Minimizing Corrosion of Outdoor Metalworks Using Dispersed Chemically Stabilized Nanoclays in Polyvinylidene Fluoride Latex Coatings

Nanoclays are small enough to appear optically transparent, yet they have large surface-to-volume and high aspect ratios that can significantly inhibit water diffusion when incorporated into protective coatings. Clear coatings, which minimally affect the aesthetics of metalworks, are commonly applied to outdoor metalworks, such as sculptures, to prevent and slow corrosion. In recent years, waterborne clear coatings, rather than solvent-based clear coatings, are increasingly used in many applications to reduce the quantity of volatile organic components in the formulation, yet the performance of dry films produced from waterborne colloidal suspensions is generally poorer. In this work, we aim to improve the barrier properties of a highly weatherable waterborne acrylic/polyvinylidene fluoride emulsion by adding a synthetic nanoclay, Laponite, into the formulation. To improve clay-polymer compatibility, the clay was covalently modified using an acetoxy or perfluoroalkyl silane monomer that is reactive with the hydroxyl groups at the edges of the Laponite platelets. Cation exchange on the clay faces using phosphorylcholine was conducted to increase the stability in water and characterized by zeta potential. Resulting changes in barrier properties of the polymer nanocomposite films were characterized by gravimetry, colorimetry, and electrochemical impedance spectroscopy. Surface ablation after accelerated artificial weathering was monitored by attenuated total internal reflectance Fourier transform infrared microspectroscopy and Raman microspectroscopy, thin film X-ray diffraction (TF-XRD) and gloss and thickness measurements. The composite films showed many improved properties: reduced water sensitivity and ultraviolet-induced polymer degradation, which increased the barrier properties and reduced the diffusion constants over both short- and long-term weathering studies compared with films without nanoclays. The diffusion constant measured for the highest performing composite film showed that the performance gap between relevant water- and solvent-borne coatings used to protect outdoor metals was narrowed by half.