Keddie, J. L., Jones, R. A. L. & Cory, R. A. Size-dependent depression of the glass transition temperature in polymer films. Europhys. Lett. 27, 59–64 (1994).Article
ADS
CAS
Google Scholar
Ellison, C. J. & Torkelson, J. M. The distribution of glass-transition temperatures in nanoscopically confined glass formers. Nat. Mater. 2, 695–700 (2003).Article
ADS
CAS
PubMed
Google Scholar
Priestley, R. D., Ellison, C. J., Broadbelt, L. J. & Torkelson, J. M. Structural relaxation of polymer glasses at surfaces, interfaces, and in between. Science 309, 456–459 (2005).Article
ADS
CAS
PubMed
Google Scholar
Fakhraai, Z. & Forrest, J. A. Measuring the surface dynamics of glassy polymers. Science 319, 600–604 (2008).Article
CAS
PubMed
Google Scholar
Yang, Z., Fujii, Y., Lee, F. K., Lam, C. H. & Tsui, O. K. Glass transition dynamics and surface layer mobility in unentangled polystyrene films. Science 328, 1676–1679 (2010).Article
ADS
CAS
PubMed
Google Scholar
Paeng, K., Swallen, S. F. & Ediger, M. D. Direct measurement of molecular motion in freestanding polystyrene thin films. J. Am. Chem. Soc. 133, 8444–8447 (2011).Article
CAS
PubMed
Google Scholar
Chai, Y. et al. A direct quantitative measure of surface mobility in a glassy polymer. Science 343, 994–999 (2014).Article
ADS
CAS
PubMed
Google Scholar
Zhang, Y. & Fakhraai, Z. Invariant fast diffusion on the surfaces of ultrastable and aged molecular glasses. Phys. Rev. Lett. 118, 066101 (2017).Article
ADS
PubMed
Google Scholar
Hao, Z. et al. Mobility gradients yield rubbery surfaces on top of polymer glasses. Nature 596, 372–376 (2021).Article
ADS
CAS
PubMed
Google Scholar
Li, Y. et al. Surface diffusion is controlled by bulk fragility across all glass types. Phys. Rev. Lett. 128, 075501 (2022).Article
ADS
CAS
PubMed
Google Scholar
Tian, H., Xu, Q., Zhang, H., Priestley, R. D. & Zuo, B. Surface dynamics of glasses. Appl. Phys. Rev. 9, 011316 (2022).Article
ADS
CAS
Google Scholar
Zhang, Y. & Fakhraai, Z. Decoupling of surface diffusion and relaxation dynamics of molecular glasses. Proc. Natl Acad. Sci. USA 114, 4915–4919 (2017).Article
ADS
CAS
PubMed
PubMed Central
Google Scholar
Peng, H., Liu, H. & Voigtmann, T. Nonmonotonic dynamical correlations beneath the surface of glass-forming liquids. Phys. Rev. Lett. 129, 215501 (2022).Article
ADS
CAS
PubMed
Google Scholar
Chen, F., Lam, C.-H. & Tsui, O. K. C. The surface mobility of glasses. Science 343, 975–976 (2014).Article
ADS
CAS
PubMed
Google Scholar
Parisi, G. & Sciortino, F. Flying to the bottom. Nat. Mater. 12, 94–95 (2013).Article
ADS
CAS
PubMed
Google Scholar
Garcia, R. et al. Identification of nanoscale dissipation processes by dynamic atomic force microscopy. Phys. Rev. Lett. 97, 016103 (2006).Article
ADS
CAS
PubMed
Google Scholar
Liu, Y. H. et al. Characterization of nanoscale mechanical heterogeneity in a metallic glass by dynamic force microscopy. Phys. Rev. Lett. 106, 125504 (2011).Article
ADS
CAS
PubMed
Google Scholar
Maeda, N., Chen, N., Tirrell, M. & Israelachvili, J. N. Adhesion and friction mechanisms of polymer-on-polymer surfaces. Science 297, 379–382 (2002).Article
ADS
CAS
PubMed
Google Scholar
Ma, J. et al. Fast surface dynamics enabled cold joining of metallic glasses. Sci. Adv. 5, eaax7256 (2019).Article
ADS
CAS
PubMed
PubMed Central
Google Scholar
Monnier, X., Colmenero, J., Wolf, M. & Cangialosi, D. Reaching the ideal glass in polymer spheres: thermodynamics and vibrational density of states. Phys. Rev. Lett. 126, 118004 (2021).Article
ADS
CAS
PubMed
Google Scholar
Cao, X., Zhang, H. & Han, Y. Release of free-volume bubbles by cooperative-rearrangement regions during the deposition growth of a colloidal glass. Nat. Commun. 8, 362 (2017).Article
ADS
PubMed
PubMed Central
Google Scholar
Monnier, X. & Cangialosi, D. Thermodynamic ultrastability of a polymer glass confined at the micrometer length scale. Phys. Rev. Lett. 121, 137801 (2018).Article
ADS
CAS
PubMed
Google Scholar
Swallen, S. F. et al. Organic glasses with exceptional thermodynamic and kinetic stability. Science 315, 353–356 (2007).Article
ADS
CAS
PubMed
Google Scholar
Singh, S., Ediger, M. D. & de Pablo, J. J. Ultrastable glasses from in silico vapour deposition. Nat. Mater. 12, 139–144 (2013).Article
ADS
CAS
PubMed
Google Scholar
Yang, Y., Tian, H., Napolitano, S. & Zuo, B. Crystallization in thin films of polymer glasses: the role of free surfaces, solid interfaces and their competition. Prog. Polym. Sci. 144, 101725 (2023).Article
CAS
Google Scholar
Yu, L. Surface mobility of molecular glasses and its importance in physical stability. Adv. Drug Deliv. Rev. 100, 3–9 (2016).Article
CAS
PubMed
Google Scholar
Yuan, H., Yan, J., Gao, P., Kumar, S. K. & Tsui, O. K. C. Microscale mobile surface double layer in a glassy polymer. Sci. Adv. 8, eabq5295 (2022).Article
ADS
CAS
PubMed
PubMed Central
Google Scholar
O’Connell, P. A. & McKenna, G. B. Rheological measurements of the thermoviscoelastic response of ultrathin polymer films. Science 307, 1760–1763 (2005).Article
ADS
PubMed
Google Scholar
Gurmessa, B. J. & Croll, A. B. Onset of plasticity in thin polystyrene films. Phys. Rev. Lett. 110, 074301 (2013).Article
ADS
PubMed
Google Scholar
Bennemann, C., Donati, C., Baschnagel, J. & Glotzer, S. C. Growing range of correlated motion in a polymer melt on cooling towards the glass transition. Nature 399, 246–249 (1999).Article
ADS
CAS
Google Scholar
Adam, G. & Gibbs, J. H. On the temperature dependence of cooperative relaxation properties in glass‐forming liquids. J. Chem. Phys. 43, 139–146 (1965).Article
ADS
CAS
Google Scholar
Ngai, K. L., Paluch, M. & Rodríguez-Tinoco, C. Why is surface diffusion the same in ultrastable, ordinary, aged, and ultrathin molecular glasses? Phys. Chem. Chem. Phys. 19, 29905–29912 (2017).Article
CAS
PubMed
Google Scholar
Ngai, K. L., Wang, L. M. & Yu, H. B. Relating ultrastable glass formation to enhanced surface diffusion via the Johari-Goldstein β-relaxation in molecular glasses. J. Phys. Chem. Lett. 8, 2739–2744 (2017).Article
CAS
PubMed
Google Scholar
Sussman, D. M., Schoenholz, S. S., Cubuk, E. D. & Liu, A. J. Disconnecting structure and dynamics in glassy thin films. Proc. Natl Acad. Sci. USA 114, 10601–10605 (2017).Article
ADS
MathSciNet
CAS
PubMed
PubMed Central
Google Scholar
Schweizer, K. S. & Simmons, D. S. Progress towards a phenomenological picture and theoretical understanding of glassy dynamics and vitrification near interfaces and under nanoconfinement. J. Chem. Phys. 151, 240901 (2019).Article
ADS
PubMed
Google Scholar
Baker, D. L., Reynolds, M., Masurel, R., Olmsted, P. D. & Mattsson, J. Cooperative intramolecular dynamics control the chain-length-dependent glass transition in polymers. Phys. Rev. X 12, 021047 (2022).CAS
Google Scholar
Colmenero, J. Are polymers standard glass-forming systems? The role of intramolecular barriers on the glass-transition phenomena of glass-forming polymers. J. Phys. Condens. Matter 27, 103101 (2015).Article
ADS
CAS
PubMed
Google Scholar
Vogel, M. Conformational and structural relaxations of poly(ethylene oxide) and poly(propylene oxide) melts: molecular dynamics study of spatial heterogeneity, cooperativity, and correlated forward–backward motion. Macromolecules 41, 2949–2958 (2008).Article
ADS
CAS
Google Scholar
Paul, W. & Smith, G. D. Structure and dynamics of amorphous polymers: Computer simulations compared to experiment and theory. Rep. Prog. Phys. 67, 1117–1185 (2004).Article
ADS
CAS
Google Scholar
Christie, D., Register, R. A. & Priestley, R. D. Role of chain connectivity across an interface on the dynamics of a nanostructured block copolymer. Phys. Rev. Lett. 121, 247801 (2018).Article
ADS
PubMed
Google Scholar
de Gennes, P. G. Glass transitions of freely suspended polymer films. C. R. Acad. Sci. Paris Ser. IV 1, 1179–1186 (2000).
Google Scholar
de Gennes, P. G. Glass transitions in thin polymer films. Eur. Phys. J. E 2, 201–205 (2000).Article
Google Scholar
Milner, S. T. & Lipson, J. E. G. Delayed glassification model for free-surface suppression of Tg in polymer glasses. Macromolecules 43, 9865–9873 (2010).Article
ADS
CAS
Google Scholar
Lipson, J. E. G. & Milner, S. T. Local and average glass transitions in polymer thin films. Macromolecules 43, 9874–9880 (2010).Article
ADS
CAS
Google Scholar
Tang, Q., Hu, W. & Napolitano, S. Slowing down of accelerated structural relaxation in ultrathin polymer films. Phys. Rev. Lett. 112, 148306 (2014).Article
ADS
PubMed
Google Scholar
Tang, Q., Müller, M., Li, C. Y. & Hu, W. Anomalous ostwald ripening enables 2D polymer crystals via fast evaporation. Phys. Rev. Lett. 123, 207801 (2019).Article
ADS
CAS
PubMed
Google Scholar
Shen, Y. R. Surface properties probed by second-harmonic and sum-frequency generation. Nature 337, 519–525 (1989).Article
ADS
CAS
Google Scholar
Tanaka, K., Takahara, A. & Kajiyama, T. Rheological analysis of surface relaxation process of monodisperse polystyrene films. Macromolecules 33, 7588–7593 (2000).Article
ADS
CAS
Google Scholar
Kajiyama, T., Tanaka, K. & Takahara, A. Surface molecular motion of the monodisperse polystyrene films. Macromolecules 30, 280–285 (1997).Article
ADS
CAS
Google Scholar
Tanaka, K., Taura, A., Ge, S. R., Takahara, A. & Kajiyama, T. Molecular weight dependence of surface dynamic viscoelastic properties for the monodisperse polystyrene film. Macromolecules 29, 3040–3042 (1996).Article
ADS
CAS
Google Scholar
Sharma, T., Konishi, M., Sekiya, K. & Takahashi, I. Thickness and substrate dependences of the relaxation of spin-coated polymethyl methacrylate ultrathin films supported on SiO2 and SiOH substrates. Macromolecules 54, 2637–2646 (2021).Article
ADS
CAS
Google Scholar
Doi, M. & Edwards, S. F. The Theory of Polymer Dynamics (Oxford Univ. Press, New York, 1986).Baljon, A. R. C., Billen, J. & Khare, R. Percolation of immobile domains in supercooled thin polymeric films. Phys. Rev. Lett. 93, 255701 (2004).Article
ADS
PubMed
Google Scholar
Keys, A. S., Hedges, L. O., Garrahan, J. P., Glotzer, S. C. & Chandler, D. Excitations are localized and relaxation is hierarchical in glass-forming liquids. Phys. Rev. X 1, 021013 (2011).
Google Scholar
Zuo, B., Zhou, H., Davis, M. J. B., Wang, X. & Priestley, R. D. Effect of local chain conformation in adsorbed nanolayers on confined polymer molecular mobility. Phys. Rev. Lett. 122, 217801 (2019).Article
ADS
CAS
PubMed
Google Scholar
Ediger, M. D. & Forrest, J. A. Dynamics near free surfaces and the glass transition in thin polymer films: a view to the future. Macromolecules 47, 471–478 (2014).Article
ADS
CAS
Google Scholar
Napolitano, S., Glynos, E. & Tito, N. B. Glass transition of polymers in bulk, confined geometries, and near interfaces. Rep. Prog. Phys. 80, 036602 (2017).Article
ADS
PubMed
Google Scholar
Zhang, A. et al. The role of intramolecular relaxations on the structure and stability of vapor-deposited glasses. J. Chem. Phys. 156, 244703 (2022).Article
ADS
CAS
PubMed
Google Scholar
Li, Y. et al. Surface diffusion in glasses of rod-like molecules posaconazole and itraconazole: effect of interfacial molecular alignment and bulk penetration. Soft Matter 16, 5062 (2020).Article
ADS
CAS
PubMed
Google Scholar
Panagopoulou, A. & Napolitano, S. Irreversible adsorption governs the equilibration of thin polymer films. Phys. Rev. Lett. 119, 097801 (2017).Article
ADS
PubMed
Google Scholar
Perez-de-Eulate, N. G., Sferrazza, M., Cangialosi, D. & Napolitano, S. Irreversible adsorption erases the free surface effect on the Tg of supported films of poly(4-tert-butylstyrene). ACS Macro Lett. 6, 354–358 (2017).Article
CAS
PubMed
Google Scholar
Xu, Q. et al. Decoupling role of film thickness and interfacial effect on polymer thin film dynamics. ACS Macro Lett. 10, 1–8 (2020).Article
ADS
PubMed
Google Scholar