Design of epoxy-silica hybrids based on cycloaliphatic diol of natural origin for conservation of lithic materials

Abstract

Abstract This work is focused on the development of sustainable stone conservation materials, based on BPA-free epoxy-silica hybrid resins, with consolidating and hydrophobic properties, for long-term treatments. For this purpose, a cycloaliphatic diol, with minor health and environmental associated issues with respect to classic phenolic derivatives, was selected to synthesize a BPA-free bio-based epoxy resins precursor, 2,2,4,4-tetramethyl-1,3-cyclobutanediol diglycidylether (CBDO-DGE). Fourier transform infrared (FT-IR) and Raman spectroscopies were employed to assess the synthesis and clean-up procedures. In addition, both 1H-NMR and 13C-NMR in solution were used to ascertain the structure and purity of the bio-based epoxy. The development of the epoxy thermosets by 1,8- diaminooctane (DAO), triethylenetetramine (TETA) and 5-amino-1,3,3-trimethylcyclohexanemethylamine (IPDA) curing agents was followed by attenuated total reflection infrared (ATR FT-IR) and Raman spectroscopies, whereas their suitability as organic counterpart of the hybrids was established by differential scanning calorimetry (DSC) and thermogravimetric (TGA) measurements. In addition, epoxy-silica hybrids were obtained by exploiting sol-gel technology, carrying out the epoxy hardening reactions also in the presence of (3-glycidyloxypropyl)trimethoxysilane (GPTMS) and octyltriethoxysilane (OcTES), as silica-forming additives. To investigate the properties of the resulting hybrid materials imparted by the selection of the different reactants, various blends were studied by a combination of scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS), ATR FT-IR and Raman analysis. Furthermore, the assessment of the hybrids tunability as materials for stone conservation was ascertained in terms of thermostability and hydrophobicity by TG-DTA, DSC, dynamic mechanical analysis (DMA) and contact angle measurements.