Mechanical and viscoelastic properties of confined amorphous polymers

Confinement of polymers to nanoscale dimensions can dramatically impact their physical properties. Substantial efforts have focused on the glass transition temperature (T-g) of polymers confined to thin films, but their mechanical properties are less studied despite their technological importance. In this review, challenges with mechanical measurements of polymer thin films are discussed along with novel metrologies that provide insight into their mechanical properties. A comparison of experimental measurements, simulations and theory provide several general conclusions about the mechanical properties under confinement. Confinement impacts the elastic modulus, rubbery compliance and viscosity of polystyrene, the archetypal polymer for confinement, but the confinement effect appears to depend on the measurement technique. This effect may be due to the details of averaging of gradients in properties that are dependent on the measurement details. Routes to minimize confinement effects are addressed. Despite progress in the measurements of mechanical properties of polymer thin films, there remain unresolved questions about the impact of confinement, which we highlight at the end of this review. (c) 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018, 56, 9-30