Rheology of Polydisperse Star Polymer Melts: Extension of the parameter-free tube model of Milner and McLeish to arbitrary arm-length polydispersity

J.J.M. Slot, Paul A.M. Steeman

    Research output: Contribution to journalArticleAcademicpeer-review

    3 Citations (Scopus)

    Abstract

    This paper considers the extension of the parameter-free tube model of Milner and McLeish for stress relaxation in melts of monodisperse star polymers to star polymers whose arms have a continuous molecular weight distribution such as the Flory distribution in the case of star-nylons and star-polyesters. Exact expressions are derived for the relaxation spectrum and the relaxation modulus for star polymers having an arbitrary continuous arm-length distribution. For a Flory distribution a comparison is made with results of dynamic measurements on a melt of 8-arm poly(-caprolactone) (PCL) stars. An excellent quantitative agreement over a large frequency range is found, however, only if one treats, in contrast with the original parameter-free tube model approach, the entanglement molecular weight that determines the relaxation spectrum as a fitting parameter independent of the entanglement molecular weight of the linear PCL. This discrepancy is not in anyway related to the polydispersity in arm-length, but a consequence of the thermorheological complexity of the PCL stars. A similar discrepancy has been observed for hydrogenated polybutadiene stars, as described by Levine and Milner.
    Original languageUndefined
    Pages (from-to)387-399
    Number of pages13
    JournalMacromolecular theory and simulations
    Volume14
    Issue number6
    DOIs
    Publication statusPublished - 2005

    Keywords

    • Melt
    • Rheology
    • Polycaprolactone
    • Theory
    • star polymers
    • METIS-231031
    • IR-72013

    Cite this

    @article{545179e283e24a9ab93f7762a8f9ea74,
    title = "Rheology of Polydisperse Star Polymer Melts: Extension of the parameter-free tube model of Milner and McLeish to arbitrary arm-length polydispersity",
    abstract = "This paper considers the extension of the parameter-free tube model of Milner and McLeish for stress relaxation in melts of monodisperse star polymers to star polymers whose arms have a continuous molecular weight distribution such as the Flory distribution in the case of star-nylons and star-polyesters. Exact expressions are derived for the relaxation spectrum and the relaxation modulus for star polymers having an arbitrary continuous arm-length distribution. For a Flory distribution a comparison is made with results of dynamic measurements on a melt of 8-arm poly(-caprolactone) (PCL) stars. An excellent quantitative agreement over a large frequency range is found, however, only if one treats, in contrast with the original parameter-free tube model approach, the entanglement molecular weight that determines the relaxation spectrum as a fitting parameter independent of the entanglement molecular weight of the linear PCL. This discrepancy is not in anyway related to the polydispersity in arm-length, but a consequence of the thermorheological complexity of the PCL stars. A similar discrepancy has been observed for hydrogenated polybutadiene stars, as described by Levine and Milner.",
    keywords = "Melt, Rheology, Polycaprolactone, Theory, star polymers, METIS-231031, IR-72013",
    author = "J.J.M. Slot and Steeman, {Paul A.M.}",
    year = "2005",
    doi = "10.1002/mats.200500008",
    language = "Undefined",
    volume = "14",
    pages = "387--399",
    journal = "Macromolecular theory and simulations",
    issn = "1022-1344",
    publisher = "Wiley-VCH Verlag",
    number = "6",

    }

    Rheology of Polydisperse Star Polymer Melts: Extension of the parameter-free tube model of Milner and McLeish to arbitrary arm-length polydispersity. / Slot, J.J.M.; Steeman, Paul A.M.

    In: Macromolecular theory and simulations, Vol. 14, No. 6, 2005, p. 387-399.

    Research output: Contribution to journalArticleAcademicpeer-review

    TY - JOUR

    T1 - Rheology of Polydisperse Star Polymer Melts: Extension of the parameter-free tube model of Milner and McLeish to arbitrary arm-length polydispersity

    AU - Slot, J.J.M.

    AU - Steeman, Paul A.M.

    PY - 2005

    Y1 - 2005

    N2 - This paper considers the extension of the parameter-free tube model of Milner and McLeish for stress relaxation in melts of monodisperse star polymers to star polymers whose arms have a continuous molecular weight distribution such as the Flory distribution in the case of star-nylons and star-polyesters. Exact expressions are derived for the relaxation spectrum and the relaxation modulus for star polymers having an arbitrary continuous arm-length distribution. For a Flory distribution a comparison is made with results of dynamic measurements on a melt of 8-arm poly(-caprolactone) (PCL) stars. An excellent quantitative agreement over a large frequency range is found, however, only if one treats, in contrast with the original parameter-free tube model approach, the entanglement molecular weight that determines the relaxation spectrum as a fitting parameter independent of the entanglement molecular weight of the linear PCL. This discrepancy is not in anyway related to the polydispersity in arm-length, but a consequence of the thermorheological complexity of the PCL stars. A similar discrepancy has been observed for hydrogenated polybutadiene stars, as described by Levine and Milner.

    AB - This paper considers the extension of the parameter-free tube model of Milner and McLeish for stress relaxation in melts of monodisperse star polymers to star polymers whose arms have a continuous molecular weight distribution such as the Flory distribution in the case of star-nylons and star-polyesters. Exact expressions are derived for the relaxation spectrum and the relaxation modulus for star polymers having an arbitrary continuous arm-length distribution. For a Flory distribution a comparison is made with results of dynamic measurements on a melt of 8-arm poly(-caprolactone) (PCL) stars. An excellent quantitative agreement over a large frequency range is found, however, only if one treats, in contrast with the original parameter-free tube model approach, the entanglement molecular weight that determines the relaxation spectrum as a fitting parameter independent of the entanglement molecular weight of the linear PCL. This discrepancy is not in anyway related to the polydispersity in arm-length, but a consequence of the thermorheological complexity of the PCL stars. A similar discrepancy has been observed for hydrogenated polybutadiene stars, as described by Levine and Milner.

    KW - Melt

    KW - Rheology

    KW - Polycaprolactone

    KW - Theory

    KW - star polymers

    KW - METIS-231031

    KW - IR-72013

    U2 - 10.1002/mats.200500008

    DO - 10.1002/mats.200500008

    M3 - Article

    VL - 14

    SP - 387

    EP - 399

    JO - Macromolecular theory and simulations

    JF - Macromolecular theory and simulations

    SN - 1022-1344

    IS - 6

    ER -