The protection of alloys against high temperature sulphidation by SiO2-coatings deposited by MOCVD

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. DiAcetoxyDitertiaryButoxySilane (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 μm. h-1. These coatings have been tested at 823°K in a sulphiclizing atmosphere with a low oxygen (9.3 10 -29 bar) and a high sulphur partial pressure (1.2 10 bar). In this environment the sulphidation resistance of various 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 outer layer consists of FeS and the lower one of CrS

The pyrolytic decomposition of metal alkoxides (di-acetoxy-di-t-butoxy-silane, DADBS) during chemical vapour deposition of thin oxide films

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.\ud \ud The thermal decomposition chemistry of one metal alkoxide (di-acetoxy-di-t-butoxy-silane, 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 ß -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 SiO2 coatings or powder

Thin alumina and silica films by chemical vapor deposition (CVD)

Alumina and silica coatings have been deposited by MOCVD (Metal Organic Chemical Vapor Deposition) on alloys to protect them against high temperature corrosion. Aluminium Tri-lsopropoxide (ATI) and DiAcetoxyDitertiaryButoxySilane (DAOBS) have been used as metal organic precursors to prepare these ceramic coatings. The influence of several process steps on the deposition rate and surface morphology is discussed. The deposition of SiO2 at atmospheric pressure is kinetically limited below 833 K and is a mixed first and second order reaction with an activation energy of 155 kJ.mole-1. The deposition of Al2O3 is kinetically limited below 673 K and is a first order reaction with an activation energy of 30 kJ.mole-1 at atmospheric pressure. The deposition of Al2O3 is kinetically limited below 623 K and is a second order reaction at low pressure (3 torr) with an activation energy of 30 kJ.mole-1. The decomposition of both precursors involves a B-hydroge n elimination reaction by which DADBS decomposes to acetic acid anhydride, 2-methyl propane, SiO2 and H2O, while ATI decomposes to 2-propanol, propane, Al2O3 and H2O

FTIR and XPS studies on corrosion resistant SiO2 coatings as a function of the humidity during deposition

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

The protection of alloys against high temperature sulphidation by SiO@#2@#-coatings deposited by MOCVD

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. DiAcetoxyDitertiaryButoxySilane (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 μm. h-1. These coatings have been tested at 823°K in a sulphiclizing atmosphere with a low oxygen (9.3 10 -29 bar) and a high sulphur partial pressure (1.2 10 bar). In this environment the sulphidation resistance of various 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 outer layer consists of FeS and the lower one of CrS

Thin alumina and silica films by chemical vapor deposition

Alumina and silica coatings have been deposited by MOCVD (Metal Organic Chemical Vapor Deposition) on alloys to protect them against high temperature corrosion. Aluminium Tri-lsopropoxide (ATI) and DiAcetoxyDitertiaryButoxySilane (DAOBS) have been used as metal organic precursors to prepare these ceramic coatings. The influence of several process steps on the deposition rate and surface morphology is discussed. The deposition of SiO2 at atmospheric pressure is kinetically limited below 833 K and is a mixed first and second order reaction with an activation energy of 155 kJ.mole-1. The deposition of Al2O3 is kinetically limited below 673 K and is a first order reaction with an activation energy of 30 kJ.mole-1 at atmospheric pressure. The deposition of Al2O3 is kinetically limited below 623 K and is a second order reaction at low pressure (3 torr) with an activation energy of 30 kJ.mole-1. The decomposition of both precursors involves a B-hydroge n elimination reaction by which DADBS decomposes to acetic acid anhydride, 2-methyl propane, SiO2 and H2O, while ATI decomposes to 2-propanol, propane, Al2O3 and H2O

The pyrolytic decomposition of metal alkoxides (di-acetoxy-di-t-butoxy-silane, DADBS) during chemical vapour deposition of thin oxide films

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-butoxy-silane, 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 ß -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 SiO2 coatings or powder

Improved SiO2-coatings against high temperature sulphidation by internal stress reduction

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