Nematic-isotropic Transition Research Articles

Textural, thermal, optical and electrical properties of Iron nanoparticles dispersed 4′-(Hexyloxy)-4-biphenylcarbonitrile liquid crystal mixture

ABSTRACTIn this work, the effect of Iron nanoparticles (Fe NPs) dispersion in 4′-(Hexyloxy)-4-biphenylcarbonitrile (6OCB) nematic liquid crystal properties has been studied. Inclusion of Fe NPs (0.25 wt. %) in 6OCB liquid crystal (LC) on textures, isotropic–nematic transition temperature (TI–N), electro-optical and dielectric properties have been investigated in planar aligned cell. The threshold voltage (Vth) and TI–N decrease after dispersion of Fe NPs. Dielectric spectroscopy in nematic phase show that relaxation frequency (fr) also decreases after dispersion of Fe NPs in 6OCB. The observed relaxation mode is due to the flip-flop motion of LC molecules about their short axis. The band gap and AC conductivity in case of 6OCB-Fe sample increase over pure 6OCB sample. A decrease in activation energy is also noticed.

Role of length polydispersity in the phase behavior of freely rotating hard-rectangle fluids.

We use the density-functional formalism, in particular the scaled-particle theory, applied to a length-polydisperse hard-rectangle fluid to study its phase behavior as a function of the mean particle aspect ratio κ_{0} and polydispersity Δ_{0}. The numerical solutions of the coexistence equations are calculated by transforming the original problem with infinite degrees of freedoms to a finite set of equations for the amplitudes of the Fourier expansion of the moments of the density profiles. We divide the study into two parts. The first one is devoted to the calculation of the phase diagrams in the packing fraction η_{0}-κ_{0} plane for a fixed Δ_{0} and selecting parent distribution functions with exponential (the Schulz distribution) or Gaussian decays. In the second part we study the phase behavior in the η_{0}-Δ_{0} plane for fixed κ_{0} while Δ_{0} is changed. We characterize in detail the orientational ordering of particles and the fractionation of different species between the coexisting phases. Also we study the character (second vs first order) of the isotropic-nematic phase transition as a function of polydispersity. We particularly focus on the stability of the tetratic phase as a function of κ_{0} and Δ_{0}. The isotropic-nematic transition becomes strongly of first order when polydispersity is increased: The coexistence gap widens and the location of the tricritical point moves to higher values of κ_{0} while the tetratic phase is slightly destabilized with respect to the nematic one. The results obtained here can be tested in experiments on shaken monolayers of granular rods.

Refractive and birefringent properties of 4-alkyl-4′-oxycyanobiphenyls at direct and reverse phase transitions

ABSTRACTStudies of temperature behavior of the mean refractive index, ordinary and extraordinary refractive indices, and birefringence have been carried out for three nematogens. The thermo-morphologic properties of the biphasic regions of the direct nematic-isotropic liquid and reverse isotropic liquid-nematic phase transitions have been investigated. The 4-n-alkyl-4′-oxycyanobiphenyls (n = 5, 6, 7) were objects of our study. Studies have been carried out for the circular cycle as the heating-cooling. Temperature behavior of the order parameter in nematic mesophase and at the nematic-isotropic liquid and isotropic liquid-nematic phase transition is discussed.

Continuous Isotropic-Nematic Transition in Amyloid Fibril Suspensions Driven by Thermophoresis

The isotropic and nematic (I + N) coexistence for rod-like colloids is a signature of the first-order thermodynamics nature of this phase transition. However, in the case of amyloid fibrils, the biphasic region is too small to be experimentally detected, due to their extremely high aspect ratio. Herein, we study the thermophoretic behaviour of fluorescently labelled β-lactoglobulin amyloid fibrils by inducing a temperature gradient across a microfluidic channel. We discover that fibrils accumulate towards the hot side of the channel at the temperature range studied, thus presenting a negative Soret coefficient. By exploiting this thermophoretic behaviour, we show that it becomes possible to induce a continuous I-N transition with the I and N phases at the extremities of the channel, starting from an initially single N phase, by generating an appropriate concentration gradient along the width of the microchannel. Accordingly, we introduce a new methodology to control liquid crystal phase transitions in anisotropic colloidal suspensions. Because the induced order-order transitions are achieved under stationary conditions, this may have important implications in both applied colloidal science, such as in separation and fractionation of colloids, as well as in fundamental soft condensed matter, by widening the accessibility of target regions in the phase diagrams.

Computer simulation of confined prolate hard spherocylinder liquids between hard walls

ABSTRACTIn present work, using canonical Monte Carlo simulation method, the packing fraction profiles and order parameters of prolate hard spherocylinder (HSC) fluid between hard walls are calculated. The hard particles and hard particle–wall interactions are considered. The confinement effects on transition packing fraction of HSCs with aspect ratios and 5 are calculated. In slit pore, while the bulk packing fraction increases, an orientationally ordered phase can form. We conclude that the required packing fraction for forming liquid crystal phases will decrease in confinement. Also while the molecular anisotropy increases, the isotropic–nematic transition packing fraction will decrease in confinement. We could not find the exact or simulation results for comparison with packing fraction profiles of confined HSCs. The results in the case of confined are compared with the simulation results of confined hard Gaussian overlap fluid of elongation . The results are corresponded, qualitatively. Also the confinement isotropic–nematic transition packing fractions are compared with the simulation and fundamental mixed measure theory (FMMT) results of bulk prolate HSCs.

QSPRs for estimating nematic transition temperatures of pyridine-containing liquid crystalline compounds

ABSTRACTQuantitative structure–property relationships were developed to predict the nematic–isotropic transition temperatures of 92 pyridine-containing liquid crystalline compounds using molecular descriptors calculated by CODESSA software and DRAGON software. The descriptors were also analysed by using principal component analysis. Essentials accounting for a reliable model were all considered carefully during model construction and assessment process. Five variables were selected out by stepwise forward regression analysis and were used as inputs to perform the multiple linear regression, support vector machine and projection pursuit regression (PPR) study. All models were validated through two ways, that is, internal cross-validation combined with a test set. Comparatively, the PPR model performs best both in the fitness and in the prediction capacity. For the test set, it gave a predictive correlation coefficient (R) of 0.991, root mean square error of 11.799 and absolute average relative deviation of 5.456, respectively. The relationships between the descriptors and the nematic–isotropic transition temperature of compounds were also discussed. The odd–even effect in the transition temperatures of mesogens in the same homologous series was also discussed.

Optical reversible behavior of poly(ethylene-b-ethylene oxide) block copolymer dispersed liquid crystal blends

Optical properties of novel polymer dispersed liquid crystal (PDLC) blends based on two different low molecular weight nematic liquid crystals, 4′-(hexyloxy)-4-biphenylcarbonitrile (HOBC) and N-(4-ethoxybenzylidene)-4-butylaniline (EBBA), and poly(ethylene-b-ethylene oxide) block copolymer (PE-b-PEO), were studied to develop optically reversible PDLC blends applying a temperature gradient. Differential scanning calorimetry (DSC) showed that the liquid crystals, HOBC and EBBA, maintain their nematic-isotropic transition in designed PDLC blends, which was visualized by optical microscopy (OM). Results obtained using photoluminescence and UV–vis spectroscopies indicated that HOBC and EBBA liquid crystals maintain their reversible optical behavior passing from opaque to transparent state when temperature gradient was applied. The reversible switching process was proved in four consecutive heating/cooling cycles. Designed thermo-responsive PDLC blends possessed interesting optical properties, which make them potential candidates to be use as temperature sensors or thermo-optical devices.

Demixing by a Nematic Mean Field: Coarse-Grained Simulations of Liquid Crystalline Polymers.

Liquid crystalline polymers exhibit a particular richness of behaviors that stems from their rigidity and their macromolecular nature. On the one hand, the orientational interaction between liquid-crystalline motifs promotes their alignment, thereby leading to the emergence of nematic phases. On the other hand, the large number of configurations associated with polymer chains favors formation of isotropic phases, with chain stiffness becoming the factor that tips the balance. In this work, a soft coarse-grained model is introduced to explore the interplay of chain stiffness, molecular weight and orientational coupling, and their role on the isotropic-nematic transition in homopolymer melts. We also study the structure of polymer mixtures composed of stiff and flexible polymeric molecules. We consider the effects of blend composition, persistence length, molecular weight and orientational coupling strength on the melt structure at the nano- and mesoscopic levels. Conditions are found where the systems separate into two phases, one isotropic and the other nematic. We confirm the existence of non-equilibrium states that exhibit sought-after percolating nematic domains, which are of interest for applications in organic photovoltaic and electronic devices.

Correlation between dielectric properties and phase transitions of 8CB/Sn2P2S6 liquid crystal nanocolloids

The effect of Sn2P2S6 ferroelectric nanoparticles dispersed in 8CB liquid crystal on the dielectric properties of the nanocolloids is studied. The experimental results are discussed by taking into account different effects: the dielectric permittivity contribution of nanoparticles, the effect of permanent polarization of nanoparticles on the liquid crystal order and the anchoring interactions between nanoparticles and liquid crystal molecules. For a homogeneous nanoparticles dispersion, the doped liquid crystal shows an increase of the dielectric anisotropy which is more improved by increasing nanoparticles concentration. For high concentrations, the presence of aggregates decreases the dielectric anisotropy due to a decrease of polarization effect. Near the nematic-isotropic phase transition, the study evidences similar behavior between the shift of the dielectric anisotropy and that of the phase-transition temperature. Near the smectic-A-nematic phase transition, the results show that the shifts of the dielectric anisotropy and of the smectic-A-nematic phase-transition temperature present different behaviors. This difference is interpreted by the coupling between smectic and nematic ordering.

Anisotropic single-particle dissipative particle dynamics model

We have developed a new single-particle dissipative particle dynamics (DPD) model for anisotropic particles with different shapes, e.g., prolate or oblate spheroids. In particular, the conservative and dissipative interactions between anisotropic single DPD particles are formulated using a linear mapping from the isotropic model of spherical particles. The proper mapping operator is constructed between each interacting pair of particles at every time step. Correspondingly, the random forces are properly formulated to satisfy the fluctuation-dissipation theorem (FDT). Notably, the model exactly conserves both linear and angular momentum. We demonstrate the proposed model's accuracy and efficiency by applying it for modeling colloidal ellipsoids. Specifically, we show it efficiently captures the static properties of suspensions of colloidal ellipsoids. The isotropic-nematic transition in an ellipsoidal suspension is reproduced by increasing its volume fraction or the aspect ratio of ellipsoid particles. Moreover, the hydrodynamics and diffusion of a single colloidal ellipsoid (prolate or oblate with moderate aspect ratios) are accurately captured. The calculated drag force on the ellipsoid and its diffusion coefficients (both translational and rotational) agree quantitatively with the theoretical predictions in the Stokes limit.

Thermodynamics of a Compressible Maier-Saupe Model Based on the Self-Consistent Field Theory of Wormlike Polymer.

This paper presents a theoretical formalism for describing systems of semiflexible polymers, which can have density variations due to finite compressibility and exhibit an isotropic-nematic transition. The molecular architecture of the semiflexible polymers is described by a continuum wormlike-chain model. The non-bonded interactions are described through a functional of two collective variables, the local density and local segmental orientation tensor. In particular, the functional depends quadratically on local density-variations and includes a Maier–Saupe-type term to deal with the orientational ordering. The specified density-dependence stems from a free energy expansion, where the free energy of an isotropic and homogeneous homopolymer melt at some fixed density serves as a reference state. Using this framework, a self-consistent field theory is developed, which produces a Helmholtz free energy that can be used for the calculation of the thermodynamics of the system. The thermodynamic properties are analysed as functions of the compressibility of the model, for values of the compressibility realizable in mesoscopic simulations with soft interactions and in actual polymeric materials.

Fluctuation shift of the nematic–isotropic phase transition temperature

A macroscopic counterpart to the microscopic mechanism of the straightening dimer mesogens conformations, proposed recently by S.M. Saliti, M.G. Tamba, S.N. Sprunt, C. Welch, G.H. Mehl, A. Jakli, and J.T. Gleeson [Phys. Rev. Lett. 116, 217801 (2016)] to explain their experimental observation of the unprecedentedly large shift of the nematic–isotropic transition temperature is discussed. The proposed interpretation is based on singular longitudinal fluctuations of the nematic order parameter. Since these fluctuations are governed by the Goldstone director fluctuations, they exist only in the nematic state. External magnetic field suppresses the singular longitudinal fluctuations of the order parameter (similarly as is the case for the transverse director fluctuations, although with a different scaling over the magnetic field). The reduction of the fluctuations changes the equilibrium value of the magnitude of the order parameter in the nematic state. Therefore, it leads to additional (with respect to the mean field contribution) fluctuation shift of the nematic–isotropic transition temperature. Our mechanism works for any nematic liquid crystals, however the magnitude of the fluctuation shift increases with decrease in the Frank elastic moduli. Since some of these moduli supposed to be anomalously small for so-called bent-core or dimer nematic liquid crystals, just these liquid crystals are promising candidates for the observation of the predicted fluctuation shift of the phase transition temperature.

Bistable director alignments of nematic liquid crystals confined in frustrated substrates.

We studied in-plane bistable alignments of nematic liquid crystals confined by two frustrated surfaces by means of Monte Carlo simulations of the Lebwohl-Lasher spin model. The surfaces are prepared with orientational checkerboard patterns, on which the director field is locally anchored to be planar yet orthogonal between the neighboring blocks. We found the director field in the bulk tends to be aligned along the diagonal axes of the checkerboard pattern, as reported experimentally [J.-H. Kim et al., Appl. Phys. Lett. 78, 3055 (2001)APPLAB0003-695110.1063/1.1371246]. The energy barrier between the two stable orientations is increased, when the system is brought to the isotropic-nematic transition temperature. Based on an elastic theory, we found that the bistability is attributed to the spatial modulation of the director field near the frustrated surfaces. As the block size is increased and/or the elastic modulus is reduced, the degree of the director inhomogeneity is increased, enlarging the energy barrier. We also found that the switching rate between the stable states is decreased when the block size is comparable to the cell thickness.

3A04 液晶の光相転移による逆オパールの光学特性の変化(フォトニクス・光デバイス)

3A04 液晶の光相転移による逆オパールの光学特性の変化(フォトニクス・光デバイス)

Cyanobiphenyl-based liquid crystal dimers and the twist-bend nematic phase

ABSTRACTThe synthesis and characterisation of several members of the 1,ω-bis(4-cyanobiphenyl-4′-yl) alkane (CBnCB) and the 1-(4-cyanobiphenyl-4′-yloxy)-ω-(4-cyanobiphenyl-4′-yl) alkane (CBnOCB) homologous series are reported. The new odd members described CB5CB, CB13CB, CB4OCB, CB8OCB and CB10OCB all exhibit twist-bend nematic and nematic phases. The members of these series already reported in literature, CB7CB, CB9CB, CB11CB and CB6OCB, were also prepared in order to allow for a direct comparison of their transitional properties. The properties of these dimers are also compared to those of the corresponding members of the 1,ω-bis(4-cyanobiphenyl-4,-yloxy) alkanes (CBOnOCB). For any given total spacer length, for odd members of these series, the nematic–isotropic transition temperatures and associated entropy changes are greatest for the CBOnOCB dimer and lowest for the CBnCB dimer. These trends are understood in terms of molecular shape. For short spacer lengths, the twist-bend nematic–nematic transition temperature (TNTBN) is higher for the CBnOCB series than for the CBnCB series but this is reversed as the spacer length increases. Of the CBOnOCB dimers, a virtual value of TNTBN was estimated for CBO3OCB and TNTBN was measured for CBO5OCB. These values are considerably lower than those observed for the corresponding members of the CBnCB or CBnOCB series. The dependence of TNTBN on molecular structure is discussed not only in terms of the molecular curvature but also in the ability of the molecules to pack efficiently. As the temperature range of the preceding nematic phase increases, so the twist-bend nematic–nematic transition entropy change decreases and the transition approaches second order for the longer spacers. For comparative purposes, the transitional behaviour of the even-membered dimers CB6CB, CB5OCB and CBO4OCB is reported and differences accounted for in terms of molecular shape.

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.

Textures and shapes in nematic elastomers under the action of dopant concentration gradients.

We explore a novel strategy of patterning nematic elastomers that does not require inscribing the texture directly. It is based on varying the dopant concentration that, beside shifting the phase transition point, affects the nematic director field via coupling between the gradients of concentration and nematic order parameter. Rotation of the director around a point dopant source causes topological modification manifesting itself in a change of the number of defects. A variety of shapes, dependent on the dopant distribution, are obtained by anisotropic deformation following the nematic-isotropic transition.

NMR of molecular endofullerenes dissolved in a nematic liquid crystal.

We report the NMR of the molecular endofullerenes H2@C60, H2O@C60 and HF@C60 dissolved in the nematic liquid crystal N-(4-methoxybenzylidene)-4-butylaniline (MBBA). The 1H NMR lines of H2 and H2O display a doublet splitting due to residual dipole-dipole coupling. The dipolar splitting depends on temperature in the nematic phase and vanishes above the nematic-isotropic phase transition. The 19F spectrum of HF@C60 dissolved in MBBA displays a doublet splitting in the nematic phase, with contributions from the 1H-19F dipole-dipole coupling and J-coupling. The phenomena are analyzed using a model in which the fullerene cages acquire a geometrical distortion, either through interaction with the liquid crystal environment, or through their interaction with the endohedral molecules. The distorted cages become partially oriented with respect to the liquid crystal director, and the endohedral molecules become partially oriented with respect to the distorted cages.

A phenomenological order approach to the volume phase transition in microgel particles.

We proposed a model to describe the volume phase transition of microgel particles, based on constitutive relations that consider the mechano-chemical coupling of deformation and solvency processes, as well as the phenomenological cooperative effect of molecular orientation of solvatable segments in the particles. We regard a nematic-isotropic like transition and define a tensor order parameter allowing analysis of the collective behaviour of water solvation mechanisms based on the Landau-De Gennes theory for liquid crystal elastomers. A complementary approach to the energy balance density is obtained with the order parameter field considering the deformation by a continuum mechanics approximation; our approach aims to extend the comprehensive understanding of the elastic behaviour and water sorption related phenomena in microgel particles. With the proposed model, we reproduce the behaviour of swelling curves through a volume phase transition of thermosensitive microgel particles by assessing characteristic parameters belonging to particular physical properties. The parameters defined within the model such as elastic and solvency related constants and characteristic temperatures were obtained by fitting of a data set mimicking the experimentally observed swelling behaviour. The obtained values of the parameters were consistent with the discussed phenomenology which shows the importance of molecular ordering interpretation as a source to describe the volume phase transition in microgel particles.

Analysis of morphological behaviour and electro-optical properties of silica nanoparticles doped polymer dispersed liquid crystal composites

We have prepared silica nanoparticles (SNPs) doped polymer dispersed liquid crystal (PDLC) composites by using varying concentrations of SNPs. The varying concentration of SNPs has a profound impact on the morphology and electro-optical properties of PDLC. The polarizing optical microscopy (POM) studies revealed a substantial non- homogeneity/dual sized droplet morphology in the LC droplet size induced by the SNPs. The relative transmission was enhanced in the SNP-PDLC composites as compared to the undoped PDLC. The threshold voltage (Vth) of the doped composites decreased as compared to the undoped PDLC but increasing SNP concentration had a slight impact on the threshold voltage (Vth) as well as transmission. The effect of SNPs on nematic-isotropic transition temperature (TN-I) and ionic conductivity was also clarified.