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.     

Oxidation of Fe-xCr-10Al (x=0, 5, 10) Alloys at 900 ℃: A Novel Example of the Third Element Effect

通过研究Ee-10Al，Fe-15Cr-10Al和Fe-10Cr-10Al(原子分数，％)合金在900℃的氧化行为，分析了二元Fe-Al合金形成选择性氧化铝膜所需的临界铝浓度．讨论了三元Fe-Cr-Al合金形成保护性氧化膜的机理，对于不发生Al的内氧化的情况，提出合金中第三组元Cr的作用机制的新解释．     

The oxidation of two ternary Fe-Cu-10 at.% Al alloys in 1 atm of pure O2 at 800-900 °C

The oxidation of two ternary Fe-Cu-Al alloys containing 10 at.% Al (Fe-65Cu-10Al and Fe-30Cu-10Al) has been studied at 800-900 °C under 1 atm O₂. Under all conditions both alloys show an initial faster stage during which Fe-65Cu-10Al corrodes more rapidly at 800 °C than at 900 °C, while Fe-30Cu-10Al follows nearly identical kinetics at both temperatures. As oxidation proceeds, a continuous alumina layer is eventually established on the surface of the two alloys, thus decreasing significantly their oxidation rates. Altogether, the Fe-rich alloy Fe-30Cu-10Al oxidizes slightly faster than the Cu-rich alloy Fe-65Cu-10Al at both temperatures. The possible reasons for the decrease in the critical Al content needed to form external alumina scales for the Cu-rich alloy in comparison with binary Cu-Al alloys are examined.     

The effect of Si additions on the high temperature oxidation of a ternary Ni-10Cr-4Al alloy in 1 atm O2 at 1100 °C

The oxidation of four Ni-10Cr-ySi-4Al alloys was studied at 1100 °C to examine the effects of Si additions (from 2 to 6 at.%) on the behavior of the alloy Ni-10Cr-4Al. Addition of 2 at.% Si prevented completely nickel oxidation, but could not form alumina scales. Larger Si additions produced alumina only over part of the alloy surface (about 20% with 4 at.% Si and 30% with 6 at.% Si), but could not prevent completely the internal oxidation of Al. The results are interpreted by extending to quaternary alloys the mechanism of the third-element effect already proposed for ternary alloys.     

The oxidation of three Ni-6Si-xAl alloys in 1 atm O2 at 1000 °C

The oxidation of three ternary Ni-6Si-xAl alloys containing 6, 10 and 15 at.% Al and of the corresponding binary Ni-Al alloys has been studied at 1000 °C under 1 atm O₂ to examine the effect of different Al additions on the behavior of ternary Ni-Al-Si alloys containing 6 at.% Si. Of the three binary Ni-Al alloys only Ni-15Al was able to form external alumina scales. Conversely, all the three ternary alloys formed an innermost layer of alumina directly in contact with the alloy following very similar and approximately parabolic kinetics after a short faster initial stage due to transient formation of NiO. Thus, the presence of silicon is very effective to reduce the critical Al content needed to form exclusive alumina scales with respect to binary Ni-Al alloys. The third-element effect due to silicon is interpreted on the basis of an extension of Wagner’s criterion for the transition from the internal to the external oxidation of the most reactive component in binary alloys.     

High temperature scaling of Ni-xSi-10 at.% Al alloys in 1 atm of pure O2

The oxidation of Ni-xSi-10Al alloys (with x = 0, 2, 4 and 6 at.%), has been studied at 900 and 1000 °C in 1 atm of pure O₂ to examine the effect of different silicon additions on the behavior of ternary Ni-Si-10Al alloys. The kinetic curves of Ni-10Al are approximately parabolic at both 900 and 1000 °C. Conversely, the kinetics of the ternary alloys at both temperatures correspond generally to a rate decrease faster than predicted by the parabolic rate law, except for the oxidation of Ni-6Si-10Al at 1000 °C, which exhibits a single nearly-parabolic stage. Oxidation of the binary alloy formed at both temperatures an internal oxidation zone beneath a layer of NiO. Oxidation of Ni-2Si-10Al at both temperatures and of the other two alloys at 900 °C formed initially a zone of internal oxidation of Al + Si. However, a layer of alumina forming at the front of internal oxidation after some time blocked the internal oxidation and produced a gradual conversion of the metal matrix of this region into NiO, with a simultaneous decrease of the oxidation rate. Conversely, the oxidation of Ni-4Si-10Al and Ni-6Si-10Al at 1000 °C did not produce an internal oxidation, but formed an alumina layer directly on the alloy surface after an initial stage when also Ni was oxidized. Therefore, silicon exerts the third-element effect by reducing the critical Al content needed for the transition from its internal to its external oxidation with respect to the corresponding Ni-Al alloy. This result is interpreted by means of an extension to ternary alloys of Wagner’s criterion for the same transition in binary alloys based on the attainment of a critical volume fraction of internal oxide.     

High temperature oxidation of Fe-Al and Fe-Cr-Al alloys: The role of Cr as a chemically active element

Good high-temperature corrosion resistance of Fe-Al alloys in oxidizing environments is due to the α-Al₂O₃ film which is formed on the surface provided temperature is above 900 °C and the Al-content of the alloy exceeds the critical value. Ab initio calculations combined with experiments on Fe-13Al, Fe-18Al, Fe-23Al and Fe-10Cr-10Al alloys show that the beneficial effect of Cr on the oxidation resistance is significantly related to bulk effects. The comparison of experimental and calculated results indicates a clear correlation between the Fe-Cr chemical potential difference and the formation of the protective oxide scales.     

The third-element effect in the oxidation of Ni–xCr–7Al (x = 0, 5, 10, 15 at.%) alloys in 1 atm O2 at 900–1000 °C

The oxidation in 1 atm of pure oxygen of Ni–Cr–Al alloys with a constant aluminum content of 7 at.% and containing 5, 10 and 15 at.% Cr was studied at 900 and 1000 °C and compared to the behavior of the corresponding binary Ni–Al alloy (Ni–7Al). A dense external scale of NiO overlying a zone of internal oxide precipitates formed on Ni–7Al and Ni–5Cr–7Al at both temperatures. Conversely, an external Al₂O₃ layer formed on Ni–10Cr–7Al at both temperatures and on Ni–15Cr–7Al at 900 °C, while the scales grown initially on Ni–15Cr–7Al at 1000 °C were more complex, but eventually developed an innermost protective alumina layer. Thus, the addition of sufficient chromium levels to Ni–7Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum. This effect is interpreted on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most reactive component in binary alloys.     

High-Temperature Scaling of Cu–Al and Cu–Cr–Al Alloys: An Example of a Non-Classical Third-Element Effect

The oxidation of three Cu–xCr–2Al and three Cu–xCr–4Al alloys (x ≅ 0,4,8 at.%) has been investigated at 800°C in 1 atm O₂. Oxidation of a binary Cu–Al alloy containing 2.2 at.% Al produced external scales composed mainly of copper oxides with small amounts of Al-rich oxide in the inner region, while the internal oxidation of Al was almost absent. The addition of 3.9 at.% Cr to this alloy was able to decrease the oxidation rate but was insufficient to prevent the oxidation of copper. Conversely, addition of 8.1 at.% Cr to the same binary alloy promoted the rather fast formation of a protective Al₂O₃ layer in contact with the metal substrate, with a simultaneous large decrease in the oxidation rate, producing a form of third-element effect. On the contrary, all the Cu–xCr–4Al alloys formed an internal Al₂O₃ layer after an initial stage during which all the alloy components were oxidized, so that the only effect of the presence of chromium was to decrease the duration of the fast initial stage. The third-element effect due to chromium additions to Cu–2Al is related to a transition from the formation of external scales composed of mixtures of Cu and Al oxides to the external growth of Al₂O₃–rich scales as a consequence of a thermodynamic destabilization of copper oxides associated with the formation of solid solutions between Al₂O₃ and Cr₂O₃.     

Effect of Zn Additions on the Oxidation of Cu–2 at.% Al and Cu–4 at.% Al Alloys in 1 atm O2 at 800 °C

Four ternary Cu–Zn–Al alloys containing 5 or 10 at.% Zn and 2 or 4 at.% Al plus an alloy containing 2 at.% Al and 15 at.% Zn have been oxidized at 800 °C in 1 atm O₂, and their behavior has been compared with that of the corresponding binary Cu–Zn and Cu–Al alloys. For the alloy containing 4 at.% Al, which is already able to form external alumina scales, the addition of Zn is only effective in reducing the mass gain during the fast, initial-oxidation stage. Conversely, the addition of 15 at.% Zn to Cu–2Al is able to prevent the formation of external scales containing mixtures of the Cu and Al oxides, resulting in the formation of external alumina scales after an initial stage of faster rate, producing a limited third-element effect. Finally, the addition of Al to both Cu–5Zn and Cu–10Zn is able to prevent the internal oxidation of Zn, producing a kind of reversed third-element effect. Possible mechanisms for these effects are examined on the basis of general treatments concerning the scaling behavior of ternary alloys.     

Protection of cobalt-based refractory alloys by chromium deposition on surface: Part I: Sub-surface enrichment in chromium by pack-cementation and diffusion

The feasibility of surface chromium enrichment by pack-cementation was assessed for different low chromium-containing cobalt alloys, in order to improve their resistance against high temperature oxidation. A binary Co-10Cr alloy, two ternary Co-10Cr-0.5C and Co-10Cr-1.0C alloys and two TaC-containing Co-10Cr-based alloys were elaborated by foundry for the study. 7.5 h-long and 15 h-long cementations at 1050 °C, followed or not by a 75 h-long heat treatment at 1200 °C were performed on these alloys. Microstructure examinations performed using a Scanning Electron Microscope and concentration profiles using Electron Probe Micro Analysis-Wavelength Dispersion Spectrometry were realized in order to analyze the level of Cr-enrichment of the sub-surface region, with as studied criteria: the nature of the external Cr-enriched zone, the maximal chromium content on surface and the depth of chromium enrichment. The Cr-enrichment of the sub-surface succeeded for the Co-10Cr alloy and for the two tantalum-containing alloys, with the formation of an external metallic zone containing around 30 wt.% Cr. In contrast the chromium carbides-containing alloys were effectively enriched in chromium in surface but in the form of a continuous chromium carbide layer which can induce other problems such as spallation and then possible fast oxidation of the denuded alloy. Finally it appeared that only the carbon-free alloys, and the alloys reinforced by carbides more stable than chromium carbides, are potentially able to be successful enriched in chromium in their sub-surface by pack-cementation.     

Oxidation of Two Ternary Fe–Cu–5 at.% Al Alloys in 1 atm of Pure O2 at 800°C

The oxidation of two two-phase ternary Fe–Cu–Al alloys containing about 5 at.% aluminium, one Fe-rich and one Cu-rich, has been studied at 800°C under 1 atm O₂. The Fe-rich alloy (Fe–15Cu–5Al) shows two parabolic stages, with a large decrease of the parabolic rate constant after about 2 hr. The presence of 5 at.% Al reduces significantly the oxidation rate of this alloy with respect to a binary Fe-Cu alloy of similar composition by forming an external alumina scale. Moreover, the addition of 15 at.% Cu is able to reduce the critical aluminium content needed to form alumina scales with respect to binary Fe–Al alloys. On the contrary, the Cu-rich Fe–85Cu–5 Al alloy presents a single parabolic stage and forms a thick and porous external scale composed of an outermost layer of copper oxides and an inner region containing a mixture of copper and Fe–Al oxides, coupled to the internal oxidation of iron and aluminium. As a result, the oxidation of the Cu-rich ternary alloy at 800°C is much faster than that of the Fe-rich ternary alloy.     

The Effect of Si Additions on the High-Temperature Oxidation of a Ternary Ni–10Cr–4Al Alloy in 1 ATM O2 AT 900–1000 °C

The oxidation of four Ni–10Cr–ySi–4Al alloys has been studied in 1 atm O₂ at 900 and 1000 °C to examine the effects of various Si additions on the behavior of the ternary alloy Ni–10Cr–4Al, which during an initial stage formed external NiO scales associated with an internal oxidation of Cr + Al, later replaced by the growth of a chromia layer at the base of the scale plus an internal oxidation of Al. The addition of 2 at.% Si was able to prevent the oxidation of nickel already from the start of the test, but was insufficient to form external alumina scales at 1000 °C, while at 900 °C alumina formed only over a fraction of the alloy surface. At 1000 °C the addition of 4 at.% Si produced external chromia scales plus a region of internal oxidation of Al and Si, a scaling mode which formed over a fraction of the alloy surface in combination with alumina scales also by oxidation at 900 °C. Conversely, the presence of about 6 at.% Si produced external alumina scales over the whole sample surface at 900 °C, but only over about 60 % of the alloy surface at 1000 °C. The changes in the oxidation modes of the ternary Ni–10Cr–4Al alloy produced by Si additions have been interpreted by extending to these quaternary alloys the mechanism of the third-element effect based on the attainment of the critical volume fraction of internal oxides needed for the transition to the external oxidation of the most-reactive-alloy component, already proposed for ternary alloys.     

High temperature corrosion of cast heat resisting steels in CO + CO2 gas mixtures

Two commercial variants of the cast heat resistant grade HP40Nb (Fe-25Cr-35Ni, Nb modified) were exposed to CO/CO₂ gases at 982 and 1080 °C in order to simulate exposure to the carbon and oxygen potentials realised in steam reformers under normal and overheated conditions. Both alloys developed external chromium-rich oxide scales, intradendritic silica precipitates and interdendritic oxide protrusions where primary, interdendritic carbides were oxidised in situ. Surprisingly, the lower silicon content alloy developed a more continuous internal silica layer, thereby slowing external scaling. Intradendritic oxidation was fast in both alloys, and is attributed to interfacial oxygen diffusion. Both alloys underwent rapid internal carburisation, indicating that their oxide scales failed to prevent carbon access to the underlying alloys under these reaction conditions.     

The Effect of Cr on the Oxidation of Ni–10 at% Al in 1 atm O2 at 900–1000°C

The oxidation of three Ni–xCr–10Al alloys with a constant Al content of 10 at% and containing 3, 5, and 10 at% Cr was investigated at 900–1000°C in 1 atm of pure oxygen and compared to the behavior of Ni–10Al. At both temperatures, an external NiO scale overlying a zone of internal-oxide precipitates formed on Ni–10Al and Ni–3Cr–10Al: in addition, a discontinuous Al₂O₃ layer formed at the front of the internal oxidation for Ni–3Cr–10Al. An exclusive external scale of Al₂O₃ formed at most places on Ni–5Cr–10Al at 900°C, while, at some sites, the same alloy formed an outer NiO layer overlying an internal oxidation zone. The scales formed on Ni–5Cr–10Al at 1000°C were complex, but eventually a protective Al₂O₃ layer developed either at the alloy surface or beneath a region containing a mixture of different oxides. Finally, an exclusive external Al₂O₃ layer formed on Ni–10Cr–10Al at both temperatures. Thus, the addition of sufficient chromium to Ni–10Al produced a classical third-element effect, inducing the transition between internal and external oxidation of aluminum under a constant Al content. A possible mechanism for the effect of chromium on the oxidation of Ni–10Al is discussed on the basis of an extension to ternary alloys of a criterion first proposed by Wagner for the transition between internal and external oxidation of the most-reactive component in binary alloys.     

High temperature oxidation of iron-manganese-aluminum based alloys

The isothermal oxidation resistance of high purity iron-manganese-aluminum alloys containing from 0 to 40% manganese and from 0 to 15% aluminum was investigated at 600, 800, and 1000°C in pure oxygen at a pressure of 200 torr for periods up to 100 hr. They were subsequently examined using SEM and metallographic techniques, and an oxide map showing the alloy structure and general oxidation behavior at 800°C was produced. Scales formed on alloys which contain insufficient aluminum to form protective alumina have structures which depend largely upon the concentration of manganese in the alloy. Alloys which contain more than 7.5% manganese form manganese rich scales, whereas alloys which contain lower levels of manganese form scales that are composed almost entirely of the oxides of iron. Small manganese oxide nodules grow through the alumina scales which form on alloys containing in excess of 9% aluminum. The most oxidation resistant alloys, having compositions within the range Fe-(5–10)%Mn-(6–10)% Al, develop continuous protective alumina scales and are totally ferritic. Austenite is detrimental to the oxidation resistance of duplex alloys as it promotes the breakdown of preexisting alumina scales and the growth of bulky manganese rich oxides. Small additions of chromium are beneficial and reduce the concentration of aluminum required to form protective alumina scales.     

Oxide scale adhesion and impurity segregation at the scale/metal interface

The chemistry at scale/metal interfaces was studied using scanning Auger microscopy after removal of the scale in ultra-high vacuum using an in situ scratching technique. Al₂O₃ and Cr₂O₃ scales formed between 900°C and 1100°C on Fe-18 wt.% Cr-5 wt.% Al and on Ni-25 wt.% Cr alloys, respectively, were investigated. The adhesion of these scales was determined qualitatively by way of micro-indentation and scratching on the surface oxide. All of the alumina scales fractured to the same degree to expose the metal surface, regardless of the oxidation temperature. The chromia-forming alloy on the other hand, developed more adherent scales at lower oxidation temperatures. About 20 at.% sulfur was found at the metal surface in all cases, and its presence was not only detected on interfacial voids, but also on areas where the scale was in contact with the alloy at temperature. Results from this study clearly demonstrated that sulfur as an alloying impurity does segregate to the scale/alloy interface. However, for alumina scales and chromia scales, the effect of this segregation on oxide adhesion is noticeably different.     

The Oxidation of Two Ternary Ni–Cu–5 at.%Al Alloys in 1 atm of Pure O2 at 800–900°C

The oxidation of a Ni-rich and a Cu-rich single-phase ternary alloy containing about 5at.% aluminum has been studied at 800 and 900°C under 1atm O₂. The behavior of the Ni-rich alloy is similar to that of a binary Ni–Al alloy with a similar Al content at both temperatures, with formation of an external NiO layer coupled to the internal oxidation of aluminum. The Cu-rich ternary alloy shows a larger tendency to form protective alumina scales, even though its behavior is borderline between protective and non-protective. In fact, at 800°C, after an initial stage of fast reaction during which all the alloy components are oxidized, this alloy is able to develop a continuous layer of alumina at the base of the scale which prevents the internal oxidation of aluminum. On the contrary, at 900°C the innermost alumina layer undergoes repeated rupturing followed by healing, so that internal oxidation of Al is only partly eliminated. As a result, the corrosion kinetics of the Cu-rich ternary alloy at 900°C are much faster than at 800°C and very similar to those of pure copper and of Al-dilute binary Cu–Al alloys. Possible reasons for the larger tendency of the Cu-rich alloy to form external alumina scales than the Ni-rich alloy are examined.     

Effect of alloy grain size and silicon content on the oxidation of austenitic Fe-Cr-Ni-Mn-Si alloys in pure O2

Austenitic Fe-18Cr-20Ni-1.5Mn alloys containing 0, 0.6, and 1.5 wt.% Si were produced both by conventional and rapid solidification processing. The isothermal and cyclic oxidation resistance of the alloys were studied at 900°C in pure O₂ to elucidate the role of alloy microstructure and Si content on oxidation properties. The conventionally-processed, large-grained alloy that contained no silicon formed Fe-rich nodules during oxidation. The nodule formation was effectively eliminated by either reducing the alloy grain size by rapid solidification or by adding Si to the alloy. The lowest weight gains were achieved when a continuous silica layer formed between the alloy and the external chromia scale. The formation of the continuous silica layer required a ombination of fine alloy grain size and high Si content. The presence of S in the alloy was found to be detrimental to oxide scale adherence when the silica layer was continuous.     

Effect of lamellar microstructure on oxidation kinetics of Fe3Al sintered by hot isostatic pressing

The present paper focuses on the investigation of the relationship between microstructure of Fe₃Al prepared by hot isostatic pressing (HIP) and kinetics of alumina layer formation during oxidation at 900 °C, 1000 °C and 1100 °C. As prepared HIPed Fe₃Al sample reveals lamellar microstructure with inhomogeneous Al distribution which originates from the preliminary mechanical activation of Fe-Al mixture. At 900 °C, Fe₃Al oxidation is characterized by selective growth of very rough alumina layer containing only transient aluminium oxides. In addition to these transient oxides, α-Al₂O₃ stable phase is formed at 1000 °C. At the highest temperature (1100 °C), continuous and relatively smooth alumina layer mainly contains fine crystallites of α-Al₂O₃. The initial lamellar structure and phase inhomogeneity in as-HIPed Fe₃Al samples are supposed to be the main factors that determine observed peculiarities after Fe₃Al oxidation at 900 °C and 1000 °C.