Abstract
The pressure dependence of the glass transition temperature (∂Tg/∂P) and the enthalpy of the densified glass were studied with a hole theory. It was found that not the assertion of the iso-free volume but that of the iso-configurational entropy (or energy) or Adam–Gibbs theory at the glass transition is supported by the observed fact (∂Tg/∂P)≅TVΔα/ΔCp<Δβ/Δα, where Δα, Δβ, and ΔCp are the differences in thermal expansion coefficient, compressibility, and heat capacity at constant pressure between the liquid and glassy states at Tg, respectively. It is also supported by the fact that the densified glass has almost the same enthalpy as the glass obtained under ordinary conditions. The inequality of (∂Tg/∂P) and Δβ/Δα, which causes the densification of the glass formed under elevated pressure, was quantitatively related to the magnitute of the densified volume. It is suggested that the inequality TVΔα/ΔCp<Δβ/Δα and the formation of the densified glass may be closely related to intrasegmental interactions or the chain conformation.
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J. M. O'Reilly, “Modern Aspects of The Vitreous State,” Vol. III, J. D. Mackenzie, Ed., Butterworths Scientific Publications Ltd., London, 1964, p 59.
M. Goldstein, J. Chem. Phys., 39, 3369 (1963).
N. Shiskkin, Sov. Phys. Solid State, 2, 322 (1960).
G. Gee, Polymer, 7, 177 (1966).
e. g. J. D. Ferry, “Viscoelastic Properties of Polymers,” John Wiley & Sons, Inc., New York, N. Y., 1961.
J. H. Gibbs and E. A. Dimarzio, J. Chem. Phys., 28, 373 (1958).
J. H. Gibbs and E. A. Dimarzio, J. Chem. Phys., 28, 807 (1958).
G. Adam and J. H. Gibbs, J. Chem. Phys., 43, 139 (1965).
T. Nose, Polym. J., 2, 437 (1971).
T. Nose, Polym. J., 2 427 (1971).
T. Nose and T. Hata, “Proceedings of the 5th International Congress on Rheology,” Vol. 3, University of Tokyo Press, Tokyo, 1970, p 215.
R. Simha and R. F. Boyer, J. Chem. Phys., 37, 1003 (1962).
K. H. Hellwege, W. Knappe, and P. Lahmann, Kolloid Z., 183, 110 (1962).
F. E. Karasz, H. E. Bair, and J. M. O'Reilly, J. Phys. Chem., 69, 2657 (1965).
J. M. O'Reilly, J. Polym. Sci., Part C, 14, 49 (1964).
B. Wunderlich, J. Phys. Chem., 64, 1052 (1960).
J. M. O'Reilly, J. Polym. Sci., 57, 429 (1962).
J. E. McKinney and H. V. Belcher, J. Res. Nat. Bur. Stand., 67A, 43 (1963).
H. Simgh and A. W. Nolle, J. Appl. Phys., 30, 337 (1959).
G. M. Martin and L. Mandelkern, J. Res. Nat. Bur. Stand., 62, 141 (1959).
J. E. McKinney, H. V. Belcher, and R. S. Marvin, Trans. Soc. Rheol., 4, 347 (1960).
N. Beckkedahl and R. B. Scott, J. Res. Nat. Bur. Stand., 29, 87 (1942).
N. Shishkin, ref 3; K. Tanaka, T. Nose and T. Hata, unpublished data.
S. Ichihara, A. Komatsu, and T. Hata, Polym. J., 2, 530 (1971).
S. I. Meeson and S. M. Lipatov, Colloid J. USSR, 21, 509 (1959).
G. Allen, R. C. Ayerst, J. R. Clevel, G. Gee, and C. Prices, J. Polym. Sci., Part C, 23, 127 (1968).
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Nose, T. A Hole Theory of Polymer Liquids and Glasses. IV. Glass Transition under Elevated Pressure and Densified Glasses. Polym J 2, 445–456 (1971). https://doi.org/10.1295/polymj.2.445
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DOI: https://doi.org/10.1295/polymj.2.445