A Twist‐Bend Nematic Phase Driven by Hydrogen Bonding

The liquid crystalline phase behavior of 4‐[6‐(4′‐cyanobiphenyl‐4‐yl)hexyloxy]benzoic acid (CB6OBA) and 4‐[5‐(4′‐cyanobiphenyl‐4‐yloxy)pentyloxy]benzoic acid (CBO5OBA) is described. Both acids show an enantiotropic nematic phase attributed to the formation of supramolecular complexes by hydrogen bonding between the benzoic acid units. In addition, CB6OBA provides the first example of hydrogen bonding driving the formation of the twist‐bend nematic phase. The observation of the twist‐bend nematic phase for CB6OBA, but not CBO5OBA, is attributed to the more bent molecular shape of the complexes formed by the former, reinforcing the view that shape is a key factor in stabilizing this new phase. Temperature‐dependent FTIR spectroscopy reveals differences in hydrogen bonding between the two nematic phases shown by CB6OBA which suggest that the open hydrogen‐bonded complexes may play an important role in stabilizing the helical arrangement found in the twist‐bend nematic phase.     

Inductive effect for the phase stability in hydrogen bonded liquid crystals,x-(p/m)BA:9OBAs

A new series of hydrogen bonded liquid crystal (HBLC) complexes, made up with substituted benzoic acids (BAs) and nonyloxy benzoic acid, viz., x-(p/m)BA:9OBAs are reported for x = F, Cl, Br and –CH₃ substituted at para (p) or meta (m) positions of BA moiety. Proton nuclear magnetic resonance (¹H-NMR) spectrum confirms the HBLC complex. Infra red (IR) spectrum confirms linear, double and complementary type of hydrogen bonding (HB) between x-(p/m)BAs and 9OBA. The liquid crystal (LC) phases are characterised by polarisation optical microscopy (POM) and differential scanning calorimetry (DSC) techniques. x-(p/m)BA:9OBA exhibit N, C and G LC phase variance. HB induces tilted phases and enhances LC phase stability. The influence of configuration, size, electronegativity, electron directing capacity and inductive nature of substituent (x) is investigated for the stability of LC phases. An overview of the LC phase data indicates predominant ‘negative inductive effect’ in HBLCs with electron withdrawing substituents. Inductive effect operates effectively for para substitutions. Results are discussed in the wake of reports in other HBLCs.     

Dielectric properties of a strongly polar nematic liquid crystal compound doped with gold nanoparticles

This study focuses on the electrical characteristics of a strongly polar nematic liquid crystal, Hexyloxy-cyanobiphenyl (6OCB), doped with a low concentration (2% by weight) of citrate buffer stabilised gold nanoparticles (GNPs) at low frequencies between 20 Hz and 35 MHz. The doped samples have lower values of nematic–isotropic transition temperature, permittivity (both parallel and perpendicular to the field direction) and dielectric anisotropy; however, relaxation time and activation energy were increased. The observed results could be explained on the basis of weakly anisotropic nature of GNPs and a local rearrangement of liquid crystal molecules surrounding the nanoparticles. Moreover, a complimentary suggestion on a possible change in the dipole–dipole correlation is made to explain the difference in changes (qualitative and quantitative) observed for permittivity of the host nematic liquid crystal doped with GNP. Temperature dependent dielectric relaxation studies indicate an increase in viscosity and potential barrier; and hence a change in strength of inter-molecular and intra-molecular interactions is suggested.     

Electro-optical and dielectric study of multi-walled carbon nanotube doped polymer dispersed liquid crystal films

The self-organising property of nematic liquid crystals (LCs) was used to align multi-walled carbon nanotubes (MWCNT) dispersed in them. MWCNT not only well integrate in the matrix but also, even at very low concentration, have a detectable effect on the LC properties that can be very attractive for display applications. In the present work, MWCNT were doped (0–0.5% wt/wt) in two different types of LCs. These MWCNT doped polymer dispersed LC (CPDLC) films were studied comprehensively using fundamental techniques. Polarising optical microscope (POM) and scanning electron microscope (SEM) techniques used for morphological study reveal that the LC droplet size remains unchanged with increase in MWCNT concentration. The electro-optical (EO) study performed by increasing voltage in steps of 10 V up to 100 V at an optimised frequency of 200 Hz and at temperature 25°C shows that the low MWCNT concentration films show good optical response than the higher one. The dielectric behaviour of CPDLC films in the frequency range 20 Hz to 20 MHz was investigated using precision impedance analyser. The obtained data were modelled with Debye and Cole-Cole methods to calculate relaxation time and distribution parameter (α). The zero value of α indicates Debye type relaxation processes.     

Dye-dependent studies on droplet pattern and electro-optic behaviour of polymer dispersed liquid crystal

In order to study the droplet pattern and electro-optic (EO) behaviour of polymer dispersed liquid crystal (PDLC) with the addition of dye, dichroic polymer dispersed liquid crystal (DPDLC) films were prepared using a nematic liquid crystal (NLC), photo-curable polymer (NOA 65) and anthraquinone blue dichroic dye (B2), in equal ratio (1:1) of polymer and liquid crystal (LC) by polymerisation induced phase separation (PIPS) technique. Dichroic dye was taken in different concentration (wt./wt. ratio) as 0.0625%, 0.125%, 0.25%, 0.5% and 1% of the LC mixture in DPDLC films. Initially, in an open circuit when there is no proviso for external electric field (0 V), LC droplets in polymer matrix exhibited bipolar pattern, though on closing the circuit with the increase of electric field pattern of droplets starts changing, LC molecules align along the direction of applied electric field and aligned completely relatively at higher field (30 V), which illustrate vertical radial pattern. Further, results show that the DPDLC film containing 0.0625% dye concentration with consistent average droplet size ~4.30 μm, exhibits the best transmission at lower operating voltage.     

Phase transition studies in symmetric dimeric liquid crystals

As a part of the systematic studies on symmetric liquid crystal dimer homologous series, α,ω-bis-(4-n-alkylaniline benzylidene-4′-oxy) alkanes, (referred to as m.OnO.m with m = 3, 4, and 5; and n = 8, 9, and 10), we present in this article the nature of phase transitions across isotropic–nematic and nematic–smectic-A (N–SmA) phases exhibited by the just mentioned compounds. The methods employed are differential scanning calorimetry and dilatometry. The compounds studied were 3.O8O.3, 4.O8O.4, and 5.O8O.5; and 3.O9.03, 5.O9O.5, 3.O10O.3, 4.O10O.4, and 5.O10O.5. Different from the case of their corresponding monomers, all these compounds exhibit a nematic phase only with the exception of 5.O8O.5 which exhibits a SA phase in addition to the nematic phase. The phase transitions viz., isotropic–nematic transitions studied in all these compounds were confirmed to be of first-order nature, whereas the N–SmA transition exhibited by the compound 5.O8O.5 only was found to be of second-order nature. We also report in this article the calculated density jumps, thermal expansion coefficient maxima, and pressure dependence of transition temperatures which are analyzed in the light of the available literature data.     

Electrical and Optical Studies of Hydrogen Bonded Ferroelectric Liquid Crystals Dispersed with MWCNT

Two hydrogen bonded ferroelectric liquid crystals (HBFLC) are dispersed with multi-walled carbon nanotubes (MWCNT) for achieving better thermal and electrical performance. Interesting feature of the present communication is the enhancement in the enthalpy value pertaining to isotropic-nematic transition in MWCNT doped liquid crystals compare to its pure counter parts. Dielectric relaxations studies are carried out in the pure and the MWCNT doped systems. It is observed that doping of MWCNT elevated the activation energies considerably. Optical shuttering action in one of the complex dispersed with MWCNT are discussed.     

Analysis of electro-optical and dielectric parameters of TiO2 nanoparticles dispersed nematic liquid crystal

The present investigation is focused on to find out the role of TiO₂ nanoparticles (NPs) on altering the dielectric and electro-optical parameters of nematic liquid crystal (NLC). In addition to this, we also optimized the concentration of dopant (0.25 wt%) for a saturation value of permittivity and dielectric anisotropy in the doped system. Dielectric spectroscopy has been performed with the variation of frequency and temperature to investigate the various dielectric parameters, which demonstrate that the investigated NLC is of positive dielectric anisotropy; the observed result shows a decrement in the value of relative permittivity and dielectric anisotropy; however, the permittivity value increases for higher concentration of dopant but remains less than that of pure NLC. Electro-optical measurements have also been performed to compute the optical response of pure and dispersed NLC. It is found that optical response decreases for the NP-doped systems. This optimized concentration of NPs in NLC matrix can have various credential applications in the field of active matrix display and holography.     

Dielectric relaxation in polar nematic liquid crystals

The relationship between the complex dielectric permittivity tensor of a polar nematic liquid crystal and the autocorrelation matrix for the permanent dipole moment of a molecule is obtained. The theory is applicable to the whole frequency range which characterizes orientational relaxation in liquid crystals (up to ∼ 5 THz). The models of rotational diffusion and extended rotational diffusion in a mean field nematic potential are used to evaluate the dielectric absorption and dispersion in nematics.     

Fluoro-substitution in hydrogen bonding liquid crystal benzoic acid: dielectric,electro-optic and optical proprieties and inducing polar nematic phase

ABSTRACT

Dielectric and electro-optic properties have been studied in order to understand the effect of the fluoro-substitution on hydrogen bonded liquid crystal proprieties. The fluoro-substitution alters the characteristics of pure LC structure and changes its physical parameters. In the present paper, variation in physical parameters like dielectric permittivity, response time, elastic constant, rotational viscosity etc. has been explained based on many factors. In addition, the fluorine substitution has lead to the appearance of the polar nematic phase.     

Enhancement of electrical conductivity,director relaxation frequency and slope of electro-optical characteristics in the composites of single-walled carbon nanotubes and a strongly polar nematic liquid crystal

In the present work, single-walled carbon nanotubes (SWCNTs) were dispersed in a room temperature nematic liquid crystal 4-pentyl-4′-cyanobiphenyl at the concentration of 0.02 and 0.05 wt%. Differential scanning calorimetry and temperature-dependent dielectric studies suggest decrease in clearing temperature of the composite materials as compared to the pure material. Ionic conductivity increases by two orders of magnitude due to the dispersion of such a low concentration (0.05 wt%) of SWCNTs. Dielectric studies also show that the presence of the SWCNTs decreases the effective longitudinal as well as transverse components of the dielectric permittivity. For homeotropic aligned samples, a relaxation mechanism has been detected in the lower MHz region both for the pure as well as dispersed samples. Presence of SWCNTs increases the relaxation frequency corresponding to flip-flop motion of molecules around their short axes. From frequency-dependent dielectric studies, important dielectric parameters such as relaxation frequency, dielectric strength and distribution parameters have been determined. Electro-optical experiments show that the threshold voltage decreases and the steepness of the transmission voltage curve improves due to the dispersion of SWCNTs.     

Complex formation in mixtures of 4,4'-disubstituted diphenyldiacetylenes with cyanobiphenyls

We investigated 1:1 mixtures of a variety of 4,4'-disubstituted diphenyldiacetylenes (PTTP series) and cyano-containing mesogens for possible complex formation. Complexes were formed when alkyl/alkoxy cyanobiphenyls (CB series) were mixed with alkyl/alkoxy PTTP homologues. We found complexes having a melting temperature higher than that for either component, and complexes with lower melting temperatures. A fluoro substituent on the PTTP gave an enhanced nematic phase and a cyclohexane ring in place of a benzene ring yielded an enhanced smectic A phase, but a cyano on the PTTP gave poor liquid crystalline properties. Phase diagrams were constructed for PTTP-24/5-CB and PTTP-24/80-CB mixtures. Both complexes formed had melting temperatures higher than those for either component. These complexes were recrystallized and shown by X-ray studies to be 1:1 complexes. The PTTP-24/5-CB complex showed only a monotropic nematic phase, but the PTTP-24/80-CB complex showed induced smectic A and hexatic B phases in addition to an enantiotropic nematic phase.     

Raman spectra of magnetic field induced cholesteric → nematic phase transition in doped p-octoxybenzoic acid

Raman spectroscopy is employed to investigate helical twist formation in nematic and smectic C phases of p-n-octoxybenzoic acid (OBA) doped with a small amount of Cholesteric Nonanoate (CN). A cholesteric→ nematic phase transition in OBA/CN is induced by an external magnetic field in the temperature range 135–148°C. The threshold field (H_c) is equal to 8.0 kGauss for 0.33 % by weight CN/OBA, and no hysteresis is observed.     

Crystal–nematic phase separation in an asymmetric liquid crystal dimer possessing a terminal hydroxyl group

We prepared an asymmetric liquid crystal dimer possessing a terminal hydroxyl group, 2-{4-{7-[4-(4-cyanophenyl)phenyloxy]heptyloxy}phenyl}-5-(6-hydroxyhexyloxy)pyrimidine, and investigated the phase transition behaviour using polarising optical microscopy and differential scanning calorimetry. The compound exhibited an enantiotropic nematic phase. On cooling, two distinct domains were formed during the nematic-to-crystal phase transition. During heating, one domain melted at 126.4°C to the N phase, whereas the other domain changed to the N phase at 144.6°C. Therefore, the crystal and nematic phases coexisted at a temperature of 18.2 K. The coexistence behaviour characteristics depend on the cooling rate. We discuss the manner in which intermolecular interactions affect the phase transition behaviour.     

A new mesogenic fluorene derivative: 2,7-bis(4-pentylphenyl)-9,9-diethyl-9H-fluorene

The title compound, 2,7-bis(4-pentylphenyl)-9,9-diethyl-9H-fluorene, is a new mesogenic compound containing the fluorene moiety. It exhibits a monotropic nematic liquid crystalline behaviour, with isotropisation temperature of 53°C. The compound is also polymorphic in the solid state, with one crystal phase melting at 103°C and another one melting at 71°C. The crystal and molecular structure of the high melting solid phase have been determined from single crystal X-ray diffraction analysis. Crystals are monoclinic, with cell dimensions a = 16.649(6) Å, b = 8.305(3) Å, c = 24.598(7) Å, β = 111.60(2)?, space group P2₁/c and four molecules in the unit cell. Refinement leads to R = 0.0558. The two terminal alkyl chains and one phenyl ring are disordered over two split positions. The imbricated molecular packing observed in the solid state seems to resemble that of the nematic phase that is formed upon cooling the melt.     

Synthesis of a New Liquid Crystalline Polymer as a Highly Active β-Nucleator and Its Effect on Melting and Crystallization Behaviors of Isotactic Polypropylene

A new nematic liquid crystalline polymer as a highly active β-nucleator (LCP-N) of isotactic polypropylene (iPP) was synthesized and characterized. The effect of LCP-N on thermal behavior of the iPP was investigated with differential scanning calorimetry. LCP-N showed a melting transition at 85.0°C and a nematic to isotropic phase transition at 278.0°C. The incorporation of LCP-N could lead to substantial changes in the thermal behavior of the iPP. The nucleating activity of LCP-N mainly depended on its content, mesogenic molecular structure, and thermal history of processing. A high content of β-form could be obtained by the combined effect of the optimum LCP-N concentration and crystallization temperature and time. The Φ_β reached 77% when the LCP-N content, crystallization temperature, and crystallization time were 0.4 wt.%, 125°C, and 1 h, respectively.     

Orientational control of liquid crystal molecules via carbon nanotubes and dichroic dye in polymer dispersed liquid crystal

Polymer dispersed liquid crystals (PDLCs) using nematic liquid crystal and photo-curable polymer (NOA 65) were prepared by polymerisation-induced phase separation technique, in equal ratio (1:1) of polymer and liquid crystal (LC). We demonstrate that doping of small amount (0.125%, wt./wt.) of multiwall carbon nanotubes (CNTs) and orange azo dichroic dye in PDLC generously controlled the molecular orientation, dynamics of LC in droplet and size of droplets. The effects of multiwall CNTs and dye on PDLCs were studied in terms of transition temperature, droplet morphology, transmittance characteristic, contrast ratio and response time. The results exhibited that the values of the threshold electric fields were reduced from 8 V/µm (pure PDLC) to 1.18 and 1.72 V/µm, doped with multiwall CNTs and dye, respectively. The CNTs-doped PDLC shows faster switching response as compared with pure PDLC and dye-doped PDLC. However, dye-doped PDLC shows much higher contrast among all PDLC samples. Further, the results also illustrate that the birefringence value of LC in PDLCs was changed with doping of CNTs and dye.     

Nanostructure and dielectric properties of a twist-bend nematic liquid crystal mixture

We present freeze-fracture transmission electron microscopy (FF-TEM), dielectric spectroscopy and electro-optic measurements on a dimeric liquid crystal mixture, which previously was proposed to form the twist-bend nematic (N_tb) phase. Our FF-TEM studies provide a direct image of a 10.5 nm periodic structure, consistent with the expected nanoscale, heliconical twist-bend modulation of the molecular orientation. Dielectric measurements in the 100 Hz to 10 MHz range reveal three nearly Debye-type dispersion processes in the nematic and the twist-bend phase. Low frequency 8 V/µm electric fields applied on planar cells cause the optical-scale stripe texture (another characteristic feature of the N_tb phase) to disappear. Higher (>16 V/µm) fields gradually realign the heliconical axis along the electric field; it relaxes back after the field removal.     

Investigation of dielectric and electro-optical properties of nematic liquid crystal with the suspension of biowaste-based porous carbon nanoparticles

ABSTRACT

The effect of biowaste porous carbon nanoparticles (PCNPs) on the dielectric and electro-optical properties of nematic liquid crystal (LC) mixture (1823A) of 4-(4-alkyl-cyclohexyl) benzene isothiocyanates and 4-(4-alkyl-cyclohexyl) biphenyl isothiocyanates has been studied. The dielectric permittivity of nematic LC has been increased with the dispersion of carbon NPs. The dielectric anisotropy has been calculated and found to be decreased with the dispersion of PCNPs into the pure nematic LC. The response time and birefringence have been also observed with the variation of temperature, frequency as well as the concentrations of carbon NPs. After the dispersion of PCNPs achieved better birefringence and faster response in the dispersed system, which is the significant application in display devices. Threshold voltage splay elastic coefficient and rotational viscosity have been calculated for both pure and NPs dispersed nematic system. Its value is increased with the dispersion of NPs. Additionally, photoluminescence and figure of merit have investigated as a comparative study of nematic matrix as well the dispersed system. The experimental results have been found to have good agreement with the theoretical data of nematic LC. An effort has been made to explain these experimental results on the basis of interaction between nematic molecules and carbon NPs.     

New insights into the role of hydrogen bonding on the liquid crystal behaviour of 4-alkoxybenzoic acids: a detailed IR spectroscopy study

ABSTRACT

Hydrogen bonding is an efficient alternative to covalent bonding as a way to stabilise liquid crystallinity, by yielding symmetric and non-symmetric complexes with increased molecular anisotropy. In designing new hydrogen-bonded liquid crystals, HBLCs, it is crucial to account for the competing hydrogen bonds that can lead to different supramolecular species coexisting in a temperature-dependent equilibrium. Thus, as part of a systematic development of this area, in the present work we study with detail the relationships between the phase behaviour and hydrogen bonding in a series of 4-n-alkoxybenzoic acids, nOBAs, which are widely used as components in HBLCs. Five acids with alkyl chain lengths of n = 1, 4, 5, 7 and 8 have been investigated using Fourier transform infrared spectroscopy, FTIR, in a broad range of temperatures under two different experimental configurations: sandwiched between potassium bromide, KBr, windows and dispersed in KBr discs. The nematic phase is correlated with the amounts of closed dimers between acid molecules, through the formation of strong hydrogen bonds. Moreover, high concentrations of open dimers are found in samples sandwiched between KBr slides, which are linked to the appearance of smectic-like aggregates that perturb the local order of the nematic phase. The results are interpreted in terms of the ability of the 4-alkoxybenzoic acids to align due to surface interactions, which are less acute in samples dispersed in the discs. These effects must be taken into account in order to correctly interpret the information about the supramolecular species present in the samples, and thus to better understand the relationships between hydrogen bond strength and mesomorphism in HBLCs.