Development of solvent- and water-borne fluoropolymer protective coatings for patina-free bronze discs

Solvent- (SB) and water-borne (WB) fluoropolymer coatings were produced for the outdoor protection of bronze. The coatings were prepared from commercially available resins with alternating fluoroethylene/vinylether copolymers. Because any application of protective coatings on works of art requires that they be removable in accordance with conservation ethics, various approaches to achieve removability of coatings were tested. The influence of modifications was verified through comparisons of hydrophobic, compact and irremovable protective coatings. Consequently, we prepared four types of coatings: two SB coatings and two WB coatings. The first SB coating was designed to have a hydrophobic compact structure (SB-c coating), and the second SB coating was modified with the addition of agents that impart strippability (SB-h coating). The same approach was used for the preparation of the two WB coatings: a compact (WB-c) coating vs. a hydrophilic (WB-h) coating, the latter being prepared through the addition of hydrophilic polyisocyanate. The surface properties of the coatings were compared using scanning electron (SEM) and atomic force (AFM) microscopy. WB coatings were found to be more homogeneous in comparison with SB coatings and to have lower surface roughness. Contact angles confirmed the more hydrophobic nature of SB coatings. Potentiodynamic polarisation measurements and accelerated corrosion tests (exposure to acid vapours) revealed that protection efficiency not only increased with thickness but significantly depended on the coating structure. The structure of coatings depended on the rheological parameters of the formulations simulating their behaviour during storage, deposition, and formation of the dry coating. Combined electrochemical and vibrational spectroscopic experiments were used to simulate long-term outdoor exposure of the protective coatings. Ex situ IR RA spectroelectrochemical measurements showed that hydration was more prevalent with WB coatings, and oxidation of bronze at the interface eventually occurred (656 cm-1 band). WB coatings with more free CO groups were more prone to degradation. In situ Raman spectroelectrochemistry confirmed the better protection efficiency of SB over WB coatings. The optical properties of the coatings on glass showed higher transmittance for WB coatings compared to SB coatings.