Equilibrium and non-equilibrium phase transitions studied by adiabatic calorimetry

An adiabatic calorimetry was used for some investigations of equilibrium and non-equilibrium phase transitions. For one of the substances studied (4,4′-di-n-heptyloxyazoxybenzene) it was possible to determine temperature dependence of an order parameter and number of clusters of high temperature phase in a region of a phase transition. For another substance (liquid 3,4 dimethylpiridine) an anomaly on the specific heat curves was interpreted as being responsible for a decay of molecules’ clusters. Non-equilibrium phase transitions were investigated for some liquid crystal substances. The process of transformation between metastable and stable phases was described quantitatively. The conclusions obtained concern the stability of metastable phases.     

Thermal analysis of phase transitions in microemulsions

Differential scanning microcalorimetric measurements on phase transitions in water-oil-surfactant mixtures are presented, demonstrating that this method is highly sensitive towards small heat changes connected with structural transitions in the samples. The values for the latent heat of phase transitions are determined and the results are compared with predictions from mean field theory, emphasizing the role calorimetric experiments can play to identify the most important contributions to the free energy describing the mixtures. Doing this, the present status of the understanding of temperature dependent phase transitions in microemulsions is reviewed.     

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.

     

Surface-functionalized ionic liquid crystal-supported ionic liquid phase materials: ionic liquid crystals in mesopores

The influence of confinement on the ionic liquid crystal (ILC) [C(18)C(1)Im][OTf] is studied using differential scanning calorimetry (DSC), polarized optical microscopy (POM), and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). The ILC studied is supported on Si-based powders and glasses with pore sizes ranging from 11 to 50 nm. The temperature of the solid-to-liquid-crystalline phase transition seems mostly unaffected by the confinement, whereas the temperature of the liquid-crystalline-to-liquid phase transition is depressed for smaller pore sizes. A contact layer with a thickness in the order of 2 nm is identified. The contact layer exhibits a phase transition at a temperature 30 K lower than the solid-to-liquid-crystalline phase transition observed for the neat ILC. For applications within the "supported ionic liquid phase (SILP)" concept, the experiments show that in pores of diameter 50 nm a pore filling of α>0.4 is sufficient to reproduce the phase transitions of the neat ILC.     

Ferroelectric smectic meso-phase formed by banana-shaped achiral liquid crystals

A new banana-shaped achiral molecule, 1,3-phenylene bis[4-(3-chloro-4-n-octyloxyphenyliminomethyl)benzoate] (PBCOB) has been synthesized, and its ferroelectric properties and homeotropic alignment investigated. The presence of a lateral chloro-substituent in the Schiff 's base moiety prevents the regular stacking of molecules and results in lowering the transition temperature and the degree of crystallinity of the switchable banana phase. Their smectic mesophases, including a switchable banana phase B₇, were characterized by differential scanning calorimetry, X-ray scattering and polarizing optical microscopy. Both the left- and right-handed helical domains are spontaneously formed upon cooling from the isotropic liquid to the switchable banana phase B₇. By X-ray study, the smectic phases showed a layer spacing of 38.1 Å, compatible with the end-to-end distance of the molecule with a bent conformation. Significantly, the smectic B7 phase exhibited a periodicity of 292 Å that corresponds to a helical structure with periodicity about 7.5 times 38.1 Å. The spontaneous polarization for PBCOB is about 50 nCcm^-2 and shows a temperature dependence. The ferroelectric lyomesophase of PBCOB showed a ferroelectric electro-optical switching range extending more than 50°C, switchable at room temperature.     

Thermal behavior of selected ferroelectric liquid crystals

Thermal properties of three ferroelectric liquid crystals, namely: 3-octyloxy-6-[2-fluor-4-(fluoroctyloxy)phenyl]-pyridine (FFP), 3-(3-fluor-nonyl)-6[4-heptyloxyphenyl]-pyridine (FNHPh-P), 4-[(S,S)-2,3-epoxyhexyloxy]phenyl 4-(decyloxy)benzoate (EHPhDB) were studied using heat flux differential scanning calorimetry method. All the transitions expected in this compounds, except the SmC^*-SmA^* and SmC^*-S₃ transitions, were detected in the DSC curves. The temperatures of the phase transitions and the enthalpy changes associated with them were determined. The transition from the liquid crystalline to the crystalline state showed significant hysteresis for all three compounds studied. The following transitions: SmA^*-Is, SmG^*-SmC^* for FNHPh-P, N^*-Is for EHPhDB, N^*-Is and SmC^*-N^* for FFP also showed a small hysteresis basing on which first-order character of all the above transitions was implied. All three substances studied in this work are characterized by a complex polymorphism in the solid state.The author is grateful to Dr. Stanislaw Wróbel for his stimulating interest, valuable discussions and supplying the samples. This work has been done in the framework of the KBN grant 2 P302 139 07.     

Strain induced homeotropic alignment in the smecticA phase of liquid crystals

We present a method to align liquid crystal (LC) samples in their SmecticA phase, useful to obtain permanent homeotropic single domains even in compounds where the nematic phase is absent. It is based on the application of a strain field, within the sample volume, which tends to align the molecules all towards a common direction. The study was carried out in samples of 4-decyl-4′-cyanobiphenyl (10CB), 4-octyl-4′-cyanobiphenyl (8CB) and n-hexyl-4′-n-pentyloxy biphenyl-4-carboxylate (65OBC) LCs, and the alignment efficiency was monitored by polarisation microscopy observations and by thermal diffusivity measurements.     

Phase transitions,optical, dielectric and viscoelastic properties of colloidal suspensions of BaTiO3 nanoparticles and cyanobiphenyl liquid crystals

We report experimental studies on the phase transitions and physical properties of colloidal suspensions of BaTiO₃ nanoparticles and two cyanobiphenyl liquid crystals (4-pentyl-4?-cyanobiphenyl and 4-octyl-4?-cyanobiphenyl). From the differential scanning calorimetric measurements, we show that the nanoparticles have antagonistic effect on the isotropic to nematic and nematic to smectic-A phase transitions. The birefringence, dielectric anisotropy and splay elastic constant remain almost unchanged, whereas the bend elastic constant and rotational viscosity decrease considerably. The experimental results are discussed based on the possible contribution of BaTiO₃ nanoparticles and free surfactant molecules in the suspensions.     

PbS nanoparticles stabilised blue phase liquid crystals

A kind of blue phase liquid crystal (BPLC), consisting of nematic liquid crystal, E7, and chiral dopants, CB15 and R1011, was investigated by doping PbS nanoparticles. The blue phase temperature range was extended from 3^oC to 4.6°C by doping PbS nanoparticles with diameters around 9.6 nm. A kind of porous texture was observed both in the forming process of PbS nanoparticles doped BPLCs as well as in the BPLCs (with/without PbS nanoparticles) under assisting electric field. The porous texture may indicate that the liquid crystals molecule should be reoriented during the formation process of PbS nanoparticles doped BPLCs.     

Equilibrium and non-equilibrium transitions studied by adiabatic calorimetry

The principle and recent technical development of adiabatic low temperature calorimetry are described with experimental results taken mostly from the authors' laboratory. Topics on the equilibrium and quasi-equilibrium heat capacities include the separation of the Schottky heat capacity from the experimental data on bromo-hydroxyphenalenone and non-Debye excess heat capacity of a glassy hydrocarbon. Relaxation of glassy crystals of rubidium cyanide and C₆₀ and stabilization of a supercooled phase of methylammonium hexachlorotellurate are discussed. A unique adiabatic calorimeter of top-loading construction recently completed in the authors' laboratory is described along with an experimental result on a glassy liquid prepared at a cooling rate 100 times greater than was possible with a calorimeter of the conventional design.     

Selected X-ray diffraction and differential scanning calorimetry measurements on nonaqueous liquid crystals and gel phases in the K-myristinate/glycerol binary system

Samples from the three selected concentrations x _KC14 = 0.25,0.37, and 0.50 of the K-myristinate/glycerol (KC₁₄/Gl) binary system have been investigated by means of small- and wide-angle X-ray diffraction measurements as well as differential scanning calorimetry (DSC) measurements as a function of temperature. The results are – The G₁ gel phase, contained in the preliminary phase diagram according to Dörfler and Senst [(1993) Colloid Polym Sci 271: 173], is nonexistent. – The same applies of the isotropic phase in the preliminary phase diagram according to Dörfler and Senst. Initially an isotropic or a cubic phase was assumed based on polarized microscopy texture observations. X-ray diffraction and DSC measurements provided no indication for their existence. – Due to the nonexistence of the G₁ and isotropic phases the preliminary phase diagram of the KC₁₄/Gl binary system had to be corrected. The region of the lamellar phase extends over a wider region. – X-ray diffraction and DSC measurements provided concordant results, which were further confirmed by electron microscopic investigation. Differences in phase-transition points from DSC data obtained for rising and falling temperatures have been observed. – The crystalline-to-gel phase transition correlates with a sharp shift in the d value of the first small-angle reflex. – The gel phase is accompanied by a distinct splitting of the first small-angle reflexes. The wide-angle reflexes show rearrangement and reduced intensity. – Similar to the crystalline-to-gel phase transition, the gel-to-lamellar phase transition is accompanied by a sharp change in the d values.     

Transfer-matrix theory of the crystal–columnar transition in polymeric liquid crystals

The statistical–mechanical problem of the transition between crystalline and columnar phases in a main-chain liquid–crystalline polymer is treated in a simple model in which only longitudinal motions of the polymer chains are permitted. A mean-field approximation for the interchain potential is used to obtain a self-consistent equation for the crystalcolumnar transition temperature. When applied to typical homopolymers this theory correctly predicts transition temperatures above the degradation temperature; when applied to a crude model of a random copolymer a temperature in the observed range is predicted.     

Inducing monodomain blue phase liquid crystals by long-lasting voltage application during temperature variation

We demonstrate a new successful technique for inducing a monodomain in blue phase (BP) liquid crystals (BPLCs). By application of an AC voltage during the cooling or heating of the material into the BP temperature range, a fairly homogeneous BP area was obtained, compared to the case without voltage. We determined that applying a voltage of 3.3 V/µm was very effective in terms of obtaining a monodomain: for four of the seven different applied cooling/heating rates an area ratio of more than 99% was obtained for one particular BP orientation. This study describes a successful and replicable technique to make a BPLC monodomain, which is important for the development of BPLCs and other applications.     

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.     

Rational tuning of melting entropies for designing luminescent lanthanide-containing thermotropic liquid crystals at room temperature

The connection of twelve peripheral and divergent dodecyloxy chains to a central tridentate aromatic binding unit provides the dodecacatenar ligand L11, for which room-temperature mesomorphism is detected. An enthalpically unbalanced large melting entropy (DeltaSmL11=226 J mol(-1) K(-1)) results from the programmed microsegregation induced in the crystalline phase, a phenomenon which is maintained in the associated lanthanide complexes [Ln(L11)(NO3)3] and [Ln(L11)(CF3CO2)3]2. Low-temperature melting processes (-43相似文献   

Investigations of solid phase transitions of low molecular organic compounds by differential scanning calorimetry

For the purpose of finding temperature standards for DTA at the temperature below 150°, some solid transitions of low molecular organic compounds were measured by differential scanning calorimetry. Among fourteen materials, we have concluded to select transitions for hexachloroethane (71°) and hexamethylbenzene (110°) as candidates for such standards.

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Zusammenfassung Zur Temperaturnormung unter 150° die DTA Methode wurden verschiedene organische Verbindungen von niedrigem Molekulargewicht und geeigneten Umwandlungen in fester Phase durch Differential Scanning Kalorimetrie geprüft. Von 14 verschiedenen Substanzen wurden Hexachloräthan (71°) und Hexamethylbenzol (110°) zum gesuchten Zweck geeignet gefunden.

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Résumé Pour le but de trouver des étalons de température au-dessous de 150°C pour l'ATD, on a examiné les transitions en phase solide de différents composés organiques de bas poids moléculaire à l'aide d'un analyseur enthalpique différentiel. Sur les 14 échantillons étudiés, on propose l'hexachloroéthane (71°) et l'hexaméthylbenzène (110°) comme étalons.

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150° . , 14 (71°) (110°), .

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The authors wish to thank Dr. H. G. McAdie of the Ontario Research Foundation, Canada, for his kind suggestions on this work.