Relaxation to steady states of a binary liquid mixture around an optically heated colloid.

We study the relaxation dynamics of a binary liquid mixture near a light-absorbing Janus particle after switching on and off illumination using experiments and theoretical models. The dynamics is controlled by the temperature gradient formed around the heated particle. Our results show that the relaxation is asymmetric: The approach to a nonequilibrium steady state is much slower than the return to thermal equilibrium. Approaching a nonequilibrium steady state after a sudden temperature change is a two-step process that overshoots the response of spatial variance of the concentration field. The initial growth of concentration fluctuations after switching on illumination follows a power law in agreement with the hydrodynamic and purely diffusive model. The energy outflow from the system after switching off illumination is well described by a stretched exponential function of time with characteristic time proportional to the ratio of the energy stored in the steady state to the total energy flux in this state.

Contribution of internal degree of freedom of soft molecules to Soret effect.

We study the Soret effect in binary dimer-monomer mixtures using nonequilibrium molecular dynamics simulations and investigate the pure contribution of the internal degree of freedom of flexible molecules to the Soret effect. We observe that the thermal diffusion factor tends to decrease and change its sign as the molecules become softer. We propose two possible mechanisms for our observations: change of the molecule structures with the temperature, causing bulkier molecules to migrate to the hotter region, and asymmetry of the restitution between rigid and flexible molecules, due to which flexible molecules show larger restitution when placed at the hotter region.

Correction: Transient coarsening and the motility of optically heated Janus colloids in a binary liquid mixture.

Correction for 'Transient coarsening and the motility of optically heated Janus colloids in a binary liquid mixture' by Juan Ruben Gomez-Solano et al., Soft Matter, 2020, DOI: 10.1039/d0sm00964d.

Transient coarsening and the motility of optically heated Janus colloids in a binary liquid mixture.

A gold-capped Janus particle suspended in a near-critical binary liquid mixture can self-propel under illumination. We have immobilized such a particle in a narrow channel and carried out a combined experimental and theoretical study of the non-equilibrium dynamics of a binary solvent around it - lasting from the very moment of switching illumination on until the steady state is reached. In the theoretical study we use both a purely diffusive and a hydrodynamic model, which we solve numerically. Our results demonstrate a remarkable complexity of the time evolution of the concentration field around the colloid. This evolution is governed by the combined effects of the temperature gradient and the wettability, and crucially depends on whether the colloid is free to move or is trapped. For the trapped colloid, all approaches indicate that the early time dynamics is purely diffusive and characterized by composition layers travelling with constant speed from the surface of the colloid into the bulk of the solvent. Subsequently, hydrodynamic effects set in. Anomalously large nonequilibrium fluctuations, which result from the temperature gradient and the vicinity of the critical point of the binary liquid mixture, give rise to strong concentration fluctuations in the solvent and to permanently changing coarsening patterns not observed for a mobile particle. The early time dynamics around initially still Janus colloids produces a force which is able to set the Janus colloid into motion. The propulsion due to this transient dynamics is in the direction opposite to that observed after the steady state is attained.

Dynamics control of an in-plane-switching liquid crystal cell using heterogeneous substrates.

The control of surface anchoring strength can be achieved by using heterogeneous substrates. In contrast to conventional substrates that control the anchoring strength by using temperature or chemical processes, heterogeneous substrates provide surface anchoring to liquid crystal molecules by using a mixed composition of (1) a zero anchoring surface and (2) planar-anchoring patches. To study the dynamics of in-plane-switching liquid crystal displays (IPS-LCDs) under external fields, a new particle-based numerical algorithm is developed to simulate both nematic liquid crystals and heterogeneous surfaces. This new method allows us to create different heterogeneous surfaces easily by adopting predefined distributions of numerical particles. The generated effective anchoring strength from the heterogeneous surface is thus calculated, and the dynamical response is found to be similar to that of conventional homogeneously processed substrates. The results suggest that the use of a heterogeneous LCD cell is a suitable alternative for creating desirable LCD substrates, for which chemical/temperature dependence can be transferred to a more controllable configurational dependence. Interestingly, we found master curves in the peak transmittance/recovery time phase space, and they appeared to be dependent solely on the cell thickness. This discovery clarifies the fundamental optical dynamics of IPS-LCD cells.

Illumination-induced motion of a Janus nanoparticle in binary solvents.

Using a fluid particle dynamics method we numerically investigate the motion of a spherical Janus particle suspended in a binary liquid mixture, which emerges under heating of one-half of a colloid surface. The method treats simultaneously the flow of the solvent and the motion of the particle, hence, the velocity of the particle can be computed directly. Our approach accounts for a phenomenon of critical adsorption, therefore, a particle that is adsorptionwise nonneutral is always completely covered by an adsorption layer (droplet). In order to establish the mechanism of self-propulsion, we study systematically various combinations of adsorption preference on both hemispheres of the Janus colloid as function of the heating power for symmetric and nonsymmetric binary solvents and for various particle sizes in three spatial dimensions. Only for a particle for which the heated hemisphere is neutral whereas the other hemisphere prefers one of the two components of the mixture does the reversal of the direction of motion occur. The particle self-propels much faster in nonsymmetric binary solvents. Self-propulsion originates from a gradient of mechanical stress, in a way similar to the Marangoni effect. This stress is not localized at the edge but distributed within the whole droplet. We compare our findings with the experimental observations and other theoretical results.

Isotropic-isotropic phase separation and spinodal decomposition in liquid crystal-solvent mixtures.

Phase separation in mixtures forming liquid crystal (LC) phases is an important yet under-appreciated phenomenon that can drastically influence the behaviour of a multi-component LC. Here we demonstrate, using polarising microscopy with active cooling as well as differential scanning calorimetry, that the phase diagram for mixtures of the LC-forming compound 4'-n-pentylbiphenyl-4-carbonitrile (5CB) with ethanol is surprisingly complex. Binary mixtures reveal a broad miscibility gap that leads to phase separation between two distinct isotropic phases via spinodal decomposition or nucleation and growth. On further cooling the nematic phase enters on the 5CB-rich side, adding to the complexity. Significantly, water contamination dramatically raises the temperature range of the miscibility gap, bringing up the critical temperature for spinodal decomposition from ∼ 2 °C for the anhydrous case to >50 °C if just 3 vol% water is added to the ethanol. We support the experiments with a theoretical treatment that qualitatively reproduces the phase diagrams as well as the transition dynamics, with and without water. Our study highlights the impact of phase separation in LC-forming mixtures, spanning from equilibrium coexistence of multiple liquid phases to non-equilibrium effects due to persistent spatial concentration gradients.

Modifying Nobili-Durand surface energy for conically degenerate anchorings at the interface of liquid crystal colloids.

We propose a surface energy for conically degenerate anchorings of uniaxial liquid crystal mesogens by modifying tensorial Nobili-Durand surface energy that is usually employed for fixed anchoring orientations with preferred polar angles. By minimizing Landau-de Gennes free energy and the proposed surface energy, we obtain the equilibrium director configuration around a spherical colloid in the uniform nematic liquid crystal. Our calculations show that the proposed surface energy can cause boojum or/and Saturn-ring defect textures depending on the equilibrium conic angle. We also study the interactions between two spherical colloids with the equilibrium conic angle 45^{∘}, where the surface energy provides both boojum and Saturn-ring defects on the surface of particles. We compare the calculated anisotropic colloidal interactions with experimental observations [B. Senyuk et al., Nat. Commun. 7, 10659 (2016)2041-172310.1038/ncomms10659]. In agreement with experiment, our results show two stable angular assemblies in the close particle-particle separations. Also, the long-range elastic interactions are almost consistent with the hexadecapolar elastic distortion.

Colloidal suspensions in one-phase mixed solvents under shear flow.

We numerically studied the behaviour of colloidal suspensions in one-phase binary liquid mixtures under shear flows. Far from the phase-separation point, the colloidal particles are well dispersed and the suspension exhibits a Newtonian viscosity. When the mixture is close to the coexistence curve, the colloidal particles aggregate by attractive interactions due to the concentration heterogeneity caused by surface wetting, and the viscosity of the suspension increases. Near the phase-separation point, the viscosity increases when the fraction of species favoured by the surface of a colloid particle is small. The mixture also exhibits shear thinning behaviour, since the aggregated structure is rearranged into small clusters due to the shear flow. Our simulations indicate that the concentration profile around each particle is not significantly disturbed by the shear flow at the onset of the structural rearrangements. The effective interaction is independent of the shear flow and remains isotropic.

Bistable director alignments of nematic liquid crystals confined in frustrated substrates.

We studied in-plane bistable alignments of nematic liquid crystals confined by two frustrated surfaces by means of Monte Carlo simulations of the Lebwohl-Lasher spin model. The surfaces are prepared with orientational checkerboard patterns, on which the director field is locally anchored to be planar yet orthogonal between the neighboring blocks. We found the director field in the bulk tends to be aligned along the diagonal axes of the checkerboard pattern, as reported experimentally [J.-H. Kim et al., Appl. Phys. Lett. 78, 3055 (2001)APPLAB0003-695110.1063/1.1371246]. The energy barrier between the two stable orientations is increased, when the system is brought to the isotropic-nematic transition temperature. Based on an elastic theory, we found that the bistability is attributed to the spatial modulation of the director field near the frustrated surfaces. As the block size is increased and/or the elastic modulus is reduced, the degree of the director inhomogeneity is increased, enlarging the energy barrier. We also found that the switching rate between the stable states is decreased when the block size is comparable to the cell thickness.

Conformational changes of polyelectrolyte chains in solvent mixtures.

We numerically investigate the behaviors of polyelectrolyte chains in solvent mixtures, taking into account the effects of the concentration inhomogeneity and the degree of the ionization. When changing the interaction parameters between the solvent components, we found a first order transition of the polymer conformation. In the mixing state far from the coexistence curve, the polymers behave as semi-flexible chains. In the phase-separated state, on the other hand, they show compact conformations included in the droplets. As the interaction parameters of the mixture are increased, an inhomogeneous concentration field develops around the polymer and induces critical Casimir attractive interactions among the monomers. The competition between the electrostatic interactions and the critical Casimir ones gives rise to drastic changes in the conformation.

Controlled motion of Janus particles in periodically phase-separating binary fluids.

We numerically investigate the propelled motions of a Janus particle in a periodically phase-separating binary fluid mixture. In this study, the surface of the particle tail prefers one of the binary fluid components and the particle head is neutral in the wettability. During the demixing period, the more wettable phase is selectively adsorbed to the particle tail. Growths of the adsorbed domains induce the hydrodynamic flow in the vicinity of the particle tail, and this asymmetric pumping flow drives the particle toward the particle head. During the mixing period, the particle motion almost ceases because the mixing primarily occurs via diffusion and the resulting hydrodynamic flow is negligibly small. Repeating this cycle unboundedly moves the Janus particle toward the head. The dependencies of the composition and the repeat frequency on the particle motion are discussed.

Nematic caps on colloidal particles in a nematogenic liquid under an electric field.

We examine the localized nematic regions (caps) on spherical colloidal particles suspended in a nematogenic liquid in the isotropic phase in the bulk by solving the Poisson equation with an orientation-dependent dielectric tensor. These caps appear and grow with an increasing applied electric field. We assume positive dielectric anisotropy of the nematogenic liquid and a high dielectric constant of the particles. Then, the electric field becomes the strongest near the poles of each particle along the field direction, leading to nematic caps. This cap formation occurs continuously for homeotropic anchoring, but is a discontinuous transition otherwise. We also discuss how the nematic caps can be observed in dielectric response, birefringence, and depolarized light scattering.

Electro-osmotic flow of semidilute polyelectrolyte solutions.

We investigate electro-osmosis in aqueous solutions of polyelectrolytes using mean-field equations. A solution of positively charged polyelectrolytes is confined between two negatively charged planar surfaces, and an electric field is applied parallel to the surfaces. When electrostatic attraction between the polymer and the surface is strong, the polymers adhere to the surface, forming a highly viscous adsorption layer that greatly suppresses the electro-osmosis. Conversely, electro-osmosis is enhanced by depleting the polymers from the surfaces. We also found that the electro-osmotic flow is invertible when the electrostatic potential decays to its bulk value with the opposite sign. These behaviors are well explained by a simple mathematical form of the electro-osmotic coefficient.

Effects of strongly selective additives on volume phase transition in gels.

We investigate volume phase transition in gels immersed in mixture solvents, on the basis of a three-component Flory-Rehner theory. When the selectivity of the minority solvent component to the polymer network is strong, the gel tends to shrink with an increasing concentration of the additive, regardless of whether it is good or poor. This behavior originates from the difference of the additive concentration between inside and outside the gel. We also found the gap of the gel volume at the transition point can be controlled by adding the strongly selective solutes. By dissolving a strongly poor additive, for instance, the discontinuous volume phase transition can be extinguished. Furthermore, we observed that another volume phase transition occurs far from the original transition point. These behaviors can be well explained by a simplified theory neglecting the nonlinearity of the additive concentration.

Dynamic coupling between a multistable defect pattern and flow in nematic liquid crystals confined in a porous medium.

When a nematic liquid crystal is confined in a porous medium with strong anchoring conditions, topological defects, called disclinations, are stably formed with numerous possible configurations. Since the energy barriers between them are large enough, the system shows multistability. Our lattice Boltzmann simulations demonstrate dynamic couplings between the multistable defect pattern and the flow in a regular porous matrix. At sufficiently low flow speed, the topological defects are pinned at the quiescent positions. As the flow speed is increased, the defects show cyclic motions and nonlinear rheological properties, which depend on whether or not they are topologically constrained in the porous networks. In addition, we discover that the defect pattern can be controlled by controlling the flow. Thus, the flow path is recorded in the porous channels owing to the multistability of the defect patterns.

Polydomain growth at isotropic-nematic transitions in liquid crystalline polymers.

We studied the dynamics of isotropic-nematic transitions in liquid crystalline polymers by integrating time-dependent Ginzburg-Landau equations. In a concentrated solution of rodlike polymers, the rotational diffusion constant D(r) of the polymer is severely suppressed by the geometrical constraints of the surrounding polymers so that the rodlike molecules diffuse only along their rod directions. In the early stage of phase transition, the rodlike polymers with nearly parallel orientations assemble to form a nematic polydomain. This polydomain pattern, with characteristic length ℓ, grows with self-similarity in three dimensions over time with an ℓ~t(1/4) scaling law. In the late stage, the rotational diffusion becomes significant, leading to a crossover of the growth exponent from 1/4 to 1/2. This crossover time is estimated to be on the order of t~D(r)(-1). We also examined the time evolution of a pair of disclinations placed in a confined system by solving the same time-dependent Ginzburg-Landau equations in two dimensions. If the initial distance between the disclinations is shorter than some critical length, they approach and annihilate each other; however, at larger initial separations, they are stabilized.

Solvation effects in phase transitions in soft matter.

Phase transitions in polar binary mixtures can be drastically altered by even a small amount of salt. This is because the preferential solvation strongly depends on the ambient composition. Together with a summary of our research on this problem, we present some detailed results on the role of antagonistic salt composed of hydrophilic and hydrophobic ions. These ions tend to segregate at liquid-liquid interfaces and selectively couple to water-rich and oil-rich composition fluctuations, leading to mesophase formation. In our two-dimensional simulation, the coarsening of the domain structures can be stopped or slowed down, depending on the interaction parameter (or the temperature) and the salt density. We realize stripe patterns at the critical composition and droplet patterns at off-critical compositions. In the latter case, charged droplets emerge with considerable size dispersity in a percolated region. We also give the structure factors among the ions, accounting for the Coulomb interaction and the solvation interaction mediated by the composition fluctuations.

Memory and topological frustration in nematic liquid crystals confined in porous materials.

Orientational ordering is key to functional materials with switching capability, such as nematic liquid crystals and ferromagnetic and ferroelectric materials. We explored the confinement of nematic liquid crystals in bicontinuous porous structures with smooth surfaces that locally impose normal orientational order on the liquid crystal. We find that frustration leads to a high density of topological defect lines permeating the porous structures, and that most defect lines are made stable by looping around solid portions of the confining material. Because many defect trajectories are possible, these systems are highly metastable and efficient in memorizing the alignment forced by external fields. Such memory effects have their origin in the topology of the confining surface and are maximized in a simple periodic bicontinuous cubic structure. We also show that nematic liquid crystals in random porous networks exhibit a disorder-induced slowing-down typical of glasses that originates from activated collisions and rearrangements of defect lines. Our findings offer the possibility to functionalize orientationally ordered materials through topological confinement.

Hydrodynamic selection of the kinetic pathway of a polymer coil-globule transition.

Recently, the role of hydrodynamic interactions in the selection of a kinetic pathway for phase transitions has attracted considerable attention. Here we study this problem numerically by taking as an example a coil-globule transition of a single polymer, which is a prototype model of protein folding. When a swollen polymer collapses into a globule state, hydrodynamic interactions accelerate the transition. We find, on the other hand, that when a rather compact polymer collapses into the same final state, hydrodynamic interactions decelerate the transition due to a slow squeezing process of the solvent. We reveal that the degree of the initial enhancement of anisotropy of the polymer configuration determines whether hydrodynamic interactions accelerate or decelerate the collapsing dynamics. We also discuss the possible relevance of squeezing flow effects in protein folding.