Scaling Laws of Polyelectrolyte Adsorption

Borukhov, Itamar; Andelman, David; Orland, Henri

doi:10.1021/ma9707300

Cited by 125 publications

(229 citation statements)

References 28 publications

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“…We note that the high salt regime can be further divided into two sub-regimes depending on the ratio of the two terms in the denominator of C 1 and F (1) p as was discussed in Ref. [26].…”

Section: Large Distance: W/2 ≫ D1mentioning

confidence: 87%

“…The saturation value of Γ is approximately twice the adsorbed amount to a single surface Γ(w → ∞) = 2Γ 1 . In a preceding work [26] we investigated adsorption onto a single surface and have shown that in the low salt limit Γ 1 ∼ 1/ √ p. This behavior is a result of two competing interactions: (i) the electrostatic attraction of the charged monomers to the surface which is proportional to p; and (ii) the Coulomb repulsion between charged monomers in the adsorbed layer which is proportional to p 2 . For strong polyelectrolytes the latter interaction dominates and the adsorbed amount Γ 1 increases as the fractional charge p decreases.…”

Section: A Low Salt Concentrationmentioning

confidence: 99%

“…In a previous work [26] we have studied polyelectrolyte adsorption to a single surface by separating the two competing length scales: (i) The adsorption length D, which characterizes the width of the adsorbed layer and (ii) the electrostatic…”

Section: Scaling Regimesmentioning

confidence: 99%

“…In the limit of large distances and low salt conditions one needs to address the question of the relative size of w/2 and κ −1 s as both lengths are large. The free energy of an isolated adsorbing surface can be approximated by [26] …”

Section: Large Distances: W/2 ≫ D1mentioning

confidence: 99%

“…19) can be generalized by introducing κ −1 s as a cut-off on the range of the electrostatic interactions (similar to what was done in Ref. [26] for the single surface case):…”

Section: Large Distance: W/2 ≫ D1mentioning

confidence: 99%

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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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“…We note that the high salt regime can be further divided into two sub-regimes depending on the ratio of the two terms in the denominator of C 1 and F (1) p as was discussed in Ref. [26].…”

Section: Large Distance: W/2 ≫ D1mentioning

confidence: 87%

Section: A Low Salt Concentrationmentioning

confidence: 99%

Section: Scaling Regimesmentioning

confidence: 99%

Section: Large Distances: W/2 ≫ D1mentioning

confidence: 99%

“…19) can be generalized by introducing κ −1 s as a cut-off on the range of the electrostatic interactions (similar to what was done in Ref. [26] for the single surface case):…”

Section: Large Distance: W/2 ≫ D1mentioning

confidence: 99%

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Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

1999

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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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Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties

Bertrand

Jonas

Laschewsky³

et al. 2000

Macromol. Rapid Commun.

1,175

1,184

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A bit of historyThe key role of surfaces for many material properties as well as for many biological processes has been recognized now. Therefore, new strategies aim at the tailoring of the material's surface only -or of a thin surface layer, respectively -, while preserving the bulk properties of the underlying support. Particular emphasis has been given to the surface modification by polymers, in an attempt to extend the known versatility of polymer bulk materials to ultrathin films and coatings, and to prepare bulk-surface composite materials. The self-organization of polymers has been increasingly explored for the preparation of well-defined surfaces and interfaces in recent years, extending the use of the established methods of low molar mass compounds (for comparative reviews, see ref. 1-3)). With such techniques, polymer films are formed spontaneously on substrates, due to balanced interactions between substrate, polymer (or its precursor) and medium. Typically, very thin, often monomolecular layers are produced. Repetitive deposition steps provide a precise control over the total thickness of the coatings, in the range from a few angstroms up to the micrometer range. Moreover, the step-by-step procedures allow for a fine structuring in the third dimension. In addition to the preparation of uniform and homogeneous coatings, gratings, gradients or steps of defined height in molecular dimensions can be easily constructed.The most recent of the self-organization techniques is the alternating physisorption of oppositely charged polyelectrolytes, the so-called "layer-by-layer" method or "electrostatic self-assembly" (ESA) [3][4][5][6][7][8][9][10] . Although some early, singular studies of self-assembly by alternating adsorption of oppositely charged polyions are reported [11][12][13] , a practical method for ESA was developed Feature Article: The article presents the state-of-the-art of alternating physisorption of oppositely charged polyelectrolytes, the so-called "layer-by-layer" method or "electrostatic self-assembly" (ESA), for the preparation of thin polymer coatings. In comparison to other, more established self-organization techniques, this recent method is distinguished by its simplicity, versatility, and speed. In particular, the tendency for self-healing is unique. Emphasis is given to the role of the molecular structure of the polyelectrolytes, and to the nature of the support. Also, various parameters for the preparation of multilayer films are highlighted, which are very important due to the kinetic control of the build-up process. The structure of the resulting coatings, their quality and stability, chemical reactions in the films, and potential applications are discussed.Macromol. Rapid Commun. 21, No. 7

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Scaling Laws of Polyelectrolyte Adsorption

Abstract: Adsorption of charged polymers (polyelectrolytes) from a semi-dilute solution to a charged surface is investigated theoretically. We obtain simple scaling laws for (i) the amount of polymer Γ adsorbed to the surface and (ii)

Cited by 125 publications

References 28 publications

Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

Effect of Polyelectrolyte Adsorption on Intercolloidal Forces

Theory of inhomogeneous weakly charged polyelectrolytes

Ultrathin polymer coatings by complexation of polyelectrolytes at interfaces: suitable materials, structure and properties

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