Papers by Author: Michael Schütze

Abstract: High temperature Ti-alloys are usually sophisticated and hence expensive. To allow the use of cheaper alloys at elevated temperatures an economic and easy to apply procedure was developed to improve their high temperature capability. The treatment consists of a combination of Al-enrichment in a shallow surface region plus additional fluorination. The Al-enrichment at elevated temperatures leads to the formation of intermetallic TiAl-phases. These phases improve the oxidation resistance of Ti-alloys but not to a sufficient extent. An additional fluorine treatment of the Al-enriched surface leads to the formation of a protective alumina scale due to the fluorine effect. In this paper results from high temperature exposure tests performed on different Ti-alloys without any treatment and with a combination of Al-treatment plus fluorination are presented. The results are discussed in the view of the use of the optimized Ti-components for several high temperature applications.

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: γ-TiAl intermetallics are attractive materials for high-temperature structural applications in the aerospace and automobile industries. However, they show environmental embrittlement at elevated temperatures that is mainly related to their low high-temperature corrosion resistance. One way how to improve the high-temperature corrosion resistance is the deposition of protective coatings on the surface of the base material. In this study, samples of a Ti-Al alloy with the chemical composition Ti-48Al-2Cr-2Nb (at.%) were covered by physically vapour deposited (PVD), by metalorganic chemically vapour deposited (MOCVD) and by high-velocity oxy-fuel (HVOF) sprayed coatings. All coatings were based on the Ti-Al alloys and contained different amounts of alloying elements. The corrosion experiments were performed in molten salts containing 75 wt.% Na₂SO₄ and 25 wt.% NaCl at 850°C up to 336 h. Both, PVD and CVD protected coatings reduced the changes in the mass of the samples over the corrosion time. Still, the formation of TiO₂ could not be avoided, as it was confirmed by glancing-angle X-ray diffraction experiments.

Abstract: Reformer materials are exposed to severe operating conditions at high temperature in aggressive catalyzer and combustion atmospheres. Therefore, materials used for the construction of the reformer reactor have to possess appropriate high temperature resistance. Diffusion coatings improve the high temperature resistance of materials by enrichment of the alloy surface with thermodynamically stable oxide formers. Beside conventional mono-element diffusion coatings (e.g. Al coating), multi-element diffusion coatings can be developed in a single process step. In this work we developed Al diffusion and Al-Si and Al-Si-RE (RE: reactive element Y, Ce) co-diffusion coatings on a low cost austenitic 18Cr10Ni-steel. The high temperature resistance of coated and uncoated 18Cr10Ni-steel, 20Cr31Ni-steel and 23Cr18Fe-Ni base alloy was tested in catalyzer and combustion atmosphere under cyclic operation conditions.

Abstract: The paper reviews the advantages of diffusion coating and the parameters deciding an optimum coating performance. Furthermore, innovative coating approaches are presented which have a significant potential beyond existing diffusion coating solutions.

Abstract: The oxidation resistance of TiAl-alloys can be improved drastically by treating the surface of the components with small amounts of fluorine. The oxidation mechanism is changed. Hence, the formation of a fast growing mixed oxide scale on untreated alloys is suppressed. Instead a thin protective alumina scale is formed on samples after fluorine treatment. The different methods only influence the surface region of the components so that the bulk properties are not affected. Recent results achieved with F-containing inorganic compounds showed that the fluorine effect can be improved even further. TiAl-specimens were treated only with fluorine and with F-containing compounds in several ways and their performance during high temperature oxidation tests in air was investigated. Results of isothermal and thermocyclic oxidation tests are presented. The results are discussed in terms of a later use of the fluorine effect for technical applications.

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: The oxidation resistance of ferritic-martensitic 9% chromium steels in water vapour containing atmospheres is not yet satisfactory. The chromia layer provides little protection because water vapour in the atmosphere is known to promote the formation of the volatile chromium species CrO₂(OH)₂. If a chromium manganese spinel is formed instead, the vapour pressure of the oxy-hydroxide is greatly reduced and evaporation can largely be avoided. Enrichment of the substrate with manganese was achieved using three different processes: using (i) a sputtering technique, (ii) electrochemical deposition both followed by a diffusion heat treatment, (iii) the pack cementation method. Uniform diffusion of manganese was obtained with all of the investigated processes. The improved oxidation behaviour of the coated samples in synthetic air with 10% water vapour at 650°C was demonstrated.

Abstract: A new model concept for predicting mechanical oxide scale failure is applied to Al₂O₃, Cr₂O₃, Fe₃O₄ and NiO. The calculated critical strain values are plotted versus the physical defect size using a simplified version of the original h-w-concept. A limited number of experimental data existing in the literature were entered into the plots and yield satisfactory agreement with the model data. Future efforts should focus on extending the experimental data basis and converting these data into h-values for the model.

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.