High Temperature Steam Oxidation Research Articles

A thermogravimetric comparative study of the high temperature steam oxidation of bare and pre-oxidized Zircaloy-4, M5Framatome and Optimized ZIRLO™

For Loss of Coolant Accident (LOCA) analysis, high-temperature oxidation kinetics in steam of Zircaloy-4 and the two Nb-bearing alloys used in French Pressurized Water Reactors (PWRs), M5Framatome11M5 and M5Framatome are trademarks or registered trademarks of Framatome or its affiliates, in the USA or other countries. and Optimized ZIRLO™22Optimized ZIRLO is a trademark or registered trademark of Westinghouse Electric Company LLC, its affiliates and/or its subsidiaries in the United States and may be registered in other countries throughout the world. All rights reserved. Unauthorized use is strictly prohibited. Other names may be trademarks of their respective owners., have been studied using Thermo-Gravimetric Analysis (TGA) technique in the temperature range of 900–1200 °C. A specific test procedure allowing the use of a high steam flow rate and good steam supply to the whole specimen surface, as well as fast heating of the specimen, has been developed. Clean kinetic data, not affected by steam starvation, were obtained on the bare, as-received alloys. For as-received claddings, oxidation kinetics are comparable and close to parabolic for the three alloys at 1100 °C and above. Below 1100 °C, a significant deviation from the parabolic kinetic regime was observed, and M5 Framatome oxidizes slower than Zircaloy-4 and Optimized ZIRLO. Thanks to the fast-heating protocol, the influence of pre-oxidation, simulating corrosion in normal reactor operation, could be investigated, avoiding evolution of the pre-oxidation scale during a slow, long heating phase. Pre-oxidized Zircaloy-4 and M5 Framatome were investigated. A strong protective effect is observed below 1200 °C, while at 1200 °C, the pre-oxidation layer appears to be much less protective, possibly due to the monoclinic to tetragonal zirconia phase transformation.

Reflood oxidation performances of Cr-coated Zr-Sn-Nb alloy cladding tubes at 1000 °C∼1200 °C

Reflood plays an important role in preventing the serious accident process. In this paper, the reflood oxidation performances of Cr-coated Zr-Sn-Nb alloy cladding tubes at 1000 °C, 1100 °C and 1200 °C were studied by high-temperature steam oxidation followed by in-situ water quenching. The oxidation kinetics, macroscopic morphology, phase transformation and microstructural evolution were investigated. Cr coating can provide excellent anti-reflood oxidation protection for Zr-Sn-Nb alloy, resulting in an oxidation rate constant of only 1/4–1/7 of that of uncoated Zr-Sn-Nb alloys. However, the cladding tube degraded into fragments due to excessive thermal stress during the in-situ water quenching after reflood oxidation at 1200 °C for 4000 s. After reflood oxidation at 1000 °C and 1100 °C, the most prominent feature of the surface is a porous flocculation structure main due to the formation of volatile products, while after 1200 °C, it is a fine mackerel scale-like structure accompanied by protruding whiskers main owing to Cr3+ rapidly migrates outward to the outer surface via short circuit paths. After oxidation, the cross-section of Cr-coated Zr-Sn-Nb alloys exhibits a multi-layer structure. The thickness of each layer changes approximately linearly with oxidation time. However, due to the redox reaction, compared to that after oxidation for 2000s, the Cr2O3 layer becomes thinner and the residual Cr coating becomes thicker after oxidation at 1200 °C for 4000 s.

Microstructural characteristics of multilayers and interfaces of Cr-coated Zircaloy-4 cladding based on elemental diffusion under high-temperature steam oxidation

A dense and well-adhered Cr coating was prepared on the surface of Zircaloy-4 cladding by arc ion plating. Oxidation tests on Cr-coated Zircaloy-4 claddings were conducted in steam at 700-1300 °C. The surface morphology and cross-sectional microstructure were investigated using SEM, EBSD, FIB and TEM techniques. The results showed that no significant cracking or spalling was observed after oxidation. The oxidized cross-sections showed characteristics of multilayers and interfaces. From the outer to the inner layer, these are, in order, a Cr oxide film and Sn precipitates on its grain boundaries, an amorphous structural layer, a residual Cr coating and (Zr,Cr)xOy oxides on its grain boundaries, a C15-type Zr(Cr,Fe)2 intermediate layer, and a (Cr,O)-rich substrate Zr. The multilayers and interfaces alter the oxygen diffusion path and reduce the oxygen diffusion rate, thus slowing down the oxidation process of the substrate. In addition, the location and cause of amorphous structures and Kirkendall cavities and their effect on microstructure and adhesion properties were discussed.

Effects of Al and Si elements on oxidation behavior in 1000–1200 °C steam for PEO/CrAlSi composite coating on Zr alloy

A PEO/CrAlSi composite coating of ~10 μm thick on Zr–2 alloy was prepared by duplex plasma electrolytic oxidation (PEO) and filtered cathode vacuum arc deposition (FCVAD) techniques. The high temperature steam oxidation behavior of bare and PEO/CrAlSi–coated Zr alloys was performed in 1000–1200 °C. Their morphologies, microstructures, compositions and phase components were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X–ray diffraction (XRD) and glow discharge optical emission spectrometer (GDOES). The effects of Al and Si elements on multilayers microstructure evolution of coated Zr–2 alloy at steam atmosphere were discussed. It was found that the composite coating significantly improved the high–temperature steam oxidation resistance of Zr–2 alloy. The mass gains of the PEO/CrAlSi–coated Zr–2 alloy after 3600 s exposure in 1000 °C, 1100 °C and 1200 °C steam were 28 %, 29 % and 44 % of the bare alloy. Through the oxidations, Al diffused both inward and outward to the substrate and the surface regions, respectively. Formation of a top oxide layer (Al2O3, Cr2O3) greatly suppressed the inward oxygen diffusion. The Si enrichment in the PEO interlayer formed a Zr2Si layer, which inhibited the Cr-Zr interdiffusion at 1000 °C and 1100 °C. At 1200 °C, the Zr2Si layer was oxidized and the CrZr2 phase was formed in the Zr alloy substrate especially at the β–Zr/α–Zr(O) interface.

Oxidation resistance of Mo/Cr bilayer coating on Zr alloy in a 1200 °C steam environment

The Cr-coated Zr alloys demonstrate excellent resistance to high-temperature steam oxidation. However, the rapid diffusion pathways for oxygen formed by the inter-diffusion between the coating and alloy at high temperatures significantly affect the steam oxidation resistance of the coated alloys. To address this issue, we developed a Mo/Cr bilayer coating on Zr alloy by a combination of dc-MS and HiPIMS surface treatments. The coating exhibits outstanding steam oxidation resistance at high temperatures, resulting in a mass gain approximately 86.6% and 44.1% lower than that of the bare Zr alloy and Cr coating, respectively, after 30 min of steam oxidation at 1200 °C. This is mainly because, during the oxidation process, the Mo interface layer undergoes a transformation into a thin and high-quality double diffusion layer structure, effectively avoiding high-temperature inter-diffusion between the Cr coating and Zr alloy, thereby inhibiting the formation of oxygen diffusion pathways.

An Overview of Mechanisms of the Degradation of Promising ATF Cladding Materials During Oxidation at High Temperatures

AbstractAccident tolerant fuel (ATF) cladding is a new type of nuclear fuel cladding designed to improve the safety and performance of nuclear reactors. In this paper, the kinetics and degradation mechanisms during high-temperature oxidation in steam of the three most promising ATF cladding materials, i.e., chromium-coated zirconium alloys, FeCrAl alloys, and silicon carbide-based composites, are described. Each system has its own degradation mechanisms leading to different maximum survival temperatures. After providing general information and data to understand the oxidation and degradation processes, illustrative examples obtained at the Karlsruhe Institute of Technology are given for each type of cladding. The maximum temperatures at which the barrier effect of the cladding can be maintained for a reasonable period of time during nuclear accident scenarios are 1200–1300 °C for Cr-coated Zr alloys, 1400 °C for FeCrAl alloys, and 1700 °C for SiC-based composite claddings.

High-temperature steam oxidation experiment of molten zirconium alloy

In this study, we investigate the steam oxidation behaviors of molten zirconium alloy at exceptionally high temperatures of 1870 ℃ and 1970 ℃. A specialized high-temperature steam oxidation apparatus was established to conduct the steam oxidation experiment. The experiments yielded crucial data including oxidation weight gain results, macroscopic appearance of the oxide surface, and section morphology. Several new phenomena: α-Zr(O) precipitates and two-layer oxide structure, were observed in this study. Based on these observations, a complete mechanism of molten zirconium oxidation in steam was developed, providing an interpretive framework for the oxidation observed in this experiment. This newly proposed mechanism reevaluates the formation process of nonceramic precipitates in the molten bulk and its consequential impact on oxidation kinetics at temperatures below 2000 ℃.

High-temperature steam oxidation behavior and failure mechanisms of Al alloyed Cr coatings on Zr-4 alloy

In this work, the Al content-dependent microstructure evolution and oxidation behavior of co-sputtered CrAl alloyed coatings on Zr-4 alloy were systematically investigated in 1000 ℃ steam. Experimental results demonstrated that the microstructure of generated oxide scale transformed from a Cr2O3 oxide layer with embedding discrete α-Al2O3 particles at low Al contents to a continuous outer (α, θ)-Al2O3 and inner Cr2O3 bi-oxide layer at high Al contents. However, there appeared a unique eutectoid-like Cr2O3/α-Al2O3 multilayered oxide scale in Cr-18.3Al coating, which conferred the sample with optimal oxidation resistance. The underlying oxidation mechanisms were rationalized by revealing the Al content dominated selective oxidation behavior.

High-Temperature Steam and Atmospheric Oxidation Characteristic of a Heat-Resistant SP2215 Steel

The high-temperature oxidation performance of SP2215 has become an important issue when they were used as superheaters and reheaters exposed to two different high-temperature environments. In this study, the oxidation behavior of SP2215 steel was investigated under steam and an atmosphere of 650–800 °C for 240 h. The microstructural and chemical characterization of the samples were performed using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), a glow discharge optical emission spectrometer (GD-OES), and atomic force microscope (AFM). The kinetic curves of oxidation revealed excellent oxidation resistance under both environments, but significant different oxidation characteristics, oxide film composition, and structure were obvious. In the steam experiment, selective intergranular oxidation was evident at relatively low temperatures, which was attributed to the preference absorption of supercritical water molecules at the grain boundary. Conversely, a double-layer structure of outer Fe2O3 and a small amount of Fe3O4 and inner Cr2O3 was formed uniformly at 800 °C. In the high-temperature atmosphere experiment, a protective chromium film was dominant at 650–700 °C, and a loose multicomponent oxide film was formed at 750–800 °C, primarily consisting of Cr2O3, spinel FeCr2O4, and CuO.

Steam oxidation properties of graphene reinforced bioinspired laminated CoCrFeNiMn high-entropy alloy matrix composites at 1000 ℃

Laminated CoCrFeNiMn high-entropy alloy (HEA) matrix composites reinforced with 1.0 wt% graphene nanoplatelets (GNPs) were fabricated by mechanical ball milling and flake powder metallurgy, and were isothermal oxidized at 1000 ℃ for 100 h. Vacuum hot-pressure sintering (VHPS) shows a distinct nacre structure with the microstructure composed of FCC matrix phase, Cr23C6, CrMn1.5O4 precipitated phases, numerous dislocations and twins. High-temperature oxidation tests showed that the composites had mass gains at 12 h intervals from 12 to 100 h respectively. The oxidation kinetic curve changes from a linear pattern in the early stages to an exponential pattern in the later stages, which demonstrates better long-term oxidation resistance. The anisotropy of the laminated structure results in excellent resistance to high-temperature steam oxidation in the vertical lamellar direction. Observation of the cross-section reveals that although Cr2O3 (inner layer) is present, (Mn, Cr)3O4 and Mn3O4 are the dominant oxides (outer layer). Elemental depletion zones for Mn and Cr exist in the region of the matrix near the oxide scales. The results show that the oxidation resistance of the laminated GNPs/CoCrFeNiMn composites is mainly influenced by the diffusion of Mn and Cr elements, the microstructure of the laminations and the internal oxidation.

High-temperature steam oxidation study of irradiated FeCrAl defueled specimens

Post irradiation examinations (PIE) were performed on irradiated iron-chromium-aluminum (FeCrAl) specimens. These FeCrAl specimens were fabricated at the US Department of Energy's Oak Ridge National Laboratory (ORNL). The experimental setup involved subjecting FeCrAl cladding, along with UO2 pellets, to irradiation in the Idaho National Laboratory Advanced Test Reactor (ATR). In parallel, the FeCrAl alloy tubing without UO2 pellets was irradiated at ORNL's High Flux Isotope Reactor (HFIR). After irradiation, the ATR-irradiated rodlet was transported to an ORNL hot cell, where it was sectioned into multiple samples for the PIE and severe-accident testing. The sectioning process revealed that the fuel was not bonded to the cladding and could be easily detached from sectioned cladding slices. Microstructural analysis of the fuel cross sections demonstrated no significant interaction between the fuel and the cladding. Additionally, high-temperature steam oxidation tests on defueled cladding segments showed minimal oxygen uptake even at 1200 °C. The ATR-irradiated specimens began to exhibit signs of enhanced oxidation upon reaching a temperature of 1300 °C. Furthermore, enhanced oxidation was observed on the inner surface of the ATR-irradiated FeCrAl specimen, which had been subjected to 1300 °C for a duration of 1 min. By contrast, high-temperature steam oxidation experiments indicated that the HFIR-irradiated FeCrAl cladding provided good thermal stability when exposed to 1300 °C for up to 4 h. Comparative analysis encompassing the oxidation behavior of the ATR-irradiated fueled FeCrAl, HFIR-irradiated unfueled FeCrAl, and unirradiated FeCrAl suggests that the fuel–cladding interaction, although not visible via standard microscale electron microscopy measurements, may accelerate the deterioration of FeCrAl cladding in beyond-design-basis accident scenarios.

Microstructure, high-temperature corrosion resistance and oxidation properties of (TiVZrCrAl)N high entropy nitride coatings with different N2/Ar ratios

The (TiVZrCrAl)N high-entropy nitride coatings were prepared on Zr-4 alloy substrates by reactive magnetron sputtering with different N2/Ar pressure ratios I values. The microstructure, nanohardness, high-temperature corrosion and steam oxidation resistance properties of the coatings were investigated. The results showed that the thickness of the coating first decreaseds and then increaseds with decreasing N2/Ar pressure ratio, but the hardness first increaseds and then decreaseds. All the coatings exhibited B1-NaCl structure. When I = 1/12, the (TiVZrCrAl)N coating had excellent high-temperature corrosion resistance and steam oxidation performance. The high-temperature steam oxidation mechanisms of the (TiVZrCrAl)N coatings were analyzed in detail.

Effect of grain refinement on high temperature steam oxidation of an FeCrAl alloy

FeCrAl alloys are promising candidates to replace Zr alloys as fuel cladding materials in nuclear light-water reactors. Grain refinement has been indicated to improve irradiation resistance. To enhance corrosion resistance as well, the effects of grain refinement on steam corrosion behavior were investigated in this work. Samples of Kanthal D alloy (Fe-21Cr-5Al) with two different grain sizes (coarse-grained and ultrafine-grained) were exposed to steam at 1200 °C for 2 hrs. Results indicate improved steam corrosion resistance in ultrafine-grained Kanthal D with formation of a thinner protective Al oxide layer and the presence of a thin underlying Cr oxide layer.

Oxidation behavior of Cr1-xAlx coated Zr-4 alloy under 1200 °C high temperature steam environment

In present study, the 1200 °C high temperature steam (HTS) oxidation behavior of Cr1-xAlx coating with different Al content (0, 35 at.%, 50 at.% and 70 at.%) deposited on Zr-4 alloy by multi-arc ion plating (MAIP) has been investigated. The results demonstrate that Cr65Al35 coating has optimal protectiveness due to the formation of compact and continuous double oxide layer, consisting of outer Al2O3-rich layer and inner Cr2O3-rich oxide layer. The severe consumption of Al element for Cr50Al50 coating during the oxidation process, leading to vacancies formation and a decrease in enrichment degree of the Al2O3 in outer oxide layer. The protectiveness of pure Cr coatings is reduced by the formation of volatile CrO3, which induces the micro voids and provides a channel for the oxygen diffusion. The Cr30Al70 coatings shows the worst protective effect because of the serious diffusion behavior of Al into Zr alloy, providing the diffusion channel for O element and causing the substrate to oxidize essentially. The effect of Al content on the oxidation resistance of Cr1-xAlx coatings is discussed in detail.

High-temperature steam oxidation resistance of Cr[sbnd]Si substitutional solid solution coating on Zr-4

Zirconium alloy has been used as fuel cladding in LWR for a long time. However, during the loss-of-coolant accident, the zirconium alloy cladding will be exposed to steam environment at 1200 °C, and the damage to the cladding is inestimable. Therefore, in this study, Cr and CrSi coating were prepared on the surface of Zr-4 alloy by magnetron sputtering, and their steam oxidation behaviors at 1200 °C were investigated. The Cr-coated Zr-4 revealed an α-Zr(O) layer with ZrO2 particles at the interface after oxidation at 1200 °C. However, the CrSi coated Zr-4 exhibited excellent oxidation resistance due to the introduction of Si atoms. During oxidation, the diffusion barrier of Zr2Si layer with ZrSi ionic bonds was formed in situ because of the inward diffusion of Si atoms, which effectively inhibited the inter-diffusion of Zr and Cr. The aggregation of ZrO2 at the grain boundaries of the coating was prevented, which cut off the short-circuit path of oxygen diffusion inward. Moreover, the first principles calculation was employed to compare the adsorption energies of the external Zr atoms by Zr2Si and ZrCr2 diffusion layers. The adsorption energy of the in situ formed Zr2Si layer for Zr atoms is higher than that of the ZrCr2 layer, which is evidence of the barrier effect of the Zr2Si layer. Thus, the CrSi coated Zr-4 in this work showed a high prospective in the practical applications.

Improving the high-temperature oxidation resistance of CrN coating by gradient deposition considering internal stress effects

In this study, two different CrN coatings were deposited on the surface of Zr-4 via a multi-arc ion-plating method using gradient and non-gradient deposition processes. The effects of two deposition processes on the high-temperature oxidation resistance and internal stress of the coatings were investigated. The microstructure and phase structure of the coatings were characterized by scanning electron microscopy, X-ray diffraction (XRD), and energy dispersive spectrometry. The high-temperature oxidation resistance of the specimens was investigated by performing thermal shock experiments and simulated loss-of-coolant accident high-temperature steam oxidation experiments. The residual stresses of both coatings during deposition were determined by XRD analysis. In addition, the thermal stresses of both coatings during the high-temperature oxidation tests were modeled and calculated. Under long-term high-temperature oxidation conditions, the gradient-deposited CrN coating exhibited improved high-temperature oxidation resistance performance than that exhibited by non-gradient-deposited CrN coating. In addition, the residual stresses of gradient-deposited CrN coating during deposition and thermal stresses during high-temperature oxidation were significantly lower than those of the non-gradient-deposited CrN coating. The results obtained herein confirm the promising potential of gradient-deposited CrN coating as an accident-tolerant fuel cladding material.

Microstructural evolution of intermetallic phase precipitates in Cr-coated Zirconium alloy cladding in high-temperature steam oxidation up to 1400 °C

The steam oxidation on the Cr-coated Zry cladding was studied up to 1400 °C to understand the oxidation behavior under the accidental conditions. The double-sided oxidation test showed that Cr coating can protect Zry cladding till 1200 °C/5 min. However, at T ≥ 1300 °C/5 min, Cr coating can no longer protect Zry cladding and the intermetallic phase of the Zr(Cr, Fe)2 phase that precipitated within the Zry formed as globule microstructures. In addition, the transition of the intermetallic phase within the Zry substrate from the solid to liquid phases was observed, where it was determined at 1400 °C/30 min within the ZrO2 phase.

Effect of aging and α’ segregation on oxidation and electrochemical behavior of FeCrAl alloys

FeCrAl alloys are promising candidates for next generation nuclear fuel cladding applications due to their high resistance to hydrothermal corrosion, high temperature steam oxidation, fretting, and creep properties. However, a potential area of concern for FeCrAl alloys is the precipitation of Cr-enriched α’ phase which could have an implication on the mechanical, oxidative degradation as well as electrochemical behavior. Studies in this area are limited since most of the past applications of FeCrAl alloys have been in high temperatures above the miscibility gap. In this work, we investigate the high temperature oxidation and electrochemical behavior of a modified APMT (Fe21Cr5Al3Mo) alloy in unaged condition in comparison with a thermally aged condition having α’ phase segregation. The α’ is shown to have no major role in steam oxidation resistance of FeCrAl alloys. The electrochemical behavior in chloride environments shows that the presence of α’ slightly reduces the pitting potential but shows an overall increase in polarization resistance indicating that α’ may enhance corrosion resistance in chloride environments by increasing passivation.

Microstructure dependent burst behavior of oxide dispersion–strengthened FeCrAl cladding

Oxide dispersion–strengthened (ODS) FeCrAl alloys are an advanced cladding material that combines the high-temperature steam oxidation resistance of conventional wrought FeCrAl with the irradiation resistance and high-temperature strength of nanostructured ferritic alloys. In the present study, the effect of microstructure on the performance of the ODS FeCrAl alloy system in light-water reactor–accident scenarios is evaluated using a combination of experimentation and modeling. ODS FeCrAl alloy with nominal composition Fe-12Cr-6Al-0.3Zr-0.3Y2O3 was produced into a thin-walled tube via high-precision tube rolling. A portion of the as-received (AR) tube was subjected to a full recrystallization heat treatment. Both variants were subjected to burst testing at Oak Ridge National Laboratory’s Severe Accident Test Station. The recrystallized tube exhibited burst temperature margins 200 °C higher than that of C26M, whereas the AR tube only achieved burst properties comparable to the wrought FeCrAl alloy. The burst experiments were simulated in the BISON finite element code through the development of new viscoplastic material databases for each heat treatment condition, informed by high temperature tensile tests of tube specimens and existing literature data on creep mechanisms. Finally, an ODS FeCrAl burst criterion was obtained using simulated burst experiments across the entire range of test conditions.

Improved oxidation resistance of Cr/FeCrAl coating on Zr alloy in high-temperature steam environment

A new bi-layer Cr/FeCrAl coating was successfully fabricated on the Zr-4 plates through multi-arc ion plating in order to take advantage of the two materials of FeCrAl and Cr. The high-temperature steam oxidation behavior of the Cr/FeCrAl-coated Zr-4 at 1000–1200 °C was investigated and compared with that of bare and single-layer FeCrAl-coated Zr-4. Various analytical techniques including scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used for the microstructural and compositional analysis of the as-deposited and oxidized samples. Results indicated that the FeCrAl-coated Zr-4 could only withstand up to 1000 °C because of the severe FeZr interdiffusion. Whereas the introduction of the Cr interlayer effectively prevented fast FeZr interdiffusion and consequently improves the overall oxidation resistance of the Zr substrate below 1200 °C steam environment. After 1100 °C steam oxidation, the weight gain of the Cr/FeCrAl-coated Zr-4 was about 8 times and 2 times lower than that of the uncoated and FeCrAl-coated Zr-4 alloys, respectively. These facts make possible the use of FeCrAl coating on Zr cladding which has excellent high-temperature mechanical properties and oxidation resistance.