COMPLAS 2023

Ruppeiner Geometry of Strain-Induced Crystallization in Polymers

  • Raza, Asif (Indian Institute of Science Bangalore)
  • Roy, Debasish (Indian Institute of Science Bangalore)

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The field of polymer science has long been interested in the complex interplay between structure, thermodynamics, and mechanical properties in polymeric materials. One of the most intriguing phenomena in this area is strain-induced crystallization (SIC), in which an initially amorphous polymer is subjected to a mechanical deformation that induces the formation of crystalline regions. It is a complex process that depends on various factors, including the temperature, the type and strength of the deformation, and the properties of the polymer chains. Despite decades of research, the underlying mechanisms that drive this process still need to be better understood. This study aims to shed new light on the fundamental physics of SIC using Ruppeiner geometry [1]. Ruppeiner geometry specificassociates thermodynamic fluctuations of a system withthermodynamic manifold. In this study, metric and curvature are determined using the free energy. Temperature, degree of crystallization, and components of the right Cauchy-Green tensor are coordinates of the thermodynamic manifold. We consider two cases of deformation: uniaxial tension and simple shear. The physical implication of curvature can be understood by comparing its variation over the manifold with those of free energy and strain energy densities. Our results [2] show that Ruppeiner geometry can provide new insights into the underlying physics of SIC in polymer materials. Specifically, we find that the curvature is intimately connected to the formation of ordered regions within the material. It imparts information on spurious isochoric energy, which arises from the conformational stretching of already crystallized segments that need to be removed to get the physically correct stresses.