Dielectric and viscoelastic investigation of segmental dynamics of polystyrene above glass transition temperature: Cooperative sequence length and relaxation mode distribution

Macromolecules

Volumn 44, Issue 11, 2011, Pages 4355-4365

  Matsumiya, Yumi ^a   Uno, Akiko ^a   Watanabe, Hiroshi ^a   Inoue, Tadashi ^b   Urakawa, Osamu ^b  

^a KYOTO UNIVERSITY   (Japan)

^b OSAKA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ANGULAR FREQUENCIES; ATACTIC POLYSTYRENES; COMPLEX MODULUS; COOPERATIVE MOTION; COOPERATIVITY; CROSS CORRELATIONS; DIELECTRIC PERMITTIVITIES; LENGTH SCALE; LOW FREQUENCY; MODE DISTRIBUTION; MONODISPERSE; RELAXATION MODES; REORIENTATIONAL MOTION; REPEATING UNIT; RHEO-OPTICAL; SEGMENTAL DYNAMICS; SEGMENTAL MOTION; SEGMENTAL RELAXATION; SEQUENCE LENGTHS; SHIFT FACTORS; TERMINAL FLOW; TIME-TEMPERATURE; TWO-REGIME;

DIELECTRIC RELAXATION; DYNAMICS; MOLECULAR WEIGHT; MOLECULES; POLYSTYRENES; TORSIONAL STRESS;

GLASS TRANSITION;

EID: 79958824165     PISSN: 00249297     EISSN: None     Source Type: Journal    
DOI: 10.1021/ma200631p     Document Type: Article

References (54)

1. Ferry, J. D. Viscoelastic Properties of Polymers, 3 rd ed.; Wiley: New York, 1980; Chapter 15.
2. Kremer, F. and Schönhals, A. The Scaling of the Dynamics of Glasses and Supercooled Liquids. In Broadband Dielectric Spectroscopy; Kremer, F. and Schönhals, A., Eds.; Springer: Berlin, 2003, Chapter 4.
3. Lunkenheimer, P. and Loidl, A. Glassy Dynamics Beyond the α-Relaxation. In Broadband Dielectric Spectroscopy; Kremer, F. and Schönhals, A., Eds.; Springer: Berlin, 2003; Chapter 5.
4. Matsuoka, S. Relaxation Phenomena in Polymers; Hanser: Munich, Germany, 1992; Chapter 2.
5. Donth, E. J. Non-Cryst. Solids 1982, 53, 325-330
6. Fischer, E. W.; Donth, E.; Steffen, W. Phys. Rev. Lett. 1992, 68, 2344-2346
7. Donth, E.; The Glass Transition: Relaxation Dynamics in Liquids and Disordered Materials; Springer: Berlin, 2001; Chapters 2 and 3.
8. Rendell, R. W.; Ngai, K. L.; Mashimo, S. J. Chem. Phys. 1987, 87, 2359-2362
9. Ngai, K. L.; Rendell, R. W.; Plazek, D. J. J. Chem. Phys. 1991, 94, 3018-3029
10. Plazek, D. J.; Ngai, K. L. Macromolecules 1991, 24, 1222-1224
11. Plazek, D. J.; Zheng, X. D.; Ngai, K. L. Macromolecules 1992, 25, 4920-4924
12. Adachi, K.; Kotaka, T. Prog. Polym. Sci. 1993, 18, 585-622
13. Kanaya, T.; Kaji, K. Adv. Polym. Sci. 2001, 154, 87-141
14. Fukao, K.; Sakamoto, A.; Kubota, Y.; Saruyama, Y. J. Non-Cryst. Solids 2005, 351, 2678-2684
15. McKenna, G. B. J. Phys.-Condensed Matter 2003, 15, S737-S763
16. Chen, K.; Schweizer, K. S. Phys. Rev. E. 2010, 82, 041804
17. Cai, W. Z.; Schmidt-Rohr, K.; Egger, N.; Gerharz, B.; Spiess, H. W. Polymer 1993, 34, 267-276
18. McGrath, K. J.; Ngai, K. L.; Roland, C. M. Macromolecules 1995, 28, 2825-2830
19. Colmenero, J.; Alegria, A.; Santangelo., P. G.; Ngai, K. L.; Roland, C. M. Macromolecules 1994, 27, 407-410
20. Schönhals, A. Macromolecules 1993, 26, 1309-1312
21. Cangialosi, D.; Alegria, A.; Colmenero, J. J. Chem. Phys. 2009, 130, 124902
22. Riande, E.; Saiz, E. Dipole Moments and Birefringence of Polymers; Prentice Hall: Englewood Cliffs, NJ, 1992.
23. Watanabe, H. Macromol. Rapid Commun. 2001, 22, 127-175
24. Inoue, T.; Okamoto, H.; Osaki, K. Macromolecules 1991, 24, 5670-5675
25. Inoue, T.; Okamoto, H.; Mizukami, Y.; Matsui, H.; Watanabe, H.; Kanaya, T.; Osaki, K. Macromolecules 1996, 29, 6240-6245
26. Inoue, T.; Matsui, H.; Osaki, K. Rheol. Acta 1997, 36, 239-244
27. Cole, R. H. J. Chem. Phys. 1965, 42, 637-643
28. Schönhals, A.; Kremer, F. Theory of Dielectric Relaxation, in Kremer, F.; Schönhals, A., Eds, Broadband Dielectric Spectroscopy: Springer: Berlin, 2003, Chapter 1.
29. Cook, M.; Watts, D. C.; Williams, G. Trans. Faraday Soc. 1970, 66, 2503-2511
30. Riande, E.; Diaz-Calleja, R. Electrical Properties of Polymers; Marcel Dekker: New York, 2004.
31. McCrum, N. G.; Read, B. E.; Williams, G. Anelastic and Dielectric Effects in Polymeric Solids; Wiley: New York, 1967.
32. Runt, J. P.; Fitzgerald, J. J. Dielectric Spectroscopy of Polymeric Materials: Fundamentals and Applications; American Chemical Society: Washington DC, 1997.
33. Hintermeyer, J.; Herrmann, A.; Kahlau, R.; Goiceanu, C.; Rössler, E. A. Macromolecules 2008, 41, 9335-9344
34. Mott, P. H.; Roland, C. M. Macromolecules 1998, 31, 7095-7098
35. Inoue, T; Osaki, K. Macromolecules 1999, 32, 4725-4727
36. Mott, P. H.; Roland, C. M. Macromolecules 1999, 32, 4728-4728
37. G) with increasing magnitude of dipole even if the molecular diffusivity is kept constant. Thus, M * does not detect the molecular motion straightforwardly and is not suitable for the direct comparison with G*. Several other examples showing unsuitableness of the direct comparison of M * and G * are also known. (38) For this reason, this paper made the direct comparison of the Δ ε*(ω) (= ε*(0)- ε*(ω)) and G*(ω) data. (This comparison has sound molecular basis, (38) as can be known from the above example of the rod-like molecules.)
38. Lee, A.; Matsumiya, Y.; Watanabe, H.; Ahn, K. H.; Lee, S. J. Nihon Reoroji Gakkaishi (J. Soc. Rheol. Jpn.) 2010, 38, 149-155
39. Steele, W. A. Adv. Chem. Phys. 1976, 34, 1-104
40. Watanabe, H.; Chen, Q.; Kawasaki, Y.; Matsumiya, Y.; Inoue, T.; Urakawa, O. Macromolecules 2011, 44, 1570-1584
41. Matsumiya, Y.; Inoue, T.; Iwashige, T.; Watanabe, H. Macromolecules 2009, 42, 4712-4718
42. Watanabe, H. Prog. Polym. Sci. 1999, 24, 1253-1403
43. Watanabe, H.; Matsumiya, Y.; Inoue, T. Macromolecules 2002, 35, 2339-2357
44. Watanabe, H. Polymer J. 2009, 41, 929-950
45. Havriliak, S.; Negami, S. J. Polym. Sci. Part C 1966, 14, 99-1170
46. Chambon, F.; Winter, H. H. J. Rheol. 1987, 31, 683-697
47. Williams, G.; Watts, D. C. Trans. Faraday Soc. 1970, 66, 80-85
48. Williams, G.; Watts, D. C.; Dev., S. B.; North, A. M. Trans. Faraday Soc. 1970, 67, 1323-1335
49. Buchenau (50b) suggested that the dielectric relaxation time of low- M molecules such as glycerol reflects not only the reorientational motion of the molecules but also relaxation of the entropy and density. For the low- M OS samples, the time evolution of the 〈 n p eq (t)• n q eq (0)〉 term included in eq 8 could be retarded by the entropy/density relaxation. If this entropy/density effect becomes less significant for high- M PS samples, the dielectric relaxation due to the segmental dynamics could be accelerated, in a relative sense, compared to the viscoelastic relaxation. This might be an additional mechanism for the crossover of the τ s [ ε ]/τ s [ G ] ratio seen in Figure 12, although the crossover of the Δ ε data does not seem to be well explained by this mechanism.
50. Buchenau, U.; Ohl, M.; Wischnewski, A. J. Chem. Phys. 2006, 124, 094505
51. Onsager, L. J. Am. Chem. Soc. 1936, 58, 1486-1493
52. c corresponds to this M*.
53. Watanabe, H.; Yao, M. L.; Osaki, K. Macromolecules 1996, 29, 97-103
54. Uno, A.; Watanabe, H.; Inoue, T. Viscoelastic Glass Transition and Local Dynamics of Polystyrene in Solution, to be submitted to Macromolecules.