Capillary-driven self-assembly of soft ellipsoidal microgels at the air-water interface.

The adsorption of ellipsoidal colloidal particles on liquid interfaces induces interfacial deformation, resulting in anisotropic interface-mediated interactions and the formation of superstructures. Soft prolate-shaped microgels at the air-water interface offer an ideal model for studying spontaneous capillary-driven self-assembly due to their tunable aspect ratio, controlled functionality, and softness. These microgels consist of a polystyrene core surrounded by a cross-linked, fluorescently labeled poly([Formula: see text]-isopropylmethylacrylamide) shell.

Growth and aging in a few phase-separating active matter systems.

Via computer simulations we study evolution dynamics in systems of continuously moving active Brownian particles. The obtained results are discussed against those from the passive 2D Ising case. Following sudden quenches of random configurations to state points lying within the miscibility gaps and to the critical points, we investigate the far-from-steady-state dynamics by calculating quantities associated with structure and characteristic length scales.

Membrane-Mediated Interactions Between Nonspherical Elastic Particles.

The transport of particles across lipid-bilayer membranes is important for biological cells to exchange information and material with their environment. Large particles often get wrapped by membranes, a process which has been intensively investigated in the case of hard particles. However, many particles in vivo and in vitro are deformable, e.

Understanding Gas Transport in Polymer-Grafted Nanoparticle Assemblies.

We rationalize the unusual gas transport behavior of polymer-grafted nanoparticle (GNP) membranes. While gas permeabilities depend specifically on the chemistry of the polymers considered, we focus here on permeabilities relative to the corresponding pure polymer which show interesting, "universal" behavior. For a given NP radius, R, and for large enough areal grafting densities, σ, to be in the dense brush regime we find that gas permeability enhancements display a maximum as a function of the graft chain molecular weight, M.

Gas Transport in Interacting Planar Brushes.

Recent experiments on melts of spherical nanoparticles (NPs) densely grafted with polymer chains show enhanced gas transport relative to the neat polymer (without NPs). As a means of understanding this unexpected behavior, we consider here the simpler case of two interacting planar brushes, under conditions representing a polymer melt far below its critical point (i.e.

Wetting transitions of polymer solutions: Effects of chain length and chain stiffness.

Wetting and drying phenomena are studied for flexible and semiflexible polymer solutions via coarse-grained molecular dynamics simulations and density functional theory calculations. This study is based on the use of Young's equation for the contact angle, determining all relevant surface tensions from the anisotropy of the pressure tensor. The solvent quality (or effective temperature, equivalently) is varied systematically, while all other interactions remain unaltered.

Blends of Semiflexible Polymers: Interplay of Nematic Order and Phase Separation.

Mixtures of semiflexible polymers with a mismatch in either their persistence lengths or their contour lengths are studied by Density Functional Theory and Molecular Dynamics simulation. Considering lyotropic solutions under good solvent conditions, the mole fraction and pressure is systematically varied for several cases of bending stiffness κ (the normalized persistence length) and chain length . For binary mixtures with different chain length (i.

Kinetics of domain growth and aging in a two-dimensional off-lattice system.

We have used molecular dynamics simulations for a comprehensive study of phase separation in a two-dimensional single-component off-lattice model where particles interact through the Lennard-Jones potential. Via state-of-the-art methods we have analyzed simulation data on structure, growth, and aging for nonequilibrium evolutions in the model. These data were obtained following quenches of well-equilibrated homogeneous configurations, with density close to the critical value, to various temperatures inside the miscibility gap, having vapor-"liquid" as well as vapor-"solid" coexistence.

Entropic Unmixing in Nematic Blends of Semiflexible Polymers.

Binary mixtures of semiflexible polymers with the same chain length, but different persistence lengths, separate into two coexisting different nematic phases when the osmotic pressure of the lyotropic solution is varied. Molecular Dynamics simulations and Density Functional Theory predict phase diagrams either with a triple point, where the isotropic phase coexists with two nematic phases or a critical point of unmixing within the nematic mixture. The difference in locally preferred bond angles between the constituents drives this unmixing without any attractive interactions between monomers.

Tuning Selectivities in Gas Separation Membranes Based on Polymer-Grafted Nanoparticles.

Polymer membranes are critical to many sustainability applications that require the size-based separation of gas mixtures. Despite their ubiquity, there is a continuing need to selectively affect the transport of different mixture components while enhancing mechanical strength and hindering aging. Polymer-grafted nanoparticles (GNPs) have recently been explored in the context of gas separations.

Structure of Polymer-Grafted Nanoparticle Melts.

The structure of neat melts of polymer-grafted nanoparticles (GNPs) is studied coarse-grained molecular dynamics simulations. We systematically vary the degree of polymerization and grafting density at fixed nanoparticle (NP) radius and study in detail the shape and size of the GNP coronas. For sufficiently high grafting density, chain sections close to the NP core are extended and form a dry layer.

Phase behavior of flexible and semiflexible polymers in solvents of varying quality.

The interplay of nematic order and phase separation in solutions of semiflexible polymers in solvents of variable quality is investigated by density functional theory (DFT) and molecular dynamics (MD) simulations. We studied coarse-grained models, with a bond-angle potential to control chain stiffness, for chain lengths comparable to the persistence length of the chains. We varied both the density of the monomeric units and the effective temperature that controls the quality of the implicit solvent.

Disentangling the Role of Chain Conformation on the Mechanics of Polymer Tethered Particle Materials.

The linear elastic properties of isotropic materials of polymer tethered nanoparticles (NPs) are evaluated using noncontact Brillouin light spectroscopy. While the mechanical properties of dense brush materials follow predicted trends with NP composition, a surprising increase in elastic moduli is observed in the case of sparsely grafted particle systems at approximately equal NP filling ratio. Complementary molecular dynamics simulations reveal that the stiffening is caused by the coil-like conformations of the grafted chains, which lead to stronger polymer-polymer interactions compared to densely grafted NPs with short chains.

Segregation in Drying Binary Colloidal Droplets.

When a colloidal suspension droplet evaporates from a solid surface, it leaves a characteristic deposit in the contact region. These deposits are common and important for many applications in printing, coating, or washing. By the use of superamphiphobic surfaces as a substrate, the contact area can be reduced so that evaporation is almost radially symmetric.

Kinetics of Vapor-Solid Phase Transitions: Structure, Growth, and Mechanism.

The kinetics of the separation between low and high density phases in a single component Lennard-Jones model is studied via molecular dynamics simulations, at very low temperatures, in the space dimension d=2. For densities close to the vapor branch of the coexistence curve, disconnected nanoscale clusters of the high density phase exhibit essentially ballistic motion. Starting from nearly circular shapes, at the time of nucleation, these clusters grow via sticky collisions, gaining filamentlike nonequilibrium structure at a later time, with a very low fractal dimensionality.

Finite-size scaling study of dynamic critical phenomena in a vapor-liquid transition.

Via a combination of molecular dynamics (MD) simulations and finite-size scaling (FSS) analysis, we study dynamic critical phenomena for the vapor-liquid transition in a three dimensional Lennard-Jones system. The phase behavior of the model has been obtained via the Monte Carlo simulations. The transport properties, viz.

Droplet growth during vapor-liquid transition in a 2D Lennard-Jones fluid.

Results for the kinetics of vapor-liquid phase transition have been presented from the molecular dynamics simulations of a single component two-dimensional Lennard-Jones fluid. The phase diagram for the model, primary prerequisite for this purpose, has been obtained via the Monte Carlo simulations. Our focus is on the region very close to the vapor branch of the coexistence curve.

Dimensionality dependence of aging in kinetics of diffusive phase separation: Behavior of order-parameter autocorrelation.

Behavior of two-time autocorrelation during the phase separation in solid binary mixtures is studied via numerical solutions of the Cahn-Hilliard equation as well as Monte Carlo simulations of the Ising model. Results are analyzed via state-of-the-art methods, including the finite-size scaling technique. Full forms of the autocorrelation in space dimensions 2 and 3 are obtained empirically.

Aging in ferromagnetic ordering: full decay and finite-size scaling of autocorrelation.

Nonequilibrium dynamics in Ising and Ginzburg-Landau models were studied for a nonconserved order parameter that mimics ordering in ferromagnets. The focus was on the understanding of the decay of the two time (t, t(w); t > tw) order-parameter correlation function. For this quantity, a full form has been obtained empirically which, for t ≫ t(w), provides a power-law ∼ (ℓ/ℓ(w))(-λ), ℓ and ℓ(w) being the characteristic lengths at t and tw, respectively.