Relaxation Characteristics of Poly(vinylidene fluoride) and Ethylene-chlorotrifluoroethylene in the Transient Uptake of Aromatic Solvents

Sang-Wha Lee

Korean Journal of Chemical Engineering, Vol.21, No.6, 1119-1125, November, 2004

DOI10.1007/BF02719483 Export Citation

Relaxation Characteristics of Poly(vinylidene fluoride) and Ethylene-chlorotrifluoroethylene in the Transient Uptake of Aromatic Solvents

Sang-Wha Lee^†

Dept. of Chemical & Bio Engineering, Kyungwon University, San 65 Bokjung-Dong, Soojung-Gu, Seongnam-City, Kyunggi-Do 461-701, Korea

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Poly(vinylidene fluoride) (PVDF) and ethylene-chlorotrifluoroethylene (ECTFE) exhibited non-Fickian diffusion behaviors in the transient uptake of aromatic solvents. The diffusional exponents at the final stage of uptake exhibited asymptotic values ranging from 0.9-1.0 for the sigmoidal sorption of PVDF and 1.2-2.0 for the drastic accelerating sorption of ECTFE. The asymptotic diffusional exponent decreased with rising temperature. PVDF film exhibited a linear increase in both machine and transverse directions with fractional uptake, whereas ECTFE film increased linearly in the transverse direction and exponentially in the machine direction. A rate-type viscoelastic [Camera-Roda and Sarti, 1990] model was applied to reproduce the anomalous sorption of fluoropolymer-solvent systems. The fitted Deborah numbers ranged from 0.2-0.3 for PVDF, and 2-5 for ECTFE. The diffusivity ratio, D_eq/D_o, of PVDFsolvent system was fitted as tenth order of magnitude lower than that of ECTFE-solvent system. The fraction of initial surface concentration, S_o, was fitted in the range of 0.6-0.8 for both ECTFE and PVDF. It is plausible to assume that diffusion coupled with comparable structural relaxation has the asymptotic diffusional exponents that are strongly dependent on accelerating curvature, and total sorption is contributed by relaxation-induced viscoelastic volume change along with concentration-driven Fickian diffusion.

Keywords:Poly(vinylidene Fluoride);Ethylene-Chlorotrifluoroethylene;Transient Sorption;Relaxation Kinetics

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[Related Articles]

[1] Aklonis JJ, Kovacs AJ, "A New Nook at the Glass Transition," in Contemporary Topics in Polymer Science, 3, 267 (1979)

[2] Alfrey T, Gumee EF, Lloyd WG, J. Polym. Sci. C, 12, 249 (1966)

[3] Astarita G, Nicolais L, Pure Appl. Chem., 55, 727 (1983)

[4] Bae SY, Kim HT, Kumazawa H, Korean J. Chem. Eng., 11(3), 211 (1994)

[5] Berens AR, Hopfenberg HB, Polym., 19, 489 (1978)

[6] Camera-Roda G, Sarti GC, Trans. Theory Stat. Physics, 15, 1023 (1986)

[7] Camera-Roda G, Sarti GC, AIChE J., 36, 851 (1990)

[8] Carbonell RG, Sarti GC, Ind. Eng. Chem. Res., 29, 1194 (1990)

[9] Crank J, "The Mathematics of Diffusion," 2nd Ed., Oxford University Press, Oxford (1975)

[10] Crank J, Park GS, "Diffusion in Polymers", Academic Press, London (1968)

[11] Doghieri F, Camera-Roda G, Sarti GC, AIChE J., 39, 1847 (1993)

[12] Durning CJ, J. Polymer Science: Polym. Phys. Edition, 23, 1831 (1985)

[13] Ferry JD, "Viscoelastic Properties of Polymers," 3rd Ed., Wiley, New York (1980)

[14] Frish HL, Polym. Eng. Sci., 20, 2 (1980)

[15] Fujita H, Fortschr. Hochpolym. Forsch, 3, 1 (1961)

[16] Imbalzano JF, Chem. Eng. Prog., 69 (1991)

[17] Jacques CHM, Hopfenberg HB, Stannet VT, "Super Case II Transport of Organic Vapors in Glassy Polymers," in Permeability of Plastic Films and Coatings to Vapors and Liquids, H. B. Hopfenberg, ed., Plenum, New York (1974)

[18] Kalospiros NS, Astarita G, Paulaitis ME, Chem. Eng. Sci., 45, 23 (1993)

[19] Kalospiros NS, Ocone R, Astarita G, Meldon JH, Ind. Eng. Chem. Res., 30, 851 (1991)

[20] Kim D, Peppas NA, Korean J. Chem. Eng., 13(2), 123 (1996)

[21] Kulkarni SS, Stern SA, J. Polymer Science: Polymer Physics Edition, 21, 441 (1983)

[22] Lee S, Knaebel KS, J. Appl. Polym. Sci., 64(3), 455 (1997)

[23] Long FA, Richman D, J. Am. Chem. Soc., 82, 513 (1960)

[24] Neogi P, AIChE J., 29, 833 (1983)

[25] Odani H, Hayashai J, Tamura M, Bull. Chem. Soc. Jpn., 34, 817 (1961)

[26] Ramesh N, Duda JL, Korean J. Chem. Eng., 17(3), 310 (2000)

[27] Rogers CE, "Polymer Permeability," Ed., J. Comyn, Elsevier Applied Science Publishers Ltd., London (1985)

[28] Sarti GC, Doghieri F, Chem. Eng. Sci., 53(19), 3435 (1998)

[29] Stern SA, Kulkarni SS, J. Polym. Sci., 21, 441 (1983)

[30] Thomas HL, Windle AH, Polym., 23, 529 (1982)

[31] Thomas HL, Windle AH, Polym., 22, 627 (1981)

[32] Williams ML, Landel RF, Ferry JD, J. Am. Chem. Soc., 77, 3701 (1955)