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The effect of sorbed penetrants on the aging of previously dilated glassy polymer powders. IV
Author(s) -
Osborne J. L.,
Hopfenberg H. B.,
Koros W. J.
Publication year - 1991
Publication title -
journal of applied polymer science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.575
H-Index - 166
eISSN - 1097-4628
pISSN - 0021-8995
DOI - 10.1002/app.1991.070431222
Subject(s) - penetrant (biochemical) , sorption , polymer , polystyrene , materials science , polymer chemistry , glass transition , relaxation (psychology) , chemical engineering , chemistry , organic chemistry , composite material , adsorption , engineering , psychology , social psychology
Uniform, submicron‐diameter polystyrene (PS) and poly(methylmethacrylate) (PMMA) microspheres were dilated by preswelling with pure organic vapors followed by rapid removal of the preswelling penetrant by protracted evacuation of the preswelling chamber to a pressure of 10 −3 mm Hg. Aging of the preswollen polymers was carried out both in vacuum and in the presence of various penetrants at sorbed concentrations typically less than 2 wt%. Inferences about relaxations of the polymers were based upon changes in concentrations of the penetrants within the microspheres, at a given temperature and penetrant activity, which result from aging in vacuum or in the presence of penetrant. The kinetics of the relaxations were monitored by probing the expanded glasses with relatively low concentrations of penetrants. In general, the continuous presence of these low concentrations of probe molecules either arrested or retarded the ensuing relaxation as compared with the aging that occurred in vacuum. A series of lower monohydric alcohols, lower n ‐alkanes, and some other similar penetrants were used as probes to test explicitly and systematically the effects of size and structure of the penetrant contacting the polymer during aging on the decay of excess sorption capacity of the preswollen glassy polymers. Decay of excess sorption in the presence of penetrant was evident only when molecularly small penetrants with interactive functional groups, alcohols for example, were sorbed into preswollen PMMA. This result suggested that the relaxation occurring in the presence of penetrant involved specific interactions between the penetrants and the carbonyl groups in the PMMA.