Published online by Cambridge University Press: 29 November 2013
The liquid crystal phase is an anisotropic mesophase, intermediate in order between the liquid and crystal phases. Liquid crystals have less translational order than crystals and more rotational order than isotropic liquids. The liquid crystal phase does not support finite shear stresses and thus behaves like a fluid. Molecules that display a liquid crystal phase are referred to as mesogenic. Mesogenic molecules exhibit shape anisotropy: either large length to diameter ratio (needlelike) or large diameter to thickness ratio (disklike). Because of their shape anisotropy, all liquid crystals display orientational order of their molecular axes.
Until 1956, all known examples of liquid crystals were low molecular weight compounds. Robinson was the first to identify liquid crystallinity in a liquid crystalline polymer (LCP) as the explanation for “a birefringent solution” of a polymeric material, poly-y-benzyl-L-glutamate, in chloroform, previously observed by Elliott and Ambrose. Chemists soon discovered that LCPs may be readily synthesized by covalently stitching small mesogenic units (e.g., rigid monomers) together into a chain using short flexible spacers. Mainchain or sidechain liquid crystal polymers may be formed (Figure 1). An example of a polymer molecule possessing a liquid crystal phase is shown in Figure 2. Liquid crystals may be thermotropic, where liquid crystallinity is exhibited over a range of temperatures, or lyotropic, where nonmesogenic solvent molecules are present in addition to the mesogens, and liquid crystallinity is observed over a range of concentrations as well.