Materials Science Forum Vols. 595-598

Abstract: Silicon-based ceramics are among the main candidates for high temperature structural components in aeronautic applications. One key drawback of silicon-based ceramics for these applications is the volatilization of the protective silica scale, in moisture and the resulting ceramic recession. Therefore, the further use of these ceramics components depends on the development of external protection against water vapour attack. Some of the most promising materials seem to be rare earth silicates. Based on much richer data in the bibliography, the purpose of this work is to investigate the influence of two yttrium silicates elaboration processes on both the capability to crystallize and the corrosion resistance in an oxidative moist atmosphere at high temperature. Taking into account the material’s morphology, composition and degree of crystallization, the composition (Y2SiO5 or Y2Si2O7) and the preferable synthesis process are discussed.

Abstract: The effect of reactive element additions (external doping as an yttrium-oxide coating on the metal) on the oxidation behaviour of a commercial FeCrAl alloy (Kanthal A1) has been investigated during isothermal exposures in air at 1373K. The scale growth kinetics of the bare alloy obey a parabolic rate law during the whole oxidation test whereas the kinetic curves of the yttrium-bearing specimen exhibit an initial transient stage during the first hours, followed by a parabolic regime. The yttrium addition to the bare alloy does not give the beneficial effect usually ascribed to the reactive elements. No significant oxidation rate improvement of the alloy is observed, the parabolic rate constants values obtained are roughly similar for the both specimens. In situ X-ray diffraction reveals a marked influence of the reactive element on the composition of the oxide scale. The oxide layer formed on the yttrium-bearing specimen revealed, in addition to α- alumina which is the main oxide also identified on the bare specimen, the presence of yttrium aluminates (YAlO3, Y3Al5O12) located in the outermost part of the layer.

Abstract: A strategy is proposed to cope with combined thermal fatigue and hot corrosion resistance affecting industrial coatings. It allows comparing different materials, coatings and geometries with respect to thermal cracking and then properly selecting protective coatings. It uses a thermo-mechanical model combining the heat transfer conditions, thermal and mechanical properties of the materials and the system geometry. The model is applied to two cases: (i) borided steel, with experimental support; (ii) multilayer coating made of a thermal barrier layer, aimed at reducing thermal gradients in the system, and a corrosion layer.

Abstract: Alloy 718 is known to be sensitive to oxidation assisted intergranular cracking. It is also demonstrated that the occurrence of jerky flow (also called Portevin-Le Châtelier effect) stops the intergranular damaging mechanism. As dynamic strain ageing is known to be linked with the alloy content of interstitial species, the aim of the present work is to study the effect of carbon, nitrogen and oxygen concentrations on the mechanical behaviour of thin tensile specimens tested under oxidation conditions close to those encountered industrially for turbo machine disks. Thanks to heat treatments performed under reducing atmosphere, the content of interstitial species in tested alloy 718 samples is gradually curbed. Tensile specimens were then tested between 550 and 700°C for the strain rate range [10-5, 10-1] s-1. The key point of this work is that, for a given testing temperature, the tensile tests clearly demonstrated that the transition from an intergranular fragile fracture mode to a transgranular ductile one was always linked with the occurrence of Portevin-Le Châtelier phenomenon but for slower strain rates in comparison with what was observed on the as received aged material tested in the same conditions. This shift of the transition of fracture mode through the lower strain rates remained true until a threshold value of the heat treatment time under reducing atmosphere. Specimens heat treated over this value systematically exhibited a fully transgranular ductile fracture mode, whatever the plastic flow regime was. Implication of such a finding on the intergranular embrittlement of alloy 718 by high temperature oxidation is then discussed.

Abstract: In this study, high temperature (T>500oC) oxidation behavior of two commercial Ni-base alloys and two experimental alloys, all containing more than 10% Molybdenum, is investigated. Experimental alloys were prepared from high purity materials using an arc-melting furnace under a protective environment. During tests, samples were exposed to the stagnant air environment of a high temperature furnace for predetermined times. Extent of oxidation was determined from sample mass change measurements as well as morphological and chemical analyses of the oxidation products. For analyses, a scanning electron microscope (SEM) equipped with backscattered electron (BE) and energy dispersive spectroscopic (EDS) detectors was used. Crystalline phases formed in the product scales over the alloy samples were identified by an x-ray diffractometer (XRD). Preliminary results indicate that although Mo in the alloy prevents the development of a protective oxide scale at the alloy surface, presence of alloying elements such as Cr or Al can decrease this negative effect of Mo on oxide scale formation.

Abstract: This paper presents comparative studies on the performance of two titanium alloys (Ti- 6Al-1Mn, Ti-45.9Al-8Nb) in an oxidizing atmosphere at 700 oC and 800 oC. Testing procedure comprised thermogravimetric measurements at a constant temperature and in thermal cycling conditions (1-h and 20-h cycles at constant temperature followed by rapid cooling). The overall duration of the cyclic oxidation tests was up to 1000 hours. The oxidized specimens were analyzed in terms of chemical composition, phase composition, and morphology (SEM/EDS, TEM/EDS, XRD). The extent and forms of alloy degradation were evaluated on the basis of microscopic observation of specimen fractures and cross-sections. Selected specimens were examined by means of XPS, SIMS and GDS. Oxidation mechanism of Ti-46Al-8Nb was assessed a two-stage oxidation method using oxygen-18 and oxygen-16. Apparently, the oxidation of this alloy proceeded in several stages. According to XPS, already after quite short reaction time, the specimens were covered with a very thin oxide film, mainly composed of aluminum oxide (corundum). A thicker layer of titanium dioxide (rutile) developed underneath. These two layers were typical of the oxidation products formed on this alloy, even when tested in thermal cycling conditions. In general, the scale had a complex multilayer structure but it was thin and adherent. Under the continuous layer of titania, there was a fine-grained zone composed of mixed oxides. The alloy/scale interface was marked with niobium-rich precipitates embedded in a titanium-rich matrix. There were some indications of secondary processes occurring under the initial continuous oxide layers (e.g. characteristic layout of pores or voids). Thickness of inner scale layers clearly increased according to parabolic kinetics, while that of the outer compact layer (mainly TiO2) changed only slightly. The distribution of oxygen isotopes across the scale/alloy interface indicated two-way diffusion of the reacting species – oxygen inward and metals outward diffusion. Silicon deposited on Ti-6Al-1Mn alloy positively affected scale adhesion and remarkably reduced alloy degradation rate.

Abstract: 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.