Effect of chirality on phase transitions in re-entrant liquid crystals

The phase diagrams for enantiomers and their racemic counterparts have been compared in order to determine the influence of chirality on re-entrant phenomena. It has been found that chirality affects the location of the partially bilayer SmAd and monolayer smectic SmA1 phase areas, while the position of the smectic X phase remains nearly unchanged. This result shows that the N-SmA phase transition is influenced by a molecular chiral discrimination effect. Moreover, in enantiomeric systems, a N* re1-N* re2 phase transition has been detected by DSC within the re-entrant nematic gap which is limited by the smectic Ad and the SmX phases. Based on preliminary data, the SmX phase seems to be either a weakly tilted SmC antiphase or an incommensurate orthogonal mesophase.     

High-pressure phase transitions in liquid crystals

Simultaneous measurements of the rate of heat evolution and changes of the mechanical variable of a transformation such as volume or pressure, performed in a p-V-T controlled scanning calorimeter have been applied to investigations of phase transitions in liquid crystals. In the instrument, the phase transitions can be induced by a controlled change of pressure, volume or temperature under isothermal, isobaric or isochoric conditions respectively. The present investigations have ben performed on 4-n-penthyl-penthylthiol-4-decycloxybenzoate which demonstrates in the liquid crystal state a nematic and three smectic phases

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Zusammenfassung In einem p-V-T-kontrollierten Scanning Kalorimeter wurden zur Untersuchung der Phasenumwandlungen in Flüssigkeitskristallen simultane Messungen der Geschwindigkeit der Wärmeentwicklung und der Veränderungen von mechanischen Größen von Umwandlungen, wie z.B. von Volumen oder Druck durchgeführt. In diesem Gerät kann die Phasenumwandlung durch eine kontrollierte Veränderung von Druck, Volumen oder Temperatur unter isothermen, isobaren oder isochoren Bedingungen ausgelöst werden. Vorliegende Untersuchungen wurden an 4-n-Pentyl-phenylthiol-4-dezyloxybenzoat durchgeführt, welches im Flüssigkristallzustand eine nematische und drei smektische Phasen aufweist.

     

Toluene-induced phase transitions in blue phase liquid crystals

ABSTRACT

We report phase transitions in blue phase-forming liquid crystals (LCs) that are triggered by exposure to toluene vapours. Specifically, we reveal that room-temperature cholesteric phase mixtures of MLC-2142 and S-811 form blue phases (BP I, II and III) with increasing vapour pressure of toluene. To probe the mechanism underlying this observation, we investigated the phase behaviour of mixtures of BP-forming LCs containing a range of non-volatile aromatic compounds (e.g. pyrene). We interpret our observations to indicate that the principal effect of small aromatic compounds is to decrease the energy penalty associated with the formation of disclination lines in BPs. We also conclude that the absorption of toluene into the BP-forming LCs lowers the energy required for the formation of disclination cores in the BP phase, thus allowing the elastically favoured double-twist cylinders to form at lower temperatures. We demonstrate that BP-forming LCs containing pyrene can be used to detect toluene at concentrations below 200 ppm at room temperature. Overall, these results guide the design of LC-based materials that respond to VOCs at concentrations relevant to occupational settings.     

Effect of carbon nanotubes on phase transitions of nematic liquid crystals

Phase diagrams of multi‐wall carbon nanotube (MWNT)/nematic liquid crystal (E7) and buckminsterfullerene (C₆₀‐I _h)/nematic liquid crystal (E7) binary systems have been investigated by means of polarizing optical microscopy and differential scanning calorimetry. It was found that the isotropic–nematic phase transition temperature (T _NI) of the liquid crystal component was enhanced by the incorporation of MWNT within a small composition gap. A chimney‐type phase diagram can be identified in the MWNT/E7 mixture over a narrow range of ～0.1–0.2% MWNT concentration. Upon substituting the nanotubes with isotropic fillers such as fullerene, the (C₆₀‐I _h)/E7 blend showed no discernible change of T _NI in the same concentration range of the chimney of the MWNT/E7 mixture, suggesting a significant contribution of anisotropy (or the aspect ratio) of the nanotubes to the entropy of the system containing liquid crystal molecules. This enhanced T _NI phenomenon may be attributed to anisotropic alignment of liquid crystal molecules along the carbon nanotube bundles.     

Effect of carbon nanotubes on phase transitions of nematic liquid crystals

Phase diagrams of multi-wall carbon nanotube (MWNT)/nematic liquid crystal (E7) and buckminsterfullerene (C₆₀-I _h)/nematic liquid crystal (E7) binary systems have been investigated by means of polarizing optical microscopy and differential scanning calorimetry. It was found that the isotropic-nematic phase transition temperature (T _NI) of the liquid crystal component was enhanced by the incorporation of MWNT within a small composition gap. A chimney-type phase diagram can be identified in the MWNT/E7 mixture over a narrow range of ∼0.1-0.2% MWNT concentration. Upon substituting the nanotubes with isotropic fillers such as fullerene, the (C₆₀-I _h)/E7 blend showed no discernible change of T _NI in the same concentration range of the chimney of the MWNT/E7 mixture, suggesting a significant contribution of anisotropy (or the aspect ratio) of the nanotubes to the entropy of the system containing liquid crystal molecules. This enhanced T _NI phenomenon may be attributed to anisotropic alignment of liquid crystal molecules along the carbon nanotube bundles.     

Luminescence-detected phase transitions in lanthanide-containing liquid crystals

Complexes between lanthanide nitrates and a pro-mesogenic 18-membered diaza-substituted coronand are luminescent both as powders and liquid crystals (between 87 and 195 degrees C), and the phase transitions are detected by monitoring luminescence intensity and lifetime.     

Phase transitions in ferroelectric liquid crystals in a restricted geometry

Abstract

Using a wedge type cell, we have studied the S_A–S*_c, S*_c–S_c and S_A–S_c phase transition lines in the ferroelectric liquid crystals 4-(2-methylbutyl)phenyl 4′-n-octylbiphenyl-4-carboxylate (CE-8) and 2-methylbutyl 4-(4-decyloxy-benzylidene)aminocinnamate (DOBAMBC) as a function of cell thickness in the planar geometry. The phase diagram is similar to the one observed using an external magnetic field. A surface induced re-entrant-like phenomenon is also observed. The experimental results are compared with the predictions of a Landau model with surface anchoring and a qualitative agreement was found. The results show that whereas disclination lines are not important for the S_A–S*_c and S_A–S_c transition lines, these defects have to be taken into account when evaluating the S*_c→S_c transition line. The form of the phase diagram has some important implications for the performance of surface stabilized ferroelectric liquid crystal cells used in electrooptic devices.     

Photomechanically induced phase transitions in ferroelectric liquid crystals

We demonstrate that the addition of small amounts of a novel azo-dye to a ferroelectric liquid crystal and illumination with low intensity (∼ 0.8 mW cm^-2) UV light can result in reversible, isothermal phase transitions and dramatic changes in the properties of the system. In particular we examine light induced transitions between the S*₁, and S*_C phases and the consequent photomechanical regulation of spontaneous polarization.     

Influence of chirality on phase transitions in ferroelectric liquid crystals

The transition temperatures between various smectic liquid crystal phases are determined as a function of the enantiomeric excess for three different chiralracemic systems (i.e. binary mixtures consisting of a chiral enantiomer and its racemate). It is shown that transitions involving a ferroelectric phase occur in the chiral compounds at higher temperatures compared to their racemates, the temperature shift being proportional to the square of the enantiometric excess. In contrast, for transitions between two non-ferroelectric phases no difference between the chiral and the racemic compounds is found. Various reasons for the experimental behaviour are discussed. A chirality dependence of the transition temperature is also observed for the smectic A-isotropic transition.     

Influence of an electric field on phase transitions in ferroelectric liquid crystals

The transition temperatures between various smectic liquid crystal phases in chiral (ferroelectric) compounds have been determined as a function of an applied DC electric field. We find that S_G-S_A and S_G-S_C transitions show a field-induced temperature shift proportional to the applied field strength similar to the already known behaviour of first order S_C-S_A transitions. In contrast, for the nonferroelectric S_B-S_A and S_E-S_B transitions no effect of the electric field is observed. The field-induced temperature shift is compared with the temperature shift occurring in chiral-racemic systems of the same compounds (see Bahr, Ch., Heppke, G., and Sabaschus, B., 1991, Liq. Crystals, 9, 31). Using Landau theory we derive a simple relation between these two quantities.     

Detection of phase transitions in liquid crystals using the mirage effect

Abstract

We describe here a novel technique which makes use of the photothermal mirage effect to study phase transition in liquid crystals. Results of the measurements done with two nematic liquid crystals are given to illustrate this technique. We observe an enhancement in the signal amplitude during phase change which is due to the large magnitude of the refractive index gradient developing at the transition temperature.     

Interface influenced phase transitions of alkylcyanobiphenyl liquid crystals A calorimetric study

Abstract

Using an AC-calorimetry technique, we report measurements of the heat capacity and the phase shift between the applied heating power and the resulting thermal oscillations on the thermotropic liquid crystal series of alkylcyanobiphenyl (nCB) above the tricritical point. Specifically, we studied the first order phase transition smectic A to isotropic as a function of substrate, under atmospheric pressure. Different combinations of sapphire, Kapton type 200H polyimide film and air, are used to vary systematically the interfaces encountered by a liquid crystal. The calorimeter uses a sapphire disk, 10 mm in diameter and 0·13 mm thick, above which the samples are placed. A second sapphire disk, or a disk-shaped Kapton film, are used to sandwich the liquid crystal. Air interface samples are droplets allowed to spread naturally on the chosen substrate. The chosen geometry is such that interface effects appear to be maximized. Striking features found in the heat capacity and the phase shift studies with 10CB and 12CB will be presented for the different interfaces.     

Investigations of phase transitions in liquid crystals by means of adiabatic scanning calorimetry

High-resolution calorimetric techniques have substantially contributed in characterising and understanding the delicate thermal behaviour near many phase transitions in liquid crystals. In this paper we describe a high-resolution adiabatic scanning calorimetric technique that has proven to be an important tool in discriminating between first-order and second-order phase transitions in addition to rendering high-resolution information on fluctuations-induced pretransitional specific heat capacity behaviour. The capabilities of adiabatic scanning calorimetry are illustrated with experimental results for the isotropic to nematic and the isotropic to smectic A transitions for a series of alkylcyanobiphenyl compounds. For the nematic to smectic A transition results are presented for pure compounds and mixtures of liquid crystals as well as on the effects of added non-mesogenic solutes and nanoparticles. For chiral molecules results for phase transitions involving blue phases and twist grain boundary phases are considered.     

Changes in the optical properties of ultrathin films of liquid crystals during phase transitions

The temperature dependences of diffuse reflection spectra and the polarization of light reflected from ultrathin Langmuir films based on liquid crystals are studied. The results are compared to the experimental data obtained on thicker liquid films. The dependences of the electric capacity of metal-film-metal structures on temperature are measured. The maximum for ultrathin films lies near 75°C, indicating the occurrence of a ferroelectric phase transition. Features in the intensity and polarization of the reflected light are registered at the phase transition temperature. It is concluded that the generality of the results obtained using samples of both types indicates the existence of a mesomorphic phase in Langmuir films. The observed differences could be associated with either dimensional effects or differences in the structures of the films.     

Anchoring transitions of liquid crystals on SiO x

Anchoring transitions were observed of nematic liquid crystal (LC) mixtures on obliquely evaporated SiO _x by varying the relative abundance of two components in the mixture. Of these two components, one has a longitudinal cyano group and another has lateral cyano groups. It was also found that both temperature and SiO _x thickness variations are able to shift the anchoring transitions. The anchoring on SiO _x has two origins: long‐range van der Waals potential and short‐range surface interactions. Since the two origins have opposite preference in LC director orientation the observed transition is caused by the change of their relative strength. Thermal absorption–desorption of molecules on SiO _x surface is important in determining the strength of short‐range interactions, whereas the layer thickness and optical properties of SiO _x are dependent on the van der Waals potential. Based on previous work by de Gennes we propose a model to describe the observed phenomenon.     

Polysaccharide-induced order-to-order transitions in lyotropic liquid crystals

We report on the order-to-order transitions of lyotropic liquid crystals formed by self-assembled monogylcerides and water in the presence of polysaccharides of various molecular weights. The phase diagram of monoglyceride-water-polysaccharide systems, their morphology, and the topology of liquid crystalline structures were determined by combining optical cross-polarization, oscillatory shear rheometry, and small-angle X-ray scattering. The presence of hydrophilic mono-, oligo-, and polysaccharides in the water domains of liquid crystalline phases resulted in a general decrease of the cubic-to-hexagonal transition temperature. Provided that the sugar could fit within the water channels, the decrease was observed to be dependent on the polysaccharide concentration but independent of its molecular weight. For isotropic bicontinuous cubic phases, monomeric sugars such as glucose were reported to shrink the lattice parameter of the structure without inducing phase transitions. However, when a polymeric form of glucose was used, such as dextran, transitions from the gyroidal Ia3d cubic phase to double diamond Pn3m cubic phases were observed at well-defined molecular weights of polysaccharide. These results were interpreted in terms of size exclusions of polymer sugars by the water domains of the liquid crystal phases as well as the different topologies of water channels. Molecular dynamics simulations of polysaccharides in the water environment were performed to support these findings.     

Heat capacities and phase transitions of the antiferroelectric liquid crystals MHPOBC and MHPOCBC

Heat capacities of the antiferroelectric liquid crystals 4-(1-methylheptyloxycarbonyl)phenyl4-octyloxybiphenyl-4-carboxylate (MHPOBC) and 4-(1-methylheptyloxycarbonyl)phenyl4-octylcarboxybiphenyl-4-carboxylate (MHPOCBC), have been measured with an adiabatic calorimeter between 350 and 460 K. MHPOBC showed three smectic subphases (ferrielectric C*, ferroelectric C* and a fancy phase C*) between antiferroelectric smectic C* and paraelectric gamma alpha smectic A, while MHPOCBC exhibited only one subphase (smectic C*). These phases are clearly discriminated by the existence of phase transitions. The enthalpies and entropies gained at the respective phase transitions were very small. A much larger phase transition from smectic A to isotropic liquid was also observed in both compounds. A alpha     

The semi-phenomenological model of antiferroelectricity in chiral smectic liquid crystals II. The phase transitions and phase diagrams

In the framework of the model of short pitch modes (SPM) developed for chiral smectics with inclined molecules, the phase transitions and diagrams in antiferroelectric systems are described. It is shown that the families of antiferro- and ferri-electric phases are controlled by a few physical parameters such as the smectic correlation length and the chirality parameter. The sequences of antiferro- and ferri-electric states are explained as being dependent on the interactions between SPM and the conventional long pitch mode (LPM), the ferrielectric states being described in terms of the obvious coexistence of LPM and several SPM.     

Influence of cooling rate on the phase transitions of ferroelectric liquid crystals, MBOPDOB and MBOPDoOB

The phase transitions of ferroelectric liquid crystals (FLCs), D-4-(2-methylbutyloxy)phenyl 4-decyloxybenzoate (MBOPDOB) and D-4-(2-methylbutyloxy)phenyl 4-dodecyloxybenzoate (MBOPDoOB), were investigated by means of differential scanning calorimetry (DSC) and polarizing microscopy. The DSC and polarizing microscopy results show that MBOPDOB and MBOPDoOB exhibit different phase transition sequences on slow cooling, whereas they have the same sequence under rapid cooling. In MBOPDoOB, we also observed a quench-induced metastable phase that differs from the normal crystal phase formed by slow cooling. The textures corresponding to the two crystal phases were observed using a polarizing microscope. X-ray diffraction (XRD) was also used to study the quench-induced phase. The influence of the alkoxy chain length on the molecular interactions in FLCs is discussed.