Emulsion rates

Ivanov et al.4 >6 5oo.5oi,562 jj yg proposed a semiquantitative theoretical approach that provides a straightforward explanation of the Bancroft rule for emulsions. This approach is based on the idea of Davies and RideaP that both types of emulsions are formed during the homogenization process, but only the one with lower coalescence rate survives. If the initial drop concentration for both emulsions is the same, the coalescence rates for the two emulsions — (Rate)i for emulsion 1 and (Rate)2 for emulsion 2 (Figure 5.44) — will be proportional to the respective coalescence rate constants, and, 2 (ss Section 5.6, below), and inversely proportional to the film lifetimes, Xj and X2 ... 

Theoretical models for the dieleetrie properties of heterogeneous mixtures [for instance, Eq. (20), or extensions of this model] are commonly applied in order to explain or predict the dieleetrie behavior also of emulsions (106, 158). However, in the present theories a homogeneous distribution of the dispersed phase is required. This requirement is rarely fulfilled in a real emulsion system where the inherent instability makes the emulsions go through different stages on the way towards complete phase separation. Proeesses like sedimentation, flocculation, and coalescence continuously alter the state of the system (Fig. 36). These processes also influence the dielectric properties (159—162). Thus, the dielectric properties of one given sample may vary considerably over a period of time (160), depending on the emulsion rate. 

Although it is hard to draw a sharp distinction, emulsions and foams are somewhat different from systems normally referred to as colloidal. Thus, whereas ordinary cream is an oil-in-water emulsion, the very fine aqueous suspension of oil droplets that results from the condensation of oily steam is essentially colloidal and is called an oil hydrosol. In this case the oil occupies only a small fraction of the volume of the system, and the particles of oil are small enough that their natural sedimentation rate is so slow that even small thermal convection currents suffice to keep them suspended for a cream, on the other hand, as also is the case for foams, the inner phase constitutes a sizable fraction of the total volume, and the system consists of a network of interfaces that are prevented from collapsing or coalescing by virtue of adsorbed films or electrical repulsions. 

Since emulsion droplets are not rigid spheres, the coefficient of 0 is around 3-6 for many emulsion systems [3-5], More concentrated emulsions are non-Newtonian depends on shear rate and are thixotropic (ri decreasing with... 

There appear to be two stages in the collapse of emulsions flocculation, in which some clustering of emulsion droplets takes place, and coalescence, in which the number of distinct droplets decreases (see Refs. 31-33). Coalescence rates very likely depend primarily on the film-film surface chemical repulsion and on the degree of irreversibility of film desorption, as discussed. However, if emulsions are centrifuged, a compressed polyhedral structure similar to that of foams results [32-34]—see Section XIV-8—and coalescence may now take on mechanisms more related to those operative in the thinning of foams. 

There are two approaches to the kinetics of emulsion flocculation. The first stems from a relationship due to Smoluchowski [52] for the rate of diffusional encounters, or flux ... 

Fig. XIV-9. Effects of electrolyte on the rate of flocculation of Aerosol MA-stabilized emulsions. (From Ref. 35.)...

For example, van den Tempel [35] reports the results shown in Fig. XIV-9 on the effect of electrolyte concentration on flocculation rates of an O/W emulsion. Note that d ln)ldt (equal to k in the simple theory) increases rapidly with ionic strength, presumably due to the decrease in double-layer half-thickness and perhaps also due to some Stem layer adsorption of positive ions. The preexponential factor in Eq. XIV-7, ko = (8kr/3 ), should have the value of about 10 " cm, but at low electrolyte concentration, the values in the figure are smaller by tenfold or a hundredfold. This reduction may be qualitatively ascribed to charged repulsion. 

The preceding treatment relates primarily to flocculation rates, while the irreversible aging of emulsions involves the coalescence of droplets, the prelude to which is the thinning of the liquid film separating the droplets. Similar theories were developed by Spielman [54] and by Honig and co-workers [55], which added hydrodynamic considerations to basic DLVO theory. A successful experimental test of these equations was made by Bernstein and co-workers [56] (see also Ref. 57). Coalescence leads eventually to separation of bulk oil phase, and a practical measure of emulsion stability is the rate of increase of the volume of this phase, V, as a function of time. A useful equation is... 

There have been some studies of the equilibrium shape of two droplets pressed against each other (see Ref. 59) and of the rate of film Winning [60, 61], but these are based on hydrodynamic equations and do not take into account film-film barriers to final rupture. It is at this point, surely, that the chemistry of emulsion stabilization plays an important role. 

In this example the number of micelles per unit volume is exactly twice the stationary-state free-radical concentration hence the rates are identical. Although the numbers were chosen in this example to produce this result, neither N nor M are unreasonable values in actual emulsion polymerizations. 

Since polymer swelling is poor and the aqueous solubiUty of acrylonitrile is relatively high, the tendency for radical capture is limited. Consequentiy, the rate of particle nucleation is high throughout the course of the polymerization, and particle growth occurs predominantiy by a process of agglomeration of primary particles. Unlike emulsion particles of a readily swollen polymer, such as polystyrene, the acrylonitrile aqueous dispersion polymer particles are massive agglomerates of primary particles which are approximately 100 nm in diameter. 

Membranes and Osmosis. Membranes based on PEI can be used for the dehydration of organic solvents such as 2-propanol, methyl ethyl ketone, and toluene (451), and for concentrating seawater (452—454). On exposure to ultrasound waves, aqueous PEI salt solutions and brominated poly(2,6-dimethylphenylene oxide) form stable emulsions from which it is possible to cast membranes in which submicrometer capsules of the salt solution ate embedded (455). The rate of release of the salt solution can be altered by surface—active substances. In membranes, PEI can act as a proton source in the generation of a photocurrent (456). The formation of a PEI coating on ion-exchange membranes modifies the transport properties and results in permanent selectivity of the membrane (457). The electrochemical testing of salts (458) is another possible appHcation of PEI. 

Kinetics and Mechanisms. Early researchers misunderstood the fast reaction rates and high molecular weights of emulsion polymerization (11). In 1945 the first recognized quaHtative theory of emulsion polymerization was presented (12). This mechanism for classic emulsion preparation was quantified (13) and the polymerization separated into three stages. 

A third source of initiator for emulsion polymerisation is hydroxyl radicals created by y-radiation of water. A review of radiation-induced emulsion polymerisation detailed efforts to use y-radiation to produce styrene, acrylonitrile, methyl methacrylate, and other similar polymers (60). The economics of y-radiation processes are claimed to compare favorably with conventional techniques although worldwide iadustrial appHcation of y-radiation processes has yet to occur. Use of y-radiation has been made for laboratory study because radical generation can be turned on and off quickly and at various rates (61). 

The newly formed short-chain radical A then quickly reacts with a monomer molecule to create a primary radical. If subsequent initiation is not fast, AX is considered an inhibitor. Many have studied the influence of chain-transfer reactions on emulsion polymerisation because of the interesting complexities arising from enhanced radical desorption rates from the growing polymer particles (64,65). Chain-transfer reactions are not limited to chain-transfer agents. Chain-transfer to monomer is ia many cases the main chain termination event ia emulsion polymerisation. Chain transfer to polymer leads to branching which can greatiy impact final product properties (66). 

Acryhc and methacryhc nonaqueous dispersions (NADs) are primarily utilized by the coatings industry to avoid certain difficulties associated with aqueous dispersion (emulsion) polymers. Water as a suspension medium has numerous practical advantages, but also some inherent difficulties a high heat of evaporation, a low boiling point, and an evaporation rate that depends on the prevailing humidity. Nonaqueous dispersions alleviate these problems, but introduce others such as flammabihty, increased cost, odor, and toxicity. 

Poly(viayl acetate) emulsions or hot-melt adhesives are typically used to form the manufacturer s or glue lap joiat of the box. The main criteria for the adhesive is that it provide a strong and tough final bond and that it set up quickly enough to allow fast box production speeds. Production rates ia excess of 240 boxes per minute are not uncommon ia the iadustry. 

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