Using dynamic light scattering, we measure for the first time the temperature-dependent elastic moduli and associated orientational viscosity coefficients of the nematic phase in a self-assembled lyotropic chromonic liquid crystal. The bend K3 and splay K1 moduli are an order of magnitude higher than the twist K2 constant. The ratio K3/K1 shows an anomalous increase with temperature; we attribute this to the shortening of the aggregates as temperature increases. The viscosity coefficients also show a significant anisotropy, as well as a strong temperature dependence; in particular, the bend viscosity is three orders of magnitude smaller than the splay and twist viscosities.
An experimental and theoretical study of lyotropic chromonic liquid crystals (LCLCs) confined in cylinders with degenerate planar boundary conditions elucidates LCLC director configurations. When the Frank saddle-splay modulus is more than twice the twist modulus, the ground state adopts an inhomogeneous escaped-twisted configuration. Analysis of the configuration yields a large saddle-splay modulus, which violates Ericksen inequalities but not thermodynamic stability. Lastly, we observe point defects between opposite-handed domains and explain a preference for point defects over domain walls.
The surface alignment of lyotropic chromonic liquid crystals (LCLCs) can be not only planar (tangential) but also homeotropic, with self-assembled aggregates perpendicular to the substrate, as demonstrated by mapping optical retardation and by three-dimensional imaging of the director field. With time, the homeotropic nematic undergoes a transition into a tangential state. The anchoring transition is discontinuous and can be described by a double-well anchoring potential with two minima corresponding to tangential and homeotropic orientation.
Nuclei of ordered materials emerging from the isotropic state usually show a shape topologically equivalent to a sphere; the well-known examples are crystals and nematic liquid crystal droplets. In this work, we explore experimentally and theoretically the nuclei of columnar lyotropic chromonic liquid crystal coexisting with the isotropic phase that are toroidal in shape. The geometry of toroids depends strongly on the molecular concentrations and presence of a crowding agent, polyethylene glycol. High concentrations result in thick toroids with small central holes, while low concentrations yi…
A lyotropic chromonic liquid crystal (LCLC) is an orientationally ordered system made by self-assembled aggregates of charged organic molecules in water, bound by weak non-covalent attractive forces and stabilized by electrostatic repulsions. We determine how the ionic content of the LCLC, namely the presence of mono- and divalent salts and pH enhancing agent, alter the viscoelastic properties of the LCLC. Aqueous solutions of the dye Sunset Yellow with a uniaxial nematic order are used as an example. By applying a magnetic field to impose orientational deformations, we measure the splay $K_1$…
Magnetically controlled double-twist director configuration of lyotropic chromonic liquid crystals in cylinders: Energetics, topological defects, and instability
Detection of chiral molecules requires amplification of chirality to measurable levels. Typically, amplification mechanisms are considered at the microscopic scales of individual molecules and their aggregates. Here we demonstrate chirality amplification and visualization of structural handedness in water solutions of organic molecules that extends over the scale of many micrometers. The mechanism is rooted in the long-range elastic nature of orientational order in lyotropic chromonic liquid crystals (LCLCs) formed in water solutions of achiral disc-like molecules. The nematic LCLC coexists wi…
We have developed a class of idealized models of chromonic molecules which are miscible in water, but which can form aggregates which in turn organize into lyotropic liquid crystal (LC) phases. By carrying out Monte Carlo simulation in a binary mixture of model chromonic and water molecules, we have studied the effect of concentration and molecular shape on the nature of resulting mesophases. We have also computed the free energy associated with the formation of chromonic columnar aggregates by umbrella sampling. Our free energy computation helps us to verify the isodesmic behavior which is ch…
We propose lyotropic chromonic liquid crystals (LCLCs) as a distinct class of materials for organic electronics. In water, the chromonic molecules stack on top of each other into elongated aggregates that form orientationally ordered phases. The aligned aggregated structure is preserved when the material is deposited onto a substrate and dried. The dried LCLC films show a strongly anisotropic electric conductivity of semiconductor type. The field-effect carrier mobility measured along the molecular aggregates in unoptimized films of LCLC V20 is 0.03 cm^2 V^(-1) s^(-1). Easy processibility, low…
We study the aggregation phenomenon in lyotropic chromonic liquid crystals as the molecular concentration changes and condensing agents are added into the system. Using properties of the critical points of the Oseen-Frank energy of a nematic liquid crystal, combined with the geometric constraints of the hexagonal columnar chromonic phases, we show that the minimizers of the total energy are topologically equivalent to tori, in agreement with available experimental evidence on chromonic liquid crystals and DNA condensates, in viral capsids as well as in free solution. We model the system as bi-…
We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering, to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogen…
Nematic and columnar phases of lyotropic chromonic liquid crystals (LCLCs) have been long studied for their fundamental and applied prospects in material science and medical diagnostics. LCLC phases represent different self-assembled states of disc-shaped molecules, held together by noncovalent interactions that lead to highly sensitive concentration and temperature dependent properties. Yet, microscale insights into confined LCLCs, specifically in the context of confinement geometry and surface properties, are lacking. Here, we report the emergence of time dependent textures in static disodiu…
In this paper, we discuss the equilibrium phases and collapse transitions of a lyotropic nematic gel immersed in an isotropic solvent. A nematic gel consists of a cross-linked polymer network with rod-like molecules embedded in it. Upon decreasing the quality of the solvent, we find that a lyotropic nematic gel undergoes a discontinuous volume change accompanied by an isotropic-nematic transition. We also present phase diagrams that these systems may exhibit. In particular, we show that coexistence of two isotropic phases, of two nematic phases, or of an isotropic and a nematic phase can occur…
We perform dynamical simulations of a two-dimensional active nematic fluid in coexistence with an isotropic fluid. Drops of active nematic become elongated, and an effective anchoring develops at the nematic-isotropic interface. The activity also causes an undulatory instability of the interface. This results in defects of positive topological charge being ejected into the nematic, leaving the interface with a diffuse negative charge. Quenching the active lyotropic fluid results in a steady state in which phase-separating domains are elongated and then torn apart by active stirring.
We report the elaboration of a hybrid mesophase combining the lamellar order of a lyotropic system of nonionic surfactant and the nematic order of a concentrated solution of inorganic nanorods confined between the surfactant layers. Highly aligned samples of this mesophase can be obtained by thermal annealing, and the orientation of the nanorods is readily controlled with a magnetic field. High-resolution synchrotron X-ray scattering and polarized optical microscopy show that, compared to their isolated counterparts, both the nematic and lamellar orders are altered, demonstrating their interpl…
Lyotropic chromonic liquid crystals (LCLCs) represent aqueous dispersions of organic disk-like molecules that form cylindrical aggregates. Despite the growing interest in these materials, their flow behavior is poorly understood. Here, we explore the effect of shear on dynamic structures of the nematic LCLC, formed by 14wt ${\%}$ water dispersion of disodium cromoglycate (DSCG). We employ in-situ polarizing optical microscopy (POM) and small-angle and wide-angle X-ray scattering (SAXS/WAXS) to obtain independent and complementary information on the director structures over a wide range of shea…
We study droplets of chromonic liquid crystals squeezed between parallel plates inducing degenerate tangential anchoring on the nematic director. In the coexistence regime, where droplets in the nematic phase are at equilibrium with the surrounding melt, our two-dimensional theoretical model predicts a regime of shape bistability for sufficiently large bipolar droplets, where tactoids (pointed shapes) and discoids (smooth shapes) coexist in equilibrium. This phenomenon has not yet been observed. Two-dimensional droplets of disodium cromoglycate (DSCG) have been the object of a thorough experim…
Chromonic liquid crystals constitute a novel lyotropic phase, whose elastic properties have so far been modeled within the classical Oseen-Frank theory, provided that the twist constant is assumed to be considerably smaller than the saddle-splay constant, in violation of one Ericksen inequality. This paper shows that paradoxical consequences follow from such a violation for droplets of these materials surrounded by an isotropic fluid. For example, tactoids with a degenerate planar anchoring simply disintegrate indefinitely in myriads of smaller ones.
We explore the structure of nuclei and topological defects in the first-order phase transition between the nematic (N) and isotropic (I) phases in lyotropic chromonic liquid crystals (LCLCs). The LCLCs are formed by self-assembled molecular aggregates of various lengths and show a broad biphasic region. The defects emerge as a result of two mechanisms. 1) Surface anisotropy mechanism that endows each N nucleus (tactoid) with topological defects thanks to preferential (tangential) orientation of the director at the closed I-N interface, and 2) Kibble mechanism with defects forming when differen…
We explore micropatterned director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating the LCLC mesophases and their elastic properties via concentration through drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films, dried from nematics, form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with z…
Lyotropic liquid crystalline quaternary mixtures of potassium laurate (KL), potassium sulphate (K2SO4)/alcohol (n-OH)/water, with the alcohols having different number of carbon atoms in the alkyl chain (n), from 1 octanol to 1-hexadecanol, were investigated by optical techniques (optical microscopy and laser conoscopy). The biaxial nematic phase domain is present in a window of values of n = nKL \pm 2, where nKL = 11 is the number of carbon atoms in the alkyl chain of KL. The biaxial phase domain got smaller and the uniaxial-to-biaxial phase transition temperatures shifted to the relatively hi…
Rod-shaped colloids with attractive tips can form linear aggregates that may subsequently undergo hierarchical self-assembly into nematic fluids. Inspired by recent modelling efforts on chromonic liquid crystals, composed of discotic building blocks, we formulate a second-virial theory for reversible supramolecular rods. Unlike chromonics, these systems are capable of forming stable nematic phases in the high-temperature, monomeric limit in the absence of polymerization. Changing the tip potential from attractive to repulsive thus enables a smooth crossover from a monomeric to a polymeric nema…
This paper reviews the research work on the liquid crystalline (LC) polymer vesicles (polymersomes), where the thermotropic nematic and smectic phases are displayed in the lyotropic bilayer polymer membrane. LC polymersomes possess the properties of both liquid crystals and polymers, the two essential soft matters. LC polymersomes offer, on the one hand, novel examples of the interplay between orientational order and the curved geometry of a two dimensional membrane. Spherical, ellipsoidal and tetrahedral vesicles are discussed. On the other hand, LC polymersomes enable novel design of stimuli…
Motivated by recent experiments, the isotropic-nematic phase transition in chromonic liquid crystals is studied. As temperature decreases, nematic nuclei nucleate, grow, and coalesce, giving rise to tactoid microstructures in an isotropic liquid. These tactoids produce topological defects at domain junctions (disclinations in the bulk or point defects on the surface). We simulate such tactoid equilibria and their coarsening dynamics with a model using degree of order, a variable length director, and an interfacial normal as state descriptors. We adopt Ericksen's work and introduce an augmented…
A lyotropic ferrocolloid is synthesized by mixing of a cationic ferrofluid and potassium laurate/1-decanol/water ternary solution. Conditions of existence of a nematic phase in this mixture, other mesophases, and their phase diagrams in the vicinity of the nematic one are obtained and characterized quantitatively. Inside of the nematic zone the lyotropic ferrocolloid becomes a ferronematic, i.e., a liquid crystal with remarkably strong magnetic properties. We found that the pH and the component concentrations dramatically affect the amount of magnetic particles stably suspended in a lyotropic …
Many lyotropic liquid crystals are composed of mesogens that display a considerable spread in size or shape affecting their material properties and thermodynamics via various demixing and multi-phase coexistence scenarios. Starting from a generalized Onsager theory we formulate a generic framework that enables locating spinodal polydispersities as well as identifying the nature of incipient size fractionation for arbitrary model potentials and size distributions. We apply our theory to nematic phases of both hard rods and disks whose main particle dimension is described by a unimodal log-norma…
Topological defects can appear whenever there is some type of ordering. Its ubiquity in nature has been the subject of several studies, from early Universe to condensed matter. In this work, we investigated the annihilation dynamics of defects and antidefects in a lyotropic nematic liquid crystal (ternary mixture of potassium laurate, decanol and deionized-destilated water) using the polarized optical light microscopy technique. We analyzed Schlieren textures with topological defects produced due to a symmetry breaking in the transition of the isotropic to nematic calamitic phase after a tempe…
We analyze the phase behavior of lyotropic nematic liquid crystals in the self-organizing flow, viz. so called active nematics (AN). Their elastic properties are mutually caused by evolution of topological defects (for instance, disclinations and boojums) and the flow regime. Such changes in elasticity of AN comparing with conventional inactive ones set the new working characteristics of these materials, have an influence on their switchable and tunable properties. In this work, we study the uniaxial droplet AN phases with topological defects in their collective flow, we apply the gauge string…
Transparent lyotropic ferronematic dispersions are synthesized by admixing a cationic ferrofluid to the lyotropic liquid crystal PL/1D/Wt. The transparency is spontaneous and time-independent. It is observed in zero magnetic field in white and polarized light for disordered layers of ferroliquid crystals of thicknesses ~1 cm in both isotropic and nematic phases. Justification of the low extinction of light in the systems of the lyotropic origin is presented.
Pattern formation in uniaxial polymeric liquid crystals is studied for different dynamic closure approximations. Using the principles of mesoscopic non-equilibrium thermodynamics in a mean-field approach, we derive a Fokker-Planck equation for the single-particle non-homogeneous distribution function of particle orientations and the evolution equations for the second and fourth order orientational tensor parameters. Afterwards, two dynamic closure approximations are discussed, one of them considering the relaxation of the fourth order orientational parameter and leading to a novel expression f…
Suspended droplets of cholesteric (chiral nematic) liquid crystals spontaneously rotate in the presence of a heat flux due to a temperature gradient, a phenomenon known as Lehmann effect. So far, it is not clear whether this effect is due to the chirality of the phase and the molecules or only to the chirality of the director field. Here, we report the continuous rotation in a temperature gradient of nematic droplets of a lyotropic chromonic liquid crystal featuring a twisted bipolar configuration. The achiral nature of the molecular components leads to a random handedness of the spontaneous t…
Disclination configurations of a nematic liquid crystal are studied within a self-consistent molecular field theory. The theory is based on a tensor order parameter, and can accommodate anisotropic elastic energies without the known divergences in the Landau-de Gennes formulation. Our results agree with the asymptotic results of Dzyaloshinsky for the Frank-Oseen energy and far from the defect core, but reveal biaxial order at intermediate distances from the core, crossing over to uniaxial, but isotropic configurations as the core is approached. The elastic terms considered in our energy allow …
We demonstrate how to construct dynamic phase diagrams for complex fluids that undergo transitions under flow, in which the conserved composition variable and the broken-symmetry order parameter (nematic, smectic, crystalline, etc.) are coupled to shear rate. Our construction relies on a selection criterion, the existence of a steady interface connecting two stable homogeneous states. We use the (generalized) Doi model of lyotropic nematic liquid crystals as a model system, but the method can be easily applied to other systems, provided non-local effects are included.
The physics of light interference experiments is well established for nematic liquid crystals. Using well-known techniques, it is possible to obtain important quantities, such as the differential scattering cross section and the saddl-splay elastic constant $K_{24}$. However, the usual methods to retrieve the latter involves an adjusting of computational parameters through the visual comparisons between the experimental light interference pattern or a $^{2}H-NMR$ spectral pattern produced by an escaped-radial disclination, and their computational simulation counterparts. To avoid such comparis…
Achieving control and tunability of lyotropic materials has been a long-standing goal of liquid crystal research. Here we show that the elasticity of a liquid crystal system consisting of a dense suspension of semiflexible biopolymers can be manipulated over a relatively wide range of elastic moduli. Specifically, thin films of actin filaments are assembled at an oil-water interface. At sufficiently high concentrations, one observes the formation of a nematic phase riddled with $\pm1/2$ topological defects, characteristic of a two-dimensional nematic system. As the average filament length incr…
Semiflexible polymers in concentrated lyotropic solution are studied within a bead-spring model by molecular dynamics simulations, focusing on the emergence of a smectic A phase and its properties. We systematically vary the density of the monomeric units for several contour lengths that are taken smaller than the chain persistence length. The difficulties concerning the equilibration of such systems and the choice of appropriate ensemble (constant volume versus constant pressure, where all three linear dimensions of the simulation box can fluctuate independently) are carefully discussed. Usin…
Polarization light microscopes are powerful tools for probing molecular order and orientation in birefringent materials. While a multitude of polarization light microscopy techniques are often used to access steady-state properties of birefringent samples, quantitative measurements of the molecular orientation dynamics on the millisecond time scale have remained a challenge. We propose polarized shearing interference microscopy (PSIM), a single-shot quantitative polarization imaging method, for extracting the retardance and orientation angle of the laser beam transmitting through optically ani…
