Abstract
Deuteron solid-state NMR techniques at high pressure are used to study the chain dynamics in the amorphous polymer atactic polypropylene. The arrest of the structural relaxation above the glass-transition temperature Tgis investigated using one- and two-dimensional deuteron NMR spectra. The slow reorientation of the main chain segments is identified with the α-process observed in mechanical relaxation experiments. On approaching the glass transition, the time scale of the collective motion of the main chain becomes longer very rapidly at decreasing temperatures. Along isobars, at pressure values up to 5 kbar, the temperature dependence of the logarithmic average correlation time is very well described by a Vogel–Fulcher function. The motion of the main chain is strongly dependent on the pressure, while its character is determined mainly by the distance to Tg. The introduction of the equation of state allows the investigation of the dynamic behavior on isothermal and isochoric paths on approaching Tg. It is found that along an isotherm the mobility as a function of the density is also of the Vogel–Fulcher form.
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REFERENCES
M. L. Williams, R. F. Landel, and J. D. Ferry, J. Am. Chem. Soc. 77:3701 (1955).
J. D. Ferry, Viscoelastic Properties of Polymers(John Wiley & Sons, New York, 1961).
H. Vogel, Z. Phys. 22:645 (1921).
G. S. Fulcher, J. Am. Ceram. Soc. 8:339, 789 (1925).
G. Tammann and W. Z. Hesse, Z. Anorg. Allgem. Chem. 156:245 (1926).
D. Schaefer, H. W. Spiess, U. W. Suter, and W. W. Fleming, Macromolecules 23:3431 (1990).
D. Schaefer and H. W. Spiess, J. Chem. Phys. 97:7944 (1992).
A. Dekmezian, D. E. Axelson, J. J. Dechter, B. Bohra, and L. Mandelkern, J. Polym. Sci. Polym. Phys. Ed. 23:367 (1985).
A. G. S. Hollander, Ph.D. thesis (University of Amsterdam, Amsterdam, 1998); copies are available on request.
J. H. Davis, K. R. Jeffrey, M. Bloom, M. I. Valic, and T. P. Higgs, Chem. Phys. Lett. 42:390 (1976).
D. Schaefer, J. Leisen, and H. W. Spiess, J. Mag. Res. A 115:60 (1995).
G. E. Pake, J. Chem. Phys. 16:327 (1948).
K. Schmidt-Rohr and H. W. Spiess, Multidimensional Solid-State NMR and Polymers(Academic Press, London, 1994).
S. Kaufmann, S. Wefing, D. Schaefer, and H. W. Spiess, J. Chem. Phys. 93:197 (1990).
C. Schmidt, B. Blümich, and H. W. Spiess, J. Mag. Res. 79:269 (1988).
S. Wefing, S. Kaufmann, and H. W. Spiess, J. Chem. Phys. 89:1234 (1988).
K. Schmidt-Rohr and H. W. Spiess, Phys. Rev. Lett. 66:3020 (1991).
R. Kohlrausch, Ann. Phys. 12:393 (1847).
G. Williams and D. C. Watts, Trans. Faraday Soc. 66:80 (1970).
S. Wefing and H. W. Spiess, J. Chem. Phys. 89:1219 (1988).
M. S. Greenfield, A. D. Ronemus, R. L. Vold, R. R. Vold, P. D. Ellis, and T. E. Raidy, J. Mag. Res. 72:89 (1987).
H. Sillescu, J. Chem. Phys. 54:2110 (1971).
A. Abragam, The Principles of Nuclear Magnetism(Clarendon Press, Oxford, 1961).
P. A. Rodgers, J. Appl. Polym. Sci. 48:1061 (1993).
R. D. Maier, R. Thomann, J. Kressler, R. Muelhaupt, and B. Rudolf, J. Polym. Sci. B Polym. Phys. 35:1135 (1997).
P. Zoller and D. J. Walsh, Standard Pressure-Volume-Temperature Data for Polymers(Technomic, Lancaster, PA, 1995).
P. G. Tait, Phys. Chem. 2:1 (1888).
G. Rehage and H.-J. Oels, High Temp. High Press. 9:545 (1977).
P. Zoller, J. Polym. Sci. Polym. Phys. 20:1453 (1982).
G. Adam and J. H. Gibbs, J. Chem. Phys. 43:139 (1965).
J. Jäckle, Rep. Prog. Phys. 49:171 (1986).
J. H. Gibbs and E. A. DiMarzio, J. Chem. Phys. 28:373 (1958).
E.A. DiMarzio and J. H. Gibbs, J. Chem. Phys. 28:807 (1958).
G. Parisi, in The Oscar Klein Centenary, U. Lindström, ed. (World Scientific, Singapore, 1995).
E. Passaglia and H. K. Kevorkian, J. Appl. Phys. 34:90 (1963).
P. J. Flory, Statistical Mechanics of Chain Molecules(Hansen, New York, 1969).
R.-J. Roe, Advances in Polymer Science 116(Springer-Verlag, Berlin Heidelberg, 1994).
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Hollander, A.G.S., Prins, K.O. NMR Study of Chain Motion in Atactic Polypropylene at High Pressure. International Journal of Thermophysics 22, 357–375 (2001). https://doi.org/10.1023/A:1010762528795
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DOI: https://doi.org/10.1023/A:1010762528795