Ageing in a system of polydisperse goethite boardlike particles showing rich phase behaviour

Using microradian x-ray scattering and polarized light microscopy the rich liquid crystalline phase behaviour of a polydisperse system of chromium-modified goethite particles has been studied for five years. We observe that the particles stay highly mobile over years and the rich phase behaviour keeps developing in novel and even surprising ways. While in many other colloidal systems particle size polydispersity suppresses the formation of ordered phases, goethite particles form multiple coexisting ordered phases. The particle polydispersity problem is then solved by particle exchange between coexisting phases. One usually expects that a less ordered phase (e.g., nematic) is formed first while crystallization of the smectic and columnar crystals might take a longer time. For goethite particles we find the opposite, i.e. the nematic phase grows over years at the expense of a better ordered smectic phase. Moreover, SAXS patterns revealed peak splitting for both the smectic and the columnar phase, meaning that the system displays fractionated crystallization. We further discovered that the centred rectangular columnar phase spontaneously forms out of the simple rectangular columnar phase. The reverse transition is observed as well. We explain the ease of these martensitic transitions by showing how slight rotation and translation of the particles triggers the transition.