Emergent biaxiality in chiral hybrid liquid crystals.

Biaxial nematic liquid crystals are fascinating systems sometimes referred to as the Higgs boson of soft matter because of experimental observation challenges. Here we describe unexpected states of matter that feature biaxial orientational order of colloidal supercritical fluids and gases formed by sparse rodlike particles. Colloidal rods with perpendicular surface boundary conditions exhibit a strong biaxial symmetry breaking when doped into conventional chiral nematic fluids.

Large-area, self-healing block copolymer membranes for energy conversion.

Membranes are widely used for separation processes in applications such as water desalination, batteries and dialysis, and are crucial in key sectors of our economy and society. The majority of technologically exploited membranes are based on solid polymers and function as passive barriers, whose transport characteristics are governed by their chemical composition and nanostructure. Although such membranes are ubiquitous, it has proved challenging to maximize selectivity and permeability independently, leading to trade-offs between these pertinent characteristics.

Crystalline restacking of 2D-materials from their nanosheets suspensions.

We report here the highly ordered restacking of the layered phosphatoantimonic dielectric materials HMSbPO, (where M = Li, Na, K, Rb, Cs and 0 ≤ ≤ 1), from their nanosheets dispersed in colloidal suspension, induced by a simple pH change using alkaline bases. HSbPO aqueous suspensions are some of the rare examples of colloidal suspensions based on 2D materials exhibiting a lamellar liquid crystalline phase. Because the lamellar period can reach several hundred nanometers, the suspensions show vivid structural colors and because these colors are sensitive to various chemicals, the suspensions can be used as sensors.

Pre-Smectic Ordering and the Unwinding Helix in Monte Carlo Simulations of Cholesteric Liquid-Crystals.

In this paper, molecular chirality is studied for liquid-crystal fluids represented by hard rods with the addition of an attractive chiral dispersion term. Chiral forces between molecular pairs are assumed to be long-ranged and are described in terms of the pseudotensor of Goossens [W. J.

Elastic response of colloidal smectic liquid crystals: Insights from microscopic theory.

Elongated colloidal rods at sufficient packing conditions are known to form stable lamellar or smectic phases. Using a simplified volume-exclusion model, we propose a generic equation of state for hard-rod smectics that is robust against simulation results and is independent of the rod aspect ratio. We then extend our theory by exploring the elastic properties of a hard-rod smectic, including the layer compressibility (B) and bending modulus (K_{1}).

Evidence of T-type structures of hard square boards in capillary confinement.

We employ Onsager's second virial density functional theory combined with the Parsons-Lee theory within the restricted orientation (Zwanzig) approximation to examine the phase structure of hard square boards of dimensions (L×D×D) uniaxially confined in narrow slabs. Depending on the wall-to-wall separation (H), we predict a number of distinctly different capillary nematic phases, including a monolayer uniaxial or biaxial planar nematic, homeotropic with a variable number of layers, and a T-type structure. We determine that the favored phase is homotropic, and we observe first-order transitions from the homeotropic structure with n layers to n+1 layers as well as from homeotropic surface anchoring to a monolayer planar or T-type structure involving both planar and homeotropic anchoring at the pore surface.

Multiphase Coexistence in Binary Hard Colloidal Mixtures: Predictions from a Simple Algebraic Theory.

A general theoretical framework is proposed to quantify the thermodynamic properties of multicomponent hard colloidal mixtures. This framework is used to predict the phase behavior of mixtures of rods with spheres and rods with plates taking into account (liquid) crystal phases of both components. We demonstrate a rich and complex range of phase behaviors featuring a large variety of different multiphase coexistence regions, including two five-phase coexistence regions for hard rod/sphere mixtures, and even a six-phase equilibrium for hard rod/plate dispersions.

Do Aqueous Suspensions of Smectite Clays Form a Smectic Liquid-Crystalline Phase?

Bottom-up strategies for the production of well-defined nanostructures often rely on the self-assembly of anisotropic colloidal particles (nanowires and nanosheets). These building blocks can be obtained by delamination in a solvent of low-dimensionality crystallites. To optimize particle availability, determination of the delamination mechanism and the different organization stages of anisotropic particles in dispersion is essential.

Capillary-driven biaxial planar and homeotropic nematization of hard cylinders.

We use the Parsons-Lee modification of Onsager's second virial theory within the restricted orientation (Zwanzig) approximation to analyze the phase behavior of hard cylindrical rods confined in narrow pores. Depending on the wall-to-wall separation we predict a number of distinctly different surface-generated nematic phases, including a biaxial planar nematic with variable number of layers, a monolayer homeotropic, and a hybrid T-type structure (a planar layer combined with a homeotropic one). For narrow pores, we find evidence of two types of second-order uniaxial-biaxial transitions depending on the aspect ratio of the particles.

Second-virial theory for shape-persistent living polymers templated by disks.

Living polymers composed of noncovalently bonded building blocks with weak backbone flexibility may self-assemble into thermoresponsive lyotropic liquid crystals. We demonstrate that the reversible polymer assembly and phase behavior can be controlled by the addition of (nonadsorbing) rigid colloidal disks which act as an entropic reorienting "template" onto the supramolecular polymers. Using a particle-based second-virial theory that correlates the various entropies associated with the polymers and disks, we demonstrate that small fractions of discotic additives promote the formation of a polymer nematic phase.

Fine tuning the structural colours of photonic nanosheet suspensions by polymer doping.

Aqueous suspensions of nanosheets are readily obtained by exfoliating low-dimensional mineral compounds like HSbPO. The nanosheets self-organize, at low concentration, into a periodic stack of membranes, a lamellar liquid-crystalline phase. Due to the dilution, this stack has a large period of a few hundred nanometres, it behaves as a 1-dimensional photonic material and displays structural colours.

Multiphase Coexistences in Rod-Polymer Mixtures.

Using recently derived analytical equations of state for hard rod dispersions, we predict the phase behavior of athermal rod-polymer mixtures with free volume theory. The rods are modeled as hard spherocylinders, while the nonadsorbing polymer chains are described as penetrable hard spheres. It is demonstrated that all of the different types of phase states that are stable for pure colloidal rod dispersions can coexist with any combination of these phases if polymers are added, depending on the concentrations, rod aspect ratio, and polymer-rod size ratio.

Nematoelasticity of hybrid molecular-colloidal liquid crystals.

Colloidal rods immersed in a thermotropic liquid-crystalline solvent are at the basis of so-called hybrid liquid crystals, which are characterized by tunable nematic fluidity with symmetries ranging from conventional uniaxial nematic or antinematic to orthorhombic [Mundoor et al., Science 360, 768 (2018)SCIEAS0036-807510.1126/science.

Thermally reconfigurable monoclinic nematic colloidal fluids.

Fundamental relationships are believed to exist between the symmetries of building blocks and the condensed matter phases that they form. For example, constituent molecular and colloidal rods and disks impart their uniaxial symmetry onto nematic liquid crystals, such as those used in displays. Low-symmetry organizations could form in mixtures of rods and disks, but entropy tends to phase-separate them at the molecular and colloidal scales, whereas strong elasticity-mediated interactions drive the formation of chains and crystals in nematic colloids.

Destabilization of the Nematic Phase of Clay Nanosheet Suspensions by Polymer Adsorption.

Complex aqueous mixtures comprised of swelling clays and hydrosoluble polymers naturally occur in soils and play a major role in pedogenesis. They are also very often used for formulating oil-well drilling fluids, paints, and personal-care products. The suspensions of some natural clays, thanks to their large nanoparticle aspect ratio, spontaneously form nematic liquid-crystalline phases where the particles align parallel to each other, which affects their flow properties.

Defying the Gibbs Phase Rule: Evidence for an Entropy-Driven Quintuple Point in Colloid-Polymer Mixtures.

Using a minimal algebraic model for the thermodynamics of binary rod-polymer mixtures, we provide evidence for a quintuple phase equilibrium; an observation that seems to be at odds with the Gibbs phase rule for two-component systems. Our model is based on equations of state for the relevant liquid crystal phases that are in quantitative agreement with computer simulations. We argue that the appearance of a quintuple equilibrium, involving an isotropic fluid, a nematic and smectic liquid crystal, and two solid phases, can be reconciled with a generalized Gibbs phase rule in which the two intrinsic length scales of the athermal colloid-polymer mixture act as additional field variables.

Algebraic equations of state for the liquid crystalline phase behavior of hard rods.

Based on simplifications of previous numerical calculations [H. Graf and H. Löwen, Phys.

Tetrahedrality Dictates Dynamics in Hard Sphere Mixtures.

The link between local structure and dynamical slowdown in glassy fluids has been the focus of intense debate for the better part of a century. Nonetheless, a simple method to predict the dynamical behavior of a fluid purely from its local structural features is still missing. Here, we demonstrate that the diffusivity of perhaps the most fundamental family of glass formers-hard sphere mixtures-can be accurately predicted based on just the packing fraction and a simple order parameter measuring the tetrahedrality of the local structure.

Rotational and translational dynamics in dense fluids of patchy particles.

We explore the effect of directionality on rotational and translational relaxation in glassy systems of patchy particles. Using molecular dynamics simulations, we analyze the impact of two distinct patch geometries, one that enhances the local icosahedral structure and the other one that does not strongly affect the local order. We find that in nearly all investigated cases, rotational relaxation takes place on a much faster time scale than translational relaxation.

Slowing down supercooled liquids by manipulating their local structure.

Glasses remain an elusive and poorly understood state of matter. It is not clear how we can control the macroscopic dynamics of glassy systems by tuning the properties of their microscopic building blocks. In this paper, we propose a simple directional colloidal model that reinforces the optimal icosahedral local structure of binary hard-sphere glasses.

Frank elasticity of composite colloidal nematics with anti-nematic order.

Mixing colloid shapes with distinctly different anisotropy generates composite nematics in which the order of the individual components can be fundamentally different. In colloidal rod-disk mixtures or hybrid nematics composed of anisotropic colloids immersed in a thermotropic liquid crystal, one of the components may adopt so-called anti-nematic order while the other exhibits conventional nematic alignment. Focussing on simple models for hard rods and disks, we employ Onsager-Straley's second-virial theory to derive scaling expressions for the elastic moduli of rods and disks in both nematic and anti-nematic configurations and identify their explicit dependence on particle concentration and shape.

Long-time anomalous swimmer diffusion in smectic liquid crystals.

The dynamics of self-locomotion of active particles in aligned or liquid crystalline fluids strongly deviates from that in simple isotropic media. We explore the long-time dynamics of a swimmer moving in a three-dimensional smectic liquid crystal and find that the mean-square displacement transverse to the director exhibits a distinct logarithmic tail at long times. The scaling is distinctly different from that in an isotropic or nematic fluid and hints at the subtle but important role of the director fluctuation spectrum in governing the long-time motility of active particles.

Hybrid molecular-colloidal liquid crystals.

Order and fluidity often coexist, with examples ranging from biological membranes to liquid crystals, but the symmetry of these soft-matter systems is typically higher than that of the constituent building blocks. We dispersed micrometer-long inorganic colloidal rods in a nematic liquid crystalline fluid of molecular rods. Both types of uniaxial building blocks, while freely diffusing, interact to form an orthorhombic nematic fluid, in which like-sized rods are roughly parallel to each other and the molecular ordering direction is orthogonal to that of colloidal rods.

Elastic moduli of a smectic membrane: a rod-level scaling analysis.

Chiral rodlike colloids exposed to strong depletion attraction may self-assemble into chiral membranes whose twisted director field differs from that of a 3D bulk chiral nematic. We formulate a simple microscopic variational theory to determine the elastic moduli of rods assembled into a bidimensional smectic membrane. The approach is based on a simple Onsager-Straley theory for a non-uniform director field that we apply to describe rod twist within the membrane.