Improving the Protectiveness of 3-Mercaptopropyl-Trimethoxysilane Coatings on Bronze by Addition of Oxidic Nano- and Microparticles

The protectiveness of coatings based on 3-mercaptopropyl-trimethoxysilane (PropS-SH) applied on bronze artworks was enhanced by investigating and tuning a variety of factors. In particular, the coating performances were optimized by proper additive choice among oxide nanoparticles (CeO2, La2O3, TiO2) and microparticles (fly ash (FA)), and by varying the aging time of the nanoparticle suspensions before coating application and the RT curing time of the coatings. Moreover, the possibility of conservation of the silane solution under refrigerated conditions was assessed. The aggressive environment was a tenfold concentrated synthetic acid rain (AR × 10). The techniques adopted comprised electrochemical tests (polarization curve recording and EIS tests) and SEM-Energy Dispersion Spectroscopy (EDS) observations. In the case of FA microparticles, never used before as additives in silane coatings, further tests were performed in FA suspensions in AR × 10 to clarify the contribution of these particles to PropS-SH coating protectiveness. The tests included pH measurements, elemental chemical analyses, and electrochemical tests on bare bronze. Improved performances of PropS-SH coatings were achieved by La2O3, CeO2, and FA addition, with La2O3 affording the best results during 20 days of immersion. The positive influence of FA was connected to its alkaline character and to the release of soluble silicates

B-IMPACT project: eco-friendly and non-hazardous coatings for the protection of outdoor bronzes

Application of protective coatings is the most widely used conservation treatment for outdoor bronzes. Eco-friendly and non-hazardous coatings are currently needed for conservation of outdoor bronze monuments. To fulfil this need, the M-ERA.NET European research project B-IMPACT (Bronze-IMproved non-hazardous PAtina CoaTings) aimed at assessing the protectiveness of innovative coatings for historical and modern bronze monuments exposed outdoors.In this project, two bronze substrates (historical Cu-Sn-Zn-Pb and modern Cu-Si-Mn alloys) were artificially patinated, by acid rain solution using dropping test and by “liver of sulphur” procedure (K2S aqueous solution)to obtain black patina, respectively. Subsequently, the application of several newly developedprotective coatings was carried out and their performance was investigated by preliminary electrochemical tests. In the following stepsof the work, the assessment of the best-performing coatings was carried out and their performance was compared to Incralac, one of the most widely used protective coatings in conservation practice. A multi-analytical approach was adopted,considering artificial ageing (carried out in representative conditions, including exposure to rain runoff, stagnant rain and UV radiation)and metal release, as well as visual aspect (so as to include aesthetical impact among the coating selection parameters) and morphological and structural evolution of the coated surfaces due to simulated outdoor exposure. Lastly, also the health impact of selected coatings was assessed by occupational hazard tests. The removability and re-applicability of the best-performing coatings were also assessed.The best alternatives to the conventional Incralac exhibited were: (i) fluoroacrylate blended with methacryloxy-propyl-trimethoxy-silane (FA-MS) applied on patinated Cu-Sn-Zn-Pb bronze and (ii) 3-mercapto-propyl-trimethoxysilane (PropS-SH) applied on patinated Cu-Si-Mn bronz

Inclusion of 5-Mercapto-1-Phenyl-Tetrazole into β-Cyclodextrin for Entrapment in Silane Coatings: An Improvement in Bronze Corrosion Protection

The corrosion protection of coatings can be reinforced by the addition of entrapped corrosion inhibitors. β-cyclodextrin (β-CD) can form inclusion complexes with small inhibiting organic molecules that, when entrapped in coatings, allow the inhibitor release and adsorption at corrosion initiation sites. In this paper, several Nuclear Magnetic Resonance (NMR)-based experiments (e.g., Complexation-Induced Shifts (CIS), NMR titration, Diffusion-Ordered Spectroscopy (DOSY)) were performed to study the stability and geometry of a complex formed by β-cyclodextrin with 5-mercapto-1-phenyl-tetrazole (MPT). The complex was also detected by Electrospray Ionization (ESI) mass spectrometry and characterized by Fourier Transform Infrared (FTIR) spectra. Its influence on the protectiveness of a silane coating against bronze corrosion was evaluated in plain (AR) and concentrated (ARX10) synthetic acid rain, under different exposure conditions. In particular, the time evolution of the polarization resistance values during 20 days in ARX10 and the polarization curves recorded at the end of the immersions evidenced a higher protectiveness of the coating with the β-CD–MPT complex in comparison to that containing only MPT or only β-CD. The cyclic AR spray test carried out on coated bronze coupons with cross-cut scratches evidenced the absence of underfilm corrosion starting from the scratches only in the complex-containing coating