The degradation of SiO2 coatings deposited on alloys by metal organic chemical vapour deposition (MOCVD) in sulphidizing high‐temperature environments is determined by delamination and crack formation. With increasing water concentration during deposition, the crack density in silica decreases and the critical thickness for delamination of SiO2 coatings increases. This improvement is supposed to be caused by compositional changes in the SiO2 coating. In this study presence of water and silanol groups as measured by Fourier transform infrared spectroscopy(FTIR) and the Si:O ratio as measured by XPS are discussed in relation to the protective properties. The FTIRmeasurements show that the coatings deposited in more humid environments contain more silanol groups and have lower stress levels. The coatings obtained under all deposition conditions consisted of stoichiometric SiO2.0 as determined by XPS. The presence of silanol groups reduces the viscosity of the coating, and stress relaxation by viscous flow becomes enhanced, thereby improving the coating performance.

Silica coatings have been deposited on various alloys by MOCVD (Metal Organic Chemical Vapor Deposition) to protect them against high temperature corrosion in coal gasification environments. DiAcetoxyDitertialyButoxySilane (DADBS) has been used as a metal organic precursor at deposition temperatures between 773-873 "K and amorphous layers were produced with a growth rate of about 1 pm. h-'. These coatings have been tested at 823°K in a sulphidizing atmosphere with a low oxygen (9.3 X 10-a bar) and a high sulphur partial pressure (1.2 X 10'' bar). In this environment the sulphidation resistance of verious alloys has improved by a factor of at least 100 by the coating. The observed corrosion reaction is local and is explained by a model in which in the first stage cracks are formed due to mechanical stresses in the coating. In the second stage metal sulphides are formed by outward diffusion of metal and inward diffusion of sulphur through the cracks. When stainless steels are used as the alloy the ouer layer consists of FeS and the lower one of CrS.

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In this study the effects of the nature of metal alkoxides on their vapour pressures and thermal decomposition chemistry are reported. The vapour pressure and the volatility of a metal alkoxide strongly depends on the steric effect of its alkoxy group.The thermal decomposition chemistry of one metal alkoxide (di-acetoxy-di-t-butoxysilane, DADBS) has been studied by mass spectrometry at temperatures between 423 and 923 K. The pyrolytic products were acetic acid anhydride and 2-methyl propene. The acetic acid anhydride is formed at temperatures above 473 K and 2-methyl propene is formed above 673 K by a P-hydride elimination mechanism. In these steps, a 6-ring intermediate is supposed to be formed. The silicon acid finally remaining is proposed to react by poly-condensation to SiOz coatings or powder.

Alloys such as AIS1 304 and AIS1 321 stainless steels and Incoloy 800H can be protected against high temperature corrosion by means of amorphous SiO2-coatings deposited by metal organic chemical vapor deposition (MOCVD). The coated alloys are only attacked locally after exposure to a 19% H2, 1% H2S, 1.5% H2O, Ar bal. environment at 823 K (pS2 = 1.2 x 10-9bar and pO2 = 9.3 x 10-29 bar). The crack density observed after sulphidation is identical for silica deposited onto all metallic substrates. Decohesion of amorphous silica coatings from AISI 304 is observed, when the coating thickness exceeds 1.7 µm, while coatings on Incoloy 800H are adherent up to 4 µm. These phenomena can be explained by the fact that the adhesion is a function of the chemical interactions between the metal and the coating, whereas crack formation is only a function of the internal stresses in the coating. Two methods are studied to reduce the coating failure by means of a reduction of internal stresses in the coating, the first is changing the deposition process and the second is reducing the thermal mismatch between the coating and the metal