title: Aging and stiction dynamics in confined films of a star polymer melt.
abstract: The stiction properties of a star polyisoprene (PIP) melt (having 22 arms and an arm molecular weight of around 5000, M(w) ≈ 110,000) confined between mica surfaces were investigated using the surface forces apparatus. Stop-start experiments were carried out and the stiction spike was measured as a function of surface stopping (aging) time t and applied pressure P; the time constants of the phase transitions in the stiction dynamics (freezing on stopping and melting on starting) were obtained from the force relaxation behaviors. The results were compared with those of a confined linear-PIP melt (M(w) ≈ 48,000) and other confined fluid systems; the effect of star architecture on the phase transitions in confinement during aging is discussed. Estimation of the molecular size gives that the confined star-PIP films consist of three molecular layers; a non-adsorbed layer sandwiched between two layers adsorbed on opposed mica surfaces. There are (at least) four time constants in the freezing transition of the confined star-PIP melt; fast (τ(1)) and slow (τ(2)) time constants for lateral force relaxation on stopping, critical aging time for freezing (τ(f)), and the logarithmic increase of the spike height against t. The three time constants on stopping, τ(1), τ(2), and τ(f), increase with the increase of P (decrease of the thickness D). As regards the melting transition on starting, spike force decay was fitted by a single exponential function and one time constant was obtained, which is insensitive to P (D). Comparison of the time constants between freezing and melting, and also with the results of linear-PIP reveals that the stiction dynamics of the star-PIP system involves the relaxation and rearrangement of segmental-level and whole molecular motions. Lateral force relaxation on stopping is governed by the individual and cooperative rearrangements of local PIP segments and chain ends of the star, which do not directly lead to the freezing of the system. Instead, geometrical rearrangements of the soft star-PIP spheres into dense packing between surfaces (analogous to the concept of a colloidal glass transition) are the major mechanism of the freezing transition (stiction) after aging. Interdigitation of PIP segments/chain ends between neighboring star molecules also contributes to the spike growth along with aging, and the melting transition on starting.
authors.affiliation: Tochigi Research Laboratories, Kao Corporation, 2606 Akabane, Ichikaimachi, Haga, Tochigi 321-3497, Japan. yamada.s@kao.co.jp
authors.forename: Shinji
authors.initials: S
authors.lastname: Yamada