44 research outputs found

    Characterization of sulfur distribution in Ni-based superalloy and thermal barrier coatings after high temperature oxidation: a SIMS analysis

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    Sulfur segregation was characterized by secondary ion mass spectrometry (SIMS) in uncoated single-crystal Ni-based AM1 superalloys with various S contents and on NiPtAl, NiAl and NiPt bondcoats of complete TBC systems. In spite of technical difficulties associated with diffuse sputtered interfaces, an original sample preparation technique and a careful choice of analysis conditions enabled a chemical characterization of S distribution below metal/oxide interfaces. An initial heterogeneous distribution of S in as-received high S (3.2 ppmw) AM1 was measured. After oxidation, a S depletion profile formed, with a slope that depended on the initial bulk S content. GDMS measurements enabled a quantitative distribution of S in oxidized low S (0.14 ppmw) AM1 to be constructed and discussed in relation to equilibrium surface segregation of S on Ni. The quantity of S integrated in the thermally grown oxide (TGO) was estimated and found to be very similar to that measured from depletion found in the metal. Localized S enrichments in Pt-containing coatings are related to a possible beneficial trapping mechanism of Pt on the adherence of oxide scales

    Oxydation et carburation d'alliages modèles chromino-formeurs dans le dioxyde de carbone

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    La capture du carbone de combustion implique le transport de gaz riches en CO2 a haute temperature. Cette etude vise a preciser les facteurs controlant l'oxydation d'alliages chromino-formeurs dans ces environnements. Des alliages modeles Fe–Cr et Fe–Cr–Ni ont ainsi ete exposes a des melanges Ar–CO2–H2O a 650 et 800 °C, et les produits de reaction examines a l'aide de techniques de metallographie conventionnelles. La precipitation de carbures sous des couches d'oxyde indique une sursaturation en carbone a l'interface metal/oxyde, par rapport a l'atmosphere exterieure. Sur la base d'un modele d'equilibre thermodynamique local, les vitesses de carburation et fractions volumiques de precipites mesurees sont utilisees pour evaluer l'influence de la composition de l'oxyde et de la presence d'H2O dans le gaz sur le transport du carbone. En analysant la depletion en chrome dans l'alliage sous-jacent, nous montrons que la carburation limitee sous une couche de chromine n'altere pas la stabilite de l'oxyde. L'evolution morphologique des nodules d'oxydes riches en fer formes a la suite de la rupture localisee de la chromine est mise en relation avec la capacite de l'alliage a fournir du chrome a l'interface metal/oxyde. L'application de modeles de germination-croissance aux cinetiques de developement de nodules permet d'evaluer la resistance des couches de chromine via des frequences de germination determinees a partir des taux de recouvrement de nodules et des gains de masse des echantillons. Nous examinons enfin l'importance relative de la germination et de la croissance des nodules dans le controle de la performance globale des alliages en fonction de la temperature de reaction. ABSTRACT : Materials to convey hot CO2-rich gases are needed in carbon capture technologies currently being developed. This work is aimed at investigating the factors controlling the oxidation of chromia-forming alloys in these atmospheres. To do so, model Fe–Cr and Fe–Cr–Ni alloys were exposed to Ar–CO2–H2O gas mixtures at 650 and 800 °C,and the reaction products examined using conventional metallography techniques. Carbide precipitation beneath oxide scales reflects a carbon supersaturation at the metal/oxide interface relative to the external atmosphere: as a gradient of oxygen potential is established across the growing scale, an elevated carbon activity results at the interface if the scale transmits carbon. On the basis of a local equilibrium model, measured carburisation rates and precipitate volume fractions were used to evaluate the influence of oxide composition and of the presence of H2O in the gas on carbon uptake/transport in the scales. Limited carburisation beneath Cr2O3 scales was shown by means of an analysis of subscale chromium depletion not to alter the oxide stability. The morphological evolution of Fe-rich oxide nodules formed as a result of localised Cr2O3 failure was studied in relation to the alloy ability to supply chromium to the metal/oxide interface. Application of nucleation-growth models to the kinetics of nodule development allowed the resistance of Cr2O3 scales to be evaluated in terms of nodule nucleation rates determined from experimental nodule surface coverages and specimen weight gains. The relative importance of nodule nucleation and growth in determining the overall alloy performance as a function of reaction temperature is discussed

    Oxidation and carburisation of model chromia-forming alloys in carbon dioxide

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    Materials to convey hot CO2-rich gases are needed in carbon capture technologies currently being developed. This work is aimed at investigating the factors controlling the oxidation of chromia-forming alloys in these atmospheres. To do so, model Fe–Cr and Fe–Cr–Ni alloys were exposed to Ar–CO2–H2O gas mixtures at 650 and 800 °C,and the reaction products examined using conventional metallography techniques. Carbide precipitation beneath oxide scales reflects a carbon supersaturation at the metal/oxide interface relative to the external atmosphere: as a gradient of oxygen potential is established across the growing scale, an elevated carbon activity results at the interface if the scale transmits carbon. On the basis of a local equilibrium model, measured carburisation rates and precipitate volume fractions were used to evaluate the influence of oxide composition and of the presence of H2O in the gas on carbon uptake/transport in the scales. Limited carburisation beneath Cr2O3 scales was shown by means of an analysis of subscale chromium depletion not to alter the oxide stability. The morphological evolution of Fe-rich oxide nodules formed as a result of localised Cr2O3 failure was studied in relation to the alloy ability to supply chromium to the metal/oxide interface. Application of nucleation-growth models to the kinetics of nodule development allowed the resistance of Cr2O3 scales to be evaluated in terms of nodule nucleation rates determined from experimental nodule surface coverages and specimen weight gains. The relative importance of nodule nucleation and growth in determining the overall alloy performance as a function of reaction temperature is discussed

    Design of novel γ’ bondcoats and interdiffusion with Re-rich superalloys

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    Increasing the life of thermal barrier coating (TBC) systems critically relies on maintaining good adhesion between the bondcoat, the thermally grown oxide (TGO) and the topcoat. A common cause of failure, rumpling occurs as stress generated by oxide growth and thermal cycling results in creep of the mechanically weak bondcoat – this currently limits the life of EB-PVD TBCs with β coatings used in aircraft turbine blades and vanes. γ’ coatings are known to present a better creep strength than β coatings and thereby markedly reduce rumpling, while still offering adequate oxidation resistance. The higher solubility of reactive elements (RE) in γ’ also provides more flexibility in optimizing RE additions, as it limits the risk of overdoping; this can be used to further improve TGO adhesion. Furthermore, γ’ compositions can, by essence, be adjusted to reduce the chemical potential mismatch with the substrate; this in turn will help curb the development of secondary reaction zones, which have become an issue when β coatings are used on Re-containing superalloys. The poster will present recent efforts made at ONERA in the development of new γ’ compositions for Re-rich substrates. Our current design strategy focuses on limiting substrate-coating interdiffusion and the associated loss of load-bearing section in the alloy. As mechanical properties improve and the bondcoat Al content is reduced, however, the bondcoat ability to maintain exclusive Al2O3 formation throughout extended cycling becomes critical to the system durability. Coating compositions are thus adjusted to a given alloy following the “equilibrium coating” concept, and then slightly modified to help maintain an appropriate composition relative to oxidation resistance. Compositions are assessed through the study of interdiffusion profiles obtained from both experiments and numerical simulations via a finite-difference method

    Experimental study and thermodynamic modeling of the Al–Co–Cr–Ni system

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    A thermodynamic database for the Al–Co–Cr–Ni system is built via the Calphad method by extrapolating re-assessed ternary subsystems. A minimum number of quaternary parameters are included, which are optimized using experimental phase equilibrium data obtained by electron probe micro-analysis and x-ray diffraction analysis of NiCoCrAlY alloys spanning a wide compositional range, after annealing at 900 °C, 1100 °C and 1200 °C, and water quenching. These temperatures are relevant to oxidation and corrosion resistant MCrAlY coatings, where M corresponds to some combination of nickel and cobalt. Comparisons of calculated and measured phase compositions show excellent agreement for the β–γ equilibrium, and good agreement for three-phase β–γ–σ and β–γ–α equilibria. An extensive comparison with existing Ni-base databases (TCNI6, TTNI8, NIST) is presented in terms of phase compositions

    Oxidation and carburisation of model chromia-forming alloys in carbon dioxide

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    La capture du carbone de combustion implique le transport de gaz riches en CO2 a haute temperature. Cette etude vise a preciser les facteurs controlant l'oxydation d'alliages chromino-formeurs dans ces environnements. Des alliages modeles Fe Cr et Fe Cr Ni ont ainsi ete exposes a des melanges Ar CO2 H2O a 650 et 800 C, et les produits de reaction examines a l'aide de techniques de metallographie conventionnelles. La precipitation de carbures sous des couches d'oxyde indique une sursaturation en carbone a l'interface metal/oxyde, par rapport a l'atmosphere exterieure. Sur la base d'un modele d'equilibre thermodynamique local, les vitesses de carburation et fractions volumiques de precipites mesurees sont utilisees pour evaluer l'influence de la composition de l'oxyde et de la presence d'H2O dans le gaz sur le transport du carbone. En analysant la depletion en chrome dans l'alliage sous-jacent, nous montrons que la carburation limitee sous une couche de chromine n'altere pas la stabilite de l'oxyde. L'evolution morphologique des nodules d'oxydes riches en fer formes a la suite de la rupture localisee de la chromine est mise en relation avec la capacite de l'alliage a fournir du chrome a l'interface metal/oxyde. L'application de modeles de germination-croissance aux cinetiques de developement de nodules permet d'evaluer la resistance des couches de chromine via des frequences de germination determinees a partir des taux de recouvrement de nodules et des gains de masse des echantillons. Nous examinons enfin l'importance relative de la germination et de la croissance des nodules dans le controle de la performance globale des alliages en fonction de la temperature de reaction.Materials to convey hot CO2-rich gases are needed in carbon capture technologies currently being developed. This work is aimed at investigating the factors controlling the oxidation of chromia-forming alloys in these atmospheres. To do so, model Fe Cr and Fe Cr Ni alloys were exposed to Ar CO2 H2O gas mixtures at 650 and 800 C,and the reaction products examined using conventional metallography techniques. Carbide precipitation beneath oxide scales reflects a carbon supersaturation at the metal/oxide interface relative to the external atmosphere: as a gradient of oxygen potential is established across the growing scale, an elevated carbon activity results at the interface if the scale transmits carbon. On the basis of a local equilibrium model, measured carburisation rates and precipitate volume fractions were used to evaluate the influence of oxide composition and of the presence of H2O in the gas on carbon uptake/transport in the scales. Limited carburisation beneath Cr2O3 scales was shown by means of an analysis of subscale chromium depletion not to alter the oxide stability. The morphological evolution of Fe-rich oxide nodules formed as a result of localised Cr2O3 failure was studied in relation to the alloy ability to supply chromium to the metal/oxide interface. Application of nucleation-growth models to the kinetics of nodule development allowed the resistance of Cr2O3 scales to be evaluated in terms of nodule nucleation rates determined from experimental nodule surface coverages and specimen weight gains. The relative importance of nodule nucleation and growth in determining the overall alloy performance as a function of reaction temperature is discussed.TOULOUSE-INP (315552154) / SudocSudocFranceF

    Mechanism of breakaway oxidation of Fe–Cr and Fe–Cr–Ni alloys in dry and wet carbon dioxide

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    Model Fe–Cr and Fe–Cr–Ni alloys were exposed to Ar–CO2 and Ar–CO2–H2O gas mixtures at 650°C. While all alloys initially formed protective Cr2O3 scales, nucleation and growth of iron-rich oxide nodules resulted in some cases in breakaway oxidation. The conditions leading to departure from the protective stage are discussed in terms of Cr2O3 thermodynamic and kinetic stability. The morphological and compositional evolutions accompanying nodule development were examined. The influence of carbide precipitation on alloy chromium diffusion and the ability of the alloy to form and maintain Cr-rich oxide layers was investigated

    Kinetics of breakaway oxidation of Fe–Cr and Fe–Cr–Ni alloys in dry and wet carbon dioxide

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    Model Fe–Cr and Fe–Cr–Ni alloys were reacted in Ar–CO2 and Ar–CO2–H2O gas mixtures at 650°C. Initially protective oxidation, due to Cr2O3 formation, was usually followed by a transition to rapid oxidation, associated with Fe-rich oxide nodule development. Nodule surface coverage and overall weight gains are modelled on the basis of continued nucleation of nodules, and their diffusion-controlled growth. In general, water vapour accelerated nucleation. Alloying with nickel decreased average nucleation rates, but austenitic alloys showed large variations in nucleation susceptibility with grain orientation. Slower nodule growth induced by high chromium and nickel levels counteracted the effects of frequent nucleation

    Carburisation of ferritic Fe–Cr alloys by low carbon activity gases

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    Model Fe–Cr alloys were exposed to Ar–CO2–H2O gas mixtures at 650 and 800 °C. At equilibrium, these atmospheres are oxidising to the alloys, but decarburising (aC ≈ 10−15 to 10−13). In addition to developing external oxide scales, however, the alloys also carburised. Carbon supersaturation at the scale/alloy interface relative to the gas reflects local equilibrium: a low oxygen potential corresponds to a high pCO/pCO2 ratio, and hence to a high carbon activity. Interfacial carbon activities calculated on the basis of scale–alloy equilibrium are shown to be in good agreement with measured carburisation rates and precipitate volume fractions, providing support for the validity of the thermodynamic model
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