Adsorption of Polyelectrolyte Solutions on Surfaces: A Debye-Hückel Theory

Châtellier, Xavier; Joanny, Jean‐François

doi:10.1051/jp2:1996156

Cited by 99 publications

(129 citation statements)

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“…Density oscillations are still observed, although the amplitude is very small. Larger oscillations have been observed in polyelectrolyte solutions, [25][26][27] but these oscillations have a different origin. It was shown that the oscillations in polyelectrolyte solutions cannot be attributed to the ordering of individual coils, but that they are due to a balance between the segment-segment electrostatic interactions and the translation entropy of the chains.…”

Section: Resultsmentioning

confidence: 99%

Coil size oscillatory packing in polymer solutions near a surface

Gucht

Besseling

Male

et al. 2000

The Journal of Chemical Physics

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The theory developed by Scheutjens and Fleer to describe polymer adsorption and depletion is used to calculate the density profile of nonadsorbing polymers near a surface. The theory predicts damped oscillations in the segment density profile with a wavelength of about the coil size. As a consequence, the interaction energy between two surfaces immersed in a solution of nonadsorbing polymers is an oscillatory function of the separation distance, too. The decay length of the oscillations is proportional to the coil size and independent of the polymer concentration. The oscillations are associated with a liquid-like layering of polymer coils near the surface. An increase in concentration or chain length causes a decrease in the amplitude of the oscillations, because the stronger interpenetration of the coils suppresses inhomogeneities. In dilute solutions no oscillations are observed, because the decay length of the oscillations is smaller than the depletion correlation length, in analogy with the Fisher-Widom criterion in simple fluids. For polymer solutions it is found that the Fisher-Widom condition coincides with the overlap concentration. Our results show that the blob size is not the only relevant length scale above the overlap concentration. The size of the individual coils plays a role, too.

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Section: Resultsmentioning

confidence: 99%

Coil size oscillatory packing in polymer solutions near a surface

Gucht

Besseling

Male

et al. 2000

The Journal of Chemical Physics

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“…Attractive interactions were also obtained by Podgornik [27] for the case of fixed adsorbed amount and without considering the nonlinear excluded volume interaction. For polyelectrolytes in a poor solvent, Châtellier and Joanny [28] have obtained oscillations in the polymer concentration as well as in the inter-surface interactions.…”

Section: Discussionmentioning

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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“…The Debye-Hückel theory has also been applied to polyelectrolyte adsorption on surfaces by Ch atellier and Joanny 24) . In order to demonstrate the effect of the ions on the interactions, we need to obtain DF in terms of the molecular densities.…”

Section: A2mentioning

confidence: 99%

Theory of inhomogeneous weakly charged polyelectrolytes

Shi

Noolandi

1999

Macromol. Theory Simul.

116

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SUMMARY: A theory of inhomogeneous multicomponent systems containing weakly charged polyelectrolytes is developed. The theory treats the polymer conformation and the electrostatics simultaneously using a functional integral representation of the partition function. A mean-field approximation to the theory leads to two sets of coupled mean-field equations: a Poisson-Boltzmann type equation describing the electrostatic potential, and a set of self-consistent field equations describing the equilibrium densities. Asymptotic forms of the theory at weak and strong segregation limits are derived. The theory can be used to study the interfacial properties, microphase structures, and adsorptions of a variety of weakly charged polyelectrolyte systems. As a simple example, the interface between the polymer-rich and polymer-poor phases of a polyelectrolyte solution is studied.

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Adsorption of Polyelectrolyte Solutions on Surfaces: A Debye-Hückel Theory

Cited by 99 publications

References 0 publications

Coil size oscillatory packing in polymer solutions near a surface

Coil size oscillatory packing in polymer solutions near a surface

Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

Theory of inhomogeneous weakly charged polyelectrolytes

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