Programmable 3D Shape-Change Liquid Crystalline Elastomer Based on a Vertically Aligned Monodomain with Cross-link Gradient

A liquid crystalline elastomer (LCE) as a kind of stimuli-responsive materials, which can be fabricated to present the three-dimensional (3D) change in shape, shows a wide range of applications. Herein, we propose a simple and robust way to prepare a 3D shape-change actuator based on gradient cross-linking of the vertically aligned monodomain of liquid crystals (LCs). First, gold nanoparticles grafted by liquid crystalline polymers (LCPs) are used to induce the homeotropic orientation of the LC monomer and cross-linkers. Then, photopolymerization under UV irradiation is carried out, which can result in the LCE film with a cross-link gradient. Different from the typical LCEs with homogenous alignment that usually show the shape change of extension/contraction, the obtained vertically aligned LCE film exhibits excellent bendability under a thermal stimulus. The nanoindentation experiment demonstrates that the deformation of LCE films comes from the difference in Young's modulus on two sides of the thin film. Simply scissoring the thin film can prepare the samples with different bending angles under the fixed length. Moreover, using a photomask to pattern the film during photopolymerization can realize the complex 3D deformation, such as bend, fold, and buckling. Further, the patterned LCE film doped with multiwalled carbon nanotubes modified by LCPs (CNT-PDB) can act as a light-fueled microwalker with fast crawl behavior.