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Register a new userTheoretical study of line and boundary tension in adsorbed colloid-polymer mixtures
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An extended theoretical study of interface potentials in adsorbed colloid-polymer mixtures is performed. To describe the colloid-polymer mixture near a hard wall, a simple Cahn-Nakanishi-Fisher free-energy functional is used. The bulk phase behavior and the substrate-adsorbate interaction are modelled by the free-volume theory for ideal polymers with polymer-to-colloid size ratios q=0.6 and q=1. The interface potentials are constructed with help from a Fisher-Jin crossing constraint. By manipulating the crossing density, a complete interface potential can be obtained from natural, single-crossing, profiles. The line tension in the partial wetting regime and the boundary tension along prewetting are computed from the interface potentials. The line tensions are of either sign, and descending with increasing contact angle. The line tension takes a positive value of 10^-14 - 10^-12 N near a first-order wetting transition, passes through zero and decreases to minus 10^-14 - 10^-12 N away from the first-order transition. The calculations of the boundary tension along prewetting yield values increasing from zero at the prewetting critical point up to the value of the line tension at first-order wetting.
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We extensively investigated the critical behavior of mixtures of colloids and polymers via the two-component Asakura-Oosawa model and its reduction to a one-component colloidal fluid using accurate theoretical and simulation techniques. In particular the theoretical approach, hierarchical reference theory [Adv. Phys. 44, 211 (1995)], incorporates realistically the effects of long-range fluctuations on phase separation giving exponents which differ strongly from their mean-field values, and are in good agreement with those of the three-dimensional Ising model. Computer simulations combined with finite-size scaling analysis confirm the Ising universality and the accuracy of the theory, although some discrepancy in the location of the critical point between one-component and full-mixture description remains. To assess the limit of the pair-interaction description, we compare one-component and two-component results.
We show that the critical behavior of a colloid-polymer mixture inside a random porous matrix of quenched hard spheres belongs to the universality class of the random-field Ising model. We also demonstrate that random-field effects in colloid-polymer mixtures are surprisingly strong. This makes these systems attractive candidates to study random-field behavior experimentally.
As first explained by the classic Asakura-Oosawa (AO) model, effective attractive forces between colloidal particles induced by depletion of nonadsorbing polymers can drive demixing of colloid-polymer mixtures into colloid-rich and colloid-poor phases, with practical relevance for purification of water, stability of foods and pharmaceuticals, and macromolecular crowding in biological cells. By idealizing polymer coils as effective penetrable spheres, the AO model qualitatively captures the influence of polymer depletion on thermodynamic phase behavior of colloidal suspensions. In previous work, we extended the AO model to incorporate aspherical polymer conformations and showed that fluctuating shapes of random-walk coils can significantly modify depletion potentials [W. K. Lim and A. R. Denton, Soft Matter 12, 2247 (2016); J. Chem. Phys. 144, 024904 (2016)]. We further demonstrated that the shapes of polymers in crowded environments depend sensitively on solvent quality [W. J. Davis and A. R. Denton, J. Chem. Phys. 149, 124901 (2018)]. Here we apply Monte Carlo simulation to analyze the influence of solvent quality on depletion potentials in mixtures of hard sphere colloids and nonadsorbing polymer coils, modeled as ellipsoids whose principal radii fluctuate according to random-walk statistics. We consider both self-avoiding and non-self-avoiding random walks, corresponding to polymers in good and theta solvents, respectively. Our simulation results demonstrate that depletion of polymers of equal molecular weight induces much stronger attraction between colloids in good solvents than in theta solvents and confirm that depletion interactions are significantly influenced by aspherical polymer conformations.
We investigated the viscoelastic properties of colloid-polymer mixtures at intermediate colloid volume fraction and varying polymer concentrations, thereby tuning the attractive interactions. Within the examined range of polymer concentrations, the samples ranged from fluids to gels. Already in the liquid phase the viscoelastic properties significantly changed when approaching the gelation boundary, indicating the formation of clusters and transient networks. This is supported by an increasing correlation length of the density fluctuations, observed by static light scattering and microscopy. At the same time, the correlation function determined by dynamic light scattering completely decays, indicating the absence of dynamical arrest. Upon increasing the polymer concentration beyond the gelation boundary, the rheological properties changed qualitatively again, now they are consistent with the formation of colloidal gels. Our experimental results, namely the location of the gelation boundary as well as the elastic (storage) and viscous (loss) moduli, are compared to different theoretical models. These include consideration of the escape time as well as predictions for the viscoelastic moduli based on scaling relations and Mode Coupling Theories (MCT).
As a generic model for liquid-vapour type transitions in random porous media, the Asakura-Oosawa model for colloid-polymer mixtures is studied in a matrix of quenched spheres using extensive Monte Carlo (MC) simulations. Since such systems at criticality, as well as in the two-phase region, exhibit lack of self-averaging, the analysis of MC data via finite size scaling requires special care. After presenting the necessary theoretical background and the resulting subtleties of finite size scaling in random-field Ising-type systems, we present data on the order parameter distribution (and its moments) as a function of colloid and polymer fugacities for a broad range of system sizes, and for many (thousands) realizations of the porous medium. Special attention is paid to the connected and disconnected susceptibilities, and their respective critical behavior. We show that both susceptibilities diverge at the critical point, and we demonstrate that this is compatible with the predicted scenario of random-field Ising universality.
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