Polymer Dynamics in PEG-Silica Nanocomposites: Effects of Polymer Molecular Weight, Temperature and Solvent Dilution

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• 作者：So Youn Kim ; Henriette W. Meyer ; Kay Saalw盲chter ; Charles F. Zukoski
• 刊名：Macromolecules
• 出版年：2012
• 出版时间：May 22, 2012
• 年：2012
• 卷：45
• 期：10
• 页码：4225-4237
• 全文大小：593K
• 年卷期：v.45,no.10(May 22, 2012)
• ISSN：1520-5835

文摘

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鈥損article 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鈥?00 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 scattering.