Investigation of the nematic-isotropic transition of a liquid crystalline polymer and determination of molecular diffusion coefficients using gas chromatography

Inverse gas chromatography has been used to study the nematic-isotropic transition of a side chain liquid crystalline polymer (LCP). The mesogenic side groups are laterally attached to a polysiloxane backbone through a flexible spacer. The nematic-isotropic transition of this LCP coated onto a glass capillary column is detected by considering the variation with temperature of the retention volume and of the theoretical plate number for the several probes. The molecular diffusion coefficients, D, of naphthalene, fluorene, pyrene and o-terphenyl have been determined at different temperatures in the nematic phase of the LCP as well as in the isotropic melt. The values ranged between 10(-14) and 10(-12) m2 s(-1) for the polynuclear aromatic hydrocarbon probes tested.     

On the relationship of the nematic-isotropic transition temperature of an oligomer to that of its constituent units

We consider the nematic-isotropic transition temperature for a rigid oligomer formed by linking identical mesogenic units together. In particular, we seek to relate the transition temperature for the oligomer to that of the constituent units, within the framework of the Maier-Saupe molecular field theory and its various parameterizations.     

Unusual electro-optical behaviour of the nematic polyacrylate

ABSTRACT

High sensitivity of liquid crystals to the electric field makes them highly demanded and widely used in different applications. Despite the large number of the electro-optical research on the low-molar-mass liquid crystals electro-optics of the liquid crystalline (LC) polymers is much less studied. Herein, the comparative electro-optical behaviour of two nematic comb-shaped polyacrylates with phenylbenzoate mesogenic side groups was studied in detail. These two polyacrylates have completely the same structure of polymer backbone and spacer length but different in the direction of the ester group in the phenylbenzoate fragments. It was found that this difference predetermines their completely opposite electro-optical properties.

The influence of the electric field of different strength and frequency on the orientation of the mesogenic groups of these polymers is studied. It is shown that application of the electric field at temperatures above the glass transition temperature (~25°C) induces reorientation of the mesogenic groups along or perpendicular to the electric field direction depending in its turn on the ester group direction. For one of the polyacrylates an unusual textural transition is found; during cooling of the polymer sample under applied field at definite temperature a sharp change in the mesogen’s orientation from homeotropic to planar one is found. This electro-optical phenomenon is observed for the first time and probably associated with sharp change in sign of anisotropy of dielectric permittivity from positive (at high temperatures) to negative one (at lower temperatures). Kinetics of the electro-optical switching at different temperatures, influence of the molar masses of the polymer and frequency of the applied AC field on electro-optical behaviour of the polymers are studied. The possibility of the fixation of the electroinduced homeotropic alignment of the mesogenic groups by photopolymerisation of the diacrylate dissolved in the polymer is demonstrated.     

Characteristic behavior of short-term dynamics in reorientation for Gay-Berne particles near the nematic-isotropic phase transition temperature

A specific transition behavior was found in the tumbling motion near the nematic-isotropic phase boundary using molecular dynamics simulations of the Gay-Berne mesogenic model under isobaric conditions at a reduced pressure P* of 2.0. The relaxation time for the motion obtained from the second-rank orientational time correlation function and the rotational diffusion coefficient showed a clear jump at the nematic-isotropic phase transition temperature. Regardless of the temperature dependence of the relaxation time, the change in the rotational diffusion coefficient evaluated from the orientational order parameters and the relaxation time agreed qualitatively with that of real mesogens. The rotational viscosity coefficients gamma(1) and gamma(2) were obtained from the simulation data for the relaxation time for the short-term dynamics and for the rotational diffusion coefficients. gamma(1) was proportional to (2), where is the second-rank orientational parameter. Furthermore, the rotational behavior of the model was compared with that of the Debye approximation in the isotropic phase.     

Understanding the dependence of the transitional properties of liquid crystal dimers on their molecular geometry

The characteristic feature of liquid crystal dimers, in which two mesogenic groups are linked by a flexible spacer, is often thought to be the strong odd-even effect exhibited by their transitional properties. That is, the nematic-isotropic transition temperature and the entropy of transition are large for dimers with an even number of groups in the spacer in comparison with those for neighbouring dimers with an odd number of groups. However, the magnitude of the odd-even effect along a homologous series of dimers is found to depend strongly on the nature of the link between the mesogenic group and the spacer. This dependence is thought to originate in the variation of the molecular geometry with the linking group, a view which is supported by detailed molecular field theory calculations involving all of the conformational states. Here we are concerned with developing a more transparent understanding of this geometrical effect using a simple model of the dimers in which all of the conformational states are replaced by just two, a linear and a bent conformer. The model has been found to exhibit a strong odd-even effect as well as a nematic-nematic transition when the bond angle is tetrahedral. We have used this model to explore the dependence of the transitional properties of liquid crystal dimers on their geometry by varying the bond angle of the bent conformer. The behaviour predicted by the model for the nematic-isotropic transition is found to be in qualitative agreement with experiment. In addition, the nematic-nematic transition is observed to exhibit a critical behaviour as the bond angle is increased. At the other extreme, when the bond angle is reduced to its limiting value of 90° there is a very strong first order transition between a discotic and a calamitic nematic.     

The intercalated smectic A phase. The liquid crystal properties of the α-(4-cyanobiphenyl-4′-yloxy)-ω)-(4-alkyloxycinnamoate)alkanes

Abstract

A novel system of non-symmetric dimers containing 4-n-alkyloxy-substituted cinnamic acid and cyanobiphenyl groups has been studied. Two series were prepared: in one the flexible spacer was varied in length while the spacer was fixed. The spacer length has a profound influence on the nematic-isotropic transition temperature of these materials and a large odd-even effect is observed for the series. The terminal chain also plays a significant role in determining the liquid crystal phase behaviour: a smectic A phase is exhibited for the ethyl and propyl homologues, in addition to a nematic phase; this smectic phase vanishes for intermediate chain lengths but then reappears for the nonyl and decyl members of the series. X-ray diffraction has revealed the structure of the smectic A phase for the ethyl homologue to be intercalated, whereas that for the decyl compound is interdigitated. The existence of the intercalated smectic A phase has previously been explained in terms of a charge-transfer interaction between unlike mesogenic groups. However, for the non-symmetric liquid crystal dimers described here this specific interaction appears unlikely and we discuss, therefore, other possible mechanisms for the formation of intercalated smectic phases.     

On the structure and the chain conformation of side-chain liquid crystal polymers

Abstract

Backbone anisotropy and the structure of the mesophases of a series of side-chain liquid crystal polymers have been studied in the bulk by neutron scattering. The backbone conformation is obtained by small-angle neutron scattering on mixtures of hydrogenous polymers with deuteriated backbones. The components of the radius of gyration parallel, R _⊥ and perpendicular, R ∥ to the magnetic field are determined as a function of temperature for both the nematic phase and the smectic phase. It is shown that the polymer backbone is deformed in both phases. When the polymer exhibits only a nematic phase, it adopts a prolate conformation, where the average backbone direction is more or less parallel to the aligned mesogenic groups. Upon transition from the smectic phase to a nematic phase, the backbone in the nematic phase assumes a slightly oblate shape. This tendency towards oblate shape is due to the smectic fluctuations which are always present in such nematic phases. The exentricity of the oblate backbone conformation in the smectic phase is always larger than in the nematic phase. This is attributed to a periodic distribution of the backbone between the mesophase layers. Then, the backbone anisotropy depends not only on the smectic structure (S_A1, S_Ad), but also on the temperature dependence of the density of aligned mesogenic groups in the layers. On the other hand, it is shown that the isotopic mixtures are no longer ideal when polymers deuteriated in the mesogenic moieties are mixed with the corresponding hydrogenous polymers.     

Obituary: Professor Frank M. Leslie FRS (1935-2000)

The synthesis of five new cholesteryl-based monomers (M-1?M-5) and the corresponding smectic comb-like polymers containing cholesteryl groups (P-1?P-5) is presented. The chemical structures were characterised by FT-IR, 1H NMR and elemental analyses. The specific optical rotations were evaluated with a polarimeter. The phase behaviour was investigated by polarising optical microscopy, differential scanning calorimetry, thermogravimetric analysis, and X-ray diffraction. The specific optical rotation values of these monomers and polymers with the same number of phenyl rings and terminal groups were nearly equal; however, they decreased with increasing the aryl numbers in the mesogenic core. The monomers M-1?M-5 showed oily streak and focal conic optical textures, or finger print textures characteristic of the chiral nematic phase. The polymers P-1?P-5 showed the smectic A phase. The melting, clearing, and glass transition temperatures increased, and the mesophase temperature ranges widened with increasing the aryl number in the mesogenic core. However, although the molecular structures of M-4 and M-5 were similar to those of M-3, namely their mesogenic cores contained three phenyl rings, their phase behaviour differed considerably, and T _m and T _i of M-4 and M-5 were less than those of M-3. In addition, M-4 and M-5 showed a clear glass transition similar to the polymer. Furthermore, the ester linkage bond and aryl arrangement in the mesogenic core also affected the phase behaviour.     

Non-equilibrium thermal behaviour of a main chain thermotropic polymer

Abstract

The effect of thermal treatment on the thermodynamic properties and structure of a nematic thermotropic main chain polymer with mesogenic groups containing 3,3′-biphenylene units and octamethylene flexible spacers (BF8) has been studied by DSC and X-ray scattering. We have found that BF8 samples do not crystallize even on very slow cooling from the isotropic state, and possessed a glassy nematic structure at room temperature. The strong influence of the cooling rate on both the enthalpy of the nematic-isotropic transition and the rise of specific heat at the glass transition for BF8 samples was observed. It was attempted to explain this result in terms of the improvement of the nematic structure during cooling.     

The Effect of Molecular Weight on the Thermal Properties of Polystyrene-Based Sidechain Liquid-Crystalline Polymers

Abstract

Sidechain liquid-crystalline polymers were prepared by the derivatization of three poly(4-hydroxystyrene) fractions of different molecular weights (M_w = 1.0 × 10⁴, 2.2 × 10⁴ and 3.0 × 10⁴). 4-Cyanoazobenzene and 4-cyanobiphenyl were incorporated as mesogenic groups with ether-linked methylene spacers of varying length. The polymers all exhibited a smectic A phase, with the exception of the propyl member of the cyanobiphenyl series for which no liquid-crystalline behavior was observed. For short spacers the thermal properties were insensitive to molecular weight changes in the backbone, whereas small but consistent differences in the transition temperatures and entropies were observed as the number of methylene groups in the spacer increased.     

Geraniol Based Side Chain Liquid Crystalline Polymer: Synthesis and Characterization

Side chain liquid crystalline (SCLC) polysiloxane polymer with a geraniol mesogenic group and polymethylene spacers were prepared, and their properties were compared with those of an equivalent SCLC polymer, SCLCP's, with phenyl benzoate mesogenic group. The phase behavior was studied by differential scanning calorimetry (DSC) and optical polarizing microscopy (OPM). The DSC curve showed a clear melting temperature and isotropization at 72 and 148°C, respectively, with a glass transition at 25°C. The observation of a fan‐shaped texture confirms the presence Smectic A phase under an optical polarized microscope.     

Nematic-isotropic pretransitional behaviour in dimers with odd and even spacer lengths

Magnetic field induced optical birefringence measurements in the isotropic phase are reported for two members of a series of phenyl benzoate dimers: one having an odd number of methylene units in the spacer and one having an even number. The discontinuity at the nematic-isotropic transition, as determined by the difference between the first order phase transition temperature TNI and the supercooling limit of the isotropic phase T*, is approximately 8 ± 3 times larger for the even species than for the odd. In addition, the product of the Cotton-Mouton coefficient dΔn/dH² and T-T* is the same for both materials. In terms of both steric and molecular field theories, the results indicate that the orientations of the terminal mesogenic groups are essentially uncorrected in the isotropic phase.     

Molecular dynamics of a smectic liquid-crystalline side-chain polymer. The dielectric properties of aligned and nonaligned material studied over a wide range of frequency and temperature

The dielectric relaxation behavior of a nonaligned and an aligned liquid-crystalline (LC) polymer are reported for the ranges 10^?3.5 to 10⁵ Hz and 274–363 K. Multiple processes (δ and α) are observed that follow a Vogel equation for the temperature dependence related to the apparent glass transition temperature. The occurrence of these processes and the variation in their relaxation strengths as sample alignment is changed is interpreted in terms of a molecular theory for the dielectric behavior of a LC polymer that involves the director order parameter S_d, the mesophase order parameter S, the dipole moment components of the mesogenic head groups, and their associated relaxation functions.     

H-shaped liquid crystals inducing nematic order in the isotropic liquid

ABSTRACT

We prepared a homologous series of H-shaped liquid crystals I-n and investigated their phase transition properties using optical microscopy and differential scanning calorimetry. All the compounds exhibited a nematic phase at room temperature. The phase transition behaviour is explained in terms of molecular shape anisotropy. Furthermore, those compounds were found to exhibit electro-optical switching in the isotropic liquid in the vicinity of the nematic–isotropic liquid transition, indicating that the microscopic nematic order with a certain coherence length of the molecules exists in the optically isotropic temperature range.     

Static and dynamic dielectric effects in the vicinity of the isotropic to nematic phase transition in 7CB

Static and dynamic dielectric measurements were performed with very high accuracy on a mesogenic compound n‐heptylcyanobiphenyl (7CB) in the isotropic (I) and nematic (N) phases. The critical‐like temperature behaviour of the static permittivity of isotropic 7CB in the vicinity of the I–N phase transition can be described with the critical exponent close to 0.5, indicating the tricritical nature of the transition. Anomalously slow rotational diffusion (subdiffusion), characterized by a fractal value of the diffusion exponent α, is observed in the vicinity of the I–N transition with a lambda‐like profile of the exponent temperature dependence.     

Using Lateral Substitution to Control Conformational Preference and Phase Behaviour of Benzanilide-based Liquid Crystal Dimers

The inclusion of secondary and tertiary benzanilide-based mesogenic groups into liquid crystal dimers is reported as a means to develop new materials. Furthermore, substitution at the nitrogen atom is shown to introduce an additional synthetic ‘handle’ to modify the molecular structure of the tertiary materials. The design of these materials has proved challenging due to the strong preferences of 3° benzanilides for the E amide conformation. In this work, lateral substitution is used to modify the conformational preferences of the amide linkage and promote liquid crystallinity for a series of N-methyl benzanilide dimers. As the proportion of the E conformer decreases, the nematic-isotropic transition temperatures increase, and enantiotropic nematic behaviour is observed. We also report the synthesis and characterisation of the analogous 2° benzanilide-based materials, which show nematic and twist-bend nematic behaviour. This approach highlights the effects that seemingly small structural modifications, such as the inclusion and position of a methyl group, can have on molecular shape and hence, liquid crystalline behaviour.     

Sensitivity of the NTB phase formation to the molecular structure of imino-linked dimers

ABSTRACT

Here we report on the synthesis and mesomorphic properties of a series of imino-linked dimeric molecules. In order to improve our understanding of the structure–N_TB phase correlations, we have studied the impact of geometric and electronic factors arising from varying mesogenic units, different spacer lengths and from the ratio (n/m) between the lengths of terminal chains (n) and spacer (m). From the perspective of the molecular geometry, the results show that the stability of the N_TB phase results from increasing effective molecular bending and with the broadening of the mesogenic unit, in particular near the spacer, and that the n/m ratio plays a substantial role in conjunction with the specific mesogenic unit. A computational study of the electronic properties shows that a broadening of the mesogenic core in the vicinity of the spacer is associated with an increased anisotropy of the electrostatic potential distribution. Within a given series of materials our study suggests that the incidence of the N_TB phase and its thermal stability are governed by the synergy of specific geometrical factors and the anisotropy of the electrostatic potential distribution of the mesogenic core.     

Synthesis of side chain liquid-crystalline polysiloxane containing trans-cyclohexane-based mesogenic side groups

Abstract

The synthesis and characterization of nine new side chain liquid-crystalline polysiloxanes containing one cyclohexyl ring and another 2-4 aromatic rings in their mesogenic side groups are described. All synthesized polymers displayed nematic mesomorphism. Most of the polymers showed a very wide mesomorphic temperature range. The mesogenic core length has profound influence on the phase transitions of the polymers. The mesomorphic temperature range increased with increasing mesogenic core length.     

Confinement of a liquid crystal to small droplets and its effect on nuclear magnetic relaxation

Abstract

The spatial dependence of the orientation of the molecular director and of the nematic order parameter is obtained by minimization of the Landau–de Gennes free energy of the nematic liquid crystal confined in a spherical droplet. Special attention is given to the vicinity of the nematic–isotropic transition. The influence of the resulting nematic structure, large liquid crystal–polymer interface and restricted molecular diffusion on the nuclear magnetic relaxation is analysed. The translationally-induced molecular reorientation and the liquid crystal–polymer cross relaxation are discussed in particular. The possibility of an indirect study of the molecular anchoring on the polymer surface is demonstrated.