Emulsion viscosity structured systems

The main factors which affect the viscosity of emulsions are listed in Table 8.6. The properties of the disperse phase, the continuous phase and the emulsifying agent or agents all influence the emulsion viscosity. Each factor does not act independently and the interpretation of emulsion viscosity data is complicated by this fact and the fact that particles can deform under shear depending on the nature of the interfacial film. As we have also discussed, emulsions are complex systems, often highly structured, and at phase boundaries or on the point of inversion are very sensitive to small perturbations in the system. We will deal here first with mobile emulsions and then consider briefly the semi-solid state. 

Emulsion polymerization is the most important process for production of elastic polymers based on butadiene. Copolymers of butadiene with styrene and acrylonitrile have attained particular significance. Polymerized 2-chlorobutadiene is known as chloroprene rubber. Emulsion polymerization provides the advantage of running a low viscosity during the entire time of polymerization. Hence the temperature can easily be controlled. The polymerizate is formed as a latex similar to natural rubber latex. In this way the production of mixed lattices is relieved. The temperature of polymerization is usually 50°C. Low-temperature polymerization is carried out by the help of redox systems at a temperature of 5°C. This kind of polymerization leads to a higher amount of desired trans-1,4 structures instead of cis-1,4 structures. Chloroprene rubber from poly-2-chlorbutadiene is equally formed by emulsion polymerization. Chloroprene polymerizes considerably more rapidly than butadiene and isoprene. Especially in low-temperature polymerization emulsifiers must show good solubility and... 

In this equation, viscosity is independent of the degree of dispersion. As soon as the ratio of disperse and continuous phases increases to the point where particles start to interact, the flow behavior becomes more complex. The effect of increasing the concentration of the disperse phase on the flow behavior of a disperse system is shown in Figure 8-41. The disperse phase, as well as the low solids dispersion (curves 1 and 2), shows Newtonian flow behavior. As the solids content increases, the flow behavior becomes non-Newtonian (curves 3 and 4). Especially with anisotropic particles, interaction between them will result in the formation of three-dimensional network structures. These network structures usually show non-Newtonian flow behavior and viscoelastic properties and often have a yield value. Network structure formation may occur in emulsions (Figure 8-42) as well as in particulate systems. The forces between particles that result in the formation of networks may be... 

In liquid-liquid systems, upon increase of concentration of the dispersed phase, at a certain concentration suddenly the dispersed and continuous liquids exchange roles. This is known as a phase inversion. Salager et al. [1983] and Minana-Perez et al. [1986] reported two types of phase transition in ionic emulsions — in the first, viscosity goes through a minimum, whereas in the second it goes through a maximum. The first type of transition (normal) is associated with a decrease of the interfacial tension coefficient and formation of a micro-emulsion. The second (catastrophic) transition is associated with an inversion of unstable structure to a stable one. 

Considering melt flow of BC, it is usually assumed that the test temperature is UCST > T > T, where T stands for glass transition temperature of the continuous phase. However, at Tg < T < T g (T g is Tg of the dispersed phase) the system behaves as a crosslinked rubber with strong viscoelastic character. At UCST > T > T, the viscosity of BC is much greater than would be expected from its composition. The reason for this behavior is the need to deform the domain structure and puU filaments of one polymer through domains of the other. Viscosity increases with increase of the interaction parameter between the BC components in a similar way as an increase of the interfacial tension coefficient in concentrated emulsions causes viscosity to rise [Henderson and Williams, 1979]. 

Time-dependent rheological properties reflect the nature of a system s structure and can be due to viscoelasticity, structural changes, or both (Cheng and Evans, 1965 Harris, 1972). Structure breakdown can result in a decrease in the viscosity of a substance. It occurs in emulsions, suspensions, and sols. The characterization of the time-dependent flow properties of food systems is important for process design and control, for product devel-... 

As a result, this equation is usually the only one needed for liquid or solid aerosols. Figure 6.18 shows several sets of experimental data compared with the Einstein equation. In practice once cp reaches between 0.1 and 0.5, dispersion viscosity increases significantly and can also become non-Newtonian (due to particle/droplet/bubble crowding or structural viscosity). The maximum volume fraction possible for an internal phase made up of uniform, incompressible spheres is 0.74, although emulsions and foams with an internal volume fraction of over 0.99 can exist as a consequence of droplet/bubble distortion. Figure 6.18 and Equation 6.33 illustrate why volume fraction is such a theoretically and experimentally favoured concentration unit in rheology. In the simplest case, a colloidal system can be considered Einsteinian, but in most cases the viscosity dependence is more complicated. 

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