Sulfidation–Oxidation Behavior of FeCrAl and TiCrAl and the Third-Element Effect

Short-term sulfidation–oxidation exposures were conducted under high pS₂ and low pO₂ conditions for TiCrAl and FeCrAl alloys at 600 and 800 °C. Low mass gains and submicron Al-and Ti-rich oxide scales were formed on TiCrAl at 600 °C, while high mass gains and FeS-based scale formation were observed for FeCrAl. Based on the good behavior of TiCrAl, third-element effect additions of Cr are not inherently detrimental under sulfidation–oxidation conditions. Rather, differences in the mechanistic action of the third-element addition of Cr between FeCrAl and TiCrAl alloys and its relevance to low oxygen potential sulfidation–oxidation environments were the key factors in determining whether or not a protective alumina scale was established.     

Oxidation of Advanced Zirconium Cladding Alloys in Steam at Temperatures in the Range of 600�C1200?��C

The oxidation kinetics of the classical pressurized water reactors (PWR) cladding alloy Zircaloy-4 have been extensively investigated over a wide temperature range from operational conditions to beyond design basis accident (BDBA) temperatures. In recent years, new cladding alloys optimized for longer operation and higher burn-up are used in Western light water reactors (LWR). This paper presents the results of thermo-gravimetric tests with Zircaloy-4 as the reference material, Duplex DX-D4, M5^® (both AREVA), ZIRLO? (Westinghouse), and the Russian E110 alloy. All materials were investigated in isothermal and transient tests in a thermal balance with steam furnace. Post-test analyses were performed by light-microscopy and neutron radiography for investigation of the hydrogen absorbed by the metal. Strong and varying differences (up to 800%) in oxidation kinetics between the alloys were found at up to 1000 °C, where the breakaway effect plays a role. Less but significant differences (ca. 30%) were observed at 1100 and 1200 °C. Generally, the M5^® alloy revealed the lowest oxidation rate over the temperature range investigated whereas the behavior of the other alloys was considerably dependent on temperature. A strong correlation was found between oxide scale structure and amount of absorbed hydrogen.     

Influence of the mode of introduction of a reactive element on the high temperature oxidation behavior of an alumina‐forming alloy. Part II: Cyclic oxidation tests

Several routes of yttrium introduction were applied to test the high temperature oxidation performance of a FeCrAl alloy. Isothermal oxidation tests were described in a previous paper (Part I of this paper in this journal, 2004, 55, 352). Cyclic oxidation tests were performed in air under atmospheric pressure on blank specimens, Y₂O₃ sol‐gel coated‐, Y₂O₃ metal‐organic chemical vapor deposited (MOCVD)‐, yttrium ion implanted‐alloys, as well as on a steel containing 0.1 wt. % of yttrium as an alloying element. For the 20 hours cycles, all the samples, except FeCrAl‐0.1Y, exhibit weight losses after a few cycles, indicating drastic spallation of the oxide scales. The MOCVD coated specimen has the highest weight loss. The oxidation kinetics of the FeCrAl‐0.1Y alloy obey a parabolic law, indicating that the alumina scale formed on its surface is protective even after more than 1200 hours of oxidation (> 50 cycles). The 100 hours cycle oxidation tests give similar results. The FeCrAl‐0.1Y alloy exhibits the best oxidation behavior with very little spallation after more than 2000 hours (85 days) of oxidation at 1100°C (20 cycles). Most of the other samples exhibit severe oxide scale spallation followed by an increase of their oxidation rate related to the formation of non‐protective iron oxides.     

Influence of Reactive Element Oxide Coatings on the High Temperature Oxidation Behavior of Alumina-Forming Alloys

Reactive-element-oxide coatings were processed by a metal-organic chemical-vapor-deposition technique on the surface of a model FeCrAl alloy. The high-temperature performances of Nd₂O₃-, Y₂O₃-coated and uncoated alloys were tested in air under atmospheric pressure at 1050, 1100 and 1200° C. The coated samples did not exhibit the expected reactive-element effects since the oxidation rates were not decreased, and the oxide-scale adherence was only slightly improved. The study of the oxide-scale morphology revealed very convoluted oxide scales, except for alumina scales formed on uncoated materials at 1100 and 1200° C. Two-stage oxidation experiments showed that the reaction proceeded by a mixed anionic–cationic diffusion process; consequently, the growth of alumina within the existing alumina layer results in convoluted scales. It is proposed that the weak incorporation of the reactive elements within the thermally growing alumina scales was responsible for the limited reactive element effects, when reactive-elements were applied as oxide coatings on alumina-forming steels.     

Oxidation of FeCrAl alloy: influence of temperature and atmosphere on scale growth rate and mechanism

The oxidation behaviour of a FeCrAl alloy with little rare earth content (Y=0.01 wt.%) was investigated. Specimens of this alloy were submitted to long-term oxidation treatments (up to 30 days) at 900 and 1200°C, under gaseous atmospheres containing 21, 10 and 2 vol.% of O₂. The weight gain for unit area was measured vs. oxidation time. The alumina scale growth was found to occur, at least during the first days of treatment, according to Wagner's parabolic law. Afterwards, the layer rate growth decreases down to that expected on the basis of this law. The values of the parabolic rate constant for scale growth (K_p) chiefly depended on the treatment temperature, while only small variations of K_p resulted from significant changes in treatment of atmosphere composition. The morphology and the composition of surface layers were studied by SEM-EDS and XRD analyses. Whatever the treatment temperature, the surface layer contained α-Al₂O₃ and non-negligible amounts of Cr and Fe. The metal/scale interface was always flat, while the morphology of the scale/gas interface changed greatly with temperature. At 900°C an irregular scale/gas interface formed; this was characterised by the presence of long α-alumina whiskers protruding towards the gaseous atmosphere. Contrary, at 1200°C a flat scale/gas interface was observed. These different morphologies can be attributed to different mechanisms of layer growth.     

Effect of Fe additions on the microstructure and properties of Nb-Mo-Ti alloys

Two Nb-Mo-Ti alloys were modified by additions of 2 at.% Fe. These small additions of Fe did not form secondary phases but noticeably increased the strength of the Nb-Mo-Ti alloys in the temperature range of 25 to 1200 °C due to solid solution strengthening effect. The oxidation resistance at 1200 °C in air was also improved considering both oxidation kinetics and the fraction of retained, un-oxidized metal alloy.     

On the Pre-oxidation Treatments of Four Commercial Ni-Based Superalloys in Air and in Ar–H<Subscript>2</Subscript>O at 950 °C

The short-term oxidation behaviour of RA 602CA, Inconel 693, Manaurite 40XO and Sumitomo 696, which are four alloys recommended for hydrocarbon processing, was studied both in air and in Ar–H₂O to determine the conditions of pre-oxidation treatments. Regardless of the considered material, the oxidation rate at 950 °C was systematically higher in Ar–H₂O than in dry air. Surface examination of the Al-containing alloys indicated that they were not uniformly oxidized all over the surface. All Al-containing alloys (from 1.6 to 3.2% wt) formed an external protective alumina scale and behaved as alumina-forming alloys in dry air at 950 °C. In contrast, these alloys developed a rate-controlling chromia scale and severe internal oxidation in a H₂O-containing atmosphere. Compared with their oxidation behaviour in air + H₂O, the phenomenon was significantly enhanced in the atmosphere that coupled water vapour with a low oxygen pressure. Consequently, the Al-containing alloys should not be pre-oxidized in a water vapour atmosphere prior to long exposure to a corrosive atmosphere. In contrast, the chromia-forming Al-free 696 alloy exhibited identical oxidation behaviour in both atmospheres, demonstrating that the degradation of this alloy was not significantly affected by water vapour.     

High temperature oxidation of FeCrAl‐alloys – influence of Al‐concentration on oxide layer characteristics

The superior high temperature oxidation resistance of FeCrAl alloys relies on the formation of a dense and continuous protective aluminium oxide layer on the alloy surface when exposed to high temperatures. Consequently, the aluminium content, i.e. the aluminium concentration at the alloy–oxide layer interface, must exceed a critical level in order to form a protective alumina layer. In the present study the oxidation behaviour of six different FeCrAl alloys with Al concentrations in the range of 1.2–5.0 wt% have been characterised after oxidation at 900 °C for 72 h with respect to oxide layer surface morphology, thickness and composition using scanning electron microscopy, energy dispersive X‐ray spectroscopy and Auger electron spectroscopy. The results show that a minimum of 3.2 wt% Al in the FeCrAl alloy is necessary for the formation of a continuous alumina layer. For Al concentrations in the range of 2.0–3.0 wt% a three‐layered oxide layer is formed, i.e. an oxide layer consisting of an inner alumina‐based layer, an intermediate chromia‐based layer and an outer iron oxide‐based layer. In contrast, the 1.2 wt% Al FeCrAl alloy is not able to form a protective oxide layer inhibiting extensive oxidation.     

Effect of Yttrium as Alloying Element on a Model Alumina-Forming Alloy Oxidation at 1100 °C

In order to study the effect of yttrium as alloying element on the high-temperature oxidation of an alumina-forming alloy, 0.093 wt% yttrium was incorporated into a model FeCrAl alloy. Yttrium has a beneficial effect on the isothermal oxidation behavior in air at 1100 °C. Glancing angle X-ray diffraction made on a sample oxidized for 1000 h under thermal cycling conditions indicated that yttrium is located at the internal interface as Y₃Al₅O₁₂. Secondary neutral mass spectrometry results showed that the diffusion mechanism is modified by the presence of yttrium as an alloying element. Moreover, the beneficial effect of yttrium on the alloy oxidation is also related to a reduced metallic grain size. The growth of metal grains during oxidation was especially observed on the yttrium-free FeCrAl alloy. It is also well established that the diffusion mechanism in the oxide scale is modified by yttrium. The aim of the present work was to show that yttrium also plays a role on the aluminum diffusion in the metallic substrate and has a strong influence on the kinetic transient stage during the FeCrAl–0.1Y oxidation.     

Optimizing the Oxidation Properties of FeCrAl Alloys at Low Temperatures

FeCrAl alloys are proposed candidate materials for liquid lead applications. Chromium is needed to assist the formation of a protective alumina layer, albeit has to be limited to avoid α′ precipitation. Reactive elements (RE) improve oxidation properties, but little is known about the RE effects at lower temperatures. An alloy matrix based on Fe–10Cr–4Al (wt%), with varying Zr, Y and Ti contents, was exposed to liquid lead up to 1 year in the temperature interval of 450–550 °C. It was found that the formation of protective alumina was dependent on the RE/carbon ratio. All alloys with ratios lower than unity showed poor oxidation properties due to the formation of Cr-carbides in the metal–oxide interface. A sufficiently high amount of Zr and Ti was shown to significantly improve the oxidation properties at both temperatures. The positive effect is related to the suppression of Cr-carbides by addition of stronger carbide formers.     

The oxidation behavior of high Cr and Al containing Nb-Si-Ti-Hf-Al-Cr alloys at 1200 and 1250 °C

The oxidation behavior of two alloys containing different content of Al and Cr from the Nb-Si-Ti-Hf-Al-Cr system has been evaluated at 1200 and 1250 °C. The alloy compositions in atomic percent are Nb-24Ti-16Si-2Hf-2Al-10Cr (B1), and Nb-24Ti-16Si-2Hf-6Al-17Cr (B2). The oxidation kinetic of B1 alloy at 1200 and 1250 °C followed a mixed parabolic-linear law, while the oxidation kinetic of B2 alloy at 1200 and 1250 °C followed a parabolic law. The weight gain of B2 alloy was 18.9 mg/cm² after oxidation at 1200 °C for 100 h, which was a seventh of the value of that of B1 alloy. Besides, oxidation became more severe as temperature increased to 1250 °C. The oxide scales of B2 alloy consisted of CrNbO₄, TiNb₂O₇ and SiO₂, which were relatively compact and protective. In addition, the oxidation mechanism of Nb-Si based alloys were also discussed.     

Influence of the Oxygen Partial Pressure on the High Temperature Corrosion of 38Ni–34Fe–25Cr Alloy in Presence of NaCl Deposit

In biomass gasification processes, some molten salts formed during the process can promite high temperature corrosion. In this study the chromia-forming austenitic alloy Haynes^® HR-120 was oxidized with a deposit of sodium chloride for 96 h at 825 and 900 °C. Two different atmospheres were selected; one with a high oxygen partial pressure (Ar/O₂ 90/10 %vol.) and one, named syngas, with a low oxygen partial pressure (CO/H₂/CO₂ 45/45/10 %vol.). While at 900 °C the behaviour of the alloy in presence of sodium chloride was catastrophic in high oxidizing conditions, the impact of sodium chloride was insignificant in the syngas atmosphere. When exposed to the Ar/O₂ mixture, the catastrophic oxidation was attributed to the setting up of an active oxidation. At 900 °C under the syngas atmosphere, the protective behaviour of the alloy seems linked to the association of a faster evaporation of the salt and a very low oxygen partial pressure. At 825 °C a catastrophic behaviour is observed under the syngas atmosphere as the NaCl evaporation rate is much slower.     

Stability of External α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Scales on Alloy 602 CA at 1100–1200 °C

An external ultrathin α-Al₂O₃ scale grown on the Ni-base alloy 602 CA during air oxidation at 800 °C was characterized by means of high-resolution TEM/EDX and electron diffraction. Alloy samples pre-oxidized at 800 °C were subsequently exposed at 1100, 1150 and 1200 °C for up to 100 h. Whereas the external alumina remained stable at 1100 °C, with the increasing exposure temperature, the pre-grown alumina scale tended to break down resulting in an external chromia scale accompanied by internal alumina precipitation. The transition from external to internal Al oxidation was investigated using SEM/EDX/EBSD. The critical Al depletion at the scale-alloy interface during the post-exposure at 1100–1200 °C was modeled using the CALPHAD-based thermodynamic-kinetic approach.     

Steam Oxidation Resistance of Advanced Steels and Ni-Based Alloys at 700 °C for 1000 h

The aim of the work was to investigate corrosion resistance of highly alloyed steels and Ni-based alloys in a steam atmosphere for 1000 h at 700 °C. In these steam oxidation experiments, two solid solution strengthened alloys; Haynes^® 230^®, 617 alloy, two gamma-prime (γ′) strengthened alloys; 263 and Haynes^® 282^® and three Cr+Ni- rich stainless steels: 309S, 310S and HR3C austenitic steels were exposed. The study showed that the materials exposed commonly developed thin oxide scales; in Ni-based alloys, these consisted of mainly MnCr₂O₄ spinels and Cr₂O₃, with the exception of 617 alloy where NiCr₂O₄ spinels and Cr₂O₃ were found. In Fe-based alloys, Cr₂O₃, MnCr₂O₄ spinels, Fe,Mn(SiO)₄, and finally Fe₃O₄ developed. No evaporation of chromia has been found within 1000 h test period. Furthermore, the development of TiO₂ was not observed into a large extent in Haynes^® 282^® and 263 alloy, in contrast to the study performed at 800 °C under the same steam environment conditions.     

The Oxidation behavior of ODS iron aluminides

Oxide-dispersed Fe-28at.% Al-2%Cr alloys were produced by a powder metallurgy technique followed by hot extrusion. A variety of stable oxides were added to the base alloy to assess the effect of these dopants on the oxidation behavior at 1200°C in air and O₂. An Al₂O₃ dispersion flattened the α-Al₂O₃ scale, but produced none of the other reactive element effects and had an adverse influence on the long-term oxidation behavior. A Y₂O₃ dispersion improved the alumina scale adhesion relative to a Zr alloy addition at 1200 and 1300°C. However, the Y₂O₃ dispersion was not as effective in improving scale adhesion in Fe₃Al as it is in FeCrAl. This inferior performance is attributed to a larger amount of interfacial void formation on ODS Fe₃Al.     

High-Temperature Oxidation Behavior of ODS–Fe3Al

The high-temperature oxidation behavior of an oxide dispersion-strengthened (ODS) Fe₃Al alloy has been studied during isothermal and cyclic exposures in oxygen and air over the temperature range 1000 to 1300°C. Compared to commercially available ODS–FeCrAl alloys, it exhibited very similar short-term rates of oxidation at 1000 and 1100°C, but at higher temperatures the oxidation rate increased because of increased scale spallation. Over the entire temperature range, the oxide scale formed was -Al₂O₃, with the morphological features typical of reactive-element doping and was similar to those formed on the ODS–FeCrAl alloys. Although initially this scale appeared to be extremely adherent to the Fe₃Al substrate, an undulating metal–oxide interface formed with increasing time and temperature, which led to cracking of the scale in the vicinity of surface undulations accompanied by a loss of small fragments of the full-scale thickness. In some instances, the surface undulations appeared to have resulted from gross outward local extrusion of the alloy substrate. Similar features developd on the FeCrAl alloys, but they were typically much smaller after a given oxidation exposure. The ODS–Fe₃Al alloy has a significantly larger coefficient of thermal expansion (CTE) than typical FeCrAl alloys (approximately 1.5 times at 900°C) and this appears to be the major reason for the greater tendency for scale spallation. The stress generated by the CTE mismatch was apparently sufficient to lead to buckling and limited loss of scale at temperatures up to 1100°C, with an increasing amount of substrate deformation at 1200°C and above. This deformation led to increased scale spallation by producing an out-of-plane stress distribution, resulting in cracking or shearing of the oxide.     

Increasing the Upper Temperature Oxidation Limit of Alumina Forming Austenitic Stainless Steels in Air with Water Vapor

A family of alumina-forming austenitic (AFA) stainless steels is under development for use in aggressive oxidizing conditions from ~600?C900 °C. These alloys exhibit promising mechanical properties but oxidation resistance in air with water vapor environments is currently limited to ~800 °C due to a transition from external protective alumina scale formation to internal oxidation of aluminum with increasing temperature. The oxidation behavior of a series of AFA alloys was systematically studied as a function of Cr, Si, Al, C, and B additions in an effort to provide a basis to increase the upper-temperature oxidation limit. Oxidation exposures were conducted in air with 10% water vapor environments from 800?C1000 °C, with post oxidation characterization of the 900 °C exposed samples by electron probe microanalysis (EPMA), scanning and transmission electron microscopy, and photo-stimulated luminescence spectroscopy (PSLS). Increased levels of Al, C, and B additions were found to increase the upper-temperature oxidation limit in air with water vapor to between 950 and 1000 °C. These findings are discussed in terms of alloy microstructure and possible gettering of hydrogen from water vapor at second phase carbide and boride precipitates.     

Oxidation and Hot Corrosion Behaviors of Service-Exposed and Heat-Treated Gas Turbine Vanes Made of IN939 Alloy

Oxidation and hot corrosion tests were conducted on service-exposed and heat-treated IN939 alloys at 830, 930 and 1030 °C for testing times up to 800 h. The degradation behaviors were studied using optical and scanning electron microscopes. The oxidation results showed no tangible weight change in the samples at 830 °C. At 930 °C, after initial weight gain, the oxidation samples showed weight loss; whereas a continuous weight loss was observed at the higher temperature of 1030 °C. In the hot corrosion tests, however, a large weight loss occurred in the samples even at 830 °C, indicating an effect of fuel impurities on the high-temperature behavior of the alloy. SEM observations revealed that the main features of oxidation and hot corrosion of the alloy were internal oxidation of aluminum and depletion of chromium in the regions beneath the surface scales.     

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.