Non-uniformities in polymer/liquid crystal mixtures

We theoretically model the nucleation of nematic droplets during phase ordering in mixtures of a flexible polymer and a low-molecular-weight liquid crystal. By appealing to classical nucleation theory (CNT), we calculate the energy barrier to nucleation and the size of a critical nucleus. We study the influence of a metastable intermediate phase on the nucleation of the nematic. Below a triple point in the phase diagram, there are two distinct mechanisms for the formation of a nematic nucleus: 1) direct nucleation from the isotropic phase and 2) nucleation via a precursor metastable isotropic phase. We calculate the crossover concentration as a function of temperature, delineating the regions of the phase diagram in which each mechanism prevails. In the latter case, the presence of a hidden metastable isotropic-isotropic binodal may either promote or delay the nucleation of a nematic phase. Received 9 August 2002 RID="a" ID="a"e-mail: matuyama@chem.mie-u.ac.jp     

Influence of a random field on particle fractionation and solidification in liquid-crystal colloid mixtures

The influence of a random-anisotropy (RA) type disorder on the phase separation of nematogen-colloid mixtures is studied theoretically by combining the phenomenological Landau-de Gennes, Carnahan-Starling, and hard-sphere crystal theories. We assume that the colloids enforce the RA disorder on the surrounding thermotropic liquid-crystal (LC) molecules. We adopt the Imry-Ma argument according to which the lower-temperature phase exhibits a domain-type pattern. The colloids impose a finite degree of orientational ordering even in the isotropic (paranematic) phase. In the ordered phase they give rise to a domain-type structure, resulting in the distorted nematic (speronematic) phase. The RA field opposes the phase separation tendency. With increasing disorder the difference between the paranematic and speronematic ordering decreases. Consequently there is a critical disorder, above which both phases become identical from the orientation point of view, but have different concentrations of colloids. We have also estimated another characteristic value of disorder above which the isotropic phase can exist only in a liquid state, the crystal phase being suppressed completely.     

The Effect of Sphere Size on the Phase Behaviors in the Rod and Sphere Mixture System

The addition of polysaccharides, such as chondroitin sulfate (Chs), to the aqueous suspension of tobacco mosaic virus (TMV) results in the TMV aggregation at very dilute TMV concentration compared with the addition of polyethylene oxide (PEO). The Chs chain has a semirigid nature, whereas the PEO has a flexible nature. In this study, we investigated the effect of the size of spherical polymer coils on the phase behaviors in the mixtures of rods and spheres using Monte Carlo simulations. As a model for TMV, we used the spherocylinder particle. The Chs and PEO chains were simplified to spherical particles having different sizes. With the addition of large spherical particles, the system changed from miscible phase to isotropic–isotropic phase separation and then isotropic–nematic phase separation states, whereas with the addition of small spherical particles, the system transformed from miscible isotropic phase to miscible nematic phase. We found that the sphere size had an important influence on the phase behaviors in the mixtures of rods and spheres.     

DNA Intercalation in Neutral Multilamellar Membranes: Experiments and Theory

We report both an experimental and a theoretical work on the effect of confinement on a biological polymer (DNA) incorporated to multilamellar phase. We can see that even when no electrostatic interaction are involved this semi-flexible polymer can be incorporated in between the membranes. X-ray provides experimental evidence for the existence of a mixed DNA/Phospholipid structure. The nature of the DNA ordering is briefly described. A theoretical model is developed to describe the phase diagram. We emphasize the role of the isotropic/nematic transition of the DNA molecules to explain the ability to confine DNA in membranes.     

Liquid-crystalline phase behavior of a colloidal rod-plate mixture

The phase behavior of rod-plate mixtures was investigated using model systems containing unambiguously rod- and plate-shaped colloids. We find that the theoretically disputed biaxial nematic phase is unstable with respect to demixing into an isotropic and two uniaxial nematic phases. The phase behavior at very high densities is exceptionally rich and includes the coexistence of up to four different liquid crystalline phases, which stem from the coupling between the employed particle shapes and polydispersity.     

Phase transitions in binary mixtures of rodlike colloids and stiff polymers

A suspension of long rodlike colloids and long stiff polymers is modelled as a mixture of hard rods. The diameter of the colloid particle is finite, while the polymer is considered in the limit of zero diameter. Two types of first-order phase transition may occur in such mixtures: an isotropic-nematic phase transition if the density (or the pressure) is high enough, and a demixing transition involving two isotropic phases. The demixing transition has a critical point, and a triple point with one nematic and two isotropic phases may also exist. Phase diagrams are calculated. For the demixing isotropic-isotropic transition to be observed the ratio between the polymer length and the colloid length must exceed 0.36.     

Entropically driven formation of hierarchically ordered nanocomposites

Using theoretical models, we undertake the first investigation into the rich behavior that emerges when binary particle mixtures are blended with microphase-separating copolymers. We isolate an example of coupled self-assembly in such materials, where the system undergoes a nanoscale ordering of the particles along with a phase transformation in the copolymer matrix. Furthermore, the self-assembly is driven by entropic effects involving all the different components. The results reveal that entropy can be exploited to create highly ordered nanocomposites with potentially unique electronic and photonic properties.     

Free energy of semiflexible polymers and structure of interfaces

The free energy of semiflexible polymers is calculated as a functional of the compositional scalar order parameter and the orientational order parameter of second-rank tensor S_ij on the basis of a microscopic model of wormlike chains with variable segment lengths. We use a density functional theory and a gradient expansion to evaluate the entropic part of the free energy, which is given in a power series of .The interaction term of the free energy is derived with a random phase approximation. For the rigid rod limit, the nematic-isotropic transition point is given by , N and w being the degree of polymerization and the anisotropic interaction parameter, respectively, and the degree of ordering at the transition point is 0.33448. We also find that the contour length of polymer chains becomes larger in a nematic phase than in an isotropic phase. Interface profiles are obtained numerically for some typical cases. In the neighborhood of isotropic-isotropic interfaces, polymer chains tend to align parallel to the interface on the polymer-rich side and perpendicular on the poor side. When an isotropic region and a nematic region coexist, orientational order parallel to the interface is preferred in the nematic region. Received: 28 May 1998 / Revised: 12 August 1998 / Accepted: 8 September 1998     

Pyroelectric investigation of the surface polarization in the isotropic phase of a nematic liquid crystal

Measurements of the temperature dependence of the pyroelectric coefficients in cells with homeotropic and planar boundary conditions were performed in order to study the surface polarization and determine its nature in the isotropic phase of a nematic liquid crystal. Analysis of these data established that the ordering polarization arising as a result of the nonuniformity of the order parameter in the near-boundary region of the liquid crystal and the polar monolayer due to the bifilar properties of the molecules of the liquid crystal at the boundary with the solid wall of the cell are responsible for the surface polarization in the isotropic phase of a nematic liquid crystal. The values of the pyroelectric coefficients of monolayers and the coefficients of the ordering polarization for planar and homeotropic orientations are estimated.     

Formation of a grating of submicron nematic layers by photopolymerization of nematic-containing mixtures

A submicron, spatially periodic, structure consisting of a sequence of oriented layers of a nematic liquid crystal (NLC), separated by isotropic polymeric walls, was obtained experimentally. This was accomplished by polymerization induced by the interference pattern of UV laser radiation in a NLC-containing prepolymer mixture. It was established that such a structure occurs when phase separation and nematic ordering are prevented during the polymerization process. These structures are the diffraction elements, whose efficiency is much greater than that of a standard grating of polymer-dispersed liquid crystals [1–4] which is obtained in the same initial mixture. Specifically, a diffraction efficiency of 60–70% was obtained for structures with the period Δ = 0.2 μm, even in mixtures where a grating with Δ < 6 μm cannot be obtained at all by the standard technique.     

Entropy driven demixing in binary mixtures of hard convex bodies: influence of molecular geometry

The recently introduced approach (Bosetti, H., and Perera, A., 2001, Phys. Rev. E, 63, 021206) for studying entropy driven demixing in binary mixtures of hard convex bodies is applied here to analyse the influence of molecular geometrical factors such as shape and size ratio on isotropic fluid-fluid phase separation. The theory is shown to be self-consistent, in the sense that it allows the calculation of both the binodal and the spinodal of the demixing, and both curves merge at the same lower consolute point. In the case of 3-dimensional fluids, demixing is usually allowed for sufficiently thick solutes, provided no orientational ordering destabilizes the mixture. Fluid—fluid demixing is explicitly forbidden in cases of equal breadth of the solute and the solvent molecules, regardless of the aspect ratio of both particles. In particular, mixtures of prolate and oblate particles will demix more easily. The influence of shape is more importantly seen at moderate elongations. Finally, within the present approximation, demixing is forbidden for binary mixtures of 2-dimensional fluids, irrespective of the shape of the bidimensional molecules.     

Electro-optical Kerr effect in the isotropic phase of the two antiferroelectric liquid crystal mixtures

We have experimentally studied for the first time the electro-optical Kerr effect and the pre-transitional behavior in the isotropic phase of two antiferroelectric liquid crystal mixtures, W-232 and W-204D, composed of rod-like ester molecules exhibiting the direct smectic-A to isotropic (SmA-I) phase transition. The Kerr law has been confirmed for the two compounds and the variation of inverse Kerr constant with temperature above the smectic–isotropic transition temperatures were determined. Both the mixtures with very broad antiferroelectric phase around room temperature have similar sequence of the phases (i.e., Cr-SmC*A-SmC*-SmA-I). Although, the pre-transitional behavior is usually complex in the isotropic phase of the chiral smectic liquid crystal compounds, the investigated compounds showed a similar behavior compared to that of nematic–isotropic behavior.     

Effects of Field Orientation on the Driven Lattice Gas

Steady states of the driven lattice gas (DLG) on triangular, hexagonal and square lattices with the field at several fixed orientations to the principal lattice vectors were studied by Monte Carlo simulation. In most cases a strong field suppressed change to a low-temperature ordered phase. On each lattice, one field orientation that caused nonequilibrium ordering was identified. On triangular and hexagonal lattices, dependence of energy and anisotropy on field strength was studied at those orientations. Anisotropic ordering along the field developed at intermediate temperatures under weak fields. Partial ordering along the field persisted to low temperature under strong fields.     

The comparison of the ability for induction of antiferroelectric phase of cyanoterminated compounds by means of miscibility studies

Ability for an induction of the antiferroelectric phase in compounds with a cyano group in a terminal position has been tested by comparison of phase diagrams of their mixtures. Most of the tested compounds do not cause the induction by themselves but they support an antiferroelectric ordering in mixtures. The core comprising biphenylate fragment has a higher tendency to support the antiferroelectric order.     

The effect of stiffness in wormlike micelles

The effect of stiffness in a 2D living polymer system is investigated by Monte-Carlo simulation in a canonical ensemble. As the flexibility decreases, the mean chain contour length decreases and goes through a local maximum. The mean end to end square distance shows a non-monotonic behaviour due to the coil-to-rod transition and the decrease in chain contour length. Near the maximum of chain ordering in the bulk, the chain length distribution adapts itself to increase the configurational entropy. With the parameters used in this simulation, it seems that the effect of the stiffness for high stiffness is to decrease as in the isotropic case, since the ordering decreases again. Received: 16 September 1997 / Revised: 27 June 1998 / Accepted: 29 June 1998     

The frozen state in the liquid phase of side-chain liquid-crystal polymers

Quenched isotropic melts of side-chain liquid-crystal polymers reveal surprisingly an anisotropic polymer conformation. This small-angle neutron-scattering (SANS) result is consistent with the identification of a macroscopic, solidlike response in the isotropic phase. Both experiments (rheology and SANS) indicate that the polymer system appears frozen on millimeter length scales and at the time scales of the observation. This result implies that the flow behavior is not the terminal behavior and that cross-links or entanglements are not a necessary condition to provide elasticity in melts.     

Burning rates of turbulent iso-octane aerosol mixtures in spherical flame explosions

Experimental studies of aerosol combustion under quiescent and turbulence conditions have been conducted to quantify the differences in the flame structure and burning rates between aerosol and gaseous mixtures. Turbulence was generated by variable speed fans to yield rms turbulence velocities between 0.5 and 4.0 m/s and this was uniform and isotropic. Homogeneously distributed and near monodispersed iso-octane-air aerosol clouds were generated using a thermodynamic condensation method. Spherically expanding flames, following central ignition, at near atmospheric pressures were employed to quantify the flame structure and propagation rate. The effects of the diameter of fine fuel droplets on flame propagation were investigated. It is suggested that the inertia of fuel droplets is an important cause of flame enhancement during early flame development. During later stages, cellular flame instability and the effective, gaseous phase, equivalence ratio becomes important. The latter effect leads has increases the flame speed of rich mixtures, but decreases that of lean ones. Droplet enhancement of burning velocity can be significant at low turbulence but is negligible at high turbulence.     

Demixed and ordered phases in hard-rod mixtures

We analyse demixing and ordering transitions in systems of hard cylindrical particles. The second virial approximation of Onsager and a bifurcation analysis, as introduced by Koda and Kimura, are used to evaluate the free energies, pressures, and density distribution functions in mixtures of equally long but differently wide cylinders. The spatial density distribution along the one relevant coordinate is of particular importance as it provides more detailed information concerning the nature of the phase transition than the bare bifurcation diagnosis. Detailed results are given for the nematic–nematic spinodal and the nematic–smectic transitions. Allowing for the absence of an isotropic phase, our results are in good qualitative agreement with those for freely orienting rods reported previously, and indicate a complex sequence of phase diagrams as the diameter dissimilarity of the two components is increased, with upper and lower critical points bounding nematic and smectic demixing regions. However, experimental results on colloidal rods show that nematic demixing occurs at a diameter ratio much smaller than ours or those for freely rotating fluids, indicating that Onsager-type theories may be insufficient to reproduce this phenomenon in a quantitative manner and, consequently, that more sophisticated approaches, presumably incorporating particle flexibility and additional interactions, are required.     

Kinetics of phase separation in polymer mixtures

Characteristic features of the liquid-liquid phase separation process in polymer systems are presented, followed by a concise review of existing studies on phase-separation kinetics in polymer solutions and mixtures. Brief discussions have been made on two selective topics in this field, i.e., applicability of Cahn's linearized theory for spinodal decomposition to polymer mixtures and the scaling law in the late stage of phase separation.     

X-ray scattering from polymer nematic liquid crystals

X-ray scattering from main chain polymer nematics is discussed from the point of view of its use in studying the ordering and fluctuations of the polymer chains that make up the nematic phase. An example of data from poly-γ-benzyl glutamate is given, with a discussion of the important features of the data, in terms of the current understanding of the nature of nematic ordering in main chain polymer systems. This includes analyses of the angular distribution function for the polymer segments, long wavelength fluctuations dictated by elastic phenomena, the effects of finite chain lengths, and effects due to the short range interactions and packing of the chains.