Charge inversion in colloidal systems

Messina, René; Holm, Christian; Kremer, Kurt

doi:10.1016/s0010-4655(02)00288-6

Cited by 17 publications

(17 citation statements)

References 12 publications

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“…In this article both effects, lateral correlations and partial release of condensed counterions after chain adsorption, contribute to charge inversion. Moreover, the effects of the discrete surface charge group distribution and the short range attraction also contribute to charge inversion in our work13 as found in other models 14. The effective charge of surface–polyelectrolyte–ion complex is defined as …”

Section: Resultssupporting

confidence: 59%

“…Local electrostatic attractions, which are enhanced in surfaces with a discrete surface charge distribution, can easily dominate the long‐range electrostatic repulsions between the adsorbed rods, especially for small Deybe screening lengths. Messina et al demonstrated the enhancement of charge inversion due to a discrete charge distribution by analyzing a macroion using Molecular dynamics simulations 14…”

Section: Resultsmentioning

confidence: 99%

“…Important aspects of surface polyelectrolyte adsorption include the effect of a discrete distribution of charges on the surface14 and specific interactions in the adsorption such as the presence of divalent salts in the medium 6. In monovalent salt solutions the condensed counterions are hydrated, and have a large fluctuation along the chain 15, 16.…”

Section: Introductionmentioning

confidence: 99%

“…Recently, some studies have analyzed the effect of discrete surface charge distributions on the counterion adsorption from the bulk 24, 25. Messina et al14 determined the effect of a discrete charge distribution on charge inversion by counterion adsorption in salt‐free solution. We find here that for weakly charged surface, the discrete distribution of surface charges and short‐range attraction can greatly enhance surface charge inversion by polyelectrolyte adsorption, and the enhancement is more remarkable with the increases of salt concentration.…”

Section: Introductionmentioning

confidence: 99%

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Rod‐like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

Cheng

Cruz

2004

J Polym Sci B Polym Phys

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We analyze the adsorption of strongly charged polyelectrolytes onto weakly charged surfaces in divalent salt solutions. We include short‐range attractions between the monomers and the surface and between condensed ions and monomers, as well correlations among the condensed ions. Our results are compared with the adsorption in monovalent salt solutions. Different surface charge densities (σ), and divalent (m) and monovalent (s) salt concentrations are considered. When the Wigner‐Seitz cells diameter (2R) is larger than the length of the rod, the maximum amount of adsorption scales like nmax ∼ σ4/3 in both monovalent and divalent solutions. For homogeneously charged surfaces, the maximum adsorption occurs at s* ∼ σ2 when s* > ϕ, where ϕ is the monomer concentration, the counterpart for divalent salt solution, m* roughly scales as σ2.2 when m* > ϕ. The effective surface charge density has a maximum absolute value at m′ < m*. A discrete surface charge distribution and short‐range attractions between monomers and surface charge groups can greatly enhance surface charge inversion especially for high salt concentration. The critical salt concentration for adsorption in divalent salt solution roughly scales as mc ∼ bσ1.9, where b is the distance between two neighboring charged monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3642–3653, 2004

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Rod‐like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

Cheng

Cruz

2004

J Polym Sci B Polym Phys

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“…1,2 Due to strong electrostatic interactions with the macroion surface and with each other, screening ions are not positioned randomly in three-dimensional space, [3][4][5][6] but form a strongly correlated liquid near the surface of macroions, which leads to the formation of electric double layers (EDLs). As a result of the competition between short-range Coulomb interactions and volume exclusion interactions, due to the finite size of ions and water molecules, the correlated liquid manifests itself in a number of ways that dramatically alter the entire picture of screening.…”

Section: Introductionmentioning

confidence: 99%

Ionic asymmetry and solvent excluded volume effects on spherical electric double layers: A density functional approach

Medasani

Ovanesyan

Thomas

et al. 2014

The Journal of Chemical Physics

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In this article, we present a classical density functional theory for electrical double layers of spherical macroions that extends the capabilities of conventional approaches by accounting for electrostatic ion correlations, size asymmetry, and excluded volume effects. The approach is based on a recent approximation introduced by Hansen-Goos and Roth for the hard sphere excess free energy of inhomogeneous fluids [J. Chem. Phys. 124, 154506 (2006); J. Phys.: Condens. Matter 18, 8413 (2006)]. It accounts for the proper and efficient description of the effects of ionic asymmetry and solvent excluded volume, especially at high ion concentrations and size asymmetry ratios including those observed in experimental studies. Additionally, we utilize a leading functional Taylor expansion approximation of the ion density profiles. In addition, we use the mean spherical approximation for multi-component charged hard sphere fluids to account for the electrostatic ion correlation effects. These approximations are implemented in our theoretical formulation into a suitable decomposition of the excess free energy which plays a key role in capturing the complex interplay between charge correlations and excluded volume effects. We perform Monte Carlo simulations in various scenarios to validate the proposed approach, obtaining a good compromise between accuracy and computational cost. We use the proposed computational approach to study the effects of ion size, ion size asymmetry, and solvent excluded volume on the ion profiles, integrated charge, mean electrostatic potential, and ionic coordination number around spherical macroions in various electrolyte mixtures. Our results show that both solvent hard sphere diameter and density play a dominant role in the distribution of ions around spherical macroions, mainly for experimental water molarity and size values where the counterion distribution is characterized by a tight binding to the macroion, similar to that predicted by the Stern model. © 2014 AIP Publishing LLC. [http://dx

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Density functional theory for chemical engineering: From capillarity to soft materials

2005

AIChE Journal

377

318

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Charge inversion in colloidal systems

Cited by 17 publications

References 12 publications

Rod‐like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

Rod‐like polyelectrolyte adsorption onto charged surfaces in monovalent and divalent salt solutions

Ionic asymmetry and solvent excluded volume effects on spherical electric double layers: A density functional approach

Density functional theory for chemical engineering: From capillarity to soft materials

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