F. Rouillard

Influence of CO2 purity on the oxidation of a 12Cr ferritic – martensitic steel at 550°C and importance of the initial stage

Abstract It has been shown that ferritic – martensitic (F/M) steels with 12 wt% Cr can form a protective oxide layer depending on the CO2 purity from the first stages of oxidation. The impurities which could explain this difference could be O2. In the case where O2 concentration in the gas phase was significant (>ppm), a thick duplex oxide layer was observed, whereas, if the O2 concentration was low (<ppm), a Cr rich oxide layer about hundred times thinner was formed. These results strongly suggested that O2 reacted before CO2 on the steel surface and that the protective oxide layer was formed by reactions between chromium and O2.

Corrosion Issues of High Temperature Reactor Structural Metallic Materials

Cooling helium of high temperature reactors (HTRs) is expected to contain a low level of impurities: oxidizing gases and carbon-bearing species. Reference structural materials for pipes and heat exchangers are chromia former nickel base alloys, typically alloys 617 and 230. And as is generally the case in any high temperature process, their long term corrosion resistance relies on the growth of a surface chromium oxide that can act as a barrier against corrosive species. This implies that the HTR environment must allow for oxidation of these alloys to occur, while it remains not too oxidizing against in-core graphite. First, studies on the surface reactivity under various impure helium containing low partial pressures of H 2 , H 2 O, CO, and CH 4 show that alloys 617 and 230 oxidize in many atmosphere at intermediate temperatures (up to 890-970°C, depending on the exact gas composition). However when heated above a critical temperature, the surface oxide becomes unstable. It was demonstrated that at the scalelalloy interface, the surface oxide interacts with the carbon from the material. These investigations have established an environmental area that promotes oxidation. When exposed in oxidizing HTR helium, alloys 617 and 230 actually develop a sustainable surface scale over thousands of hours. On the other hand, if the scale is destabilized by reaction with the carbon, the oxide is not protective anymore, and the alloy surface interacts with gaseous impurities. In the case of CH 4 -containg atmospheres, this causes rapid carburization in the form of precipitation of coarse carbides on the surface and in the bulk. Carburization was shown to induce an extensive embrittlement of the alloys. In CH 4 -free helium mixtures, alloys decarburize with a global loss of carbon and dissolution of the pre-existing carbides. As carbides take part in the alloy strengthening at high temperature, it is expected that decarburization impacts the creep properties. Carburization and decarburization degrade rapidly the alloy properties, and thus result in an unacceptably high risk on the material integrity at high temperature. Therefore, the purification system shall control the gas composition in order to make this unique helium atmosphere compatible with the in-core graphite, as well as with structural materials. This paper reviews the data on the corrosion behavior of structural materials in HTRs and draws some conclusions on the appropriate helium chemistry regarding the material compatibility at high temperature.

Comparison of the High Temperature Surface Reactivity in Impure Helium of Two Materials for Gas Cooled Reactors

Nickel base alloys Haynes 230 and Inconel 617 are of interest for gas cooled reactors. At high temperature in impure helium, they generally form surface chromium-rich oxides. However above a critical temperature called TA, the scales are not stable anymore and the chromia destruction comes with a production of carbon monoxide. Reactivity tests on model alloys, with and without carbon, prove that chromia is reduced by the carbon from the alloy. TA vs P(CO) curves were also plotted for the two commercial alloys based on the experimental determination of TA in various atmospheres with increasing partial pressures of carbon monoxide. Unexpectedly, both materials exhibit an almost identical behavior although a basic equilibrium approach suggests that the chromia scale would be reduced in different conditions due to the thermodynamic particularity of the interfacial alloy/scale system.

Thermodynamic Modelling of the Destruction of the Surface Cr2O3 on Alloy 230 in the Impure Helium Atmosphere of a Gas Cooled Reactor

Above a given temperature called TA, the chromium rich oxide which has been developed on the surface of Haynes 230® and model NiCrWC alloys at a lower temperature becomes unstable in impure helium: carbon monoxide is released. Actually, oxide is reduced by carbon from the alloy. A thermodynamic model is developed to rationalize the variation of TA as a function of the partial pressure of CO in the gas phase. It was found that, at the early stages of the scale reduction, the relevant reaction occurs at the oxide/metal interface between chromia and carbon from the alloy. The interfacial activity of carbon in the alloy can be calculated based on measurements of the interfacial weight percentage of chromium and using ThermoCalc® software. Excellent agreement is observed between experimental values of TA and theoretical predictions.

Direct measurements of the chromium activity in complex nickel base alloys by high temperature mass spectrometry

Chromium rich, nickel based alloys Haynes 230 and Inconel 617 are candidate materials for the primary circuit and intermediate heat exchangers (IHX) of (Very)-High Temperature Reactors. The corrosion resistance of these alloys is strongly related to the reactivity of chromium in the reactor specific environment (high temperature, impure helium). At intermediate temperature – 900°C for Haynes 230 and 850°C for Inconel 617 – the alloys under investigation are likely to develop a chromium-rich surface oxide scale. This layer protects from the exchanges with the surrounding medium and thus prevents against intensive corrosion processes. However at higher temperatures, it was shown that the surface chromia can be reduced by reaction with the carbon from the alloy [1] and the bare material can quickly corrode. Chromium appears to be a key element in this surface scale reactivity. Then, quantitative assessment of the surface requires an accurate knowledge of the chromium activity in the temperature range close to the operating conditions (T ≈ 1273 K). High temperature mass spectrometry (HTMS) coupled to multiple effusion Knudsen cells was successfully used to measure the chromium activity in Inconel 617 and Haynes 230 in the 1423- 1548 K temperature range. Appropriate adjustments of the experimental parameters and in-situ calibration toward pure chromium allow to reach accuracy better than ± 5%. For both alloys, the chromium activities are determined. Our experimental results on Inconel 617 are in disagreement with the data published by Hilpert [2]. Possible explanations for the significant discrepancy are discussed.

Initiation and propagation of a single pit on stainless steel using a local probe technique

Experiments about single pit initiation and propagation were performed on 316L stainless steel with the aim to determine the pitting corrosion behaviour for nuclear waste containers. The experimental setup permits to control the pit development at will and to create reproducible single pits in three dimensions. Radial and deep evolutions of a disc shaped pit were studied for propagation times of up to 10 hours. These evolutions were used to determine what limiting mechanism takes place during long-term pit propagation. Special attention has been paid to the chloride ion action on pitting. A minimum chloride concentration was found to be necessary in the bulk electrolyte to support pit propagation. The existence of a critical pit depth of 230 μm was also underlined.

Corrosion Issues of HTR Structural Metallic Materials

Cooling helium of HTRs is expected to contain a low level of impurities: oxidizing gasses and carbon-bearing species. Reference structural materials for pipes and heat exchangers are chromia-former nickel base alloys — typically alloys 617 and 230 — and, as is generally the case in any high temperature process, their long term corrosion resistance relies on the growth of a surface chromium-oxide that can act as a barrier against corrosive species. This implies that the HTR environment must allow for oxidation of these alloys to occur, while it remains not too oxidizing against in-core graphite. First, studies on the surface reactivity under various impure helium containing low partial pressures of H2, H2O, CO and CH4 show that alloys 617 and 230 oxidize in many atmospheres from intermediate temperatures up to 890–970°C, depending on the exact gas composition. However when heated above a critical temperature, the surface oxide becomes unstable: it was demonstrated that at the scale/alloy interface the surface oxide interacts with the carbon from the material. These investigations have established an environmental area that promotes oxidation. When expose in oxidizing HTR helium, alloys 617 and 230 actually develop a sustainable surface scale over thousands of hours. On the other hand if the scale is destabilized by reaction with the carbon, the oxide is not protective anymore and the alloy surface interacts with gaseous impurities. In the case of CH4-containg atmospheres, this causes rapid carburization in the form of precipitation of coarse carbides on the surface and in the bulk. Carburization was shown to induce an extensive embrittlement of the alloys. In CH4-free helium mixtures, alloys decarburize with a global loss of carbon and dissolution of the pre-existing carbides. As carbides take part to the alloy strengthening at high temperature, it is expected that decarburization impacts the creep properties. Carburization and decarburization degrade rapidly the alloy properties and thus result in an unacceptably high risk on the material integrity at high temperature. Therefore, the purification system shall control the gas composition in order to make this unique helium atmosphere compatible with the in-core graphite as well as with structural materials. This paper reviews the data on the corrosion behavior of structural material in HTR and draws some conclusion on appropriate helium chemistry regarding the material compatibility at high temperature.Copyright