Thermodynamic Ultrastability of a Polymer Glass Confined at the Micrometer Length Scale

We employ fast scanning calorimetry to assess the thermodynamic state attained after a given cooling rate and the molecular mobility of glassy poly(4-tert-butylstyrene) confined at the micrometer length scale. We show that, for such a large confinement length scale, thermodynamic states with a fictive temperature (T_{f}) 80 K below the polymer glass transition temperature (T_{g}) are attained, which allows to bypass the geological timescales required for bulk glasses. Access to such states is promoted by a fast mechanism of equilibration. Importantly, the tremendous T_{f} decrease takes place while the molecular mobility remains bulklike, indicating marked decoupling between vitrification kinetics and molecular mobility.