Journal of Thermal Analysis and Calorimetry
Volume/Issue:
Volume 102: Issue 2
Diffusion in polymers dependence on crosslink density
Eyring approach to mechanism
Author:
Vadim Krongauz Baxter Healthcare Corporation, Device Center of Excellence, Applied Science and Technology, Rt. 120 & Wilson Rd., RLT-14, Round Lake, IL 60073, USA

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Pages:
435–445
Online Publication Date:
26 Jun 2010
Publication Date:
01 Nov 2010
Article Category:
Research Article
DOI:
https://doi.org/10.1007/s10973-010-0922-6
Keywords:
Polymer; Diffusion; Crosslink density; Activation energy; Mechanism; Evaporation; Eyring; Theory; Photo-polymerization
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Abstract  

Kinetics of N-methyl pyrrolidone evaporation from swollen photo-crosslinked polyacrylate was monitored thermogravimetrically at temperatures ranging from 323 to 398 K. Crosslink density dependence of evaporation kinetics was investigated in photo-crosslinked polyacrylates with crosslinked density ranging from ≈1.2 × 102 to ≈1.7 × 104 mol m−3 and number of main chain atoms between crosslinks ranging from ≈70 atoms to ≈6 atoms, respectively. As was shown, evaporation kinetics was controlled by the solvent diffusion in polymer. Activation energies of evaporation (diffusion) were deduced from the rate measurements at different temperatures. Apparent activation energy of evaporation decreased from 48.7 to 31.1 kJ mol−1 with crosslink density increase. Activation energy of pure N-methyl pyrrolidone evaporation was 50.6 kJ mol−1. Decrease of the rate of solvent diffusion and unexpected decrease of diffusion activation energy with increase of crosslink density of swollen polymer matrix was explained by decrease in polymer chain segments mobility, as indicated by Eyring’s approach to diffusion in polymers.

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Cover Journal of Thermal Analysis and Calorimetry
Journal of Thermal Analysis and Calorimetry
Print ISSN:
1388-6150
Online ISSN:
1572-8943

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Journal of Thermal Analysis and Calorimetry
Language English
Size A4
Year of
Foundation		 1969
Volumes
per Year		 1
Issues
per Year		 24
Founder Akadémiai Kiadó
Founder's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
Publisher Akadémiai Kiadó
Springer Nature Switzerland AG
Publisher's
Address		 H-1117 Budapest, Hungary 1516 Budapest, PO Box 245.
CH-6330 Cham, Switzerland Gewerbestrasse 11.
Responsible
Publisher		 Chief Executive Officer, Akadémiai Kiadó
ISSN 1388-6150 (Print)
ISSN 1588-2926 (Online)

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