Glassy, polydomain azobenzene liquid crystal polymer networks (azo-LCNs) have been synthesized, characterized, and modeled to understand composition dependence on large amplitude, bidirectional bending, and twisting deformation upon irradiation with linearly polarized blue-green (440–514 nm) light. These materials exhibit interesting properties for adaptive structure applications in which the shape of the photoresponsive material can be rapidly reconfigured with light. The basis for the photomechanical output observed in these materials is absorption of actinic light by azobenzene, which upon photoisomerization dictates an internal stress within the local polymer network. The photoinduced evolution of the underlying liquid crystal microstructure is manifested as macroscopic deformation of the glassy polymer film. Accordingly, this work examines the polarization-controlled bidirectional bending of highly concentrated azo-LCN materials and correlates the macroscopic output (observed as bending) to measured blocked stresses upon irradiation with blue-green light of varying polarization. The resulting photomechanical output is highly dependent on the concentration of crosslinked azobenzene mesogens employed in the formulation. Experiments that quantify photomechanical bending and photogenerated stress are compared to a large deformation photomechanical shell model to quantify the effect of polarized light interactions with the material during static and dynamic polarized light induced deformation. The model comparisons illustrate differences in internal photostrain and deformation rates as a function of composition and external mechanical constraints.

Azobenzene liquid crystal polymers and polymer networks are adaptive materials capable of converting light into mechanical work. Often, the photomechanical output of the azobenzene liquid crystal network (azo-LCN) is observed as a bending cantilever. The response of these materials can be either static (e.g. a simple bending cantilever) or dynamic (e.g. oscillating cantilever of 20–270 Hz). The resulting photomechanical output is dependent upon the domain orientation of the polymer network and the wavelength and polarization of the actinic light. Polydomain azobenzene liquid crystal polymer networks, which have the capability of bending both backwards and forwards with the change of polarization angle, are of particular interest. In the current study, three azo-LCNs are compared — two of them are equivalent in all respects except for one contains pendant azobenzene mesogens (1azo, azo-monoacrylate) and the other contains crosslinked azobenzene mesogens (2azo, azo-diacrylate). The third specimen has a combination of both mesogens. The mechanical behavior at different temperatures and examination of structure-property relationships in the polymerization process, including curing temperatures and liquid crystal cell alignment rubbing methods, were explored. Using dynamic mechanical analysis (DMA) the mechanical properties and the photogenerated stress and strain in the polymer are examined. It is found the differences in chemistry do correlate to small variation in the speed of photodirected bending, elastic modulus, and glass transition temperature. Despite these differences, all three azo-LCNs display nearly equivalent photogenerated stresses.