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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 4580-4583 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the dynamics of concentration fluctuations of a weakly charged polyelectrolyte solution in the limit where they are controlled by hydrodynamic interactions. We find three relaxation modes: a plasmon mode corresponding to the fast relaxation of charge fluctuations; a diffusive mode involving mainly the motion of the small ions (salt and counterions) to restore the "Donnan equilibrium,'' and a slower cooperative diffusion mode corresponding to the breathing motion of the polyelectrolyte chains and ions. In the limit where the electrostatic effects are dominant, at zero wave vector, the cooperative diffusion constant has a nonmonotonic variation with the monomer concentration. Contrary to what happens in neutral polymer solutions, in the limit of low ionic strength, it decreases with the monomer concentration in agreement with recent experimental observations of Schosseler et al. on gels.The cooperative diffusion constant as a function of wave vector shows a minimum for a wave vector corresponding approximately to the peak in the structure factor.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 6257-6273 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We study the adsorption of grafted polymer layers on a planar surface parallel to the grafting surface. The layer consists of two types of chains: nonadsorbed chains with a free end and adsorbed chains forming bridges between the two plates. In the limit of strong adsorption a dead zone exists in the vicinity of the adsorbing plate; its size increases with the adsorption strength. Two adsorption mechanisms are possible: adsorption of the last monomer only and adsorption of all the monomers. In both cases the adsorption regimes at equilibrium (when no external force acts on the plates) are discussed within the framework of the self-consistent mean-field theory. We also give scaling laws taking into account excluded volume correlations. Finally, we consider situations where a finite external force, either tangential or normal to the plates, is applied on the adsorbing plate. Pulling and tangential forces both reduce the fraction of bridges and eventually lead to rupture, whereas compressional forces favor bridging. For normal forces, force vs distance profiles between planes and crossed cylinders are given.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 1543-1554 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We consider polyampholyte polymers containing both positive and negative monomers randomly dispersed along the chain. Neutral chains collapse into a globule due to attractive electrostatic interactions. The behavior of the charges inside the globule is similar to that of charges in a small volume of simple electrolyte. A screening length κ−1p coming from the polymeric charge may be defined as in Debye–Hückel theory. The internal structure of the globule is that of close packed blobs of radius equal to the screening length. When salt is added this further screens the interactions and reduces the attractions. The globule begins to increase in size when the concentration of salt becomes larger than the concentration of charge on the polymer itself. Screened Coulomb interactions in a neutral chain behave like a negative contribution to excluded volume. For a chain in a good solvent there is a θ salt concentration at which the net excluded volume becomes zero. Chains are swollen above this concentration of salt, and collapsed below this concentration. For small sections of chain the Coulomb interactions are unscreened and cannot be treated as a modification to excluded volume. Chains with a strong net charge of one sign tend to behave as conventional polyelectrolyte with charges of only one sign. We determine the criterion for the value of the net charge at which the repulsions (polyelectrolyte effect) begin to dominate the attractions (polyampholyte effect). The predictions are found to be in good qualitative agreement with experiments.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Langmuir 8 (1992), S. 989-995 
    ISSN: 1520-5827
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 20 (1987), S. 1935-1943 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 89 (1985), S. 2119-2120 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 24 (1991), S. 6040-6042 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 3673-3681 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Insoluble Langmuir monolayers are investigated in the presence of dipolar forces which can have two origins: permanent dipoles in neutral monolayers and induced dipoles in charged monolayers. The main effect of the additional long-range repulsive interactions is to stabilize undulating phases at thermodynamic equilibrium. Phase diagrams are obtained in two limits: close to the liquid–gas critical point via a Ginzburg–Landau expansion of the free energy (mainly within a mean-field approximation), and at low temperatures by free energy minimization. Possible applications of this theory to experiments at the liquid–gas, liquid expanded–liquid condensed, and solid–liquid transitions are discussed.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 6 (1997), S. 479-505 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: We study theoretically the pull-out of polymer chains from an adsorbed polymer layer by sticking of the chain ends on an opposing surface using scaling arguments and a mean field theory. When only one chain is pulled out from the layer, we extend previous results obtained for a single adsorbed chain and calculate the force necessary to extract the chain from the layer. We then discuss end adsorption from an adsorbed layer of polymers bearing specific end groups onto a second surface. Two bridging regimes are predicted: a diffuse layer regime at weak separations (or/and weak interaction) and a large separation strong interaction regime where the bridges stretch into a brush like structure. Bridging fractions and force profiles are displayed that could be compared to atomic force microscope or surface force apparatus experiments.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Macromolecular Theory and Simulations 4 (1995), S. 45-51 
    ISSN: 1022-1344
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The molecular weight of a Gaussian polymer chain can be obtained from the intercept of the asymptote in a plot of the inverse structure factor 1/S(q) as a function of the square of the wave vector q2. Using an ∊ expansion and scaling arguments, we show that in a good solvent the situation is more complex and that the molecular weight determination is difficult to justify. The corrections to the asymptotic behavior of the structure factor at large wave vector involve several terms that are difficult to separate experimentally. This is qualitatively explained by the nonuniform swelling of a polymer chain in a good solvent due to the existence of the chain ends.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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