Electrostatics surfactant-polymer systems

Functionalized polyelectrolytes are promising candidates for photoinduced ET reaction systems. In recent years, much attention has been focused on modifying the photophysical and photochemical processes by use of polyelectrolyte systems, because dramatic effects are often brought about by the interfacial electrostatic potential and/or the existence of microphase structures in such systems [10, 11], A characteristic feature of polymers as reaction media, in general, lies in the potential that they make a wider variety of molecular designs possible than the conventional organized molecular assemblies such as surfactant micelles and vesicles. From a practical point of view, polymer systems have a potential advantage in that polymers per se can form film and may be assembled into a variety of devices and systems with ease. 

The Polymer, Surfactant, Salt phase diagram (11b) shows overall less coacervate than the Salt, Surfactant, Polymer diagram (11a) and the No Salt diagram. In this experiment, the polymer and surfactant were allowed to mix before salt was added, which promotes ion-exchange interactions. However, once the salt was added, the chemical potential of the system shifts such that ion-exchange is reversed which leads to a resolubilization of the coacervate formed via electrostatic interactions at some compositions. 

These include electrostatic interaction between the particles and interaction of particles with the fluid governed by their wettability, morphology and density (17-19) the extent of adsorption of the polymer and its influence on the interaction of particles, the orientation or configuration of the adsorbed polymers (and surfactant when it is present) and resultant interaction of adsorbed layers the hydrodynamic state of the system and its influence on the interaction of floes themselves. 

Surfactants are employed in emulsion polymerizations to facilitate emulsification and impart electrostatic and steric stabilization to the polymer particles. Sicric stabilization was described earlier in connection with nonaqueous dispersion polymerization the same mechanism applies in aqueous emulsion systems. Electrostatic stabilizers are usually anionic surfactants, i.e., salts of organic acids, which provide colloidal stability by electrostatic repulsion of charges on the particle surfaces and their associated double layers. (Cationic surfactants are not commonly used in emulsion polymerizations.)... 

Classical theories of emulsion stability focus on the manner in which the adsorbed emulsifier film influences the processes of flocculation and coalescence by modifying the forces between dispersed emulsion droplets. They do not consider the possibility of Ostwald ripening or creaming nor the influence that the emulsifier may have on continuous phase rheology. As two droplets approach one another, they experience strong van der Waals forces of attraction, which tend to pull them even closer together. The adsorbed emulsifier stabilizes the system by the introduction of additional repulsive forces (e.g., electrostatic or steric) that counteract the attractive van der Waals forces and prevent the close approach of droplets. Electrostatic effects are particularly important with ionic emulsifiers whereas steric effects dominate with non-ionic polymers and surfactants, and in w/o emulsions. The applications of colloid theory to emulsions stabilized by ionic and non-ionic surfactants have been reviewed as have more general aspects of the polymeric stabilization of dispersions. ... 

Some colloidal systems such as polymer solutions and surfactant solutions containing micelles are thermodynamically stable and form spontaneously. These types of colloids are called lyophilic colloids. However, most systems encountered contain lyophobic colloids (particles insoluble in the solvent). In the preparation of such lyophobic colloidal dispersions, the presence of a stabilizing substance is essential. Because van der Waals forces usually tend to lead to agglomeration (flocculation) of the particles, stability of such colloids requires that the particles repel one another, either by carrying a net electrostatic charge or by being coated with an adsorbed layer of large molecules compatible with the solvent. 

The following rationale accounts for these experimental findings. Sodium lauryl sulfate interacts with polymer primarily through an electrostatic interaction, and the net result is to neutralize the charge of the polymer and thereby reduce its affinity for keratin. Amphoterics do not neutralize the charge of the cationic polymer as effectively as do anionics. Therefore, cationic polymers demonstrate a greater affinity for keratins in an amphoteric surfactant system than in an anionic surfactant system. 

---