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1.
J Chem Phys ; 149(16): 164905, 2018 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-30384730

RESUMO

In this paper, we present a Monte Carlo simulation study on the structure of the electrical double layer around a spherical colloid surrounded by a binary electrolyte composed of spherical and non-spherical ions. Results are provided for the radial distribution functions between the colloid and ions, the orientation correlations between the colloid and non-spherical particles, and the integrated charge. Work is reported mainly for non-spherical particles modeled as spherocylinders, although a particular comparison is made between spherocylindrical particles and dimers. For the conditions investigated here, spherocylinders and dimers produce essentially the same structural information. Additionally, it is shown that spherocylinders mostly orient tangentially to the colloid at its surface; this preferred orientation disappears for larger distances. We also evidence that, near the colloid, the integrated charge attenuates monotonically when the macroparticle is highly charged, whereas for intermediate and low charged states of the colloid, the integrated charge can display charge reversal, overcharging, or both, with magnitudes that are sensitive to the salt concentration and to the localization of charge inside the spherocylinders.

2.
J Phys Chem B ; 122(27): 7002-7008, 2018 07 12.
Artigo em Inglês | MEDLINE | ID: mdl-29911869

RESUMO

Most theoretical and simulation studies on charged suspensions are at infinite dilution and are focused on the electrolyte structure around one or two isolated particles. Some classic experimental studies with latex particle solutions exhibit interesting phenomenology which imply very-long-range correlations. Here, we apply an integral equation theory to a model charged macroion suspension, at finite volume fraction, and find an amplitude-modulated charge inversion structure, with outsized amplitudes and of very-long-range extension. These inversions are different from the standard charge inversions in that they occur at finite macroions' volume fraction, far away from the central macroion, are outsized, and increase, not decrease, with increasing particle charge and distance to the central particle, which is indicative of long-range correlations. We find our results to be in agreement with our Monte Carlo simulations and qualitatively consistent with existing experimental results.

3.
J Chem Phys ; 148(15): 154703, 2018 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-29679975

RESUMO

The capacitive compactness has been introduced very recently [G. I. Guerrero-García et al., Phys. Chem. Chem. Phys. 20, 262-275 (2018)] as a robust and accurate measure to quantify the thickness, or spatial extension, of the electrical double layer next to either an infinite charged electrode or a spherical macroion. We propose here an experimental/theoretical scheme to determine the capacitive compactness of a spherical electrical double layer that relies on the calculation of the electrokinetic charge and the associated mean electrostatic potential at the macroparticle's surface. This is achieved by numerically solving the non-linear Poisson-Boltzmann equation of point ions around a colloidal sphere and matching the corresponding theoretical mobility, predicted by the O'Brien and White theory [J. Chem. Soc., Faraday Trans. 2 74, 1607-1626 (1978)], with experimental measurements of the electrophoretic mobility under the same conditions. This novel method is used to calculate the capacitive compactness of NaCl and CaCl2 electrolytes surrounding a negatively charged polystyrene particle as a function of the salt concentration.

4.
Phys Chem Chem Phys ; 20(1): 262-275, 2017 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-29204593

RESUMO

The spatial extension of the ionic cloud neutralizing a charged colloid or an electrode is usually characterized by the Debye length associated with the supporting charged fluid in the bulk. This spatial length arises naturally in the linear Poisson-Boltzmann theory of point charges, which is the cornerstone of the widely used Derjaguin-Landau-Verwey-Overbeek formalism describing the colloidal stability of electrified macroparticles. By definition, the Debye length is independent of important physical features of charged solutions such as the colloidal charge, electrostatic ion correlations, ionic excluded volume effects, or specific short-range interactions, just to mention a few. In order to include consistently these features to describe more accurately the thickness of the electrical double layer of an inhomogeneous charged fluid in planar geometry, we propose here the use of the capacitive compactness concept as a generalization of the compactness of the spherical electrical double layer around a small macroion (González-Tovar et al., J. Chem. Phys. 2004, 120, 9782). To exemplify the usefulness of the capacitive compactness to characterize strongly coupled charged fluids in external electric fields, we use integral equations theory and Monte Carlo simulations to analyze the electrical properties of a model molten salt near a planar electrode. In particular, we study the electrode's charge neutralization, and the maximum inversion of the net charge per unit area of the electrode-molten salt system as a function of the ionic concentration, and the electrode's charge. The behaviour of the associated capacitive compactness is interpreted in terms of the charge neutralization capacity of the highly correlated charged fluid, which evidences a shrinking/expansion of the electrical double layer at a microscopic level. The capacitive compactness and its first two derivatives are expressed in terms of experimentally measurable macroscopic properties such as the differential and integral capacity, the electrode's surface charge density, and the mean electrostatic potential at the electrode's surface.

5.
J Phys Condens Matter ; 24(37): 375107, 2012 Sep 19.
Artigo em Inglês | MEDLINE | ID: mdl-22889965

RESUMO

Using the generalized Langevin equation formalism and the process of contraction of the description we derive a general memory function equation for the thermal fluctuations of the local density of a simple atomic liquid. From the analysis of the long-time limit of this equation, a striking equivalence is suggested between the long-time dynamics of the atomic liquid and the dynamics of the corresponding Brownian liquid. This dynamic equivalence is confirmed here by comparing molecular and Brownian dynamics simulations of the self-intermediate scattering function and the long-time self-diffusion coefficient for the hard-sphere liquid.

6.
Langmuir ; 28(14): 5934-9, 2012 Apr 10.
Artigo em Inglês | MEDLINE | ID: mdl-22429101

RESUMO

Coalescence processes in double emulsions, water-in-oil-in-water, are studied by optical microscopy. The time evolution of such systems is determined by the interplay of two coalescence processes, namely, between inner water droplets and between the inner water droplets and the continuous external water phase. The predominance of one of those processes over the other, regulated by the relative amount of hydrophilic and lipophilic surfactants, leads to different evolutions of the system. We present here results for a class of systems whose evolution follows a master behavior. We also implemented a computer simulation where the system is modeled as a spherical cavity filled with smaller Brownian spheres. Collisions between spheres allow coalescence between them with probability P(i), whereas collisions between a sphere and the wall of the cavity allow coalescence with the external phase with probability P(e). The phenomenology observed in the experimental systems is well reproduced by the computer simulation for suitable values of the probability parameters.

7.
Phys Rev E Stat Nonlin Soft Matter Phys ; 67(5 Pt 1): 050403, 2003 May.
Artigo em Inglês | MEDLINE | ID: mdl-12786123

RESUMO

The pair correlation function g(r) between like-charged colloidal particles in quasi-two-dimensional geometries is measured by optical microscopy for a wide range of particle concentrations and various degrees of confinement. The effective pair potential u(r) is obtained by deconvoluting g(r) via Monte Carlo computer simulations. Our results confirm the existence of a long-range attractive component of u(r) and the appearance of an extra attractive term under stringent confinement.

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