Rheology and microstructure of polymer nanocomposite melts: variation of polymer segment-surface interaction.

We have studied the effects of particle packing fraction, polymer molecular weight (MW), and polymer-segment-particle-surface affinity on the phase behavior of 44 nm silica dispersions in unentangled, low MW polyethylene oxide (PEO), polyethylene oxide dimethyl ether (PEODME), and polytetrahydrofuran (PTHF) through rheological measurement and small-angle X-ray scattering. Particles are shown to be stable in PEO nanocomposites up to high volume fractions due to an adsorbed layer of polymer segments that stabilizes particles in the melt. Comparison of the PEO nanocomposite to PEODME and PTHF nanocomposites reveals little evidence of an adsorbed layer in the spirit of the PEO nanocomposite. Measurement of the PTHF nanocomposite viscosity reveals evidence of segment slip at the particle surface by the particle intrinsic viscosity being less than Einstein's value. At higher particle volume fractions, the viscosity diverges, yielding an elastic response. The elastic response of the PEO nanocomposite has the signatures of a colloidal glass, while the PEODME and PTHF nanocomposites resemble a gel. Measurement of the particle structure factor reveals a change from overall repulsive particles in PEO to attractive particles in PTHF as the segment-surface interaction is changed.