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Defects in Polymer Crystals

Published online by Cambridge University Press:  29 November 2013

Bernhard Wunderlich  and
Stefan N. Kreitmeier
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Extract

The development of early knowledge about crystals of flexible macromolecules (usually called simply “polymers”) and their defects was reviewed in Reference. Much of the initial research followed the information gathered on crystals of small molecules, metals, salts, and ceramics. Very quickly, however, the special nature of polymers became obvious. It was suggested some time ago to describe semicrystalline polymers with the help of zero- to three-dimensional defects. The present status of this scheme is summarized in this article.

Crystallized polymers are rarely in equilibrium. Therefore, the phase rule, which permits the presence of only one phase with two degrees of freedom (temperature and pressure) for a onecomponent material, does not apply. This nonequilibrium state is kept metastable by restrictions caused by the molecules that cross the interfaces (two-dimensional defects). The strain propagated to the noncrystalline areas produces three-dimensional defects of limited mobility. The overall structure can also be described as being microphase-separated.

Often the sizes of the different phases can be as small as the nanometer scale. One-dimensional or line defects, also called dislocations, became obvious in polymers with the first observations of solution-grown crystals of polyethylene that showed frequent growth spirals. Because of the molecular chain struc ture, many of these dislocations are sessile (immobile) and cannot participate for example, in deformation mecha nisms. Until recently, zero-dimensiona or point defects were understood largely because of molecular-mechanics calculations.

Type
Defects in Polymers
Information
MRS Bulletin , Volume 20 , Issue 9 , September 1995 , pp. 17 - 22
Copyright
Copyright © Materials Research Society 1995

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References

1.Wunderlich, B., Macromolecular Physics, 1. Crystal Structure, Morphology, Defects; II. Nucleation, Crystallization, Annealing; III. Crystal Melting (Academic Press, New York, 1973, 1976, and 1980).Google Scholar
2. For example, see The Chemistry of Imperfect Crystals, Craggier, F.A. (North-Holland Publishers, Amsterdam, 1964); or W. Shockley, J.H. Holloman, R. Maurer, and F. Seitz, eds., Imperfections in Nearly Perfect Crystals (Wiley, New York, 1952).Google Scholar
3.Wunderlich, B., Polym. 5 (1964) p. 125.CrossRefGoogle Scholar
4. See Reference 1, vol. 1, Sections 3.2.1 and 4.3.3.Google Scholar
5. See Reference 1, vol. 1, Sections 4.2.3 and 4.3.Google Scholar
6.Sumpter, B.G., Noid, D.W., Liang, G.L., and Wunderlich, B., Adv. Polym. Sci. 116 (1994) p. 55.Google Scholar
7.Cheng, S.Z.D., Wu, Z.Q., and Wunderlich, B., Macromolecules 20 (1987) p. 2,801.Google Scholar
8.Suzuki, H., Grebowicz, J., and Wunderlich, B., Brit. Polym. J. 17 (1985) p. 1; J. Menczel and B. Wunderlich, J. Polym. Sci. Polym. Lett. Ed. 19 (1981) p. 261.CrossRefGoogle Scholar
9.Fu, Y., Busing, W.R., Jin, Y., Affholter, K.A., and Wunderlich, B., Macromolecules 26 (1993) p. 2,187; Y. Fu, W.R. Busing, Y. Jin, K.A. Affholter, and B. Wunderlich, Macromol. Chem. 195 (1994) p. 803; Y. Fu, B. Annis, A. Boiler, Y. Jin, and B. Wunderlich, J. Polym. Sci., Polym. Phys. 32 (1994) p. 2,289.CrossRefGoogle Scholar
10.Takayanagi, M., Imada, K., and Kajiyama, T., J. Polym. Sci., Part C 15 (1966) p. 263.Google Scholar
11.Fu, Y., Chen, W., Pyda, M., Londono, D., Annis, B., Cheng, J., Boiler, A., and Wunderlich, B., J. Macromol. Sci., Part B, in press.Google Scholar
12.Geil, P.H., Polymer Single Crystals (Wiley-Interscience, New York, 1963); A.E. Woodward, Atlas of Polymer Morphology (Hanser Publishers, Munchen, 1988); and Reference 1.Google Scholar
13.Dawson, I.M. and Vand, V., Proc. R. Soc. London A206 (1951) p. 555.Google Scholar
14.Agar, A.W., Frank, F.C., and Keller, A., Philos. Mag. 4 (1959) p. 32; P. Predecki and W.O. Statton, J. Appl. Phys. 37 (1966) p. 4,053.CrossRefGoogle Scholar
15.Liang, G.L., Noid, D.W., Sumpter, B.G., and Wunderlich, B., J. Phys. Chem. 98 (1994) p. 11,739.CrossRefGoogle Scholar
16.Wilson, P.M. and Martin, D.C., J. Mater. Res. 7 (1992) p. 3,150.CrossRefGoogle Scholar
17.Peterlin, A., J. Mater. Sci. 6 (1971) p. 490.CrossRefGoogle Scholar
18.Wunderlich, B., Möller, M., Grebowicz, J., and Baur, H., in Advanced Polymer Science, vol. 87 (Springer Verlag, Berlin, 1988).Google Scholar
19. For example, see Reneker, D.H., J. Polym. Sci. 59 (1962) p. S39; T.F. Schatzki, J. Polym. Sci. 57 (1962) p. 496; W. Pechhold, S. Blasenbrey, and S. Woerner, Kolloid Z.Z. Polym. 189 (1963) p. 14; K.H. Illers, Rheol. Acta 3 (1964) p. 202; P.E. McMahon, R.L. McCullough, and A.A. Schlegel, J. Appl. Phys. 38 (1967) p. 4,123.CrossRefGoogle Scholar
20.Noid, D.W., Sumpter, B.G., Wunderlich, B., and Pfeffer, G.A., J. Comp. Chem. 11 (1990) p. 236; D.W. Noid, B.G. Sumpter, and R.L. Cox, J. Comp. Chem. 1 (1991) p. 161.CrossRefGoogle Scholar
21.Sumpter, B.G., Noid, D.W., and Wunderlich, B., Macromolecules 25 (1992) p. 7,247.CrossRefGoogle Scholar
22.Kreitmeier, S.N., Liang, G.L., Noid, D.W., and Sumpter, B.G., J. Thermal Analysis in press.Google Scholar