Nematic Colloids Research Articles

Collective dynamics and conformal ordering in electrophoretically driven nematic colloids

We present a theoretical framework to understand the collective dynamics of an ensemble of electrophoretically driven colloidal particles that are forced to assemble around a single topological defect in a nematic liquid crystal by an alternating current electric field. Our generic model combines phoretic propulsion with electrostatic interactions and liquid-crystal-mediated hydrodynamics, which are effectively cast into a long-range interparticle repulsion, while nematic elasticity plays a subdominant role. Simulations based on this model fully capture the collective organization process observed in the experiments and other striking effects as the emergence of conformal ordering and a nearly frequency-independent repulsive interaction above 10Hz. Our results demonstrate the importance of hydrodynamic interactions on the assembly of driven microscale matter in anisotropic media.

Electrostatically controlled surface boundary conditions in nematic liquid crystals and colloids

Differing from isotropic fluids, liquid crystals exhibit highly anisotropic interactions with surfaces, which define boundary conditions for the alignment of constituent rod-like molecules at interfaces with colloidal inclusions and confining substrates. We show that surface alignment of the nematic molecules can be controlled by harnessing the competing aligning effects of surface functionalization and electric field arising from surface charging and bulk counterions. The control of ionic content in the bulk and at surfaces allows for tuning orientations of shape-anisotropic particles like platelets within an aligned nematic host and for changing the orientation of director relative to confining substrates. The ensuing anisotropic elastic and electrostatic interactions enable colloidal crystals with reconfigurable symmetries and orientations of inclusions.

Elastic colloidal monopoles and reconfigurable self-assembly in liquid crystals.

Monopole-like electrostatic interactions are ubiquitous in biology1 and condensed matter2-4, but they are often screened by counter-ions and cannot be switched from attractive to repulsive. In colloidal science, where the main goal is to develop colloidal particles2,3 that mimic and exceed the diversity and length scales of atomic and molecular assembly, electrostatically charged particles cannot change the sign of their surface charge or transform from monopoles to higher-order multipoles4. In liquid-crystal colloids5-7, elastic interactions between particles arise to minimize the free energy associated with elastic distortions in the long-range alignment of rod-like molecules around the particles5. In dipolar6,8, quadrupolar8-12 and hexadecapolar13 nematic colloids, the symmetries of such elastic distortions mimic both electrostatic multipoles14 and the outermost occupied electron shells of atoms7,15,16. Electric and magnetic switching17,18, spontaneous transformations19 and optical control20 of elastic multipoles, as well as their interactions with topological defects and surface boundary conditions, have been demonstrated in such colloids21-23. However, it has long been understood5,24 that elastic monopoles should relax to uniform or higher-order multipole states because of the elastic torques that they induce5,7. Here we develop nematic colloids with strong elastic monopole moments and with elastic torques balanced by the optical torques induced by ambient light. We demonstrate the monopole-to-quadrupole reconfiguration of these colloidal particles by unstructured light, which resembles the driving of atoms between the ground state and various excited states. We show that the sign of the elastic monopoles can be switched, and that like-charged monopoles attract whereas oppositely charged ones repel, unlike in electrostatics14. We also demonstrate the out-of-equilibrium dynamic assembly of these colloidal particles. This diverse and surprising behaviour is explained using a model that considers the balance of the optical and elastic torques that are responsible for the excited-state elastic monopoles and may lead to light-powered active-matter systems and self-assembled nanomachines.

Optical properties of metamaterial split ring nematic colloids

The fabrication of 3D bulk metamaterials, optical materials with sub-wavelength building blocks, is an open challenge, along with the tuning of their optical properties, such as transmissivity or exit polarization where a possible approach is to embed liquid crystalline materials into metamaterials and use their tunable birefringence. In this work, we explore using numerical modelling the photonic properties of a composite of split ring resonator colloidal particles, dispersed in nematic liquid crystal, which was optimised to enable self-assembly fully. Specifically, using generalised FDTD simulations for light propagation in birefringent profiles, we demonstrate the photonic response of single particles, 2D and 3D colloidal crystals. The material transmittance is shown to exhibit clear resonant behaviour with the resonances tunable with the birefringence in the order of ~5%. Electric and magnetic field modes emergent on the particles are shown, as affected by the surrounding nematic birefringence, both the in the slit region of the split ring resonator (SRR) particles as well as around the particles. Observed photonic response is further explained by introducing basic equivalent LC circuits. Finally, this work is aimed at developing soft and fluid metamaterials, which exhibit optical anisotropy in the photonic response as a potent mechanism for controlling the flow of light at wavelength and even sub-wavelength scales.

Inhomogeneous assembly of driven nematic colloids.

We present a quantitative analysis of the nonequilibrium assembly of colloidal particles dispersed in a nematic liquid crystal. The driven particles assemble into reconfigurable circular clusters by liquid-crystal-enabled electrokinetic phenomena generated by an AC electric field that provides propulsion along the local director. We identify the coexistence of different aggregation states, including a central, jammed core, where short-range elastic attraction dominates, surrounded by a liquid-like corona where particles retain their mobility but reach a mechanical equilibrium that we rationalize in terms of a balance between centripetal phoretic drive and pairwise repulsion. An analysis of the compressible liquid-like region reveals a linear density profile that can be tuned with the field frequency, and a bond-orientational order that reaches a maximum at intermediate packing densities, where elastic effects are minimized. Since the phoretic propulsion force acts also on assembled particles, we compute the mechanical pressure and show that a hard-disk equation of state can be used to describe the assembly of this driven system.

Optical manipulation of nematic colloids at the interfaces in azo-dye-doped liquid crystals.

This study demonstrates the optical manipulation of colloids dispersed in azo-dye-doped liquid crystals (DDLCs) where the accumulation occurs at the interfaces of the phase domains. We explain the mechanism related to the formation of the domains and the movement of the colloids in DDLCs with respect to the isomerization of azo-dye molecules via the illumination of laser beams. The colloids are dragged to the interfaces of the isotropic/nematic domain and the air bubble/isotropic domain by molecular interaction and Marangoni flows.

Nematic colloidal knots in topological environments.

The role of environment in shaping material properties is of great significance, but less is known about how non-trivial topology of the environment couples to material states, which can be of non-trivial topology themselves. In this paper, we demonstrate the role of the topology of the environment on the formation of complex nematic fields and defect structures, specifically in the system of nematic colloidal knots. The topological environments around knotted colloidal particles are suggested to exist as spherical surface-patterned nematic cavities imposing radial, uniform or hyperbolic nematic profiles. We show that topologically different nematic environments significantly affect and create differences in the colloidal field structure created within the environment, such as the location, profile and number of topological defects. Specifically, we demonstrate that topological environments in combination with knotted colloidal particles of non-trivial topology lead to the formation of diverse nematic knotted and linked fields. These fields are different adaptations of the knotted shape of the colloidal particles, creating knots and links of topological defects as well as escaped-core defect-like solitonic structures. These are observed in chiral nematic media but here are stabilised in achiral nematic media as a result of the distinct shape of the knotted colloidal particle, with a double helix segment and nematic environmental patterns. More generally, this paper is a contribution towards understanding the role of environment, especially its topology, on the response and defect formation in elastic fields, such as in nematic liquid crystal colloids.

Multiscale Models of Metallic Particles in Nematic Liquid Crystals

In this paper we use the method of homogenization to derive a set of approximate equations which describe a nematic liquid crystal colloid in which the dopants are freely rotating metallic particle...

Nematic Liquid-Crystal Colloids.

This article provides a concise review of a new state of colloidal matter called nematic liquid-crystal colloids. These colloids are obtained by dispersing microparticles of different shapes in a nematic liquid crystal that acts as a solvent for the dispersed particles. The microparticles induce a local deformation of the liquid crystal, which then generates topological defects and long-range forces between the neighboring particles. The colloidal forces in nematic colloids are much stronger than the forces in ordinary colloids in isotropic solvents, exceeding thousands of kBT per micrometer-sized particle. Of special interest are the topological defects in nematic colloids, which appear in many fascinating forms, such as singular points, closed loops, multitudes of interlinked and knotted loops or soliton-like structures. The richness of the topological phenomena and the possibility to design and control topological defects with laser tweezers make colloids in nematic liquid crystals an excellent playground for testing the basic theorems of topology.

Chiral liquid crystal colloids.

Colloidal particles disturb the alignment of rod-like molecules of liquid crystals, giving rise to long-range interactions that minimize the free energy of distorted regions. Particle shape and topology are known to guide this self-assembly process. However, how chirality of colloidal inclusions affects these long-range interactions is unclear. Here we study the effects of distortions caused by chiral springs and helices on the colloidal self-organization in a nematic liquid crystal using laser tweezers, particle tracking and optical imaging. We show that chirality of colloidal particles interacts with the nematic elasticity to predefine chiral or racemic colloidal superstructures in nematic colloids. These findings are consistent with numerical modelling based on the minimization of Landau-de Gennes free energy. Our study uncovers the role of chirality in defining the mesoscopic order of liquid crystal colloids, suggesting that this feature may be a potential tool to modulate the global orientated self-organization of these systems.

Coulomb-like elastic interaction induced by symmetry breaking in nematic liquid crystal colloids

It is generally thought that colloidal particles in a nematic liquid crystal do not generate the first multipole term called deformation elastic charge as it violates the mechanical equilibrium. Here, we demonstrate theoretically and experimentally that this is not the case, and deformation elastic charges, as well as dipoles and quadrupoles, can be induced through anisotropic boundary conditions. We report the first direct observation of Coulomb-like elastic interactions between colloidal particles in a nematic liquid crystal. The behaviour of two spherical colloidal particles with asymmetric anchoring conditions induced by asymmetric alignment is investigated experimentally; the interaction of two particles located at the boundary of twist and parallel aligned regions is observed. We demonstrate that such particles produce deformation elastic charges and interact by Coulomb-like interactions.

Rheological studies on liquid-crystal colloids prepared by dispersing spherical microparticles with homeotropic surface anchoring

ABSTRACTWe report rheological studies on the liquid-crystal colloids prepared by dispersing silica microparticles with homeotropic surface anchoring in 8CB liquid crystal. In nematic colloids, a shear-thickening behaviour is observed in low shear rate region. The apparent yield stress of both the nematic and smectic-A (SmA) phases increases with increasing volume fraction of particles . The critical strain amplitude (, i.e., crossover of and ) in SmA colloids decreases significantly with increasing . The frequency-dependent storage modulus of SmA colloids show a power-law behaviour and the loss modulus exhibits a shallow minimum. The optical rheomicroscopy shows that the nematic colloids form a network structure which are stretched and broken at high shear rate. When the temperature is decreased to SmA phase, the networks collapse showing regions of high-density particles. The variation of storage modulus with indicates that the SmA colloids response is dominated by defects.

Fractal nematic colloids

Fractals are remarkable examples of self-similarity where a structure or dynamic pattern is repeated over multiple spatial or time scales. However, little is known about how fractal stimuli such as fractal surfaces interact with their local environment if it exhibits order. Here we show geometry-induced formation of fractal defect states in Koch nematic colloids, exhibiting fractal self-similarity better than 90% over three orders of magnitude in the length scales, from micrometers to nanometres. We produce polymer Koch-shaped hollow colloidal prisms of three successive fractal iterations by direct laser writing, and characterize their coupling with the nematic by polarization microscopy and numerical modelling. Explicit generation of topological defect pairs is found, with the number of defects following exponential-law dependence and reaching few 100 already at fractal iteration four. This work demonstrates a route for generation of fractal topological defect states in responsive soft matter.

Repulsion-attraction switching of nematic colloids formed by liquid crystal dispersions of polygonal prisms.

Self-assembly of colloidal particles due to elastic interactions in nematic liquid crystals promises tunable composite materials and can be guided by exploiting surface functionalization, geometric shape and topology, though these means of controlling self-assembly remain limited. Here, we realize low-symmetry achiral and chiral elastic colloids in the nematic liquid crystals using colloidal polygonal concave and convex prisms. We show that the controlled pinning of disclinations at the prism edges alters the symmetry of director distortions around the prisms and their orientation with respect to the far-field director. The controlled localization of the disclinations at the prism's edges significantly influences the anisotropy of the diffusion properties of prisms dispersed in liquid crystals and allows one to modify their self-assembly. We show that elastic interactions between polygonal prisms can be switched between repulsive and attractive just by controlled re-pinning the disclinations at different edges using laser tweezers. Our findings demonstrate that elastic interactions between colloidal particles dispersed in nematic liquid crystals are sensitive to the topologically equivalent but geometrically rich controlled configurations of the particle-induced defects.

Colloidal Surfaces with Boundaries, Apex Boojums, and Nested Elastic Self-Assembly of Nematic Colloids.

Self-assembly of colloidal particles is poised to become a powerful composite material fabrication technique, but remains challenged by a limited control over the ensuing structures. We develop a new breed of nematic colloids that are physical analogs of a mathematical surface with boundary, interacting with the molecular alignment field without inducing defects when flat. However, made from a thin nanofoil, they can be shaped to prompt formation of self-compensating defects that drive preprogramed elastic interactions mediated by the nematic host. To show this, we wrap the nanofoil on all triangular side faces of a pyramid, except its square base. The ensuing pyramidal cones induce point defects with fractional hedgehog charges of opposite signs, spontaneously align with respect to the far-field director to form elastic dipoles and nested assemblies with tunable spacing. Nanofoils shaped into octahedrons interact as elastic quadrupoles. Our findings may drive realization of low-symmetry colloidal phases.

Optical density and microstructure-related properties of photoactive nematic and cholesteric liquid crystal colloids with carbon nanotubes

The optical density, microstructure and electrical conductivity in nematic (ZhK440, 5CB and their mixtures) and cholesteric (the mixtures of ZhK440, 5CB with chiral M5) colloids with single-walled carbon nanotubes (CNTs) were studied. The azoxy nematic ZhK440 is photoactive, and the effects of UV-irradiation and restoring irradiation were also investigated for the LC composites containing ZhK440. In the nematic mixtures ZhK440+5CB anomalous behavior of optical density and electrical conductivity close to the compensation point of dielectric anisotropy was observed. It was speculated that CNTs can increase the tendency towards nematic ordering of LC molecules and destroy the intermolecular complex by preferential adsorption of 5CB molecules on the surface of CNTs. In cholesteric mixtures of ZhK440+ M5, the optical density vs. CNT concentration D(Cn) dependences were markedly non-monotonous, with a pronounced maximum and minimum. For these composites, UV-irradiation resulted in shifting the location of these extremums. The effects were explained accounting for interactions between cholesteric oily streaks and CNT networks, localisation of CNT inside the cholesteric defects, impact of CNTs on the structure of defects, and impact of cholesteric medium on the structure of CNT aggregates, their compactness and shape anisometry.

Edge pinning and transformation of defect lines induced by faceted colloidal rings in nematic liquid crystals.

Nematic colloids exhibit a large diversity of topological defects and structures induced by colloidal particles in the orientationally ordered liquid crystal host fluids. These defects and field configurations define elastic interactions and medium-mediated self-assembly, as well as serve as model systems in exploiting the richness of interactions between topologies and geometries of colloidal surfaces, nematic fields, and topological singularities induced by particles in the nematic bulk and at nematic-colloidal interfaces. Here we demonstrate formation of quarter-strength surface-pinned disclinations, as well as a large variety of director field configurations with splitting and reconnections of singular defect lines, prompted by colloidal particles with sharp edges and size large enough to define strong boundary conditions. Using examples of faceted ring-shaped particles of genus g=1, we explore transformation of defect lines as they migrate between locations in the bulk of the nematic host to edge-pinned locations at the surfaces of particles and vice versa, showing that this behavior is compliant with topological constraints defined by mathematical theorems. We discuss how transformation of bulk and surface defect lines induced by faceted colloids can enrich the diversity of elasticity-mediated colloidal interactions and how these findings may impinge on prospects of their controlled reconfigurable self-assembly in nematic hosts.

A mesh adaptivity scheme on the Landau–de Gennes functional minimization case in 3D, and its driving efficiency

This paper presents a 3D mesh adaptivity strategy on unstructured tetrahedral meshes by a posteriori error estimates based on metrics derived from the Hessian of a solution. The study is made on the case of a nonlinear finite element minimization scheme for the Landau–de Gennes free energy functional of nematic liquid crystals. Newton's iteration for tensor fields is employed with steepest descent method possibly stepping in.Aspects relating the driving of mesh adaptivity within the nonlinear scheme are considered. The algorithmic performance is found to depend on at least two factors: when to trigger each single mesh adaptation, and the precision of the correlated remeshing. Each factor is represented by a parameter, with its values possibly varying for every new mesh adaptation. We empirically show that the time of the overall algorithm convergence can vary considerably when different sequences of parameters are used, thus posing a question about optimality.The extensive testings and debugging done within this work on the simulation of systems of nematic colloids substantially contributed to the upgrade of an open source finite element-oriented programming language to its 3D meshing possibilities, as also to an outer 3D remeshing module.

Hexadecapolar colloids.

Outermost occupied electron shells of chemical elements can have symmetries resembling that of monopoles, dipoles, quadrupoles and octupoles corresponding to filled s-, p-, d- and f-orbitals. Theoretically, elements with hexadecapolar outer shells could also exist, but none of the known elements have filled g-orbitals. On the other hand, the research paradigm of ‘colloidal atoms' displays complexity of particle behaviour exceeding that of atomic counterparts, which is driven by DNA functionalization, geometric shape and topology and weak external stimuli. Here we describe elastic hexadecapoles formed by polymer microspheres dispersed in a liquid crystal, a nematic fluid of orientationally ordered molecular rods. Because of conically degenerate boundary conditions, the solid microspheres locally perturb the alignment of the nematic host, inducing hexadecapolar distortions that drive anisotropic colloidal interactions. We uncover physical underpinnings of formation of colloidal elastic hexadecapoles and describe the ensuing bonding inaccessible to elastic dipoles, quadrupoles and other nematic colloids studied previously.

Analytical description of the Saturn-ring defect in nematic colloids.

We derive an analytical formula for the Saturn-ring configuration around a small colloidal particle suspended in nematic liquid crystal. In particular we obtain an explicit expression for the ring radius and its dependence on the anchoring energy. We work within Landau-de Gennes theory: Nematic alignment is described by a tensorial order parameter. For nematic colloids this model had previously been used exclusively to perform numerical computations. Our method demonstrates that the tensorial theory can also be used to obtain analytical results, suggesting a different approach to the understanding of nematic colloidal interactions.