Structure of weakly charged polyelectrolytes at a solid-liquid interface

Varoqui, R.

doi:10.1051/jp2:1993186

Cited by 50 publications

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“…potential only consists of the electrostatic term zy, see references [11][12][13]; II) The model as used by Andelman and co-workers, including Flory-Huggins volume exclusion in the low-φ limit, based on equations (20) and (30); III) The same as II) but without linearizing the Flory-Huggins expression; IV) The same as III) but including volume effects of polymer on the electrostatic equations -based on equations (22) and (28). Clearly, not linearizing the FH expression already gives a significant effect, while the influence of the polymer volume on the electrostatic equations results in a further decrease of adsorbed amount.…”

Section: Resultsmentioning

confidence: 99%

“…In Figure 3b we see that a net depletion of polyelectrolyte occurs below λ ∼ 0.015 nm −1 with φ 0 rapidly going to zero for lower values of λ. Interestingly, similar non-monotonous adsorption profiles as in Figure 2 were calculated before (Refs. [11,12,14,21]) but based on the assumption of φ 0 = 0 (corresponding to a strongly repulsive, or hard, surface, Refs. [13,15]).…”

Section: Resultsmentioning

confidence: 99%

“…Of earlier aSCF work based on the ground-state dominance approximation [2,4,[11][12][13][14][15], only Andelman and coworkers [2,4,14,15] include a Flory-Huggins mixing freeenergy contribution (in the low-φ limit). Comparing with that work, we define the ionic strength n ∞ in a (virtual) phase without polyelectrolyte, ∞, and not in the bulk phase, b, that contains polyelectrolyte.…”

Section: Theorymentioning

confidence: 99%

“…A significant simplication of nSCF methods can be made for long polyelectrolyte chains when the ranking number dependence can be neglected [2,4,[11][12][13][14][15]. This is the ground-state dominance approximation which results in a (semi)analytical version of the self-consistent field equations (aSCF).…”

Section: Introductionmentioning

confidence: 99%

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Volume exclusion effects in the ground-state dominance approximation for polyelectrolyte adsorption on charged interfaces

Biesheuvel

2005

Eur. Phys. J. E

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Abstract. We consider the problem of polyelectrolyte molecules adsorbing on oppositely charged interfaces. For sufficiently long chains, the ground-state dominance approximation can be used which results in a (semi-)analytical solution of the self-consistent field equations (aSCF). Whereas existing aSCF theory assumes a low polyelectrolyte density, here the required electrostatic corrections for a high polymer density are implemented. Adsorbed polymer excludes volume for the solvent and small ions, a volume effect that also leads to a reduced dielectric permittivity and a resulting polarization term in the exchange potential. Calculations show the influence of volume exclusion on the polymer density profile.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Theorymentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Volume exclusion effects in the ground-state dominance approximation for polyelectrolyte adsorption on charged interfaces

Biesheuvel

2005

Eur. Phys. J. E

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“…The relation between the polymer order parameter and the monomer concentration is analogous to the relation between the wave function and the probability density of a particle in quantum mechanics. The excess free energy with respect to the bulk can be divided into three contributions [22][23][24][25]:…”

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confidence: 99%

Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

1999

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The behavior of polyelectrolytes between charged surfaces immersed in semi-dilute solutions is investigated theoretically. A continuum mean field approach is used for calculating numerically concentration profiles between two electrodes held at a constant potential. A generalized contact theorem relates the inter-surface forces to the concentration profiles. The numerical results show that over-compensation of the surface charges by adsorbing polyelectrolytes can lead to effective attraction between equally charged surfaces. Simple scaling arguments enable us to characterize qualitatively the inter-surface interactions as function of the fraction of charged monomers p and the salt concentration c b . In the low salt regime we find strong repulsion at short distances, where the polymers are depleted from the inter-surface gap, followed by strong attraction when the two adsorbed layers overlap. The magnitude of this attraction scales as p 1/2 and its dominant length scale is proportional to a/p 1/2 , where a is the monomer size. At larger distances the two adsorbing surfaces interact via a weak electrostatic repulsion. For strong polyelectrolytes at high salt concentration the polymer contribution to attraction at short distances scales as p/c 1/2 b and the length scale is proportional to κsa 2 /p, where κ −1 s is the Debye-Hückel screening length. For weak polyelectrolytes at high salt concentration the interaction is repulsive for all surface separations and decays exponentially with a decay length equal to κ −1 s . The effect of irreversible adsorption is discussed as well and it is shown that inter-surface attraction can be obtained in this case as well. 61.25.H, 68.10, 36.20, 41.10D

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Theory of Polyelectrolyte Solutions

Barrat¹,

Joanny²

1996

Advances in Chemical Physics

391

309

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TABLE OF CONTENTS 1. Introduction 2. Charged chains at infinite dilution -asymptotic properties 2.1 Definition of the model and Flory-like calculation 2.2 Variational approaches 2.3 Renormalization group calculations2.4 Screening of electrostatic interactions 2.5 Annealed and quenched polyelectrolytes 3. Local aspects of screening 3.1 Counterion condensation 3.2 Poisson Boltzmann approach 3.3 Attractive electrostatic interactions 4. Electrostatic rigidity 4.1 The Odijk-Skolnick-Fixman theory 4.2 Alternative calculations for flexible chains 4.3 The case of poor solvents 5. Charged gels and brushes 5.1 Grafted polyelectrolyte layers 5.2 Polyelectrolyte gels 6. Semidilute solutions 6.1 Ordering transitions in polyelectrolyte solutions 6.2 Correlation length and osmotic pressure of semi-dilute polyelectrolyte solutions 6.3 Electrostatic rigidity in semidilute solutions 6.4 Concentrated solutions of flexible polyelectrolytes 6.5 Mesophase formation in poor solvents 7. Dynamical properties 7.1 Mobility and electrophoretic mobility of a single charged chain 7.2 Viscosity of polyelectrolyte solutions 8. Conclusions

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Structure of weakly charged polyelectrolytes at a solid-liquid interface

Cited by 50 publications

References 0 publications

Volume exclusion effects in the ground-state dominance approximation for polyelectrolyte adsorption on charged interfaces

Volume exclusion effects in the ground-state dominance approximation for polyelectrolyte adsorption on charged interfaces

Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

Theory of Polyelectrolyte Solutions

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