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Title: Review and reproducibility of forming adsorbed layers from solvent washing of melt annealed films
Recent studies suggest chain adsorption in the melt may be responsible for a number of property changes in thin films by making correlations between the residual adsorbed layer thickness h ads ( t ) measured after a given solvent washing procedure as a function of annealing time t of the film at an elevated temperature prior to this solvent rinse. This procedure, frequently called “Guiselin's experiment”, refers to the thought experiment proposed in a 1992 theoretical treatment by Guiselin that assumed chain segments in contact with the surface are irreversibly adsorbed whereby unadsorbed chains could be washed away by solvent without disturbing the adsorbed substrate contact points in the melt. In the present work, we review this recent literature, identifying and experimentally testing a common protocol for forming adsorbed layers h ads ( t ) from solvent washing melt films. We find h ads ( t ) curves to be far less reproducible and reliable than implied in the literature, strongly dependent on solvent washing and substrate cleaning conditions, and annealing at elevated temperatures is unnecessary as densification of films sitting at room temperature makes the glassy film harder to wash off, leaving behind h ads of comparable thickness. This review also summarizes literature understanding developed over several decades of study on polymer adsorption in solution, which experimentally demonstrated that polymer chains in solution are highly mobile, diffusing and exchanging on the surface even in the limit of strong adsorption, contradicting Guiselin's assumption. Preformed adsorbed layers of different thicknesses h ads are shown to not affect the average glass transition temperature or physical aging of 30 nm thick films. In summary, a number of open questions and implications are discussed related to thin films and polymer nanocomposites.  more » « less
Award ID(s):
1905782 1709132
NSF-PAR ID:
10166509
Author(s) / Creator(s):
; ;
Date Published:
Journal Name:
Soft Matter
Volume:
16
Issue:
23
ISSN:
1744-683X
Page Range / eLocation ID:
5366 to 5387
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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