Das, S and Raza, A and Roy, D (2022) Geometric thermodynamics of strain-induced crystallization in polymers. In: Physical Review E, 106 (1).
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Abstract
Going beyond the classical Gaussian approximation of Einstein's fluctuation theory, Ruppeiner gave it a Riemannian geometric structure with an entropic metric. This yielded a fundamental quantity, the Riemannian curvature, which was used to extract information on the nature of interactions between molecules in fluids, ideal gases, and other open systems. In this article, we examine the implications of this curvature in a nonequilibrium thermodynamic system where relaxation is sufficiently slow so as not to invalidate the local equilibrium hypothesis. The nonequilibrium system comprises a rubbery polymer undergoing strain induced crystallization. The curvature is found to impart information on a spurious isochoric energy arising from the conformational stretching of already crystallized segments. This unphysical component perhaps arises as the crystallized manifold is considered Euclidean with the stretch measures defined via the Euclidean metric. The thermodynamic state associated with curvature is the key to determine the isochoric stretch and hence the spurious energy. We determine this stretch and propose a form for the spurious free energy that must be removed from the total energy in order for the correct stresses to be recovered.
| Item Type: | Journal Article |
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| Publication: | Physical Review E |
| Publisher: | American Physical Society |
| Additional Information: | The copyright for this article belongs to the Author(s). |
| Keywords: | Geometry, Extract informations; Fluctuation theory; Gaussian approximations; Geometric structure; Ideal gas; Local equilibrium; Non equilibrium thermodynamics; Riemannian curvature; Strain induced crystallisation; Thermodynamic systems, Free energy |
| Department/Centre: | Division of Mechanical Sciences > Civil Engineering |
| Date Deposited: | 19 Sep 2022 08:56 |
| Last Modified: | 19 Sep 2022 08:56 |
| URI: | https://eprints.iisc.ac.in/id/eprint/76600 |
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