Parametric Study on APTES Silanization of Coal Fly Ash for Enhanced Rubber Composite Performance

The surface modification of coal fly ash (CFA) with silane coupling agents improves its compatibility with polymer matrices and supports its use as a sustainable filler in composite materials. This study examined the effects of the solvent system, reaction temperature, and pH on the grafting of 3-aminopropyltriethoxysilane (APTES) onto CFA surfaces. Functionalization was assessed by Fourier-transform infrared spectroscopy (FTIR), focusing on the CH2 symmetric and asymmetric stretching bands of pure APTES at 2919 and 2957 cm−1, noting that a slight shift in these bands can be expected following the change in the local chemical environment upon grafting. Solvent mixtures containing water (ethanol/water, acetone/water, and sulfuric acid/water) produced stronger coupling than the toluene solvent, which indicated the importance of water for APTES hydrolysis and silanol formation. Coupling efficiency increased with temperature and reached a maximum at 80 °C, where the balance between hydrolysis and condensation favored the formation of stable Si–O–Si bonds. The highest degree of functionalization was observed at pH 9, which corresponds to the point of zero charge of alumina in CFA, where neutral surface hydroxyl groups were available to react with silanols. These results define the optimal conditions for APTES grafting onto CFA and demonstrate its potential as a silane-modified filler in polymer composites. Atomic force microscopy (AFM) provided direct visual evidence of significant surface texture modifications induced by APTES treatment in the ethanol/water solvent system.