Influence of minor additions on the emissivity of the oxide scale of FeCrAlY alloys during resistance heating

Chromium aluminum yttrium (FeCrAlY) alloys owe their low oxidation rate to the formation of a slow growing α‐alumina scale. For material used for heating elements not only the life time and the behavior of the resistance during the life time is of relevance, but also the emission coefficient of the oxide scale. The power density J_S produced by resistance heating of strip with 50 µm thickness and about 5–6 mm width at 1050 °C is approximately equal to the radiant flux density, which is according to Stefan–Boltzmann's law proportional to the total emission coefficient ε_g. Resistance heating tests were performed on samples made from FeCrAlY alloys with different zirconium and carbon content. The “high zirconium” containing FeCrAlY alloys (zirconium > about 0.10%) have a higher power density/emissivity than the “low zirconium” alloys. In parallel with this, all samples with higher power density/emissivity have internal oxidation and therefore a “rough” metal–oxide interface. Thus, one cause for the increase of the emissivity of the scale could be this rough metal–oxide interface; other causes could be a higher amount of zirconium incorporated into the scale, more pores and/or different grain structure in the scale. Additionally the carbon content influences the appearance of a higher emissivity and the internal oxidation.     

The transition from internal oxidation to continuous-film formation during oxidation of dilute Ni-Si alloys

The oxidation of Ni-2.05Si and Ni-4.45Si was studied in oxygen over the range of 600°–1000°C for 18 hr. The oxidation kinetics did not follow a parabolic rate law, bur rather a power law of the form (w)ⁿ=kt was followed. The value of n ranged from 2.7 to 4.9 for Ni-2.05Si and from 3.0 to 6.4 for Ni-4.45Si. The low-silicon alloy exhibited extensive internal oxidation, whereas the higher-silicon alloy did not internally oxidize. In general, NiO containing little or no silicon formed as an exterior layer on both alloys. The internal oxidation zone in Ni-2.05Si was highly irregular in thickness, and in some areas there was no internal oxidation. The higher-silicon alloy formed a continuous layer of a silicon-rich oxide. X-ray diffraction did not detect silica (amorphous), and no evidence of Ni₂SiO₄ was observed, although EDAX analysis suggests that small amounts of the silicate might have formed. Theaverage thickness of the internal oxidation zone was found to agree well with calculated values based on oxygen solubility and diffusivity data. No enrichment of silicon occurred in the internal oxidation zone. Calculated values, 0.033 and 0.038 (depending on the model used), of the mole fraction of silicon required for the transition from internal oxidation to continuous silica film formation agreed well with experimental data obtained in both this study and with others reported in the literature.     

Selective oxidation of Fe-Cr alloys

The phenomenon of selective oxidation is briefly reviewed with particular reference to the Fe-Cr system. The results of experiments with a binary Fe-13%Cr alloy and a commercial steel, carried out over the temperature range 400–800°C in various hydrogen-water vapor mixtures are reported. Modes of growth are postulated and the protective qualities of the films shown to be dependent more upon morphology and structure than upon composition. Although protective, -Cr₂O₃ films can be grown on the binary alloy, the presence of 0.7%Mn in the commercial steel results in the preferential formation of a nonprotective Mn-Cr spinel. In addition to -Cr₂O₃ and the Mn-Cr spinels other oxide phases are identified and their effects considered.     

The influence of superficially applied oxide powders on the high-temperature oxidation behavior of Cr2O3-forming alloys

The effects of superficially applied CeO₂, mixed rare earth oxides, Co₃O₄, and Cr₂O₃ powders on the isothermal and cyclic oxidation of Ni-Cr alloys and the effects of CeO₂ and MgO powders on the isothermal oxidation of Fe-25 wt.% Cr have been studied over the temperature range 940–1150°C in pure oxygen and dry air. The rates of oxidation of both the Ni- and Fe-base alloys were markedly reduced by the application of CeO₂ powder. The presence of CeO₂ also improved the scale adherence and resulted in marked changes in the oxidation morphology. The presence of Co₃O₄ or Cr₂O₃ powders on Ni-Cr alloys or MgO on Fe-Cr also produced changes in the oxidation morphology but did not decrease the rate of oxidation. These results are interpreted in terms of the influence of the oxide powders on the development of scale microstructure and their effectiveness in decreasing grain boundary transport in Cr₂O₃.This paper is based in part on the Ph.D. thesis of G. M. Ecer (1975) and in part on the M.S. thesis of R. B. Singh (1977).     

Improvement of nonisothermal oxidation behavior of fe and fe-cr alloys by superficially applied reactive oxide coatings

The nonisothermal oxidation behavior of pure iron and a few iron-chromium alloys in dry air has been studied. The effects of a superficial coating of a reactive oxide, CeO₂, on the oxidation behavior were studied. Linear heating rates of 3 K/min and 6 K/min were maintained up to a final temperature ranging from 1273–1473 K. Coatings were applied either from a slurry or an aqueous bath. The CeO₂ coating has been found to be effective not only in decreasing the nonisothermal oxidation rate but also in improving the scale adherence. Moreover, the coated samples withstood a number of heating cycles without scale rupture. The mass gain of the samples as a function of temperature was recorded by means of a sensitive balance, and the scales have been characterized by SEM, EPMA, and x-ray diffraction analysis.     

Effect of niobium additions on CO2-enhanced oxidation of titanium-aluminum intermetallic alloys

In a recent study, CO₂ has been reported to enhance the oxidation rate of binary titanium-aluminum alloys. The detrimental effect of CO₂ was not, however, observed in a ternary alloy containing niobium. In this paper, possible explanations for these observations are examined. First, results from the literature regarding the effects of niobium in improving the resistance of titanium-aluminum alloys are briefly reviewed. Second, a thermodynamic analysis which offers a possible explanation for the beneficial effect of niobium in eliminating the CO₂-enhanced oxidation of titanium-aluminum alloys is presented.     

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.     

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.     

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.     

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.     

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.     

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.     

High-temperature oxidation behavior of iridium-based alumina-forming ternary intermetallics

The oxidation behavior of iridium-based intermetallics in the ternary iridium-aluminum-silicon system has been investigated. Additions of up to 20 at. % silicon to iridium-aluminum binary alloys reduce the aluminum concentration necessary for the formation of a protective alumina scale from greater than 55 at.% in the absence of silicon to as low as 20 at.% when 20 at.% silicon is present. Ternary iridium-aluminum-silicon alloys with 30–50 at.% aluminum and 8–10 at.% silicon exhibit parabolic oxidation behavior, and the rate constants are in good agreement with those previously determined for binary iridium-aluminum alloys. The oxidation rate of ternary iridium-aluminum-silicon alloys with 10 at.% silicon and 30–40 at.% aluminum deviates from the parabolic-oxidation behavior for alumina scale growth in the later oxidation stage, presumably due to the formation of a silica inner layer. Thermal cycling of the Ir-50 Al-8Si and Ir-60-Al samples does not result in scale spallation due to the coefficient of thermal expansion match between the alumina scale and intermetallic substrate.     

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.     

Observations on the oxidation behavior of Ni-Cr alloys containing minor additions of group III,IV, or V elements

The corrosion of a number of experimental ternary Ni-15 wt. % Cr-0.5wt. %X alloys (where X= Y, La, Ce, Sm, Th, U, Zr, or V) has been assessed in pure oxygen at 900° C for periods of exposure up to 450 hr, and compared with the behavior of an Ni-15% Cr control alloy. It has been established that while all of the alloys oxidize in accordance with a protective, approximately parabolic regime, considerable differences in oxidation rates are exhibited. In particular, additions of La, Ce, and Th bring about progressively enhanced rates of oxidation relative to the binary alloy, whereas Y, Sm, V, U, and Zr effect increasingly reduced rates of oxidation in the order given. The rate constant for the Th-bearing alloy is about two orders of magnitude larger than that for the alloy containing Zr. Such differences in behavior seem to be associated with subtle variations in the morphology/composition of the corrosion products from alloy to alloy. The observations are considered in the light of earlier published literature concerning the effects of rare-earth and other reactive elements on the oxidation behavior of Ni/Cr alloys.This work has been carried out with the support of Procurement Executive, Ministry of Defence.     

Distribution and characterization of high temperature air corrosion products on iron-chromium alloys by Raman microscopy

Raman microscopy has been used to study the nature and distribution of corrosion products formed on iron and iron-chromium alloys in air at high temperatures. Fe and Fe-Cr alloys containing 2, 5, 14, and 18% Cr were oxidized at 400, 600, and 850°C for 2 hr, in addition samples of each alloy were oxidized for 24 hr at 400°C to obtain thicker scales at this temperature. The corroded samples showed varying distributions of the oxides Fe₂O₃, Fe₃O₄, Cr₂O₃, and FeCr₂O₄. Fe₂O₃ and Fe₃O₄ were formed exclusively on the pure iron and the 2 and 5% chromium alloys at all temperatures and on the 14% chromium alloy at 400°C. The 14 and 18% Cr alloys formed scales containing Cr₂O₃ and FeCr₂O₄ at the higher temperatures (600 and 850°C). Examples of small regions of Fe₂O₃ being formed within Cr₂O₃-FeCr₂O₄ scales are suggested as possible indications of breakaway corrosion initiation sites.     

High-temperature oxidation behavior of Nb-Si-Cr alloys with Hf additions

The oxidation behavior of two alloys from the Nb-Si-Cr system containing hafnium has been investigated under isothermal and cyclic conditions. Nb-20Si-20Cr-(5,10)Hf alloys (composition in atomic percent) were exposed to air for 24 and 168 h over a range of temperatures from 700 °C to 1400 °C. A gravimetric method was used to determine the oxidation kinetics; weight gain per unit area as a function of temperature or time. Computed isothermal sections of the quaternary Nb-Si-Cr-Hf phase diagrams were used for alloy selection. XRD, SEM and EDS were used to characterize the phases present in the oxidation products and the alloys. Oxidation experiments revealed extremely good oxidation resistance at 700 °C and 800 °C and above 1200 °C under isothermal conditions for both alloys. Partial pesting was observed when the samples were exposed to 800 °C. Complete oxide formation was observed above 1000 °C for 5Hf and above 900 °C for 10Hf up to 1200 °C. Beneficial effects have been observed with the addition of 10Hf to the alloy compared to 5Hf at 700 °C, 1200 °C and 1300 °C resulting in a reduction of weight gain per unit area.     

Further aspects of the oxidation of binary two-phase alloys

The corrosion behavior of binary, two-phase alloys is considered in which the matrix contains mostly the less-noble metal that forms a fast-growing oxide, while the second phase is rich in a component that forms a more stable but slowly-growing oxide. It is assumed that the second phase exists as a dispersion of isolated, rod-like particles. It is further assumed that both phases form external films with no internal oxidation. It is shown that the oxidation behavior of this type of alloy depends on both the oxidation time and the size of the second-phase particles. In particular, for short oxidation times and large second-phase particles the matrix will oxidize faster than the dispersed phase, so that the dispersed particles will be only partly corroded or even incorporated into the matrix-oxide scale as unoxidized islands, forming an irregular alloy-scale interface. On the contrary, for long times and small particle sizes the two phases will tend to oxidize at approximately the same rate, leading to the formation of regular alloy-scale interfaces. The time for the transition between the two corrosion regimes depends not only on the ratio between the rate constants for the growth of the two oxides but also on the size of the dispersed-phase particles, smaller sizes producing shorter transition times. Eventually, under favorable conditions the formation of the fast-growing oxide may even stop, leading to the formation of a protective layer of the most-stable oxide.     

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.     

Influence of prior internal oxidation on the oxidation of dilute Co-Cr alloys in oxygen

The influence of an initial preinternal oxidation treatment in Co/CoO on the subsequent oxidation behavior of a series of dilute Co-Cr alloys (containing 0–1.5 wt. % Cr) in 10⁵ and 10³ Pa oxygen at 1473–1623 Khas been investigated. Particular emphasis has been placed on determining the solubility and mobility of Cr³⁺ ions in CoO. Use has been made of subsequent annealing in argon .