A Direct Quantitative Measure of Surface Mobility in a Glassy Polymer

Polymer Film Behavior An ongoing debate in the understanding of the behavior of thin-film glassy polymers is whether there is nanoconfinement of large molecules or enhanced mobility near a free surface. Chai et al. (p. 994; see the Perspective by Chen et al.) prepared polymer films with a sharp step in the profile by depositing broken film fragments onto a uniform underlay. Atomic force microscopy revealed changes to the overall film profile with time at various temperatures. A transition was observed from localized motions to relaxation of the entire film at a temperature close to that of the bulk glass transition temperature. A step geometry is used to probe the behavior of a glassy polymer above and below its glass transition temperature. [Also see Perspective by Chen et al.] Thin polymer films have striking dynamical properties that differ from their bulk counterparts. With the simple geometry of a stepped polymer film on a substrate, we probe mobility above and below the glass transition temperature Tg. Above Tg the entire film flows, whereas below Tg only the near-surface region responds to the excess interfacial energy. An analytical thin-film model for flow limited to the free surface region shows excellent agreement with sub-Tg data. The system transitions from whole-film flow to surface localized flow over a narrow temperature region near the bulk Tg. The experiments and model provide a measure of surface mobility in a simple geometry where confinement and substrate effects are negligible. This fine control of the glassy rheology is of key interest to nanolithography among numerous other applications.

• Publication year

  2014

• Venue

  Science

• Publication date

  2014-02-27

• Fields of study

  Medicine, Materials Science, Physics

• Identifiers
  DOI 10.1126/science.1244845arXiv 1402.6949PMID 24578574
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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