The effect of the spacer length on the nature of coupling in side chain liquid crystals polymers and elastomers

Side chain liquid crystal polymers and elastomers exhibit a rich phase behaviour which arises from the antagonistic influences of the entropically disordered polymer chain configuration and the long range orientational ordering of the mesogenic units. This competition arises since the natural macroscopic phase separation is inhibited by the inherent chemical connectivity of the system. At the heart of this connectivity is the spacer link and we consider here its influence on the phase behaviour. In particular we consider a series of elastomers in which the number of alkyl units in the spacer is systematically varied from 2 to 6. The lengthening of the coupling spacer is accompanied by an alternation of the sign of coupling between the polymer chain and the mesogenic unit. These results demonstrate the dominating influence of the so-called hinge effect in determining the phase behaviour. In addition to the alternation of the sign there is some decrease in the magnitude of the coupling with increasing spacer length.

Discotic Nematic - Calamitic Nematic Phase Transition in Sodium Dodecyl (lauryl) Sulphate-Decanol-D2O

The optical characterization of uniaxial nematic liquid crystals gives basic information on its birefringence and on the shape anisotropy of micelles in nematic lyotropic phases. In this work, these optical parameters were determined as a function of temperature along the sequence discotic nematic (ND) - coexistence (ND+NC) - calamitic nematic (NC) - isotropic (I) in a lyotropic mixture of the sodium dodecyl (lauryl) sulphate (SDS) - decanol (DeOH) and D2O for a specific concentration. Results for the uniaxial phases agree with previous assignments. Results in the coexistence region indicate an inhomogeneous mixture of the two uniaxial phases.

Effects of Side-Chain and Electron Exchange Correlation on the Band Structure of Perylene Diimide Liquid Crystals: A Density Functional Study

The structural and electronic properties of perylene diimide liquid crystal PPEEB are studied using ab initio methods based on the density functional theory (I)FT). Using available experimental crystallographic data as a guide, we propose a detailed structural model for the packing of solid PPEEB. We find that due to the localized nature of the band edge wave function, theoretical approaches beyond the standard method, such as hybrid functional (PBE0), are required to correctly characterize the band structure of this material. Moreover, unlike previous assumptions, we observe the formation of hydrogen bonds between the side chains of different molecules, which leads to a dispersion of the energy levels. This result indicates that the side chains of the molecular crystal not only are responsible for its structural conformation but also can be used for tuning the electronic and optical properties of these materials.

Forces due to structure in a thin liquid crystal film

Measurements of the force as a function of distance between two solids separated by a liquid crystal film give information on the structure of the film. We report such measurements for two molecularly smooth surfaces of mica separated by the nematic liquid crystal 4'-n-pentyl 4-cyanobiphenyl (5CB) in both the planar and homeotropic orientations at room temperature. The force is determined by measuring the deflection of a spring supporting one of the mica pieces, while an optical technique is used to measure the film thickness to an accuracy of ± (0.1-0.2) nm. The technique also allows the refractive indices of the nematic to be measured, and hence a determination of the average density and order parameter of the liquid crystal film as a function of its thickness. Three distinct forces were measured, each reflecting a type of ordering of the liquid crystal near the mica surfaces. The first one results from elastic déformation in the liquid crystal ; it was only observed in a twisted planar sample where the 5CB molecules are oriented in different directions at the two mica surfaces. The second, measured in both the planar and homeotropic orientations, is attributed to an enhanced order parameter near the surfaces. Both of these are monotonic repulsive forces measurable below 80 nm. Finally, there is a short-range force which oscillates as a function of thickness, up to about six molecular layers, between attraction and repulsion. This results from ordering of the molecules in layers adjacent to the smooth solid surface. It is observed in both the planar and homeotropic orientations, and also in isotropic liquids.

Polymeric materials with ordered nanostructures templated from hexagonal lyotropic liquid crystals

In this study, successful methods have been established to retain the ordered nanostructures in polymer materials templated from hexagonal lyotropic liquid crystals, which potentially renders broad applications as biomedical and membrane materials.

Organic Solvent-Based Graphene Oxide Liquid Crystals: A Facile Route toward the Next Generation of Self-Assembled Layer-by-Layer Multifunctional 3D Architectures

We introduce soft self-assembly of ultralarge liquid crystalline (LC) graphene oxide (GO) sheets in a wide range of organic solvents overcoming the practical limitations imposed on LC GO processing in water. This expands the number of known solvents which can support amphiphilic self-assembly to ethanol, acetone, tetrahydrofuran, N-dimethylformamide, N-cyclohexyl-2-pyrrolidone, and a number of other organic solvents, many of which were not known to afford solvophobic self-assembly prior to this report. The LC behavior of the as-prepared GO sheets in organic solvents has enabled us to disperse and organize substantial amounts of aggregate-free single-walled carbon nanotubes (SWNTs, up to 10 wt %) without compromise in LC properties. The as-prepared LC GO-SWNT dispersions were employed to achieve self-assembled layer-by-layer multifunctional 3D hybrid architectures comprising SWNTs and GO with unrivalled superior mechanical properties (Young’s modulus in excess of 50 GPa and tensile strength of more than 500 MPa).

Phase behaviour and properties of microemulsions and lyotropic liquid crystals

This research study has developed new ways to control bulk properties of self-assembled microemulsions and lyotropic liquid crystals (LLCs) by manipulations of their corresponding precursor phase behaviour. Investigation into relating phase behaviour with the morphology, porosity, thermal stability, rheological property, and photoresponse of these assemblies has been carried out.

Reversible photorheological lyotropic liquid crystals

We describe novel lyotropic liquid-crystalline (LLC) materials based on photoresponsive amphiphiles that exhibit rapid photoswitchable rheological properties of unprecedented magnitude between solidlike and liquidlike states. This was achieved through the synthesis of a novel azobenzene-containing surfactant (azo-surfactant) that actuates the transition between different LLC forms depending on illumination conditions. Initially, the azo-surfactant/water mixtures formed highly ordered and viscous LLC phases at 20-55 wt % water content. Spectroscopic, microscopic, and rheological analysis confirmed that UV irradiation induced the trans to cis isomerization of the azo-surfactant, leading to the disruption of the ordered LLC phases and a dramatic, rapid decrease in the viscosity and modulus resulting in a 3 orders of magnitude change from a solid (20,000 Pa) to a liquid (50 Pa) at rate of 13,500 Pa/s. Subsequent exposure to visible light reverses the transition, returning the viscosity essentially to its initial state. Such large, rapid, and reversible changes in rheological properties within this LLC system may open a door to new applications for photorheological fluids.

Enhancing thermal stability and mechanical properties of lyotropic liquid crystals through incorporation of a polymerizable surfactant.

We present a facile method to prepare thermally stable and mechanically robust crosslinked lyotropic liquid crystals (LLCs) through incorporation of a polymerizable amphiphile into a binary LLC system comprising commercially available surfactant Brij 97 and water. Thermal stability and mechanical properties of the polymerized LLCs were significantly enhanced after polymerization of the incorporated polymerizable surfactant. The effect of incorporating a polymerizable amphiphile on the phase behavior of the LLC system was studied in detail. In situ photo-rheology was used to monitor the change in the mechanical properties of the LLCs, namely the storage modulus, loss modulus, and viscosity, upon polymerization. The retention of the LLC nanostructures was evaluated by small angle X-ray scattering (SAXS). The ability to control the thermal stability and mechanical strength of LLCs simply by adding a polymerizable amphiphile, without tedious organic synthesis or harsh polymerization conditions, could prove highly advantageous in the preparation of robust nanomaterials with well-defined periodic structures.

Control of partial coalescence of self-assembled metal nano-particles across lyotropic liquid crystals templates towards long range meso-porous metal frameworks design

The formation of purely metallic meso-porous metal thin films by partial interface coalescence of self-assembled metal nano-particles across aqueous solutions of Pluronics triblock lyotropic liquid crystals is demonstrated for the first time. Small angle X-ray scattering was used to study the influence of the thin film composition and processing conditions on the ordered structures. The structural characteristics of the meso-structures formed demonstrated to primarily rely on the lyotropic liquid crystal properties while the nature of the metal nano-particles used as well as the their diameters were found to affect the ordered structure formation. The impact of the annealing temperature on the nano-particle coalescence and efficiency at removing the templating lyotropic liquid crystals was also analysed. It is demonstrated that the lyotropic liquid crystal is rendered slightly less thermally stable, upon mixing with metal nano-particles and that low annealing temperatures are sufficient to form purely metallic frameworks with average pore size distributions smaller than 500 nm and porosity around 45% with potential application in sensing, catalysis, nanoscale heat exchange, and molecular separation.

Existence and stability of new nanoreactors: Highly swollen hexagonal liquid crystals

We report the preparation of direct hexagonal liquid crystals, constituted of oil-swollen cylinders arranged on a triangular lattice in water. The volume ratio of oil over water, rho, can be as large as 3.8. From the lattice parameter measured by small-angle X-ray scattering, we show that all the oil is indeed incorporated into the cylinders, thus allowing the diameter of the cylinders to be controlled over one decade range, provided that the ionic strength of the aqueous medium and rho are varied concomitantly. These hexagonal swollen liquid crystals (SLCs) have been first reported with sodium dodecyl sulfate as anionic surfactant, cyclohexane as solvent, 1-pentanol as co-surfactant, and sodium chloride as salt (Ramos, L.; Fabre, P. Langmuir 1997, 13, 13). The stability of these liquid crystals is investigated when the pH of the aqueous medium or the chemical nature of the components (salt and surfactant) is changed. We demonstrate that the range of stability is quite extended, rendering swollen hexagonal phases potentially useful for the fabrication of nanomaterials. As illustrations, we finally show that gelation of inorganic particles in the continuous aqueous medium of a SLC and polymerization within the oil-swollen cylinders of a SLC can be conducted without disrupting the hexagonal order of the system.

Zirconia needles synthesized inside hexagonal swollen liquid crystals

We report the synthesis of zirconia microneedles by the direct nucleation of particles inside a hexagonal swollen liquid crystal (SLC) (cell parameter a = 27 nm) prepared by mixing with the proper ratio, an aqueous solution of sulfated zirconium colloids, a cationic surfactant (cetylpyridinium chloride), cychlohexane as swelling agent with an oil over water ratio of 2.5 (vol.), and 1-pentanol as cosurfactant. After a slow crystallogenesis that can be enhanced by an initial induction step under moderate temperature, particles in the centimeter range can be obtained, with a very high shape ratio (over 100). These particles are made of crystalline octahydrate zirconium oxychloride containing pores of 20 nm diameter, aligned along the main axis of the liquid crystal, as the fingerprint of the oil cylinders present in the hexagonal phase. The morphology of these particles confirms that the shaping mechanism is based on true liquid crystal templating (TLCT). Further thermal treatment of these particles, after extraction from the SLC, leads to the crystallization of zirconia with the same needlelike morphology as the zirconium oxychloride.

Competition between anchoring and reversible photo-induced alignment of a nematic liquid crystal

We investigated the alignment induced on a nematic liquid crystal (LC) by a photo-aligned polymer film with azo-dye side groups. The orientation of the LC molecules can be manipulated in a reversible manner by irradiating the film with polarized light. We analyzed the competition between the orientation induced by the main chain, through rubbing of the film and that induced by the photo-aligned polymer. Anchoring strength for the different processing conditions are reported. The changes in film morphology caused by rubbing or photo-alignment could be captured by atomic force microscopy. The reversibility of the photo-induced alignment and the competition between the two anchoring mechanisms may allow recording and erasing of information in a LC display.

Highly swollen liquid crystals as new reactors for the synthesis of nanomaterials

Synthesis and self-assembly of nanomaterials can be controlled by the properties of soft matter. on one hand, dedicated nanoreactors such as reverse microemulsions or miniemulsions can be designed. on the other hand, direct shape control can be provided by the topology of liquid crystals that confine the reacting medium within a specific geometry. In the first case, the preparation of micro- or miniemulsions generally requires energetic mechanical stirring. The second approach uses thermodynamically stable systems, but it remains usually limited to binary (water + surfactant) systems. We report the preparation of different families of materials in highly ordered quaternary mediums that exhibit a liquid crystal structure with a high cell parameter. They were prepared with the proper ratios of salted water, nonpolar solvent, surfactant. and cosurfactants that form spontaneously swollen hexagonal phases. These swollen liquid crystals can be prepared from all classes of surfactants (cationic, anionic, and nonionic). They contain a regular network of parallel cylinders, whose diameters can be swollen with a nonpolar solvent, that are regularly spaced in a continuous aqueous salt solution. We demonstrate in the present report that both aqueous and organic phases can be used as nanoreactors for the preparation of materials. This property is illustrated by various examples such as the synthesis of platinum nanorods prepared in the aqueous phase or zirconia needles or the photo- or gamma-ray-induced polymerization of polydiacetylene in the organic phase. In all cases, materials can be easily extracted and their final shapes are directed by the structure-directing effect imposed by the liquid crystal.