A high-temperature oxidation-resistant Fe-Mn-Al-Si alloy

To develop satisfactory alloys without Cr or Ni for high-temperature application up to 1100C, three alloys based on Fe-10%Al-Si with differing fourth (or fifth) element additions were oxidized in air at 1100°Cfor 24 hr. A low carbon, Fe-30Mn-10Al-Si alloy exhibited excellent high-temperature oxidation resistance. The total weight gain for 24 hr oxidation in air at 1100°C was only 1.03 mg/cm ². After air oxidation for 6 days at 1100°C, no nodule formation or breakthrough oxidation occurred. Post-oxidation SEM and EDAX examination showed that a thin, compact, protective alumina scale formed on the alloy.Visiting Scientist (People's Republic of China).     

Comparison of the effects of small additions of silicon or aluminum on the oxidation of iron-chromium alloys

A study has been undertaken of the oxidation behavior of Fe-26 wt.% Cr-1 wt.% Al and Fe-26 wt.% Cr-1 wt.% Si at 800° and 1000°C in oxygen, in order to determine the usefulness of the two tertiary elements in facilitating the development of the Cr₂O₃ external scale. The research has also permitted a comparison of the modes of internal oxidation of these elements, with a view to ascertaining the ease of establishment of the tertiary element oxides as healing layers at the scale/alloy interface. It has been shown that aluminum is the more effective addition in this respect, due to formation of a higher population density of internal oxide nuclei in the early stages. However, in the 1% Al alloy, the precipitates penetrate inward, to considerable depths, as continuous platelets, making development of a complete healing layer difficult. In practice, a higher aluminum concentration is necessary for the closely spaced precipitates to coalesce to form the healing layer, but the process then occurs rapidly. The initial internal oxide nuclei in the 1% Si alloy have a much smaller population density and are restricted to a location very close to the surface. Thus, a healing layer can be established, but the large interparticle spacing makes this a very slow process. Even at a higher silicon concentration, it takes a significant period to be completed. The effects are discussed and accounted for, particularly in terms of the relative stabilities of the various oxides.     

Oxidation kinetics of Y‐doped FeCrAl‐alloys in low and high pO2 gases

A model Fe‐20Cr‐5Al‐0.05Y alloy was oxidized in Ar‐20%O₂ and Ar‐4%H₂‐7%H₂O at 1200–1300 °C. Two‐stage oxidation experiments using oxygen isotope tracers showed that inward oxygen diffusion was predominant in both gases, but more isotope exchange was observed in the H₂/H₂O gas reaction. The alumina scales formed in both gases were composed of columnar grains, the lateral size of which increased linearly with depth beneath the scale surface. Thermogravimetric measurement of oxygen uptake revealed kinetics which were intermediate to parabolic and cubic kinetic rate laws. A model based on grain boundary diffusion control coupled with competitive oxide grain growth accounts satisfactorily for the results when the requirement for a divergence‐free flux within the scale is imposed. This treatment shows that the oxide grain boundary diffusion coefficient is lower when H₂O is the oxidant. It is concluded that hydrogen slows the grain boundary diffusion process by altering the nature of the diffusing species.     

Comparative Study of the Alumina-Scale Integrity on MA 956 and PM 2000 Alloys

The present work analyzes the oxidation kinetics of MA 956 and PM 2000 alloys at 900 and 1100°C for exposure times up to 1000 hr. Special emphasis was placed on a comparison of the alumina-scale integrity formed at 1100°C by means of electrochemical tests at room temperature, which have been shown to be very reliable methods to detect the presence of microdefects within oxide scales. To check whether a preoxidation treatment makes these materials corrosion resistant against aggressive fluids, an electrolyte containing chloride ions was chosen. The mass gain of MA 956 was found to be slightly lower than that of PM 2000 up to 200 hr exposure at 1100°C and for the whole exposure range at 900°C. A subparabolic time dependence (n=0.3) of the oxide growth rate was determined for both alloys at both temperatures. On the other hand, the electrochemical-impedance spectroscopy (EIS) and anodic-polarization tests performed on preoxidized alloys (1100°C/100 hr) revealed good room-temperature corrosion behavior for both alloys, the corrosion resistance and polarization values being somewhat higher for preoxidized PM 2000. Consideration of these results and those of both surface and cross-section examinations of the scale, the better room-temperature corrosion behavior of preoxidized PM 2000 denotes the formation of a denser and mechanically more stable alumina scale containing a lower number of microdefects. This could result from the higher aluminum content of this alloy and the lower density of chemical heterogeneities within the scale. The higher mass gain of PM 2000 could be related to the higher concentration of oxide nodules on top of the alumina scale, as deduced from SEM examination.     

Quantification of Aluminum Outward Diffusion During Oxidation of FeCrAl Alloys

The outward flux of aluminum during the oxidation of four similar alumina-forming alloys is determined using two types of experiments. One is measurement of the total thickness of the oxide and the ratio of the thickness of the characteristic equiaxed layer to the total oxide thickness. The second is measurement of the new oxide formed along the grain boundaries of the oxide upon re-oxidation. The former provides information about the ratio of outward diffusion of aluminum to inward diffusion of oxygen during oxidation. The latter experiment directly quantifies the outward flux of aluminum as a function of oxide thickness. Both the outward aluminum flux and the ratio of inward to outward diffusional fluxes are found to vary with the minor concentrations of reactive element alloying additions. Specifically, Y in solution in the alloy is found to limit outward aluminum diffusion more than Zr in solution, with Y₂O₃ limiting aluminum diffusion more than Zr, Y, and ZrO₂.     

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.     

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.     

The internal oxidation of two-phase binary alloys under low oxidant pressures

The main features of the internal oxidation in two-phase binary alloys are examined for insignificant and important diffusion of the most-reactive component and are compared with the behavior of corresponding single-phase systems. It is shown that two-phase alloys may have two different types of internal oxidation, one of which is similar to that of the single-phase alloys (classical type), producing a uniform distribution of small oxide particles in the zone of internal oxidation, while another is typical of two-phase systems and involves the in situ conversion of the most-reactive component into its oxide. It is also shown that, under the same values of all the relevant parameters, the classical internal oxidation of two-phase alloys involves faster kinetics and smaller degrees of enrichment of the most-reactive component in the zone of internal oxidation than for single-phase alloys. As a consequence of this, the transition to the external oxidation of the most-reactive component in these systems involves higher overall concentrations of the most-reactive component than in corresponding single-phase alloys.     

Development of preferential intergranular oxides in nickel-aluminum alloys at high temperatures

The development of intergranular oxides in dilute Ni-Al alloys containing 0.55–4.10% Al in Ni-NiO packs and in 1 atm oxygen at 800–1100°C has been examined. In the Ni-NiO packs, preferential intergranular oxide penetration as well as internal oxidation occurs in every case, except in the higher aluminum-containing alloys at 1100°C. Several different types of intergranular oxide morphology were observed, depending on alloy aluminum concentration and on temperature. The oxides in the more dilute alloys are thin and relatively continuous and are accompanied by preferential penetration of internal oxide particles in the adjacent grains. Thicker intergranular oxides are precipitated in the more concentrated alloys while, in some situations, numerous fine oxide particles are formed well ahead of the main intergranular oxide. The intergranular oxidation is facilitated by high stress development in the specimens due to increases in volume as internal and intergranular oxides are formed. These stresses create microvoids in the grain boundaries immediately ahead of the advancing internal and intergranular oxides, resulting in preferential nucleation and growth of further intergranular oxides. This is the case particularly at the lower temperatures where other stress-relief processes cannot operate. The resulting relatively continuous, incoherent intergranular oxide-metal interface allows a high flux of oxygen to the advancing intergranular oxide front. Preferential intergranular oxidation is much less extensive in the presence of a thickening external NiO scale, due to accommodation of the volume increases on internal oxide formation by vacancies injected into the alloy from the growing cationdeficient scale.British Nuclear Fuels, Windscale Works, Seascale, Cumbria, U.K.     

In situ SEM study of the high-temperature oxidation of an Fe-Mn-Al-Si alloy

The oxidation behavior of a low-carbon Fe-30Mn-10Al-Si alloy was studied at 1100 and 1150C in a hot-stage environmental scanning electron microscope. The oxidation experiments were performed in pure oxygen at a partial pressure of 10 ^–4 atm. Under these conditions, nodule nuclei of manganese and iron oxide appeared after a few minutes of oxidation, indicating the local destruction of the protective Al₂O₃ scale. The nodules grew and coalesced and finally overgrew the entire specimen surface. The composition of the nodules changed during the growth process; the amount of iron decreased, and the manganese content increased to about 95 wt%. All the nodules were located in symmetrically shaped pits which intrude into the metal.     

Effects of minor additions and impurities on oxidation behaviour of FeCrAl alloys. Development of novel surface coatings compositions

In the present work the effects of single or combined minor additions of Zr, Hf, Ti and C on the oxidation behaviour of Y‐containing, FeCrAl alloys have been studied. For this purpose high‐purity, model alloys with single or multiple minor alloying additions were used. The results of long term discontinuous oxidation tests and detailed kinetics studies using thermogravimetry were complemented with extensive microstructural characterisation of the formed alumina scales using SEM and STEM. Hence, the oxidation kinetics and scale spallation rates and failure modes were correlated with the oxide composition and microstructure. The results demonstrate that the frequently reported positive effect of Zr, Hf and Ti on the lifetime oxidation behaviour of FeCrAl alloys can only be fully exploited if the concentrations of the above elements are carefully adjusted and the interaction with typical alloy impurities, such as carbon, is considered.     

High-temperature oxidation of copper-manganese alloys

The oxidation behavior of copper-manganese alloys (2–35 wt. % Mn) in pure oxygen at 760 Torr was investigated at 100° intervals between 550 and 850°C. Gravimetric measurements of the oxidation kinetics have been combined with microstructural studies of the reacted samples in order to evaluate the reaction mechanisms. The scales formed on Cu-2Mn, Cu-5Mn, Cu-10Mn are always composed of three different layers; in any case manganese is present only in the inner layer. The scales formed on Cu-20Mn and Cu-35Mn are composed of two layers, both containing manganese, with a more Cu-rich outer layer. In all the samples internal oxidation in combination with external scale formation is observed.     

Possible scaling modes in high-temperature oxidation of two-phase binary alloys. II: Low oxidant pressures

The main possible modes of the high-temperature corrosion of binary two-phase alloys by a single oxidant under gas-phase pressures sufficient to corrode only the most-reactive alloy component are examined to compare their behavior with that of single-phase alloys. In the absence of important diffusion processes of the metal components in the alloy, the scale structures expected are different from those typical of single-phase alloys. Moreover, when diffusion in the alloy becomes important, these systems may develop an outer single-phase layer depleted in the most-reactive component, which may lead to different possible scale structures. The conditions for the transition between the various oxidation modes as well as the effect of the various parameters of kinetic, thermodynamic, and structural nature over the corrosion behavior of two-phase alloys are also examined.     

The possible scaling modes in the high-temperature oxidation of two-phase binary alloys. Part I: High oxidant pressures

The main possible modes of the high-temperature corrosion of binary twophase alloys by a single oxidant under gas-phase pressures sufficient to corrode both alloy components are examined to highlight the differences in their behavior with respect to single-phase alloys. It is shown that in the absence of important diffusion processes of the metal components in the alloy the expected scale structures are significantly different from those typical of single-phase alloys. The effects due to the existence of different degrees of deviation from equilibrium as a result of kinetics hindrances for the formation of the most stable oxide and in the absence of alloy diffusion are then examined. It is also shown that when diffusion in the alloy becomes important the alloy may develop an outer single-phase layer depleted in the most-reactive component, which may lead to various possible scale structures. The conditions for the transition between the various oxidation modes as well as the effect of the various parameters of kinetics, thermodynamic and structural nature over the corrosion behavior of two-phase alloys are also examined.     

The cyclic oxidation resistance of cobalt-chromium-aluminum alloys at 1100 and 1200° C and a comparison with the nickel-chromium-aluminum alloy system

A series of Co-rich alloys in the Co-Cr-Al system were cyclically oxidized in still air for 500 1 -hr heating cycles at 1100° C and 200 1 -hr heating cycles at 1200°C, The specific weight-change data for each sample were then used to determine both an oxide growth constant, k₁, and a spoiling constant, k₂, for each alloy, using the regression equation W/A=k ₁ ^1/2 t^1/2— k₂t±. These in turn were combined to form an oxidation attack parameter, K_a, where K_a=(k ₁ ^1/2 +10k₂). These attack parameters, along with X-ray diffraction results, were then compared with K_a values determined for comparable Al and Cr compositions in the Ni-rich Ni-Cr-Al system. The K_a and X-ray diffraction results indicated that initially, if the Cr and Al contents in both systems are high enough, protective -Al₂O₃ and aluminate spinel(s) are formed. However, in the long run, when the scales eventually start to fail, mainly CoO is formed in the Co-Cr-Al system and mainly NiO in the Ni-Cr-Al system. The Ni-Cr-Al system is considered more oxidation resistant since CoO leads to massive spalling and sudden drastic weight loss, while NiO fails in a more gradual, predictive manner. Both sets of alloys were melted in zirconia crucibles and the resultant Zr pickup increased the cyclic oxidation resistance of the alloys in both systems.     

用双面氧化弯曲方法测定Al2O3膜生长应力

提出了一种测定氧化膜生长应力的双面氧化弯曲方法,经不象常规弯曲法那样为防止试样一个侧在发生氧化度制保护除层,因而可用于较高温度及较长时间的氧化情况并可测定Ａｌ２Ｏ３膜的生长应力,由于高温下合金及薄氧化膜发生蠕变,从而释放膜内应力。新方法应用于合金的蠕变数据,并采用数值计算来获得氧化膜应力值,用这种方法测定Ｆｅｃｒａｌｌｏｙ（Ｆｅ－２２Ｃｒ－５Ａｌ－０．３Ｙ）合金在１０００℃空气中氧化中形成的Ａｌ２     

Oxidation of nickel-manganese alloys in the temperature range 873–1273 K

Ni-Mn alloys containing up to 38% Mn have been oxidized in pure oxygen between 873 and 1273 K and the parabolic rate constants measured. The scale morphologies and oxide compositions are interpreted in terms of modifications to the scale on pure Mn caused by the presence of Ni. The scales are composed predominantly of two layers at all temperatures, giving the sequences of phases alloy/cubic monoxide (Ni, Mn)O/ternary spinel, with the cubic (Ni, Mn)O layer always having the greater thickness. There is limited evidence for a third, very thin, outer layer in the scales on all alloys at 873 K and for Ni-38%Mn at 1073 K, which is tentatively considered to be Mn₂O₃, giving layers in the order alloy/cubic monoxide/ternary spinel/Mn₂O₃, by analogy with the scale formed on pure Mn. The distribution of the alloy components in the scale is discussed in relation to the Ni-Mn-O phase diagram and in terms of recent theoretical treatments of solid solution scale formation on binary alloys, as far as the available diffusion data allow. The occurrence of internal and intergranular oxidation and the formation of a Mn-depleted zone coincident with the band of uniform internal oxide are considered briefly.Deceased.     

Observations of nodule growth during the oxidation of pure binary iron-aluminum alloys

Oxidation studies were carried out in oxygen at 800°C, on a series of pure binary iron-based alloys with between 1.9 and 9.8 wt. % aluminum. The results are presented in conjunction with the existing literature and these permit the development of a classification of scale morphologies based on alloy composition. Alloys with less than about 2.4 wt. % aluminum form bulky stratified scales composed of Fe₂O₃ and Fe₃O₄ with FeAl₂O₄ and Al₂O₃ at the scale-metal interface. Alloys with between 2.4 and 6.9 wt. % form an external Al₂O₃ scale but this is interspersed with iron oxide nodules that penetrate the alloy substrate. Only alloys with greater than 6.9 wt. % aluminum form completely protective Al₂O₃ scales. Models based on oxide nucleation are presented for the growth of bulky scales and also the iron oxide nodules.     

Cyclic oxidation method for studying scale-resistant metallic materials

A cyclic method has been developed to measure the spalling resistance of metals. The method involves the determination of sample weight as a function of the number of heating cycles. The shape of the curve provides a quick evaluation and, in some cases, the scale resistance can be ascertained after just a few cycles. The technique is simpler than present methods and eliminates the need to remove the scale to determine metal recession. Minimum thickness requirements must be met, however, to avoid complications from the depletion of alloying elements from the surface. The technique has been applied to various steels and to Fe-Cr-Al alloys.