Dual Role of Lithium on the Structure and Self-Healing Ability of PMMA-Silica Coatings on AA7075 Alloy.

In this work, structural and active corrosion inhibition effects induced by lithium ion addition in organic-inorganic coatings based on poly(methyl methacrylate) (PMMA)-silica sol-gel coatings have been investigated. The addition of increasing amounts of lithium carbonate (0, 500, 1000, and 2000 ppm), yielded homogeneous hybrid coatings with increased connectivity of nanometric silica cross-link nodes, covalently linked to the PMMA matrix, and improved adhesion to the aluminum substrate (AA7075). Electrochemical impedance spectroscopy (EIS), performed in 3.5% NaCl aqueous solution, showed that the improved structural properties of coatings with higher lithium loadings result in an increased corrosion resistance, with an impedance modulus up to 50 GΩ cm2, and revealed that the lithium induced self-healing ability significantly improves their durability. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and X-ray photoelectron spectroscopy (XPS) suggest that the regeneration process occurs by means of lithium ions leaching from the adjacent coating toward the corrosion spot, which is restored by a protective layer of precipitated Li rich aluminum hydroxide species. An analogue mechanism has been proposed for artificially scratched coatings presenting an increase of the impedance modulus after salt spray test compared to the lithium free coating. These results evidence the active role of lithium ions in improving the passive barrier of the PMMA-silica coating and in providing through the self-restoring ability a significantly extended service life of AA7075 alloy exposed to saline environment.

Structure and properties of epoxy-siloxane-silica nanocomposite coatings for corrosion protection.

HYPOTHESIS: The fraction of the silica/siloxane phase is a crucial parameter, which determines the structure and thus the properties of epoxy-siloxane-silica hybrid coatings. A careful adjustment of the colloidal precursor formulation allows tuning the nanostructure towards a highly condensed and cross-linked hybrid nanocomposite, suitable as an efficient anticorrosive coating. EXPERIMENTS: Novel epoxy-siloxane-silica hybrids have been prepared through the curing reaction of poly(bisphenol A-co-epichlorohydrin) (DGEBA) with diethyltriamine (DETA) and (3-glycidoxypropyl)methyltriethoxysilane (GPTMS), followed by hydrolytic condensation of tetraethoxysilane (TEOS) and GPTMS. At a constant proportion of the organic phase, the effects of the varying molar proportions of siloxane (GPTMS) and silica (TEOS) on the film properties have been investigated. FINDINGS: A detailed structural analysis suggests for intermediate TEOS to GPTMS ratios a structure of highly condensed silica-siloxane domains covalently bonded to the embedding epoxy phase. The homogeneous distribution of the quasi-spherical sub-nonmetric silica-siloxane nodes is in agreement with low surface roughness (<5 nm), observed by atomic force microscopy. This dense nanostructure results in high thermal stability (>300 °C), strong adhesion to steel substrate and excellent barrier property in saline solution, with corrosion resistance in the GΩ cm2 range.