Korea-Australia Rheology Journal

The Korean Society of Rheology (한국유변학회)
권호 표지

Investigation of entanglement dynamics of flexible polymer chains via comparison of dielectric and viscoelastic properties: a review of recent findings

  • Watanabe, H. (Institute for Chemical Research, Kyoto University)
  • Published : 2001.12.01
Download PDF
⟨ Previous Next ⟩

Abstract

This review article summarizes results of recent viscoelastic and dielectric studies for entangled cis-polyisoprene (PI) chains. The PI chains have the so-called type-A dipoles parallel along the chain backbone, and their slow viscoelastic and dielectric relaxation processes reflect the same global chain motion. However, this motion is differently averaged in the viscoelastic and dielectric properties, the former representing the isochronal orientational anisotropy of individual entanglement segments while the latter detecting the orientational correlation of the segments at two separate times (0 and t). On the basis of this difference, the viscoelastic and dielectric data of the entangled PI chains were compared to elucidate detailed features of the chain dynamics. Specifically, the molecular picture of dynamic tube dilation (DTD) incorporated in recent models was tested for linear and star PI chain. The comparison revealed that the DTD picture was valid for linear PI chains but failed for the star PI chains in the dominant part of the terminal relaxation. The failure for the star chains was related to the pre-requisite for the DTD process, rapid equilibration of successive entanglement segments through their constraint release (CR) motion: For the star chains, the dilated tube diameter expected in the terminal regime was considerably large because of a broad distribution of motional modes of the chains, so that the CR-equilibration required for DTD could not occur in time. The terminal relaxation of the star chain appeared to occur through the CR process before the expected DTD process was completed. The situation was different for the linear chain exhibiting narrowly distributed motional modes. The dilated tube expected for the linear chain was rather thin and the required CR-equilibration occurred in time, resulting in the success of the DTD picture. These detailed features of the chain dynamics was revealed only when the viscoelastic and dielectric properties were compared, demonstrating the importance of this comparison.

Keywords

References

  1. Macromolecules v.22 Dynamic dilution and the viscosity of star polymer melts Ball,R.C.;T.C.B.McLeish
  2. Macromolicules v.19 Self-diffusion in branched polymer melts Bartles,C.R.;B.Crist;L.J.Fetters;W.W.Graessley
  3. J. Chem. Soc. Faraday Trans. 2 v.74 Dynamics of concentrated polymer systems. part 2. molecular motion under flow Doi,M.;S.F.Edwards
  4. The Theory of Polymer Dynamics Doi,M.;S.F.Edwards
  5. Viscoelastic Properties of Polymers (3rd ed.) Ferry,J.D.
  6. Macromolecules v.26 Rheological behavior of star-shaped polymers Fetters,L.J.;A.D.Kiss;D.S.Pearson;G.F.Quack;F.J.Vitus
  7. Adv. Polym. Sci. v.47 Entangled linear, branched and network polymer systems-molecular theories Graessley,W.W.
  8. Polymer melt rheology and flow birefringence Janeschitz-Kriegl,H.
  9. Macromolecules v.11 The onset of entangled behavior in semidilute and concentrated polymer solutions Klein,J.
  10. Macromolecules v.22 Fourier transform infrared dichroism study of orientation relaxation using isotropically labeled polystyrene stars Lantman,C.W.;J.F.Tassin;L.Monnerie;L.J.Fetters;E.Helfand;D.S.Pearson
  11. J. Polym. Sci. Polym. Phys. Ed. v.23 Relaxation by reptation and tube enlargement: a model for polydisperse polymers Marrucci,G.
  12. Macromolecules v.33 Comparison of dielectric and viscoelastic relaxation functions of cis-poly-isoprenes: test of tube dilation molecular picture Matsumiya,Y.;H.Watanabe;K.Osaki
  13. Macromolecules v.34 Further test of the tube dilation process in star-branched cis-polyisoprene: role of branching-point fluctuation Matsumiya,Y.;H.Watanabe
  14. Macromolecules v.30 Parameter-free theory for stress relaxation in star polymer melts Milner,S.T.;T.C.B.McLeish
  15. Macromoecules v.31 Arm-length dependence of stress relaxation in star polymer melts Milner,S.T.;T.C.B.McLeish
  16. Macromolecules v.17 Viscoelastic properties of star-shaped polymers Pearson,D.S.;E.Helfand
  17. Dipole Moments and Birefringence of Polymers Riande,E.;E.Saiz
  18. Macromolecules v.21 Diffusion of macromolecular stars in linear, microgel, and network matrices Shull,K.R.;E.J.Kramer;G.Hadzioannou;M.Antonietti;H.Sillescu
  19. Macromolecules v.21 Infragred dichroism study of the relaxation of selected segments along a strectched ploymer chain and comparison with theoretical models Tassin,J.F.;L.Monnerie;L.J.Fetters
  20. Macromolecules v.29 Comparison of dielectric and viscoelastic behavior of polyisoprene solutions: coherence in subchain motion Watanabe,H.;M.L.Yao;K.Osaki
  21. Macromolecules v.31 Dynamics of dipole-inverted cis-polyisoprene chains in a matrix of long, entangling chains. 2 effects of constraint release on the coherence of the subchain motion Watanabe,H.;Y.Matsumiya;K.Osaki;M.L.Yao
  22. Prog. Polym. Sci. v.24 Viscoelasticity and dynamics of entangled polymers Watanabe,H.
  23. J. Polym. Sci. Part B Polym. Phys. v.38 Tube dilation process in star-branched cis-polyisoprenes Watanabe,H.;Y.Matsumiya;K.Osaki
  24. Macromol. Rapid Commun. v.22 Dielectric relaxation of type-A polymers in melts and solutions Watanabe,H.
  25. Proceedings of ICAPP2001 Yonezawa Dielectric and viscoelastic properties of star-branched cis-polyisoprene: test of tube dilation mechanism Watanabe,H.;Y.Matsumiya
  26. Macromolecules Dielectric and viscoelastic relaxation of highly entangled polyisoprene stars: quantiative test of tube dilation model Watanabe,H.;Y.Matsumiya;T.Inoue
  27. Rheol. Acta v.29 Relaxation dynamics of selected polymer chain segments and comparison with theoretical models Ylitalo,C.M.;G.G.Fuller;V.Abetz;R.Stadler;D.S.Pearson
  28. Polymer J. v.21 Dielectric normal mode process of star-shaped polyisoprenes Yoshida,H.;K.Adachi;H.Watanabe;T.Kotaka