Viscoelastic rheology of colloid-liquid crystal composites.

Gelation in colloidal suspensions is mostly induced by attractive interparticle potentials. Beside these interactions, the mechanical properties of the gel are influenced by morphological aspects like fractality. In suspensions of liquid crystal (LC) and polymeric colloids, solvent-particle interactions dominate and can be changed when the mesogen undergoes phase transition from isotropic to nematic. In case of poly(methyl methacrylate) colloids and 4-pentyl-4'-cyanobiphenyl (5CB), cooling through the isotropic-nematic phase transition results in a cellular network. Such network formation is accompanied by a strong evolution of the mechanical properties. Shear moduli reach values up to 10(6) Pa for temperatures of 15 K below the transition. Until now, the mechanical response of the gel was attributed to the elastic interactions of the LC with the colloids. However, the dynamic viscoelastic stiffening with decreasing temperature could not be explained satisfactorily. We used a homemade piezorheometer to measure the complex shear modulus of the sample in parallel plate geometry. Since the applied strains are very small, only the linear viscoelastic regime was tested. This limit guarantees a high degree of reproducibility. We gained insight into the underlying processes by measuring the frequency response for the whole cooling process. Temperature and frequency showed a strong correlation allowing for a superposition of the frequency spectra to form a single master curve similar to time-temperature-superposition. We propose that this superposition behavior is connected to the thermodynamics of the isotropic-nematic phase transition of 5CB located in the network walls. Additional experimental observations, such as hysteresis effects, support this assumption. Morphological aspects were found to be of minor relevance.

Frequency-dependent deformation of liquid crystal droplets in an external electric field.

Nematic droplets suspended in the isotropic phase of the same substance were subjected to alternating electrical fields of varying frequency. To keep the system at a constant nematic/isotropic volume ratio with constant droplet size, we carefully kept the temperature in the isotropic/nematic coexistence region, which was broadened by adding small amounts of a non-mesogenic liquid. Whereas the nematic droplets remained spherical at low (in the order of 10 Hz) and high frequencies (in the order of 1 kHz), at intermediate frequencies we observed a marked flattening of the droplets in the plane perpendicular to the applied field. Droplet deformation occurred both in liquid crystals (LCs) with positive and negative dielectric anisotropy. The experimental data can be quantitatively modelled with a combination of the leaky dielectric model and screening of the applied electric field due to finite conductivity.

Measuring contact angle and meniscus shape with a reflected laser beam.

Side-view imaging of the contact angle between an extended planar solid surface and a liquid is problematic. Even when aligning the view perfectly parallel to the contact line, focusing one point of the contact line is not possible. We describe a new measurement technique for determining contact angles with the reflection of a widened laser sheet on a moving contact line. We verified this new technique measuring the contact angle on a cylinder, rotating partially immersed in a liquid. A laser sheet is inclined under an angle φ to the unperturbed liquid surface and is reflected off the meniscus. Collected on a screen, the reflection image contains information to determine the contact angle. When dividing the laser sheet into an array of laser rays by placing a mesh into the beam path, the shape of the meniscus can be reconstructed from the reflection image. We verified the method by measuring the receding contact angle versus speed for aqueous cetyltrimethyl ammonium bromide solutions on a smooth hydrophobized as well as on a rough polystyrene surface.

Time-resolved X-ray microscopy of nanoparticle aggregates under oscillatory shear.

Of all the current detection techniques with nanometre resolution, only X-ray microscopy allows imaging of nanoparticles in suspension. Can it also be used to investigate structural dynamics? When studying the response to mechanical stimuli, the challenge lies in its application with a precision comparable with the spatial resolution. In the first shear experiments performed in an X-ray microscope, this has been accomplished by inserting a piezo actuator driven shear cell into the focal plane of a scanning transmission X-ray microscope. Thus shear-induced re-organization of magnetite nanoparticle aggregates could be demonstrated in suspension. As X-ray microscopy proves suitable for studying structural change, new prospects open up in physics at small length scales.

Shear-induced undulation of smectic-A: Molecular Dynamics simulations vs. analytical theory.

Experiments on a variety of systems have shown that layered liquids are unstable under shear even if the liquid layers are planes of constant velocity. We investigate the stability of smectic- A like liquids under shear using Molecular Dynamics simulations and a macroscopic hydrodynamic theory (including the layer normal and the director as independent variables). Both methods show an instability of the layers, which sets in above a critical shear rate. We find a remarkable qualitative and reasonable quantitative agreement between both methods for the spatial homogeneous state and the onset of the instability.