Isotropic-nematic Research Articles

Entropic Wetting and the Free Isotropic−Nematic Interface of Hard Colloidal Platelets

We study bulk and interfacial properties of a model suspension of hard colloidal platelets with continuous orientations and vanishing thickness using both density functional theory, based on either a second virial approach or fundamental measure theory (FMT), and Monte Carlo (MC) simulations. We calculate the bulk equation of state, bulk isotropic-nematic (IN) coexistence, and properties of the (planar) free IN interface and of adsorption at a planar hard wall, where we find complete wetting of the nematic phase at the isotropic-wall interface upon approaching bulk IN coexistence. We investigate in detail the asymptotic decay of correlations at large distances. In all cases, the results from FMT and MC agree quantitatively. Our findings are of direct relevance to understanding interfacial properties of dispersions of colloidal platelets.

Phase equilibria and phase separation dynamics in a polymer composite containing a main‐chain liquid crystalline polymer

AbstractVarious topological phase diagrams of blends of main‐chain liquid crystalline polymer (MCLCP) and flexible polymer have been established theoretically in the framework of Matsuyama–Kato theory by combining Flory–Huggins (FH) free energy for isotropic mixing, Maier–Saupe (MS) free energy for nematic ordering in the constituent MCLCP, and free energy pertaining to polymer chain‐rigidity. As a scouting study, various phase diagrams of binary flexible polymer blends have been solved self‐consistently that reveal a combined lower critical solution temperature (LCST) and upper critical solution temperature (UCST), including an hourglass phase diagram. The calculated phase diagrams exhibit liquidus and solidus lines along with a nematic–isotropic (NI) transition of the constituent MCLCP. Depending on the strengths of the FH interaction parameters and the anisotropic (nematic–nematic) interaction parameters, the self‐consistent solution reveals an hourglass type phase diagram overlapping with the NI transition of the constituent MCLCP. Subsequently, thermodynamic parameters estimated from the phase diagrams hitherto established have been employed in the numerical computation to elucidate phase separation dynamics and morphology evolution accompanying thermal‐quench induced phase separation of the MCLCP/polymer mixture. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3621‐3630, 2006

Shear mechanical anisotropy of side chain liquid-crystal elastomers: Influence of sample preparation

We study the mechanical anisotropy of a series of uniaxial side chain nematic elastomers prepared with the same chemical composition but with different preparation protocols. For all the compounds, the experiments performed as a function of temperature show no discontinuity in both G' (//) and G' ( perpendicular) (the labels // and perpendicular stand for the director parallel, respectively perpendicular to the shear displacement) around the nematic-isotropic (N-I) phase transition temperature determined by DSC. They also all show a small decrease in G' (//) starting at temperatures well above this temperature (from approximately 4( degrees ) C to approximately 20( degrees ) C depending on the compound studied) and leading to a small hydrodynamic value of the G' ( perpendicular)/G' (//) ratio. The measurements taken as a function of frequency show that the second plateau in G' (//) and the associated dip in G (//)" expected from dynamic semi-soft elasticity are not observed. These results can be described by the de Gennes model, which predicts small elastic anisotropy in the hydrodynamic and linear regimes. They correspond to the behavior expected for compounds beyond the mechanical critical point, which is consistent with the NMR and specific heat measurements taken on similar compounds. We also show that a reduction in the cross-linking density does not change the non-soft character of the mechanical response. From the measurements taken as a function of frequency at several temperatures we deduce that the time-temperature superposition method does not apply. From these measurements, we also determine the temperature dependence of the longest relaxation time tau(E) of the network for the situations where the director is either parallel or perpendicular to the shear velocity. Finally, we discuss the influence on the measurements of the mechanical constraint associated with the fact that the samples cannot change their shape around the pseudo phase transition, because of their strong adherence on the sample-bearing glass slides.

Phase Behaviour and Structure of Weakly Perturbed Liquid Crystals

ABSTRACT We study influence of a weak disorder on 1st and 2nd order phase transitions in which a continuous symmetry is broken. As illustrative cases we choose the isotropic-nematic (I-N) and nematic-smectic A (N-SmA) liquid crystal phase transitions. We yield an explanation for the established domain pattern and estimate the phase behaviour as a function of the disorder strength.

Power law relaxation and glassy dynamics in Lebwohl-Lasher model near the isotropic-nematic phase transition

Orientational dynamics in a liquid crystalline system near the isotropic-nematic (IN) phase transition is studied using molecular dynamics simulations of the well-known Lebwohl-Lasher model. As the IN transition temperature is approached from the isotropic side, we find that the decay of the orientational time correlation functions (OTCF) slows down noticeably, giving rise to a power law decay at intermediate time scales. The angular velocity time correlation function also exhibits a rather pronounced power law decay near the IN boundary. In the mean squared angular displacement at comparable time scales, we observe the emergence of a subdiffusive regime which is followed by a superdiffusive regime before the onset of the long-time diffusive behavior. We observe signature of dynamical heterogeneity through pronounced non-Gaussian behavior in orientational motion particularly at lower temperatures. This behavior closely resembles what is usually observed in supercooled liquids. We obtain the free energy as a function of orientational order parameter by the use of the transition matrix Monte Carlo method. The free energy surface is flat for the system considered here and the barrier between isotropic and nematic phases is vanishingly small for this weakly first-order phase transition, hence allowing large scale, collective, and correlated orientational density fluctuations. This might be responsible for the observed power law decay of the OTCFs.

Molecular dynamics simulations of nanoparticles in dense isotropic nematogens: The role of matrix-induced long-range repulsive interactions

We have carried out molecular dynamics simulation studies of binary mixtures of spherical nanoparticles (NPs) in a matrix of dense isotropic rod-shaped nematogens, with the size of the nematogen length being similar to that of the NP diameter. NPs at even low concentrations were found to shift the isotropic-nematic (I-N) transition significantly to higher pressure at a given temperature, indicative of long-range perturbation of the nematogenic matrix by the NPs. The NPs were found to be dispersed in the dense isotropic nematogenic matrix over a wide range of NP concentrations due to long-range (compared with the molecular size of the nematogens) repulsion caused by NP-induced local order fluctuations and reduced local orientational correlation in the isotropic nematogenic matrix, in contrast to the phase separation predicted and observed in other studies where the particles were much larger or smaller than the nematogens. Furthermore, since the repulsion observed in the NP-nematogen mixtures is only microscopically long range (on the order of about ten molecular lengths of the nematogens), globally ordered clustering observed in mixtures of colloidal particles in nematic matrices resulting from macroscopically long-range interaction is not observed in our simulations.

Pretransitional behavior in the isotropic phase of a nematic liquid crystal with the transverse permanent dipole moment

The results presented give the evidence for the quasicritical, pretransitional behavior of dielectric properties in the isotropic phase of a rodlike nematic liquid crystal with the transverse permanent dipole moment. Studies were conducted in 2-cyano-4-pentylbiphenyl 4-(trans-4-pentylcyclohexyl) benzoate, focusing on the static-and ionic-dominated low-frequency (LF) regions. For the static dielectric permittivity [epsilon(')(T)] the application of the derivative analysis revealed the pretransitional anomaly associated with the specific heat exponent alpha approximately 0.5. For the LF domain the contribution to epsilon(')(T) from residual ionic impurities follows a linear temperature dependence on approaching the isotropic-nematic (I-N) transition. This dependence and pretransitional anomalies of electric conductivity and dielectric modulus can be associated with the influence of prenematic fluctuations. "Linear" dielectric studies were supported by the static nonlinear dielectric effect measurements, which delivered reliable estimations of the temperature of the hypothetical continuous phase transition T(*) and the discontinuity of the I-N transition DeltaT approximately 1.7 K.

Vibrational and orientational relaxations in complex liquids: The case of ME6N liquid crystal in the isotropic phase

In the context of the dynamical characterisation of liquid systems, in this paper we critically compare methodological approaches formulated for the determination of the dynamics in complex molecular liquids. We will show that the experimental vibrational relaxation of the ν(CN) mode of the ME6N liquid crystal in the isotropic phase is successfully reproduced, at long times ( t > 3 ps), by the non-Markovian modelling of the perturbation modulation proposed by Rothschild et al.. The non-hydrodynamic behavior of the orientational relaxation times obtained for the same normal mode confirms the picture of pseudo-nematic domains persisting in the isotropic phase of this liquid crystal well above the nematic–isotropic (N-I) transition. Finally, the comparison of the time and frequency domain methods for the determination of dynamical parameters indicates their qualitative equivalence.

Isotropic–nematic transition in liquid crystals confined between rough walls

The effect of rough walls on the phase behaviour of a confined liquid crystal (LC) fluid is studied using constant pressure Monte Carlo simulations. The LC is modelled as a fluid of soft ellipsoidal molecules and the rough walls are represented as a hard wall with a number of molecules randomly embedded in them. It is found that the isotropic–nematic (IN) transition is shifted to higher pressures for rougher walls.

Structure and Thermodynamics of Weakly Segregated Rod−Coil Block Copolymers

The self-assembly of a series of monodisperse rod−coil block copolymers is studied in the weak segregation limit. This unusual weakly segregated system consists of polyisoprene (PI) coil blocks and poly(alkoxyphenylene vinylene) (PPV) rod blocks solubilized with alkoxy side groups. The order to microphase disorder transition (ODT) and nematic isotropic (NI) transition are experimentally investigated to produce a rod−coil block copolymer phase diagram in a system that follows polymeric scaling relationships. Small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), polarized optical microscopy, depolarized light scattering, and wide-angle X-ray scattering (WAXS) are used to map the phase diagram. As the symmetric diblock copolymer is heated, a series of transitions from lamellar to nematic to isotropic phases are observed. The NI transition temperature decreases with increasing coil fraction, and at high coil fractions only an isotropic phase is observable. The phase behavior is in qualitative agreement with weak segregation calculations based on Landau expansions reported by other groups. Transmission electron microscopy (TEM) reveals unusual grain structures in the low-temperature lamellar phase. The high bending energy of the rod microdomains results in lamellae with long persistence lengths and grain boundaries defined by broken lamellae. Changes in domain spacing with temperature suggest rod rearrangements within the lamellar phase.

Effect of aerosil dispersions on the nematic-to-isotropic interface

The effect of silica aerosils on the kinetics of the first-order nematic-isotropic (NI) phase transition is phenomenologically described in the framework of the time-dependent Landau-Ginzburg equation. A steady-state solution to the equation is presented such that the NI interface may propagate with a solitary-like wave profile under constant quenching. The results provide a plausible basis for the interpretation of the dynamical effects of quenched disorder in the liquid-crystal systems, caused by randomly interconnected porous media, such as aerosils. In the low silica aerosil rho(s) ( < or =0.1 g/cm;3) regime, the calculated values of the interface velocity v(T,rho(s)), the interface thickness kappa(T,rho(s)), and the critical radius of a spherical nucleus of new nematic phase in a bulk isotropic environment, composed of polar molecules, such as 4-n-octyl- 4(')- cyanobiphenyl and 4-n-heptyl- 4(')- cyanobiphenyl shows that the effect of silica aerosils on the kinetics is reflected in a shifting of the set of temperature-dependent curves to lower temperature values.-1.

Phase behavior and interfacial properties of nonadditive mixtures of Onsager rods

Within a second virial theory, we study bulk phase diagrams as well as the free planar isotropic-nematic interface of binary mixtures of nonadditive thin and thick hard rods. For species of the same type, the excluded volume is determined only by the dimensions of the particles, whereas for dissimilar ones it is taken to be larger or smaller than that, giving rise to a nonadditivity that can be positive or negative. We argue that such a nonadditivity can result from modeling of soft interactions as effective hard-core interactions. The nonadditivity enhances or reduces the fractionation at isotropic-nematic (IN) coexistence and may induce or suppress a demixing of the high-density nematic phase into two nematic phases of different composition (N(1) and N(2)), depending on whether the nonadditivity is positive or negative. The interfacial tension between coexisting isotropic and nematic phases shows an increase with increasing fractionation at the IN interface, and complete wetting of the IN(2) interface by the N(1) phase upon approach of the triple-point coexistence. In all explored cases bulk and interfacial properties of the nonadditive mixtures exhibit a striking and quite unexpected similarity with the properties of additive mixtures of different diameter ratio.

Anomalous viscoelasticity near the isotropic-nematic phase transition in liquid crystals.

Recent optical Kerr effect experiments have shown that orientational relaxation of nematogens shows a pronounced slow down of the response function at intermediate times and also a power law decay near the isotropic-nematic (I-N) transition. In many aspects, this behavior appears to be rather similar to the ones observed in the supercooled liquid near-glass transition. We have performed molecular dynamics simulations of model nematogens (Gay-Berne with aspect ratio 3) to explore the viscoelasticity near the I-N transition and also investigated the correlation of viscoelasticity (if any) with orientational relaxation. It is found that although the viscosity indeed undergoes a somewhat sharper than normal change near the I-N transition, it is not characterized by any divergence-like behavior (like the ones observed in the supercooled liquid). The rotational friction, on the other hand, shows a much sharper rise as the I-N transition is approached. Interestingly, the probability distribution of the amplitude of the three components of the stress tensor shows anisotropy near the I-N transition-similar anisotropy has also been seen in the deeply supercooled liquid. Frequency dependence of viscosity shows several unusual behaviors: (a) There is a weak, power law dependence on frequency [eta(')(omega) approximately omega(-alpha)] at low frequencies and (b) there is a rapid increase in the sharp peak observed in eta(')(omega) in the intermediate frequency on approach to the I-N transition density. These features can be explained from the stress-stress time correlation function. The angular velocity correlation function also exhibits a power law decay in time. The reason for this is discussed.

Influence of a long-chain alkane on the photoinduced nematic-isotropic transition.

We investigated the phenomenon of photoinduced nematic-isotropic (N-I) transition for different concentrations of a long-chain alkane, viz., octadecane (OD), and a host liquid crystalline material having a small quantity (4.5 mol %) of a photoactive azo compound. As expected, the N-I transition temperature diminishes with increasing concentration of OD. Data of time-resolved measurements of the dielectric constant through both the UV-activated trans-cis transformation and the thermal back relaxation process are presented. With increasing concentration of OD, although the response time for the former process increases slightly by less than a factor of 2, the thermal back relaxation shows a greater increase by more than an order of magnitude. As a possible explanation for this surprising result, we discuss an argument based on the structural incompatibility of the constituents of the system investigated.

Interaction of colloids with a nematic-isotropic interface.

The Landau-de Gennes free energy is used to calculate the interaction between long cylindrical colloids and the nematic-isotropic (NI) interface. This interaction has two contributions: one is specific of liquid crystals and results from the deformation of the director field close to the particles or to the interface, while the other is generic and results from wetting and surface tension effects. Deep in the nematic phase the director field of long cylindrical colloids, with strong homeotropic anchoring, exhibits two half-integer defect lines. As the colloid moves towards the interface, the director configuration changes through a series of discontinuous transitions, where one or two of the defects are annihilated. In addition, the NI interface bends towards the colloid in order to minimize the elastic free energy in the nematic. In the isotropic phase, the colloid is surrounded by a thin nematic layer that reduces the surface free energy under favorable wetting conditions. The interaction has a well-defined minimum near the interface. In this region the director and interfacial structures are complex and cannot be described analytically. Using the numerical results for the Landau-de Gennes free energy in the harmonic region, we obtained simple scaling laws for the (linear) force on the colloid.

Effect of silica aerosils on the nematic to isotropic transition: A theoretical treatment.

The effect of silica aerosils on a first-order nematic-isotropic (NI) transition temperature shift DeltaT(NI)(rho(s)) and on the enthalpy jump DeltaH(rho(s)) is phenomenologically described in the framework of the Landau-de Gennes theory. It is shown that the aerosil network dispersed in the liquid crystal phase creates an additional curvature perturbation, resulting in linear and nonlinear slopes both in the transition temperature shift DeltaT(NI)(rho(s))=-T(NI)(0)alpharho(s) and in the enthalpy jump DeltaH(rho(s))=1 / 4DeltaH(0)(1+sqrt[1-kapparho(s)])(2)(1-alpharho(s)), where rho(s) is the aerosil density, and both alpha and kappa are constants of the theory. In the low rho(s)(</=0.2 g/cm(3)) regime, both the calculated and the measured values of DeltaH(rho(s)) for polar liquid crystals, such as 4-n-octyl-4(')-cyanobiphenyl (8CB) and 4-n-heptyl-4(')-cyanobiphenyl (7CB) show a good agreement between theory and experiment. The comparisons between the calculated and measured values of DeltaT(NI)(rho(s)), in the low-rho(s) regime, show a better agreement in the 7CB+aerosil than in the 8CB+aerosil systems.

Thermal and optical study of the kinetics of the nematic-isotropic transition in octylcyanobiphenyl

It is shown in this paper that the kinetics of the nematic-isotropic (NI) transition in 30-microm-thick octylcyanobiphenyl liquid crystal films is strongly affected by the cell walls. We have found that this is due to the modification of the wetting properties of the liquid crystal depending on the surface treatment. The results have been obtained with an experimental setup which allows the simultaneous high resolution study of the sample thermal properties and texture evolution with temperature. An accurate determination of the width of the two phase coexistence region associated with the NI transition has been possible and it is shown that it is affected by the presence of a surfactant. The results have been interpreted with a simple model which is based on the possible presence of a well-defined interface between the nematic and the isotropic phases in the coexistence region, which depends not only on the thermal gradients in the sample but also on the surface treatments.

Magnetic-field-induced changes of the isotropic-nematic phase transition in side-chain polymer liquid crystals.

The isotropic-nematic (I-N) phase transition of side-chain polymer liquid crystals is intrinsically a weak first-order transition with a biphasic region spread over a wide temperature interval. In the presence of high magnetic fields we find the I-N transition to become a strong first order. The I-N biphasic region shrinks its temperature window as larger magnetic fields are applied, until it completely disappears and the transition completes at a fixed temperature. We interpret this behavior as a consequence of the nonlinear coupling of the magnetic field to the system free energy, via the suppression of the order fluctuations in the nematic mesophase at the I-N transition crossing.

New types of phase behaviour in binary mixtures of hard rod-like particles

The phase behaviour of binary mixtures of hard rod-like particles has been studied using Parsons—Lee theory (Parsons, J. D., 1979, Phys. Rev. A, 19, 1225); Lee, S. D., 1987, J. Chem. Phys., 87, 4972). The stability of the isotropic-nematic (I-N) transition with respect to isotropic—isotropic (I-I), and nematic—nematic (N-N) demixing is investigated. The individual components in the mixtures are modelled as hard cylinders of diameters Di and lengths Li (i = 1,2). The aspect ratios ki = Li/Di of the components are kept fixed (with values of k 1 = 15 and k 2 = 150), and the phase behaviour of the mixtures is studied for varying diameter ratios d = D 1/D 2. When the diameter ratio is relatively large, e.g., for values of d = 50, component 1 may be considered a large colloidal particle, while the second component plays the role of a weakly interacting solvent. This mixture exhibits only an I-N phase transition which is driven by the excluded volume interaction between the large particles (no I-I or N-N demixing is seen). A decrease in the diameter ratio enhances the contribution of the smaller component to the free energy (especially in terms of the unlike excluded volume term), and I-I as well as N-N demixing transitions are observed. The character of the N-N transition is rather unusual, a single region bounded by a lower critical point (in the pressure—composition plane) is seen for a diameter ratio of d = 3.2, while two demixed nematic regions bounded by lower and upper critical points are observed for d = 3.13. A further decrease in the diameter ratio (e.g., to d = 3) leads to systems with a phase behaviour in which the two demixed N-N regions meet, giving rise to a large demixed region with very strong fractionation in composition, and no N-N critical points. The I-I demixing transition is always accompanied by a lower critical point and occurs for systems with intermediate size (diameter) ratios. A diameter ratio of d = 4.5 corresponds to systems with significant like and unlike excluded volume interactions, and in this case the I-N transition takes place over the whole composition range with weak fractionation and one azeotropic point. Surprisingly, the coexisting nematic phase is of lower packing fraction than the isotropic phase for some of the compositions, i.e., an inversion of packing fraction takes place. In addition to this, the longer rods can be less ordered that the shorter rods for certain values of the composition.

Observation of surface and bulk phase transitions in nematic liquid crystals.

The behaviour of liquid crystal (LC) molecules near a surface is of both fundamental and technological interest: it gives rise to various surface phase-transition and wetting phenomena, and surface-induced ordering of the LC molecules is integral to the operation of LC displays. Here we report the observation of a pure isotropic-nematic (IN) surface phase transition-clearly separated from the bulk IN transition-in a nematic LC on a substrate. Differences in phase behaviour between surface and bulk are expected, but have hitherto proved difficult to distinguish, owing in part to the close proximity of their transition temperatures. We have overcome these difficulties by using a mixture of nematic LCs: small, surface-induced composition variations lead to complete separation of the surface and bulk transitions, which we then study independently as a function of substrate and applied magnetic field. We find the surface IN transition to be of first order on surfaces with a weak anchoring energy and continuous on surfaces with a strong anchoring. We show that the presence of high magnetic fields does not change the surface IN transition temperature, whereas the bulk IN transition temperature increases with field. We attribute this to the interaction energy between the surface and bulk phases, which is tuned by magnetic-field-induced order in the surface-wetting layer.