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Diffusion in polymers dependence on crosslink density

Eyring approach to mechanism

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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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Acknowledgements

Most helpful discussion with Professor Sergey Vyazovkin, University of Alabama at Birmigham, and his valuable suggestion to consider pre-exponential factors behavior added to the diffusion mechanism discussion and are gratefully acknowledged.

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  1. Baxter Healthcare Corporation, Device Center of Excellence, Applied Science and Technology, Rt. 120 & Wilson Rd., RLT-14, Round Lake, IL, 60073, USA

    Vadim V. Krongauz

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Krongauz, V.V. Diffusion in polymers dependence on crosslink density. J Therm Anal Calorim 102, 435–445 (2010). https://doi.org/10.1007/s10973-010-0922-6

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