Structural studies of sol-gel urea/polydimethylsiloxane barrier coatings and improvement of their corrosion inhibition by addition of various alkoxysilanes

A sol-gel organic-inorganic hybrid precursor, bis[(ureapropyl)triethoxysilane]bis(propyl)-terminated-polydimethylsiloxane 1000 (PDMSU, for short), was tested as a corrosion barrier coating for AA 2024 aluminium alloy. The PDMSU coatings were prepared in either ethanol (PDMSU/EtOH) or propanol (PDMSU/PrOH) solvents. XRD measurements of xerogels showed the diffraction peak of amorphous silica domains at 21.5° and a broad peak at approximately 12.2°, which could be associated with the presence of the polyhedral silsesquioxane structural units (T2 and T3) determined in our previous investigations from the 29Si NMR spectra. The structure of thin coatings on AA 2024 prepared by heat-treatment at 140 °C was studied with the surface-sensitive IR reflection-absorption (IR RA) spectroscopic technique. Results revealed that in both coatings the poly(dimethylsiloxane) (PDMS) chain segments were projecting from the metal surface, however, this effect was more pronounced for the PDMSU/PrOH than for the PDMSU/EtOH coatings. Information gathered from the structural studies (IR, IR RA, 29Si NMR and XRD) enabled some correlations to be drawn between the coatings' structure and the effectiveness of the corrosion inhibition, which was assessed from the potentiodynamic and salt-spray measurements. Results showed the improved corrosion inhibition of PDMSU/PrOH coatings attributed to their denser and more compact sol-gel network and also to their higher hydrophobicity, i.e. lower surface energy determined from the contact angle measurements. Addition of various tetraalkoxysilanes and alkyltriethoxysilanes further improved the corrosion inhibition of PDMSU coatings due to more extensive cross-linking. The salt-spray tests showed that tetraethoxysilane and phenyltriethoxysilane were the most effective additives.