Free volume, molecular grains, self-organisation, and anisotropic entropy : machining materials

In this article, the relationship between molecular architecture and the formation of twist-bend phases is reviewed under the context of shape dependency. We conclude that the twist-bend phase is a universal phenomenon, which occurs in a wide variety of materials, for dimers through to main chain polymers. In the process, the chemical information on molecular design is effectively lost or irrelevant, and molecular topology takes precedence over electrostatic interactions in mesophase formation. As a consequence of this macro-scale material, engineering by shape alone becomes a possibility, potentially more phases may be realised, and entropy is anisotropic.