Film thickness and strain rate dependences of the mechanical properties of polystyrene-b-polyisoprene-b-polystyrene block copolymer ultrathin films forming a spherical domain.

While the mechanical properties of ultrathin polymer films have been extensively studied, only few studies have focused on the ultrathin block copolymer films with complex topologies. The structure-property relationship of ultrathin films (thickness = 35–1000 nm) of polystyrene- b -polyisoprene- b -polystyrene (SIS) containing 14 wt% polystyrene (PS) is established in this study. Grazing-incidence small-angle X-ray scattering, dynamic secondary ion mass spectrometry, and atomic force microscopy were used to characterize the film structure. The difference in surface energy and interfacial energy of the domains resulted in the SIS thin films to primarily consist of three layers: a PS-rich subsurface layer (30 wt%), a spherical PS bulk layer (14 wt%), and a PS-rich interface layer (20 wt%). The film-on-water tensile test was used to investigate both the film thickness and strain rate dependences of mechanical properties. We found that the Young's modulus increased dramatically as film thickness decreased, although only few PS-rich layers consisting of disperse cylindrical and spherical PS domains existed at the surface and interface. Furthermore, the strain rate dependence of the modulus and stress relaxation was more significant for thinner films than for thicker films. The increase in modulus and unusual relaxation behavior are hypothesized to be the result of a combination of different factors, including PS domain alignment, confinement effects, and surface and interface interactions. [Display omitted] • The structure-property relationship of ultrathin SIS films is analyzed. • Young's modulus increases upon decreasing thickness. • The extent of stress relaxation is larger for thinner films. • The stiffening may result from PS domain alignment. [ABSTRACT FROM AUTHOR]