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Diffusion and localized swelling resistances in glassy polymers
Author(s) -
Gostoli C.,
Sarti G. C.
Publication year - 1982
Publication title -
polymer engineering and science
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.503
H-Index - 111
eISSN - 1548-2634
pISSN - 0032-3888
DOI - 10.1002/pen.760221603
Subject(s) - penetrant (biochemical) , swelling , materials science , sorption , fick's laws of diffusion , diffusion , polymer , relaxation (psychology) , stress relaxation , composite material , thermodynamics , creep , chemistry , organic chemistry , psychology , social psychology , physics , adsorption
The sorption of swelling penetrants in glassy polymers is modeled as a diffusion problem with moving boundary. The velocity of the swelling front is related to the stress exerted by the penetrant on the glassy matrix at the moving boundary. The solvent stress is considered as the sum of the osmotic tension and of the differential swelling stress. The latter increases as the residual thickness of the glassy core is reduced, giving rise to an acceleration of the front velocity (Super Case II). It is shown that the stress relaxation properties in the swollen region must be taken into account in order to obtain a thickness‐dependent Super Case II effect, which disappears in thick samples, according to experimental evidence. All the observed sorption behaviors, including Fickian diffusion, Case II, and Super Case II sorption, are properly accommodated in the theory.