Gradient measurement technique to identify phase transitions in nano-dispersed liquid crystalline compounds

Characterization and phase transitions in pure and 0.5% BaTiO₃ nano-dispersed liquid crystalline (LC) N-(p-n-heptyloxybenzylidene)-p-n-nonyloxy aniline, 7O.O9, com-pounds are carried out using a polarizing microscope attached with hot stage and camera. We observed that when any of these images are distorted, different local structures suffer from various degradations in a gradient magnitude. So, we examined the pixel-wise gradient magnitude similarity between the reference and distorted images combined with a novel pooling strategy – the standard deviation of the GMS map – to determine the overall phase transition variations. In this regard, MATLAB software is used for gradient measurement technique to identify the phase transitions and transition temperature of the pure and nano-dispersed LC compounds. The image analysis of this method proposed is in good agreement with the standard methods like polarizing microscope (POM) and differential scanning calorimeter (DSC). 0.5% BaTiO₃ nano-dispersed 7O.O9 compound induces cholesteric phase quenching the nematic phase, which the pure compound exhibits.     

Orientational order in three nO.m liquid crystalline compounds

Refractive index and density measurements have been carried out on three nO.m liquid crystalline compounds, namely, 4O.2, 4O.3 and 1O.10 belonging to the N-(p-n-alkoxybenzylidene)-p-n-alkylaniline series. From the data, the orientational order parameter has been estimated using Vuks and Neugebauer local field models. Furthermore, the orientational order parameter has been calculated directly from refractive index data employing the Vuks scaling factor method, Neugebauer f(B) parameter, effective geometry parameter and a method proposed by Kuczyński et al. It is observed that order parameter values estimated from different methods agree well near the nematic–isotropic transition and diverge as the nematic phase attains equilibrium. The temperature gradient of refractive indices and the nematic crossover temperatures have also been estimated for these compounds. The results obtained are compared and discussed.     

Phase transitions in liquid crystal 6O.4 (p-<Emphasis Type="Italic">n</Emphasis>-hexyloxybenzylidine-p′-<Emphasis Type="Italic">n</Emphasis>-butylaniline)

DSC measurements on p-n-hexyloxybenzylidine-p′-n-butylaniline (6O.4) showed that the crystalline to liquid crystalline (K-S _H) transition at 33.7°C observed in the heating cycle does not revert even when the sample is cooled down to −100°C. Hence it is inferred that a physically stable supercooled liquid crystalline phase is formed on cooling 6O.4. To investigate the K-S _H transition further the techniques of polarized microscopy and X-ray diffraction were used which concurred with the DSC results. Quasielastic neutron scattering measurements carried out to study the re-orientational motions in the ordered phases of 6O.4 (K and S _H) show that while in the crystalline phase (at RT) the re-orientational motion is found to involve only the core of the molecule, in the S _H phase (at 45°C) the dynamics involves the whole molecule and this motion is found to persist even when the sample cools back to room temperature corroborating the results of the DSC, microscopy and X-ray diffraction.      

A study on polymorphism of hydrogen-bonded thermotropic liquid crystals

A novel mesogenic homologous series comprising of eight hydrogen-bonded liquid crystalline complexes are isolated and analyzed by forming a hydrogen bond between p-n alkyloxy benzoic acids (where n represent alkyloxy carbon number which varies from 5 to 12) and mesaconic acid, respectively. Eight synthesized complexes are subjected to Fourier transform infra-red spectroscopy, polarizing optical microscopy and differential scanning calorimetry studies to meet the basic characterization. The variation of optical tilt angle with respect to temperature in various conventional and smectic X phases are investigated and analyzed. A phase diagram is constructed to elucidate the mesogenic behavior of novel liquid crystalline series. The Cox ratio that reveals the order of various mesophases and the stability factor, to invoke the thermal stability of mesophases, is studied under the results of DSC thermogram.     

Synthesis and characterization of wide range mesogenic esters based on asymmetrical 2,5-disubstituted 1,3,4-thiadiazole

A homologous series of new 13 esters, 4-(5-(p-tolyl)-1,3,4-thiadiazol-2-yl)-phenyl-4-alkoxybenzoate, (IV_n), based on 1,3,4-thiadiazole core has been synthesized. The structures of these esters were confirmed by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance and mass techniques. Their mesophases behavior was investigated with hot-stage polarizing optical microscope and differential scanning calorimetry. The thermal stability for most of these derivatives was measured by thermal gravimetric analysis. All the target esters showed enantiotropic mesomorphic behaviors with nematic and nematic/smectic C phases. The phase transition temperatures and liquid crystalline properties were affected by the nature of heterocyclic ring and the length of the alkoxy chain. Only the nematic phase was observed in the first 10 derivatives, (n = 1–10), while the last 3, (n = 12, 16 and 18) showed nematic and smectic C phases. These compounds demonstrated high liquid crystalline ranges, both in heating and cooling cycles. The mesomorphic results obtained were compared with the reported analogs of similar constituents.     

Orientational order parameter studies on 3.Om and 3O.Om liquid crystals

Orientational order parameter S is evaluated in the nematic phase of six liquid crystal compounds, N-(p-n-propyl benzylidene)-p-n-alkoxy anilines, 3.Om and N-(p-n-propyloxy benzylidene)-p-n-alkoxy anilines, 3O.Om compounds with m = 6, 7 and 8, using different methods. The techniques employed are S from birefringence δn, Haller's approximation from (1?T/T_c) ^β, effective geometry parameter α_g and Vuks’ scaling factor S_C. The values of S obtained using the above methods are compared with one another and with the results on a number of liquid crystals; the liquid crystals favor isotropic Vuks’ method.     

Experimental and computational studies on induced thermochromic effect and re-entrant smectic phase in linear double hydrogen-bonded binary liquid crystal mixtures

Design and synthesis of the hydrogen-bonded liquid crystalline (HBLC) mixtures are accomplished from diglycolic acid and 4-n-alkoxybenzoic acid (n?=?9–12). Spectroscopic characterization such as UV–Vis, FT-IR, and DSC has supported the presence of molecular geometry of HBLC mixtures. Thermochromic effect is analyzed for the polarizing filter applications. Induced new phases (Smectic X and Smectic Cr) and their first-order transitions are confirmed through DSC along with its corresponding textures using polarizing optical microscope. Furthermore, the induced re-entrant smectic ordering due to the lone pair to π* transition is reported using density functional theory (DFT) studies. Dipole moment studies (DFT) clearly give a strong evidence of the existence of nematic and smectic phases due to the monopole–dipole interaction in the present HBLC mixtures. Band gap of the present HBLCs is 5.175?eV, which is calculated by the HOMO–LUMO analysis and is validated using experimental observations. Liquid crystal parameters such as transition temperature, enthalpy values, stability factor and tilt angles are reported.     

Synthesis and mesomorphic properties of nonsymmetric liquid crystalline dimers containing azobenzene groups

Four novel nonsymmetric dimers containing azobenzene mesogenic groups were synthesized. The nonsymmetric dimers compounds namely, ethyl 4-[(4-{4-(4-((4-nitrophenyl)diazenyl)phenoxy)alkyloxy}phenyl)diazenyl]benzoate were obtained from the alkylation of ethyl 4-[(4-(4-bromoalkyloxy)phenyl)diazenyl]benzoate with 4-[(4-nitrophenyl)diazenyl]phenol. The mesomorphic properties of the compounds were determined by DSC and polarizing optical microscopy. The first member of the series was nonliquid crystalline while all other homologues display nematic and smectic A phases. The trans-azobenzene groups of the dimers display a high-intensity π–π* transition at about 365 nm and a low-intensity n–π* transition at around 465 nm, therefore, photochromism can be achieved by the introduction of the azo linkage to the dimeric liquid crystalline molecules.     

Synthesis,characterization and phase transition studies in 4-hexyloxy benzylidene 4’-alkoxyanilines

Synthesis and the characterization through polarizing optical microscope (POM) textures in number of 4-hexyloxy benzylidene 4’-alkoxyanilines, 6O.Om with m = 4, 6 to 10 liquid crystalline materials are carried out. Furthermore, the density and thermal expansion coefficient results reveal that the phase transitions present, viz., isotropic–nematic, nematic–SmC and SmC–SmI show first-order nature as expected. The transition temperatures obtained thorough the differential scanning calorimetry is found to be in agreement with the literature data. The first two compounds exhibit only the nematic phase while the next four compounds show enantiotropic SmC phase as per the literature data. The compound with m = 10 exhibits monotropic SmI phase. However, we, the authors, are able to observe this phase in addition to SmC and nematic through POM only as per the literature. The parameters calculated across the phase transitions and in the phases are in agreement with the body of the data available.     

Dynamics and phase behaviour of materials in confined geometry

Phase transitions and dynamics of the liquid crystal MBBA [N-( p-methoxybenzylidene)-p-n-butylaniline] microconfined within porous glasses of average pore diameters: 82 and 337 Å were investigated by ¹H Nuclear Magnetic Resonance (NMR). Confinement is found to favour the depression of phase transition temperatures below the corresponding transitions of bulk MBBA. Confinement induces further effects for the molecular dynamics related to the phase investigated. The correlation times of the molecular motions were obtained and the results are discussed by making comparison with the bulk analysis.     

DSC,density and refractive index studies on two nematogenic p-alkylphenyl-2-chloro-4-(p-alkylbenzoyloxy)-benzoates and their mixtures

The compounds p-pentylphenyl-2-chloro-4-(p-pentylbenzoyloxy)-benzoate [PCPB] and p-octylphenyl-2-chloro-4-(p-heptylbenzoyloxy)-benzoate [OCHB], and mixtures of different mole fractions of them, show a nematic phase with a supercooling effect. From DSC studies both ΔH and ΔS at T _NI are found to have minimum values for the equimolar mixture, which happens to be an eutectic mixture (Mix-II). However the density of this mixture is found to be less than that of the pure compounds. Refractive indices (n _o, n_e) are measured by thin prism method at different temperatures for pure components and the eutectic mixture. The birefringence values of the eutectic mixture are less than those of the individual components at higher temperature region, and are in-between at lower temperatures. The principal polarizibilities (α _o, α _e) of all the compounds have been calculated using both Vuks’ and Neugebauer's methods. These values have been compared with those calculated from additivity rules of bond polarizability. The average polarizability α increases with chain length. The orientational order parameter (P ₂) at different temperatures has been calculated using Haller's extrapolation procedure. (P ₂) values of OCHB are found to be greater than those of PCPB and Mix-II at higher temperatures, and are consistent with those determined from our X-ray studies. The temperature dependence of (P ₂) of all the compounds has been compared with Maier-Saupe theoretical values.     

Effect of carbon nanotubes on the isotropic to nematic and the nematic to smectic- A phase transitions in liquid crystal and carbon nanotubes composites

A high-resolution ac-calorimetric study on the weakly first-order isotropic to nematic (I -N and the continuous nematic to smectic-A (N -SmA phase transitions of the liquid crystal octyl-cyanobiphenyl (8CB) doped with well-dispersed multiwall carbon nanotubes (CNTs) as a function of CNT concentrations is reported. Thermal scans were performed for all samples having CNT weight fraction from f_w \phi_{{w}}^{} = 0.0005 to 0.0060 over a wide temperature range well above and below the two transitions in pure 8CB. Both the I -N and the N -SmA transitions evolve in character and have their transition temperatures qualitatively offset by ∼ 1.10 K lower as compared to that in pure 8CB for all 8CB+CNTs samples. The enthalpy change associated with each phase transition is essentially the same as that of pure 8CB and remains unchanged with increasing f_w \phi_{{w}}^{} . However, there is an evidence that the thermal transport properties of the composites differ from the pure LC upon cooling below a f_w \phi_{{w}}^{} -dependent temperature within the nematic phase. In addition, a new C_p feature is resolved for intermediate f_w \phi_{{w}}^{} samples that appears to be correlated to this onset temperature.     

Induced Smectic-G Phase Through Intermolecular Hydrogen Bonding,Part XIII: Impact of a Nematogen on Phase Behaviour of Hydrogen-Bonded Liquid Crystals

A series of hydrogen-bonded mesogens, p-( p′-methoxybenzylidene)-cyanoaniline:p-n-alkoxybenzoic acids (MBCA:nABA), is synthesised by using liquid-crystalline p-n-alkoxybenzoic acids (nABA) (where n represents alkoxy carbon numbers, 3-10 and 12) and a nematogen, p-( p′-methoxybenzylidene)-cyanoaniline (MBCA). The thermal and phase behaviour of these compounds is studied by thermal microscopy (TM) and differential scanning calorimetry (DCS) techniques. These studies reveal the induction of smectic-G phase in all the compounds. The structural elucidation pertaining to the formation and stabilisation of intermolecular hydrogen bonding is carried out by a detailed IR spectral investigation. The impact of imino group of the nematogen, MBCA, on the liquid-crystallinity of the present series is realised from the comparative studies made on the reported analogous series, p-aminobenzonitrile:p-n-alkoxybenzoic acids (ABN:nABA).     

Mesomorphic behaviors of a series of heterocyclic thiophene-imine-ester-based liquid crystals

The synthesis and characterization of a series of heterocyclic liquid crystal, 4-{[(thiophen-2-yl)methylidene]amino}phenyl 4-alkoxybenzoates possessing even number of carbon atoms at the alkoxy chain (C_nH_2n+1O-, n = 6, 8, 10, 12, 14, 16, 18) are reported. The molecular structures of title compounds were elucidated using Fourier-transform infrared spectroscopy (FTIR) and Nuclear Magnetic Resonance (NMR) spectroscopic techniques along with mass spectrometric analysis. The phase behavior of these compounds was characterized and studied by differential scanning calorimetry and polarizing optical microscopy. All members exhibited enantiotropic nematic phase except for the highest member (n = 18) which is a non-mesogen. Influence of alkoxy chain length on the transition temperatures of crystal-to-nematic (melting point) and nematic-to-isotropic (clearing point) was studied. Nematic phase range was found to increase from n = 6 to n = 10, then it started to descend from n = 12 to n = 16 and finally the nematic phase disappeared when n changed to 18.     

Synthesis and phase transition behaviours of laterally substituted liquid crystals containing methylhydroquinone: emerging of smectic C phase for higher homologues

A series of laterally substituted low-molar-mass liquid crystals with molecular geometry were constructed with three phenyl rings bridged through ester central groups as the rigid core and a lateral methyl group as the flexible part of a molecule, with a view to understanding and establishing the effect of molecular structure on liquid crystal behaviour. Low-molar-mass mesogens known as 1,4-bis[(4′-n-alkyloxybenzoyl)oxy]toluene with different number of carbon (n) at the alkyl chain have been prepared. Their molecular structures were proposed via physical measurements and spectroscopic techniques. Mesomorphic properties were studied by using differential scanning calorimetry, optical polarizing microscopy and powder X-ray diffraction techniques. The results showed that the melting points as well as the clearing temperatures decreased upon lengthening of the terminal alkyloxy chain lengths. Members with the shorter chain (n = 2–10) exhibited nematic phase. As for higher homologues, members with n = 12, 14, 16 and 18 showed polymorphism, whereby these compounds displayed both smectic and nematic properties.     

Phase behavior of four homologous compounds of 4-n-alkyl-4′-isothiocyanatobiphenyl (nBT) under pressure

The phase behavior of four homologous compounds of 4-n-nonyl-, 4-n-decyl-, 4-n-undecyl-, and 4-n-dodecyl-4′-isothiocyanatobiphenyl (9BT, 10BT, 11BT, and 12BT) was reinvestigated to characterize their high-pressure mesophases under pressures up to 150 MPa using a polarizing optical microscope equipped with a high-pressure optical cell and a wide-angle X-ray diffractometer equipped with a high-pressure sample vessel. The pressure-induced mesophases of 9BT and 10BT appearing under pressures above about 60 and 100 MPa, respectively, were identified as nematic (N) and smectic A (SmA) phases, which indicate the reversible Cr–CrE–N–I and Cr–CrE–SmA–I phase transitions under elevated pressure. Both the 11BT and 12BT exhibited the reversible transition of Cr–CrE–SmA–I in the low-pressure regions below about 5 and 23 MPa, respectively. Both the stable CrE phases changed into the monotropic (and metastable) one under higher pressures, which the Cr–SmA–I and I–SmA–CrE–Cr phase transitions on heating and cooling processes were recognized, respectively.     

Synthesis/structural and mesomorphic properties of substituted hydrazide based calamitic molecules

A set of rod-shaped molecules with central hydrazide moiety has been synthesized and characterized using standard spectroscopic techniques. The thermal behaviors of the final compounds were established by the combination of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and high-temperature powder X-ray method (XRD). The structure and conformation of the molecules were achieved by FTIR, ¹H NMR, ¹³C NMR spectroscopy and DFT calculations. It is found that two compounds are non-liquid crystalline and two compounds are liquid crystalline (LC). The structure property correlations with alkyl chain, connecting position, hydrogen bonding and without hydrogen bonding were established. The studies envisaged that LC properties are induced due to hydrogen bonding and elongation of the molecular length.