SAXS reveals the magnetic alignment pathway of the goethite columnar liquid crystal phase.

The alignment of board-like colloidal goethite particles in the dense rectangular centred columnar liquid crystal phase in an external magnetic field is studied using small angle X-ray scattering (SAXS). Transient SAXS-patterns show broadening of the columnar reflections in specific directions. While the reflections along the field stay at a constant Q-value, the other reflections do not. These results imply a certain pathway of reorientation. It appears that alignment proceeds via collective rotation of domains inducing 'nanoshear' between the layers of particles, which slide over each other. The results support the recently suggested martensitic transition pathway for the simple and centred rectangular columnar phases, which were found to spontaneously transform into each other in another goethite system. The results also provide a fine example of how SAXS can be used to study reorientation behaviour of liquid crystals at the nanoscale.

Tuning biaxiality of nematic phases of board-like colloids by an external magnetic field.

We study the influence of a magnetic field on the biaxial nematic phase of board-like goethite colloids both experimentally and theoretically. Using synchrotron small angle X-ray scattering techniques we find that applying a magnetic field along the main director of the biaxial nematic phase leads to a clear decrease in biaxiality with increasing magnetic field strength. Above a certain magnetic field strength the biaxiality is completely suppressed and the biaxial nematic phase transforms into an ordinary prolate uniaxial nematic phase. In order to interpret the physical mechanism behind this phenomenon, we develop a mean-field theory for the liquid crystal phase behaviour of the suspension. Within this theory the magnetic properties of the particles are modelled by taking into account the effect of both the permanent and the induced magnetic dipoles. The resulting phase diagrams support our experimental findings of the field-induced biaxial nematic to prolate uniaxial nematic transition. They additionally predict that for more plate-like particles, which initially would only display oblate nematic ordering of the shortest axis, the rare biaxial phase can be induced by applying a magnetic field with a carefully chosen field strength, a parameter which can be easily tuned.

Lyotropic hexagonal columnar liquid crystals of large colloidal gibbsite platelets.

We report the formation of hexagonal columnar liquid crystal phases in suspensions of large (570 nm diameter), sterically stabilized, colloidal gibbsite platelets in organic solvent. In thin cells these systems display strong iridescence originating from hexagonally arranged columns that are predominantly aligned perpendicularly to the cell walls. Small angle X-ray scattering and polarization microscopy indicate the presence of orientational fluctuations in the hexagonal columnar liquid crystal phase. The presence of decoupling of the average platelet orientation and the column axis as well as column undulations leading to a decrease of the effective column diameter are discussed. The fact that these phenomena are particularly pronounced in the vertical direction and are enhanced toward the bottom part of the system points to the role of gravitational compaction on the structure.

Size fractionation in a phase-separated colloidal fluid.

Phase separation of a polydisperse colloidal dispersion implies size fractionation. An application of this effect is given by size-selective purification procedures associated with the colloidal synthesis of so-called monodisperse nanoparticles. We used electron microscopy to determine detailed particle size distributions of coexisting colloidal fluid phases containing highly polydisperse iron oxide nanoparticles with a log-normal distribution (sigma = 0.54 for the total system). Analysis of N approximately 10000 particles per phase yields the first five statistical moments of the distributions. Within experimental error, the interdependence of the statistical moments is in quantitative agreement with the "universal law of fractionation" proposed by Evans, Fairhurst, and Poon [Phys. Rev. Lett. 1998, 81, 1326], even though the theory was derived in the limit of slight polydispersity.