We present an investigation into the dynamic relaxation mechanisms of a polybutadiene blend composed of a four-arm star (10 wt. %) and alinear polymer matrix in the presence of an applied shear flow. Our focus was the response of the star polymer, which cannot be unambiguously assessed via linear viscoelastic measurements since the signature of the star polymer can barely be detected due to the dominant contribution of the linear matrix. By utilizing small-angle neutron scattering (SANS) coupled with a Couette shear device and a deuterated matrix polymer, we investigated the dynamics of the minority star component of the blend. Our results confirm that the stars deform anisotropically with increasing shear rate. We have compared the SANS data with predictions from the well-established scattering adaptation of the state-of-the-art tube model for entangled linear polymer melts undergoing shear, i.e., Graham, Likhtman, Milner, and McLeish (GLaMM) approach, appropriately modified following earlier studies in order to apply to the star. This modified model, GLaMM-R, includes the physics necessary to understand stress relaxation in both the linear and nonlinear flow regimes, i.e., contour length fluctuations, constraint release, convective constraint release, and chain retraction. The full scattering signal is due to the minority star component and, although the contribution of the linear chains is hidden from the neutron scattering, they still influence the star polymer molecular dynamics, with the applied shear rate ranging from approximately 8 to 24 s−1 , below the inverse relaxation time of the linear component. This study provides another confirmation that the combination of rheology and neutron scattering is an indispensable tool for investigating the nonlinear dynamics of complex polymeric systems.
Bibliographical noteKAUST Repository Item: Exported on 2020-10-01
Acknowledgements: Professor Evelyne van Ruymbeke is thanked for helpful discussions. This project was primarily supported by the IMMS/LANL program at UCSB. The authors also acknowledge partial support by the European Commission (ITN “Supolen,” No. FP7-607937, and Horizon 2020-INFRAIA2016-1, EUSMI Project No. 7310219).