A single-site anisotropic soft-core model for the study of phase behavior of soft rodlike particles

A novel mesoscopic simulation model is proposed to study the liquid crystal phase behavior of the anisotropic rodlike particles with a soft repulsive interaction,which possesses a modified anisotropic conservative force type used in dissipative particle dynamics.The influences of the repulsion strength and the particle shape on the phase behavior of soft rodlike particles are examined.In the simulations,we observe the formation of the nematic phase and smectic-A phase from the initially isotropic phase.More...     

Smectic, nematic, and isotropic phases in binary mixtures of thin and thick hard spherocylinders

A second-virial Onsager theory, based on Parsons-Lee rescaling and suitably extended to deal with multicomponent systems and smectic phases, has been used to calculate the phase diagram of a collection of binary mixtures of thin and thick hard spherocylinders. In particular, two types of phase diagrams are investigated. First, a number of binary mixtures where the two components have the same total length have been considered; in addition, the phase diagram of a binary mixture where the two components have the same volume has been calculated. For the particles of one of the two components, the length of the cylindrical part and the diameter have always been set equal to 5 and 1, respectively. Spherocylinders of the same total length and different diameter tend to demix considerably as soon as the diameter ratio deviates from unity. This happens especially at high pressures, when at least the phase richer in the thicker component is smectic. In the case where the two components have equal volumes, demixing is further increased due to the disparity not only in particle diameter but also in particle lengths. The incorporation of inhomogeneous layered phases is seen to alter significantly the phase diagrams calculated if only homogeneous phases are allowed, since transitions to a smectic phase often preempt those to a nematic or an isotropic phase. The apparent versatility of the recent experimental techniques suggests that the phase diagram features predicted by the theory might be also observed in real systems.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

 用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

Phase and orientational ordering of low molecular weight rod molecules in a quenched liquid crystalline polymer matrix with mobile side chains

We study the phase diagram and orientational ordering of guest liquid crystalline (LC) rods immersed in a quenched host made of a liquid crystalline polymer (LCP) matrix with mobile side chains. The LCP matrix lies below the glass transition of the polymer backbone. The side chains are mobile and can align to the guest rod molecules in a plane normal to the local LCP chain contour. A field theoretic formulation for this system is proposed and the effects of the LCP matrix on LC ordering are determined numerically. We obtain simple analytical equations for the nematic/isotropic phase diagram boundaries. Our calculation show a nematic-nematic (N/N) first order transition from a guest stabilized to a guest-host stabilized region and the possibility of a reentrant transition from a guest stabilized nematic region to a host only stabilized regime separated by an isotropic phase. A detailed study of thermodynamic variables and interactions on orientational ordering and phases is carried out and the relevance of our predictions to experiments and computer simulations is presented.     

Phase behavior of polarizable spherocylinders in external fields

Applied electric fields are known to induce significant changes in the properties of systems of polarizable molecules or particles. For rod-shaped molecules, the field-induced behavior can be rather surprising, as in the case of the negative electric birefringence of concentrated solutions of rodlike polyelectrolytes. We have investigated the interplay of shape anisotropy and field-induced anisotropy in molecular dynamics simulations of systems of polarizable soft spherocylinders in an electric field, in the limit of infinitely anisotropic polarizability, taking full account of mutual induction effects. We find a novel crystalline structure (K(2)) in the high-field limit, whose formation is driven by interactions between induced dipoles. For high pressures, the phase diagram exhibits a polar nematic phase between the hexagonal close-packed crystal phase and the K(2) phase. We also compare this system with an analogous system of spherocylinders with permanent electric dipoles and find that qualitatively similar behavior is obtained in the limit of strong coupling of the permanent dipoles to the external field.     

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.     

Pair formation and global ordering of strongly interacting ferrocolloid mixtures: an integral equation study

Using the reference hypernetted chain (RHNC) integral equation theory and an accompanying stability analysis we investigate the structural and phase behaviors of model bidisperse ferrocolloids based on correlations of the homogeneous isotropic high-temperature phase. Our model consists of two species of dipolar hard spheres (DHSs) which dipole moments are proportional to the particle volume. At small packing fractions our results indicate the onset of chain formation, where the (more strongly coupled) A species behaves essentially as a one-component DHS fluid in a background of B particles. At high packing fractions, on the other hand, the RHNC theory indicates the appearance of isotropic-to-ferromagnetic transitions (volume ratios close to one) and demixing transitions (smaller volume ratios). However, contrary with the related case of monodisperse DHS mixtures previously studied by us [Phys. Rev. E 70, 031201 (2004)], none of the present bidisperse systems exhibit demixing within the isotropic phase, rather we observe coupled ferromagnetic/demixing phase transitions.     

聚苯撑苯并二噻唑的甲基磺酸溶液的相转变过程及其动力学研究

用退偏振光强度法及偏光显微镜研究了溶致性液晶高分子聚苯撑苯并二噻唑的甲基磺酸溶液(PBT/MSA)由液晶相至各向同性相(N→I转变),及由各向同性相至液晶相(I→N转变)的相变过程.液晶相的形成(I→N)服从Av-rami方程,Avrami指数为1左右,表明该体系的液晶相是以一维棒状方式形成的.相转变温度与浓度有关,提高温度可加速在应力下液晶相长程有序结构的形成.     

Theory of volume phase transitions of side-chain liquid crystalline gels

We present a mean field theory to describe volume phase transitions of side-chain liquid crystalline gels. Three different uniaxial nematic phases (N(1), N(2), and N(3)) are defined by using orientational order parameter S(m) of side-chain liquid crystals (mesogens) and S(b) of backbone chains. We derive the free energy for the three nematic phases of side-chain liquid crystalline gels dissolved in isotropic solvents and calculate the swelling curve of the gel, the order parameters of a backbone chain and of side-chain liquid crystals, and the deformation of the gel as a function of temperature and an electric field. We find isotropic-nematic (N(1), N(2), and N(3)) and N(1)N(2) phase transitions of the gels, depending on the interaction between a backbone chain and a side-chain liquid crystal.     

Density-functional study of model bidisperse ferrocolloids in an external magnetic field

We present phase diagrams of a model bidisperse ferrocolloid consisting of a binary mixture of dipolar hard spheres (DHSs) under the influence of an external magnetic field. The dipole moments of the particles are chosen proportional to the particle volume to mimic real ferrocolloids, and we focus on dipole-dominated systems where isotropic attractive interactions are absent. Our results are based on density-functional theory in the modified mean-field (MMF) approximation. For one-component DHS fluids in external fields, and for corresponding mixtures dominated by one of the components, MMF theory predicts the tricritical point of the transition between an isotropic gas and a ferromagnetic liquid occurring at zero field to be changed into a critical point separating two magnetically ordered phases of different density. The corresponding critical temperature displays a nonmonotonic dependence on the field strength. Completely different behavior is found for the critical temperature related to the demixing phase transitions appearing in strongly asymmetric mixtures [G. M. Range and S. H. L. Klapp, Phys. Rev. E 70, 061407 (2004)]. For such systems, we find a monotonic decrease of the demixing critical temperature with increasing field. The field strength dependence of the critical temperature can therefore be tuned between nonmonotonic and monotonic behaviors just by changing the composition of the mixture--e.g., by adjusting the chemical potentials. This allows us to efficiently control the influence of external magnetic fields on the phase behavior over a large temperature interval.     

Phase equilibria and photopolymerisation-induced phase transitions of mesogenic diacrylate monomer and low molecular mass liquid crystal mixture

Experimental phase diagrams of binary mesogenic mixtures of reactive mesogenic diacrylate (RM257) monomer and low molar mass liquid crystals (E7) were determined by means of differential scanning calorimetry and optical microscopy. The combined free energy densities of Flory–Huggins for liquid–liquid demixing, Maier–Saupe for nematic ordering, and phase field free energy for crystal solidification was proposed to describe the phase diagrams of the starting E7/RM257 mixtures. The phase diagram thus constructed is an ideal mixing type, exhibiting a narrow loop of isotropic + nematic (I + N) coexistence region followed by the crystal + nematic (Cr1 + N) region in descending order of temperature. Of particular interest is the permanent fixation of the mesophase structures upon photopolymerisation of neat RM257 in the corresponding nematic and crystalline phases. Upon photopolymerisation of a low RM257 content mixture in both isotropic and nematic states, the nematic–isotropic transition of E7 was found to persist. The permanent structural anchoring is seen upon photo-curing of the 90/10 RM257/E7 mixture in the crystalline state.     

Induced smectic phases in phase diagrams of binary nematic liquid crystal mixtures

To elucidate induced smectic A and smectic B phases in binary nematic liquid crystal mixtures, a generalized thermodynamic model has been developed in the framework of a combined Flory-Huggins free energy for isotropic mixing, Maier-Saupe free energy for orientational ordering, McMillan free energy for smectic ordering, Chandrasekhar-Clark free energy for hexagonal ordering, and phase field free energy for crystal solidification. Although nematic constituents have no smectic phase, the complexation between these constituent liquid crystal molecules in their mixture resulted in a more stable ordered phase such as smectic A or B phases. Various phase transitions of crystal-smectic, smectic-nematic, and nematic-isotropic phases have been determined by minimizing the above combined free energies with respect to each order parameter of these mesophases. By changing the strengths of anisotropic interaction and hexagonal interaction parameters, the present model captures the induced smectic A or smectic B phases of the binary nematic mixtures. Of particular importance is the fact that the calculated phase diagrams show remarkable agreement with the experimental phase diagrams of binary nematic liquid crystal mixtures involving induced smectic A or induced smectic B phase.     

Morphology of polymer networks polymerized in highly ordered liquid crystalline phases

The morphology and optical properties of polymer stabilized liquid crystals formed in a more highly ordered low molecular weight liquid crystal solvent were studied. Tetrafunctional, mesogenic monomers (with and without flexible spacers) were polymerized in isotropic, nematic and smectic phases of the LC solvent (4′-octyl-4-cyanobiphenyl) and studied with scanning electron microscopy and cross-polarized light microscopy. The network morphology of the nematic and isotropic phase polymerizations showed strong similarities with the corresponding polymerizations in other solvents. Polymerization in the smectic phase, however, resulted in marked increases in network order and directionality. Most dramatically, even the polymer without flexible spacer formed a fibrous network of rodlike units, in contrast to the random, beaded texture formed by the same polymer in nematic or isotropic conditions. Correspondingly, a large increase in birefringence demonstrated significant polymer orientation and more effective orientational interaction with the liquid crystalline solvent.     

Density functional theory of freezing of a system of conjugated oligomers parameterised via Gay–Berne potential

Density functional theory (DFT) of freezing is used to study the isotropic–nematic, isotropic–smectic A and nematic–smectic A phase transitions in a system of large, semi-flexible conjugated oligomers parameterised within Gay–Berne (GB) potential. The pair correlation functions of the isotropic fluid, used as structural inputs in the DFT, are calculated by solving the Percus–Yevick integral equation theory. Large number of spherical harmonic coefficients of each orientation-dependent functions has been considered to ensure the numerical accuracy at different densities and temperatures for the system of these model GB ellipsoids having large aspect ratio (length-to-breadth ratio). We found that the system of GB ellipsoids parameterised for conjugated oligomers shows stable isotropic, nematic and smectic A phases. At low temperatures, on increasing the density, isotropic fluid makes a direct transition to smectic A phase. Nematic phase get stabilised in between the isotropic and smectic A phases on increasing the temperature. Using the transition parameter obtained through the DFT, we have plotted the temperature–density and pressure–temperature phase diagrams which are found to be qualitatively similar to the one obtained in simulations for the systems with low aspect ratio GB particles.     

The role of attractive interactions in rod-sphere mixtures

We present a computer simulation study of binary mixtures of prolate Gay-Berne particles and Lennard-Jones spheres. Results are presented for three such rod-sphere systems which differ from each other only in the interaction between unlike particles. Both the mixing-demixing behavior and the transitions between the isotropic and any liquid crystalline phases are studied for each system, as a function of temperature and concentration ratio. For systems which show macroscopic demixing, the rod-sphere interaction is shown to give direct control over interfacial anchoring properties, giving rise to the possibility of micellar phase formation in the case of homeotropic anchoring. Additionally, it is shown that on incorporating high concentrations of spheres into a system of rods with weak demixing properties, microphase-separated structures can be induced, including bicontinuous and lamellar arrangements.     

Mesoscale constitutive modeling of magnetic dispersions

A constitutive model for dispersions of acicular magnetic particles has been developed by modeling the particles as rigid dumbbells dispersed in a solvent. The effects of Brownian motion, anisotropic hydrodynamic drag, a steric force in the form of the Maier-Saupe potential, and, most importantly, a mean-field magnetic potential are included in the model. The development is similar to previous models for liquid-crystalline polymers. The model predicts multiple orientational states for the dispersion, and this phase behavior is described in terms of an orientational order parameter S and an average alignment parameter J; the latter is introduced because the magnetic particles have distinguishable direction due to polarity. A transition from isotropic to nematic phases at equilibrium is predicted. Multiple nematic phases-both prolate and oblate-are predicted in the presence of steady shear flow and external magnetic field parallel to the flow. The effect of increasing magnetic interparticle interactions and particle concentration is also presented. Comparisons with experimental data for the steady shear viscosity show very good agreement.     

Theory of a helicoidal cholesteric phase induced by an external field

We present a mean field theory to describe a helicoidal cholesteric phase for mixtures of a chiral nematic liquid crystal (LC) and a polymer chain as well as for pure chiral nematic LC molecules in the presence of a longitudinal external field parallel to the pitch axis of a cholesteric (Ch) phase. The free energy of the helicoidal Ch phase (Ch_H) is derived as a function of a usual orientational order parameter and an order parameter of the Ch_H phase. On increasing the strength of the external field, we find that the Ch phase changes to the nematic (N) phase through the Ch_H phase. Depending on the temperature and the strength of the external field, we find the second-order N–Ch_H and Ch_H–Ch phase transitions and the first-order paranematic (pN)–N, pN–Ch_H and pN–Ch phase transitions. We also predict phase diagrams in mixtures of a flexible polymer and a Ch LC molecule under the external field.     

The effect of surface treatment on the alignment and phase transition of a polypeptide liquid crystal

Poly(γ-benzyl-L-glutamate) (PBLG), was utilized as a surface coating agent in order to obtain parallel molecular orientation in thin layers of PBLG liquid-crystalline solutions confined between coated surfaces. It was found that in a thickness range much larger than the cholesteric pitch value, the texture was predominantly planar cholesteric. At film thickness comparable or smaller than the pitch, isotropic spherulites developed from a homeotropic nematic phase. Because of the coupling between the solution concentration and nematic director, as well as large differences in the elastic moduli of PBLG liquid-crystalline solutions, the long-range intermolecular interaction was unfavorable. Competition between parallel orientation induced by the surface coating of PBLG and inherent perpendicular orientation induced by PBLG molecules in the bulk would favor a short-range helix-coil transition mechanism, which results into a reentrant isotropic phase.     

Coupling of the phase and relaxation transitions in polymer mixtures

The coupling and the competition of two phase transitions (demixing and crystallization) and the coupling of both demixing and vitrification are investigated during phase transformations under far-from-equilibrium conditions. The coupling leads to formation of the different non-equilibrium morphologies and to kinetic pecularities of phase transformations.