Skip to main content
SpringerLink
Log in

Modeling macromolecular movement in polymer melts and its relation to nonlinear rheology

  • Original Contribution
  • Published:
Rheologica Acta Aims and scope Submit manuscript

Abstract

We present direct evidence of the macromolecular network behavior at high deformation rates based on macroscopic simulation of these systems by a group of elastics as a model of flexible-chain polymer concentrated solutions or melts. It was shown that at low deformation rates, the disentanglement process really takes place providing a possibility to irreversible deformations (flow), while at high deformation rates, the dominating effect is the formation of large inhomogeneous structures (“grains” or “bundles”) consisting of flocks of entangled chains. This is a model of the deformation induced flow-to-rubbery transition, which makes the irreversible flow impossible. The attempt to increase the deformation rate leads to the rupture of elastics. So, we constructed a model for the deformation-induced fluid-to-rubber transition at high rates and confirmed it by direct measurements of elastic-to-plastic strain ratio as a function of deformation rate.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4

Similar content being viewed by others

Notes

  1. This experiment was carried out with a sample of poly(dimethyl siloxane) used for preparing “silly-putty.”

References

  • Auhl D, Ramirez J, Likhtman AE, Chambron P, Fernybough Ch (2008) Linear and nonlinear flow behavior of monodisperse polyisoprene melts with a large range of molecular weights. J Rheol 52:801–835

    Article  CAS  Google Scholar 

  • Doi M, Edwards S (1985) The theory of polymer dynamics. Clarendon, Oxford

    Google Scholar 

  • Ferri D, Canetti M (2006) Spurt and melt flow distortions of linear styrene-isopreene-styrene triblock copolymers. J Rheol 50:611–624

    Article  CAS  Google Scholar 

  • Furukawa A, Tanaka H (2010) Inhomogeneous flow and fracture of glassy materials. PRCR-5, Sapporo, Japan. Paper A-7-6

  • Graham RS, Likhman AE, McLeish TCB, Milner ST (2003) Microscopic theory of linear, entangled polymer chains under rapid deformation including chain stretch and convective constraint release. J Rheol 47:1171–1200

    Article  CAS  Google Scholar 

  • Malkin AYa, Teishev AE (1991) Flow curve—molecular weight distribution: is the solution of inverse problem possible? Polym Eng Sci 31:1590–1596

    Article  CAS  Google Scholar 

  • Malkin AYa, Petrie CJS (1997) Some conditions for rupture of polymer liquids in extension. J Rheol 41:1–25

    Article  CAS  Google Scholar 

  • Malkin AYa, Isayev A (2006) Rheology: concepts, methods and applications. ChemTec, Toronto

  • McLeish T (2008) Molecular polymeric matter, Weissenberg, Astbury and the pleasure of being wrong (Weissenberg Award Lecture 2007). Rheol Acta 47:479–498

    Article  CAS  Google Scholar 

  • Park HF, Lim ST, Smillo F, Dealy JM (2008) Wall slip and spurt flow of polybutadiens. J Rheol 52:1201–1239

    Article  CAS  Google Scholar 

  • Saito Sh, Matsuzaka K, Hashimoto T (1999) Structures of a semidilute polymer solution under oscillatory shear flow. Macromolecules 32:4879–4888

    Article  CAS  Google Scholar 

  • Semakov AV, Kulichikhin VG (2009) Self-assembly and elastic instability in polymer flows. Polym Sci Ser A 51:1313–1328

    Article  Google Scholar 

  • Vinogradov GV, Malkin AYa, Yanovski YuG, Borisenkova EK, Yarlykov BV, Berezhnaya GV (1972) Viscoelastic properties and flow of narrow distribution polybutadiens and polyisoprenes. J Polym Sci 10:1061–1084

    CAS  Google Scholar 

Download references

Acknowledgements

The authors are grateful to Russian Foundation for basic research for financial support, Grant 10-03-00079.

Author information

Authors and Affiliations

  1. Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninskii pr., 29, Moscow, 119991, Russia

    Alexander Ya. Malkin, A. V. Semakov & V. G. Kulichikhin

Authors
  1. Alexander Ya. Malkin
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. A. V. Semakov
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. V. G. Kulichikhin
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Alexander Ya. Malkin.

Additional information

This paper is dedicated to Professor Helmut Münstedt, Friedrich-Alexander Universität Erlangen-Nürnberg on the occasion of his 70th birthday.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Malkin, A.Y., Semakov, A.V. & Kulichikhin, V.G. Modeling macromolecular movement in polymer melts and its relation to nonlinear rheology. Rheol Acta 50, 485–489 (2011). https://doi.org/10.1007/s00397-011-0556-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00397-011-0556-z

Keywords

Search

Navigation