Coincident Molecular Auxeticity and Negative Order Parameter in a Liquid Crystal Elastomer

"Auxetic" materials have the counter-intuitive property of expanding rather than contracting perpendicular to an applied stretch, formally they have negative Poisson's Ratios (PRs).[1,2] This results in properties such as enhanced energy absorption and indentation resistance, which means that auxetics have potential for applications in areas from aerospace to biomedical industries.[3,4] Existing synthetic auxetics are all created by carefully structuring porous geometries from positive PR materials. Crucially, their geometry causes the auxeticity.[3,4] The necessary porosity weakens the material compared to the bulk and the structure must be engineered, for example, by using resource-intensive additive manufacturing processes.[1,5] A longstanding goal for researchers has been the development of a synthetic material that has intrinsic auxetic behaviour. Such "molecular auxetics" would avoid porosity-weakening and their very existence implies chemical tuneability.[1,4-9] However molecular auxeticity has never previously been proven for a synthetic material.[6,7] Here we present a synthetic molecular auxetic based on a monodomain liquid crystal elastomer (LCE). When stressed perpendicular to the alignment direction, the LCE becomes auxetic at strains greater than approximately 0.8 with a minimum PR of -0.8. The critical strain for auxeticity coincides with the occurrence of a negative liquid crystal order parameter (LCOP). We show the auxeticity agrees with theoretical predictions derived from the Warner and Terentjev theory of LCEs.[10] This demonstration of a synthetic molecular auxetic represents the origin of a new approach to producing molecular auxetics with a range of physical properties and functional behaviours. Further, it demonstrates a novel feature of LCEs and a route for realisation of the molecular auxetic technologies that have been proposed over the years.