The polymer mat: Arrested rebound of a compressed polymer layer

Compression of an adsorbed polymer layer distorts its relaxed structure. Surface force measurements from different laboratories show that the return to this relaxed structure after the compression is released can be slowed to the scale of tens of minutes and that the recovery time grows rapidly with molecular weight. We argue that the arrested state of the free layer before relaxation can be described as a Guiselin brush structure1, in which the surface excess lies at heights of the order of the layer thickness, unlike an adsorbed layer. This brush structure predicts an exponential falloff of the force at large distance with a decay length that varies as the initial compression distance to the 6/5 power. This exponential falloff is consistent with surface force measurements. We propose a relaxation mechanism that accounts for the increase in relaxation time with chain length.