Macromolecules, Vol.42, No.14, 5317-5327, 2009
Demixing and Remixing Kinetics in Aqueous Dispersions of Poly(N-isopropylacrylamide) (PNIPAM) Brushes Bound to Gold Nanoparticles Studied by Means of Modulated Temperature Differential Scanning Calorimetry
The demixing and remixing kinetics in aqueous dispersions of poly(N-isopropylacrylamide) (PNIPAM) brushes covalently bound to the surface of the gold nanoparticles, which are denoted as Au-PNIPAM, is studied by means of modulated temperature differential scanning calorimetry (MTDSC) in both nonisothermal and quasi-isothermal modes. The nonisothermal measurements show double demixing peaks in both the heat flow and the heat capacity traces for dispersions with a weight fraction of Au-PNIPAM (f(w)) below 50 wt %. The lower phase transition corresponds to an inner layer of PNIPAM segments on the surface of the gold core, while the upper transition corresponds to an outer layer. The dispersions follow a lower critical solution temperature phase behavior with a threshold demixing temperature at about 11.4 degrees C for f(w) of 45.3 wt %. Comparison with aqueous solutions of PNIPAM with different molar masses shows that the gold core reduces the miscibility of PNIPAM with water. The process kinetics throughout the phase transition is studied by quasi-isothermal heat capacity measurements, through the effect of the modulation frequency, by changing the heating rate and repeated heating-cooling cycles. Overall, the response for Au-PNIPAM dispersions is markedly faster than for PNIPAM solutions, which might be the result of water remaining Finely dispersed within the polymer matrix. Close to the gold core, the restricted collapse of the PNIPAM chains, as a result of steric hindrance by neighboring anchored chains, might result in the presence of water inside the collapsed nanoparticle. Notwithstanding the occurrence of partial vitrification in the polymer-rich phase during heating, the Au-PNIPAM dispersions retain their thermoresponsive behavior after repeated heating-cooling cycles.