Nematic Suspensions Research Articles

Generalized Swift-Hohenberg models for dense active suspensions.

In describing the physics of living organisms, a mathematical theory that captures the generic ordering principles of intracellular and multicellular dynamics is essential for distinguishing between universal and system-specific features. Here, we compare two recently proposed nonlinear high-order continuum models for active polar and nematic suspensions, which aim to describe collective migration in dense cell assemblies and the ordering processes in ATP-driven microtubule-kinesin networks, respectively. We discuss the phase diagrams of the two models and relate their predictions to recent experiments. The satisfactory agreement with existing experimental data lends support to the hypothesis that non-equilibrium pattern formation phenomena in a wide range of active systems can be described within the same class of higher-order partial differential equations.

Twist-Bend Stage in the Relaxation of Sheared Chiral Nematic Suspensions of Cellulose Nanocrystals.

Aqueous suspensions of cellulose nanocrystals (CNCs), prepared from natural cellulose by sulfuric acid hydrolysis, form stable chiral nematic suspensions above a critical CNC concentration. The chiral nematic organization may be preserved in films prepared from the suspensions by evaporation. However, shrinkage, gelation, and shear during film formation impair the optical properties of the dry film. In this article, we report an unusual behavior for a sample in which gelation occurred before the sample reached iridescent pitch values. In attempting to decouple changes in texture due to evaporation from those due to shear relaxation effects for this sample, we observed a transitory nematic-like texture that was induced by shear during the preparation of the sample for polarized light microscopy. We propose that the transition between chiral nematic and nematic structures involves a twist–bend-like intermediate and not an untwisting of the chiral nematic phase.

Synchronized oscillations of dimers in biphasic charged fd-virus suspensions.

Micron-sized colloidal spheres that are dispersed in an isotropic-nematic biphasic host suspension of charged rods (fd-virus particles) are shown to spontaneously form dimers, which exhibit a synchronized oscillatory motion. Dimer formation is not observed in the monophase of isotropic and nematic suspensions. The synchronized oscillations of dimers are connected to the inhomogeneous state of the host suspension of charged rods (fdviruses) where nematic domains are in coexistence with isotropic regions. The synchronization of oscillations occurs in bulk states, in the absence of an external field. With a low field strength of an applied electric field, the synchronization is rather reduced, but it recovers again when the field is turned off. In this Rapid Communication, we report this observation as an example of the strange attractor, occurring in the mixture of PS (polystyrene) dimers in an isotropic-nematic coexistence biphasic fd-virus network. Furthermore, we highlight that the synchronization of PS-dimer oscillations is the result of a global bifurcation diagram, driven by a delicate balance between the short-attractive "twisted" interaction of PS dimers and long-ranged electrostatic repulsive interactions of charged fd rods. The interest is then in the local enhancement of "twist-nematic" elasticity in reorientation of the dimer oscillations. An analysis of image-time correlations is provided with the data movies and Fourier transforms of averaged orientations for the synchronized oscillations of dimers in the biphasic I-N coexistence concentration of charged fd-virus suspensions.

Stability and Orientational Order of Gold Nanorods in Nematic Suspensions: A Small Angle X-ray Scattering Study

Stable suspensions of gold nanorods in 4-cyano-4′-pentylbiphenyl (5CB) have been prepared by capping the nanoparticles with polyethylene glycol (PEG). Small angle X-ray scattering has been used to characterize the orientational order of the gold nanorods and the properties of any aggregates. It was found that the nanorods had a very high degree of orientational order with respect to the director of the 5CB matrix and this could be redirected by an applied electric field at 2kHz. Two different PEG molecular weights were investigated and it was found that the lower (1.9kDa) gave exceptionally high order parameters, above 0.9.

Kinetic attractor phase diagrams of active nematic suspensions: the dilute regime.

Large-scale simulations by the authors of the kinetic-hydrodynamic equations for active polar nematics revealed a variety of spatio-temporal attractors, including steady and unsteady, banded (1d) and cellular (2d) spatial patterns. These particle scale activation-induced attractors arise at dilute nanorod volume fractions where the passive equilibrium phase is isotropic, whereas all previous model simulations have focused on the semi-dilute, nematic equilibrium regime and mostly on low-moment orientation tensor and polarity vector models. Here we extend our previous results to complete attractor phase diagrams for active nematics, with and without an explicit polar potential, to map out novel spatial and dynamic transitions, and to identify some new attractors, over the parameter space of dilute nanorod volume fraction and nanorod activation strength. The particle-scale activation parameter corresponds experimentally to a tunable force dipole strength (so-called pushers with propulsion from the rod tail) generated by active rod macromolecules, e.g., catalysis with the solvent phase, ATP-induced propulsion, or light-activated propulsion. The simulations allow 2d spatial variations in all flow and orientational variables and full spherical orientational degrees of freedom; the attractors correspond to numerical integration of a coupled system of 125 nonlinear PDEs in 2d plus time. The phase diagrams with and without the polar interaction potential are remarkably similar, implying that polar interactions among the rodlike particles are not essential to long-range spatial and temporal correlations in flow, polarity, and nematic order. As a general rule, above a threshold, low volume fractions induce 1d banded patterns, whereas higher yet still dilute volume fractions yield 2d patterns. Again as a general rule, varying activation strength at fixed volume fraction induces novel dynamic transitions. First, stationary patterns saturate the instability of the isotropic state, consisting of discrete 1d banded or 2d cellular patterns depending on nanorod volume fraction. Increasing activation strength further induces a sequence of attractor bifurcations, including oscillations superimposed on the 1d and 2d stationary patterns, a uniform translational motion of 1d and 2d oscillating patterns, and periodic switching between 1d and 2d patterns. These results imply that active macromolecular suspensions are capable of long-range spatial and dynamic organization at isotropic equilibrium concentrations, provided particle-scale activation is sufficiently strong.

Near equilibrium dynamics and one-dimensional spatial—temporal structures of polar active liquid crystals

We systematically explore near equilibrium, flow-driven, and flow-activity coupled dynamics of polar active liquid crystals using a continuum model. Firstly, we re-derive the hydrodynamic model to ensure the thermodynamic laws are obeyed and elastic stresses and forces are consistently accounted. We then carry out a linear stability analysis about constant steady states to study near equilibrium dynamics around the steady states, revealing long-wave instability inherent in this model system and how active parameters in the model affect the instability. We then study model predictions for one-dimensional (1D) spatial—temporal structures of active liquid crystals in a channel subject to physical boundary conditions. We discuss the model prediction in two selected regimes, one is the viscous stress dominated regime, also known as the flow-driven regime, while the other is the full regime, in which all active mechanisms are included. In the viscous stress dominated regime, the polarity vector is driven by the prescribed flow field. Dynamics depend sensitively on the physical boundary condition and the type of the driven flow field. Bulk-dominated temporal periodic states and spatially homogeneous states are possible under weak anchoring conditions while spatially inhomogeneous states exist under strong anchoring conditions. In the full model, flow-orientation interaction generates a host of planar as well as out-of-plane spatial—temporal structures related to the spontaneous flows due to the molecular self-propelled motion. These results provide contact with the recent literature on active nematic suspensions. In addition, symmetry breaking patterns emerge as the additional active viscous stress due to the polarity vector is included in the force balance. The inertia effect is found to limit the long-time survival of spatial structures to those with small wave numbers, i.e., an asymptotic coarsening to long wave structures. A rich set of mechanisms for generating and limiting the flow structures as well as the spatial—temporal structures predicted by the model are displayed.

Optimized combination of intrinsic and form birefringence in oriented LaPO4 nanorod assemblies

The birefringence of colloidal nematic suspensions and thin films of aligned LaPO4 nanorods is quantitatively studied. Single crystalline hexagonal hydrated-LaPO4 nanorods are synthesized with the c-axis along the rod long dimension. Films are prepared on a glass substrate by blade coating deposition from concentrated colloidal suspensions of rods, allowing for their alignment through the effect of shear stress. The obtained material exhibits a high degree of rod alignment and a resulting high birefringence (Δn ≈ 0.13). This remarkable value is shown to result from the optimized combination of both the intrinsic birefringence originating from the rod crystalline anisotropy and the form birefringence due to the high rod aspect ratio. The birefringence is measured over the spectral range between 250 nm and 2000 nm and is found to be almost constant while the material transmittance is close to unity. In the highly oriented soft state of colloidal rod suspension, the form birefringence, although reduced by a weakened refractive index contrast between the rods and the surrounding medium (solvent), still provides a significant contribution to the overall birefringence which can be exploited in electro-optical devices.

Formation of chiral nematic films from cellulose nanocrystal suspensions is a two-stage process.

The evaporation of aqueous suspensions of cellulose nanocrystals (CNCs) gives iridescent chiral nematic films with reflection colors at visible wavelengths. A key problem is controlling the chiral nematic pitch, P, and hence the reflection colors of CNC films. By adding D-(+)-glucose to the suspension, we show that the change in P during evaporation occurs in two distinct stages. The first stage is the decrease in P as the concentration of CNC in the chiral nematic suspension increases due to evaporation; the addition of glucose causes a decrease in P at this stage. In a second stage, a concentration of CNC is reached where the formation of ordered gels and glasses prevents further major changes in P. The addition of glucose lowers the CNC concentration at which this occurs, leading to an increase in P and hence an overall shift to the red end of the spectrum in the final film.

X-ray scattering in the vorticity direction and rheometry from confined fluids.

An X-ray flexure-based microgap rheometer (X-FMR) has been designed for combining rheology and in situ small-angle X-ray scattering from the vorticity plane. The gap distance can be varied continuously from 500 μm down to several μm, which provides the unique possibility to generate a strong confinement for many complex fluids. A singular advantage of this setup is the possibility to directly probe the vorticity direction of the flow field with a microfocus X-ray beam and to probe the structural response of the fluid to combined shear and confinement in the vorticity plane. The sliding-plate setup operates over a wide range of shear rates of γ = 10(-3)-10(3) s(-1) and strains in the range of 10(-4)-10(2). The flexure-based bearing maintains the plate parallelism within 10(-5) rad. The X-FMR requires very small sample volumes on the order of 10 μl. The applicability of the device is demonstrated here with limited examples of a nematic suspension of fd virus (rods), and a crystalline suspension containing sterically stabilized polystyrene-butylacrylate latex particles.

Effect of BaTiO<sub>3</sub> Nanoparticle on Electro-Optical Properties of Polymer Dispersed Liquid Crystal Displays

Ferro nematic suspensions are the prominent materials to enhance the electro optical performance of liquid crystal displays. Electro optical properties of polymer dispersed liquid crystal (PDLC) display with the introduction of Barium Titanate nanoparticles have been investigated in this article and it is shown that there is a considerable enhancement in electro-optical response of the displays. The nanoparticles lower the switch-on electric field and thereby increase the optical transmission at certain voltages of the displays. The electro-optical characteristics of the PDLC cells were investigated with a He-Ne laser followed by MatLab calculations.

Electric-Field Alignment of Chitin Nanorod–Siloxane Oligomer Reactive Suspensions

Uniaxially anisotropic chitin-silica nanocomposite solids have been obtained thanks to the electric field-induced macroscopic alignment of liquid-crystalline reactive cosuspensions. We demonstrate how chitin nanorods (260 nm long, 23 nm thick) can be aligned upon the application of an alternating current (ac) electric field, and within water-ethanol suspensions containing reactive siloxane oligomers (D(h) ∼ 3 nm). The alignment at the millimeter length scale is monitored by in situ small-angle X-ray scattering (SAXS) and polarized light optical microscopy. The composition and state (isotropic, chiral nematic) of the cosuspensions are proven to be determining factors. For nematic phases, the alignment is preserved when the electric field is switched off. Further solvent evaporation induces sol-gel transition, and uniaxially anisotropic chitin-silica nanocomposites are formed after complete drying of the aligned nematic suspensions. Here, the collective response of colloidal mesophases to external electric fields and the subsequent formation of ordered nanocomposite solids would represent a new opportunity for materials design.

Nanocrystalline cellulose for covert optical encryption

Nanocrystalline cellulose (NCC) solid films derived from spruce pulp exhibit iridescence when cast from chiral nematic aqueous phase suspensions of the nanocrystals. The iridescence has potential for overt encryption as an anti-counterfeiting measure and also offers an intrinsic level of covert encryption since films of NCC reflect left-circularly polarized light. Addition of TINOPAL, an optical brightening agent (OBA), adds a third level of (covert) encryption potential since the chromophore exhibits strong fluorescence when excited with ultraviolet (UV) light. The overall result is a selectively polarizing fluorescent iridescent film. We examined the impact of additions of OBA on NCC iridescence, optical activity, and physical structure variation with polarized optical microscopy, circular dichroism (CD) spectropolarimetry, and zeta potential analysis. Increasing OBA additions increase the chiral nematic pitch of NCC films and alter chiral nematic domain structure in the solid film. Under low-concentration conditions, OBA yields intense UV fluorescence without compromising the visible light iridescent properties of the film. The potential security offered by the NCC film can be authenticated using a UV light source, a circular polarizer in conjunction with an iridescent feature that can be verified by the eye or by chiral spectrometry.

Banding, excitability and chaos in active nematic suspensions

Motivated by the observation of highly unstable flowing states in suspensions of microtubules and kinesin, we analyse a model of mutually propelled filaments suspended in a solvent. The system undergoes a mean-field isotropic–nematic transition for large enough filament concentrations when the nematic order parameter is allowed to vary in space and time. We analyse the model in two contexts: a quasi-one-dimensional channel with no-slip walls and a two-dimensional box with periodic boundaries. Using stability analysis and numerical calculations we show that the interplay between non-uniform nematic order, activity, and flow results in a variety of complex scenarios that include spontaneous banded laminar flow, relaxation oscillations and chaos.

Orientational Order of Carbon Nanotube Guests in a Nematic Host Suspension of Colloidal Viral Rods

In order to investigate the coupling between the degrees of alignment of elongated particles in binary nematic dispersions, surfactant stabilized single-wall carbon nanotubes (CNTs) have been added to nematic suspensions of colloidal rodlike viruses in aqueous solution. We have independently measured the orientational order parameter of both components of the guest-host system by means of polarized Raman spectroscopy and by optical birefringence, respectively. Our system allows us therefore to probe the regime where the guest particles (CNTs) are shorter and thinner than the fd virus host particles. We show that the degree of order of the CNTs is systematically smaller than that of the fd virus particles for the whole nematic range. These measurements are in good agreement with predictions of an Onsager-type second-viral theory, which explicitly includes the flexibility of the virus particles, and the polydispersity of the CNTs.

Liquid crystal of nanocellulose whiskers’ grafted with acrylamide

Abstract 12% acrylamide (AM) was grafted onto the surface of nanocellulose whiskers (NCW), which was self-assembled to be the chiral nematic suspension at 3% content. The acrylamide grafted NCW (AM-g-NCW) was characterized with Fourier Transform Infrared Spectroscopy (FTIR). The grafting ratio was measured by elemental analysis. The degrees of crystallinity of the AM-g-NCW were measured by X-ray diffraction (XRD). The liquid crystalline properties of the AM-g-NCW were investigated by the polarizing optical microscopy (POM). The AM-g-NCW was found to self-assembly to be a lyotropic state.

Electric-field and magnetic-field alignment of liquid-crystalline clay suspensions and clay/polymer composites

Nematic and isotropic aqueous suspensions of beidellite clay sheets have been submitted to magnetic and a. c. electric fields. The nematic suspensions have positive anisotropy of magnetic susceptibility and negative anisotropy of electric susceptibility because the clay sheets orient their normals parallel to the magnetic field but perpendicular to the electric field. Moreover, the isotropic phase shows a large electric-field-induced birefringence. By dissolving acrylamide monomers in the clay suspensions and photopolymerization, clay/polymer composite gels could be elaborated. Aligned and patterned composites could be produced by application of an electric field during polymerization.

Anisotropic Thin Films of Single-Wall Carbon Nanotubes from Aligned Lyotropic Nematic Suspensions

Lyotropic nematic aqueous suspensions of single-wall carbon nanotubes can be uniformly aligned in thin cells by shearing. Homogeneous anisotropic thin films of nanotubes can be prepared by drying the nematic. Optical transmission between parallel or crossed polarizers is measured and described in order to estimate the dichroic ratio. The order parameter is measured using polarized Raman spectroscopy and found to be quite weak due to entanglement of the nanotubes and/or to an intrinsic viscoelastic behavior of the nanotube suspensions.

Orientational Order and Instabilities in Suspensions of Self-Locomoting Rods

The orientational order and dynamics in suspensions of self-locomoting slender rods are investigated numerically. In agreement with previous theoretical predictions, nematic suspensions of swimming particles are found to be unstable at long wavelengths as a result of hydrodynamic fluctuations. Nevertheless, a local nematic ordering is shown to persist over short length scales and to have a significant impact on the mean swimming speed. The consequences of the large-scale orientational disorder for particle dispersion are also discussed.

Diffusion of spheres in isotropic and nematic networks of rods: Electrostatic interactions and hydrodynamic screening

Translational diffusion of a small charged tracer sphere in isotropic and nematic suspensions of long and thin charged rods is investigated as a function of ionic strength and rod concentration. A theory for the diffusive properties of a small sphere is developed, where both (screened) hydrodynamic interactions and charge interactions between the tracer sphere and the rod network are analyzed. Hydrodynamic interactions are formulated in terms of the hydrodynamic screening length. As yet, there are no independent theoretical predictions for the hydrodynamic screening length for rod networks. Experimental tracer-diffusion data are presented for various ionic strengths as a function of the rod concentration, both in the isotropic and nematic states. Orientational order parameters are measured for the same ionic strengths as a function of the rod concentration. The hydrodynamic screening length is determined from these experimental data and scaling relations obtained from the above mentioned theory. For the isotropic networks, a master curve is found for the hydrodynamic screening length as a function of the rod concentration. For the nematic networks the screening length turns out to be a very sensitive function of the orientational order parameter.

Monodomain dynamics for rigid rod and platelet suspensions in strongly coupled coplanar linear flow and magnetic fields

Extensional flows and magnetic fields induce similar steady alignment responses when applied to liquid crystals (LCs), liquid crystal polymers (LCPs) and nematic (rigid rod or platelet) suspensions. This observation is explained for LCs by a classical analogy, expressed as a symmetry, between hydrodynamic and magnetic fields in the Leslie-Ericksen theory [de Gennes and Prost, The Physics of Liquid Crystals (Oxford University Press, New York, 1993); Chandrasekhar, Liquid Crystals (Cambridge University Press, London, 1992)]. Our purpose here is to extend this analogy: first, to LCPs and nematic suspensions where an excluded volume potential couples either to a linear flow [Hess, Z. Naturforsch. A 31a, 1034–1037 (1976); Doi and Edwards, The Theory of Polymer Dynamics (Clarendon, Oxford, 1986)] or to a magnetic field [Bhandar and Wiest, J. Colloid Interface Sci.257, 371–382 (2003)]; and second, to the strong coupling of excluded volume interactions, planar linear flows, and a coplanar magnetic field. The gene...