Composition, Microstructure, and Water Vapor Effects on Internal/External Oxidation of Alumina-Forming Austenitic Stainless Steels

A family of creep-resistant austenitic stainless steels based on alumina (Al₂O₃) scale formation (AFA alloys) for superior high-temperature oxidation resistance was recently identified. Excellent oxidation behavior was observed at 650 and 700 °C in air with 10% water vapor. However, particularly at 800 °C, the presence of water vapor greatly increased the tendency for internal oxidation of Al. Water vapor also enhanced subscale Al depletion in some AFA alloys relative to dry air exposure. Increased levels of Nb additions were found to significantly improve oxidation resistance, as were reactive element additions of Hf and Y. Computational thermodynamic calculations of the austenitic matrix phase composition and the volume fraction of MC, B2-NiAl, and Fe₂Nb base Laves phase precipitates were used to interpret oxidation behavior in terms of two-phase oxidation theory, reservoir effect, and the third-element effect of Cr. Of particular interest was the enrichment of Cr in the austenitic matrix phase by additions of Nb, which aided the establishment and maintenance of alumina. Higher levels of Nb additions also increased the volume fraction of B2-NiAl precipitates, which served as an Al reservoir during long-term oxidation. Implications of these findings for the design of AFA alloys with increased upper use temperature limits are discussed.     

High-Temperature Corrosion Behaviour of Aluminized-Coated and Uncoated Alloy 718 Under Cyclic Oxidation and Corrosion in NaCl Vapour at 750 °C

To evaluate the suitability of HR3C and 22Cr–25Ni–2.5Al AFA steels as the heat-resistant alloys, the oxidation behavior of them was investigated in air at 700, 800, 900 and 1000 °C. The evolution of oxide layer on the surface and subsurface was investigated using a combination of compositional/elemental (SEM, EDS) and structural (XRD, GDOES) techniques. A dense and continuous Cr₂O₃ healing layer on the HR3C was formed at the temperature of 700 or 800 °C, but the Cr₂O₃ oxide film on HR3C was unstable and partly converted into a less protective MnCr₂O₄ with the increase in temperature to 900 or 1000 °C. The composition and structure of oxide film of 22Cr–25Ni–2.5Al AFA steels are significantly different to the HR3C alloys. The outer layer oxides transformed from Cr₂O₃ to Al-containing oxides, leading to a better oxidation resistance at 700 or 800 °C compared to HR3C. Further, the oxide films consist of internal Al₂O₃ and AlN underneath the outer loose layer after 22Cr–25Ni–2.5Al AFA oxidized at 900 or 1000 °C. It can be proved that the internal oxidation and nitrogen would make 22Cr–25Ni–2.5Al AFA steels have worse oxidation resistance than HR3C alloys at 900 or 1000 °C.     

Roles of Manganese in the High-temperature Oxidation Resistance of Alumina-forming Austenitic Steels at above 800?°C

A new family of alumina-forming austenitic (AFA) stainless steels is under development for uses in aggressive oxidizing conditions. This paper investigates the effect of manganese additions on the oxidation kinetics and alumina scale formation in two series of AFA steels, i.e., Fe–20Ni–14Cr–2.5Al and Fe–18Cr–25Ni–3Al base. At 800?°C in dry air, the oxidation resistance was moderately degraded with additions of larger than 1 wt% Mn in the AFA steels based on Fe–14Cr–20Ni–2.5Al. At 900?°C in air with 10?% water vapor, however, additions of Mn in these AFA steels based on Fe–18Cr–25Ni–3Al would significantly destabilize the alumina scale formation and degrade the oxidation resistance. Our analysis revealed that additions of Mn stimulated formation of the coarse spinel CrMn_1.5O₄ and Cr₂O₃ oxide and destroyed the continuity of the protective alumina scales, thus worsening the oxidation performance. In addition, it was found that there exists an upper limit for the Mn additions which is decreased with the increase of the service temperatures and presence of aggressive oxidizing agents.     

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.     

Effect of Addition of 4 % Al on the High Temperature Oxidation and Nitridation of a 20Cr–25Ni Austenitic Stainless Steel

In high temperature applications, the alumina forming austenites (AFA) have recently gained more focus. These utilise the advantageous effect of Al on oxidation resistance, and also have good mechanical properties. Two experimental alloys [20Cr–25Ni–1Mn–0.5Si–Fe (wt.%)] were prepared. To one of the alloys 3.77 wt.% Al was added. The alloys were studied in air and air/water at 700 °C and 1,000 °C, in a sulphidising/chlorinating environment at 700 °C and in a nitriding atmosphere at 1,000 °C. The time of exposure was 100 h, except for one 1,000 h exposure in air/water. At 700 °C in air and air/water, the AFA displayed lower mass gain than the reference material. After exposure in the sulphidising-chlorinating environment, the material displayed a surface alumina layer with some spallation. In air or air/water at 1,000 °C, internal aluminium nitride and alumina formation occurred, appreciably reducing the sound metal thickness. The nitridation was enhanced in the nitriding environment.     

Influence of Alloy Composition and Exposure Conditions on the Selective Oxidation Behavior of Ni–Al Alloys

Ni–Al coating alloys, which are commonly used in gas turbine engines operating in marine environments, are highly susceptible to hot corrosion attack. The effect of alloy composition and exposure conditions on the development of a protective alumina scale, which is important for the hot corrosion resistance of the alloy, and how they affect the transition of alumina from the θ to the α polymorph have been evaluated. A series of Ni–Al model alloys with a base composition of Ni–36 at.% Al, and 5 at.% additions of Cr, Pt and Si were exposed in dry air and in air–10%H₂O at 900 °C. The presence of water vapor in the gas led to higher oxidation rates and retarded the θ- to the α-Al₂O₃ transformation. The oxidation behavior of the alloys and the alumina polymorph which formed differed depending on the alloying element considered. Additions of Cr accelerated the θ to α transformation, while Pt and Si retarded it.     

The Oxidation of Ferritic Stainless Steels in Simulated Solid-Oxide Fuel-Cell Atmospheres

The cyclic oxidation of a variety of chromia-forming ferritic stainless steels has been studied in the temperature range 700–900°C in atmospheres relevant to solid-oxide fuel-cell operation. The most detrimental environment at 800°C and 900°C was found to be air with 10% water vapor. This resulted in excessive oxide spallation or rapid scale growth. Impurities in the alloys, particularly Al and Si, were found to have a significant effect on the oxidation behavior. Oxide growth was slow at 700°C but the higher-Cr-content alloys were observed to form sigma-phase at this temperature. The sigma phase formation was accelerated by higher silicon contents, and remarkably, by the presence of water vapor in the exposure environment. Alloys containing Mn were observed to form an outer layer of MnCr₂O₄ over the chromia scale. The potential for this overlayer to suppress reactive evaporation of the chromia scales has been analyzed.     

Long-Term Oxidation of Candidate Cast Iron and Stainless Steel Exhaust System Alloys from 650 to 800 °C in Air with Water Vapor

The oxidation behavior of candidate cast irons and cast stainless steels for diesel exhaust systems was studied for 5,000 h at 650–800 °C in air with 10 % H₂O. At 650 °C, Ni-resist D5S exhibited moderately better oxidation resistance than did the SiMo cast iron. However, the D5S suffered from oxide scale spallation at 700 °C, whereas the oxide scales formed on SiMo cast iron remained relatively adherent from 700 to 800 °C. The oxidation of the cast chromia-forming austenitics trended with the level of Cr and Ni additions, with small mass losses consistent with Cr oxy-hydroxide volatilization for the higher 25Cr/20–35Ni HK and HP type alloys, and transition to rapid Fe-base oxide formation and scale spallation in the lower 19Cr/12Ni CF8C plus alloy. In contrast, small positive mass changes consistent with protective alumina scale formation were observed for the cast AFA alloy under all conditions studied. Implications of these findings for exhaust system components are discussed.     

Influence of High-Temperature Water Vapor on Titanium Film Surface

This paper describes and analyzes the appearance, phase, and photocurrent of titanium film surfaces after exposure to water vapor at 100–1000 °C. The experimental results show that water vapor at higher than 300 °C can cause measurable oxidation of the titanium surface, and the oxidation product is changed into rutile from anatase in a gradual phase transformation with temperature. In the reaction, the product produced at 500–900 °C is a mixed phase of rutile and anatase. The titanium film surface appearance can change regularly with temperature, and an acicular rutile oxidation product can be produced on the surface at 800 °C. The photocurrent density on titanium surface increases with reaction temperature, and comes to a maximum value at 800 °C. However, with further increase in reaction temperature, the density decreases.     

Oxidation behavior of atomized Fe40Al intermetallics doped with boron and reinforced with alumina fibers

Isothermal oxidation resistance of Fe40 (at.%) Al-based atomized and deposited intermetallic alloys has been evaluated. The alloys included Fe40Al, Fe40Al + 0.1B, and Fe40Al + 0.1B + 10Al₂O₃ at 800, 900, 1000, and 1100 °C. The tests lasted approximately 100 h, although in most cases there was scale spalling. At 800 and 900 °C, the Fe40Al + 0.1B alloy had the lowest weight gain, whereas the Fe40Al alloy had the highest weight gain at 800 °C (0.10 mg/cm²) and the Fe40Al + 0.1B + 10Al₂O₃ alloy was the least oxidation resistant at 900 °C with 0.20 mg/cm². At 1000 °C, the Fe40Al + 0.1B alloy showed the highest weight gain with 0.12 mg/cm² and the Fe40Al alloy the lowest. At 1100 °C, again, as at 900 °C, the Fe40Al alloy was the least resistant, whereas the Fe40Al + 0.1B alloy performed the best, but the three alloys exhibited a paralinear bahavior on the weight-gain curves, indicating the spalling, breaking down, and rehealing of the oxides. This spalling was related to voids formed at the metal-oxide interface.     

Lifetime of Thermal Barrier Coatings Deposited on γ-TiAl Based Alloys Using Intermetallic Ti–Al–Cr Bond Coats with Additions of Yttrium and Zirconium

Thermal barrier coatings (TBC) of yttria stabilized zirconia were deposited on the γ-TiAl based alloy Ti–45Al–8Nb (at.%) using electron-beam physical vapor deposition. The bond coats used were 10 μm thick intermetallic Ti–Al–Cr layers with additions of the reactive elements Y and Zr produced by magnetron sputtering. Cyclic oxidation tests at 900 and 1,000 °C in air revealed excellent oxidation resistance of the Ti–Al–Cr–Y bond coat associated with the precipitation of Y-rich particles in the thermally grown alumina scale as well as in the intermetallic layer. A less protective behavior was found with the zirconium containing bond coat. Lifetimes exceeding 1,000 1-h cycles were determined for both TBC systems at 900 °C. Edge chipping of the zirconia topcoat occurred at 1,000 °C. As observed by cross-sectional examination, a continuous alumina scale was still present on the samples with Ti–Al–Cr–Y bond coat, whereas the Ti–Al–Cr–Zr layer was severely degraded and a thick mixed oxide scale formed after 1,000 cycles at 1,000 °C.     

Oxidation of Slurry Aluminide Coatings on Cast Stainless Steel Alloy CF8C-Plus at 800 °C in Water Vapor

A new, cast austenitic stainless steel, CF8C-Plus (CF8C-P), has been developed for a wide range of high temperature applications, including diesel exhaust components, turbine casings and turbocharger housings. CF8C-P offers significant improvements in creep rupture life and creep rupture strength over standard CF8C steel. However, at higher temperatures and in aggressive environments such as those containing significant water vapor, an oxidation-resistant protective coating will be necessary to extend service life. The oxidation behavior of alloys CF8C and CF8C-P with various aluminide coatings were compared at 800 °C in air plus 10 vol% water vapor. Due to their affordability, slurry aluminides were the primary coating system of interest, although chemical vapor deposition and pack cementation coatings were also compared. Additionally, a preliminary study of the low-cycle fatigue (LCF) behavior of aluminized CF8C-P was conducted at 800 °C. Each type of coating provided substantial improvements in oxidation behavior, with simple slurry aluminides exhibiting very good oxidation resistance after 3,000 h testing in water vapor. Preliminary LCF results indicated that thicker aluminide coatings degraded high temperature fatigue properties of CF8C-P, whereas thinner coatings did not. Results suggest that appropriately designed slurry aluminide coatings are a viable option for economical, long-term oxidation protection of austenitic stainless steels in water vapor.     

AlCoCrFeNiTi_(0.5)高熵合金的高温氧化行为

采用水冷铜坩埚真空感应悬浮熔炼法制备AlCoCrFeNiTi_(0.5)多主元高熵合金,研究合金在800、900、1000和1100℃下的高温氧化行为,采用XRD,SEM及EDS对氧化膜的成分及形貌进行了分析,探索了合金的氧化机制。结果表明,合金的氧化动力学曲线在800和900℃时近似遵循六次方抛物线规律,在1000和1100℃时近似遵循四次方抛物线规律。合金具有优异的抗氧化性,在800、900和1100℃下为抗氧化级别,而在1000℃下为完全抗氧化级别。合金的氧化主要发生在枝晶间和共晶区,呈岛状团聚堆叠生长,1100℃氧化时该区域的氧化物发生明显剥落,氧化产物主要是TiO_2、Fe_2TiO_5和FeCr_2O_4等;而枝晶相的氧化产物较单一,1000℃及以下温度氧化时为弥散分布的Al_2O_3颗粒,1100℃氧化时为致密的Al_2O_3氧化层。高温氧化后,合金基体相结构稳定,未出现软化现象。     

Thermogravimetric Study of Oxidation-Resistant Alloys for High-Temperature Solar Receivers

Three special alloys likely to be suitable for high-temperature solar receivers were studied for their resistance to oxidation up to a temperature of 1050°C in dry atmospheres of CO₂ and air. The alloys were Haynes HR160, Hastelloy X, and Haynes 230, all nickel-based alloys with greater than 20% chromium content. The oxidation rate of specimens cut from sample master alloys was followed by thermogravimetry by continuously monitoring the weight change with a microbalance for a test duration of 10 h. The corrosion resistance was deduced from the total weight increase of the specimens and the morphology of the oxide scale. The surface oxide layer formed (scale) was characterized by scanning electron microscopy and energy dispersive x-ray spectroscopy and in all cases was found to be chromia. Oxidation was analyzed by means of parabolic rate law, albeit in some instances linear breakaway corrosion was also observed. For the temperature range investigated, all alloys corroded more in CO₂ than in air due to the formation of a stronger and more protective oxide scale in the presence of air. At 1000°C, the most resistant alloy to corrosion in CO₂ was Haynes 230. Alloy Haynes HR160 was the most oxidized alloy at 1000°C in both CO₂ and air. Hastelloy X oxidized to a similar extent in CO₂ at both 900°C and 1000°C, but in air, it resisted oxidation better at 1000°C than either at 900°C or 1000°C.     

Oxidation Behavior of ODS Fe–Cr Alloys

Four experimental oxide dispersion strengthened (ODS)Fe-(13–14 at. %)Cr ferritic alloys were exposed for up to 10,000 hr at 700–1100 °C in air and in air with 10vol.% water vapor. Their performance has been compared to other commercial ODS and stainless steel alloys. At 700–800°C, the reaction rates in air were very low for all of the ODS Fe–Cr alloys compared to stainless steels. At 900°C, a Y₂O₃ dispersion showed a distinct benefit in improving oxidation resistance compared to an Al₂O₃ dispersion or no addition in the stainless steels. However, for the Fe-13 %Cr alloy, breakaway oxidation occurred after 7,000 hr at 900°C in air. Exposures in 10 % water vapor at 800 and 900°C and in air at 1000 and 1100°C showed increased attack for this class of alloys. Because of the relatively low Cr reservoirs in these alloys, their maximum operating temperature in air will be below 900°C.     

Effect of Specimen Thickness on the Oxidation Rate of High Chromium Ferritic Steels: The Significance of Intrinsic Alloy Creep Strength

Previous studies revealed that initial sample thickness affects the growth rate of oxide scales formed during 800 or 900 °C air exposure. The effect is partially related to differences in depletion of minor alloying additions such as Mn, Ti, La in thick and thin specimens. However, it has previously been proposed that the specimen thickness dependence is partially governed by differences in creep strength of thick and thin substrates. To investigate this hypothesis, discontinuous air oxidation experiments were carried out with the Laves phase strengthened ferritic steel Crofer 22 H at 800 °C. Comparing the data for solution annealed and pre-aged (500 h, 900 °C) materials it could be shown that intrinsic creep strength of the alloy substantially affects oxidation rates. The observations can qualitatively be explained by assuming the relaxation of oxide growth stresses by plastic deformation of the metallic substrate to be an important parameter affecting the kinetics of oxide scale growth.     

Effect of Cr and Ni Contents on the Oxidation Behavior of Ferritic and Austenitic Model Alloys in Air with Water Vapor

Ferritic and austenitic model alloys with various contents of Cr and Ni ranging between 10–20% and 0–30%, respectively, were oxidized in air + 10% water vapor during 1 hr cyclic oxidation at 650°C and 800°C. Depending on the alloy composition and temperature, either a thin protective oxide scale was observed or accelerated attack occurred which sometimes included spallation. For austenitic model alloys, increasing either the Cr or Ni contents delayed the accelerated attack. For lower Cr and Ni contents at 800°C, accelerated attack, including spallation, occurred at short exposure times. No spallation was observed for the ferritic model alloys. However, accelerated attack can occur quickly with low Cr contents. Increasing the temperature delayed the breakaway observed on ferritic alloys whereas it reduced the protective-oxide-growth stage for austenitic alloys.     

Influence of Silicon and Aluminum Additions on the Oxidation Resistance of a Lean-Chromium Stainless Steel

The effect of Si and Al additions on the oxidation of austenitic stainless steels with a baseline composition of Fe–16Cr–16Ni–2Mn–1Mo (wt.%) has been studied. The combined Si and Al content of the alloys did not exceed 5 wt.%. Cyclic-oxidation tests were carried out in air at 700 and 800°C for a duration of 1000 hr. For comparison, conventional 18Cr–8Ni type-304 stainless steel specimens were also tested. The results showed that at 700°C, alloys containing Al and Si, and alloys with only Si additions showed weight gains about one half that of the conventional type-304 alloy. At 800°C, alloys that contained both Al and Si additions showed weight gains approximately two times greater than the type-304 alloy. However, alloys containing only Si additions showed weight gains four times less than the 304 stainless. Further, alloys with only Si additions preoxidized at 800°C, showed zero weight gain in subsequent testing for 1000 hr at 700°C. Clearly, the oxide-scale formation and rate-controlling mechanisms in the alloys with combined Si and Al additions at 800°C were different than the alloys with Si only. ESCA, SEM, and a bromide-etching technique were used to analyze the chemistry of the oxide films and the oxide–base-metal interface, in order to study the different oxide film-formation mechanisms in these alloys.     

Oxidation Behavior of Graded NiCrAlYRe Coatings at 900, 1000 and 1100 °C

A graded NiCrAlYRe coating was prepared by combining arc ion plating (AIP) with chemical vapor deposition (CVD) aluminizing. Quasi-isothermal oxidation tests of the graded NiCrAlYRe coating and the conventional NiCrAlYRe coating were performed in air at 900, 1000 and 1100 °C for up to 1000, 1000 and 200 h, respectively. The results showed that the graded NiCrAlYRe coating exhibited better long time oxidation resistance than the conventional NiCrAlRe coating. This favorable oxidation behavior was attributed to the rapid formation of a protective α-Al₂O₃ scale and a sufficient Al reservoir. The structures and morphologies of oxide scales varied under different oxidation conditions. θ-Al₂O₃ was observed on both coatings during oxidation at 900 °C, however, the graded coating showed more favorable conditions for θ-Al₂O₃ to grow than the conventional coating. For the graded coating, phase transformation from θ-Al₂O₃ to α-Al₂O₃ resulted in a sharp decrease in the parabolic rate constant k_p between 900 and 1,000 °C.     

Oxidation Behavior of a Fine-grained Chromium-containing Ni3 Al Alloy Prepared by Powder Metallurgy

The oxidation behavior of a fine-grained Cr-containing Ni₃Al based alloy was evaluated between 500 and 1000°C for exposures up to 2000 h. The alloy showed low oxidation rates over the entire temperature interval due to the formation of a thin protective alumina layer. The growth of this healing layer was promoted by both the fine microstructure of the alloy and the chromium additions. Rapid formation of the alumina layer was observed even at temperatures as low as 500°C. During the whole exposure at temperatures below 800°C the alumina layer remained adherent. However, at 800 and 900°C some spalling was observed. Usually, spalling took place at the core of the alumina layer but not at the oxide/metal interface.