Biomedical subjects

R L C Vink

Publications and source records attributed to R L C Vink.

13 recordsLinked to original sources

PubMed2006

Phase diagram and structure of colloid-polymer mixtures confined between walls.

The influence of confinement, due to flat parallel structureless walls, on phase separation in colloid-polymer mixtures, is investigated by means of grand-canonical Monte Carlo simulations. Ultrathin films, with thicknesses between D=3-10 colloid diameters, are studied. The Asakura-Oosawa model [J. Chem. Phys. 22, 1255 (1954)] is used to describe the particle interactions. To simulate efficiently, a "cluster move" [J. Chem. Phys. 121, 3253 (2004)] is used in conjunction with successive umbrella sampling [J. Chem. Phys. 120, 10925 (2004)]. These techniques, when combined with finite size scaling, enable an accurate determination of the unmixing binodal. Our results show that the critical behavior of the confined mixture is described by "effective" critical exponents, which gradually develop from values near those of the two-dimensional Ising model, to those of the three-dimensional Ising model, as D increases. The scaling predictions of and Fisher and Nakanishi [J. Chem. Phys. 75, 5875 (1981)] for the shift of the critical point are compatible with our simulation results. Surprisingly, however, the colloid packing fraction at criticality approaches its bulk (D-->infinity) value nonmonotonically, as D is increased. Far from the critical point, our results are compatible with the simple Kelvin equation, implying a shift of order 1/D in the coexistence colloid chemical potential. We also present density profiles and pair distribution functions for a number of state points on the binodal, and the influence of the colloid-wall interaction is studied.

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PubMed2006

Coexistence diameter in two-dimensional colloid-polymer mixtures.

We demonstrate that the law of the rectilinear coexistence diameter in two-dimensional mixtures of nonspherical colloids and nonadsorbing polymers is violated. Upon approach to the critical point, the diameter shows logarithmic singular behavior governed by a term t ln t, with t the relative distance from the critical point. No sign of a term t2beta could be detected, with beta the critical exponent of the order parameter, indicating a very weak or absent Yang-Yang anomaly. Our analysis thus reveals that nonspherical particle shape alone is not sufficient for the formation of a pronounced Yang-Yang anomaly in the critical behavior of fluids.

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PubMed2006

Critical behavior in colloid-polymer mixtures: theory and simulation.

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 [A. Parola and L. Reatto, 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.

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PubMed2006

Critical behavior of a colloid-polymer mixture confined between walls.

We investigate the influence of confinement on phase separation in colloid-polymer mixtures. To describe the particle interactions, the colloid-polymer model of Asakura and Oosawa [J. Chem. Phys. 22, 1255 (1954)] is used. Grand canonical Monte Carlo simulations are then applied to this model confined between two parallel hard walls, separated by a distance D = 5 colloid diameters. We focus on the critical regime of the phase separation and look for signs of crossover from three-dimensional (3D) Ising to two-dimensional (2D) Ising universality. To extract the critical behavior, finite size scaling techniques are used, including the recently proposed algorithm of Kim et al [Phys. Rev. Lett. 91, 065701 (2003)]. Our results point to "effective" critical exponents that differ profoundly from 3D Ising values, and that are already very close to 2D Ising values. In particular, we observe that the critical exponent of the order parameter in the confined system is smaller than in 3D bulk, yielding a "flatter" binodal. Our results also show an increase in the critical colloid packing fraction in the confined system with respect to the bulk. The latter seems consistent with theoretical expectations, although subtleties due to singularities in the critical behavior of the coexistence diameter cannot be ruled out.

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PubMed2006

Critical behavior of the Widom-Rowlinson mixture: coexistence diameter and order parameter.

The critical behavior of the Widom-Rowlinson [J. Chem. Phys. 52, 1670 (1970)] is studied in d = 3 dimensions by means of grand canonical Monte Carlo simulations. The finite-size scaling approach of Kim et al. [Phys. Rev. Lett. 91, 065701 (2003)] is used to extract the order parameter and the coexistence diameter. It is demonstrated that the critical behavior of the diameter is dominated by a singular term proportional to t(1-alpha), with t the relative distance from the critical point, and alpha the critical exponent of the specific heat. No sign of a term proportional to t(2beta) could be detected, with beta the critical exponent of the order parameter, indicating that pressure mixing in this model is small. The critical density is measured to be rhosigma3 = 0.7486 +/- 0.0002, with sigma the particle diameter. The critical exponents alpha and beta, as well as the correlation length exponent nu, are also measured and shown to comply with d = 3 Ising criticality.

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PubMed2005

Bulk and interfacial properties in colloid-polymer mixtures.

Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points in the phase-coexistence region, without the use of any fit parameters.

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PubMed2005

Isotropic-nematic interfacial tension of hard and soft rods: application of advanced grand canonical biased-sampling techniques.

Coexistence between the isotropic and the nematic phase in suspensions of rods is studied using grand canonical Monte Carlo simulations with a bias on the nematic order parameter. The biasing scheme makes it possible to estimate the interfacial tension gamma(IN) in systems of hard and soft rods. For hard rods with LD=15, we obtain gammaIN approximately 1.4kBT/L2, with L the rod length, D the rod diameter, T the temperature, and kB the Boltzmann constant. This estimate is in good agreement with theoretical predictions, and the order of magnitude is consistent with experiments.

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PubMed2005

Simulation and theory of fluid demixing and interfacial tension of mixtures of colloids and nonideal polymers.

An extension of the Asakura-Oosawa-Vrij model of hard sphere colloids and nonadsorbing polymers is studied with grand canonical Monte Carlo simulations and density functional theory. Polymer nonideality is taken into account through a repulsive step-function pair potential between polymers. Simulation results validate previous theoretical findings for the shift of the bulk fluid demixing binodal upon increasing strength of polymer-polymer repulsion, indicating suppression of phase separation. For increasing strength of the polymer-polymer repulsion, simulation and theory consistently predict the interfacial tension of the free interface between the colloidal liquid and the colloidal gas phase to decrease significantly for fixed colloid density difference in the coexisting phases, and to increase for fixed polymer reservoir packing fraction.

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PubMed2005

Interfacial tension of the isotropic-nematic interface in suspensions of soft spherocylinders.

The isotropic to nematic transition in a system of soft spherocylinders is studied by means of grand canonical Monte Carlo simulations. The probability distribution of the particle density is used to determine the coexistence densities of the isotropic and the nematic phases. The distributions are also used to compute the interfacial tension of the isotropic-nematic interface, including an analysis of finite size effects. Our results confirm that the Onsager limit is not recovered until for very large elongation, exceeding at least L/D=40 , with L the spherocylinder length and D the diameter. For smaller elongation, we find that the interfacial tension increases with increasing L/D , in agreement with theoretical predictions.

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PubMed2005

Capillary waves in a colloid-polymer interface.

The structure and the statistical fluctuations of interfaces between coexisting phases in the Asakura-Oosawa model [J. Chem. Phys. 22, 1255 (1954)] for a colloid-polymer mixture are analyzed by extensive Monte Carlo simulations. We make use of a recently developed grand canonical cluster move with an additional constraint stabilizing the existence of two interfaces in the (rectangular) box that is simulated. Choosing very large systems, of size L x L x D with L=60 and D=120, measured in units of the colloid radius, the spectrum of capillary wave-type interfacial excitations is analyzed in detail. The local position of the interface is defined in terms of a (local) Gibbs surface concept. For small wave vectors capillary wave theory is verified quantitatively, while for larger wave vectors pronounced deviations show up. When one analyzes the data in terms of the concept of a wave vector-dependent interfacial tension, a monotonous decrease of this quantity with increasing wave vector is found. Limitations of our analysis are critically discussed.

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PubMed2005

Critical phenomena in colloid-polymer mixtures: interfacial tension, order parameter, susceptibility, and coexistence diameter.

The critical behavior of a model colloid-polymer mixture, the so-called Asakura-Oosawa (AO) model, is studied using computer simulations and finite size scaling techniques. Investigated are the interfacial tension, the order parameter, the susceptibility, and the coexistence diameter. Our results clearly show that the interfacial tension vanishes at the critical point with exponent 2nu approximately 1.26 . This is in good agreement with the 3D Ising exponent. Also calculated are critical amplitude ratios, which are shown to be compatible with the corresponding 3D Ising values. We additionally identify a number of subtleties that are encountered when finite size scaling is applied to the AO model. In particular, we find that close to the critical point, the finite size extrapolation of the interfacial tension is most consistent when logarithmic size dependences are ignored.

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PubMed2004

Grand canonical Monte Carlo simulation of a model colloid-polymer mixture: coexistence line, critical behavior, and interfacial tension.

Grand canonical Monte Carlo simulations are used to study phase separation in a simple colloid-polymer model, the so-called Asakura-Oosawa model. To overcome the problem of small acceptance rates of the grand-canonical moves, cluster moves are introduced. Successive umbrella sampling, recently introduced by Virnau and Muller [J. Chem. Phys. 120, 10925 (2004)], is used to access the phase-separated regime. The unmixing binodal and the interfacial tension are measured and compared to theoretical predictions. By means of finite-size scaling, the behavior close to the critical point is also investigated. Close to criticality, we observe substantial deviations from mean-field behavior.

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PubMed2002

Configurational entropy of network-forming materials.

We present a computationally efficient method to calculate the configurational entropy of network-forming materials. The method requires only the atomic coordinates and bonds of a single well-relaxed configuration. This is in contrast to the multiple simulations that are required for other methods to determine entropy, such as thermodynamic integration. We use our method to obtain the configurational entropy of well-relaxed networks of amorphous silicon and vitreous silica. For these materials we find configurational entropies of 0.93k(B) and 0.88k(B) per silicon atom, respectively.

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