Dynamically Crystalizing Liquid-Crystal Elastomers for an Expandable Endplate-Conforming Interbody Fusion Cage.

Degenerative disc disease (DDD) is the leading cause of low back pain and radiating leg pain. DDD is commonly treated surgically using spinal fusion techniques, but in many cases failure occurs due to insufficient immobilization of the vertebrae during fusion. The fabrication and demonstration of a 3D-printed semi-crystalline liquid crystal elastomer (LCE) spinal fusion cage that addresses these challenges in particular subsidence are described. During implantation of the fusion cage, the LCE is rubbery and capable of deforming around and conforming to delicate anatomy. In the hours following implantation, the device crystallizes into a rigid, structural material with the modulus increasing tenfold from 8 to 80 MPa. In the crystalline regime, a 3D-printed prototype device is capable of enduring 1 million cycles of physiologic compressive loading with minimal creep-induced ratcheting. Effects of LCE molecular architecture on the rate and magnitude of modulus increase, material processability, and mechanical properties are explored. This fundamental characterization informs a proof-of-concept device-the first bulk 3D printed LCE demonstrated to date. Moreover, the novel deployment strategy represents an exciting new paradigm of spinal fusion cages, which addresses real clinical challenges in expandable interbody fusion cages.

High strain actuation liquid crystal elastomers via modulation of mesophase structure.

Control of the mesophase in liquid crystalline elastomers (LCEs) is a critical aspect in harnessing their unique stimuli-responsive properties. Few studies have compared nematic and smectic main-chain LCEs in a direct way. Traditionally, it is believed that the mesogen core and synthetic route determines the phase behavior. In this study, we hypothesized that tuning the LC phases in main-chain LCE systems can be achieved by varying the spacer length while maintaining the same mesogen (RM257). By increasing the length of dithiol alkyl spacers containing two to eleven carbons along the spacer backbone (C2 to C11), we can modulate the mesophase from nematic to smectic, tailor the nematic to isotropic transition temperature between 90 and 140 °C, and increase the average work capacity from 128 to 262 kJ m-3. Phase nano-segregation resulting in the smectic C phase is achieved at room temperature for the C6, C9, and C11 spacers. In a shape switching system, this manifests in impressive actuation stroke of 700%. Upon heating from room temperature, these samples transition into the nematic and later, the isotropic phase. Furthermore, this segregation occurs along with polymer chain crystallinity, which increases the modulus of the networks by an order of magnitude; however, the crystallization rate is highly time dependent on the spacer length and can vary between 5 minutes for the C11 spacer and 24 hours for shorter spacers. This study presents several possibilities of a thiol-acrylate reaction in modulation of the thermomechanical and liquid-crystalline properties of LCEs and discusses their potential use for biomedical applications.