Phase Behavior Of Colloids Research Articles

Equilibrium and non-equilibrium cluster phases in colloids with competing interactions.

The phase behavior of colloids that interact via competing interactions - short-range attraction and long-range repulsion - is studied by computer simulation. In particular, for a fixed strength and range of repulsion, the effect of the strength of an attractive interaction (ε) on the phase behavior is investigated at various colloid densities (ρ). A thermodynamically stable equilibrium colloidal cluster phase, consisting of compact crystalline clusters, is found below the fluid-solid coexistence line in the ε-ρ parameter space. The mean cluster size is found to linearly increase with the colloid density. At large ε and low densities, and at small ε and high densities, a non-equilibrium cluster phase, consisting of elongated Bernal spiral-like clusters, is observed. Although gelation can be induced either by increasing ε at constant density or vice versa, the gelation mechanism is different in either route. While in the ρ route gelation occurs via a glass transition of compact clusters, gelation in the ε route is characterized by percolation of elongated clusters. This study both provides the location of equilibrium and non-equilibrium cluster phases with respect to the fluid-solid coexistence, and reveals the dependencies of the gelation mechanism on the preparation route.

Hydrodynamics Determines Collective Motion and Phase Behavior of Active Colloids in Quasi-Two-Dimensional Confinement

We study the collective motion of confined spherical microswimmers such as active colloids which we model by so-called squirmers. To simulate hydrodynamic flow fields including thermal noise, we use the method of multiparticle collision dynamics. We demonstrate that hydrodynamic near fields acting between squirmers as well as between squirmers and bounding walls crucially determine their collective motion. In particular, with increasing density we observe a clear phase separation into a gaslike and cluster phase for neutral squirmers whereas strong pushers and pullers more gradually approach the hexagonal cluster state.

Theory of two-dimensional self-assembly of Janus colloids: crystallization and orientational ordering

We study the rich crystalline phase behavior of amphiphilic spherical Janus colloids using a new formulation of self-consistent phonon theory that includes coupled translational and rotational entropic and enthalpic contributions to the free energy. In contrast to homogeneous spheres, broken rotational symmetry can result in more exotic crystals that possess distinct orientational patterns, and also plastic crystals. Ground states are identified based on the compatibility between the patch geometry of particles (e.g., patch coverage, number, shape) and lattice symmetry. We derive the explicit coupled self-consistent equations for translational and rotational localization parameters for effectively 2-dimensional dense monolayers of Janus crystals. The equations are numerically solved for a given crystal symmetry, thermodynamic state, and patch orientational order, and the thermodynamic stability of different phases is determined. For hexagonal packing, we predict with increasing temperature or decreasing attraction strength the possibility of a phase sequence of maximally bonded zigzag stripe, trimer, and rotationally disordered plastic crystal phases (or a phase sequence of trimer, dimer, and plastic crystal), which depends sensitively on particle chemical composition (Janus balance) and pressure. The role of rotational entropy in stabilizing the intermediate trimer (or dimer) phase at intermediate temperatures and high pressures is discussed in detail. Evolution of the center-of-mass vibrational and rotational amplitudes with thermodynamic state and Janus balance is also determined.

Phase behavior of the modified-Yukawa fluid and its sticky limit

Simple model systems with short-range attractive potentials have turned out to play a crucial role in determining theoretically the phase behavior of proteins or colloids. However, as pointed out by D. Gazzillo [J. Chem. Phys. 134, 124504 (2011)], one of these widely used model potentials, namely, the attractive hard-core Yukawa potential, shows an unphysical behavior when one approaches its sticky limit, since the second virial coefficient is diverging. However, it is exactly this second virial coefficient that is typically used to depict the experimental phase diagram for a large variety of complex fluids and that, in addition, plays an important role in the Noro-Frenkel scaling law [J. Chem. Phys. 113, 2941 (2000)], which is thus not applicable to the Yukawa fluid. To overcome this deficiency of the attractive Yukawa potential, D. Gazzillo has proposed the so-called modified hard-core attractive Yukawa fluid, which allows one to correctly obtain the second and third virial coefficients of adhesive hard-spheres starting from a system with an attractive logarithmic Yukawa-like interaction. In this work we present liquid-vapor coexistence curves for this system and investigate its behavior close to the sticky limit. Results have been obtained with the self-consistent Ornstein-Zernike approximation (SCOZA) for values of the reduced inverse screening length parameter up to 18. The accuracy of SCOZA has been assessed by comparison with Monte Carlo simulations.

Temperature-sensitive colloidal phase behavior induced by critical Casimir forces

We report Monte Carlo simulations of phase behavior of colloidal suspensions with near-critical binary solvents using effective pair potentials from experiments. At off-critical solvent composition, the calculated phase diagram agrees well with measurements of the experimental system, indicating that many-body effects are limited. Close to the critical composition, however, agreement between experiment and simulation becomes poorer, signaling the increased importance of many-body effects. Both at and off the critical solvent concentration, the colloidal phase diagram is qualitatively similar to those of molecular systems and obeys the principle of corresponding states with one striking difference: it occurs in a narrow temperature interval of <1 °C below the solvent phase separation temperature.

Charged colloidal model systems under confinement in slit geometry: A new setup for optical microscopic studies

A new experimental setup for optical microscopic studies of charged colloidal model systems under confinement between two flat walls is presented. The measurement cell consists of optically flat quartz substrates attached to piezo actuators. Those facilitate fast and flexible adjustment of the confining geometry. Optionally, the local cell height can be quantitatively controlled by in situ interferometric measurements. Proper choice of materials guarantees sufficient chemical inertia against contamination with salt ions. For efficient preparation of charged colloidal suspensions under strongly deionized conditions, the cell can be connected to a conventional pump circuit including a mixed bed ion exchanger column. The usefulness of this setup, in particular for investigating the equilibrium phase behavior of colloids at low background salt concentrations, is demonstrated recalling recent experiments.

Generating an in situ tunable interaction potential for probing 2-D colloidal phase behavior

Download options Please wait... Supplementary files Supplementary movie AVI (770K) Supplementary information PDF (117K) Supplementary movie AVI (185K) Supplementary movie AVI (241K) Supplementary movie AVI (182K) Article information DOI https://doi.org/10.1039/C3SM27620A Article type Paper Submitted 14 Nov 2012 Accepted 07 Feb 2013 First published 11 Mar 2013 Download Citation Soft Matter, 2013,9, 6867-6875 BibTex EndNote MEDLINE ProCite ReferenceManager RefWorks RIS Permissions Request permissions Generating an in situ tunable interaction potential for probing 2-D colloidal phase behavior D. Du, D. Li, M. Thakur and S. L. Biswal, Soft Matter, 2013, 9, 6867 DOI: 10.1039/C3SM27620A To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page. If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given. If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page. Read more about how to correctly acknowledge RSC content. Social activity Tweet Share Search articles by author Di Du Dichuan Li Madhuri Thakur Sibani Lisa Biswal

Phase behaviour of colloids with short-range repulsions plus nonadsorbing polymer chains

The colloidal gas–liquid phase behaviour has been studied for aqueous mixtures of well-defined spherical particles with short-ranged repulsions mixed with relatively monodisperse poly(ethylene oxide) polymers. We show that our set of experimental phase diagrams are in quantitative agreement with theoretical predictions using generalized free volume theory [G. J. Fleer and R. Tuinier, Phys. Rev. E, 2007, 76, 041802]. The determination of the equilibrium composition of coexisting phases reveals qualitative deviations between the two, for which we propose a tentative explanation.

Effect of controlled corrugation on capillary condensation of colloid–polymer mixtures

We investigate with Monte Carlo computer simulations the capillary phase behaviour of model colloid–polymer mixtures confined between a flat wall and a corrugated wall. The corrugation is modelled via a sine wave as a function of one of the in-plane coordinates leading to a depletion attraction between colloids and the corrugated wall that is curvature dependent. We find that for an increased amplitude of corrugation the region of the phase diagram where capillary condensation occurs becomes larger. We derive a Kelvin equation for this system and compare its predictions to the simulation results. We find good agreement between the theory and simulation indicating that the primary reason for the stronger capillary condensation is an increased contact area between the fluid and the corrugated substrate. On the other hand, the colloid adsorption curves at colloid gas–liquid coexistence show that the increased area is not solely responsible for the stronger capillary condensation. Additionally, we analyse the dimensional crossover from a quasi-2D to a quasi-1D system and find that the transition is characterised by the appearance of a metastable phase.

Procedure to construct a multi-scale coarse-grained model of DNA-coated colloids from experimental data

We present a quantitative, multi-scale coarse-grained model of DNA coated colloids. The parameters of this model are transferable and are solely based on experimental data. As a test case, we focus on nano-sized colloids carrying single-stranded DNA of length comparable to the colloids' size. We show that in this regime, the common theoretical approach of assuming pairwise additivity of the colloidal pair interactions leads to quantitatively and sometimes even qualitatively wrong predictions of the phase behaviour of DNA-grafted colloids. Compared to experimental data, we find that our coarse-grained model correctly predicts the equilibrium structure and melting temperature of the formed solids. Due to limited experimental information on the persistence length of single-stranded DNA, some quantitative discrepancies are found in the prediction of spatial quantities. With the availability of better experimental data, the present approach provides a path for the rational design of DNA-functionalised building blocks that can self-assemble into complex, three-dimensional structures.

The entropic impact of tethering, multivalency and dynamic recruitment in systems with specific binding groups

This Highlight Article discusses the important yet frequently overlooked entropic effects in soft matter systems that have one or more tethered binding groups. We show that the effective interactions depend sensitively on a combination of configurational, combinatorial and translational entropy factors, which have to do with the tethering of the binding groups, the binding state multiplicity in multivalent systems, and the dynamic recruitment of surface-mobile binding groups. Importantly, these entropic effects can give rise to qualitatively new behavior, e.g. in the phase behavior of DNA-functionalized colloids or in the targeting of ligand-functionalized nanoparticles to cell receptors. A better understanding of the thermodynamics of tethered (multivalent) bond interactions thus impacts a wide range of fields, including soft materials science, biophysics, nanomedicine and biosensing, supramolecular and colloidal self-assembly, and nanofabrication.

Phase behavior of colloids and proteins in aqueous suspensions: Theory and computer simulations

The fluid phase behavior of colloidal suspensions with short-range attractive interactions is studied by means of Monte Carlo computer simulations and two theoretical approximations, namely, the discrete perturbation theory and the so-called self-consistent Ornstein-Zernike approximation. The suspensions are modeled as hard-core attractive Yukawa (HCAY) and Asakura-Oosawa (AO) fluids. A detailed comparison of the liquid-vapor phase diagrams obtained through different routes is presented. We confirm Noro-Frenkel's extended law of scaling according to which the properties of a short-ranged fluid at a given temperature and density are independent of the detailed form of the interaction, but just depend on the value of the second virial coefficient. By mapping the HCAY and AO fluids onto an equivalent square-well fluid of appropriate range at the critical point we show that the critical temperature as a function of the effective range is independent of the interaction potential, i.e., all curves fall in a master curve. Our findings are corroborated with recent experimental data for lysozyme proteins.

Inhomogeneous fluids of colloidal hard dumbbells: Fundamental measure theory and Monte Carlo simulations

Recently, a density functional theory for hard particles with shape anisotropy was developed, the extended deconvolution fundamental measure theory (edFMT). We apply edFMT to hard dumbbells, arguably the simplest non-convex shape and readily available experimentally in the form of colloids. We obtain good agreement between edFMT and Monte Carlo simulations for fluids of dumbbells in a slit and for the same system under gravity. This indicates that edFMT can be successfully applied to nearly all colloidal shapes, not just for the convex shapes for which edFMT was originally derived. A theory, such as edFMT, that allows a fast and general way of mapping the phase behavior of anisotropic colloids, can act as a useful guide for the design of colloidal shapes for various applications.

Polymer Mediated Depletion Attraction and Interfacial Colloidal Phase Behavior

We report direct measurements of poly(ethylene oxide) (PEO) mediated depletion attraction between colloids and surfaces using total internal reflection microscopy (TIRM) and in quasi-2D colloidal phase behavior using video microscopy (VM). PEO concentration dependent particle-wall depletion attraction is accurately quantified by a modified Asakura–Oosawa (AO) potential. The modified AO potential employs an equation of state, depletion length, and partition coefficient computed using results from renormalization group (RG) theory. Quasi-2D phase behavior measurements are in excellent agreement with Monte Carlo (MC) simulations using the same modified AO potential. The analytically simple modified AO depletion potential accurately captures depletion attraction for a realistic excluded volume polymer system, which suggests it can be generalized to other material systems.

Design Rule for Colloidal Crystals of DNA-Functionalized Particles

We report a Monte Carlo simulation study of the phase behavior of colloids coated with long, flexible DNA chains. We find that an important change occurs in the phase diagram when the number of DNAs per colloid is decreased below a critical value. In this case, the triple point disappears and the condensed phase that coexists with the vapor is always liquid. Our simulations thus explain why, in the dilute solutions typically used in experiments, colloids coated with a small number of DNA strands cannot crystallize. We understand this behavior in terms of the discrete nature of DNA binding.

Recent advances in colloidal and interfacial phenomena involving liquid crystals.

This feature article describes recent advances in several areas of research involving the interfacial ordering of liquid crystals (LCs). The first advance revolves around the ordering of LCs at bio/chemically functionalized surfaces. Whereas the majority of past studies of surface-induced ordering of LCs have involved surfaces of solids that present a limited diversity of chemical functional groups (surfaces at which van der Waals forces dominate surface-induced ordering), recent studies have moved to investigate the ordering of LCs on chemically complex surfaces. For example, surfaces decorated with biomolecules (e.g., oligopeptides and proteins) and transition-metal ions have been investigated, leading to an understanding of the roles that metal-ligand coordination interactions, electrical double layers, acid-base interactions, and hydrogen bonding can play in the interfacial ordering of LCs. The opportunity to create chemically responsive LCs capable of undergoing ordering transitions in the presence of targeted molecular events (e.g., ligand exchange around a metal center) has emerged from these fundamental studies. A second advance has focused on investigations of the ordering of LCs at interfaces with immiscible isotropic fluids, particularly water. In contrast to prior studies of surface-induced ordering of LCs on solid surfaces, LC-aqueous interfaces are deformable and molecules at these interfaces exhibit high levels of mobility and thus can reorganize in response to changes in the interfacial environment. A range of fundamental investigations involving these LC-aqueous interfaces have revealed that (i) the spatial and temporal characteristics of assemblies formed from biomolecular interactions can be reported by surface-driven ordering transitions in the LCs, (ii) the interfacial phase behavior of molecules and colloids can be coupled to (and manipulated via) the ordering (and nematic elasticity) of LCs, and (iii) the confinement of LCs leads to unanticipated size-dependent ordering (particularly in the context of LC emulsion droplets). The third and final advance addressed in this article involves interactions between colloids mediated by LCs. Recent experiments involving microparticles deposited at the LC-aqueous interface have revealed that LC-mediated interactions can drive interfacial assemblies of particles through reversible ordering transitions (e.g., from 1D chains to 2D arrays with local hexagonal symmetry). In addition, recent single-nanoparticle measurements suggest that the ordering of LCs about nanoparticles differs substantially from micrometer-sized particles and that the interactions between nanoparticles mediated by the LCs are far weaker than predicted by theory (sufficiently weak that the interactions are reversible and thus enable self-assembly). Finally, LC-mediated interactions between colloidal particles have also been shown to lead to the formation of colloid-in-LC gels that possess mechanical properties relevant to the design of materials that interface with living biological systems. Overall, these three topics serve to illustrate the broad opportunities that exist to do fundamental interfacial science and discovery-oriented research involving LCs.

Charged Micelle Depletion Attraction and Interfacial Colloidal Phase Behavior

Ensemble total internal reflection microscopy (TIRM) is used to directly measure the evolution of colloid-surface depletion attraction with increasing sodium dodecyl sulfate (SDS) concentration near the critical micelle concentration (CMC). Measured potentials are well described by a modified Asakura-Oosawa (AO) depletion potential in addition to electrostatic and van der Waals contributions. The modified AO potential includes effects of electrostatic interactions between micelles and surfaces via effective depletant dimensions in an excluded volume term and partitioning in an osmotic pressure term. Directly measured colloid-surface depletion potentials are used in Monte Carlo (MC) simulations to capture video microscopy (VM) measurements of micelle-mediated quasi-two-dimensional phase behavior including fluid, crystal, and gel microstructures. Our findings provide information to develop more rigorous and analytically simple models of depletion attraction in charged micellar systems.

Colloidal phase behavior of pH-responsive, amphiphilic PEGylated poly(carboxylic acid)s and effect on kinetic solubility under acidic conditions

PEGylated poly(carboxylic acid)s, PEG-b-PCAs, were evaluated as additives for solubilized oral formulations of weakly acidic compounds. Micelles of poly(ethylene glycol)-block-poly(acrylic acid), PEG-b-PAA, and poly(ethylene glycol)-block-poly(methacrylic acid), PEG-b-PMAA, were prepared. Fluorescence spectroscopy and dynamic light scattering revealed that both polymers assemble into nanoscopic structures (< 200 nm) in acidic media and exhibit pH-sensitive colloidal phase behavior. Using a solvent evaporation technique, the block copolymers and corresponding PCA homopolymers were incorporated into PEG3350-based solid dispersions. The kinetic solubility profile of a BMS compound, BMS-A (Seq ~ 12.5 μg/mL at pH 1.1) in 0.1 N HCl was monitored as a function of polymer composition. While BMS-A precipitated rapidly in 0.1 N HCl in the absence of PEG-b-PCAs, a supersaturated level of ca. 400 μg/mL was maintained for variable lengths of time in the presence of PEG-b-PCAs. Although the kinetic solubility of BMS-A was also enhanced in the presence of the PCA homopolymers, the relative magnitude and duration of supersaturation as a function of polymer composition suggests that micellar solubilization, rather than specific interaction, contributes to enhanced solubility of BMS-A in 0.1 N HCl. Under acidic conditions, pH-responsive PEG-b-PCAs may offer the kinetic supersaturation necessary to minimize precipitation of compounds which have limited solubility in acidic milieu.

Study on crystallization kinetics of binary alloys through model colloidal mixtures

Since the discovery of amorphous alloys, extensive attentions have been paid to understand the mechanism of glass-forming. The structural studies on its underlying mechanism have met challenge on direct structural characterization. It has been shown that the phase behavior of colloids dispersed in a solvent is thermodynamically equivalent to that of atoms and small molecules, however, colloids can be studied with optical microscopy due to their relatively large size. In this work, we use a binary colloidal model system with the particle size ratio comparable to atomic ratio of reported binary bulk metallic glasses to study the topological effect on crystallization and glass-forming ability of binary metallic alloys (Cu–Hf and Cu–Zr systems). The crystallization kinetics and structure of the colloid system were studied by real-time optical examination and light scattering technique. The results exhibit that there are two confined regions in the mixing ratio (composition) range in the colloid system with an enhanced glass-forming ability and retarded crystallization kinetics. The agreement between results of the model system and the experimental data on the binary bulk metallic glass formation suggests that purely topological factor plays an important role in determining the glass-forming ability.

Phase behavior of repulsive polymer-tethered colloids

We report molecular dynamics simulations of a system of repulsive, polymer-tethered colloidal particles. We use an explicit polymer model to explore how the length and the behavior of the polymer (ideal or self-avoiding) affect the ability of the particles to organize into ordered structures when the system is compressed to moderate volume fractions. We find a variety of different phases whose origin can be explained in terms of the configurational entropy of polymers and colloids. Finally, we discuss and compare our results to those obtained for similar systems using simplified coarse-grained polymer models, and set the limits of their applicability.