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Published March 2021 | Submitted + Supplemental Material + Published
Journal Article Open

Photochemical-induced phase transitions in photoactive semicrystalline polymers


The emergent photoactive materials obtained through photochemistry make it possible to directly convert photon energy to mechanical work. There has been much recent work in developing appropriate materials, and a promising system is semicrystalline polymers of the photoactive molecule azobenzene. We develop a phase field model with two order parameters for the crystal-melt transition and the trans-cis photoisomerization to understand such materials, and the model describes the rich phenomenology. We find that the photoreaction rate depends sensitively on temperature: At temperatures below the crystal-melt transition temperature, photoreaction is collective, requires a critical light intensity, and shows an abrupt first-order phase transition manifesting nucleation and growth; at temperatures above the transition temperature, photoreaction is independent and follows first-order kinetics. Further, the phase transition depends significantly on the exact forms of spontaneous strain during the crystal-melt and trans-cis transitions. A nonmonotonic change of photopersistent cis ratio with increasing temperature is observed accompanied by a reentrant crystallization of trans below the melting temperature. A pseudo phase diagram is subsequently presented with varying temperature and light intensity along with the resulting actuation strain. These insights can assist the further development of these materials.

Additional Information

© 2021 American Physical Society. Received 1 December 2020; accepted 26 February 2021; published 16 March 2021. This work was motivated by the experimental work of Alexa S. Kuenstler, Hantao Zhou, and Ryan Hayward, and we are grateful to them for numerous interesting discussions. We are also grateful for the support of the Office of Naval Research through the MURI on Photomechanical Material Systems (Grant No. ONR N00014-18-1-2624).

Attached Files

Published - PhysRevE.103.033003.pdf

Submitted - 2012.00905.pdf

Supplemental Material - Movie_1.mov

Supplemental Material - Movie_2.mov


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August 22, 2023
October 23, 2023