Viscoelasticity and self-diffusion in melts of entangled asymmetric star polymers

Carol B. Gell, William W. Graessley*, Vasilis Efstratiadis, Marinos Pitsikalis, Nikos Hadjichristidis

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

80 Scopus citations


The crossover from linear to branched polymer dynamics in highly entangled melts was investigated with a series of asymmetric three-arm stars of poly(ethylene-alt-propylene). Two arms of equal length formed a linear backbone, kept constant through the series, while branches of various length were appended as the third arm. The materials were made by carbanionic polymerization of isoprene and the judicious application of chlorosilane linking chemistry. Subsequent saturation of the polymeric double bonds with deuterium and hydrogen, followed by fractionation, led to a set of structurally matched, nearly monodisperse pairs of deuterium-labeled and fully hydrogenous samples. Dynamic moduli were measured over wide ranges of frequency and temperature. With increasing branch length, the resulting master curves evolve smoothly, but with surprising rapidity, from the relatively narrow terminal spectrum of linear polymers to the much broader spectrum of symmetric stars. The viscosity η0 increases rapidly with branch length, and the diffusion coefficient D, obtained by forward recoil spectrometry, decreases even more rapidly. The product η0, however, distinguishes the transition from linear to branched polymer dynamics most clearly: for a backbone with about 38 entanglements, the crossover is already approaching completion for a single mid-backbone branch with only about three entanglements.

Original languageEnglish (US)
Pages (from-to)1943-1954
Number of pages12
JournalJournal of Polymer Science, Part B: Polymer Physics
Issue number12
StatePublished - Sep 15 1997
Externally publishedYes


  • Branching
  • Entanglement
  • Polymer melt
  • Self-diffusion
  • Viscosity

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry
  • Polymers and Plastics
  • Materials Chemistry


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