Conformation of polymeric surfactants

Understanding the adsorption and conformation of polymeric surfactants at interfaces is key to understanding how these molecules act as stabilizers for suspensions and emulsions. Most basic theories on polymer adsorption and conformation have been developed for the solid/liquid interface (9). The same concepts may be applied for the liquid/liquid interface, with some modifications whereby some part of the molecule may reside within the oil phase, rather than simply staying at the interface. Such modifications do not alter the basic concepts, particularly when one deals with the stabilization by these molecules. 

Figure 16.1. Various conformations of polymeric surfactants adsorbed on a plane surface (a) random conformations of loops-trains-tails (homopolymer) (b) preferential adsorption of short blocks (c) chain lying flat on the surface (d) AB block copolymer with loop-train conformation of B and long tail of A (e) ABA block copolymer, as in (d) (f) BA graft with backbone B forming small loops and several tails of A ( teeth )...

This chapter described the basis principles involved in stabilization of dispersions by polymeric surfactants. The first part described polymeric surfactants and their solution properties. The second part described the adsorption of polymeric surfactants and their conformation at the interface. The methods that can be applied to determine the adsorption and conformation of polymeric surfactants were briefly described. The third part dealt with the stabilization mechanism produced using polymeric surfactants. Two main repulsive forces were considered. The first arises from the unfavorable mixing of the chains on close approach of the particles or droplets, when these chains are in good solvent conditions. This is referred to as mixing or osmotic repulsion. The second force of repulsions... 

Understanding the adsorption and conformation of polymeric surfactants at interfaces is key to knowing how these molecules act as stabilizers. Most basic ideas on adsorption and conformation of polymers have been developed for the solid/liquid... 

Fig. 3.14 Various conformations of polymeric surfactants adsorbed on a plane surface.

This chapter will start with a short account of the general classification and description of polymeric surfactants. This is followed by a summary on then-solutions properties. The adsorption and conformation of polymeric surfactants at the solid-liquid interface will be discussed at a fundamental level and some experimental results will be presented to illustrate the prediction of the theories. The interaction energies between particles or droplets containing adsorbed polymeric surfactants will be briefly described. The final section will give some applications of polymeric surfactants in suspensions, emulsions, and multiple emulsions. 

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. 

Surfactants are used in a wide variety of applications such as ore flotation, cleaning, polymerization processes, and pharmaceuticals and agriculture. The usual role for the surfactant is to modify interfacial properties, whether they be liquid/liquid, solid/liquid, or gas/liquid interfaces. To be effective in any of these applications, however, the surfactant must adsorb strongly at the interface. In addition to its concentration at the interface, the conformation of the surfactant at the interface is also an important factor. While the influence of solution properties such as concentration, ionic strength, and pH on surfactant adsorption are well known, the properties of the other phase also exert a significant influence. 

This chapter, will begin with a brief description of polymeric surfactants and their solution properties, followed by a description of the fundamental principles of using polymeric surfactants for stabilization of emulsions (as well as suspensions), starting with a section on the adsorption and conformation of these molecules at the interface. This is followed by a section on stabilization of dispersions by polymeric surfactants. Particular... 

This section will deal with the above interfacial aspects starting with the equilibrium aspects of surfactant adsorption at the air/water and oil/water interfaces. Due to the equilibrium aspects of adsorption (rate of adsorption is equal to the rate of desorption) one can apply the second law of thermodynamics as analyzed by Gibbs (see below). This is followed by a section on dynamic aspects of surfactant adsorption, particularly the concept of dynamic surface tension and the techniques that can be applied in its measurement. The adsorption of surfactants both on hydrophobic surfaces (which represent the case of most agrochemical solids) as well as on hydrophilic surfaces (such as oxides) will be analyzed using the Langmuir adsorption isotherms. The structure of surfactant layers on solid surfaces will be described. The subject of polymeric surfactant adsorption will be dealt with separately due to its complex nature, namely irreversibility of adsorption and conformation of the polymer at the solid/liquid interface. 

This section will introduce some of the basic factors controlling the behavior and function of polymeric surfactants in solution and in colloidal systems. Polymeric surfactants, in principle, at least, can perform all the same functions of normal surfactants the main differences between the two are the wide variation in molecular mass between the two classes of materials, the higher-order structural conformations found for polymeric materials in solution, and the energetic and kinetic consequences of those conformations and changes to them imparted by changes in the complete functional system. 

Aqueous dispersions of polymerizable lipids and surfactants can be polymerized by UV irradiation (Fig. 18). In the case of diacetylenic lipids the transition from monomeric to polymeric bilayers can be observed visually and spectroscopically. This was first discussed by Hub, 9) and Chapman 20). As in monomolecular layers (3.2.2) short irradiation brings about the blue conformation of the poly(diacetylene) chain. In contrast, upon prolonged irradiation or upon heating blue vesicles above the phase transition temperature of the monomeric hydrated lipid the red form of the polymer is formed 23,120). The visible spectra of the red form in monolayers and liposomes are qualitatively identical (Fig. 19). 

The extremely low CMCs have been advantageous for several applications, since only traces of polymer are required to form micelles. High dilution effects, that are problematic in the case of classical surfactants, do not alter polymeric micelles. The surface activity at the air - water, of the amphiphilic block copolymer or polymeric surfactants must be different from the classical surfactants, because of their much lower diffusion coefficients and their much complex conformations. 

Diblock copolymers consisting of soluble and insoluble parts (Fig. 2b) act much as grafted chains once they are adsorbed on the surface. However, the thermodynamics of the initial solution, consisting primarily of micelles, and the conformation of the insoluble blocks on the surface affect the coverage in ways not well understood (e.g., Munch and Gast, 1988 Marques et al., 1988 Gast, 1989). Many dispersants or polymeric surfactants are synthesized in this way (Reiss et al, 1987). 

In addition to giving information about the shape and internal structure of colloidal aggregates, SANS studies can also be used profitably to determine the thickness and conformation of polymer layers adsorbed onto the surface of colloidal particles such as latex nanoparticles, and in some special cases, the surface of emulsion droplets. ° In such studies, the particles on which the polymer is adsorbed must generally be very accurately contrast matched to the solvent so as to allow information to be obtained only about the adsorbed layer. SANS studies have also been recently used in combination with differential scanning calorimetry and visual inspection of the solutions, to draw up a (simplified) partial phase diagram of the aggregation behavior of a polymeric surfactant in water.t ... 

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