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Probe Diffusion during Sol–Gel Transition of a Radical Polymerization System Using Isorefractive Dynamic Light Scattering
journal contribution
posted on 2017-12-14, 17:35 authored by Nobuyuki Watanabe, Xiang Li, Mitsuhiro ShibayamaProbe diffusion in a gelation process
provides unique information
such as local viscosity and sol/gel fraction that general scattering
and rheological measurements do not provide. In this study, we revisited
a gelation process of radical copolymerization of monomers and cross-linkers
by conducting a series of probe diffusion experiments with dynamic
light scattering (DLS). By using an isorefractive solvent to the gel
system, we exclusively monitored the dynamics of gold nanoparticles
during its real-time gelation process at multiscattering angles. The
obtained time-correlation functions (g2(τ) – 1) were analyzed by fitting with empirical stretched
exponential functions. The ratio of mobile particles to the total
particles, the relaxation time of mobile particles, and the heterogeneity
of their dynamics were obtained as the fitting parameters. With those
fitting parameters, the gel point, heterogeneity of local environment,
and the local viscosity were evaluated. In addition, a unique up-and-down
transition was found in the relaxation time, suggesting the local
viscosity that the particles feel changes drastically around the gel
point. This transition point in the relaxation time matches the gel
point for homogeneous gels but showed a systematic deviation in heterogeneous
gels by changing q–1 and the size
of probe particles.