Untangling the Effects of Chain Rigidity on the Structure and Dynamics of Strongly Adsorbed Polymer Melts

JMY Carrillo and SW Cheng and R Kumar and M Goswami and AP Sokolov and BG Sumpter, MACROMOLECULES, 48, 4207-4219 (2015).

DOI: 10.1021/acs.macromol.5b00624

We present a detailed analysis of coarse-grained molecular dynamics simulations of semiflexible polymer melts in contact with a strongly adsorbing substrate. We have characterized the segments in the interfacial layer by counting the number of trains, loops, tails, and unadsorbed segments. For more rigid chains, a tail and an adsorbed segment (a train) dominate while loops are more prevalent in more flexible chains. The tails exhibit a nonuniformly stretched conformation akin to the "polydisperse pseudobrush" originally envisioned by Guiselin. To probe the dynamics of the segments, we computed the layer z-resolved collective intermediate dynamic structure factor, S(q,t,z), mean-square displacement of segments, and the second Legendre polynomial of the time autocorrelation of unit bond vectors, < P-2(n) over right arrow (i)(t,z).(n) over right arrow (i)(0,z)>. Our results show that segmental dynamics is slower for stiffer chains, and there is a strong correlation between the structure and dynamics in the interfacial layer. There is no "glassy layer", and the slowing down in dynamics of stiffer chains in the adsorbed region can be attributed to the densification and a more persistent layering of segments.

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