Macromolecules, Vol.45, No.15, 6158-6167, 2012
Correlation between Dielectric/Electric Properties and Cross-Linking/Charge Density Distributions of Thermally Sensitive Spherical PNIPAM Microgels
Thermally sensitive poly(N-isopropylacrylamide) (PNIPAM) spherical microgels with different charge distribution were prepared by different monomer and comonomer feeding methods. The frequency (f, 10(-2)-10(7) Hz) and temperature (T, 5-50 degrees C) dependent complex dielectric/electric properties of these microgels were analyzed by dielectric relaxation spectroscopy. Each microgel can be treated as a large multicharged macroion surrounded by many small counterions, and the relative displacement and the diffusion of counterions contribute to the permittivity and conductivity of the microgel dispersion. Both the dielectric permittivity at f > 10(3) Hz and the conductivity at f > 10(6) Hz decrease when the microgels shrink at temperatures higher than the lower critical solution temperature (LCST) of PNIPAM due to the shrink-induced counterion dissociation. The variation of either permittivity or conductivity with temperature reveals a sharper transition for the microgels or the microgel shell with a more uniform charge distribution than those with an inhomogeneous dense core-loose shell structure, indicating a more gradual chain shrinkage for the latter. By detecting the counterions' behaviors, we can use dielectric relaxation spectroscopy to probe the microscopic structural and dynamic heterogeneities of PNIPAM microgel dispersions.