Engineering Mesophase Stability and Structure via Incorporation of Cyclic Terminal Groups

We report on the characterisation of a number of liquid-crystalline materials featuring cyclic terminal groups, which lead to significant enhancements in the temperature range of the mesomorphic state. Materials with only short terminal chains are able to support lamellar mesophase formation by appending a large terminal cyclic unit at the end of a short methylene spacer. X-ray scattering experiments reveal that the layer spacings of the lamellar smectic phase are significantly larger when a cyclic end-group is present than for equivalent linear unsubstituted materials, but there is no effect on orientational order. Fully atomistic molecular dynamics simulations faithfully reproduce experimental layer spacings and orientational order parameters, and indicate that the cyclic terminal units spontaneously segregate into diffuse sub-layers and thus cause the increased layer spacing. This shape segregation predicted by molecular dynamics simulations is observed in the crystalline solid state by X-ray diffraction.

Orientation of Liquid Crystalline Molecules on PDMS Surfaces and within PDMS Microfluidic Systems

The unique components of PDMS-based microfluidic systems are those combined with liquid crystalline materials. Their functionality, especially when it comes to optical applications, highly depends on the LC molecular arrangement. This work summarizes experimental investigations on the orientation of molecules within LC:PDMS structures according to the manufacturing technologies. The availability of high-quality molds to pattern PDMS is a significant barrier to the creation of advanced microfluidic systems. The possibility of using inexpensive molds in the rapid and reproducible fabrication process has been particularly examined as an alternative to photolithography. Different geometries, including an innovative approach for the electrical control of the molecular arrangement within PDMS microchannels, are presented. These studies are critical for novel optofluidic systems, introducing further research on LC:PDMS waveguiding structures.

PHASE TRANSITION STUDIES OF CHOLESTERYL PALMITATE, CHOLESTERYL DECANOATE AND THEIR MIXTURES USING DIELECTRIC, EPR AND DTA TECHNIQUES

The phase transition of two liquid crystalline materials, namely cholesteryl palmitate and cholesteryl decanoate and their mixtures (by weight)are studied using dielectric, Electron paramagnetic resonance (EPR) and differential thermal analysis (DTA) techniques. From the dielectric measurements, the phase transition temperatures were determined from the discontinuities in the curve between dielectric constant and temperatures for all the samples investigated. Further, since mixing of two liquid crystals modifies the transition of phases, the measurements were carried out on the mixtures of the two liquid crystals. Order parameter for each sample was calculated at varying temperatures by measuring the hyperfine splitting of three line EPR spectrums. The discontinuities in the curve between order parameter and the temperature again indicated the phase transition of the liquid crystals and their mixtures. A DTA study on these samples was also carried out in order to probe further their transitional behaviour. The DTA records of both the liquid crystals and their mixtures support the transition behaviour observed from the dielectric and EPR measurements.

Synthesis, Phase Behavior and Computational Simulations of a Pyridyl-Based Liquid Crystal System

A homologous set of liquid crystalline materials (Tn) bearing Schiff base/ester linkages were prepared and investigated via experimental and theoretical techniques. Terminal flexible groups of different chain lengths were connected to the end of phenylbenzoate unit while the other end of molecules was attached to the heterocyclic pyridine moiety. The molecular structures of the designed molecules were evaluated by FT-IR, NMR spectroscopic analyses, whereas their mesomorphic properties were investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). They all exhibited dimorphic properties with the exception of the members having the shortest and longest terminal flexible chains (n = 6 and 16), which were monomorphic. The T16 derivative was further found possessing purely smectic A (SmA) mesophase while others have their lengths covered by nematic (N) phase. Moreover, the computational evaluation of the azomethine derivatives was carried out using a DFT approach. The polarity of the investigated derivatives was predicted to be appreciably sensitive to the size of the system. Furthermore, the Frontier molecular orbitals analysis revealed various distributions of electron clouds at HOMO and LUMO levels.

Surface equilibration mechanism controls the molecular packing of glassy molecular semiconductors at organic interfaces

Glasses prepared by physical vapor deposition (PVD) are anisotropic, and the average molecular orientation can be varied significantly by controlling the deposition conditions. While previous work has characterized the average structure of thick PVD glasses, most experiments are not sensitive to the structure near an underlying substrate or interface. Given the profound influence of the substrate on the growth of crystalline or liquid crystalline materials, an underlying substrate might be expected to substantially alter the structure of a PVD glass, and this near-interface structure is important for the function of organic electronic devices prepared by PVD, such as organic light-emitting diodes. To study molecular packing near buried organic–organic interfaces, we prepare superlattice structures (stacks of 5- or 10-nm layers) of organic semiconductors, Alq3 (Tris-(8-hydroxyquinoline)aluminum) and DSA-Ph (1,4-di-[4-(N,N-diphenyl)amino]styrylbenzene), using PVD. Superlattice structures significantly increase the fraction of the films near buried interfaces, thereby allowing for quantitative characterization of interfacial packing. Remarkably, both X-ray scattering and spectroscopic ellipsometry indicate that the substrate exerts a negligible influence on PVD glass structure. Thus, the surface equilibration mechanism previously advanced for thick films can successfully describe PVD glass structure even within the first monolayer of deposition on an organic substrate.

Low-Mass Liquid Crystalline Materials Blended in Recycled Thermoplastic Polyester Elastomer for Corrosion Inhibitor Application

In this work, the development and application of multicomponents obtained from recycled polyethylene terephthalate (r-PET) waste and monotropic liquid crystals as anticorrosion coatings are reported. The r-PET raw material was alcoholyzed and reproduced as a thermoplastic polyester elastomer (TPEE) with different amounts (n%, n = 0, 1, 3, and 5) of 1,6-hexanediamine (HDA). Then, a fluorine-containing liquid crystal (4-cyano-3-fluorophenyl 4-ethylbenzoate (4CFE)) was incorporated into the TPEE mixture via solvent blending to modify and enhance the water resistance. The adhesion behavior of the coating on glass and iron substrates was evaluated by cross-cut tests and immersion tests in aqueous NaCl. In the corrosion resistance measurements, all of the coating samples fabricated with 10 ± 1 mm thickness were less active toward electrochemical corrosion (PEF% > 99%) than the bare iron plate, indicating that our work provided better protection against corrosion of the iron plate.

Light Propagation in Confined Nematic Liquid Crystals and Device Applications

Liquid crystals are interesting linear and nonlinear optical materials used to make a wide variety of devices beyond flat panel displays. Liquid crystalline materials can be used either as core or as cladding of switchable/reconfigurable waveguides with either an electrical or an optical control or both. In this paper, materials and main device structures of liquid crystals confined in different waveguide geometries are presented using different substrate materials, such as silicon, soda lime or borosilicate glass and polydimethylsiloxane. Modelling of the behaviour of liquid crystal nanometric molecular reorientation and related refractive index distribution under both low-frequency electric and intense optical fields is reported considering optical anisotropy of liquid crystals. A few examples of integrated optic devices based on waveguides using liquid crystalline materials as core for optical switching and filtering are reviewed. Reported results indicate that low-power control signals represent a significant feature of photonic devices based on light propagation in liquid crystals, with performance, which are competitive with analogous integrated optic devices based on other materials for optical communications and optical sensing systems.

Synthesis and Mesomorphic and Electrical Investigations of New Furan Liquid Crystal Derivatives

New homologues set liquid crystalline materials, based on furfural derivatives, namely, (E)-4-((furan-2-ylmethylene)amino)phenyl 4-alkoxybenzoate (Fn), were synthesized and investigated for their mesomorphic and optical characteristics. The prepared homologues series constitutes three derivatives that bear different terminal flexible alkyl chain lengths that vary between 6 and 12 carbons and attached to the phenyl ring linked to the ester group. A furfural moiety is introduced into the other terminal of the molecular structure. Mesomorphic characterizations of the prepared derivatives were measured using differential scanning calorimetry (DSC) and polarized optical microscopy (POM). Molecular structures were elucidated via elemental analyses, FTIR, and NMR spectroscopy. DSC and POM showed that all the synthesized furfural derivatives are purely nematogenic, exhibiting an enantiotropic nematic (N) mesophase, except for the longest chain derivative (F12) that is dimorphic possessing a monotropic smectic A phase and an enantiotropic N mesophase. Results indicated that the incorporation of the heterocyclic furfural ring into the molecular skeleton affected both the mesophase range and stability of investigated homologue. Analysis of the optical properties revealed that the shortest chain compound (F6) possesses two direct band gaps, at 2.73 and 3.64 eV, in addition to higher absorption than the higher homologues, F10 and F12. On the other hand, all the synthesized homologues (Fn) showed Ohmic behaviors, with electric resistances in the GΩ range. The values of the electrical resistances are 103.71, 12.91, and 196.85 GΩ at 0.05 V for F6, F10, and F12, respectively.