Effect of the addition of functionalized TiO2 nanotubes and nanoparticles on properties of experimental resin composites

Abstract

Objective: To evaluate the influence of the addition of functionalized and non-functionalized TiO₂ nanostructures on properties of a resin composite.

Methods: TiO₂ nanostructures were synthesized and functionalized, using 3-(aminopropyl)triethoxysilane (APTMS) and 3-(trimethoxysilyl)propyl methacrylate (TSMPM). Characterizations were performed with XRD, EDS, TEM, and TGA. Resin composites containing Bis-GMA/TEGDMA, CQ, DABE, and barium-aluminum silicate glass were produced according to TiO₂ nanostructure (nanotube or nanoparticle), concentration (0.3 or 0.9 wt%), and functionalization (APTMS or TSMPM). The resin composite without nanostructures was used as control. The amount of fillers was kept constant at 78.3 wt% for all materials. The degree of conversion (DC - at 0 h and 24 h), maximum polymerization rate (Rp_max), and Knoop microhardness (KHN before and after ethanol softening) were evaluated. Data were analyzed with two-way ANOVA with repeated measures and Tukey's HSD (α = 0.05).

Results: TGA results demonstrated that functionalizations were effective for both nanostructures. For DC, resin composites, time and interaction effect were significant (p < 0.001). Higher DC was found for 0.3-wt%-functionalized-nanotubes at 24 h. For nanoparticles, only 0.9-wt%-non-functionalized and 0.3-wt%-APTMS-functionalized showed DC similar to the control and all other groups showed higher DC (p < 0.05). Rp_max was higher for 0.3-wt%-APTMS-nanotubes, which corresponded to higher DC after 24 h. The lowest Rp_max occurred for 0.9-wt%-TSMPM-nanotubes, which showed smaller DC at 0 h. For KHN, resin composites, ethanol softening and interaction effect were significant (p < 0.001). KHN decreased after ethanol softening all groups, except for 0.3-wt%-TSMPM-nanotubes, 0.9-wt%-TSMPM-nanotubes, and 0.3-wt%-non-functionalized-nanoparticles.

Conclusion: The resin with 0.3-wt%-TSMPM-nanotubes showed higher DC after 24 h, while being the most stable material after the ethanol softening.

Significance: The addition of functionalized TiO₂ nanostructures in resin-based materials may improve the properties of the material.

Keywords: Functionalization; Methacrylates; Nanostructures; Polymer structure; Titanium dioxide.