Synthesis of nanoparticles/organics modified polyacrylate-based materials for stone cultural relics protection /
Ma Chuang
- xv, 162 pages : illustrations ; 30 cm. + 1 CD-ROM
Faculty of Chemical and Process Engineering Technology
Thesis (Doctor of Philosophy) -- Universiti Malaysia Pahang Al Sultan Abdullah - 2025
Include bibliographical reference
Stone cultural artifacts represent one of the most important forms of heritage, as they contain extensive ancient information about human civilization. However, many of these artifacts have undergone prolonged deterioration in outdoor environments due to freeze-thaw cycles, acid rain, ultraviolet (UV) radiation, and microbial decomposition. Recently, protective coatings are drawing more and more attention due to their special properties, however, the comprehensive properties and simple synthesis method still need to improve. Hence, in this study, fluorinated poly(MMA-co-BA) (FPA), fluorinated poly(MMA-co-BA) modified by vinyltriethoxysilane (FPAV), fluorinated poly(MMA-co-BA) modified by nano SiO2 (FPAS), fluorinated Poly(MMA-co-BA) modified by nano SiO2/TiO2 (FPAST) and fluorinated poly(MMA-co-BA) modified by vinyltriethoxysilane, nano SiO2/TiO2 (FPAVST) were synthesized via one-pot method, and the preparation formulation has been optimized. The protection effect was tested by coated the stone samples from Chengde Mountain Resort and Outlying Temples in northern China. The physical properties of polymer coatings then were characterized using Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), Thermal Gravimetric Analysis (TGA), Scanning Electron Microscope (SEM), and Transmission Electron Microscope (TEM), the adhesion and breathability of polymer coatings were tested. Protective properties, including hydrophobicity, chromaticity, transparency and mass loss rate were systematically evaluated. Furthermore, the anti-aging performance of the polymer coatings was assessed and analyzed through simulated freeze/thaw, acid aging and UV aging experiments, their efficacy in inhibiting moss growth was also evaluated. The optimum preparation conditions have been identified, especially the amount of Hexafluorobutyl methacrylate, organic silica, inorganic silica and the nano titanium dioxide. The results revealed that FPA with 20% HFMA content exhibited a contact angle of 110.46° and excellent resistance to freeze/thaw, acid, and UV aging. FPAV with 16% VTES achieved optimal properties, while FPAS with 0.1 g nano-silica demonstrated improved UV resistance without compromising hydrophobicity. The incorporation of nano titanium dioxide in FPAST enhanced UV resistance and antimicrobial properties, although excessive amounts reduced transparency. FPAVST, combining vinyltriethoxysilane, nano silica, and nano titanium dioxide, showed superior overall performance due to their synergistic effects. At nanosilica content of 0.1 g and the incorporation of titanium dioxide at 6% by mass relative to the nanosilica content, the FPAVST polymer coating achieved 113.84° of water contact angle, and a color difference (ΔE) of 1.98 before aging. The coatings remained good contact angles and color stability after undergoing freeze/thaw cycles, acid aging, and UV aging tests. FPAVST polymer coating synthesized has potential for application of stone cultural relics conservation. The comprehensive evaluation confirmed FPAVST as a multifunctional coating material with excellent anti-aging properties and the ability to inhibit microbial growth. Therefore, this study provides a theoretical foundation for the application of FPAVST in protecting stone cultural relics, particularly in cold northern regions of China, and offers a viable method for addressing the challenges of relic conservation.
THE0010345 (Local)
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