Photochemical-induced phase transitions in photoactive semicrystalline polymers

Dear Colleagues,

Please find our new paper titled "Photochemical-induced phase transitions in photoactive semicrystalline polymers" published in Physical Review E. We used phase field model to investigate photochemical phase transitions in semicrystalline polymers.

Author: Ruobing Bai, Eric Ocegueda, and Kaushik Bhattacharya

Abstract: 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.

https://journals.aps.org/pre/abstract/10.1103/PhysRevE.103.033003