Confinement effect of inter-arm interactions on glass formation in star polymer melts

We utilized molecular dynamic simulation to investigate the glass formation of star polymer melts in which the topological complexity is varied by altering the number of star arms (f). Emphasis was placed on how the "confinement effect" of repulsive inter-arm interactions within star polymers influences the thermodynamics and dynamics of star polymer melts. All the characteristic temperatures of glass formation were found to progressively increase with increasing f, but unexpectedly the fragility parameter KVFT was found to decrease with increasing f. As previously observed, stars having more than 5 or 6 arms adopt an average particle-like structure that is more contracted relative to the linear polymer size having the same mass and exhibit a strong tendency for intermolecular and intramolecular segregation. We systematically analyzed how varying f alters collective particle motion, dynamic heterogeneity, the decoupling exponent ζ phenomenologically linking the slow β- and α-relaxation times, and the thermodynamic scaling index γt. Consistent with our hypothesis that the segmental dynamics of many-arm star melts and thin supported polymer films should exhibit similar trends arising from the common feature of high local segmental confinement, we found that ζ increases considerably with increasing f, as found in supported polymer films with decreasing thickness. Furthermore, increasing f led to greatly enhanced elastic heterogeneity, and this phenomenon correlates strongly with changes in ζ and γt. Our observations should be helpful in building a more rational theoretical framework for understanding how molecular topology and geometrical confinement influence the dynamics of glass-forming materials more broadly.