A scattering study of nucleation phenomena in polymer crystallisation

Abstract

The mechanism of primary nucleation in polymer crystallisation has been investigated experimentally and theoretically. Two types of experiments have been performed on polypropylene, polyethylene, and poly(ethylene terpthalate). Crystallisations with long induction times, studied by small and wide angle X-ray scattering (SAXS and WAXS), reveal the onset of large scale ordering prior to crystal growth. Rapid crystallisations studied by melt extrusion indicate the development of well resolved oriented SAXS patterns associated with large scale order before the development of crystalline peaks in the WAXS region. The results suggest pre-nucleation density fluctuations play an integral role in polymer crystallisation. A theoretical model has been developed which qualitatively describes the experimental results.

References

1. A. N. Wilkinson and A. J. Ryan, Polymer Processing and Structure Development, Kluwer, Amsterdam, 1998.
2. (a) J. I. Lauritzen and J. D. Hoffman, J. Res. Natl. Bur. Stand. Sect. A, 1960, 64, 73; (b) J. D. Hoffman, J. I. Lauritzen, E. Passaglia, G. S. Ross, L. J. Frohlen and J. J. Weeks, Kolloid. Z. Poly., 1969, 231, 564; (c) J. D. Hoffman, G. T. Davis and J. I. Lauritzen, Treatise on Solid State Chemistry, Plenum, New York, 1976; (d) J. Petermann, R. M. Gohil, J. M. Schultz, R. W. Hendricks and J. S. Lin, J. Polym. Sci. Polym. Phys. Edn., 1982, 20, 523; (e) D. M. Sadler, Polym. Commun., 1986, 27, 140; (f) D. M. Sadler, Polymer, 1987, 28, 1440.
3. R. J. Young and P. A. Lovell, Introduction to Polymers, Chapman and Hall, London, 2nd edn., 1991.
4. See, for example, A. Keller and H. W. H. Kolnaar, in Materials Science and Technology, ed. R. W. Cahn, P. Haasen and E. J. Kramer, Wiley-VCH, Weinheim, 1997, vol. 18, ed. H. E. H. Meijer; P. Barham, in Materials Science and Technology, ed. R. W. Cahn, P. Haasen and E. J. Kramer, Wiley-VCH, Weinheim, 1993, vol. 12, ed. E. L. Thomas.
5. G. Eder and H. Janeschitz-Kriegel, in Materials Science and Technology, ed. R. W. Cahn, P. Haasen and E. J. Kramer, Wiley-VCH, Weinheim, 1997, vol.18, ed. H. E. H. Meijer.
6. D. C. Basset, Principles of Polymer Morphology, Cambridge University Press, Cambridge, 1981.
7. G. Strobl, The Physics of Polymers, Springer-Verlag, Berlin, 1996.
8. M. Imai, K. Kaji, T. Kanaya and Y. Sakai, Phys. Rev. B, 1995, 52, 12696.
9. M. Imai, K. Mori, T. Mizukami, K. Kaji and T. Kanaya, Polymer, 1992, 33, 4451; ibid, 1992, 33, 4457.
10. M. Imai, K. Kaji and T. Kanaya, Macromolecules, 1994, 27, 7103.
11. T. A. Ezquerra, E. López-Cabarcos, B. S. Hsiao and F. J. Baltà-Calleja, Phys. Rev. E, 1996, 54, 989.
12. N. J. Terrill, J. P. A. Fairclough, E. Towns-Andrews, B. U. Komanschek, R. J. Young and A. J. Ryan, Polymer, 1998, 39, 2381.
13. J. W. Cahn and J. E. Hilliard, J. Chem. Phys., 1958, 28, 25; J. D. Gunton, M. San Miguel and P. S. Sahni, in Phase Transitions and Critical Phenomena, ed. C. Domb and M. S. Green, Academic, New York, 1983, vol. 8.
14. H. Janeschitz-Kriegel, Colloid Polym. Sci., 1997, 81, 1121.
15. P. D. Olmsted, W. C. K. Poon, T. C. B. McLeish, N. J. Terrill and A. J. Ryan, Phys. Rev. Lett., 1998, 81, 373.
16. N. V. Pogodina and H. H. Winter, Macromolecules, 1998, 31, 7103.
17. E. Ratajski and H. Janeschitz-Kriegel, Colloid Polym. Sci., 1996, 274, 938.
18. I. W. Hamley, J. P. Fairclough, N. J. Terrill, A. J. Ryan, P. Lipic, F. S. Bates and E. Towns-Andrews, Macromolecules, 1996, 29, 8835.
19. W. Bras and A. J. Ryan, Adv. Colloid Interface Sci., 1998, 75, 1.
20. W. Bras, G. E. Derbyshire, J. Cooke, B. E. Komanschek, A. Devine, S. M. Clark and A. J. Ryan, J. Appl. Cryst., 1994, 28, 26.
21. http://www.dl.ac.uk/SRS/NCD/manual.otoko.html.
22. I. W. Hamley, R. C. Denny, M. Matsen, B. Liao, C. Booth and A. J. Ryan, Macromolecules, 1997, 38, 509 http://wserv1.dl.ac.uk:800/SRS/CCP13/program/fit.html.
23. A. J. Ryan, J. L. Stanford, W. Bras and T. M. W. Nye, Polymer, 1997, 38, 759.
24. M. Avrami, J. Chem. Phys., 1939, 7, 1103; ibid, 1940, 8, 212; ibid 19419177; L. Marker, F. M. Hay and G. P. Tilley, J. Polym. Sci., 1959, 38, 107.
25. Polypropylene, ed. J. Karger-Kocsis, Chapman & Hall, London, 1995, vol. 1.
26. R. K. Verma and B. S. Hsiao, Trends In Polymer Science, 1996, 4, 312; B. S. Hsiao, B. B. Sauer, R. K. Verma, H. G. Zachmann, S. Seifert, B. Chu and P. Harney, Macromolecules, 1995, 28, 6931; M. Bark and H. G. Zachman, Acta Polymerica, 1993, 44, 259.
27. P. W. Atkins, Physical Chemistry, OUP, Oxford, 6th edn., 1997.
28. A. Keller and F. M. Willmouth, J. Macromol. Sci., 1972, B6, 493.
29. O. Glatter and O. Kratky, Small Angle X-ray Scattering, Academic Press, NY, 1982.
30. A. Guinier and G. Fournet, Small Angle Scattering of X-rays, Chapman & Hall, London, 1955.
31. B. Hsaio, personal communication.
32. M. Cakmak, A. Teitge, H. G. Zachmann and J. L. White, J. Polym. Sci. Polym. Phys. Edn., 1993, 31, 371.
33. K. Katayama, Kolloid Z. Z. Polym., 1968, 226, 125.
34. H. E. Cook, Acta Metall., 1970, 18, 297.
35. P. Pincus, J. Chem. Phys., 1981, 75, 1996.
36. F. S. Bates and P. Wiltzius, J. Chem. Phys., 1989, 91, 3258.
37. K. Binder, in Materials Science and Technology, ed. R. W. Cahn, P. Haasen and E. J. Kramer, Wiley-VCH, Weinheim, 1993, vol. 5, ed. P. Haasen.
38. H. Tadokoro, Structure of Crystalline Polymers, John Wiley & Son, 1979.
39. J. E. Mark, Physical properties of Polymers, American Institute of Physics, NY, 1996.
40. J. W. Cahn, Trans. Metall. Soc. AIME, 1968, 242, 166.
41. See, J. W. Martin, R. D. Doherty and B. Cantor, Stability of microstructures in metallic systems, Cambridge University Press, Cambridge, 1997.
42. W. C. K. Poon, A. D. Pine and P. N. Pusey, Faraday Discuss., 1995, 101, 65; M. R. L. Evans, W. C. K. Poon and M. E. Cates, Europhys. Lett., 1997, 38, 595.
43. S. Harrington, R. Zhang, P. H. Poole, F. Sciortino and H. E. Stanley, Phys. Rev. Lett., 1997, 78, 2409.
44. M. Dettenmaier, E. W. Fischer and M. Stamm, Colloid Polymer Sci., 1980, 258, 343.
45. L. R. Pratt, C. S. Hsu and D. Chandler, J. Chem. Phys., 1978, 68, 4202.
46. S. Alexander and J. McTague, Phys. Rev. Lett., 1978, 41, 702.
47. J. Brandrup and E. H. Immergut, Polymer Handbook, Wiley, NY, 3rd edn., 1989.
48. P. J. Flory, Statistical Mechanics of Chain Molecules, Oxford University Press, Oxford, 1989.
49. Flow-induced Crystallization in Polymers Systems, ed. R. L. Miller, Gordon and Breach, NY, 1979.
50. P. R. ten Wolde and D. Frenkel, Science, 1997, 277, 1975.
51. D. J. Blundell, D. H. McKerron, W. Fuller, A. Mahendrasingham, C. Martin, R. J. Oldman, R. J. Rule and C. Riekel, Polymer, 1996, 37, 3303.
52. T. Kanaya, A. Patkowski, E. W. Fischer, J. Seils, H. Glaser and K. Kaji, Acta Polym., 1994, 45, 137.
53. N. P. Balsara, B. A. Garetz, M. C. Newstein, B. J. Bauer and T. J. Prosa, Macromolecules, 1998, 31, 7668.
54. M. Gahleitner, J. Wolfschwenger, C. Bachner, K. Bernreitner and W. Neissl, J. Appl. Polym. Sci., 1996, 61, 649.