and niobium oxides (Nb₂O₅ or/and NbO₂), which formed from both alloy phases Ni₈Nb and Ni₃Nb. No important depletion of niobium was observed in the alloy close to the interface with the zone of internal oxidation, while the depth of this region is generally much higher than measured for the corrosion of the same alloys under low oxygen pressures at the same temperatures. The corrosion mechanism of these alloys is examined with special reference to the effects of the low solubility of niobium in nickel.     

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

The oxidation of two Co–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 at 700 and 800°C, below the dissociation pressure of cobalt oxide. At 600 and 700°C both alloys showed only a region of internal oxidation composed, of a mixture of alpha cobalt and of niobium oxides (NbO₂ and Nb₂O₅) and at 700°C also the double oxide CoNb₂O₆, which formed from the Nb-rich Co₃Nb phase. No Nb-depleted layer formed in the alloy at the interface with the region of internal oxidation at these temperatures. Upon oxidation at 800°C a transition between internal and external oxidation of niobium was observed, especially for Co–30Nb. This corrosion mode is associated with the development of a single-phase, Nb-depleted region at the surface of the alloy. The corrosion mechanism of these alloys is examined with special reference to the effect of the low solubility of niobium in cobalt and to the relation between the microstructures of the alloys and of the scales.     

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.     

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.     

Oxidation behavior of Ti–46Al–8Nb alloy with boron and carbon addition under thermal cycling conditions

Oxidation behavior of Ti–46Al–8Nb (in at.%) alloy with boron and carbon addition under thermal cycling conditions was investigated. Oxidation of Ti–46Al–8Nb, Ti–46Al–8Nb–1B and Ti–46Al–8Nb–1B-0.25C (in at.%) alloys was carried out at 1073 K in laboratory air for 42 cycles (1 cycle, 24 h), 1008 h in total. The mass loss rates of Ti–46Al–8Nb and Ti–46Al–8Nb–1B measured during the oxidation were similar. The best oxidation resistance was found for Ti–46Al–8Nb–1B-0.25C alloy with the smallest mass change. XRD and SEM-EDS investigations showed that in all cases, the oxide scales compositions were substantially similar. The scale consisted of an outer layer built of Al₂O₃ with the presence of some amounts of TiO₂, an intermediate layer of the scale consisting of TiO₂, an inner layer composed of oxides and nitrides. Additionally, niobium rich particles at the scale/substrate interface were present. The oxidation mechanism of Ti–46Al–8Nb was studied via two-stage isothermal oxidation (24 h in ¹⁶O₂ followed by 24 h in ¹⁸O₂) at 1073 K combined with secondary neutral mass spectroscopy (SNMS). These results indicate that the oxidation mechanism depends on a mixed diffusion process, consisting of outward transport of cations and simultaneous oxygen inward transport.     

High temperature corrosion of pure Fe, Cr and Fe-Cr binary alloys in O2 containing trace KCl vapour at 750 °C

Pure Fe, Cr and Fe-Cr binary alloys were corroded in O₂ containing 298 ppm KCl vapour at 750 °C. The corrosion kinetics were determined, and the microstructure and the composition of oxide scales were examined. During corrosion process, KCl vapour reacted with the formed oxide scales and generated Cl₂ gas. As Cl₂ gas introduced the active oxidation, a multilayer oxide scales consisted of an outmost Fe₂O₃ layer and an inner Cr₂O₃ layer formed on the Fe-Cr alloys with lower Cr concentration. In the case of Fe-60Cr or Fe-80Cr alloys, monolayer Cr₂O₃ formed as the healing oxidation process. However, multilayer Cr₂O₃ formed on pure Cr.     

Oxidation behavior of several chromia-forming commercial nickel-base superalloys

Several commercially available Ni-base superalloys were exposed isothermally in air at temperatures between 750° and 1000°C and also under cyclic conditions at 1000°C. The kinetics of oxidation were determined and the scales were analyzed by electron microscopy and X-ray diffraction. Thin adherent chromia-rich scales formed on the alloys at 750°C after 1000 hr. Although Waspaloy showed the lowest weight gain in this test, it also showed the deepest internal corrosion due to oxidation of the grain-boundary carbides. At temperatures up to 1000°C the external scales were also chromia-rich but there was greater internal corrosion. Titanium in the alloys oxidized, diffusing through the chromia scale to form faceted rutile (TiO₂) grains at the surface as well as forming TiO₂ and TiN internally. The amount of rutile at the oxide surface increased with temperature and alloy Ti concentration. Alumina formed as discrete internal oxides below the chromia scale, although Astroloy when oxidized isothermally at 1000°C developed a semicontinuous internal layer of alumina due to its higher Al content. Under cyclic conditions Astroloy formed a thicker, less-protective scale of transition oxides probably due to its lower Cr content.     

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.     

Carburisation of ferritic Fe–Cr alloys by low carbon activity gases

Model Fe–Cr alloys were exposed to Ar–CO₂–H₂O gas mixtures at 650 and 800 °C. At equilibrium, these atmospheres are oxidising to the alloys, but decarburising (a_C ≈ 10⁻¹⁵ to 10⁻¹³). In addition to developing external oxide scales, however, the alloys also carburised. Carbon supersaturation at the scale/alloy interface relative to the gas reflects local equilibrium: a low oxygen potential corresponds to a high p_CO/p_CO2 ratio, and hence to a high carbon activity. Interfacial carbon activities calculated on the basis of scale–alloy equilibrium are shown to be in good agreement with measured carburisation rates and precipitate volume fractions, providing support for the validity of the thermodynamic model.     

The oxidation of Fe?Nb alloys in 1 atm of pure oxygen at 600–800°C

The corrosion of two Fe-Nb alloys containing 15 and 30 wt% Nb has been studied at 600–800°C under 1 atm of pure oxygen. The reaction followed the parabolic rate law to a reasonable approximation with rate constants much lower than for the oxidation of pure iron under the same conditions. Internal oxidation and depletion of niobium in the alloy have never been observed. The external scales were composed of a matrix of Fe₂O₃ containing a dispersion of double Fe-Nb oxide, while FeO and Fe₃O₄ were not observed. The oxidation behavior of these alloys is interpreted with reference to an approximate phase diagram of the ternary system Fe? Nb? O, taking into account the effects of the low solubility of niobium in the base metals and of the presence of two metal phases in the alloy.     

Internal oxidation and carburisation of heat-resistant alloys

The commercial alloys Nicrofer-HT, Alloy 800 and Type 304 stainless steel have been exposed under thermal cycling conditions to CO-CO₂ gas mixtures at temperatures of 650-750 °C. Thermal cycling led to repeated scale spallation which accelerated chromium depletion from the alloy subsurface regions. Subsequent dissolution of carbon and oxygen into the alloys led to extensive internal precipitation of carbides and oxides. The large volume fractions of carbide and oxide left small quantities of iron-nickel-rich metal. The in situ oxidation of internal carbides in the stainless steel led to large volume expansions and the development of mechanical stress. This was increased during thermal cycling, leading to disintegration of the surface regions. Temperature and surface treatment were both found to be significant factors in the resistance of alloys to the CO-CO₂ atmosphere.     

Oxidation of a quaternary three-phase Cu-20Ni-20Cr-5Fe alloy at 700-900 °C in 1 atm of pure O2

The oxidation of a quaternary Cu-Ni-Cr-Fe alloy containing approximately 20 at.% Ni, 20 at.% Cr and 5 at.% Fe, balance Cu (Cu-20Ni-20Cr-5Fe), was studied at 700-900 °C in 1 atm of pure oxygen. The alloy is composed of a mixture of three phases, where the lightest α phase with the largest Cu content forms the matrix, while the other two, much richer in Cr, form a dispersion of isolated particles. At variance with the ternary three-phase Cu-20Ni-20Cr alloy examined previously, which was unable to form protective chromia scales over the alloy surface even after an extended period of oxidation, the present alloy formed complex external scales containing mixtures of the oxides of the various components plus a deep internal region containing a mixture of alloy and oxide phases. With time, a very irregular and thin but essentially continuous chromia layer formed at the bottom of the mixed internal oxidation region, producing a gradual decrease of the oxidation rate. Thus, the addition of 5 at.% Fe to Cu-20Ni-20Cr alloy is able to decrease the critical Cr content required to form the most stable oxide and promotes the formation of a continuous chromia scale under a lower Cr content in spite of the simultaneous presence of three different phases.     

两种Co-Nb合金在60O℃～800℃1大气压纯氧中的氧化

研究了含Ｎｂ１５和３０ｗｔ％的Ｃｏ－Ｎｂ二元合金在ｌａｔｉｎ纯氧中６００～８００℃的氧化特性。它们的氧化动力学近似地遵循抛物线规律,而其瞬时氧化速率常数随时间而减低、且以６００℃氧化者尤甚。两合金的氧化速率均高于纯Ｃｏ,但其速率增量颇低。在所有的实验条件下,两合金都发生了外氧化与内氧化,外氧化膜的外侧为连续的纯氧化钴带,其下为两个二元Ｃｏ－Ｎｂ氧化物（ＣＯＮｂ２Ｏ６和ＣＯ４Ｎｂ２Ｏ９）与基金属氧化物的混合。内氧化带为氧化钴、氧化铌（Ｎｂ２Ｏ５或／和ＮｂＯ２）的混合,而在该带的最外侧还有源于富Ｎｂ合金相的二元氧化物。在合金－氧化膜界面处都没有观察到贫铌带。从合金的和所生成氧化膜的显微组织特征,尤其是从铌在钴中溶解度低的角度,对合金的氧化行为进行了讨论。     

The air oxidation of two-phase Cu-Ag alloys at 650–750°C

The corrosion of three two phase Cu-Ag alloys containing 25, 50, and 75 wt% Ag has been studied at 650 and 750°C. In all cases the alloys formed external scales of copper oxides. At the same time, an internal precipitation of Cu₂O within a silver matrix was also produced, with an oxide volume fraction larger for the alloys richer in Cu. Beneath this mixed layer a region of single-phase solid solution of Cu in silver formed for Cu-50Ag and especially for Cu-75Ag. Silver metal remained in the metal-consumption zone, acting essentially as an inert marker, except for a few particles with were incorporated into the growing scales. Both pure Cu and the alloys corroded parabolically, but the rate constants for the alloys decreased with increased Ag content under constant temperature. The various aspects of the corrosion of these alloys are examined by taking into account the possible effects associated with the presence of two metal phases.     

Isothermal oxidation behaviour of Nb-W-Cr Alloys

A study of the effect of Cr content on the microstructure and isothermal oxidation behaviour of four alloys from the Nb-Cr-W system has been performed. Selection of specific alloy compositions has been based on the ternary isothermal sections. Oxidation experiments were conducted in air at 900 and 1300 °C for 24 h under isothermal conditions. Weight gain per unit area as function of the temperature has been used to evaluate the oxidation resistance. The phases present in the alloys and the oxide scales were characterized by XRD, SEM, and EDS. Microstructure consists of Nb solid solution and NbCr₂, Laves phase. The oxidation kinetics follows a parabolic behaviour at 1300 °C; the addition of 30% Cr resulted in the significant reduction of the parabolic oxidation rate. At 900 °C, alloys with higher Cr content exhibit higher oxidation rates in comparison to alloys with lower Cr content. The oxidation products are a mixture of CrNbO₄ and Nb₂O₅ and the amount of each oxide present in the mixture is related to the intermetallic phase content and the oxidation temperature. The characterization results delineate the effect of the Cr content on the oxidation mechanisms of these alloys that represent a promising base for high-temperature alloy development.     

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. 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.