Open AccessPolymer Dynamics in PEG-Silica Nanocomposites: Effects of Polymer Molecular Weight, Temperature and Solvent Dilution
Author(s) -
So Youn Kim,
Henriette W. Meyer,
Kay Saalwächter,
Charles F. Zukoski
Publication year - 2012
Publication title -
macromolecules
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.994
H-Index - 313
eISSN - 1520-5835
pISSN - 0024-9297
DOI - 10.1021/ma300439k
Subject(s) - polymer , volume fraction , materials science , particle (ecology) , chemical engineering , molecular dynamics , nanocomposite , polymer chemistry , polymer nanocomposite , neutron scattering , chemical physics , chemistry , composite material , scattering , computational chemistry , optics , oceanography , engineering , geology , physics
The mechanical properties of particulate nanocomposites strongly depend upon the particle dispersion, as well as on the closely related properties in thin polymer films covering the particle surface. The length scale of such changes is relevant for the understanding of particle-particle interactions, which ultimately dominate the mechanical response. Using well-defined 44 nm diameter silica nanoparticles dispersed in poly(ethylene glycol), we focus on surface-induced changes in polymer dynamics. Using proton time-domain NMR, we distinguish three polymer phases of different mobility, i.e., a strongly adsorbed, solid-like fraction, a fraction with intermediate relaxation times and a highly mobile fraction. We explore how these fractions change as we vary polymer molecular weight from 300 to 20 000 and particle volume fraction up to 0.3. A multiple-quantum experiment enables a closer analysis of the mobile component which we show consists of two fractions, one resembling the bulk melt-like and another one showing network-like properties. We demonstrate that above a polymer molecular weight-dependent volume fraction, polymers form elastically active links between particles, resulting in the physical gelation observed in such systems. Our results provide a quantitative picture of network formation, which is described by the amount and length of network-like chains as well as heterogeneities in the polymer dynamics. We relate changes in polymer dynamics to particle microstructure obtained from small angle neutron scatteringclose181