Frank Giesselmann

One-piece micropumps from liquid crystalline core-shell particles

Responsive polymers are low-cost, light weight and flexible, and thus an attractive class of materials for the integration into micromechanical and lab-on-chip systems. Triggered by external stimuli, liquid crystalline elastomers are able to perform mechanical motion and can be utilized as microactuators. Here we present the fabrication of one-piece micropumps from liquid crystalline core-shell elastomer particles via a microfluidic double-emulsion process, the continuous nature of which enables a low-cost and rapid production. The liquid crystalline elastomer shell contains a liquid core, which is reversibly pumped into and out of the particle by actuation of the liquid crystalline shell in a jellyfish-like motion. The liquid crystalline elastomer shells have the potential to be integrated into a microfluidic system as micropumps that do not require additional components, except passive channel connectors and a trigger for actuation. This renders elaborate and high-cost micromachining techniques, which are otherwise required for obtaining microstructures with pump function, unnecessary.

Temperature and bias-field dependences of dielectric behaviour in the antiferroelectric liquid crystal, (R)-MHPOBC

Temperature and bias-field dependences of dielectric behaviour in the antiferroelectric liquid crystal, R-MHPOBC, were investigated (see also previous paper). There are mainly two relaxation modes in the SmC*alpha and SmC* phases: one behaves as the soft-mode, which shows significant slowing down in the SmA* and SmC*alpha phases; the other one appears at lower frequencies and changes the dielectric strength remarkably, especially in the SmC* phase, which is considered to relate to the azimuthal phase-fluctuation of molecules in the parallel tilt sequences of the smectic layers. These two modes show different bias field dependences in different C* subphases. In the SmC*A phase, two other types of relaxation mode were observed, which are probably due to the in-phase and anti-phase azimuthal angle fluctuations of molecules in the anti-tilt pairs.

INVESTIGATIONS OF THE STRUCTURE OF A CHOLESTERIC PHASE WITH A TEMPERATURE INDUCED HELIX INVERSION AND OF THE SUCCEEDING SC-ASTERISK PHASE IN THIN LIQUID-CRYSTAL CELLS

Abstract Investigations of 4-[(S, S)-2, 3 epoxyhexyloxy]-phenyl-4-(decyloxy)-benzoate by polarizing microscopy, the Cano-Grandjean method, optical rotation dispersion and UV-VIS spectroscopy reveal a cholesteric phase with temperature induced reversal of the helical twist. Switching time experiments in the Sc* phase show that the intrinsic helix can be unwound reversibly and irreveribly by application of electric fields of different strengths.

Columnar Mesophases Controlled by Counterions in Potassium Complexes of Dibenzo[18]crown-6 Derivatives

Dibenzo[18]crown-6 derivatives 1 with two lateral tetraalkyloxy o-terphenyl units were prepared and converted to the corresponding complexes KX1 (X = halide, BF(4), PF(6), SCN) and NH(4)PF(6)1. Complexation was probed by MALDI-TOF spectrometry and NMR spectroscopy. Downfield shifts of (1)H NMR signals for complexes with soft anions Br, I, SCN, and PF(6) indicated the presence of tight ion pairs, whereas complexes with hard anions F, Cl, or BF(4) showed no or little shifts. In (13)C NMR spectra, upfield shifts were detected for soft anions. The character of the anion also influenced the mesomorphic properties of complexes MX1 (M = K, NH(4)), which were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), and XRD in comparison to neat 1. Hard anions slightly stabilize or even destabilize the mesophase. Soft anions, however, improve the mesomorphic properties yielding mesophases with up to 70 degrees C phase widths in the case of KI1, KPF(6)1, and NH(4)PF(6)1. For complexes KSCN1 with a soft and bridging anion, the balance between mesophase stabilization and high order is shifted in favor of the plastic crystal phase.

Ferroelectric polysiloxane liquid crystals with ‘de Vries’-type smectic A*–smectic C* transitions

We report preliminary results of optical and small angle X-ray scattering (SAXS) experiments on the smectic A*−smectic C* transition in two ferroelectric liquid crystalline polysiloxanes. Although the optical tilt angle in the SmC* phases reaches values up to 30°, temperature-dependent SAXS measurements clearly reveal that the smectic layer spacing is basically conserved during the A*–C* transition as well as in the subsequent C* phase. Connected with the A*–C* transition we further observed a significant increase in birefringence, hence reflecting an increase of orientational order. The practical absence of layer shrinkage and the enhanced orientational ordering are consistent with the de Vries diffuse cone model of smectic A−smectic C transitions.

On the origin of high optical director tilt in a partially fluorinated orthoconic antiferroelectric liquid crystal mixture

We have investigated the orthoconic antiferroelectric liquid crystal mixture W107 by means of optical, X-ray and calorimetry measurements in order to assess the origin of the unusally high tilt angle between the optic axis and the smectic layer normal in this material. The optical birefringence increases strongly below the transition to the tilted phases, showing that the onset of tilt is coupled with a considerable increase in orientational order. The layer spacing in the smectic A* (SmA*) phase is notably smaller than the extended length of the molecules constituting the mixture, and the shrinkage in smectic C* (SmC*) and smectic Ca* (SmCa*) is much less than the optical tilt angle would predict. These observations indicate that the tilting transition in W107 to a large extent follows the asymmetric de Vries diffuse cone model. The molecules are on average considerably tilted with respect to the layer normal already in the SmA* phase but the tilting directions are there randomly distributed, giving the phase its uniaxial characteristics. At the transition to the SmC* phase, the distribution is biased such that the molecular tilt already present in SmA* now gives a contribution to the macroscopic tilt angle. In addition, there is a certain increase of the average tilt angle, leading to a slightly smaller layer thickness in the tilted phases. Analysis of the wide angle scattering data show that the molecular tilt in SmCa* is about 20° larger than in SmA*. The large optical tilt (45°) in the SmCa* phase thus results from a combination of an increased average molecule tilt and a biasing of tilt direction fluctuations.

Substituted crown ethers as central units in discotic liquid crystals: effects of crown size and cation uptake

In this paper, a series of crown ether-based liquid crystals was synthesised. The effect of different crown ether ring sizes, terminal groups and complexed salts on the mesomorphic properties was investigated. The first example of [12]crown-4 as the central core of a discotic liquid crystal is described. Columnar hexagonal phases were found for the [12]crown-4-ethers carrying o-terphenyl (1) and triphenylene (2) groups. The [24]crown-8 ethers showed columnar hexagonal phases when substituted with o-terphenyl groups (7) while no mesophases could be detected in the case of the triphenylene substituted derivatives 8. It was found that an increase in the size of the macrocycle leads to a decrease in the clearing points and phase stabilities. Depending on the size of the crown ether, uptake of suitable cations can lead to drastic increases in the clearing temperatures and phase stabilities due to structural rearrangements or ion pair formation, as deduced from 1H and 13C NMR spectroscopy.

The Orientational order in So-Called de Vries Materials

There is a great interest in smectic materials that show no layer shrinkage (NLS) in the transition from smectic A to smectic C. Such materials are often discussed in terms of “de Vries materials” or “de Vries behavior” after A. de Vries, who proposed different mechanisms for this NLS behavior, involving a significant tilt β of the individual molecules in the smectic A phase. According to the original proposition of de Vries, the molecules are already tilted in this kind of smectic A phase, with a large constant tilt and the same tilt direction in each layer but random tilt direction between different layers. Despite the individual molecular tilt the smectic A phase remains uniaxial and the transition to the biaxial smectic C state is seen as a global ordering in the tilt directions. The model thus ad hoc predicts that there is zero layer shrinkage at the A – C transition. We refer to this model as the “hollow cone distribution”. As later pointed out by de Vries there are, however, other possible models for describing a tilt disorder (thermodynamically unavoidable) in the A phase. Nevertheless, the hollow cone has been a widely accepted model in the literature and is repeatedly referred to in discussing de Vries behavior or even taken as a basis for theories describing it. We discuss different smectic A orientational distribution functions that could be related to de Vries behavior or de Vries transitions. We find that two opposite models have comparable predictive power but only one gives a consistent picture together with existing data. Our conclusion is that the smectic A – smectic C transition can have a continuously changing character from a “pure tilt” to a “pure de Vries”, and we illustrate the orientational distribution functions in the A and C phases for these two limiting cases. We find that de Vries behavior is not related to any exotic distribution of hollow cone or similar kind in the A phase, but instead to an unusual combination of low nematic order and high smectic order in the de Vries smectic A. As the technical interest in such materials is considerable, a directed effort toward the synthesis of new optimized materials would be important.

Tuning ‘de Vries-like’ properties in siloxane- and carbosilane-terminated smectic liquid crystals

Smectic liquid crystals with ‘de Vries-like’ properties are characterized by a maximum layer contraction of ≤1% upon transition from the non-tilted SmA phase to the tilted SmC phase. To expand the current library of ‘de Vries-like’ liquid crystals, we have developed a rational design strategy based on a concept of frustration between two structural elements, one promoting the formation of a SmA phase (chloro-terminated side-chain) and another promoting the formation of a SmC phase (siloxane-terminated side-chain). In this paper, we show that one can tune this apparent frustration—and further improve de Vries-like properties—by substituting the 2-phenylpyrimidine core in our first-generation siloxane-terminated mesogens with one of three cores known to be stronger SmC-promoting elements: 6-phenylpyridazine, 2-phenylpyridine and 2-phenylthiadiazole. We also address a fundamental design flaw of siloxane-terminated mesogens, i.e., the hydrolytic instability of siloxane oligomers, by substituting the siloxane end-group with a chemically inert carbosilane end-group. As a result of this study, we found a carbosilane-terminated 2-phenylthiadiazole mesogen that forms a SmC phase at room temperature with de Vries-like properties that are comparable to those of bona fide de Vries-like liquid crystals.

Molecular model for de Vries type smectic-A-smectic-C phase transition in liquid crystals

We develop both phenomenological and molecular-statistical theory of smectic- A -smectic- C phase transition with anomalously weak smectic layer contraction. Using a general mean-field molecular model, we demonstrate that a relatively simple interaction potential suffices to describe the transition both in conventional and de Vries type smectics. The theoretical results are in excellent agreement with experimental data. The approach can be used to describe tilting transitions in other soft matter systems.