Papers by Author: G. Bonnet

Abstract: Novel, unconventional type of high temperature coating systems can be elaborated by depositing Al micro-particles on nickel base substrates, using an appropriate binder, and converting them into a thermal barrier type coating by a two-step heat treatment under argon. Final result is a coating structure consisting of a quasi-foam top coat, constituted by spherical hollow alumina particles, surmounting a β-NiAl diffusion layer able to form during high-temperature oxidation a protective alumina scale. In this work, pure nickel was employed as a model material to evaluate the effects of moderate temperatures (550-700°C), dwelling times and Al particle size on the final characteristics of the coatings. Almost no diffusion occurred below 600°C. In contrast, a Ni₂Al₃ layer very quickly formed at 650 or 700°C. The rapidity of coating formation was attributed to the appearance of a liquid phase at the coating/substrate interface. The increase of dwelling time did not provide any significant thickness increase as the Al particles got practically emptied after 2h. In addition, the use of different micro-sized particles resulted in similar Al diffusion coatings under the investigated conditions.

Abstract: The use of thermal barrier coating systems allows superalloys to withstand higher operating temperatures in aeroengine turbines. Aiming at providing oxidation protection to such substrates, an aluminum-rich layer is deposited to form the α-Al₂O₃ scale over which a ceramic layer (i.e. YSZ layer) is applied to provide thermal insulation. A new approach is now being investigated within the FP7 European project « PARTICOAT », in which a single step process is employed by applying micro-sized aluminum particles. The particles are mixed in a binder and deposited by brushing or spraying on the substrate surface. During a heat treatment, the particles sinter and oxidize to form a top coat composed of hollow con-joint alumina spheres and simultaneously, an Al-rich diffusion zone is formed in the substrate. For a better understanding of the diffusion / growth processes, preliminary tests were carried out on pure nickel and Ni20Cr model alloys prior to further application on commercial superalloys. The effect of the heat treatment on the coating characteristics (number of layers, thickness, composition, homogeneity, etc.) was particularly investigated to emphasize the mechanisms of diffusion governing the growth of the coatings. The establishment of the diffused layers occurred very readily even at intermediate temperatures (650 and 700°C). However, the layers formed did not match perfectly with the thermodynamic modeling because of the quick incorporation of Ni into molten Al at intermediate temperatures (650°C). In contrast, at higher temperatures (700 and 1100°C) the phases predicted by Thermocalc are in good agreement with the observed thickness of the diffused layers. The incorporation of Cr as an alloying element restrained Al ingress by segregation of Cr even at very low temperatures aluminizing temperatures (625°C).

Abstract: Rare earth oxides are commonly employed as dopants or coatings to improve the development and adherence of alumina scales. However, for practical applications, doping is difficult to control and the use of coatings is preferred. Nevertheless the thickness of such coatings is relatively limited for long term exposures at high temperatures and thicker coatings are hence required. With this in mind, the cathodic electrodeposition technique has been investigated in this work. The results show that deposits of about 20 µm RE_xOOH_y coatings can be obtained on a Ni superalloy in 20 min. The applied current density and time significantly influence the microstructure, thickness, crystallite size and number of oxygen vacancies of the coatings. Their needle-like microstructure is indicative of non negligible amounts of rare earth hydroxides. However, the hydroxide peaks overlap with the oxide peaks in the X-ray diffraction (XRD) patterns. XRD also suggests that the coatings are either amorphous or of nanocrystalline nature, as supported by Raman spectroscopy. Their multicracked morphology is related to the shear stresses between the coating and the substrate, hydrogen bubbling and mostly by drying of the coatings in air. The number of cracks is increased after a heat treatment which also allows full crystallization of the RE_xO_y coating and pre-oxidation (α-Al₂O₃) of the superalloy. The combined effect of both oxides results in an improved oxidation resistance of the Ni-base superalloy at 1100°C in air.

Abstract: Isothermal oxidation experiments at 1100°C in air were carried out to evaluate the protective capability of a new rare earth oxide coating realized by electrodeposition onto a Ni-base single crystal superalloy. A subsequent heat treatment of the RE_xO_y coating already allowed the establishment of a very thin and discontinuous inwardly grown alumina scale. Under isothermal conditions at 1100°C in air a fully parabolic regime installed from 25h leading to parabolic rate constants of 2.5 10^-7 mg².cm^-4.s^-1 after 200h, similar to those of conventional β-NiAl coatings. The initial, transition and parabolic regimes were ascribed to the major development of NiAl₂O₄/Al₂O₃ mixed oxides by in situ high temperature X-ray diffraction (HT-XRD). No major transient alumina was observed. The α-Al₂O₃ scale intensity increased with increasing oxidation time, in particular with respect the rare earth oxide coating signal. The scanning electron microscopy (SEM) images showed an oxide system consisting on a top NiAl₂O₄ oxide and a bottom α-Al₂O₃ scale underneath the RE_xO_y coating. Alumina grew within the substrate surface. After 500 and 1000h of oxidation, very scarce nodules grew between the alumina and the rare earth oxide deposit. Despite the thermodynamic calculations suggested a REAlO_y perovskite at the alumina-RE_xO_y interface, this was not observed experimentally either by XRD or scanning electron microscopy (SEM).

Abstract: Cathodic electrodeposition was used to generate a rare earth (RE)-containing deposit on a single crystal Ni-based superalloy. The deposition parameters were optimised in order to get a RE oxy-hydroxide coating with a “well-fitted” dry-mud like morphology, i.e. presenting a multi-cracks network. A further thermal treatment was applied to dehydrate the deposit to obtain a well crystallised oxide coating (RE_xO_y). The uncoated and RE_xO_y-coated substrates were then submitted to cyclic oxidation tests at 1100°C in laboratory air. They demonstrated the efficiency of the coating as uncoated samples severely spalled after a few cycles whereas the coated ones did not lose their protective oxide layer even after 2000 cycles. This result was attributed to the formation of a duplex oxide scale very similar to that obtained on g/g’ coatings, to the presence of nanograins at the RE_xO_y/scale interface and to the Hf-rich oxide pegs at the scale/substrate interface.

Abstract: The early stages of the scale growth process were studied of two FeCrAl alloys: one synthetic (Fe23Cr5Al) and one commercial (Kanthal APM alloy). In addition, Yttrium was implanted to the Fe23Cr5Al alloy. Oxidation exposures were carried out at 1000°C using two-stage-oxidation exposures in atmospheres containing significantly different amounts of ¹⁸O₂-tracer. The scales were analyzed in terms of SIMS, PLS and SEM. The distribution of oxygen isotopes which corresponded to the location of new oxide formation, the scale phase composition, scale morphology and microstructure were determined which enabled description of the scale evolution on all studied alloys. Similar evolution stages were observed, but minor differences were related to the rate of disappearing of the transient aluminium oxides.

Abstract: Nitriding by low energy high flux processing has been carried out at about 400°C in fcc metal substrates (pure Ni, Ni-20Cr model alloy and a conventional AISI 304L stainless steel). The gradual ingress of this element into the structures will be shown to depend markedly on the chemical composition of the substrate. The associated expansion of the fcc lattices and surface roughness will be discussed in this work with the support of X-ray diffraction, atomic force, scanning and transmission electron microscopy techniques. In light of the resulting composition, microstructures and thickness of nitrided layers, some preliminary results of their behaviour under isothermal oxidation conditions at high temperatures will be discussed. The high temperatures will provoke decomposition of the expanded austenite into a conventional gamma phase and some chromium nitrides. Trapping of chromium therefore shall explain a reduction of the high temperature oxidation resistance against the untreated substrates.

Abstract: TiAl, TA6V and titanium coupons were treated by a phosphoric acid solution by dipping. They were then submitted to a heat treatment and, in the case of TiAl and TA6V, to high temperature discontinuous oxidation under laboratory air. The H3PO4 treatment allowed to decrease the mass gains for TiAl and TA6V, in particular during the first 100 hours. XRD analyses demonstrated for the three substrates the formation of a pyrophosphate layer during the heating period. This pyrophosphate evolved towards TiO2 with oxidation time increase, quicker for smaller aluminium content (or higher titanium content) in the metallic substrate. The decrease of mass gains was attributed to a diffusion barrier effect of the pyrophosphate layer as long as it was present.

Abstract: Using Raman microprobe spectroscopy made it possible to study the buckling phenomenon in chromia films grown at 900°C in air from a Ni30at%Cr alloy. Blisters have been optically observed to be circular and, from the top view, the mean radius has been measured with an accuracy of about 1%m. An autofocus device allows the characterisation of the profile of each blister and the shift of the A1g Raman peak of chromia gave the local stress far from the blister and all along the buckled zone. From these observations, the induced spalling has been related to the blister morphology.

Abstract: In this work, growth stresses have been investigated in relation with the microstructure in the case of α-Cr2O3 growing oxide films on NiCr30 alloy. The equibiaxial growth stresses have been measured thanks to a technique coupling Raman spectroscopy and in situ high temperature oxidation of the NiCr30 alloy in the temperature range [700°C-900°C]. The low acquisition time necessary to obtain a Raman spectrum allows to follow the chromia growth kinetic with sufficient accuracy. It is demonstrated that the growth stress in such oxide films can attain more than 2 GPa, before additional thermal stress arises on cooling. Moreover, the growth stress kinetic - subsequent establishment and relaxation - are highly microstructure sensitive: in particular, as the oxidation temperature rises, the chromia grain size also increases, and it consequently retards the occurrence of the creep relaxation phenomena which needs an additional stress to start.