Synthesis of four liquid crystals and study of alkyl chain effect on the nematic range for application in GC

Four liquid crystals (LCs) compounds which contain the 1,3,4-oxadiazole group were synthesized and characterized with spectroscopic techniques (IR, ¹H- and ¹³C NMR), their thermal properties were analyzed by the Differential Scanning Calorimetry (DSC) and the polarizing microscope (POM). A comparative study of the mesomorphic properties of these LCs and three other compounds which have already been used as a stationary phase in gas chromatography (GC) was carried out. These compounds have the same main nucleus. LCs V1, LC1, LC2 and LC3 gave a nematic (N) phase to the heating, LCs V2 and V3 recorded smectic A (SmA) and N phases. However, the range (N) has disappeared in V4.     

Specific features of electromechanical conversion in various liquid crystalline phases

Electromechanical effect in various liquid crystalline phases—nematic, smectic A, and smectic C—is studied. It is shown that a liquid crystal (LC) sample in the nematic phase does not differ from an electromechanical converter containing an isotropic dielectric and exhibits no features characteristic of LCs at electromechanical conversion. A phenomenon similar to the piezoelectric effect may occur in ferroelectric LCs due to their biaxiality.     

Liquid crystal–gold nanoparticle composites

Nanoparticles (NPs) have emerged as extremely promising materials to alter and improve the properties of liquid crystals (LCs) used, for example, in device applications. In this paper, we summarise recent work from our lab that aims to provide a fundamental understanding of structure–property and composition–property relationships governing LC–NP interactions, which may point to new directions for major improvements in the efficiency of LCs used in display applications. A variety of LC hosts (phases) doped with surface-functionalised gold NPs have been systematically studied ranging from one-dimensionally ordered nematic over two-dimensionally ordered smectic to three-dimensionally ordered columnar phases. Significant progress with respect to LC–NP interactions was made for NP-doped nematic phases. Here, the observation of an unusual texture for Au NP-doped nematic LCs, that is, the formation of birefringent stripe textures and the induction of homeotropic alignment of the nematic LC similar to chiral finger (or fingerprint) textures, provided the basis for numerous experimental studies using Au NPs with different core sizes and surface functionalities.     

λ-Shaped mesogens based on chalconyl ester core having variable side chain: Synthesis and characterisation

In present study, we have synthesized two newly chalconyl-ester core LCs having variable side chain and fixed disubstituted butoxy group at another terminal end. All this compounds were well characterized by elemental analysis, FT-IR, ¹H NMR. The mesomorphic properties of these compounds were observed by optical polarized light microscopy (POM) and also confirmed by using differential scanning calorimetry (DSC) and X-ray diffraction pattern (XRD). Detailed XRD investigation endorses the presence of the nematic phase in higher angle region and SmC phase in lower angle region. In addition, it is found that all the prepared materials display enantiotropic LCs phases except first four members in series-1 and first member in series-2. Thermal stability of SmC and nematic phase of series-1 is higher as compare to series-2. To get more insights, the DFT based HOMO, LUMO studies are carried out which supports intramolecular charge transfer interactions and stability in this class of mesogens.     

Structure of poorly crystalline MoS2 — A modeling study

Current interest in amorphous and poorly crystallized phases of the layered transition metal dichalcogenides arises primarily from their unique catalytic and electrochemical properties not present in the corresponding crystalline phases. Computer calcultions of the scattered X-ray intensity from model structures of poorly crystalline (px-) MoS₂ are compared here with experimental patterns from materials prepared at different temperatures. The results are used to identify the salient features of the observed diffraction patterns of px-MoS₂ in which the measured diffuse scattered intensity may be clearly attributed to the stacking and rotational disorder of the layers as well as the limited number of these layers. A procedure for the interpretation of the X-ray diffraction pattern of px-MoS₂ has thereby been developed in which the entire scattering pattern may be calculated without separation into Bragg peaks (of varying breadth and shape) and diffuse background.     

The Effects of Polymeric Additives on the Crystallization of Compounds Found in the Evaporator Scales of Australian Sugar Mills (I), Compositions of the Scale Deposits

The composition of scales formed in multiple evaporator units at three Australian sugar mills have been determined using X-ray fluorescence (XRF), high performance liquid chromatography (HPLC), X-ray diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA) and other analytical methods. The composition of the scales formed in each mill have been found to be significantly different and to depend on whether they originated from early or later stages of the evaporation process. Calcium oxalate (present as the di and monohydrate) was identified as a major component of the scales from one mill but was found to be only a minor component of the scales from the other two. The latter were shown to contain two or more forms of calcium phosphate as dominant phases. Amorphous or crystalline silica was found to be present in most of the scales examined.     

Synthesis of nanocrystalline zinc blende ZnTe by mechanical alloying

Nanocrystalline ZnTe was prepared by mechanical alloying from equiatomic powder mixture. X-ray diffraction and differential scanning calorimetry techniques were used to study the structural and thermal properties of the milled powder. An annealing of the as-milled sample at 600 °C for 6 h was performed to clarify thermal reactions showed in its calorimetry measurement. Minority crystalline phases (Te and ZnO) and residual amorphous ones were observed for both annealed and as-milled samples. The structural parameters, phase fractions, mean crystallite sizes and strains of all crystalline phases were obtained from Rietveld analyses of the X-ray patterns using the program package GSAS.     

X-ray Analysis of Chiral Thermotropic Liquid Crystal Copolyesters Based on Linear and Nonlinear Aromatic Ester Triads

A series of chiral thermotropic liquid crystalline copolyesters, based on linear mesogenic triads and nonlinear nonmesogenic triads consisting of two p-oxybenzoyl units coupled by a terephthaloyl or phthaloyl residue respectively, is studied by X-ray diffraction. Complementary data of differential calorimetry and polarizing microscopy are presented. The degree of crystallinity is found to depend significantly on the relative content of the nonlinear counit and to vary with thermal history. The occurrence of cholesteric phases is established, whose stability and breadth can be modulated on the basis of appropriate chemical compositions. The structural data of the investigated copolymer samples are compared with those previously obtained for an analogous series of copolymer samples based on the same linear aromatic triad and an isomeric triad containing a central isophthaloyl residue.

Keywords: liquid crystalline polymers, chiral thermotropic polymers, cholesteric copolyesters, 4,4'-(terephthaloyldioxy)dibenzoate mesogen, X-ray diffraction     

Solubilization of Immiscible Liquids Into Mesophases Formed from Amphiphilic Block Copolymers

Optical microscopy and X-ray diffraction studies reveal the presence of highly swollen mesophases in four-component systems containing amphiphilic triblock copolymers. According to the composition of the system, lamellar phases or hexagonal structures are produced. The polymeric mesophases exhibit textures very similar to those encountered in low molecular weight liquid crystalline phases.     

X-ray powder diffraction study of polytetrafluoroethylene

Samples of polytetrafluoroethylene were studied by X-ray diffraction. A quantitative X-ray powder diffraction analysis of three components of the polymer was performed for the first time. All samples of polytetrafluoroethylene were found to be three-phase and consist of one crystalline and two amorphous phases. One of the amorphous phases is composed of low-molecular-weight products. The structure of the latter phase was established for the first time by X-ray diffraction methods and computer simulation.     

Liquid crystals: applications and industry

Liquid crystals (LCs) are mesogenic phases of matter which combine liquid fluidity with crystalline solid properties. Precise knowledge of the molecular orientations – close to the boundaries and within the material bulk – is necessary for understanding their flow behaviour, especially in microfluidic settings. While the boundary conditions are set, passively, by surface-induced molecular orientations, the bulk orientation in flow is determined, actively, by the anisotropic coupling between the flow and the molecular orientation. Together, the surface and the bulk orientations offer a range of topological constraints within microfluidic channels, which affect the evolution and sustenance of flow-induced phenomena in LC-based systems. The concept of topological microfluidics can be extended to different classes of anisotropic fluids, allowing us to explore and to employ such fluids as complex functional materials for microfluidics, thereby significantly broadening the reach of conventional microfluidics.     

Active and Passive LC Based Polarization Elements

Passive and active polarization elements were created by surface and bulk photo-alignment of LCs, reactive LCs, photo-sensitive LCP and photo-curable monomer/LC composites. The use of different photo­sensitive liquid crystalline materials for the development of highly anisotropic elements with high spatial resolution and stability or, alternatively, fast switch ability will be discussed. Photo-active and voltage tunable polarization and diffraction elements are presented. For active micro-optic application a photo-addressed patterned retarder was created. Electrically switchable diffraction gratings were generated by interference exposure of photo-curable LC composites at room temperature characterized by droplet free morphology. These polarization sensitive diffraction elements are characterized be excellent optical properties and low switching times.     

Mesomorphous Properties of Azo- and Azoxyarylethanes as Potential Stationary Phases in Gas Chromatography

Two series of compounds have been synthesized: 1,2-bis(4′-butoxybenzeneazobenzene-4)ethanes and 1,2-bis(4′-butoxybenzeneazoxybenzene-4)ethanes. The effects of lateral substituents (CH₃, Cl, CN) on temperature are tested as well as the molar enthalpies and entropies of their phase transitions determined. The application of those compounds as liquid-crystalline stationary phases in gas chromatography is suggested.     

Betrachtungen zur Struktur aufgedampfter Metallschichten für Widerstandsbauelemente

The possibility of forming two phases or more is a prerequisite for a vapour-deposited metallic layer being suited for manifacturing resistance components for utilization in the field of electrotechnics. The electrotechnic qualities demanded result from such a structure of the layer which deviates from crystalline order. The structure of these layers is an X-ray amorphous one. The optimum electric qualities of resistance components are to be found in a narrow range, situated near crystalline order. Repeatability of layer qualities depends on “hit accuracy” of this structure of layers during production.     

Biphenyl-based liquid crystal precursors with alkanoate and hydroxyl group

We synthesized a series of 4′-hydroxy-[1,1′-biphenyl]-4-yl alkanoate with a potentially reactive functional hydroxyl group as a LC precursor, which facilitates reaction with other chemical groups to tailor biphenyl-based liquid crystals (LCs) for specific applications. Several liquid crystalline materials were also synthesized based on these LC precursors to show high probability to generate various potential LCs. With increasing chain length, the melting point decreased and R_f (retardation factor: migration distance of substance ÷ migration distance of solvent front) of the synthesized LC precursor increased. This LC precursor series provides a useful first synthesis step to design tunable biphenyl/ester-based LCs.     

Phason strains on growth, stability and structure of icosahedral phases

Growth, stability and structure of icosahedral (i-) phases have been studied by electron diffraction and X-ray diffraction in relation with the phason strains. Three alloy systems; AlPdCr, AlPdMn and AlCuV were chosen in this study. An i- Al₇₂Pd₂₅Cr₃ grain has been analysed to have a phason matrix toward to a tetragonal or orthorhombic structure. Stability of the i-phases correlated with the phason relaxation was discussed in Al-Pd-Mn system. A quenched i-Al₇₄Pd₁₇Mn₉ close to but containing significant phason strains, revealed that the phason relaxation induced by precipitation of crystalline phases upon annealing. Phason disorder dominated by the chemical composition was evidenced in a composition study in Al-Pd-Mn system. A high density random phasons characterized the icosahedral glass phase was observed in AlCuV alloys.     

X-Ray diffraction study of the evolution of phase and structural state and macroscopic stress during annealing of soft magnetic Fe95 − x Zr5N x films prepared by ion-plasma deposition

The evolution of the phase composition, nanostructure parameters, and macroscopic stress in soft magnetic Fe_{95 ? x} Zr₅N _x films (prepared by ion-plasma deposition onto quartz substrates) during their annealing has been investigated by X-ray diffraction. During deposition, depending on the N content, either a mixed structure composed of an X-ray amorphous phase enriched in Zr and N and a crystalline phase (α-Fe(N) solid solution) or an X-ray amorphous phase enriched in Fe, Zr, and N is formed in the films. During annealing, depending on the temperature and nitrogen content, different combinations of crystalline phases (α-Fe(N) and Zr(N) solid solutions, α-Fe, Fe₄N, Fe₂N, ZrO₂) are formed in the films. The large compressive stress formed in the films during deposition changes to a lower tensile stress during annealing.     

Non-isothermal crystallization kinetics of ZnO-BaO-B2O3-SiO2 glass

Glass of composition 40SiO₂-30BaO-20ZnO-10B₂O₃ (mol%) was made by conventional melting and casting process. Crystallization kinetics of above glass has been investigated under non-isothermal conditions, using the formal theory of transformations for heterogeneous nucleation. The procedure is applied to the experimental data obtained by differential thermal analysis (DTA), using continuous-heating techniques. The crystallization results are analyzed, and both the activation energy of crystallization process as well as the crystallization mechanism is characterized. Dilatometric measurement of this glass was also done and data obtained was used to calculate the viscosity of the formed glass. Development of crystalline phases on thermal treatments of the glass at various temperatures has been analyzed by X-ray diffraction. Microstructure of the crystalline phases was investigated by scanning electron microscopy (SEM) and the development of various structural features with variation in heat treatment cycle was observed. The nucleation and growth of these phases in the matrix of glass has been described and discussed.     

Thermodynamics of Solutions of Various Nonmesomorphic Solutes in the Nematic and Isotropic Phases of 7CB

Thermodynamic results from gas-liquid chromatography, (GLC) are reported for thirty two nonmesomorphic solutes, at infinite dilution, in the nematic and isotropic phases of p-n-heptyl-p'-cyanobiphenyl (7CB). The solutes fall into five categories; normal alkanes, branched alkanes, alkenes, hexadienes and aromatics. The results are examined within the framework of statitical thermodynamic models. The observed trends are interpreted on the basis of solute structure (e.g. shape, size, flexibility, polarity and polarizability). The results conclusively show that the presence of one or more double bonds in the solute structure increases its compatibility with the nematic and isotropic phases of the liquid crystalline solvent. This effect is more drastic when the double bonds are conjugated. Other implications of this study include shape selective GLC separation of geometric isomers and an examination of the effect of solute structure on the stability of the nematic phase at finite solute concentrations.