Polymer osmotic stress

Interactions with neutral and anionic polymers (osmotic stress)... 

Bibette has used this method to study the effect of osmotic pressure on the stability of thin films in concentrated o/w emulsions [96], by means of an osmotic stress technique. The emulsion is contained in a dialysis bag, which is immersed in an aqueous solution of surfactant and dextran, a water-soluble polymer. The bag is permeable to water and surfactant, but impermeable to oil and polymer. The presence of the polymer causes water to be drawn out of the emulsion, increasing the phase volume ratio and the deformation of the dispersed droplets (Fig. 10). 

Concentration-independent diffusion only occurs at low temperatures and/or low penetrant "activities". At high penetrant activities over a range of temperatures well below Tg the transport of penetrant into the polymer is accompanied by solvent crazing or cracking the osmotic stresses produced by the penetrant are sufficiently large to cause local fracture of the material. 

Sarti, G. C. Solvent Osmotic Stresses and the Prediction of Case II Transport Kinetics, Polymer, in press... 

Another aspect of current interest associated with the lipid-water system is the hydration force problem.i -20 When certain lipid bilayers are brought closer than 20-30 A in water or other dipolar solvents, they experience large repulsive forces. This force is called solvation pressure and when the solvent is water, it is called hydration pressure. Experimentally, hydration forces are measured in an osmotic stress (OS) apparatus or surface force apparatus (SFA)2o at different hydration levels. In OS, the water in a multilamellar system is brought to thermodynamic equilibrium with water in a polymer solution of known osmotic pressure. The chemical potential of water in the polymer solution with which the water in the interlamellar water is equilibrated gives the net repulsive pressure between the bilayers. In the SEA, one measures the force between two crossed cylinders of mica coated with lipid bilayers and immersed in solvent. 

In parallel, another important (although less direct) technique for measuring forces between macromolecules or lipid bilayers was developed, namely, the osmotic stress method [39-41]. A dispersion of vesicles or macromolecules is equilibrated with a reservoir solution containing water and other small solutes, which can freely exchange with the dispersion phase. The reservoir also contains a polymer that cannot diffuse into the dispersion. The polymer concentration determines the osmotic stress acting on the dispersion. The spacing between the macromolecules or vesicles is measured by X-ray diffraction (XRD). In this way, one obtains pressure-versus-distance curves. The osmotic stress method is used to measure interactions between lipid bilayers, DNA, polysaccharides, proteins, and other macromolecules [36]. It was particularly successful in studying the hydration... 

The interaction of water soluble polymers with lamellar dispersions has implications in many practical applications such as consumer products, drug delivery, bioseparations, and industrial processes. The osmotic stress method for studying membrane biophysics involves the addition of water soluble polymers such as poly (ethylene glycols) (PEGs) to phospholipid vesicles and measuring the changes in... 

The osmotic stress method has also been applied to colloidal dispersions [1238,1246], emulsions [1247], colloidal crystals [1248], clays [1249, 1250], block copolymers [1251], a mixed nanoparticle/polymer system [1252], and colloids with polyelectrolyte multilayers [1253]. 

Direct quantitative measurements of steric repulsion were made with the surface forces apparatus [1353-1360] and the atomic force microscope [1361-1364]. Although we focused on the interaction between solid surfaces, steric forces also act between fluid interfaces. The first force versus distance curves of steric repulsion were recorded across a liquid foam lamellae with a thin film balance by Lyklema and van Vhet [1365]. Another example is the force measurement between vesicles using the osmotic stress method by Kenworthy et cd. [1366]. Experimentally, the Milner, Witten, and Cates and the de Gennes model both fit force curves measured between polymer bmshes in good solvents reasonably well. 

Microreticular Resins. Microreticular resins, by contrast, are elastic gels that, in the dry state, avidly absorb water and other polar solvents in which they are immersed. While taking up solvent, the gel structure expands until the retractile stresses of the distended polymer network balance the osmotic effect. In nonpolar solvents, little or no swelling occurs and diffusion is impaired. 

At least two different techniques are available to compress an emulsion at a given osmotic pressure H. One technique consists of introducing the emulsion into a semipermeable dialysis bag and to immerse it into a large reservoir filled with a stressing polymer solution. This latter sets the osmotic pressure H. The permeability of the dialysis membrane is such that only solvent molecules from the continuous phase and surfactant are exchanged across the membrane until the osmotic pressure in the emulsion becomes equal to that of the reservoir. The dialysis bag is then removed and the droplet volume fraction at equilibrium is measured. 

An emulsion that is, for instance, stable over many years at low droplet volume fraction may become unstable and coalesce when compressed above a critical osmotic pressure 11. As an example, when an oil-in-water emulsion stabilized with sodium dodecyl sulfate (SDS) is introduced in a dialysis bag and is stressed by the osmotic pressure imposed by an external polymer solution, coarsening occurs through the growth of a few randomly distributed large droplets [8]. A microscopic image of such a growth is shown in Fig. 5.1. 

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