Nonequilibrium thermodynamics of dilute polymer solutions in flow

Journal Article · Fri Nov 07 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4900880· OSTI ID:22415329

Latinwo, Folarin; Hsiao, Kai-Wen ^[1]

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1. Department of Chemical and Biomolecular Engineering, University of Illinois, Urbana, Illinois 61801 (United States)

Modern materials processing applications and technologies often occur far from equilibrium. To this end, the processing of complex materials such as polymer melts and nanocomposites generally occurs under strong deformations and flows, conditions under which equilibrium thermodynamics does not apply. As a result, the ability to determine the nonequilibrium thermodynamic properties of polymeric materials from measurable quantities such as heat and work is a major challenge in the field. Here, we use work relations to show that nonequilibrium thermodynamic quantities such as free energy and entropy can be determined for dilute polymer solutions in flow. In this way, we determine the thermodynamic properties of DNA molecules in strong flows using a combination of simulations, kinetic theory, and single molecule experiments. We show that it is possible to calculate polymer relaxation timescales purely from polymer stretching dynamics in flow. We further observe a thermodynamic equivalence between nonequilibrium and equilibrium steady-states for polymeric systems. In this way, our results provide an improved understanding of the energetics of flowing polymer solutions.

• OSTI ID: 22415329
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 17 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DEFORMATION
ENTROPY
FREE ENERGY
MOLECULES
NANOCOMPOSITES
POLYMERS
PROCESSING
SIMULATION
SOLUTIONS
THERMODYNAMICS