The oxidation behaviour of cobalt-base alloys containing dispersed oxides formed by internal oxidation

CoCr alloys containing a dispersed oxide phase have been produced by internally oxidizing alloys to which 1 wt % of a reactive element—Hf, Ti or Zr—has been added. Internal oxidation was carried out in a sealed quartz capsule containing a 50/50 powder mixture of CrCr₂O₃, or X-40-Cr₂O₃. The alloys produced in this way show all the beneficial characteristics demonstrated by similar alloys made by other techniques: (a) a continuous protective Cr₂O₃ scale is established at a chromium level of 10%, considerably below that required (approximately 25%) in the absence of a dispersoid; (b) a reduction in the growth rate of the Cr₂O₃ compared to particle-free alloys, particularly at high temperatures, and (c) greatly improved adhesion of the protective scale to the substrate. The beneficial effects appear to be independent of the composition of the dispersoid, and also its distribution. Oxidation of the CoCr-1 Hf, Zr or Ti alloys without pre-treatment produces scales characteristic of the chromium content of a corresponding binary alloy, indicating that some internal oxidation treatment is necessary and it is not sufficient to rely on the internal oxides formed during normal oxidation.     

The high-temperature oxidation of nickel-20 wt. % chromium alloys containing dispersed oxide phases

Alloys of Ni-20 wt. % Cr containing 3 vol. % of a dispersed oxide phase have been prepared by a mechanical alloying method and oxidized in oxygen at 100 Torr in the temperature range of 900 to 1200°C. It appears that the dispersed oxide has four distinct effects on the oxidation: (1) the selective oxidation of chromium to form a continuous protective Cr ₂ O ₃ scale is promoted; (2) the rate of growth of Cr ₂ O ₃ is reduced compared with particle-free alloys; (3) the adhesion of the Cr ₂ O ₃ is greatly improved; and (4)the scale-forming reaction appears to be at the scale-metal interface in alloys containing a dispersion, but at the scale-oxygen interface in alloys without a dispersion. It appears that the nature of the dispersed oxide is not important, since very similar effects can be obtained with ThO ₂,Y ₂ O ₃,and CeO ₂ dispersions. It is demonstrated that a logical deduction from this evidence is that the growth of Cr ₂ O ₃ scales on dispersion-free systems must involve short-circuit diffusion of chromium through the scale, and that it seems probable that an effect of the dispersion must be to retard or eliminate this short-circuit process. It is suggested that the oxide particles act as nucleation centers for the oxide, thus reducing the oxide grain size; and it is shown that this simple hypothesis is sufficient to explain a number of the experimental observations.This work has been supported by the Naval Air Systems Command under Contract No. N00019-71-C-0079.     

Effect of Y2O3 dispersoids in 80Ni-20Cr alloy on the early stages of oxidation at low-oxygen potential

Specimens of a 80Ni-20Cr type alloy, with and without Y₂O₃ dispersoid particles, were oxidized at 1000°C in H₂/H₂O mixtures where the partial pressure of oxygen (P _{O 2}) was varied between 10₃ and 10₂₄ atm. Oxide particles nucleated homogeneously on both alloys, and preferential nucleation on dispersoid particles at the surface was not observed. Continuous Cr₂O₃ films formed slightly faster at aP _{O 2} of 10^–21 atm on the alloy containing the dispersoid, but the difference was negligible at higher pressures. Oxidation atP _{O 2}=10^-19 and 10^–21 atm involved both the formation of Cr₂O₃ and the evaporation of chromium. Thin films of -Al₂O₃ were observed on both alloys after oxidation atP _{O 2}.     

The oxidation of Ni-20 wt. % Cr-2ThO2

The oxidation of TD NiCr (Ni-20 wt. % Cr-2ThO₂) has been investigated between 900 and 1200°C, and the oxidation behavior is compared with Ni-30 wt. % Cr and Co-35 wt. % Cr alloys. All alloys develop Cr₂O₃ scales but the weight changes obtained for the NiCr and CoCr alloys show an increase with time whereas above 1000° C the TD NiC shows a progressive loss in weight from the evaporation of CrO₃ from the scale, and the reaction products appear to be formed mainly at the alloy-scale interface. However, no mechanism for its formation has been established.     

The functional form of rate curves for the high-temperature oxidation of dispersion-containing alloys forming Cr2O3 Scales

It has been shown recently in a number of investigations that the presence of dispersed stable oxides in chromium-containing alloys can result in the formation of protective Cr ₂ O ₃ scales, which appear to grow considerably slower than similar scales on alloys not containing dispersoids. In addition, Cr ₂ O ₃ is removed by further oxidation to the volatile species CrO ₃,and the rate of this process is unaffected by the dispersoid. Simple kinetic models have been used to describe the results, but it is suggested, on the basis of a curve-fitting analysis, that these approaches are incorrect.This work has been supported by the Naval Air Systems Command under Contract No. N00019-71-C-0079.     

The effect of an Al2O3 dispersion on the adhesion of Al2O3 scales on aluminized Co-10% Cr alloys

The beneficial effect of dispersions of reactive-metal oxide particles on the adhesion of Cr₂O₃ and Al₂O₃ scales formed on heat-resisting alloys is wellknown. It has been shown that an Al₂O₃ dispersion in an alloy can improve the adhesion of a Cr₂O₃ scale, and it is of particular interest in assessing the various theoretical proposals for the effect to determine whether such a dispersion can affect the adhesion of an Al₂O₃ scale. In this investigation, a Co–10% Cr–1 % Al alloy was first internally oxidized to form an Al₂O₃ dispersion. This alloy was then aluminized so that on subsequent oxidation an Al₂O₃ scale developed. It was shown that the dispersion did indeed improve the scale adhesion. The implications of this result are discussed.     

Effect of Y2O3 additions on the plasticity of sintered Cr2O3

We have carried our constant strain-rate compression tests on polycrystalline Cr₂O₃ and Cr₂O₃ doped with 0.09 wt. % Y₂O₃ to establish whether there exists an effect of Y₂O₃ on the plasticity of Cr₂O₃. This study is motivated by previous work on the oxidation of alloys containing reactive-element additions. In that work, it has been observed that the addition of oxygen-active elements, such as Y to alloys that form Cr₂O₃ or Al₂O₃ oxide layers upon exposure at high temperature, strongly enhances the adhesion of the oxide layer to the base alloy as compared with alloys without reactive-element additions. We have found that at 1200°C (1) chromia exhibits limited plasticity at high temperatures, and (2) the presence of Y in the oxides does not enhance plasticity compared with addition-free oxides.     

Relation between impurities and oxide-scale growth mechanisms on Ni-34Cr and Ni-20Cr alloys. II. Influence of sulphur

The oxidation of presulphidized Ni-Cr alloys has been studied by taking into account the influence of the two distinct oxidation mechanisms described in part I of this article. Sulphur enters the Cr₂O₃ scale (in Ni-34Cr alloys) mainly as S^2– species, which at high temperatures increases the V_Cr content, and hence the oxidation kinetics. Sulphur is randomly distributed in the scale, except at the inner oxide-alloy interface, where intergranular microsulphides are analyzed in the oxide-scale zone. In the case of NiO, NiCr₂O₄, Cr₂O₃ oxide multilayers (in a Ni-20Cr alloy), sulphur in the S^2– state is distributed in the oxide layers or at Si-precipitate interfaces. Such a distribution leads to crack formation, especially during cooling.     

Oxidation of Fe-3 wt.% Cr alloy

The oxidation behavior and the oxide microstructure on Fe-3 wt. % Cr alloy were investigated at 800°C in dry air at atmospheric pressure. Two distinct oxidation rate laws were observed: initial parabolic oxidation was followed by nonparabolic growth. The change in the oxidation kinetics was caused by microchemical and microstructural developments in the oxide scale. Several layers developed in the oxide scale, consisting of an innermost layer of (Fe,Cr)₃O₄ spinel, an intermediate layer of (Fe,Cr)₂O₃ sesquioxide, and two outer layers of Fe₂O₃ hematite, each with different morphologies. Wustite (Fe_1–xO) and distorted cubic oxide (-(Fe,Cr)₂O₃) were observed during the iniital parabolic oxidation only.     

The high-temperature oxidation resistance of Co-Al alloys

Most Ni and Co-base alloys used for high-temperature service rely on the production of a compact, stable Cr₂O₃ scale for their oxidation resistance. However, as operating temperatures have risen above 900–950° C, the loss of Cr₂O₃ as the volatile CrO₃ has led to an inadequate life span of these alloys, particularly in rapidly flowing, turbulent gas streams. As a result of this, it has been necessary to examine the possibility of using Al₂O₃ as the protective scale. Al₂O₃ has a lower growth rate than Cr₂O₃, it is nonvolatile, and, unlike Cr-containing systems, it is less likely to form compound oxides such as spinels. In this study, the amount of Al which must be present in the Co-Al system to form a continuous layer of Al₂O₃ in the temperature range 800–1000° C has been determined. The quantity was found to rise from about 7–10 wt. % at 800° C to 10–13 wt. % at 900° C and 13 wt. % at 1000° C. Notice has also been taken of the abilities of the alumina-forming alloys to re-form a protective oxide in the event of spalling, blistering, or any other disruptions of the scale, and some cyclic-oxidation checks have been conducted on the Co13Al alloy at 900 and 1000° C.This work has been partly supported by the Science Research Council and one of us (G.N.I.) wishes to thank them for the award of a Science Research Council Research Studentship     

The oxidation behaviour of austenitic FeCrNi alloys containing dispersed phases

The high temperature oxidation behaviour of FeCrNi austenitic alloys containing 1% Ti which, in some cases, had been converted into an oxide dispersion has been examined. The oxide dispersions were produced by an internal oxidation treatment using a 50/50 Cr/Cr₂O₃ powder mixture in a sealed quartz capsule at 1100°C: the samples were not in direct contact with the powders. Generally, the effect of the dispersed oxide was much less pronounced than in corresponding nickel-free, ferritic alloys. Nevertheless, the time-to-breakaway of the protective Cr₃O₃ scale which developed on Fe18CrNi alloys was substantially increased, although the differences between the untreated and the internally oxidized alloys reduced with increasing nickel content. An Fe14Cr20Ni alloy did not show any improvement after internal oxidation. Unlike the ferritic alloys, no coarsening of the dispersoid phase was observed during exposure.     

The effect of particle size of alumina dispersions on the oxidation resistance of Ni-Cr alloys

The oxidation behavior of Ni-Cr alloys with various chromium concentrations and particle sizes of a dispersion of 10 vol.% Al₂O₃ was observed in 1 atm of oxygen at 1000°C. This study was intended to determine the critical chromium concentration to form a protective Cr₂O₃ oxide layer for different Al₂O₃ particle sizes. The oxidation rate of Ni-Cr alloys containing 10 vol.% Al₂O₃ followed a parabolic rate law and a Cr₂O₃ protective layer continuously formed when the oxidation rate decreased rapidly. Times to form a continuous and protective Cr₂O₃ layer during the initial oxidation shortened as the size of the dispersion decreased. The critical chromium concentration to form a protective Cr₂O₃ layer in the oxide scale was 69 wt.% and was related strongly to the particle size of the Al₂O₃ dispersion.     

The oxidation of Iron-Chromium-Manganese alloys at 900°C

The oxidation of nine ternary iron-chromium-manganese alloys was studied at 900°C in an oxygen partial pressure of 26.7 kPa. The manganese concentration was set at 2, 6, and 10 wt. %, and chromium at 5, 12, and 20 wt. %. The scales formed on the low-chromium alloys consisted of (Mn,Fe)₂O₃, -Fe₂O₃, and Fe₃O₄. These alloys all exhibited internal oxidation and scale detachment upon cooling. The scales formed on the higher-chromium alloys were complicated by nodule formation. Initially, these scales had an outer layer of MnCr₂O₄ with Cr₂O₃ underneath, adjacent to the alloy. With the passage of time, however, nodules formed, and the overall reaction rate increased. This tendency was more marked at higher manganese contents. Although these alloys contained a high chromium content, the product chromia scale usually contained manganese. It was concluded that the presence of manganese in iron-chromium alloys had an adverse effect on the oxidation resistance over a wide range of chromium levels.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

Oxidation of iron-nickel aluminum alloys in oxygen at 600–800° C

The oxidation behavior of iron-nickel-aluminum alloys containing 0–40 wt.% nickel and 0–30 wt.% aluminum has been investigated at 600 and 800° C. Through the construction of oxide maps it can be shown that three possible oxide morphologies may exist: Alloys containing less than approximately 5 wt.% aluminum form scales consisting of predominantly Fe₂O₃ and spinel; alloys with between 5 and 10 wt.% aluminum form Al₂O₃ scales interspersed by Fe₂O₃ nodules, and alloys with greater than 10 wt.% aluminum form predominantly -Al₂O₃ scales.     

The role of nickel in the high-temperature oxidation of Fe-Cr-Ni alloys in oxygen

The oxidation of several largely austenitic Fe-Cr-Ni alloys in 1 atm oxygen at 800–1200°C has been studied thermogravimetrically, metallographically, and in detail by electron probe micro analysis. Fe-Cr-Ni alloys of this type are protected by Cr₂O₃-healed scale, which thickens slower than on the corresponding binary Fe-Cr and Ni-Cr alloys, presumably because nickel and iron ions dope the Cr₂O₃ more effectively together than singly and/or because the alloy composition and ability to absorb cation vacancies are such as to produce a smaller vacancy activity gradient or level in the scale, or voids within it. The scale adhesion, as on Ni-Cr alloys, is generally good after long times, at least partly due to the convoluted alloy-oxide interface, in some cases to large intergranular Cr₂O₃-rich stringers, and possibly to the general specimen mechanical properties. Nonprotective stratified scale development is relatively unusual and often produces nickel-rich, alloy-particle-containing nodules, as on Fe-Ni alloys. Careful selection of ternary and more complex alloys with appropriate alloy interdiffusion coefficients and oxygen solubilities and diffusivities should permit development of materials with the best compromise between ease of Cr₂O₃ establishment, avoidance of breakaway, and readiness of scale healing.     

Sulfidation and sulfidation-oxidation of nickel- and cobalt-base alloys containing dispersions of stable oxides

The presence of a fine dispersion of a stable oxide is known to have a beneficial effect on the oxidation resistance of nickel- and cobalt-base heat-resisting alloys. This paper presents some preliminary experimental results relating to the hot-corrosion resistance of these alloys. Alloys forming Cr ₂O₃ scales appear to be resistant to oxidation when coated with sodium sulfate, whereas an alloy normally forming an Al ₂O₃ scale suffers accelerated attack. During sulfidation some of the alloys suffer an accelerated degradation, with sulfur penetrating rapidly along what appear to be grain boundaries. The same effect is noted in sulfidation-oxidation experiments, when the Cr ₂O₃-forming alloys suffer accelerated oxidation, the effect of the dispersoid being apparently removed. An Al ₂O₃-forming alloy resists this form of attack well. The sodium sulfate-coated test is probably a good guide to the behavior under weakly corroding conditions, whereas the sulfidation-oxidation test may give a better indication of the behavior under highly aggressive conditions.     

Development,growth, and adhesion of Al2O3 on platinum-aluminum alloys

The development, growth, and adhesion of -Al₂O₃ scales on platinum-aluminum alloys containing between 0.5 and 6 wt.% aluminum have been studied at temperatures in the interval between 1000 and 1450° C. The morphologies and microstructures of the -Al₂O₃ scales were found to be influenced by the temperature, oxygen pressure, and the microstructures of the alloys. The oxidation rates of the alloys appeared to be controlled by transport of oxygen along grain boundaries in the -Al₂O₃ scales. The -Al₂O₃ scales adhered to the platinum-aluminum substrates even after extensive periods of cyclic oxidation. The good adhesion of the -Al₂O₃ may result from mechanical keying of the oxide to the alloys due to the development of irregular oxide-alloy interfaces.This work was supported by the U.S. Army Research Office, Durham, under Contract Number DAHCO 4 73 C 0021.     

The Effects of Molybdenum on the High-Temperature Oxidation Resistance of Thin Foils of Fe–20Cr–5Al at Very High Temperatures

Thin foils of Fe–20Cr–5Al alloys are susceptible to breakawayoxidation once the aluminum content of the substrate has fallen below somecritical value. The combined addition of 0.1 wt.% lanthanum and 0, 1, or 2wt% molybdenum has a beneficial effect on the high-temperature oxidation ofsuch foils. Lanthanum has the well-known reactive-element effect on adhesionof the protective alumina scale, thereby increasing the time to onset ofbreakaway oxidation, while, for alloys containing molybdenum, breakawayoxide spreads relatively slowly over the specimen in comparison to alloysthat contain no molybdenum. In particular, molybdenum-containing alloys areable to develop a protective Cr₂O₃ layer at the breakawayoxide–substrate interface. Conversely, molybdenum-free alloys form aninternal-oxide zone in the substrate adjacent to this interface, rather thana Cr₂O₃ layer, so breakaway oxide spreads rapidly. A martensitic phase isobserved in the substrate adjacent to the breakaway oxide formed on Fe–20Cr–5Al–La specimens, which means that the-phase has transferred to the -phase at the temperature ofthe oxidation test (1150°C). Conversely, -phase is retained inthe molybdenum-containing alloy, even after breakaway takes place, sincemolybdenum, which is a strong ferrite former, is enriched in the alloyadjacent to areas of breakaway oxide. The diffusion rate of chromium isslower in the than in the -phase so a continuouschromium-rich oxide layer, which is effective in inhibiting breakawayoxide from spreading, cannot be established at the breakawayoxide–substrate interface for the molybdenum-free alloys.