Nanoconfinement Controls Mechanical Properties of Elastomeric Thin Films.

Mastering mechanical properties of polymers at nanometer scale is highly demanded yet remains challenging. Pioneering advances determined Young's modulus in ultrathin polymer films and attained unprecedented results including rubbery stiffening. However, many viscoelastic properties such as dynamic mechanical behavior of freestanding nanoconfined polymer films are still unknown. Here we demonstrate striking changes of stiffness and the ratio between elastic and viscous responses in thin PDMS films, using a microvibrational system which enables direct measurements of dynamic stress-strain relation of freestanding films. The results show that elastic modulus is enhanced by a factor of 135 in 50 nm films than the bulk, while the viscous response substantially increases at strains >0.05 in 125 nm films. These observations exhibit significant alterations of viscoelasticity under nanoconfinement. With insights on the underlying mechanism of these results, this study is expected to provide new evidence toward gaining a comprehensive understanding of nanoconfinement effect of soft matter.