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The emergent photoactive materials through photochemistry make it possible todirectly convert photon energy to mechanical work. There is much recent work indeveloping appropriate materials and a promising new system is semi-crystallinepolymers of the photoactive molecule azobenzene. We develop a phase field modelwith two order parameters for the crystal-melt transition and the trans-cisphoto-isomerization to understand such materials, and the model describes therich phenomenology. We find that the photo-reaction rate depends sensitively ontemperature: at temperatures below the crystal-melt transition temperature,photoreaction is collective, requires a critical light intensity and shows anabrupt first order phase transition manifesting nucleation and growth; attemperatures above the transition temperature, photoreaction is independent andfollows first order kinetics. Further, the phase transition dependssignificantly on the exact forms of spontaneous strain during the crystal-meltand trans-cis transitions. A non-monotonic change of photo-persistent cis ratiowith increasing temperature is observed accompanied by a reentrantcrystallization of trans below the melting temperature. A pseudo phase diagramis subsequently presented with varying temperature and light intensity alongwith the resulting actuation strain. These insights can assist the furtherdevelopment of these materials.

Photochemical-induced phase transitions in photoactive semicrystalline polymers