ISSN:
0032-3888
Keywords:
Chemistry
;
Chemical Engineering
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
,
Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
,
Physics
Notes:
The molecular kinetic theory near the glass transition, bused on the existence of free volume distribution, is extended to incorporate the effects of stress and stress rate. The fundamental equations for the volume relaxation and recovery in stressed amorphous polymers are derived in accordance with the balance of nonequilibrium statistical entropy. Using these kinetic equations, an earlier nonequilibrium criterion for the glass transition temperature, Tg, is generalized to include the effects of stress and stress rate. In contrast to the prevalent thinking toward free volume theories, an explicit expression between Tg and stress is developed and reveals that Tg does not continue to increase at all pressures but levels off to a “universal” asymptote at very high pressure (〉10 K bars). The expression is applicable to any tension and compression stress conditions. A comparison between theory and experiment under constant stresses determines the activation volume tensor which reveals the molecular mechanism relating Tg and the plastic yield of glassy polymers.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pen.760241111
