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Fig. 1. Experimental depth profiles T_g^ne(z) taken at the surface of various c-PMMA polymers. Dashed lines are the best fits to a linear gradient.

Fig. 2. Simulation results revealing intrinsic nonequilibrium effects on near-surface ��(z) of long-chain films. (A) Segmental relaxation time �� vs. inverse temperature for various segmental layers at different distances z/�� from the surface (�� is the length scale of the bead-spring potential). The dotted lines represent the low-temperature cutoff for inclusion of equilibrium relaxation time data and �� = t_ANN,max = 10⁶. The curved lines show fits of the data to an established model for equilibrium dynamics. (B) Normalized alteration gradients of T_g^eq and T_g^ne relative to bulk for systems with t_ANN,max = 10⁵ and 10⁶. The solid line shows a fit of T_g^eq (z) to an exponential gradient form to the T_g^eq data, while the dotted lines represent linear fits to the surface region.

  Փ��朽ӣ�www.pnas.org/doi/10.1073/pnas.2406262121

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