High Pressure Steam Oxidation of Alloys for Advanced Ultra-Supercritical Conditions

A steam oxidation test was conducted at 267 ± 17 bar and 670 °C for 293 h. A comparison test was run at 1 bar. All of the alloys showed an increase in scale thickness and oxidation rate with pressure, and TP304H and IN625 had very large increases. Fine-grained TP304H at 267 bar behaved like a coarse grained alloy, indicative of high pressure increasing the critical Cr level needed to form and maintain a chromia scale. At 267 bar H230, H263, H282, IN617 and IN740 had k_p values a factor of one–to-two orders of magnitude higher than at 1 bar. IN625 had a four order of magnitude increase in k_p at 267 bar compared to 1 bar. Possible causes for increased oxidation rates with increased pressure were examined, including increased solid state diffusion within the oxide scale and increased critical Cr content to establish and maintain a chromia scale.     

Cyclic Oxidation Behavior of IN 718 Superalloy in Air at High Temperatures

Ni-base superalloy IN 718 was cyclically oxidized in laboratory air at temperatures ranging from 750 to 950 °C for up to 12 cycles (14 h/cycle). The kinetic behaviour as well as the surface morphology, and the oxide phases of the scales were characterized by means of weight gain measurements, cyclic oxidation kinetics, scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS), and X-ray diffraction (XRD) analysis techniques. The results showed that as the oxidation temperature increased, the oxidation rate, the external scale thickness, and internal oxidation zone increased. It was suggested that the oxidation rate was controlled by the diffusion of substrate elements in the alloy and the inward diffusion of oxygen through the oxide scale. The oxidation kinetics followed a sub-parabolic rate law and, the activation energy of oxidation was 249 ± 20 kJ mol^?1. The scaling process was controlled mainly by the diffusion of chromium, titanium, manganese, and oxygen ions through the chromia scale. IN 718 showed low weight gain and very slow reaction rates of substrate elements at 750 °C. At 850 °C, a continuous and very thin oxide scale was formed. At 950 °C, XRD and EDS-elemental mapping analysis revealed that a complex oxide scale had formed. It consisted of an outermost layer of TiO₂?CMnCr₂O₄ spinels, inner layer of Cr₂O₃, and the inner most layer composed of Ni₃Nb enriched with Nb, Ti and Al oxides underneath the chromia layer. The oxide scale at this temperature seemed to be thicker layer, significant spallation and volatilization had apparently occurred, and greater internal corrosion was identified. The doping effect of titanium was observed, where it was found to be diffused through the chromia scale to form TiO₂ at the oxide-gas interface as well as internally and at the oxide alloy interface. The amount of rutile (TiO₂) at the oxide surface increased with temperature. In view of Mn contents in the alloy, the manganese?Cchromium spinel oxide was inferred to have played an important role in cyclic oxidation behaviour of IN 718, where the change in oxidation kinetic was noted. The Al contents would cause internal Al-rich oxide formation at grain boundaries.     

Oxidation of Ni-base alloys in atmospheres with widely varying oxygen partial pressures

The oxidation behavior of the Ni-base alloys IN 617, IN 713 LC, Ni20Cr, and Ni20Cr+Si has been investigated in the temperature range from 850°C to 1000°C in air and at low-oxygen partial pressure p(O₂) (10^–19 to 10^–16 bar). With the exception of alloy IN 713 LC, the materials show no influence of p(O₂) on the oxidation mechanisms and the kinetics. This result can be explained by the formation of a dense Cr₂O₃ layer, the growth rate of which is controlled by the Cr ion interstitial concentration in Cr₂O₃ at the phase boundary oxide/alloy and the mobility of Cr ions in Cr₂O₃. For the alloy IN 713 LC which develops a dense Al₂O₃ layer in air, a modified transition mechanism at low p(O₂) leads to the formation of Cr₂O₃ at the surface and a strong internal oxidation of Al.     

Thermal degradation behavior of inconel 617 alloy

Inconel 617 alloy is a candidate material for potential use as an intermediate heat exchanger (IHX) and as a hot gas duct (HGD) in high-temperature gas-cooled reactors (HTGRs) for H₂ production. This alloy supports severe operating conditions of a pressure over 8 MPa and temperature that exceed 950 °C in He gas with some impurities. In this work, the oxidation behavior of Inconel 617 alloy was studied after exposure at 1050 °C for 2000 h in both air and He atmospheres. The external oxide scale was mainly composed of Cr₂O₃ and small amount of TiO₂. The internal oxide was observed just below the external oxide scale and was distributed on the grain boundaries. The internal oxide was confimed as Al₂O₃. The Cr-depleted zone and internal oxide in both environments became thicker as the exposure time increased. The Cr₂O₃ in air at 2000 h was thinned in terms of its scale by CrO₃ evaporation and delamination. The Cr₂O₃ in He was constantly maintained.     

Cyclic Oxidation Kinetics and Oxide Scale Morphologies Developed on the IN600 Superalloy

The oxidation behavior of the IN600 Ni?CCr?CFe superalloy was investigated in air at temperatures ranging from 750 to 950 °C, for up to 12 cycles. Oxidation kinetics and oxide scale morphologies were examined using weight gain measurements, SEM-EDS, and X-ray diffraction. The cyclic oxidation kinetic results suggested that the oxidation behavior of the IN600 alloy approximately followed a sub-parabolic rate and the scaling process was controlled by the formation of a chromia scale. At 850 °C, SEM-EDS observations indicated that the formed oxide scale was primarily composed of Cr₂O₃, and the internal oxidation of Cr and Ti occurred. At 950 °C, a fast initial stage with high weight gain was observed, followed by a steady-state stage with gradual weight gain. Additionally, a considerable change in the oxidation kinetic occurred. SEM-EDS observations and XRD results indicated that the external scale was relatively thick with a localized porous, preferential adherent, and a complex oxide scale was developed. This complex oxide scale consisted of an outermost thin layer composed of MnCr₂O₄?CCr₂O₃ mixed together with a small amount of isolated TiO₂, an intermediate relatively thick layer, composed of Cr₂O₃, and an innermost discrete layer formed at the scale/alloy interface, which enriched by Ni/NiO mixed with Ti-, Al-, and Fe-oxides. Finally, only the Al alloying element was internally oxidized to form Al₂O₃ fingers, which create a discrete and narrow internal oxidation zone. Al oxide was observed as a dark area and primarily grows along the alloy grain boundaries in the vicinity of the inward chromia pegs.     

High Temperature Oxidation Behavior of Alloy 617 and Haynes 230 in Impurity-Controlled Helium Environments

The high temperature oxidation behavior of alloy 617 and Haynes 230 have been investigated for VHTR intermediate heat exchanger applications. Oxidation tests were carried out for up to 500 h at 900 °C and 1000 °C in impure helium environments containing H₂, H₂O, CO, CO₂, and CH₄. The oxidation kinetics of the alloys followed a parabolic rate law in all cases. In the impure helium environments with very low oxygen, the external oxides of alloy 617 were composed of a Cr₂O₃ layer, TiO₂ ridges on the grain boundaries, and isolated MnCr₂O₄ grains on top of the Cr₂O₃ layer. On the other hand, those of Haynes 230 consisted of a Cr₂O₃ inner layer and a protective MnCr₂O₄ outer layer, which increased the oxidation resistance. The effect of small amounts of CH₄ and H₂ on the oxidation kinetics of the alloys was insignificant. Irregular oxide morphology, such as cellular Cr₂O₃ oxides for alloy 617 and MnCr₂O₄ platelets for Haynes 230, was formed in the impure helium environment at 900 °C. For Haynes 230, along with platelets, whiskers were frequently found at the tip of the MnCr₂O₄ oxide crystals.     

Effects of oxygen partial pressure and atomic oxygen on the microstructure of oxide scale of ZrB2–SiC composites at 1500 °C

The oxidation behaviour of ZrB₂-20 vol.% SiC composites was investigated based on the microstructural evolution of oxide scale under different oxygen partial pressures at 1500 °C, and the similar experiment was performed in atomic oxygen for comparison. The thickness of the oxide scale increases first and then gradually decreases as the pressure decreases, which is strongly dependent on both total pressure and oxygen partial pressure. The atomic oxygen significantly enhances the oxidation of ZrB₂–SiC composites, but has little effect on the microstructure of oxide scale. The oxidation mechanism of ZrB₂–SiC composites is also discussed in detail.     

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.     

Cyclic Oxidation Behavior of the Ti–6Al–4V Alloy

The cyclic oxidation behavior of the Ti–6Al–4V alloy has been studied under heating and cooling conditions within a temperature range from 550 to 850 °C in air for up to 12 cycles. The mass changes, phase, surface morphologies, cross-sectional morphologies and element distribution of the oxide scales after cyclic oxidation were investigated using electronic microbalance, X-ray diffractometry, scanning electron microscopy and energy dispersive spectroscopy. The results show that the rate of oxidation was close to zero at 550 °C, obeyed parabolic and linear law at 650 and 850 °C, respectively, while at 750 °C, parabolic—linear law dominated. The double oxide scales formed on surface of the Ti–6Al–4V alloy consisted of an inner layer of TiO₂ and an outer layer of Al₂O₃, and the thickness of oxide scales increased with an increasing oxidation temperature. At 750 and 850 °C, the cyclic oxidation resistance deteriorated owing to the formation of voids, cracks and the spallation of the oxide scales.     

Improving the High-Temperature Oxidation Resistance of TiAl Alloy by Anodizing in Methanol/NaF Solution

An aluminum- and fluorine-enriched anodic film was fabricated on TiAl alloy by anodizing in NaF-contained methanol solution. The high-temperature oxidation resistance and protection mechanism of the anodized TiAl alloy were investigated. It showed that the formation of aluminum-enriched oxide scale originates from halogen effect and quite small anodization current density is essential to improving the high-temperature oxidation resistance. Upon oxidation at 850 °C for 100 h, no cracks and/or spallation were exhibited on the anodized TiAl alloy. At temperature higher than 300 °C, titanium fluoride will sublimate, accompanying with the transformation of aluminum fluoride into protective Al₂O₃ layer, as was indicated by XPS analysis. This freshly generated Al₂O₃ layer, together with the anodization formed one, can efficiently inhibit the outward diffusion of Al and inward diffusion of oxygen, thereby improving the high-temperature oxidation resistance of the TiAl.     

Selective Oxidation of Chromium by O2 Impurities in CO2 During Initial Stages of Oxidation

This study shows that the corrosion behaviour of 12 wt% Cr steel in CO₂ at 550 °C is determined in the first stage of oxidation by reaction with O₂ impurities. Depending on the amount of theses impurities and the thermal ramp rate, selective oxidation of chromium could lead to the formation of a protective chromium-rich oxide. An oxidation model describing qualitatively the nature of the oxide layer formed in the initial period of oxidation is presented. From these observations, surface engineering processes for protecting 9–12 wt% chromium steels from fast corrosion rate have emerged.     

Volatilization and Transport Mechanisms During Cr Oxidation at 300 °C Studied In Situ by ToF-SIMS

The oxidation of chromium at 300 °C was investigated in situ by ToF-SIMS for three different oxygen pressures (\(P_{{{\text{O}}_{2} }} = 2.0 \times 10^{ - 7}\), 6.0 × 10^?7 and 2.0 × 10^?6 mbar). Sequential exposure to the ¹⁸O isotopic tracer was performed to reveal the governing transport mechanism in the oxide film. The evolution of the oxide thickness was monitored. Volatilization of Cr₂O₃ was evidenced. A model was used to describe the kinetics resulting from the measurements. Both the parabolic and volatilization constants showed a dependence on oxygen partial pressure like \(P_{{{\text{O}}_{2} }}^{ - 1/n}\), with n = 1.9 ± 0.1, indicating a defect structure mainly consisting of oxygen vacancies. The re-oxidation in ¹⁸O₂ shows a growth of the oxide layer at the metal/oxide interface, demonstrating an oxidation process governed by anionic transport via oxygen vacancies. The diffusion coefficient of oxygen in the oxide was determined by fitting the ToF-SIMS depth profiles. It is 2.0 × 10^?18 cm² s^?1.     

Investigation on the oxidation behaviour of gamma titanium aluminides coated with thermal barrier coatings

In the present study, the applicability of thermal barrier coatings (TBCs) on γ‐TiAl alloys was investigated. Two alloys with the chemical compositions of Ti‐45Al‐8Nb‐0.2B‐0.15C and Ti‐45Al‐1Cr‐6Nb‐0.4W‐0.2B‐0.5C‐0.2Si were used. Before TBC deposition, the specimens were pre‐oxidised in laboratory air or low partial pressure oxygen atmosphere. Yttria partially stabilised zirconia top coats were then deposited using electron‐beam physical vapour deposition (EB‐PVD). The oxidation behaviour of the γ‐TiAl specimens with TBC was studied by cyclic oxidation testing in air at 850 and 900 °C. Post‐oxidation analysis of the coating systems was performed using scanning electron microscopy with energy‐dispersive X‐ray spectroscopy (EDS). No spallation of the TBC was observed for pre‐oxidised specimens of both alloys when exposed to air at 850 °C for 1100 cycles of 1 h dwell time at high temperature. SEM micrographs of the thermally grown oxide scale revealed outer mixed TiO₂/Al₂O₃ protrusions with a columnar structure. The protrusions contained small particles of zirconia and a low amount of about 0.5 at% zirconium was measured by EDS analysis throughout this outer oxide mixture. The TBCs exhibited excellent adherence on the oxide scale. Intercolumnar gaps and pores in the root area of the TBC were filled with titania and alumina. Below the outer columnar oxide scale, a broad porous zone of predominant titania was observed. The transition region between the oxide scale and substrate consisted of a discontinuous nitride layer intermixed with alumina particles and intermetallic phases rich in niobium formed at the nitride layer/substrate interface. When thermally cycled at 900 °C, the oxide scales on the alloy Ti‐45Al‐8Nb‐0.2B‐0.15C pre‐oxidised in low partial pressure oxygen spalled off after 540 cycles. For the sample with TBC, spallation was observed after 810 cycles. Failure occurred in the thermally grown oxide near the oxide/nitride layer interface. Microstructural examinations revealed again oxide scales with columnar structure beneath the zirconia top coat and good adherence of the TBC on the thermally grown oxides formed at 900 °C.     

Influence of Moisture on the oxidation of γ-TiAl

The influence of water vapour on the oxidation of Ti-50 at.% Al was studied at 900°C. Thick, well-adherent oxide scales were formed consisting of an outer TiO₂ layer and an inner heterogeneous mixture of TiO₂ and Al₂O₃. The interface between these layers is marked by large pores and Al₂O₃ particles embedded in TiO₂. No compact Al₂O₃ barrier layer was observed. The oxidation leads to formation of a two phase, oxygen enriched subsurface zone, which is Al-depleted by inner oxidation of Al to Al₂O₃. The oxidation kinetics were followed by continuous thermogravimetry. Exposure in moist oxygen leads to an accelerated attack compared with oxidation in dry oxygen. In moist oxygen the rate is linear after a short transition period. The oxidation rate is influenced by water partial pressure and oxygen partial pressure.     

Isothermal Oxidation Comparison of Three Ni-Based Superalloys

Ni-based superalloys are used for high-temperature components of gas turbines in both industrial and aerospace applications due to their ability to maintain dimensional stability under conditions of high stress and strain. The oxidation resistance of these alloys often dictates their service lifetime. This study focuses on the isothermal oxidation behavior of three Ni-based superalloys, namely, polycrystalline cast IN738LC, single-crystal N5, and a ternary Ni-Fe-Cr (TAS) powder metallurgy alloy. The isothermal oxidation tests were conducted at 900 °C in the static air up to 1000 h, and the specific aspects studied were the oxidation behavior of these chromia-forming and alumina-forming alloys that are used extensively in industry. In particular, the behavior of oxide scale growth and subsurface changes were analyzed in detail using various techniques such as SEM, EDS, and AFM. From the isothermal oxidation kinetics, the oxidation rate constant, k _p, was calculated for each alloy and found to be; k _p = 2.79 × 10^?6 mg² cm^?4 s^?1 for IN738LC, k _p = 1.42 × 10^?7 mg² cm^?4 s^?1 for N5 and k _p = 1.62 × 10^?7 mg² cm^?4 s^?1 for TAS. Based on a microstructural analysis, IN738LC exhibited a continuous dense outer scale of Cr₂O₃ and discontinuous inner scale of Al₂O₃, whereas N5 and TAS showed a dense outer scale of Al₂O₃ alone. The results suggested that the N5 and PM-TAS alloys are more oxidation resistant than the IN738LC under these conditions.     

Microstructural Analysis of IN617 and IN625 Oxidised in the Presence of Steam for use in Ultra-Supercritical Power Plant

The nickel based alloys IN617 and IN625 that have been selected for their candidacy in the construction of the hottest regions of the supercritical steam cycle have been oxidised under isothermal conditions at 750 °C and atmospheric pressure in atmospheres of 100 % steam, 50/50 % steam/argon and air for up to 4,200 h. Both alloys developed a thin protective oxide under each condition. Scale thickness measurements using SEM micrographs were performed and showed that exposures in steam exhibited a higher rate of scale formation than exposures in air in both alloys. IN617 developed an extensive internal network of alumina which resulted in the formation of alloy protrusions into the scale altering scale growth kinetics, IN625 also formed alumina to a lesser extent. Voids formed in the matrix below the scale in both alloys in each environment. The extent of alumina formation alters the void morphology which eventually impacts the scale growth rate as inward scale growth occurred into the voids in IN625 but not in IN617.     

Oxidation of FeCrAlY Fibers at Low Oxygen Potentials

The oxidation of Fe-15Cr-5Al-0.3Y (wt.%) coupons and 22-μm-diameter fibers has been studied in a helium atmosphere containing ～150 ppm oxygen at temperatures of 750–950 °C. Thermogravimetric analysis was used to follow kinetics, and oxide scales were analyzed with scanning-electron microscopy, electron-microprobe analysis, and photostimulated luminescence. The observed kinetics behavior of the coupons and fibers is attributed to effects of both transitional aluminas and aluminum depletion in the alloy. Distinct differences are observed with the fibers as compared to the coupons at 900 and 950 °C, but similar behavior is observed at 850 °C. Pre-oxidation treatments of the fibers at 1,100 °C in air formed a thin layer of α-Al₂O₃ and slowed oxidation dramatically at 850 °C. The fibers showed aluminum depletion and formed mixed alumina-chromia scales, which appeared adherent and protective.     

Oxidation behaviour of zirconium diboride–silicon carbide ceramic composites under low oxygen partial pressure

The oxidation behaviour of ZrB₂-based ceramics under low oxygen partial pressure ranged from 0.5 to 1.5 kPa was investigated. Low oxygen partial pressure was found to have remarkable effect on phase composition of the surface and the structures of oxide scale. And the thickness and microstructures of oxide scale was characterized by using scanning electron microscopy and X-ray diffraction analysis. The results indicate that the oxidation mechanism of ZrB₂-based ceramics changes under low oxygen partial pressure, and the oxidation resistance increases with the reduction of oxygen partial pressure.     

Oxide Growth Characterization During Short-Time Oxidation of a Commercially Available Chromia-Forming Alloy (HR-120) in Air at 1,050 °C

This study focuses on the oxidation behavior of commercially available HR120 in air at 1,050 °C from 30 min to 100 h. The oxidation kinetics were first studied by thermogravimetry and isothermal exposure. The oxidation products were fully characterized using ex and in situ X-ray diffraction (XRD) and FEG-SEM observations. HR120 experienced at 1,050 °C a non protective transient stage and formed a multilayered oxide scale (SiO₂–Cr₂O₃–XCr₂O₄ with X = Mn and/or Fe, Ni). A series of complementary characterization methods (gold and isotopic marker experiments, photoelectrochemistry (PEC)) were implemented to elucidate the oxidation mechanism. The study identified a n-type semi-conductivity accompanied by an inward growth of the scale. Thus, assuming that diffusion in the oxide scale controlled chromia-scale growth, the oxygen vacancy was the major point defect governing the solid state transport. This result was attributed to the presence of a MnCr₂O₄ spinel layer at the top of chromia that strongly decreased the oxygen pressure at the interface spinel/chromia.     

Steam Oxidation Behavior of Advanced Steels and Ni-Based Alloys at 800 °C

This publication studies the steam oxidation behavior of advanced steels (309S, 310S and HR3C) and Ni-based alloys (Haynes^® 230^®, alloy 263, alloy 617 and Haynes^® 282^®) exposed at 800 °C for 2000 h under 1 bar pressure, in a pure water steam system. The results revealed that all exposed materials showed relatively low weight gain, with no spallation of the oxide scale within the 2000 h of exposure. XRD analysis showed that Ni-based alloys developed an oxide scale consisting of four main phases: Cr₂O₃ (alloy 617, Haynes^® 282^®, alloy 263 and Haynes^® 230^®), MnCr₂O₄ (alloy 617, Haynes^® 282^® and Haynes^® 230^®), NiCr₂O₄ (alloy 617) and TiO₂ (alloy 263, Haynes^® 282^®). In contrast, advanced steels showed the development of Cr₂O₃, MnCr₂O₄, Mn₇SiO₁₂, FeMn(SiO₄) and SiO₂ phases. The steel with the highest Cr content showed the formation of Fe₃O₄ and the thickest oxide scale.