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Probing Submillimeter Dynamics to Access Static Shear Elasticity from Polymer Melts to Molecular Fluids

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Liquid Crystalline Polymers

Part of the book series: Polymers and Polymeric Composites: A Reference Series ((POPOC))

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Abstract

At the millimeter scale and above, liquids and viscoelastic liquids are characterized by an absence of shear elasticity at low frequency (~Hz) in contrast to solids or plastic fluids that need to exceed a stress threshold to flow. Below the millimeter scale, the dynamic response exhibits viscoelastic moduli much higher than those measured at larger scale and reveals that fluids possess finite shear elasticity at low frequency. The low-frequency shear elasticity is identified on unentangled and entangled polymers away from the glass transition, molecular glass formers, alkanes, and H-bond liquids, from several tenths to hundredths of millimeter scales. It indicates that liquid molecules are long-range elastically correlated Consequently the thermal and density fluctuations are also elastically correlated, highlighting on the liquid state new mechanisms to consider to understand the microfluidic scale. How to conciliate the low frequency shear elasticity and viscoelasticity theory when the scale goes down to the submillimeter scale? The polymer viscoelasticity theory is founded on the predominance of the molecular dynamics (major intrachain contribution). In contrast, the dynamics of simple liquids is governed by intermolecular forces. How to conciliate intra- versus intermolecular interactions when the polymer weight decreases down to simple liquids whose dynamics are governed by intramolecular interactions? What are the underlying assumptions and their limitations? This entry traces a brief history of the foundations of the viscoelasticity theory, its empirical origin, and presents new developments revealing that the conventional viscoelastic and viscous behaviors might be the asymptotic part of a much broader dynamic response of the liquid state.

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Acknowledgments

This work has benefited from the AAP2014 “Instrumentation aux limites” CNRS funding. The author is very pleased to thank her collaborators, Patrick Baroni, Hakima Mendil, Philipp, Kahl, Eni Kume and Ursula Windberger. She also would like to thank F. Volino, F. Aitken, D. Aubry, K. Trachenko and A. Zaccone for discussions and theoretical feedback, and R. Ewoldt for stimulating discussion around surface tension. A special thought to the late P.G. de Gennes who chaired the first PhD thesis (www-llb.cea.fr/theses/mendil_2006.pdf) on the low-frequency shear elasticity in fluids.

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Authors and Affiliations

  1. Laboratoire Léon Brillouin (CEA-CNRS), Université Paris-Saclay, CEA-Saclay, Gif-sur-Yvette Cédex, France

    Laurence Noirez

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  1. Laurence Noirez
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Correspondence to Laurence Noirez .

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Editors and Affiliations

  1. Department of Macromolecular Science and Engineering, Case Western Reserve University, Cleveland, OH, USA

    Lei Zhu

  2. Department of Materials Science and Engineering, Drexel University, Philadelphia, PA, USA

    Christopher Y. Li

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Noirez, L. (2020). Probing Submillimeter Dynamics to Access Static Shear Elasticity from Polymer Melts to Molecular Fluids. In: Zhu, L., Li, C. (eds) Liquid Crystalline Polymers. Polymers and Polymeric Composites: A Reference Series. Springer, Cham. https://doi.org/10.1007/978-3-030-43350-5_54

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