Thermally Reversible Aggregation of Gold Nanoparticles in Polymer Nanocomposites through Hydrogen Bonding

Abstract

The ability to tune the state of dispersion or aggregation of nanoparticles within polymer-based nanocomposites, through variations in the chemical and physical interactions with the polymer matrix, is desirable for the design of materials with switchable properties. In this study, we introduce a simple and effective means of reversibly controlling the association state of nanoparticles based on the thermal sensitivity of hydrogen bonds between the nanoparticle ligands and the matrix. Strong hydrogen bonding interactions provide excellent dispersion of gold nanoparticles functionalized with poly(styrene-r-2-vinylpyridine) [P(S-r-2VP)] ligands in a poly(styrene-r-4-vinyl phenol) [P(S-r-4VPh)] matrix. However, annealing at higher temperatures diminishes the strength of these hydrogen bonds, driving the nanoparticles to aggregate. This behavior is largely reversible upon annealing at reduced temperature with redispersion occurring on a time-scale of ~30 min for samples annealed 50 °C above the glass transition temperature of the matrix. Using ultraviolet-visible absorption spectroscopy (UV-vis) and transmission electron microscopy (TEM), we have established the reversibility of aggregation and redispersion through multiple cycles of heating and cooling.