Macromolecules, Vol.48, No.22, 8369-8375, 2015
The Role of Nanoparticle Rigidity on the Diffusion of Linear Polystyrene in a Polymer Nanocomposite
The impact of the inclusion of a nanoparticle in a polymer matrix on the dynamics of the polymer chains is an area of recent interest. In this article, we describe the role of nanopartide rigidity or softness on the impact of the presence of that nanopartide on the diffusive behavior of linear polymer chains. The neutron reflectivity results clearly show that the inclusion of similar to 10 nm soft nanoparticles in a polymer matrix (R-g similar to 20 nm) increases the diffusion coefficient of the linear polymer chain. Surprisingly, thermal analysis shows that these nanocomposites exhibit an increase in their glass transition temperature, which is incommensurate with an increase in free volume. Therefore, it appears that this effect is more complex than a simple plasticizing effect. Results from small-angle neutron scattering of the nanoparticles in solution show a structure that consists of a gel like core with a corona of free chain ends and loops. Therefore, the increase in linear polymer diffusion may be related to an increase in constraint release mechanisms in the reptation of the polymer chain, in a similar manner to that which has been reported for the diffusion of linear polymer chains in the presence of star polymers.