Main chain liquid crystalline ionic polymers with thermotropic and lyotropic mesophases

An ionogenic main chain liquid crystalline polymer was synthesized. In contrast to previous studies the charged sites were incorporated into the flexible spacer and not into the mesogenic group. This was done through quaternization of 1,2-bis(4-pyridylethane) with a biphenyl-4,4′-nonanoxytoluenesulphonate. The polymer displayed thermotropic and lyotropic me-sophases. The thermotropic mesophase was smectic. Organic counterions such as meth-ylsulfonates and p-toluenesulfonates were found to be favorable to the development of mesophases, due to the increased solubility and lower isotropisation temperatures, when compared to bromide counterion containing polymers. Easy supercooling, dependence on thermal history, and the development of batonnet textures on cooling from the melt were also observed. © 1995 John Wiley & Sons, Inc.     

Flow-induced structure in a thermotropic liquid crystalline polymer as studied by SANS

Small-angle neutron scattering is utilized to determine the flow induced alignment of a model thermotropic liquid crystalline polymer (LCP) as a function of shear rate and temperature. The results demonstrate that the flow-induced structures in thermotropic liquid crystalline polymers have similarities and differences to those in lyotropic liquid crystalline polymer solutions. The shear rate dependence of the alignment shows that the flow-induced alignment correlates very well to the viscosity behavior of the LCP in the shear thinning regime, while temperature variation results in a change in the extent of alignment within the nematic phase. Relaxation results also demonstrate that the flow-induced alignment remains essentially unchanged for up to an hour after the shear field has been removed. Last, there exists a regime at low shear rate and low temperature where alignment of the LCP molecule perpendicular to the applied shear flow is stable. These results provide important experimental evidence of the molecular level changes that occur in a thermotropic liquid crystalline polymer during flow, which can be utilized to develop theoretical models and more efficiently process thermotropic polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 3017–3023, 1998     

Lamellar lyomesophases under shear as studied by deuterium nuclear magnetic resonance

The lamellar phases of two aqueous ethylene oxide surfactants, tetra(ethylene oxide) dodecyl ether and hexa(ethylene oxide) dodecyl ether, have been investigated by deuterium nuclear magnetic resonance spectroscopy during shear. The evolution of the shear-induced NMR line shapes and their dependence on surfactant concentration, shear geometry and shear history is analyzed. Two of three previously described shear-induced states (Diat O, Roux D, Nallet F (1993) J Phys II France 3: 1427–1452), namely the state of aligned lamellae with the layer normal parallel to the velocity gradient, which occurs at low shear rates, and the vesicular state at intermediate shear rates are found and identified by their characteristics NMR line shapes.     

Internal molecular disorder in the nematic and smectic phases of thermotropic liquid crystals studied by NMR SPDE experiments

The recently developed NMR SPDE experiment is shown to provide a new and particularly convenient technique for probing the conformational dynamics of mesogens in thermotropic liquid crystals. Measurements have been made in the nematic and smectic phases of the 4,4′-di-n-alkoxyazoxybenzenes. It is shown for the first time that the internal disorder of the alkyl end chains is intimately related to the molecular organization of these mesophases.     

Synthesis,liquid crystalline mesophases and morphologies of diblock copolymers composed of a poly(dimethylsiloxane) block and a nematic liquid crystalline block

In this study, a series of liquid crystalline diblock copolymers, composed of a soft poly(dimethylsiloxane) (PDMS) block with a de?ned length and a side-on liquid crystalline poly(3??-acryloyloxypropyl 2,5-di(4?-butyloxybenzoyloxy) benzoate) (P3ADBB) block with different lengths, are synthesised by the atom transfer radical polymerisation. The macromolecular structures, liquid crystalline properties and the microphase-separated morphologies of the diblock copolymer are investigated by ¹H NMR, FT-IR, GPC, POM, DSC and TEM. The results show that the well-de?ned diblock copolymers (PDMS_n-b-P3ADBB_m) possess four different soft/rigid ratios (n = 58, m = 10, 25, 42, 66) and relatively narrow molecular distributions (PDI ≤ 1.30). P3ADBB blocks of the copolymers show nematic sub-phases, which are identical to the mesomorphic behaviour of the homopolymer P3ADBB. After being annealed at 90°C in a vacuum oven for 48 h, the copolymers form a lamellar morphology when m = 10 and morphologies of PDMS spheres embedded in P3ADBB matrix when m = 25, 42 and 66.     

Ordering in a nematic side-chain polymer. A proton and deuterium nuclear magnetic resonance study

 The aim of this work is to study in detail the orientational structure of liquid-crystalline polymers with different molecular weight. The advantage of our approach is the use of broad-band ¹H and ²H NMR spectroscopy for the analysis of the orientational order of the main-chain and mesogenic groups in conjunction with small-angle neutron scattering results. Investigations of a series of partially deuterated side-chain polymers with methoxybenzylbenzoate mesogenic groups have been carried out. The deuteration of the main chain enables separate access to order and orientation effects of the side chain and the main chain. The molecular orientation of the substances investigated can be frozen in its nematic phase below the glass-transition temperature. It is independent of the molecular weight, whereas the dynamics of the director reorientation (rotational viscosity) in the nematic phase strongly depends on the molecular weight. The main-chain deuterons provide powder spectra after orientation of the polymer in magnetic fields, indicating a very weak or lacking orientational anisotropy. A complete decoupling of the main and the side group can be deduced. Received: 15 September 1999 Accepted: 7 February 2000     

Molecular dynamics and ordering of side chain liquid crystal polymers as studied by paramagnetic resonance

Abstract

Molecular dynamics of side chain liquid crystalline polymers (LCP) and their components were studied using the technique of paramagnetic resonance. A cigar shape spin probe (COL) and a nearly spherical spin probe (TPL) were used to study the motions and order of the LCPs. Computer simulations of the observed spectra were performed. Both rotational correlation times and order parameters were extracted from these simulations. We found that LCPs containing 30 per cent and 50 per cent of mesogenic side chains had about the same viscosity as indicated by nearly equal tumbling times at the same temperature. In addition, the LCPs motion is considerably slower than that of the monomeric liquid crystal indicating that the spacer couples the motions of the side chains to those of the main chain. Rotations about axes perpendicular to the side chain are slowed more than rotations about an axis parallel to the side chain. DSC measurements were employed to study the phase transitions. The 30 and 50 per cent LCPs displayed first order NS_A transitions, but the 50 per cent LCPs transition was much weaker, in agreement with McMillan's theory which predicts a first order transition for T _NS/T _NI>0.87 (observed ratios are 0.98, 0.90 and 0.86 for 30, 50 and 100 per cent LCPs, respectively). The 30 per cent LCP has a very short nematic range so that the nematic order, which is not saturated at the NS transition, can couple with the smectic order. This was indicated by a sharp change in slope of the order parameter versus temperature plot as the smectic is entered. The LCPs studied formed a highly ordered glass when cooled in a 1 T field. If one could find a LCP with similar ordering properties whose glass temperature is well above room temperature, then one would have a useful binder for the manufacture of haze-free polymer dispersed liquid crystal displays.     

Behavior of a thermotropic nematic liquid crystal confined to controlled pore glasses as studied by 129Xe NMR spectroscopy

The behavior of nematic liquid crystal (LC) Merck Phase 4 confined to controlled pore glass (CPG) materials was investigated using 129Xe nuclear magnetic resonance (NMR) spectroscopy of xenon gas dissolved in the LC. The average pore diameters of the materials varied from 81 to 2917 A, and the measurements were carried out within a wide temperature range (approximately 185-370 K). The spectra contain lots of information about the effect of confinement on the phase of the LC. The theoretical model of shielding of noble gases dissolved in liquid crystals on the basis of pairwise additivity approximation was applied to the analysis of the spectra. When pore diameter is small, smaller than approximately 150 A, xenon experiences on average an isotropic environment inside the pore, and no nematic-isotropic phase transition is observed. When the size is larger than approximately 150 A, nematic phase is observed, and the LC molecules are oriented along pore axis. The orientational order parameter of the LC, S, increases with increasing pore size. In the largest pores, the orientation of the molecules deviates from the pore axis direction to magnetic field direction, which implies that the size of the pores (approximately 3000 A) is close to magnetic coherence length. The decrease of magnetic coherence length with increasing temperature is clearly seen from the spectra. When the sample is cooled rapidly by immersing it in liquid nitrogen, xenon atoms do not squeeze out from the solid, as they do during gradual freezing, but they are occluded inside the solid lattice, and their chemical shift is very sensitive to crystal structure. This makes it possible to study the effect of confinement on the solid phases. According to the measured 129Xe NMR spectra, possibly three different solid phases are observed from bulk liquid crystal in the used temperature region. The same is also seen from the samples containing larger pores (pore size larger than approximately 500 A), and the solid-solid phase-transition temperatures are the same. However, no first-order solid-solid phase transitions are observed from the smaller pores. Melting point depression, that is, the depression of solid-nematic transition temperature observed from the pores as compared with that in bulk LC, is seen to be very sensitive to the pore size, and it can be used for the determination of pore size of an unknown material.     

Quasi-binary picture of thermotropic liquid crystals and its application to cubic mesophases

A quasi-binary (QB) picture of thermotropic liquid crystals is proposed on the basis of thermodynamic observations. The experimental conformational entropy of long alkyl chains attached to a (semi)rigid core of mesogenic molecules indicates that the chain is highly disordered in liquid crystalline states. These disordered chains serve as ‘intramolecular solvent’ or ‘self-solvent’ judging from a close resemblance between phase diagrams of neat (against chain length) and binary (against composition) systems. The application of the QB picture to the classic examples of thermotropic cubic mesophases (in ANBC series) shows that the essential structural motif is triply periodic minimal surface.     

Molecular orientation gradients in thermotropic liquid crystalline fiber

The degree of molecular alignment averaged over meso-length scale areas within thermotropic liquid crystalline polymer (LCP) fibers has been intensely studied over recent years. In this work, the degree of molecular orientation is found from spatially-resolved electron diffraction of areas as small as 100 nm in diameter to relieve structural averaging of lower resolution techniques. This investigation reveals that the maximum degree of molecular alignment across a fiber 18 μm in diameter is approximately 1 μm from the fiber surface. Dark-field imaging shows region with little crystallinity adjacent to the fiber surface. The banded structure, typical of TLCP fibers, is also less apparent in the surface region. Copyright © 2003 John Wiley & Sons, Ltd.     

The first liquid crystalline diol compound which exhibits nematic,smecticA +, and smecticC + mesophases in the presence of water

A new amphiphilic ethane-1,2-diol derivative with a rodlike 2-phenylpyrimidine rigid core has been synthesized. From the combined results of differential scanning calorimetry and optical polarization microscopy a phase diagram amphiphile/water was constructed. The system exhibits a nematic phase at a very low water content, a smecticA ⁺ and a smecticC ⁺ phase at higher water concentrations. Such a phase sequence has been found for a lyotrophic system for the first time.     

The twist-bend nematic phase: translational self-diffusion and biaxiality studied by 1H nuclear magnetic resonance diffusometry

ABSTRACT

Recently, there has been a surge of interest in mesogens exhibiting the twist-bend nematic (N_TB) phase that is shown to be chiral even though formed by effectively achiral molecules. Although it now seems to be clear that the N_TB phase in the bulk is formed by degenerate domains having opposite handedness, the presence of a supramolecular heliconical structure proposed in the Dozov model has been contradicted by the Hoffmann et al. model in which the heliconical arrangement is replaced by a polar nematic phase. The evidence in support of this is that the quadrupolar splitting tensor measured in various experiments is uniaxial and not biaxial as expected for the twist-bend nematic structure. In this debate, among other evidence, the molecular translational diffusion, and its magnitude with respect to that in the nematic phase above the N_TB phase, has also been invoked to eliminate or to confirm one model or the other. We attempt to resolve this issue by reporting the first measurements of the translational self-diffusion coefficients in the nematic and twist-bend nematic phases formed 1″,7″-bis-4-(4′-cyanobiphenyl-4′-yl) heptane (CB7CB). Such measurements certainly appear to resolve the differences between the two models in favour of that for the classic twist-bend nematic phase.     

Biaxial ordering and field-induced configurational transition in nematic liquid crystals

We show that the competition between the correlation of liquid crystalline order and the orienting effect of applied field is crucial in determining the characteristic behaviour of local ordering in the boundary layer, close to the substrates with strong anchoring. The equilibrium states for the low and the high field are found to be distinct. In particular, varying the field strength can induce a phase transition, across which the order parameter configuration changes continuously from one to the other of the two limiting equilibrium states.     

Silver nitrate-acetonitrile and iodine-benzene complexes as studied by NMR in thermotropic liquid crystals

Silver nitrate-acetonitrile and π iodine-benzene complexes in thermotropic liquid crystals have been studied by ¹H, ²H, and ¹³C NMR spectroscopy and by optical microscopy. Evidence for at least two silver complexes in each liquid crystal is presented.     

Conformation and orientation of tetraalanine in a lyotropic liquid crystal studied by nuclear magnetic resonance

The (1)H NMR spectra of two isotopomers of tetraalanine deuterated on the two external methyl groups and on the two internal ones, respectively, were recorded in the lyotropic solvent cesium pentadecafluorooctanoate (CsPFO)/water. Eight dipolar couplings could be estimated from the spectra. The set of dipolar couplings was fitted assuming that one rigid conformer is present. Of the four major conformers considered, selected on the basis of theoretical calculations, the one characterized by the two couples of internal dihedral angles in the Ramachandran region of PPII resulted to be the only one to fit the set of couplings within experimental error. The data indicate that the molecule is oriented with the long molecular axis tilted with respect to the surface of the micelles formed by CsPFO.     

Synthesis and liquid crystalline properties of thermotropic homo- and copolycarbonates

Nondirect-type thermotropic homo- and copolycarbonates which have flexible spacers between mesogens and carbonate linkages (-mesogenic unit-flexible spacer-carbonate link-flexible spacer-) were derived from dihydroxyalkyleneoxy derivatives containing biphenyl, i.e., 4,4′-bis (ω-hydroxyalkyleneoxy)biphenyl (Ia and Ib), as mesogens and the structure-liquid crystallinity relationships were evaluated by thermal analysis and with polarizing microscope. Homopolycarbonates with high molecular weight were prepared from (Ia) and (Ib), and alkylene diphenyl dicarbonates (II) by melt polycondensation. The polymers form mesomorphic phases and exhibit linear decrease of phase-transition temperatures with increment of alkylene spacer lengths without displaying odd-even number fluctuations. They show lower phase-transition temperatures and narrower mesomorphic temperature ranges than analogous direct-type (-mesogenic unit-functional group-flexible spacer-) biphenyl-containing polycarbonates \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm OMOC}({\rm O}){\rm O}({\rm CH}_2)_m {\rm OC}({\rm O})\rlap{--})_x $\end{document} and polyesters \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm OMOC}({\rm O})({\rm CH}_2)_m {\rm C}({\rm O})\rlap{--})_x $\end{document}, but have wider temperature ranges than nondirect-type (-mesogenic unit-flexible spacer-functional group-flexible spacer-) biphenyl-containing polyesters \documentclass{article}\pagestyle{empty}\begin{document}$ \rlap{--} ({\rm O}({\rm CH}_2)_n {\rm OMO}({\rm CH}_2)_n {\rm OC}({\rm O})({\rm CH}_2)_m {\rm C}({\rm O})\rlap{--})_x $\end{document}. These results indicate that by the incorporation of alkylene segments between mesogens and carbonate linkages the polymers having reasonable phase-transition temperatures and wider mesophasic temperature ranges can be obtained. Copolycarbonates were prepared from mixtures of (Ib) and 1,4-bis(2-hydroxyethyleneoxy)benzene (IV), nonmesogenic moiety, taken in definite molar ratio in feed and (II) (m = 2 and 4). These copolymers except polymers having only nonmesogenic moiety show liquid crystalline mesophases and have wider phase-transition temperature ranges than the homopolymers. Maximum temperature ranges are observed in the copolymers of composition ratio of 1 : 1. Stable mesophases can be obtained over the entire range of compositions, even though the copolymers contain nonmesogenic units in the backbones.     

Liquid crystalline dendrimer of the fifth generation: From lamellar to columnar structure in thermotropic mesophases

The structure of a liquid crystalline (LC) carbosilane dendrimer of the fifth generation bearing 128 terminal cyanobiphenyl mesogenic groups has been studied. This dendrimer was synthesized by a hydrosilylation reaction and then the cyanobiphenyl mesogenic groups were chemically linked to the dendritic matrix via a-OOC-(CH2)10-Si(CH3)2OSi(CH3)2-spacer. Structural studies carried out by polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction methods revealed unusual phase behaviour. At room temperature the dendrimer forms a lamellar (smectic A) phase which develops in-plane ordering above 40C.This is due toa tendency to form columns ofmolecules which areprobably perpendicular to the layers. Above 121C the material transforms into another more disordered mesophase which is probably a disordered hexagonal columnar phase. The proposed structures and molecular packing in these different types of mesophase are discussed.     

Rotation in a magnetic field of nematic liquid crystalline samples with a negative anisotropy of their magnetic susceptibility

The behaviour of the mesophase directors when a sample with a negative anisotropy Deltachi in the magnetic susceptibility is rotated at a speed omega in a magnetic field B0 about an axis inclined at an angle beta is investigated by deuterium NMR spectroscopy. There are combinations of beta and omega which lead to the directors aligning along the spinning axis (stable region), and other combinations where the directors are either unaffected by the rotation, or have a timedependent distribution (unstable region). These two regions are separated by a line (the q line) whose position depends on beta and omegac DeltachiB02/2mu0gamma1, where gamma1 is a twist viscosity coefficient. Experiments on 4-n-propyl-4-cyanobicyclohexane (CCH3) are used to demonstrate how the q line, and hence omegac may be determined. Combining this result with a measurement of the anisotropy in the magnetic susceptibility, Deltachi, yields a value for gamma1.