Role De La Masse Moleculaire Dans L'apparition Des Phases Nematiques Thermotropes

The thermotropic nematic phases of pure aromatic oligo and polyazomethines and their binary mixtures in a nematic solvent of the same chemical nature have been studied by optical microscopy. The transition temperatures of the pure compounds increase very rapidly with molecular weight; the polymeric materials decompose before melting. When a methyle group is randomly fixed on the phenylene diamine rings, the melting temperature of the crystal is depressed; this is a good way of helping the formation of thermotropic nematic phases with rigid polymers. Apart from the solution of the 3 ring compound in the nematic solvent, the mixtures we have considered are not ideal.     

Liquid Crystal Polymers: Conformation of Deuterated Parts by SANS

Comb like liquid crystal polymers are polymers on each monomer is grafted a hanging liquid crystal molecule. The bulk state has the classical liquid crystal phases (nematic, smectic); what is the conformation of a chain in these phases is the problem to solve with the help of small angle neutron scattering. The values of the global sizes R _|| and R _‖ of a chain (in the direction parallel and perpendicular to the director) are discussed as a function of the chemical species and the temperature. Strange results are discussed in terms of segregation of labelled parts.     

Chiral phases in a system of biaxial molecules

Chiral phases in a system of biaxial molecules are investigated based on a theory of biaxial liquid crystals, which we have presented in past work. Four chiral phases are identified, corresponding to a uniaxial nematic phase, two biaxial nematic phases, and a discotic phase, respectively. We find that in the chiral uniaxial nematic phase, the pitch of the chiral structures does not depend on temperature. In contrast, in the two chiral biaxial nematic phases, as well as in the chiral discotic phase, the pitch is temperature-dependent.     

Conoscopic image of a biaxial nematic phase in a sodium decyl sulfate – decanol – D2O mixture

ABSTRACT

The nematic phases of a lyotropic system NadS/ decanol/ heavy water are investigated using optical conoscopy and image processing. The phase diagram obtained from these lyotropic materials predicts the occurrence of a direct phase transition, which does not present the biaxial nematic phase, between the discotic (N_D) and calamitic (N_C) nematic phases. A biaxial nematic (N_B) phase is optically characterized and confirmed through conoscopic image, inside the biaxial range, between the two uniaxial nematic phases. Also, their respective transition points are determined by means of image processing. The N_B phase observed here is discussed as part of the nature of the micellar configuration of lyotropic materials which exhibit uniaxial nematic phases.     

Macroscopic Phenomena in Polymer Liquid Crystals

Rigid and semirigid backbone polymers based on either helical structures or conjugated aromatic bonding often exhibit nematic ordering in solution or as melts. Because of the large axial ratio of these molecules, the resulting nematic phases exhibit hiahly anisotropic elastic and viscous properties. The study of macroscopic phenomena in these liquid crystals serves two purposes. First is the elucidation of the relationship between macroscopic material parameters and molecular properties. Second is the understanding of the consequence of the highly anisotropic nature of these materials, namely new phenomena not observed in low molecular weight liquid crystals. Several new phenomena will be described related to the Frederiks transition and flow instabilities.     

Liquid crystal–gold nanoparticle composites

Nanoparticles (NPs) have emerged as extremely promising materials to alter and improve the properties of liquid crystals (LCs) used, for example, in device applications. In this paper, we summarise recent work from our lab that aims to provide a fundamental understanding of structure–property and composition–property relationships governing LC–NP interactions, which may point to new directions for major improvements in the efficiency of LCs used in display applications. A variety of LC hosts (phases) doped with surface-functionalised gold NPs have been systematically studied ranging from one-dimensionally ordered nematic over two-dimensionally ordered smectic to three-dimensionally ordered columnar phases. Significant progress with respect to LC–NP interactions was made for NP-doped nematic phases. Here, the observation of an unusual texture for Au NP-doped nematic LCs, that is, the formation of birefringent stripe textures and the induction of homeotropic alignment of the nematic LC similar to chiral finger (or fingerprint) textures, provided the basis for numerous experimental studies using Au NPs with different core sizes and surface functionalities.     

Frequency dependence of the threshold voltage of the Freedericksz effect in nematic and nematic reentrant phases

In four substances exhibiting reentrant nematic phases the threshold voltage of the Freedericksz transition was measured as function of the frequency in the nematic and reentrant nematic phases. The isotropy frequency and the relaxation frequency were calculated using the experimental data. We found that extrapolated to the same temperature the relaxation frequency of the reentrant nematic phase is larger than that of the nematic phase.     

Density Studies in Polymorphic Liquid Crystal N- (p-n-Heptyloxybenzylidene) p-n-Pentylaniline

Density studies in polymorphic liquid crystal, N-(p-n-heptyloxybenzylidene) p-n-pentyl-aniline is carried out in isotropic liquid, nematic, smectic A, smectic C, smectic B and smectic G phases. The temperature variation of density in all the mesophases confirms that isotropic liquid to nematic, nematic to smectic A, smectic C to smectic B, smectic B to smectic G transitions are of first order while smectic A to smectic C transition is of second order. The density variation across smectic C to smectic B is greater than that of any other transition. Thermal expansion coefficients are also calculated.     

The Orientational Order of a Re-entrant Nematic Phase. an Electron Resonance Investigation

We have investigated the orientational order in a re-entrant nematic and its preceding phases using steroidal and alkyl nitroxide spin probes. The order parameter for the steroidal spin probe in the re-entrant nematic phase is found to be an extension of its value in the preceding smectic A phase. In contrast the gradient of the order parameter for the alkyl spin probe exhibits a marked discontinuity at the smectic A - re-entrant nematic transition.     

Viscoelastic Parameters of a Side-Chain Nematic Polymer: II—Analysis of NMR Results in Terms of the Anisotropic Dumbbell Model

The two viscoelastic parameters of a siloxane side-chain nematic polymer—twist viscosity coefficient, and static order parameter—deduced from the NMR study of Reference 1, are discussed in terms of the anisotropic dumbbell model of Brochard using structural information obtained by small angle neutron scattering. It is found that this model, originally developed for dilute solutions of flexible polymers in low molecular mass nematics, describes satisfactorily the data, supporting the idea that the backbone polymer chains are not entangled in the nematic melt. An average elastic constant is deduced. This constant is found to increase sharply as the nematic-smectic A phase is approached. The twist elastic constant is calculated using splay and bend elastic constant values of a very similar polymer. Some (possibly only apparent) difficulties associated with the dumbbell model are pointed out.     

Colloidal structures in confined nematic liquid crystals

Colloidal structures in confined nematics offer novel routes for designing complex optical materials with micrometre and submicrometre functionality. In this paper, we review some of our recently assembled colloidal structures that form in confined nematic cells. We present effective elastic binding via nematic distortion as a mechanism for the assembly of two-dimensional colloidal crystals of elastic dipoles and elastic quadrupoles. We introduce entangled colloids as novel types of structures, where particles are topologically bound by delocalised defect loops, producing robust and possibly chiral structures. The concept of hierarchical assembly is demonstrated in colloids with particles of various scales. In cholesteric blue phases, the assembly of three-dimensional colloidal crystals is shown based on naturally occurring three-dimensional arrays of trapping sites produced by blue phases.     

Calorific Effect of the Magnetically Induced Phase Transition in Induced Chiral Nematic Systems

The study of the calorific effect of the magnetically-induced phase transition in doped nematic phases is described. The systems examined consisted of PCB as a nematic host phase and S-N-1-phenylethyl-4n-alkylbenzamides as non-mesogenic optically active dopants. The calorific effect was estimated indirectly from the temperature dependence of the magnetic-field-threshold of the helical unwinding and of the reverse process; i.e. the helical winding. It appears that it is the ratio of the length of an optically active dopant and that of the nematic host which determines the temperature dependencies of such parameters as the helical pitch, microscopic twisting power, and latent heat. A comparison with the magnetocaloric effect in nematic liquid crystals¹ is also made.     

Dielectric relaxation in nematic,smectic A and C phases in the MHz region

The dielectric properties of four 4-n-alkyloxyphenyl 4-n-alkyloxybenzoates with nematic, smectic C and partly additional S_A phases were investigated. In 2 substances for ϵ′ reproducible values also in the smectic phases resulted allowing to conclude on a good orientation in the samples. In all 4 substances the dielectric relaxation in the MHz region was measured and the respective activation energies were determined. The molecular mobility in the S_C phases is higher than in the S_A phases, however comparable with that of the nematic phases. In all 3 phase types a single relaxation mechanism exists, which is explained as rotation of the molecules around a short axis.     

Material Highlights: Liquid Crystal Polymers

Abstract

A key issue in the area of side chain liquid crystal polymers concerns the conformation of the backbone within the mesophase. In order to resolve this matter, Noirez and co-workers (Liquid Crystals, 1995, 18 129) have studied a wide range of polymers exhibiting both nematic and smectic behaviour using small angle neutron scattering. Their results combined with a survey of those in the literature reveal that if the polymer is solely nematogenic, then the backbone adopts a prolate conformation in which on average it lies along the director. By contrast, in a smectic phase the backbone adopts an oblate shape and on average lies perpendicularly with respect to the director. This arises from a microphase separation in which the backbones are distributed between the mesogenic layers. However, the backbones can cross the mesogenic layers although their ability t o do so depends on, amongst other factors, the degree of polymerization. If the polymer exhibits both nematic and smectic behaviour, then in the nematic phase the backbone adopts a slightly oblate shape resulting from smectic fluctuations.     

Truxene Derivatives

Eight hexa-n-alkanoyloxy truxenes are presented. These new disc-like liquid crystals exhibit both columnar and N _D nematic phases. The N _D nematic phase is the first low temperature one. All these compounds show an inverted nematic-columnar sequence: the fluid N _D nematic phase is observed while heating after the crystalline phase below one or two viscous columnar phases and shows a phenomenon quite similar to the reentrant nematic behaviour.     

Landau Theory of Biaxial Nematic Liquid Crystals

The orientational order of molecules in a liquid crystal is traditionally described by spatial or temporal averages of functions that are quadratic in the direction cosines of molecular axes with respect to laboratory fixed axes. The free energy describing the nematic phase must be independent of the choice of coordinate systems and therefore rotationally invariant with respect to both laboratory and molecular frames. A Landau theory for biaxial and uniaxial nematics based on six fundamental invariants is developed which is properly rotationally invariant. Four possible nematic phases, two uniaxial and two biaxial, result. NMR experiments should be able to identify which of these actually occur in specific materials.     

Self-Diffusion in Uniaxial Liquid Crystals

Expressions are given for the translational diffusion parameters of non-spherical solutes in nematic and smectic-A phases, as measured by magnetic field gradient spin-echo NMR.     

A Polyester Forming a Thermotropic Cholesteric Phase

Mesomorphic polyesters were synthesized from 4, 4′-dihydroxy-α-methylstilbene and adipic acid (P-6) or (+)-3-methyl adipic acid (P-6M). P-6 forms a thermotropic nematic phase and P6-M a thermotropic cholesteric phase. The nematic phase of P-6 could easily be identified by optical microscopy. For both polymers we observed a biphasic region in which the isotropic and liquid crystalline phases coexist. Bright colors were obtained by increasing the pitch of P6-M by admixture with either a low molecular weight nematogen or with polymer P-6, and also by synthesizing a copolymer containing the two dibasic acids. The copolymeric cholesteric phase, which is stable between 199 and 282[ddot]C, had a predominately planar texture, and these features could be retained in the solid state by quenching to produce a film having a deep blue color at room temperature. The role of the degree of polymerization upon the development of organization, and parameters, of the mesophase is discussed.     

Biphenylbenzoates: Synthesis and Thermodynamic Properties

Two homologous series of twelve compounds each of biphenylbenzoates have been synthesised and their mesomorphic properties characterised. Heats of transition for both series of compounds have also been measured using differential scanning calorimetry. In the biphenyl 4-p-n-alkoxybenzoate series the first few members are monotropic nematic and the higher ones exhibit enantiotropic nematic as well as smectic phases, whereas in the biphenyl 4-p-n-alkyl benzoate series only the monotropic nematic phase is observed. In both series of compounds the plot of the nematic-isotropic transition temperature against the number of carbon atoms in the alkyl chain exhibit smooth curve relationships.