Micelles stabilisation

Initiation takes place in aqueous solution and is followed by prc agation in the aqueous phase. At some point the growing oligomer becomes insoluble in water and requires stabilisation. This can be achieved by the species entering a polymer particle, a monomer droplet or a surfactant micelle. Stabilisation can also occur by radical adsorption onto a surfactant molecule in solution. It is this method which is most inqtortant in the early stages of polymerisation. 

Phosphorescence can also be detected when the phosphor is incorporated into an ionic micelle. Deoxygenation is still required either by degassing with nitrogen or by the addition of sodium sulphite. Micelle-stabilised-room temperature phosphorescence (MS RTP) promises to be a useful analytical tool for determining a wide veuiety of compoimds such as pesticides and polyaromic hydrocarbons. 

As reaction proceeds the micelles become swollen with monomer and polymer and they eject polymer particles. These particles which are stabilised with soap molecules taken from the micelles become the loci of further polymerisation, absorbing and being swollen by monomer molecules. 

Emulsion polymerisation is initiated using a water-soluble initiator, such as potassium persulfate. This forms free radicals in solution which may initiate some growing chains in solution. These radicals or growing chains pass to the micelles and diffuse into them, which causes the bulk of the polymerisation to occur in these stabilised droplets. 

The foaming propensity of surfactants generally reaches a maximum at the critical micelle concentration, beyond which there appears to be little further contribution to foam density. Foam stabilisers are also added in some cases. The two important steps in the foam treatment of textile materials are generating the foam and applying it to the substrate ... 

Very recently, ESR techniques have been employed to study the packing of surfactant molecules at the oil/water interface in w/o HIPEs [102,103], By including an amphiphilic ESR probe, which is adsorbed at the oil/water interfaces, it is possible to determine the microstructure of the oil phase from the distribution of amphiphiles between the films surrounding the droplets and the reverse micelles. It was found that most of the surfactant is located in the micelles, over a wide range of water fraction values. However, when the water content is very high (water droplets of the emulsion, to stabilise the large interfacial area created. 

Figure 4 (A) A spherical reversed micelle of a negatively charged micro droplet of water stabilised by cationic surfactant molecules. (B) Schematic representation of the steric interactions in the reversed micelle which favors the formation of linear alkyl rhodium intermediates.

The mechanism of emulsion polymerisation is complex. The basic theory is that originally proposed by Harkins21. Monomer is distributed throughout the emulsion system (a) as stabilised emulsion droplets, (b) dissolved to a small extent in the aqueous phase and (c) solubilised in soap micelles (see page 89). The micellar environment appears to be the most favourable for the initiation of polymerisation. The emulsion droplets of monomer appear to act mainly as reservoirs to supply material to the polymerisation sites by diffusion through the aqueous phase. As the micelles grow, they adsorb free emulsifier from solution, and eventually from the surface of the emulsion droplets. The emulsifier thus serves to stabilise the polymer particles. This theory accounts for the observation that the rate of polymerisation and the number of polymer particles finally produced depend largely on the emulsifier concentration, and that the number of polymer particles may far exceed the number of monomer droplets initially present. 

Emulsions made by agitation of pure immiscible liquids are usually very unstable and break within a short time. Therefore, a surfactant, mostly termed emulsifier, is necessary for stabilisation. Emulsifiers reduce the interfacial tension and, hence, the total free energy of the interface between two immiscible phases. Furthermore, they initiate a steric or an electrostatic repulsion between the droplets and, thus, prevent coalescence. So-called macroemulsions are in general opaque and have a drop size > 400 nm. In specific cases, two immiscible liquids form transparent systems with submicroscopic droplets, and these are termed microemulsions. Generally speaking a microemulsion is formed when a micellar solution is in contact with hydrocarbon or another oil which is spontaneously solubilised. Then the micelles transform into microemulsion droplets which are thermodynamically stable and their typical size lies in the range of 5-50 nm. Furthermore bicontinuous microemulsions are also known and, sometimes, blue-white emulsions with an intermediate drop size are named miniemulsions. In certain cases they can have a quite uniform drop size distribution and only a small content of surfactant. An interesting application of this emulsion type is the encapsulation of active substances after a polymerisation step [25, 26]. 

Dairy phospholipids are important structurally, because they are able to stabilise emulsions and foams, and to form micelles and membranes (Jensen and Newburg, 1995). Phospholipids also have the potential to be pro-oxidants, because they contain mono-unsaturated and poly-unsaturated fatty acids and have the ability to attract metal ions. Phosphatidyl ethanolamine binds copper strongly and is believed to be important in copper-induced oxidation in milk (O Connor and O Brien 1995 Deeth, 1997). The polyunsaturated fatty acids and metal ions accelerate lipid oxidation, especially when heat is applied hence, phospholipids can be degraded during the processing of milk. However, in dairy products, the situation is complex and it appears that phospholipids are able to act as either pro-oxidants or antioxidants, depending on the pH, ratio of water and phospholipid species (Chen and Nawar, 1991). 

Phosphorescence is most easily attained in a solid state rather than in the liquid state. In solid-state dissipation of energy by virtue of collision is minimised and time to the excited state increased. This result in increase in probability of inter system crossing and consequently to phosphorescent. Solid like rigidity and phosphorescence can also be attained by absorption of molecule on a surface or by using a Micelle to stabilise the molecules. 

In w/o emulsions the hydrocarbon chains of the adsorbed molecules protrude into the oily continuous phase. Stabilisation arises from steric repulsive forces as described in section 7.2.2. Emulsions are more complex than suspensions, because of the possibility (a) of movement of the surfactant into either the continuous or disperse phase, (b) micelle formation in both phases, and (c) the formation under suitable conditions of liquid crystalline phases between the disperse droplets. 

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