Aggregation and self-assembly of amphiphilic block copolymers in aqueous dispersions of carbon nanotubes

The self-assembly (SA) of amphiphilic block copolymers (poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)) was investigated in dispersions of single-walled and multiwalled carbon nanotubes (SWNT and MWNT, respectively)as a function of temperature. Differential scanning calorimetry (DSC) was used for characterization of the thermal behavior of the combined polymers-nanostructures system, and spin-probe electron paramagnetic resonance (EPR) was employed for probing the local dynamic and polarity of the polymer chains in the presence of nanostructures. It was found that SWNT and MWNT modify the temperature, enthalpy, and dynamic behavior of polymer SA. In particular, SWNT were found to increase the cooperativity of aggregating chains and dominate aggregate dynamics. MWNT reduced the cooperativity, while colloidal carbon black additives, studied for comparison, did not show similar effects. The experimental observations are consistent with the suggestion that dimensional matching between the characteristic radius of the solvated polymer chains and the dimensions of additives dominate polymer SA in the hybrid system.