Abstract
In sol-gel chemistry, hydrolysis is the key step in the formation of the reactive hydroxide groups that are responsible for the formation of inorganic networks via the occurrence of condensation reactions. Though previous studies have investigated the effect of the hydrolysis conditions on the structure of organically modified silicates (ormosils), no study, to our knowledge, has investigated this variable on the structure of hybrid materials prepared by combinations of an ormosil and a transition metal (TM). Here, we propose to investigate this effect in a hybrid material composed of 3-trimethoxysilylpropylmethacrylate and a zirconium complex. To also highlight the effects of the precursor’s concentrations on the hydrolysis and condensation reactions of the hybrid materials, their relative content was altered along with the hydrolysis degree. The anticorrosion barrier properties were identified by characterisation of coatings deposited on AA2024-T3 substrates and correlation between the structure and the anticorrosion properties of the coatings were performed based on results obtained from structural characterisations (DLS, FTIR, 29Si-NMR, DSC, AFM and SEM) and corrosion testing (EIS and NSS). It is demonstrated that competition in the formation of siloxane and Si-O-Zr bonds takes place and can be controlled by the degree of hydrolysis and the concentration of the zirconium complex. This effect was found to dramatically alter the morphology of the coatings and their subsequent anticorrosion performances. At short-term exposure times, it is found that the most condensed materials exhibited a higher corrosion resistance while over longer periods the performances were found to level. This article highlighted the critical impact of the hydrolysis degree and zirconium concentration on the connectivity of hybrid sol-gel coatings and the impact this has on corrosion performances.
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Highlights
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Conjugated effects of the hydrolysis degree and transition metal concentration on the structure and anticorrosion properties of hybrid sol-gel coatings are investigated.
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Correlation between the structure and anticorrosion performances of hybrid sol-gel coatings is proposed. The structure of the materials is characterised by 29Si-NMR, FTIR, DLS, DSC, AFM and SEM, while the anticorrosion performances are identified by EIS and NSS.
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The condensation of the coatings is found to be strongly relying on the hydrolysis degree and transition metal concentration.
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The short term anticorrosion performances are optimum for highly condensed coatings, while long term resistances are similar regardless of the condensation of the coatings.
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The nature of the coating/metal interface is dependent on the condensation of the materials.
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Cullen, M., O’Sullivan, M., Kumar, A.M. et al. The role of the hydrolysis and zirconium concentration on the structure and anticorrosion performances of a hybrid silicate sol-gel coating. J Sol-Gel Sci Technol 86, 553–567 (2018). https://doi.org/10.1007/s10971-018-4657-3
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DOI: https://doi.org/10.1007/s10971-018-4657-3