Papers by Keyword: Oxidation Protection

Abstract: The oxidation protection of TiAl-alloys at temperatures above 750°C can be improved by the fluorine effect. The results of thermodynamical calculations predict a corridor for a positive fluorine effect. Ion implantation of F was performed because of giving the best results. After a high F-loss during heating a thin protective alumina scale acts as a diffusion barrier. The F-depth profiles show a distinct maximum at the metal/oxide interface. The diffusion coefficient of F in TiAl for 900°C was determined. The stability of the F-effect after long oxidation time at 900°C and 1000°C can be explained by the existence of a constant F-amount at the metal/oxide interface ensuring a slow growth of the alumina scale. The fluorine effect was also applied to Ni-base superalloys to improve their high temperature oxidation resistance by forming a dense continuous protective alumina scale.

Abstract: A new method is proposed to achieve a dense protective alumina scale for Ni-base superalloys with an Al-content lower than 10 wt.% at temperatures above 1000°C. The method is based on the halogen effect. Thermodynamical calculations show the existence of a region for a positive fluorine effect at temperatures between 900-1200°C for the alloys IN738 and IN939. By using fluorine ion implantation in combination with Monte Carlo simulation of the fluorine profiles these results were transformed into a region of F-concentrations at the metal surface. A dense protective alumina scale was formed for IN738 after oxidation at 1050°C. Due to the very low Al-content no alumina scale was found for IN939.

Abstract: In rocket engine combustion chambers, the cooling channels experience extremely high temperatures and environmental attack. Thermal protection can be provided by Thermal Barrier Coatings. Due to the need of good heat conduction, the inner combustion liner is made of copper. The performance of a standard coating system for nickel based substrates is investigated on copper substrates. Thermal cycling experiments are performed on the coated samples. Due to temperature limitations of the copper substrate material, no thermally grown oxide forms at the interface of the thermal barrier coating and the bond coat. Delamination of the coatings occurs at the interface between the substrate and the bond coat due to oxide formation of the copper at uncoated edges. In real service a totally dense coating can probably not be assured which is the reason why this failure mode is of importance. Different parameters are used for thermal cycling to understand the underlying mechanisms of delamination. Furthermore, laser heating experiments account for the high thermal gradient in real service. Pilot tests which led to a delamination of the coating at the substrate interface were performed successfully.

Abstract: Sufficient oxidation stability of advanced carbon based materials is a key feature for their application in fusion, fission, aerospace and chemical engineering. These materials were examined as part of the EU research projects ExtreMat and Raphael-ML. This paper discusses the presently available oxidation model, outlines its limits on basis of respective experiments and proposes improvements. Methods for oxidation protection of advanced carbon based materials as doping and coating with different components are discussed. Experimental oxidation results on EX10, a carbon fibre in SiC matrix, in air at high flow rates and high temperatures are presented.

Abstract: In this study the oxidation resistance of Ti-45Al-8Nb (at.%) alloy coated with quaternary Ti-Al-Cr-X layers (X = Si, Hf, Y, Zr and W) was investigated. The Ti-Al-Cr-Si, Ti-Al-Cr-Hf and Ti-Al-Cr-Y coated specimens were exposed to air at 950°C under cyclic conditions, whereas the samples with Ti-Al-Cr-Zr and Ti-Al-Cr-W coatings were thermally cycled at 1000°C. After the maximum exposure time period of 1000 1h-cycles or failure cross-sections of the samples were examined by means of SEM and EDS to analyse the microstructural evolution. At initial stages of exposure, all intermetallic layers formed a thin alumina layer on top, providing a diffusion barrier to oxygen. But interdiffusion between coating and substrate caused depletion of the Ti(Cr,Al)2 Laves phase in the intermetallic layers, which promoted the formation of alumina, as well as transformation into Ti-rich B2-phase. Coarsening of the latter phase beneath the alumina scale resulted in a higher oxidation resistance compared to that of ternary Ti-Al-Cr coating.

Abstract: The use of carbon fibre reinforced carbon composites in oxidizing atmospheres is limited to temperatures below 400 °C. To benefit from their excellent mechanical strength that is still preserved at high temperatures, suitable oxidation protection coating systems have to be developed. Composites which are capillary infiltrated with Si and coated with SiC via chemical vapour deposition show significantly enhanced oxidation resistance. For the increase of service temperature above 1300 °C, high temperature stable materials with low oxygen diffusivities such as yttrium silicates have to complement the SiC coating. The electrophoretic deposition performed under constant current conditions leads to relatively high green densities and therefore good sinterability of the applied coatings. In this work we present the preparation of suspensions, their characterization regarding particle size and electrophoretic mobility for yttrium silicate powder prepared by the solid state method. Depending on particle charge and conductivity of the investigated suspensions iodine is employed to increase particle charge. The use of current densities between 0.5-5mA/cm² leads to smooth and homogeneous layers. Layers sintered as low as 1400 °C for 2h already show promising protection of the C/C-Si-SiC substrate during thermogravimetric analysis.

Abstract: An overview on parameters influencing the oxidation behaviour of carbon based materials in oxidizing gases is presented in order to support the development of advanced carbon containing materials with high oxidation resistance. Facilities for testing the oxidation behaviour, as operated in FZJ, are explained. Results of exemplary oxidation tests in air at 700°C on diverse new developed materials are presented: Ti and Zr dopings and coatings were found less efficient, whereas Si coatings/dopings significantly reduce oxidation rates. Low oxidation rates of 3D-CFCs without doping/coating, which were manufactured under temperature treatment of > 2200°C and used high purity starting materials, point out the relevance of the latter parameters. Future work on oxidation resistance of carbon based materials is shortly discussed.

Abstract: The use of ceramic composite materials in aerospace applications requires the development of oxidization protection coatings which can withstand very high temperatures. HfO2 is a promising material as a high temperature oxidization protective layer. HfO2 coatings have been deposited by radiation frequency magnetron sputtering all over the surface of SiC substrates and were tested under re-entry conditions. Also their oxidization resistance in air in the temperature range 1100 to 1450°C has been examined. The coatings were found to be stable and well-adhering to the substrate even after 100 re-entry cycles. No oxidization of the underlying SiC structure is observed. Re-entry and oxidization tests result in the formation of HfSiO4 at the HfO2/SiC interface, which further promotes their oxidization resistance.

Abstract: The SIBOR® (Si-10B-2C) oxidation protective coating was applied onto molybdenumand molybdenum – 3 wt% zirconia samples by APS (= Atmospheric Plasma Spraying) with a subsequent heat treatment. Then the coated samples were submitted to ramp oxidation tests with heating rates of 10°C / hour up to a temperature of 1450°C. This procedure simulates the heating up of a glass melting tank where SIBOR® coated parts are most frequently used. Some of the samples which could be oxidized without any defect were then immersed in various molten glasses to determine the dissolution rate of the SIBOR® substrate system. This simulates the situation when the glass melting tank is filled and operated with molten glass. SIBOR® proved to be an excellent oxidation protective coating for the molybdenum – zirconia – material like for pure molybdenum. The coating was fairly good dissolved by opal glass and – slightly less – by soda lime glass. With borosilicate glass a much slower interaction was found. In all cases some discolouration and bubbles were found in the glasses after one week.

Abstract: The preparation of mullite coatings for the oxidation protection of carbon fibre reinforced composites using a combination of sol-gel synthesis and electrophoretic deposition (EPD) has been investigated. Mullite precursor sols were synthesised by controlled hydrolysis and condensation reactions of the metal alkoxides TEOS (tetraethoxysilane) and Al(OBus)3 (aluminiumtri-sec-butylate). The structure and properties of the mullite precursor were strongly influenced by the synthesis parameters, especially by the water to TEOS ratio (rw/Si) and the pH value of the water. A variety of synthesis conditions was tested for optimising the mullite precursor sols regarding their suitability for the electrophoretic deposition. The electrokinetic behaviour of the sols and the charging of the sol particles which is necessary for a successful EPD were investigated by measurements of the Electrokinetic Sonic Amplitude (ESA signal). 29Si CP/MAS NMR measurements were used to get information about the coordination of the silicon and the homogeneity of the Al/Si distribution in the precursors. Heat-treated samples were characterised by X-ray diffraction for investigating the mullite formation. Coatings prepared by EPD and sintering at 1300 °C in Ar enabled an effective oxidation protection in the temperature range 1200 °C ≤ T ≤ 1550 °C.