Correlating bulk properties and nanoscale rearrangement during UV-initiated gelation of hybrid nanoparticle/ block copolymer systems

We use rheology and Small Angle X-Ray Scattering (SAXS) to investigate UV initiated gel formation in aqueous dispersions of clay nanoparticles in the presence of poly(ethyleneoxide-b-propyleneoxide-b-ethyleneoxide) block copolymer surfactants (Pluronics\textregistered ) and small amounts of a photoacid generator (PAG). This material system demonstrates stable liquid-like behavior in the absence of UV but undergoes bulk gelation upon UV exposure. Rheology was used to monitor the bulk properties of a series of samples undergoing UV exposure and confirm bulk gel formation. We further probe nanoparticle rearrangement using time resolved synchrotron SAXS with simultaneous UV exposure. Time dependent SAXS indicate an absence of long range order and crystallinity while changes in the scattering profile are related to short range interparticle interactions leading to a stable or arrested structure. Finally, we compare the time scales for structural rearrangement of nanoparticles with the bulk gelation behavior. Our results show that the kinetics for local structural changes between particles and bulk gelation from UV exposure are strongly correlated.