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 effects of prior thermal and swelling history on the kinetics and apparent equilibria of subsequent n-hexane sorption in monodisperse, submicrometer diameter, glassy polystyrene microspheres were studied. Repetitive sorption and desorption cycling was compared with continuous sorption and desorption experiments. The apparent equilibrium uptake of n-hexane in preswollen samples decreased monotonically with the cumulative time under vacuum independent of the cycle frequency or the number of sorption-desorption cycles. This consolidation was modeled as a first order relaxation process with a single characteristic relaxation time. “As-received” samples swelled in the presence of the penetrant and the apparent equilibrium n-hexane content increased monotonically with the time under n-hexane. The Berens-Hopfenberg diffusion-relaxation model accurately describes the cyclic and continuous swelling behavior of the “as-received” sample. At each temperature studied, a true equilibrium n-hexane content was approached asymptotically for the preswollen and “as-received” samples after sufficient time under vacuum or n-hexane, respectively. Whereas the apparent sorption equilibria were controlled by the cumulative time under vacuum or n-hexane for the preswollen and “as-received” samples, respectively, the absorption kinetics are subject to a systematic variation which depends only on the immediate prior vacuum history of the sample. The temperature dependence of the kinetic and equilibrium parameters describing diffusion, consolidation, and swelling suggests a unified molecular interpretation of these diverse glassy-state transport and relaxation processes.
Additional Material:
7 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/pen.760200117
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