Isotropic-nematic Research Articles

Binary Nematic Liquid Crystals Mixture with Enhanced Electro-Optics Properties for Photonic Applications

Purpose: In this work, we mix two simple nematic liquid crystals (NLCs) and investigated the binaryNLCs mixtures of 7CB/PCH5 of different mixing ratios. Methodology: The pure liquid crystals 7CB and PCH5 and binary mixtures of them of high temperature stability were thermally analyzed by differential scanning calorimetry. The mixture 7CB/PCH5:30/70 wt% has the highest thermal stability with a nematic-isotropic (N-I) transition temperature at 50oC. The electrooptic properties of 7CB, PCH5, and the mixture 7CB/PCH5:30/70 wt% at room temperature were also investigated using an amplitude modulated electric signal (1 kHz - 100 Hz) by increasing diving peak voltage from 0 V to 10 V. The threshold volage is relatively reduced for the binary mixture in comparison to that value for PCH5. In comparison to the pure LCs, the mixture 7CB/PCH5:30/70 wt% has the fastest response times of values 2.36 ms total time response, 0.41 ms rise time, and 1.95 ms fall time. It has also the highest contrast ratio. Moreover, it has a maximum measured transmission that is higher than those for PCH5 and 7CB by about 17 % and 8%, respectively, at a field strength of 2V/mm. Findings: The obtained results indicate that the electrooptic properties of PCH5 was improved when mixed with a proper ratio of 7CB, of lower cost, more stablity , and higher potential for photonic applications. Unique Contriburibution to Theory, Practice and Policy: This expermental study shows that simply by mixing two relatively low cost NLCs materials, one of high thermal stability and low electro-optic properties with other one of low thermal stability and better electro-optic properties; this would improve the stability, response, and transmition of the binary mixture. If the a suitable driving method is applied, without doping with other orgnic or inorganic matrial.

Orientational Order Parameter Undecyloxy-Cyanobiphenyl (11OCB) and DodecyloxyCyanobiphenyl (12OCB) by using Optical Birefringence Method

High resolution optical birefringence studies throughout the nematic and smectic A phases of undecyloxy-cyanobiphenyl (11OCB) and dodecyloxy-cyanobiphenyl (12OCB) have been performed to evaluate orientational order parameter (<P2>) as a function of temperature at wavelength λ=632.8 nm. The temperature dependence of the birefringence (n) data have been exploited to assess <P2> using a well-known Haller’s extrapolation method. Effectively, in the nematic and smectic A phases the values of <P2> have been fitted with the estimated values from Maier-Saupe mean field theory for nematic liquid crystals and McMillan mean field theory for smectic liquid crystals. Experimentally obtained <P2> values have been compared with those achieved from Maier-Saupe mean field theory and McMillan mean field theory. The agreement between experimental and calculated <P2> values at nematic-isotropic (N-I) is much higher than experimental <P2> values.

Room-temperature ferroelectric nematic liquid crystal showing a large and diverging density.

The ferroelectric nematic phase (NF) is a recently discovered phase of matter in which the orientational order of the conventional nematic liquid crystal state is augmented with polar order. Atomistic simulations suggest that the polar NF phase would be denser than conventional nematics owing to contributions from polar order. Using an oscillating U-tube densitometer, we obtain detailed temperature-dependent density values for a selection of conventional liquid crystals with excellent agreement with earlier reports. Having demonstrated the validity of our method, we then record density as a function of temperature for M5, a novel room-temperature ferroelectric nematic material. We present the first experimental density data for a NF material as well as density data for a nematic that has not previously been reported. We find that the room-temperature NF material shows a large (>1.3 g cm-3) density at all temperatures studied, notably including phases without polar order. An increase in density at phase transitions is observed. The magnitude of the increase for the intermediate-to-ferroelectric nematic (NX-NF) transition is an order of magnitude smaller than the isotropic-nematic (I-N) transition. We then probe potential consequences that may result from an elevated density through measurement of the refractive indices (no and ne). The navg of M5 is compared with 5CB and polar smectic liquid crystals. We observe how the highly polar nature of the system counteracts the effects of an increase in density. With knowledge of experimental density, we are able to derive an approximation that yields the polar order parameter, 〈P1〉, from polarisation measurements. Present results may be typical of ferroelectric nematic materials, potentially guiding material development, and is especially relevant for informing ongoing studies into this emerging class of materials.

Near-continuous isotropic – nematic transition in compressed rod-like liquid crystal based nanocolloid

Landau-de Gennes mean-field model predicts the discontinuous transition for the isotropic – nematic (I-N) transition, associated with uniaxial ordering and a quadrupolar order parameter in three dimensions. This report shows pressure-related dielectric studies for rod-like nematogenic pentylcyanobiphenyl (5CB) and its nanocolloids with BaTiO3 nanoparticles. The scan of the dielectric constant revealed the near-continuous I-N phase transition in the compressed nanocolloid with a tiny amount of nanoparticles (x = 0.1%).For the nematic phase in 5CB and its x = 1% nanocolloid the enormous values of the dielectric constant and the bending–type, long-range pretransitional behavior were detected. The impact of prenematic fluctuations was also noted for the ionic-related contribution to dielectric permittivity in the isotropic liquid phase. For the high-frequency relaxation domain, this impact was tested for the primary relaxation time pressure evolution and the translational–orientational decoupling.

High-resolution dielectric anisotropy investigation of carbon nanotube-smectic-A liquid crystal dispersions: An upper limit of the latent heat and the pretransitional anomaly at the nematic-smectic-A transition.

Within the entire mesomorphic range, high-precision dielectric anisotropy data with the high-temperature resolution is presented for a highly polar smectic-A liquid crystal 8CB (octylcyanobiphenyl) as well as 8CB nanocomposites doped with both pristine multi-walled carbon nanotubes (p-MWCNTs) and carboxyl group (-COOH) functionalized MWCNTs (f-MWCNTs). The temperature variation of the nematic order parameter across both the nematic-isotropic (N-I) and the nematic-smectic-A (N-Sm-A) phase transitions of the neat 8CB and 8CB+MWCNT nanocomposites has then been derived from the dielectric anisotropy data within the framework of the Maier-Meier theory. With the inclusion of MWCNTs, both the N-I and the N-Sm-A transition temperatures have been noted to shift to lower temperatures as compared to the 8CB host. Also, for all 8CB+MWCNT nanocomposites, regardless of the surface functionalization, it has been well documented that the N-I transition is weakly first order, whereas the N-Sm-A transition remains continuous within the experimental resolution. For all investigated samples, the temperature dependence of the nematic order parameter has been shown to be quasitricritical, within the experimental resolution. From the attentive inspection of the dielectric anisotropy data in the vicinity of the N-Sm-A transition, the upper limits for a possible latent heat ΔH_{NA} for the 8CB host and all 8CB+MWCNT composites, for the first time, have been derived. The so-derived ΔH_{NA} values for all investigated samples have also been compared with those extracted from the optical birefringence data, and an excellent consistency has then been noted. The N-Sm-A pretransitional anomaly has been investigated and the effective specific heat capacity exponent α values have been yielded from the power-law analysis of our high-resolution Δɛ(T) data across the N-Sm-A transition for all investigated samples. It has been well documented that the incorporation of MWCNTs to the 8CB host leaves the N-Sm-A transition essentially bulklike. We discussed that, to some extent, the compliance of MWCNTs does not drive the N-Sm-A transition to 3D-XY-like behavior, that is the strength of de Gennes coupling will remain the same for all nanocomposites. This issue can be ascribed to the weaker nature of MWCNT disorder. In this work, for the first time, high-resolution Δɛ(T) data has been shown to be very adequate and offer an easy way to investigate the N-Sm-A transition as compared to calorimetric methods.

Orientational phase transition in monolayers of multipolar straight rigid rods: The case of 2-thiophene molecule adsorption on the Au(111) surface.

Monte Carlo simulations and finite-size scaling theory have been carried out to study the critical behavior and universality for the isotropic-nematic (IN) phase transition in a system of straight rigid pentamers adsorbed on a triangular lattice with polarized nonhomogeneous intermolecular interactions. The model was inspired by the deposition of 2-thiophene molecules over the Au(111) surface, which was previously characterized by experimental techniques and density functional theory. A nematic phase, observed experimentally by the formation of a self-assembled monolayer of parallel molecules, is separated from the isotropic state by a continuous transition occurring at a finite density. The precise determination of the critical exponents indicates that the transition belongs to the three-state Potts universality class. The finite-size scaling analysis includes the study of mutability and diversity. These two quantities are derived from information theory and they have not previously been considered as part of the conventional treatment of critical phenomena for the determination of critical exponents. The results obtained here contribute to the understanding of formation processes of self-assembled monolayers, phase transitions, and critical phenomena from novel compression algorithms for studying mutual information in sequences of data.

Simulating the nematic-isotropic phase transition of liquid crystal model via generalized replica-exchange method.

The nematic-isotropic (NI) phase transition of 4-cyano-4'-pentylbiphenyl was simulated using the generalized replica-exchange method (gREM) based on molecular dynamics simulations. The effective temperature is introduced in the gREM, allowing for the enhanced sampling of configurations in the unstable region, which is intrinsic to the first-order phase transition. The sampling performance was analyzed with different system sizes and compared with that of the temperature replica-exchange method (tREM). It was observed that gREM is capable of sampling configurations at sufficient replica-exchange acceptance ratios even around the NI transition temperature. A bimodal distribution of the order parameter at the transition region was found, which is in agreement with the mean-field theory. In contrast, tREM is ineffective around the transition temperature owing to the potential energy gap between the nematic and isotropic phases.

The nematic-isotropic transition of the Lebwohl-Lasher model revisited.

We revisited the nematic-isotropic (NI) transition of the Lebwohl-Lasher lattice model with a detailed investigation of samples containing 200 × 200 × 200 particles. The large-scale Monte Carlo (MC) simulations involved were carried out following the standard Metropolis, as well as the cluster MC Wolff algorithms. A notable free-energy barrier was observed between the isotropic and nematic phase, leading to long-lived metastable states and hysteresis. We provide an improved estimate of the nematic-isotropic transition temperature TNI, of the supercooling and superheating temperatures, of the temperature of divergence of pretransitional effects [Formula: see text] as well as an analysis of the size distribution of the ordered domains above TNI, contributing to a better understanding of this transition of key importance for liquid crystals. This article is part of the theme issue 'Topics in mathematical design of complex materials'.

Experimental evidence of continuous isotropic-nematic phase transition in CdS nanowire nanocomposites of a nematic liquid crystal

ABSTRACT The calamitic nematic liquid crystal generally exhibits a discontinuous weakly first-order isotropic-nematic (I-N) phase transition. We found that, on the incorporation of CdS nanowire in the nematic host, the weakly first-order discontinuous I-N phase transition evolved as a continuous phase transition. The parallel and perpendicular components of dielectric permittivity and bulk conductivity of nanocomposites of CdS nanowires of a nematic liquid crystal (NLC) are found to follow continuous I-N phase transition in contrast to the discontinuous weakly first-order transition of the pure host nematic liquid crystal. This was further confirmed from scattered iGntensity measurements on the CdS nanocomposite samples of nematic liquid crystal in homeotropically aligned cells. Such measurements indicate a continuous phase transition for the nanocomposites of NLC having concentrations less than 0.2 wt% of CdS nanowires in NLC. The dielectric anisotropy, birefringence, threshold voltage of nanocomposites of CdS nanowire in a calamitic nematic liquid crystal with varying concentration of the nanowire have been measured. The ionic conductivity of nanocomposites of CdS nanowires of NLC increases with increasing concentration of CdS nanowires.

Inhomogeneous nematic-isotropic phase transition of a thermotropic liquid crystal doped with iron oxide nanoparticles

We elucidate the local distribution and aggregated structure of iron oxide nanoparticles (IONPs; 6 nm in diameter) doped in the matrix of a nematic liquid crystal (LC), 4-cyano-4'-pentylbiphenyl, utilizing in situ cryogenic transmission electron microscopy and polarized light microscopy. We show that tens of IONPs aggregate into a sphere-like morphology, and the aggregates combine into elongated clusters with a length of hundreds of nm. With the IONP-doped LC matrix confined to a thin glass cell, we study the nematic-isotropic (N-I) phase transition, and suggest that local heterogeneity of LC textures as seen in polarized microscopy is caused by the existence of IONP aggregate clusters. These clusters act also as nuclei for the formation of isotropic domains upon heating.

Validation study of using the free volume approximation to confined thermotropic and lyotropic liquid-crystalline fluids.

We examined the accuracy of the free volume approximation (FVA) to calculate the isotropic-nematic (IN) transition properties of thermotropic and lyotropic rods between two parallel hard walls. This approximation has been proposed to ease the calculation of the confined systems. It approximates the free energy of the confined particles with a bulk free energy. It predicts a special point for these two types of liquid crystals where the first-order IN transition changes to the second one by decreasing either the temperature, the density or the pore width. This prediction is in contradiction (in spite of some qualitative agreement) with those of the other publications where the authors note that the discontinuous transition terminates at the critical point when the walls are completely impenetrable.

Isotropic-nematic transition of self-propelled rods in three dimensions.

Using overdamped Brownian dynamics simulations we investigate the isotropic-nematic (IN) transition of self-propelled rods in three spatial dimensions. For two well-known model systems (Gay-Berne potential and hard spherocylinders) we find that turning on activity moves to higher densities the phase boundary separating an isotropic phase from a (nonpolar) nematic phase. This active IN phase boundary is distinct from the boundary between isotropic and polar-cluster states previously reported in two-dimensional simulation studies and, unlike the latter, is not sensitive to the system size. We thus identify a generic feature of anisotropic active particles in three dimensions.

Phase Separation and Stack Alignment in Aqueous Cellulose Nanocrystal Suspension under Weak Magnetic Field.

Isotropic-nematic (I-N) transitions in cellulose nanocrystal (CNC) suspension and self-assembled structures in the isotropic and nematic phases were investigated using scattering and microscopy methods. A CNC suspension with a mass fraction of 7.4% spontaneously phase separated into an isotropic phase of 6.9% in the top layer and a nematic phase of 7.9% in the bottom layer. In both the phases, the CNC particles formed stacks with an interparticle distance being of ≈37 nm. One-dimensional small-angle neutron scattering (SANS) profiles due to both phases could be fitted using a stacking model considering finite particle sizes. SANS and atomic force microscopy studies indicate that the nematic phase in the bottom layer contains more populations of larger particles. A weak magnetic field of ≈0.5 T was able to induce a preferred orientation of CNC stacks in the nematic phase, with the stack normals being aligned with the field (perpendicular to the long axis of CNC particles). The Hermans orientation parameter, ⟨ P2⟩, was ≈0.5 for the nematic phase; it remained unchanged during the relaxation process of ≈10 h. The fraction of oriented CNC populations decreased during the relaxation; dramatic decrease occurred in the first 3 h. The top layer remained isotropic in the weak field. Polarized microscopy studies revealed that the nematic phase was chiral. Adjacent particles in a stack form a twisting angle of ≈0.6 °, resulting in a helix pitch distance of ≈22 μm.

Phase transitions in a system of long rods on two-dimensional lattices by means of information theory.

The orientational phase transitions that occur in the deposition of longitudinal polymers of length k (in terms of lattice units) are characterized by information theory techniques. We calculate the absolute value of an order parameter δ, which weights the relative orientations of the deposited rods, which varies between 0.0 (random orientation) and 1.0 (fully oriented in either of the two equivalent directions in an L×L square lattice). A Monte Carlo (MC) algorithm is implemented to induce a dynamics allowing for accommodation of the rods for any given density or coverage θ (ratio of the occupied sites over all the sites in the lattice). The files storing δ(t) (with time t measured in MC steps) are then treated by data recognizer wlzip based on data compressor techniques yielding the information content measured by a parameter η(θ). This allows us to recognize two maxima separated by a well-defined minimum for η(θ) provided k≥7. The first maximum is associated with an isotropic-nematic (I-N) phase transition occurring at intermediate density, while the second maximum is associated with some kind of nematic-isotropic transition at high coverage. In the cases of k<7, the curves for η(θ) are almost constant, presenting a very broad maximum which can hardly be associated with a phase transition. The study varies L and k, allowing for a basic scaling of the found critical densities towards the thermodynamic limit. These calculations confirm the tendency obtained by different methods in the case of the intermediate-density I-N phase transition, while this tendency is established here in the case of the high-density phase transition.

Polydispersity reduction of colloidal plates via size fractionation of the isotropic-nematic phase transition.

Controlling the size polydispersity of colloidal particles is important for their phase transitions, resulting structures, and properties. In this study, a fractionation method was established to control the polydispersity of colloidal plates based on the isotropic-nematic (I-N) phase transition. The size ratio of nanoplates between the N phase and the I phase (DN/DI) was relatively large, whereas the size polydispersities in both the N phase and the I phase were smaller than that of the original sample before fractionation. The degree of fractionation was dependent on the time since the phase transition began and the polydispersity of the original sample. A long time resulted in a small DN/DI and a small degree of polydispersity reduction. The experimental data confirmed a quadratic scaling of DN/DI with polydispersity that was predicted by simulations. Large to small particles were segregated sequentially by sedimentation because of self-assembly and gravity. The polydispersity reduction based on the I-N phase transition can be utilized to select nanoplates with a certain size with improved size monodispersity.

Liquid crystal alignment at macroscopically isotropic polymer surfaces: Effect of an isotropic-nematic phase transition.

We study the effect of an isotropic-nematic (I-N) phase transition on the liquid crystal alignment at untreated polymer surfaces. We demonstrate that the pattern at the untreated substrate in the planar cell where the other substrate is uniformly rubbed strongly depends on the temperature gradient across the cell during the I-N phase transition, being macroscopically isotropic if the untreated substrate is cooled faster, but becoming almost homogeneous along the rubbing direction in the opposite temperature gradient. We interpret the observed effect using complementary models of heat transfer and nematic elasticity. Based on the heat transfer model we show that the asymmetric temperature conditions in our experiments provide unidirectional propagation of the I-N interface during the phase transition and determine the initial director orientation pattern at the test's untreated surface. Using the Frank-Oseen model of nematic elasticity, we represent the three-dimensional director field in the nematic cell as a two-dimensional (2D) pattern at the untreated surface and perform 2D numeric simulations. The simulations explain the experimental results: Different initial director orientations at the untreated surface evolve into different stationary patterns.

Aspect Ratio Dependence of Isotropic-Nematic Phase Separation of Nanoplates in Gravity

Abstract We studied isotropic-nematic (I-N) phase separation via gravity sedimentation in suspensions of plate-like colloidal particles of identical thickness but different lateral sizes (diameters). It is well-known that I-N phase transition occurs at a higher concentration for particles with larger aspect ratio (thickness/diameter) than for particles with smaller aspect ratio. Here we report that for the larger aspect ratios of nanoplates, gravity-driven I-N phase separation is faster. In a homogenously mixed I-N biphasic suspension of nanoplates, nematic tactoids nucleate, grow, and then undergo sedimentation in gravity, leading to the formation of a clear horizontal interface between the I and N phase. For I-N coexistent suspension of nanoplates with different aspect ratios but the same amount of nematic fractions, the larger the aspect ratio, the faster the formation of nematic tactoids and interface between isotropic liquid and nematic liquid crystal phase. The tactoid formation rate is governed by the rotational and translational diffusion rates, which are faster at larger aspect ratios. The time required for I-N separation (t*, seconds) varies inversely with the mean aspect ratio (&lt; ξ &gt;) of nanoplates and follows the relation, t * = α &lt; ξ &gt; n , where α = 0.97 ± 1.30 s and n = −2.1 ± 0.2. The phase separation kinetics studied in our experiments offers guidance for the selection of aspect ratio of nanoplates for samples to be studied at the International Space Station (ISS).

Screening out the non-Arrhenius behaviour of nematic-isotropic transition by room temperature ionic liquid.

Differential Scanning Calorimetry (DSC) and optical polarization microscopy of a mixture of the liquid crystalline material (N-(4-methoxybenzylidene)-4-butylaniline, MBBA) and a Fe-based room temperature ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate ([Emim](+) [FeCl4](-), EMIF) indicate a decrease in the nematic-isotropic (N-I) phase transition temperature (T(NI)) with an increase in EMIF concentration, explained by a proposed model of Coulomb "screening" of MBBA quadrupoles by the EMIF ions along with ionic "self screening." DSC studies of EMIF-MBBA and pure EMIF and comparison with pure MBBA results show that the major transitions in pure EMIF have Arrhenius behaviour, but more importantly the previously found convex Arrhenius behaviour of the pristine MBBA [K. Dan et al., Europhys. Lett. 108, 36007 (2014)] becomes Arrhenius in the mixture, indicating a conversion of the entropic N-I activation barrier to an enthalpic one. In presence of EMIF, a drastic decrease in the intensity of out-of-plane distortions of benzene rings in MBBA is found from Fourier transform infrared spectroscopy, consistent with significant reduction in the conformational states of MBBA. This suppression of large amplitude motion is again consistent with a Coulomb screening and gives a molecular basis for the entropic-to-enthalpic conversion of the N-I activation barrier.

Strong Orientational Coupling of Block Copolymer Microdomains to Smectic Layering Revealed by Magnetic Field Alignment.

We elucidate the roles of the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) transitions in the magnetic field directed self-assembly of a liquid crystalline block copolymer (BCP), using in situ X-ray scattering. Cooling into the nematic from the disordered melt yields poorly ordered and weakly aligned BCP microdomains. Continued cooling into the SmA, however, results in an abrupt increase in BCP orientational order with microdomain alignment tightly coupled to the translational order parameter of the smectic layers. These results underscore the significance of the N-SmA transition in generating highly aligned states under magnetic fields in these hierarchically ordered materials.

Entropic screening preserves non-equilibrium nature of nematic phase while enthalpic screening destroys it.

The present manuscript describes the role of entropic and enthalpic forces mediated by organic non-polar (hexane) and polar (methanol) solvents on the bulk and microscopic phase transition of a well known nematic liquid crystalline material MBBA (N-(4-methoxybenzylidene)-4-butylaniline) through Differential Scanning calorimetry (DSC), UV-Visible (UV-Vis), and Fourier Transform Infrared (FTIR) spectroscopy. DSC study indicates continuous linear decreases in both nematic-isotropic (N-I) phase transition temperature and enthalpy of MBBA in presence of hexane while both these parameters show a saturation after an initial decay in methanol. These distinct transitional behaviours were explained in terms of the "depletion force" model for entropic screening in hexane and "screening-self-screening" model for methanol. Heating rate dependent DSC studies find that non-Arrhenius behaviour, characteristic of pristine MBBA and a manifestation of non-equilibrium nature [Dan et al., J. Chem. Phys. 143, 094501 (2015)], is preserved in presence of entropic screening in the hexane solution, while it changes to Arrhenius behaviour (signifying equilibrium behaviour) in presence of enthalpic screening in methanol solution. FTIR spectra show similar dependence on the solvent induced screening in the intensities of the imine (-C = N) stretch and the out-of-plane distortion vibrations of the benzene rings of MBBA with hexane and methanol as in DSC, further establishing our entropic and enthalpic screening models. UV-Vis spectra of the electronic transitions in MBBA as a function of temperature also exhibit different dependences of intensities on the solvent induced screening, and an exponential decrease is observed in presence of hexane while methanol completely changes the nature of interaction to follow a linear dependence.