Mark Vis

Donnan Potentials in Aqueous Phase-Separated Polymer Mixtures

A promising approach to texturize water is by the addition of mutually incompatible polymers, leading to phase separation. Here, we demonstrate that the phase stability of aqueous polymer solutions is affected not only by chemical differences between the polymers but also by their electric charge. Direct electrochemical measurements are performed of the electric potential difference between two coexisting phases in aqueous solutions of the charged protein fish gelatin (nongelling) and the uncharged polysaccharide dextran. Charge counteracts demixing because of the entropic cost of confining the counterions to one phase, resulting in a strong shift of the critical point upon an increase of the charge on one of the polymers. Upon phase separation, the charged polymer is spatially confined, and due to the Donnan effect, an interfacial electric potential is developed. A direct proportionality is found between this Donnan potential and the difference in gelatin concentration in the two phases, for which we propose a theoretical explanation. The electrostatics may provide a new handle in the development of stable water-in-water emulsions.

Composition, concentration and charge profiles of water–water interfaces

The properties of interfaces are discussed between coexisting phases in phase separated aqueous solutions of polymers. Such interfaces are found in food, where protein-rich and polysaccharide-rich phases coexist. Three aspects of such interfaces are highlighted: the interfacial profiles in terms of polymer composition and polymer concentration, the curvature dependence of the interfacial tension, and the interfacial potential, arising when one of the separated polymers is charged. In all three cases a theoretical approach and methods for experimental verification are presented.

Liquid crystal phase transitions in systems of colloidal platelets with bimodal shape distribution.

We have studied a system of polydisperse, charged colloidal gibbsite platelets with a bimodal distribution in the particle aspect ratio. We observe a density inversion of the coexisting isotropic and nematic phases as well as a three-phase equilibrium involving a lower density nematic phase, an isotropic phase of intermediate density, and a higher density columnar phase. To relate these phenomena to the bimodality of the shape distribution, we have calculated the liquid crystal phase behavior of binary mixtures of thick and thin hard platelets for various thickness ratios. The predictions are based on the Onsager-Parsons theory for the isotropic-nematic (I-N) transition combined with a modified Lennard-Jones-Devonshire cell theory for the columnar (C) state. For sufficiently large thickness ratios, the phase diagram features an I-N density inversion and triphasic I-N-C equilibrium, in agreement with experiment. The density inversion can be attributed to a marked shape fractionation among the coexisting phases with the thick species accumulating in the isotropic phase. At high concentrations, the theory predicts a coexistence between two columnar phases with distinctly different concentrations. In experiment, however, the demixing transition is pre-empted by a transition to a kinetically arrested, glassy state with structural features resembling a columnar phase.

Chemical physics of water–water interfaces

A brief review is given on recent progress in experimental and theoretical investigations of the interface between coexisting aqueous phases of biopolymers. The experimental aspects are introduced using results obtained from a model system consisting of aqueous mixtures of nongelling gelatin and dextran. The focus is on the interfacial tension and interfacial electric potential (Donnan potential). These quantities are experimentally accessible and can be shown to be closely related.

Nematic and lamellar liquid-crystalline phases in suspensions of charged silica-coated gibbsite platelets

Computer simulations, theoretical investigations and experiments carried out over the last 20 years have demonstrated that suspensions of hard plate-like colloids display a rich liquid-crystal phase behaviour including nematic and columnar phases. Recently, it has become clear that charged colloidal platelets display an even richer phase behaviour including smectic A and smectic B phases. Here, we report on the formation of liquid crystals in suspensions of charged silica-coated gibbsite platelets in dimethylformamide in the presence of 1 mM salt and without added salt. A nematic phase is observed in the system with added salt, while in the system without added salt a lamellar (smectic A) liquid-crystalline phase is formed as demonstrated by optical observations and synchrotron small angle X-ray scattering measurements. The observed phases are in contrast with the columnar phase that would be expected if the platelets were interacting through hard-core repulsions. A bifurcation analysis suggests that, on decreasing ionic strength, first the columnar phase is destabilised in favour of nematic order, which in turn is destabilised in favour of lamellar order. Our experimental and theoretical results support the suggestion that the appearance of nematic and lamellar phases is related to the strength and range of the double-layer repulsion.

Interfacial Tension of Phase-Separated Polydisperse Mixed Polymer Solutions

Aqueous two-phase systems provide oil-free alternatives in the formulation of emulsions in food and other applications. Theoretical interpretation of measurements on such systems, however, is complicated by the high polydispersity of the polymers. Here, phase diagrams of demixing and interfacial tensions are determined for aqueous solutions of two large polymers present in a mass ratio of 1:1, dextran (70 kDa) and nongelling gelatin (100 kDa), with or without further addition of smaller dextran molecules (20 kDa). Both in experiments and in calculations from Scheutjens–Fleer self-consistent field lattice theory, we find that small polymers decrease the interfacial tension at equal tie-line length in the phase diagram. After identifying the partial contributions of all chemical components to the interfacial tension, we conclude that excess water at the interface is partially displaced by small polymer molecules. An interpretation in terms of the Gibbs adsorption equation provides an instructive way to describe effects of polydispersity on the interfacial tension of demixed polymer solutions.

Polyelectrolytes adsorbed at water-water interfaces

Polyelectrolytes can show strong adsorption at water-water interfaces formed by phase separation of two polymers in aqueous solution. We demonstrate this for a model system consisting of neutral polymer A and weakly positively charged polymer B. When polyelectrolyte is added with similar chemical composition as polymer A, but charge of opposite sign as polymer B, interfacial accumulation is observed. We hypothesize this accumulation to be complexation at the water-water interface. This adsorption surprisingly persists even at high salt concentrations and has only a limited effect on the interfacial tension. Complexation of polyelectrolytes at water-water interfaces may provide a new path towards the stabilization of water-in-water emulsions.