Liquid crystals of disc-like molecules

Thermotropic mesomorphism has been observed in pure compounds consisting of simple disc-like molecules, viz., benzene-hexa-n-alkanoates. Thermodynamic, optical and x-ray studies indicate that the mesophase is a highly ordered lamellar type of liquid crystal. Based on the x-ray data, a structure is proposed in which the discs are stacked one on top of the other in columns that constitute a hexagonal arrangement, but the spacing between the discs in each column is irregular. Thus the structure has translational periodicity in two dimensions and liquid-like disorder in the third.     

Structure of trans-1,4-polybutadiene synthesized with a new catalyst system

Abstract

The structure, phase composition, and temperature behavior of two trans-1,4-polybutadienes (TPBs) were studied by means of x-ray scattering and differential scanning calorimetry (DSC) techniques. The two samples examined were (1) PB synthesized using an immobilized titanium-magnesium catalyst and (2) a random copolymer based on PB prepared with a homogeneous vanadium-containing catalyst used as a reference material. It was found that the nascent structure of the first PB involves three phases: crystalline, mesomorphic (low-temperature form), and amorphous. In the vicinity of 65°C, a first-order phase transition occurs. The system becomes biphasic and contains the high-temperature form of the mesophase, as well as the amorphous phase, component. Above 165°C, the polymer melts to form a single-phase isotropic melt with a structure typical of liquids. The lateral dimension of crystallites reversibly changes at the crystal-mesophase transition. It is suggested that during annealing of the mesophase formed by cooling of the isotropic melt, the chains acquire an extended conformation. Loss of regularity of the structure of macromolecules of TPB causes a reduction of phase transition temperatures, an increase of the imperfection of the crystalline phase, and a contraction of the temperature range of existence of the mesophase.     

Microwave‐assisted facile synthesis of liquid crystalline non‐symmetrical hexaalkoxytriphenylenes containing a branched chain and their characterization

Two novel series of liquid crystalline non‐symmetrical hexaalkoxytriphenylenes containing a branched alkyl chain have been prepared using microwave dielectric heating. Series 1 contains 2‐ethyl hexyloxy group as the branched chain whereas series 2 contains 3,7‐dimethyl octyloxy as the branched chain along with five normal alkoxy chains. The number of carbon atoms varies from four to eight in the normal alkoxy chains. Mesophase behaviour of the compounds has been characterized by polarizing optical microscopy, differential scanning calorimetry and mesophase structure has been characterized by X‐ray diffractometry. All the compounds show enantiotropic mesophase transitions with columnar hexagonal structure. In series 1 ( 4a – e ) the mesophase range and transition temperatures of all the compounds are lowered as compared to the parent compounds whereas in series 2 ( 5a – e ) the transition temperatures of all the compounds are lowered, mesophase range for lower members are decreased, however, higher members show more mesophase stability. Both melting and clearing temperatures of series 2 ( 5a – e ) show strong odd–even effect. The intercolumnar distance increases as expected for compounds of both the series with increase in alkyl chain length with some degree of interdigitation of the alkyl chains. The intercolumnar distances for the compounds of the series 2 are slightly higher than the compounds of the series 1 . Compound 4c displays homeotropic alignment without using any special technique for alignment of the columnar phase or application of any external force. Copyright © 2007 John Wiley & Sons, Ltd.     

Growth kinetics of polymer crystals in bulk

Temperature-dependent measurements of spherulite growth rates carried out for i-polystyrene, poly(ε -caprolactone) and linear polyethylene show that the controlling activation barrier diverges at a temperature which is 14K, 22K and 12K, respectively, below the equilibrium melting points. We discuss the existence of such a “zero growth temperature” T _zg in the framework of a recently introduced thermodynamic multiphase scheme and identify T _zg with the temperature of a (hidden) transition between the melt and a mesomorphic phase which mediates the crystal growth. The rate-determining step in our model of crystal growth is the attachment of chain sequences from the melt onto the lateral face of a mesomorphic layer at the growth front. The necessary straightening of the sequence prior to an attachment is the cause of the activation barrier. A theory based on this view describes correctly the observations. With a knowledge of T _zg it is possible to fully establish the nanophase diagram describing the stability ranges of crystalline and mesomorphic layers in a melt. An evaluation of data from small-angle X-ray scattering, calorimetry and optical growth rate measurements yields heats of transition and surface free energies of crystals and mesophase layers, as well as the activation barrier per monomer associated with the chain stretching. According to the theory, the temperature dependence of the crystallization rate is determined by both the activation energy per monomer and the surface free energy of the preceding mesomorphic layer. Data indicate that the easiness of crystallization in polyethylene is first of all due to a particularly low surface free energy of the mesomorphic layer.     

Transport properties of mesomorphic syndiotactic polystyrene

Amorphous syndiotactic polystyrene (sPS) films were annealed at 110° and 115°C for 24 h. The annealing at the higher temperature produced the mesomorphic form of sPS, characterized by conformational order, as shown both by the presence of the zigzag band in the infrared spectrum and by the presence of characteristic peaks in the x-ray diffractogram. The crystalline form was not formed at the investigated temperatures. Differential scanning calorimetry of the mesomorphic sample shows that the transformation of the mesophase into the crystalline phase occurs during the heating run. The transport properties of dichloromethane show that the mesophase is impermeable to the vapors at low activity and becomes permeable at higher activities. At low activity it is therefore possible to derive the fraction of impermeable phase, which corresponds to the fraction of mesophase. This fraction was about 50%.     

Phase transition properties of polyethylene glycol-cellulose blends and their miscibility in mixed solvents

The phase transition properties of blends of polyethylene glycol (PEG) with cellulose (CELL) prepared from solution in N,N-dimethylacetamide/lithium chloride (DMAC/LiCI) and those from solution in dimethylsulfoxide/paraform- aldehyde (DMSO/PF) were found to be completely different. The differences of the phase transition properties were probably related to the different miscibilities of these two polymers in the two solvent systems. In DMAC/LiCl, the miscibility of CELL and PEG was limited; the composite obtained exhibited a solid- liquid phase transition and had a small phase transition enthalpy. However, in DMSO/PF, these two polymers had a high level of miscibility; the composite obtained exhibited a solid-solid phase transition and had a large phase enthalpy. It is suggested that the differences of miscibility and the phase transition properties were caused by the different dissolving mechanisms of CELL and the different interactions in these two solutions.     

Measurements of the complex shear modulus of polymers under hydrostatic pressure usina the quartz resonator method

Abstract

The quartz resonator method measures the complex shear modulus or compliance of viscoelastic materials in the frequency range from 50 kHz to 140 MHz at temperatures between ?150°C and 300°C and pressures up to 1 GPa. This method can be applied to viscous fluids or polymer melts -even in their glassy or seminystalline regime.

The phase diagram of poly(diethylsiloxane) PDES (a mesophase polymer) was determined for two samples with different molecular weight at pressures up to 400 MPa and temperatures between 20°C and 100°C. Phase transitions are indicated by a sharp bend in the shear compliance although the volume effect of the mesophase-isotropic transition vanishes around 80 MPa.

The pressure dependence of the glass relaxation process (in PVAc), was studied by measuring the change of the complex shear modulus with pressure at constant temperatures between 95°C and 145°C and pressures up to 600 MPa. Additionally to the relaxation process, also the pressure dependence of the real part of the shear modulus in the glassy region can be determined for testing the dislocation concept in the meandermodell by W. Pechhold.     

A thermodynamic multiphase scheme treating polymer crystallization and melting

A comparison of transition and melting temperatures of n-alkanes with experimentally determined ticknesses and melting points of polyethylene lamellae shows that the variation of the thickness with the crystallization temperature virtually agrees with the chain length dependence of the crystalline-mesomorphic phase transition in n-alkanes. Mesomorphic polyethylene layers are stable objects up to the thickness set by this phase transition. The findings lend further support to the view that polymer crystallization generally uses a route which includes a passage via a mesomorphic phase. We construct a thermodynamic scheme dealing with the transitions between melt, mesomorphic layers and lamellar crystallites, assuming for the latter ones that they exist both in an initial “native” and a final “stabilized” form. Application of the scheme in a reconsideration and quantitative evaluation of SAXS and DSC results previously obtained for PE, sPP, iPS and P(epsilonCL) yields the equilibrium transition temperatures between the various phases, latent heats of transition and surface free energies. According to the results the mesomorphic phases are not liquid-like, but have thermodynamic properties which place them truly intermediate between melt and crystals.     

Bent-shaped mesogenic oxadiazoles and thiadiazoles with terminal methyl group

Rod-shaped 4-methylbenzoic acid-N′-(4′-n-alkoxybenzoyl) hydrazide (series I) have been synthesized by the Schotten–Baumann reaction of 4-methylbenzhydrazide with 4-n-alkoxy benzoyl chloride using dry pyridine, as a solvent. The series I compounds have been cyclized to bent-shaped mesogenic 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-oxadiazoles (series II) and 2-(4′-methylphenyl)-5-(4″-n-alkoxyphenyl)-1,3,4-thiadiazole (series III) using POCl₃ and Lawesson's reagent, respectively. The synthesized compounds are characterized by the combination of elemental analysis and standard spectroscopic methods. In series II, lower and middle members are non-mesogenic. n-Dodecyloxy to n-hexadecyloxy derivatives exhibit enantiotropic nematic mesophase. In series III, all the compounds synthesized exhibit enantiotropic nematic mesophase. n-Tetradecyloxy and n-hexadecyloxy derivatives also exhibit enantiotropic SmA mesophase. The mesomorphic properties of the series II and III used in this study are compared with each other and with other structurally related compound to evaluate the effect of different heterocyclic moieties as well as terminal substituents on mesomorphism.     

Thermal and dielectric studies of self-assembly systems formed by hydroquinone and alkyloxy benzoic acids

Self-assembly systems formed by hydroquinone and alkyloxy benzoic acids are isolated and characterized. Hydroquinone formed double hydrogen bonds with p-n-alkyloxy benzoic acids. Various hydrogen bonded complexes have been synthesized with hydroquinone and pentyloxy to dodecyloxy benzoic acid, respectively. FTIR studies confirm the hydrogen bond formation in the complex. Polarizing Optical Microscopic (POM) studies revealed the textural information while the transition and enthalpy values are experimentally deduced from Differential Scanning Calorimetry (DSC) studies. Phase diagram has been constructed from the POM and DSC data. The members of the present homologous complexes are characterized by POM, DSC, optical tilt angle and dielectric studies. Odd-even effect has been evinced in enthalpy values and transition temperatures corresponding to the isotropic to nematic phase transition. Optical tilt angle in Smectic C phase data has been fitted to a power law and it has been observed that the temperature variation of the tilt angle follows Mean Field theory prediction. Results of Fourier Transform Infrared Spectra (FTIR), POM, DSC, tilt angle and dielectric studies are discussed.     

Changes of thermo-morphologic and thermotropic properties of liquid crystals at direct and reverse nematic mesophase ↔ isotropic liquid phase transitions: surface-induced effect

In this work, the effect of thin films on the thermo-morphologic and thermotropic properties of the phase transitions between the nematic mesophase and isotropic liquid has been investigated. Investigations have been carried out for both the heating and cooling processes. The temperature and linear widths of the biphasic regions of the direct and reverse phase transitions in nematic liquid crystals versus thickness of the thin films have been calculated with a high accuracy. The shift of the nematic mesophase–isotropic liquid and the isotropic liquid–nematic mesophase phase transition temperatures to higher temperatures and the enlargement of the temperature and linear widths of the biphasic regions as the effect of surfaces have been found.     

Quenchedn-vectorp-spin model

A disorderedn-vector model withp spin interactions previously introduced is studied for the quenched case by means of the replica method and a generalized Parisi theory. We present formal solutions for generaln andp and then study the casep . The high-temperature solution is stable at all temperatures and there is only one phase transition at a temperatureT _g. Only longitudinal lowtemperature solutions are possible. There is one spin-glass solution, and it is stable for allT _g. The phase transition atT _g is of first order and displays a jump discontinuity in the order parametersq _j ^(L) andd. The spin-glass free energy is temperature dependent forn > 1 while it is constant whenn = 1.     

Twisted Grain Boundary Phases in the Binary Mixtures of 3ß-Chloro-5-Cholestene and 4-N-Decyloxybenzoic Acid

From the thermodynamical, optical texture and dielectric studies of the binary mixtures of 3β-chloro-5-cholestene (ChCl) and 4-n-decyloxybenzoic acid (DOBA), the phase diagram has been drawn. It has been observed that low concentrations of ChCl (1 to 7 mol%) in DOBA induce various types of twisted grain boundary (TGB) submesophases, whereas higher concentrations induce a smectic A (SmA) mesophase. Various optical textures of the TGB phases under different conditions of molecular anchoring have been observed. Weak transitions related with TGB phases have been detected from the temperature dependence of dielectric permittivity. The observed phase diagram of ChCl-DOBA binary system is in complete conformity with the theoretically predicted mean-field phase diagram derived by Renn within the framework of the chiral Chen-Lubenski model     

Mesophase formation in lyotropic polymers

Summary The behaviour of polymers for which the mesomorphic property is primarily related to rigidity or partial rigidity of the chain backbone is discussed. The former part of the paper includes an outline of current theories, which describe the phase equilibria of both low-and high-molecular-weight mesogens in the undiluted and diluted states. In the latter part of the paper phase behaviours of rigid and semi-rigid polymers are briefly reviewed. Detailed phase diagrams are considered for the systems poly-γ-benzyl-L-glutamate/dimethylformamide and poly-p-benzamide/dimethylacetamide-LiCl. The correlations between experiments and theory are discussed. The mesomorphic behaviour of cellulose and its derivatives and ternary systems involving two rodlike solutes or mixtures of rodlike and random coiled polymers are also considered. Experimental results provide substantial confirmation for the theoretical predictions of mesophase formation in lyotropic polymers. Paper presented at the ?Meeting on Lyotropics and Related Fields”, held in Rende, Cosenza, September 13–18, 1982.     

General formula for phonon-assisted n-photon absorption in solids

A general formula for phonon-assisted n-photon absorption in solids is obtained by (n+1)-th order perturbation technique. The complicated calculation process for transition element of n-photon absorption is simply demonstrated by a diagram approach that is proposed in this work. We find that the transition element for the n-photon absorption has a simple form, i.e., it is just the first term of the n-th order fist kind Bessel function.     

Size effects on melting and wetting in the Ga–Pb nano-alloy

Ga–Pb alloys with 15 at% Pb mean concentration have been prepared at the nanoscale by means of evaporation-condensation technique in ultra high vacuum conditions. Transmission electron microscope images indicate that at room temperature, the system is a two-components breath figure composed of liquid Ga nanodrops containing Pb nanocrystals. Some thermodynamic properties of this nano-alloy are investigated for different temperatures and particle sizes. The results obtained put in evidence a large modification of the Ga–Pb bulk phase diagram: a decrease of the melting temperatures of the two components as well as the ones of the miscibility gap. Changes in the microscopic structure of the system as a function of temperature have been investigated and a full wetting transition from a dry to a completely wet state has been put in evidence.     

The vortex-like excitations detected by Nernst signals in high-Tc superconductors

The nature of the pseudogap state and its relation to the d-wave superconductivity in high-T _c superconductors is still an open issue. The vortex-like excitations detected by the Nernst effect measurements exist in a certain temperature range above superconducting transition temperature T _c, which strongly support that the pseudogap phase is characterized by finite pairing amplitude with strong phase fluctuations and imply that the phase transition at T _c is driven by the loss of long-range phase coherence. We first briefly introduce the electronic phase diagram and pseudogap state of high-T _c superconductors, and then review the results of Nernst effect for different high-T _c superconductors. Related theoretical models are also discussed.     

Etude dilatométrique et mesure des paramètres volumiques de la série des acétyl-4 n-alkanoyloxy-4′ azobenzènes

Summary In this paper, we present a dilatometric study of the even members of the following homologous series of liquid crystals: 4-acetyl-4′-n-alkanoyloxyazobenzene. The nature of all the transitions occurring as a function of temperature is shown to be of first order. At the transition from the crystal to the mesomorphic state (smecticA or nematic), the aliphatic chains of the molecules melt in one step. At the transition between the smecticA phase and the isotropic phase, only the aromatic stems play a role in the melting process.

Pour accélérer la publication, les auteurs de cet article ont agrée à ne pas recevoir les épreuves pour la correction.     

Mesomorphic behaviors of a series of heterocyclic benzothiazole-imine-ester-based liquid crystals

A series of new calamitic liquid crystals, 2-[4-(4-alkoxybenzoyloxy)benzylidenamino]benzothiazoles comprising a heterocyclic (benzothiazole) and two phenyl rings core system, terminal alkoxy chain, imine and ester linkers were prepared and characterized. This series comprises eight members wherein the members vary by the length of alkoxy chain (C_nH_2n+1O-, where n?=?4, 6, 8, 10, 12, 14, 16, 18). Spectral analysis results were in conformity with the expected structure. Their thermotropic behaviors were studied by using differential scanning calorimetry, optical polarizing microscopy and powder X-ray diffraction techniques. A single mesophase (nematic) was observed for the first member of the series (n?=?4). As the alkoxy chain increased to n?=?6, 8, 10, 12, 14, the nematic phase appeared together with an additional SmA phase. When moving from n?=?16 until the highest member (n?=?18), the nematic phase disappeared and these compounds only exhibited a single mesophase (SmA).