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Jan Forsman

Publications and source records attributed to Jan Forsman.

9 recordsLinked to original sources
PubMed2006

Repulsion between oppositely charged surfaces in multivalent electrolytes.

In answer to recent experimental force measurements between oppositely charged surfaces we here reproduce the repulsion in the presence of multivalent salt using Monte Carlo simulations within the primitive model. Our osmotic pressure curves are in good agreement with experimental results. In contrast with Poisson-Boltzmann calculations, both repulsion and charge inversion are seen in the simulations. Repulsion is observed only for conditions under which there is charge inversion at large separations. However, in these cases, the repulsion is present also at intermediate separations, where there is no charge inversion. The charge inversion is thereby not the cause of the repulsion. Instead the repulsion appears to be an effect of the large amount of excess salt in the slit. Both phenomena, however, are closely linked and a consequence of ion-ion correlations, promoted by a strong electrostatic coupling.

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PubMed2006

Surface forces mediated by charged polymers: effects of intrinsic chain stiffness.

The strength and range of surface forces in a system consisting of charged polymers with variable intramolecular stiffness confined between two charged planar surfaces have been investigated by Monte Carlo simulations. The negatively charged surfaces are neutralized by polymers carrying charges of opposite sign. Introducing the intermediate intrinsic stiffness of the chains gives rise to a weaker, but more long-ranged attraction between the surfaces. In the limit of infinitely stiff chains, this bridging attraction is lost, but it is replaced by a strong correlation attraction at short distances. Comparisons with predictions by a correlation-corrected polyelectrolyte Poisson-Boltzmann theory are made. The theory predicts surface attractions that are somewhat too weak, but all qualitative features are correctly reproduced. Given the crudeness of the model, the quantitative agreement is satisfactory.

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PubMed2006

Surface transition in athermal polymer solutions.

According to a recently developed density functional theory, athermal polymer solutions, in which the solvent particles are smaller than the monomers, may undergo a bulk fluid-fluid phase separation, driven by excluded volume effects. In recent work, we showed that an inert surface immersed in the dilute polymer phase can, in principle, be wetted by the condensed phase. However, we show here that the "prewetting transition" we assumed in our earlier studies is in fact a different type of surface transition. Rather than completely wet the surface at coexistence, the condensed phase layer which forms in the presence of the dilute bulk remains globally stable (and is finite in width) even as the bulk coexistence conditions are approached. Hence, the adsorbed phase inhibits complete wetting of the surface by the dilute phase. The surface transition is first order for the systems we study here and, for longer polymers, the surface phase coexistence line meets the bulk coexistence curve nontangentially to give rise to a lower transition point. For short polymers, we find that the surface transition can occur for a supercritical bulk. We develop a simple one-component thermal model, which displays analogous behavior at an adsorbing surface and provides us with some insight into the qualitative mechanisms responsible.

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PubMed2006

Ion adsorption and lamellar-lamellar transitions in charged bilayer systems.

Using a primitive model approach, we analyze the influence of ion specific adsorption on the phase behavior of charged lamellar systems. The presence of a weak short-ranged surface potential, attracting monovalent counterions, induces a phase separation, where the separate phases have different repeat distance. If the adsorption potential is very weak, the more narrow phase never forms. An opposite behavior is found for strong surface affinities. Both Monte Carlo simulations and a recently developed correlation-corrected Poisson-Boltzmann theory are adopted, with a nearly quantitative agreement between the approaches. Different counterions are discriminated by the adsorption potential strength, and with physically reasonable values, experimental observations on these systems are well reproduced. The study highlights the importance of electrostatic correlations, even though only monovalent ions are present.

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PubMed2005

Prewetting and layering in athermal polymer solutions.

Coexistence conditions for prewetting and layering at a hard surface in additive hard sphere polymer solutions, where the solvent particles are smaller than the monomers, have been calculated by density functional methods. Various chain lengths and pressures have been investigated. An unexpected finding is that prewetting in these systems may proceed below the bulk critical pressure. We rationalize this behavior in terms of local properties of the pressure tensor. For longer chains, a different behavior is observed where the systems display a lower wetting pressure, i.e., a low pressure bound for surface wetting.

Colloids↗
PubMed2004

Simulation of phase equilibria in lamellar surfactant systems.

The coexistence of two lamellar liquid crystalline phases has been investigated by means of Monte Carlo simulations. The surfaces of the negatively charged bilayers formed by the surfactant molecules are modeled as planar infinite walls with a uniform surface charge density. Water is treated as a dielectric continuum, and only electrostatic interactions are considered. The counterions are mono- and divalent point ions, and their ratio is allowed to vary. Monovalent counterions lead to a repulsive osmotic pressure at all separations, while an attractive region exists when the counterions are divalent. In the latter case, one would expect a phase separation to take place, although it is not observed experimentally due to the limited stability of the lamellar phase at high water content. In a system with mixed counterions, however, the osmotic pressure exhibits a van der Waals loop under such conditions that two phases can coexist. A phase diagram is constructed, and the agreement with experimental data is excellent.

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PubMed2004

Surface forces in polymer fluids: a comparison between simulations and density functional theory.

A polymer density functional theory is evaluated in terms of its ability to predict interactions between large surfaces in a polymer fluid. Comparisons are made with results from simulations in an expanded isotension ensemble. The variation of the net surface-surface interaction with adsorption strength is examined. Cases where the monomers interact via a pure hard sphere potential are investigated, but we have also studied the effect of attractions between the monomers. In all cases, we obtain an almost quantitative agreement between the simulated results and the predictions from the polymer density functional theory.

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PubMed2004

Evaluating the accuracy of a density functional theory of polymer solutions with additive hard sphere diameters.

We assess the accuracy of a density functional theory for athermal polymer solutions, consisting of solvent particles with a smaller radius than that of the monomers. The monomer and solvent density profiles in a slit bound by hard, flat, and inert surfaces are compared with those obtained by a Metropolis Monte Carlo simulation. At the relatively high density at which the comparison is performed, there are considerable packing effects at the walls. The density functional theory introduces a simple weight function to describe nonlocal correlations in the fluid. A recent study of surface forces in polymer solutions used a different weighting scheme to that proposed in this article, leading to less accurate results. The implications of the conclusions of that study are discussed.

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