Large-Scale Diffusion of Entangled Polymers along Nanochannels

作者：Lange Frank; Judeinstein Patrick; Franz Cornelius; Hartmann Azanza Brigitte; Ok Salim; Steinhart Martin; Saalwaechter Kay

来源：ACS Macro Letters, 2015, 4(5): 561-565.

DOI：10.1021/acsmacrolett.5b00213

Changes in large-scale polymer diffusivity along interfaces, arising from transient surface contacts at the nanometer scale, are not well understood. Using proton pulsed-gradient NMR, we here study the equilibrium micrometer-scale self-diffusion of poly(butadiene) chains along 100 pm long, 20 and 60 nm wide channels in alumina, which is a system without confinement-related changes in segmental relaxation time. Unlike previous reports on nonequilibrium start-up diffusion normal to an interface or into particulate nanocomposites, we find a reduction of the diffusivity that appears to depend only upon the pore diameter but not on the molecular weight in a range between 2 and 24 kg/mol. We rationalize this by a simple volume-average model for the monomeric friction coefficient, which suggests a 10-fold surface-enhanced friction on the scale of a single molecular layer. Further support is provided by applying our model to the analysis of published data on large-scale diffusion in thin films.

• 出版日期2015-5
• 单位中国地震局