Physical Aging, the Local Dynamics of Glass-Forming Polymers under Nanoscale Confinement

The glass transition temperature marks a point below which a material's properties change significantly, and it is well-established that confinement to the nanoscale modifies the properties of glass-forming materials. We use molecular dynamics simulations to investigate the dynamics and aging behavior of model glass-forming polymers near and below the glass transition temperature of bulk and confined films. We show that both relaxation times and physical age rates vary similarly throughout a freestanding polymer film at temperatures close to the bulk glass transition temperature, where the surfaces have both lower relaxation times and physical age rates. Moreover, we provide evidence suggesting that string lengths in the bulk control dynamic length scales in the film. This realization, combined with the similarity between aging behavior and dynamic profiles, has implications for design rationale in the microelectronics industry.