4.5 Review

Some open challenges in polymer physics

Journal

POLYMER ENGINEERING AND SCIENCE
Volume 62, Issue 5, Pages 1325-1355

Publisher

WILEY
DOI: 10.1002/pen.25938

Keywords

cyclic macromolecules; DNA; fictive temperature; glass and glass transition; ideal glass; LAOS; macromolecular rings; mechanical spectral hole burning; molecular rheology; nonlinear viscoelasticity; polymer dynamics; ultrastable glass

Funding

  1. American Chemical Society Petroleum Research Fund [60750-ND7]
  2. John R. Bradford Endowment at Texas Tech University
  3. US Department of Energy, Office of Science, Basic Energy Sciences [DESC0018657]
  4. US National Science Foundation [CBET-1603943, DMR-2022732, MOMS1662474]

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The present article outlines three subjects in the field of polymer and soft matter physics. The first subject focuses on the concept of an ideal glass transition and presents research on ultra-stable glass. The second subject explores the relationship between polymer nonlinear viscoelasticity and dynamic heterogeneity. The last subject addresses the rheology of circular macromolecules, discussing both historical perspective and recent research findings.
Three subjects in polymer and soft matter physics are outlined in the present article. The first relates to concepts of an ideal glass transition. We describe work on ultra-stable glass, either a 20-million-year-old amber or a vapor deposited amorphous fluoropolymer, which examines the temperature dependence of the dynamics in a window between a low fictive temperature and the glass transition temperature. From this finesse of the problem of the geological time scales in sub-glass temperature systems strong evidence that the divergence of the relaxation times at finite temperature from WLF-types of extrapolation is not correct. The second topic is polymer nonlinear viscoelasticity as it relates to dynamic heterogeneity. We show results from mechanical hole burning experiments that suggest that dynamic heterogeneity arises from the nature of specific relaxation mechanisms rather than heterogeneous changes in, for example, the fictive temperature. Included is a discussion of large amplitude oscillatory shear testing and how it relates to characterization of nonlinear viscoelastic materials. The last topic addressed is the rheology of circular macromolecules. Here, we take a historical perspective and describe important new results from several laboratories that seem inconsistent. New works from our own studies on circular DNA are also discussed.

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