Nonlinear screening and gas-liquid separation in suspensions of charged colloids

We calculate phase diagrams of charged colloidal spheres (valency Z and radius a) in a 1:1 electrolyte from multicentered nonlinear Poisson-Boltzmann theory. Our theory takes into account charge renormalization of the colloidal interactions and volume terms due to many-body effects. For valencies as small as Z = 1 and as large as 10(4) we find a gas-liquid spinodal instability in the colloid-salt phase diagram provided Z lambdaB/a > or similar 24+/-1, where lambdaB is the Bjerrum length.     

On the gas-liquid phase transition

A new approach to the problem of the gas-liquid phase transition, based on the Mayer cluster expansion of the partition function, is proposed. It is shown that the necessary and sufficient condition for phase transition to occur is that there exist a temperatureT= T_c > 0 such that forT T _c, all theb _l (except perhaps a finite number of them) are positive, where theb _l, are the cluster integrals (as defined by Mayer) in the thermodynamic limit. Explicit expressions for the isotherms for gas-saturated vapor and liquid phases are given.     

Light induced gas-liquid phase transition

The resonant radiation is proved to be capable of effectively changing critical parameters and coexistence region of the gas-liquid system.     

Critique of the paper “on the gas-liquid phase transition”

The proof of a recently enunciated theorem on the occurrence of a gas-liquid phase transition is shown to be defective in several respects. Also, it is argued that the theorem itself very probably does not hold.The paper, On the Gas-Liquid Phase Transition by A. C. Biswas appeared inJournal of Statistical Physics 7:131 (1973).     

Sticky model of charged colloids

Summary We use the Sticky Electrolyte Model, which we solved before in PY/MSA, to obtain the equation of state of a charge colloid taking into account both sticky and charge contribution. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Dynamic phase transition of charged dilaton black holes

The dynamic phase transition of charged dilaton black holes is investigated in this paper. The Gibbs free energy landscape is introduced, and the corresponding \begin{document}$G_{\rm L}$\end{document} is calculated for the dilaton black hole. We numerically solve the Fokker-Planck equation constrained by only the reflecting boundary condition. The effects of dilaton gravity on the probabilistic evolution of dilaton black holes are explored. Firstly, the horizon radius difference between a large dilaton black hole and a small dilaton black hole increases with the parameter \begin{document}$\alpha$\end{document}. Secondly, with increasing \begin{document}$\alpha$\end{document}, the system needs much more time to achieve a stationary distribution. Finally, the values attained for \begin{document}$\rho(r_{\rm l},t)$\end{document} and \begin{document}$\rho(r_{\rm s},t)$\end{document} vary with \begin{document}$\alpha$\end{document}. Additionally, by resolving the Fokker-Planck equation constrained by both the reflecting boundary condition and absorbing boundary condition, we investigate the first passage process of dilaton black holes. The initial peak decays more slowly with increasing\begin{document}$\alpha$\end{document}, which can also be observed via the slowing decay of \begin{document}$\Sigma(t)$\end{document} (the sum of the probability of the black hole system not having completed a first passage by time t). Moreover, the time corresponding to the single peak of the first passage time distribution is found to increase with the parameter \begin{document}$\alpha$\end{document}. Considering these observations, the dilaton field is found to slow down the dynamic phase transition process between a large black hole and a small black hole.     

Reversible phase transition of colloids in a binary liquid solvent

We report fluid-fluid and fluid-solid phase transitions of charge-stabilized polystyrene particles suspended in a binary liquid mixture of 3-methylpyridine and water. These thermally reversible phase transitions occur in the homogeneous phase of the binary liquid mixture below the coexistence temperature of the two liquids. Close density matching of the particles and the solvent allows us to follow the phase behavior until complete coexistence of macroscopic phases with temperature as the control parameter. We use small angle x-ray scattering to characterize these phases as colloidal gas, liquid, fcc crystal, and glass.     

Virial expansion for charged colloids and electrolytes

Using a field-theoretic approach, we derive the first few coefficients of the exact low-density (“virial”) expansion of a binary mixture of positively and negatively charged hard spheres (two-component hard-core plasma, TCPHC). Our calculations are nonperturbative with respect to the diameters d₊ and d_- and charge valences q₊ and q_- of positive and negative ions. Consequently, our closed-form expressions for the coefficients of the free energy and activity can be used to treat dilute salt solutions, where typically d ₊∼d _- and q ₊∼q _-, as well as colloidal suspensions, where the difference in size and valence between macroions and counterions can be very large. We show how to map the TCPHC on a one-component hard-core plasma (OCPHC) in the colloidal limit of large size and valence ratio, in which case the counterions effectively form a neutralizing background. A sizable discrepancy with the standard OCPHC with uniform, rigid background is detected, which can be traced back to the fact that the counterions cannot penetrate the colloids. For the case of electrolyte solutions, we show how to obtain the cationic and anionic radii as independent parameters from experimental data for the activity coefficient. Received 6 September 2001 / Received in final form 20 May 2002 Published online 24 September 2002     

Role of the gas-liquid phase transition in the theory of nuclear matter

A sufficient condition for the two-nucleon interaction to produce a gaseous instability in the form of the appearance of inhomogeneous-spatial-density single-particle states of lower energy than the (homogeneous) plane-wave states is found to be simply that it gives binding in first order. The critical density at which the instability occurs thus signals the unambiguous breakdown of a plane-wave-based Hartree-Fock perturbation expansion for the ground state properties. Several examples are analysed.     

Epitaxial crystal growth of charged colloids

A pattern of repulsive, charged lines is shown to direct three-dimensional (3D) crystallization in a system of long-range repulsive, density-matched colloids. At volume fractions where the bulk phase behavior leads to bcc crystallization, the 1D template was found to induce formation of a metastable fcc crystal. The bcc crystals were oriented with the (100) or the (110) plane, with twofold twinning, parallel to the template. The template further induced prefreezing of the (100) plane. At a large mismatch between template and interparticle spacing, 1D strings form in the surface layer of a 3D crystal.     

Noncentral forces in crystals of charged colloids

The elastic properties of fcc crystals consisting of charge stabilized colloidal particles are determined from real space imaging experiments using confocal microscopy. The normal modes and the force constants of the crystal are obtained from the fluctuations of the particles around their lattice sites using the equipartition theorem. We show that the Cauchy relation is not fulfilled and that only noncentral many-body forces can account for the elastic properties.     

Order-disorder transition in the solid phase of a charged hard sphere model

We investigate the solid phases of the restricted primitive model (RPM). Monte Carlo simulations show the existence of an order-disorder transition from a substitutionally disordered face centered cubic lattice (fcc) to a new ordered fcc structure which is proposed as the ground state of the RPM at the close packing density. Our results suggest that the new phase might turn out in a new triple point in the RPM phase diagram involving three solid phases: CsCl, fcc ordered and fcc disordered structures. The order-disorder transition is also studied using the cell theory. The theory shows good agreement with the simulation results and suggests that the transition is weakly first order.     

Three-dimensional binary superlattices of oppositely charged colloids

We report the equilibrium self-assembly of binary crystals of oppositely charged colloidal microspheres at high density. By varying the magnitude of the charge on near equal-sized spheres we show that the structure of the binary crystal may be switched between face-centered cubic, cesium chloride, and sodium chloride. We interpret these transformations in terms of a competition between entropic and Coulombic forces.     

High-frequency driven capillary flows speed up the gas-liquid phase transition in zero-gravity conditions

Under weightlessness conditions, the phase transition of fluids is driven only by slow capillary flows. We investigate the effect of high-frequency vibrations to reproduce some features of gravity effects and show that such vibrations can greatly modify the phase transition kinetics. The investigation is performed in H2 near its critical point (critical temperature 33 K) where critical slowing down enables the phase transition process to be carefully studied. Gravity effects are compensated in a strong magnetic field gradient.     

Direct numerical simulations of electrophoresis of charged colloids

We propose a numerical method to simulate electrohydrodynamic phenomena in charged colloidal dispersions. This method enables us to compute the time evolutions of colloidal particles, ions, and host fluids simultaneously by solving Newton, advection-diffusion, and Navier-Stokes equations so that the electrohydrodynamic couplings can be fully taken into account. The electrophoretic mobilities of charged spherical particles are calculated in several situations. The comparisons with approximation theories show quantitative agreements for dilute dispersions without any empirical parameters; however, our simulation predicts notable deviations in the case of dense dispersions.     

Evidence for out-of-equilibrium crystal nucleation in suspensions of oppositely charged colloids

We report a numerical study of the rate of crystal nucleation in a binary suspension of oppositely charged colloids. Two different crystal structures compete in the thermodynamic conditions under study. We find that the crystal phase that nucleates is metastable and, more surprisingly, its nucleation free-energy barrier is not the lowest one. This implies that, during nucleation, there is insufficient time for subcritical nuclei to relax to their lowest free-energy structure. Such behavior is in direct contradiction with the common assumption that the phase that crystallizes most readily is the one with the lowest free-energy barrier for nucleation. The phenomenon that we describe should be relevant for crystallization experiments where competing solid structures are not connected by an easy transformation.     

Cooper pairs and the gas-liquid transition

The question whether the gas-liquid phase transition occurs in the many-Cooper pair system is studied. When the idea of Yang-Lee zeros is applied to the grand partition function equivalent to the BCS model, its impossibility is proved.     

Critical adsorption of polyelectrolytes onto charged spherical colloids

The adsorption of a flexible polyelectrolyte in a salt solution onto an oppositely charged spherical surface is investigated. An analytical solution is derived, which is valid for any sphere radius and consistently recovers the result of a planar surface in the limit of large sphere radii, by substituting the Debye-Hückel potential via the Hulthén potential. Expressions for critical quantities such as the critical radius and the critical surface charge density are provide. A comparison of our theoretical results with experiments and computer simulations yields remarkable good agreement.