Laurence Noirez

Observation of shear-induced nematic-isotropic transition in side-chain liquid crystal polymers.

Flow-induced phase transitions are a fundamental (but poorly understood) property of non-equilibrium systems, and are also of practical importance for tuning the processing conditions for plastics, petroleum products, and other related materials. Recognition that polymers may exhibit liquid crystal properties has led to the discovery of the first tailored side-chain liquid crystal polymers (SCLCPs), which are formed by inserting a spacer between the main polymer chain and the lateral mesogen liquid–crystalline graftings. Subsequent research has sought to understand the nature of the coupling between the main polymer chain and the mesogens, with a view to obtaining better control of the properties of these tailored structures. We show here that the parallel or perpendicular orientation of the mesogens with respect to the main chain can be reversed by the application of an external field produced by a shear flow, demonstrating the existence of an isotropic nematic phase transition in SCLCPs. Such a transition, which was theoretically predicted for low-molecular-weight liquid crystals but never observed, is shown to be a general property of SCLCPs too. We expect that these SCLCPs will prove to be good candidate systems for the experimental study of these non-equilibrium phenomena.

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 back...

Self-Assembly of PEGylated Peptide Conjugates Containing a Modified Amyloid β-Peptide Fragment

The self-assembly of PEGylated peptides containing a modified sequence from the amyloid beta peptide, FFKLVFF, has been studied in aqueous solution. PEG molar masses PEG1k, PEG2k, and PEG10k were used in the conjugates. It is shown that the three FFKLVFF-PEG hybrids form fibrils comprising a FFKLVFF core and a PEG corona. The beta-sheet secondary structure of the peptide is retained in the FFKLVFF fibril core. At sufficiently high concentrations, FFKLVFF-PEG1k and FFKLVFF-PEG2k form a nematic phase, while PEG10k-FFKLVFF exhibits a hexagonal columnar phase. Simultaneous small angle neutron scattering/shear flow experiments were performed to study the shear flow alignment of the nematic and hexagonal liquid crystal phases. On drying, PEG crystallization occurs without disruption of the FFKLVFF beta-sheet structure leading to characteristic peaks in the X-ray diffraction pattern and FTIR spectra. The stability of beta-sheet structures was also studied in blends of FFKLVFF-PEG conjugates with poly(acrylic acid) (PAA). While PEG crystallization is only observed up to 25% PAA content in the blends, the FFKLVFF beta-sheet structure is retained up to 75% PAA.

Nematic and Columnar Ordering of a PEG-Peptide Conjugate in Aqueous Solution

The self-assembly in aqueous solution of a PEG-peptide conjugate is studied by spectroscopy, electron microscopy, rheology and small-angle X-ray and neutron scattering (SAXS and SANS). The peptide fragment, FFKLVFF is based on fragment KLVFF of the amyloid beta-peptide, Abeta(16-20), extended by two hydrophobic phenylalanine units. This is conjugated to PEG which confers water solubility and leads to distinct self-assembled structures. Small-angle scattering reveals the formation of cylindrical fibrils comprising a peptide core and PEG corona. This constrained structure leads to a model parallel beta-sheet self-assembled structure with a radial arrangement of beta sheets. On increasing concentration, successively nematic and hexagonal columnar phases are formed. The flow-induced alignment of both structures was studied in situ by SANS using a Couette cell. Shear-induced alignment is responsible for the shear thinning behaviour observed by dynamic shear rheometry. Incomplete recovery of moduli after cessation of shear is consistent with the observation from SANS of retained orientation in the sample.

Two-dimensional neutron scattering in a floating heavy water bridge

When a high voltage is applied to pure water in two filled beakers kept close to each other, a connection forms spontaneously, giving the impression of a floating water bridge. This phenomenon is of special interest, since it comprises a number of phenomena currently tackled in modern water science. In this work, the first two-dimensional structural study of a floating heavy water bridge is presented as a function of the azimuthal angle. A small anisotropy in the angular distribution of the intensity of the first structural peak was observed, indicating a preferred orientation of a part of the D2O molecules along the electric field lines without breaking the local tetrahedral symmetry. The experiment is carried out by neutron scattering on a D2O bridge.

Liquid Crystal Polymers: A Small Angle Neutron Scattering Study

Abstract One reports Small Angle Neutron Scattering (SANS) studies on mesogenic comb-like polymers. One has drawn attention on different polymethacrylates specially in nematic phase. A way to determine the conformation of these polymers, consists to measure their quadratic sizes by the labelling method. One has also tested this method in function of the molecular length of a LC-polysiloxane. It appears that wathever the chemical species, the backbone of polymers prefer to be perpendicular to their mesogenic groups in the smectic phase. The situation is less simple in the nematic phase.

Neutron scattering study and discussion of the backbone conformation in the nematic phase of a side chain polymer

Abstract A small angle neutron scattering study of a mesomorphic side chain polyacrylate in the nematic phase shows that the backbone adopts a prolate conformation. This observation is discussed in relation to the previous determinations of backbone anisotropy in the nematic phase of other side chain polymers. On the basis of the comparison with these previous determinations and also with the results obtained on other related systems, the assumption is made that, provided that the spacers are long enough, the natural tendency of the backbones is to adopt a prolate shape in any nematic phase devoid of smectic fluctuations.

Growth and Branching of Charged Wormlike Micelles as Revealed by Dilution Laws

The successive transitions of morphology in aqueous solutions of interacting micelles are directly evidenced by the position q* of the correlation peak of the small angle neutron scattering profiles. As the volume fraction Phi increases, q* successively fits to the dilution laws expected for spheres and cylinders, and eventually gets close to the one expected for sheets when the micelles get branched. Data in between the swelling laws are quantitatively analyzed in terms of aggregation number and junction density. Varying the temperature in the dilute regime yields the end-cap energy which varies with molecular structure and scales as Phi(-1/2). In the semidilute regime, the junction density scales as nu(j) approximately Phi(1.8), close but slightly faster than theoretically expected. The boosting effect of intermicellar repulsion on growth and branching is pointed out by the present results which directly show that both condensation processes keep the micelles further apart.

Side-chain liquid crystal polymers. A study by neutron diffraction of the backbone distribution profile in the smectic A phase

Abstract Two mesomorphic side-chain polymethacrylates, called PMA(R)OC4H9, and only differing in the fact that one was deuteriated on the backbone (R = D) have been studied by neutron diffraction in the smectic A phase. The comparison between their respective smectic reflection intensities allows one to deduce quantitatively the backbone distribution profile along the normal to the layers. As the temperature decreases, the polymer backbones are more and more segregated from the sublayers of mesogenic cores. However, even at room temperature, there are still about 25 per cent of the backbone segments localized in the mesogenic core sublayers. These measurements, together with the previous determinations of the gyration radii of the backbones provide a detailed description of how the backbones of PMAOC4H9 are affected by the smectic ordering. In addition, the evolution with temperature of the different smectic reflection intensities is also discussed.

Some relevant parameters on the ‘jacketed’ effect in side-on fixed polysiloxanes

Abstract New ‘side-on’ attached liquid crystal polysiloxanes have been synthesized with different fixation ratios of side groups and various degrees of polymerization. For these syntheses, a series of random copoly(hydrogenmethyl-dimethylsiloxane)s, used a precursors, has been realized. Both thermal properties and small angle neutron scattering experiments on these polymers show a decrease in the nematic ‘jacketed’ effect as the number of mesogenic groups fixed to the backbone decreases and as the main chain length increases.