Adsorption, polymeric surfactants

The number of polymer particles is the prime determinant of the rate and degree of polymerization since it appears as the first power in both Eqs. 4-5 and 4-7. The formation (and stabilization) of polymer particles by both micellar nucleation and homogeneous nucleation involves the adsorption of surfactant from the micelles, solution, and monomer droplets. The number of polymer particles that can be stabilized is dependent on the total surface area of surfactant present in the system asS, where as is the interfacial surface area occupied by a surfactant molecule and S is the total concentration of surfactant in the system (micelles, solution, monomer droplets). However, N is also directly dependent on the rate of radical generation. The quantitative dependence of N on asS and R,- has been derived as... 

A characteristic increase of 90 after the horizontal section is apparently more pronounced when the potassium oxalate K2C2O4 is used as the electron donor instead of the sulfide ions (Fig. 2.25). A qualitative similarity of the adsorption isotherms and the MO concentration dependence on the initial quantum yield indicates that the adsorbed dye molecules take part in the reaction. Note that all kinetic curves attain the same value of the stationary quantum yield ratio depends on the nature of polymeric surfactant used for stabilization of CdS colloid. With PAA, this ratio equals ca. 0.5, and 0.6 with PVS. 

Perhaps the simplest type of a polymeric surfactant is a homopolymer, that is formed from the same repeating units, such as PEO or poly(vinyl pyrrolidone). These homopolymers have minimal surface activity at the O/W interface, as the homopolymer segments (e.g., ethylene oxide or vinylpyrroUdone) are highly water-soluble and have little affinity to the interface. However, such homopolymers may adsorb significantly at the solid/liquid (S/L) interface. Even if the adsorption energy per monomer segment to the surface is small (fraction of kT, where k is the Boltzmann constant and T is absolute temperature), the total adsorption energy per molecule may be sufficient to overcome the unfavourable entropy loss of the molecule at the S/L interface. 

Adsorption of Polymeric Surfactants at the Solid/Liquid Interface... 

Experimental Techniques for Studying Polymeric Surfactant Adsorption... 

As mentioned above, in order to fully characterize polymeric surfactant adsorption, three parameters must be determined (i) the adsorbed amount F (mgm or mol m ) as a function of the equihbrium concentration that is, the adsorption isotherm (ii) the fraction of segments in direct contact with the surface p (the number of segments in trains relative to the total number of segments) and (iii) the segment density distribution p(z) or the hydrodynamic adsorbed layer thickness 5. ... 

Examples of the Adsorption Isotherms of Nonionic Polymeric Surfactants... 

Polymers are also essential for the stabilisation of nonaqueous dispersions, since in this case electrostatic stabilisation is not possible (due to the low dielectric constant of the medium). In order to understand the role of nonionic surfactants and polymers in dispersion stability, it is essential to consider the adsorption and conformation of the surfactant and macromolecule at the solid/liquid interface (this point was discussed in detail in Chapters 5 and 6). With nonionic surfactants of the alcohol ethoxylate-type (which may be represented as A-B stmctures), the hydrophobic chain B (the alkyl group) becomes adsorbed onto the hydrophobic particle or droplet surface so as to leave the strongly hydrated poly(ethylene oxide) (PEO) chain A dangling in solution The latter provides not only the steric repulsion but also a hydrodynamic thickness 5 that is determined by the number of ethylene oxide (EO) units present. The polymeric surfactants used for steric stabilisation are mostly of the A-B-A type, with the hydrophobic B chain [e.g., poly (propylene oxide)] forming the anchor as a result of its being strongly adsorbed onto the hydrophobic particle or oil droplet The A chains consist of hydrophilic components (e.g., EO groups), and these provide the effective steric repulsion. 

The adsorption of polymeric surfactants is more complex, since in this case the process is irreversible and produces a high-affinity isotherm with a steep rise in the adsorption value at low polymer concentrations (in this region most of the molecules are completely adsorbed). Subsequently, the adsorbed amount remains virtually constant, giving a plateau value that depends on the molecular weight, temperature and solvency of the medium for the chains (this topic was discussed in detail in Chapter 6). 

During emulsification an increase in the interfacial area A takes place and this causes a reduction in T. The equilibrium is restored by the adsorption of surfactant from the bulk, but this takes time (shorter times occur at higher surfactant activity). Thus, e is small whether a is small or large. Because of the lack or slowness of equilibrium with polymeric surfactants, e will not be the same for expansion and compression of the interface. 

The addition of electrolytes in the continuous phase this has the effect of enhancing the polymeric surfactant adsorption and thus preventing particle entry into the oil droplets. 

In both cases a plateau adsorption value F is reached at a given value of C2. In general, the value of F is reached at a lower C2 for polymeric surfactant adsorption when compared to small molecules. The high-affinity isotherm obtained with polymeric surfactants implies that the first added molecules are virtually... 

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