Rheological emulsion coalescence

Assessment and Prediction of Emulsion Coalescence Using Rheological Techniques I 459... 

Many different combinations of surfactant and protective coUoid are used in emulsion polymerizations of vinyl acetate as stabilizers. The properties of the emulsion and the polymeric film depend to a large extent on the identity and quantity of the stabilizers. The choice of stabilizer affects the mean and distribution of particle size which affects the rheology and film formation. The stabilizer system also impacts the stabiUty of the emulsion to mechanical shear, temperature change, and compounding. Characteristics of the coalesced resin affected by the stabilizer include tack, smoothness, opacity, water resistance, and film strength (41,42). 

A typical characteristic of many food products is that these are multi-phase products. The arrangement of the different phases leads to a microstructure that determines the properties of the product. Mayonnaise, for example, is an emulsion of about 80% oil in water, stabilized by egg yolk protein. The size of the oil droplets determines the rheology of the mayonnaise, and hence, the mouthfeel and the consumer liking. Ice cream is a product that consists of four phases. Figure 1 shows this structure schematically. Air bubbles are dispersed in a water matrix containing sugar molecules and ice crystals. The air bubbles are stabilized by partial coalesced fat droplets. The mouthfeel of ice cream is determined by a combination of the air bubble size, the fat droplet size and the ice crystal size. 

The non-aqueous HIPEs showed similar properties to their water-containing counterparts. Examination by optical microscopy revealed a polyhedral, poly-disperse microstructure. Rheological experiments indicated typical shear rate vs. shear stress behaviour for a pseudo-plastic material, with a yield stress in evidence. The yield value was seen to increase sharply with increasing dispersed phase volume fraction, above about 96%. Finally, addition of water to the continuous phase was studied. This caused a decrease in the rate of decay of the emulsion yield stress over a period of time, and an increase in stability. The added water increased the strength of the interfacial film, providing a more efficient barrier to coalescence. 

Many epoxy dispersions are compatible with most types of latex emulsions including acrylic, urethane, styrene butadiene, vinyl chloride, and polyvinyl acetate. The epoxy dispersion can be used as a modifier for these emulsions to alter handling and application characteristics such as emulsion rheology, foaming tendencies, pH sensitivity, wetting properties, and coating coalescence. They can also be reacted into the latex resin either by reacting the epoxy with a functionalized latex or by use of an epoxy with a coreactant. In this way adhesive systems can be formulated that are cured at room or elevated temperatures. 

Dickinson, E., Murray, B.S., Stainsby, G. 1988. Coalescence stability of emulsion-sized droplets at a planar oil-water interface and the relationship to protein film surface rheology. J. Chem. Soc., Faraday Trans. I, 84, 871-883. 

Princen and Kiss [13] have studied the rheological properties of emulsions in which the effects of drainage, coalescence and diffusion transfer is much less expressed than in foams. A concentric-cylinder viscometer was used. The slip was estimated by rheograms in the t vs. 0) lx form (t is the stress measured on the inner cylinder wall, co is the angular velocity of the outer cylinder). The Xq values obtained are conform well with those from Eq. (8.24) but Xo (y) function is not a Bingham one, i.e. does not obey Eq. (8.11) at rj = const. 

Hallworth and Carless (1 ) discuss several possibilities for the effect of light liquid paraffin on the stability of emulsions with light petroleum or chlorobenzene as the main components. They seem to prefer an explanation previously advanced by them and several other authors for the effect of fatty alcohol, namely that the increased stability is due to the formation of an interfacial complex between the additive and sodium hexadecyl sulphate. The condenced mixed film will resist coalescence primarily by virtue of its rheological properties. With mixed films of the present type, the importance of the film viscoelasticity lies in its ability to maintain electrical repulsion between approaching droplets by preventing lateral displacement of the adsorbed ions. The effective paraffinic oil has chains at least as long as those of the alkyl sulphate and will be associated by van der Waals forces with the hydrocarbon chain of the alkyl sulphate at the interface. 

Stevens et al. [86] proposed the replacement of the surfactant with fluids to modify the rheological properties and stabilize the emulsion. The aim was to slow the drainage of the film between the coalescing drops, thereby increasing the stability of the membrane. Their study on the removal of chromium with Alamine 336 showed that the emulsion stabihty could be controlled with the addition of smaU amounts of polymer to the organic phase and that demulsification could be achieved by heating the system. 

In more realistic situations there is a certain probability of the emulsion droplets coalescing with the bulk oil phase or a part of the bulk oil becoming emulsified. The physics of such complex fiow conditions is not well understood at present. The starting point of describing such a fiow would be to treat it as a normal two-phase flow and use the concept of relative permeability and a model for the rheological properties of the emulsion phase. To account for the material exchange between the bulk phase and the emulsion phase, some form of droplet population balance model will be needed. 

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. ... 

Care should be taken when analysing the rheological results as coalescence leads to an increase in droplet size that is usually followed by a reduction in the viscosity of the emulsion. This trend is only observed if the coalescence is not accompanied by flocculation of the emulsion droplets (which results in an increase in the viscosity). Ostwald ripening can also complicate the analysis of rheological data. 

It should be emphasised that polymeric surfactants prevent the coalescence of water droplets in the multiple emulsion drops, as well as coalescence of the latter drops themselves. This is due to the interfacial rheology of the polymeric surfactant films. As a result of the strong lateral repulsion between the stabilising chains at the interface (PHS chains at the W/O interface and PEO chains at the O/W interface), these films resist deformation under shear and hence produce a viscoelastic film. On approach of the two droplets, this film prevents deformation of the interface so as to prevent coalescence. 

We have recently reported (6, 7) that those surfactant formulations which yield good oil recovery exhibit both low interfacial tensions and low interfacial viscosities. Our experiments have shown that surfactant formulations which ensure low interfacial viscosity will promote the coalescence of oil droplets and thereby decrease the emulsion stability, thus enhancing the formation of a continuous oil bank. It has been demonstrated that the requirements for emulsion stability are the presence of an interfacial film of high viscosity and a film of considerable thickness. We have observed that the surfactant concentration which minimizes the interfacial tension may not simultaneously minimize the interfacial viscosity. Hence, our results indicate both interfacial tension and interfacial rheology must be considered in selecting surfactant formulations for tertiary oil recovery. 

---