E. van den Pol

Uniaxial and biaxial liquid crystal phases in colloidal dispersions of board-like particles

Dispersions of board-like goethite (α-FeOOH) particles with short-range repulsive interaction form a versatile colloidal model system, showing a nematic, smectic A and columnar phase. In high magnetic fields a biaxial nematic phase is induced with the shortest dimension of the particles aligned along the field. Moreover, if particles have a shape almost exactly in between rod-like and plate-like they can spontaneously, without external magnetic field, form biaxial nematic and biaxial smectic A phases, which is in accordance with theoretical predictions. The macroscopic domains were oriented by a magnetic field and their structure was revealed by small-angle X-ray scattering. Our results suggest that biaxial phases can be readily obtained by a proper choice of the particle shape.

Influence of polydispersity on the phase behavior of colloidal goethite

The effect of fractionation on the phase behavior of colloidal goethite dispersions with different polydispersities (17%, 35%, and 55% in length) has been studied by small angle x-ray scattering and transmission electron microscopy. All systems show at least nematic and smectic phases. The occurrence of the latter phase at such a high polydispersity is remarkable. It is shown that in the highly polydisperse systems strong fractionation occurs, which is able to reduce the local length polydispersity up to a factor of 2. A columnar phase was only found in the 35% and 55% polydisperse systems. It seems that the columnar phase accommodates the particles that do not fit into the smectic layers and, thus, reduces the length polydispersity within the smectic phase even further. The fact that a columnar phase was not found in the system of lowest polydispersity indicates that the smectic phase is the most stable phase at higher concentrations.

Simple Rectangular Columnar Phase of Goethite Nanorods and Its Martensitic Transition to the Centered Rectangular Columnar Phase

Using high-resolution small-angle X-ray scattering, we observed a new type of the columnar phase with a simple rectangular (R(S)) structure in colloidal goethite dispersions. Furthermore, it displays a martensitic transition into the usual centered rectangular (R(C)) structure in an external magnetic field. The findings are rationalized in terms of entropic effects within a simple cell model. We interpret the results as an effect of the particle shape and the available degrees of freedom on the delicate balance between the space available for particle translations and rotations within the two structures.

The isotropic-nematic interface of colloidal goethite in an external magnetic field

Polarization microscopy was used to study the behavior around the isotropic-nematic interface of colloidal goethite dispersions in a magnetic field. It has been found before that the nematic phase is favored in an external field. In the case of goethite this was also observed; nematic droplets formed inside the isotropic phase and coalesced with the nematic phase. However, the behavior was found to be much richer because of the particle rotation around a certain critical field strength. The simultaneous occurrence of (parallel)nematic-(perpendicular)nematic phase separation under the influence of a magnetic field also plays a role here.

Chromium-modified goethite in an external magnetic field

The behaviour of the different liquid crystalline phases observed in colloidal dispersions of goethite has been studied by small angle x-ray scattering. The particles align parallel to a small magnetic field and perpendicular to a large magnetic field, which was observed in the isotropic and nematic phase. The smectic phase also aligned parallel to a small magnetic field but it formed an aligned columnar phase with a distorted hexagonal structure in higher magnetic fields. The columnar phase mainly aligned in higher magnetic fields. Goethite particles were successfully modified with chromium. The Cr-modified goethite particles show similar phase behaviour as normal goethite particles but with different magnetic properties. The relative importance of the permanent and induced magnetic moment was found to have changed.

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.