Emulsion film-formation

Data on emulsion film formation from insoluble surfactant monolayer are rather poor. It is known, however, that such films can be obtained when a bubble is blown at the surface of insoluble monolayers on an aqueous substrate [391,392]. Richter, Platikanov and Kretzschmar [393] have developed a technique for formation of black foam films which involves blowing a bubble at the interface of controlled monolayer (see Chapter 2). Experiments performed with monolayers from DL-Py-dipalmitoyl-lecithin on 510 3 mol dm 3 NaCl aqueous solution at 22°C gave two important results. Firstly, it was established that foam films, including black films, with a sufficiently long lifetime, formed only when the monolayer of lecithin molecules had penetrated into the bubble surface as well, i.e. there are monolayers at both film surfaces on the contrary a monolayer, however dense, formed only at one of the film surfaces could not stabilize it alone and the film ruptured at the instant of its formation. Secondly, relatively stable black films formed at rather high surface pressures of the monolayer at area less than 53A2 per molecule, i.e. the monolayer should be close-packed, which corresponds to the situation in black films stabilized with soluble surfactants. 

The emulsion film formation process described by Feng et al. [1995] involves three stages ... 

The authors of this review envisaged (Benichou et al., 2007a, b) WPI/poly-saccharide conjugates to stabilize the outer interface of W/O/W and the inner interface of O/W/O multiple emulsions and found significant improvement both in the stability and in the release of markers (glucose, vitamin Bi, lipohilic veterinary drug) compared to the use of the protein only. These new amphiphilic adducts serve as good steric stabilizers, improve stability and shelf-life, and slow the release of the markers. They therefore play a double role in the emulsions film formation and barrier to the release of small molecules at the internal interface, and steric stabilizers of the inner oil-water interface. 

For emulsions, film formation takes place through water loss forcing the spherical particles into a closely packed network of circular platelets. The resultant discs merge or coalesce together to give a continuous film ... 

The energetics and kinetics of film formation appear to be especially important when two or more solutes are present, since now the matter of monolayer penetration or complex formation enters the picture (see Section IV-7). Schul-man and co-workers [77, 78], in particular, noted that especially stable emulsions result when the adsorbed film of surfactant material forms strong penetration complexes with a species present in the oil phase. The stabilizing effect of such mixed films may lie in their slow desorption or elevated viscosity. The dynamic effects of surfactant transport have been investigated by Shah and coworkers [22] who show the correlation between micellar lifetime and droplet size. More stable micelles are unable to rapidly transport surfactant from the bulk to the surface, and hence they support emulsions containing larger droplets. 

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). 

Plasticizers soften the film and increase the adhesion and the setting speed. The most common are phthalates, adipates and benzoates. The amount added can be in a broad range of 10-50%. They affect the swelling and softening of the PVAc emulsion particles, ensure film formation at room temperature, and the tack of the still wet adhesive. They also provide improved moisture resistance of the bond. Disadvantages are the lower resistance of the bond line against heat, possible migration of the plasticizers and enhanced cold flow. 

A separate approach to the problem of VOC release during film formation is the use of polymer films cast from aqueous emulsions. Alkyd emulsions in particular have been proposed as new environmentally friendly paints and have therefore... 

DEMULSIFICATION TESTS. Demulsification tests were conducted using standard bottle test procedures to evaluate the relative performance of Thin Film Spreading Agents in coalescing emulsions of formation brine in crude oil under reservoir conditions. 

Sunflower Seed. Emulsion capacity of defatted sunflower meal was investigated by Huffman et al. (45) at three pH levels (5.2, 7.0, 10.8), blender speeds (4500, 6500, 9000 rpm), and oil addition rates (30, 45, 60 ml/min). With low mixing speeds and rapid rates of oil addition, optimum emulsion capacity occurred at pH 7.0. These authors related the observed emulsification properties to protein solubility, surface area and size of oil droplets, and rate of protein film formation. 

A similar technique can be used to study the rheological properties of liquid films. Figure 4 shows the formation of a W/O/W emulsion film with two, identical aqueous phases (such as in water-in-oil emulsions) at the tip of the capillary. A pre-requisite of the experiment is that the surface of the capillary must be well wetted by the film phase, i.e., it should be hydrophobic in this case. First, an aqueous drop is formed inside the oil (film liquid) and the aqueous phase is in the bottom of the cuvette. Then, the level of the aqueous phase is slowly increased. As the oil/water interface passes the drop, a cap shaped oil film, bordered by a circular meniscus, covers the drop. This film can be studied in equilibrium and in dynamic conditions, similar to the single interfaces (See above). The technique can be used to study films from oil or aqueous phase which can be sandwiched between identical or different liquid or gas phases. 

When conventional surfactants are used in emulsion polymerization, difficulties are encountered which are inherent in their use. Conventional surfactants are held on the particle surface by physical forces thus adsorption/des-orption equilibria always exist, which may not be desirable. They can interfere with adhesion to a substrate and may be leached out upon contact with water. Surfactant migration affects film formation and their lateral motion during particle-particle interactions can cause destabilization of the colloidal dispersion. 

The emulsifier provides sites for the particle nucleation and stabilizes growing or the final polymer particles. Even though conventional emulsifiers (anionic, cationic, and nonionic) are commonly used in emulsion polymerization, other non-conventional ones are also used they include reactive emulsifiers and amphiphilic macromonomers. Reactive emulsifiers and macromonomers, which are surface active emulsifiers with an unsaturated group, are chemically bound to the surface of polymer particles. This strongly reduces the critical amount of emulsifier needed for stabilization of polymer particles, desorption of emulsifier from particles, formation of distinct emulsifier domains during film formation, and water sensitivity of the latex film. 

An illustration of the application of an emulsified liquid bandage is shown in Fig. 2.5. The microscopic view of this film formation shows microscopic spherical particles coalescing to form a continuous film. The advantage of the emulsion is that it is a waterborne and contains no solvents (i.e., organic solvents) which is preferred over organic solvents for the biocompatible property. 

The dried film was very wearable and comfortable even after showing and exercising. Due to the nature of film formation on moist tissue, the film contained a significant amount of water (>20%) because the copolymer is hydrophilic and slightly crosslinked to absorb water. The formation of a film on a moist surface by the water-based emulsion is not conducive to a perfectly continuous dense film as is demonstrated in Fig. 2.10. The particles can be seen coalescing with each other, but they do not form a perfectly coherent and, therefore, not a continuous film as viewed in (c). 

Acrylic emulsion - The emulsion consisted of suspended crosslinked (gel) particles that are not water-soluble and form a film upon evaporation of the aqueous phase. However, the water did not evaporate quickly enough to form a continuous film on agar because agar is 95% water, and it continuously provided moisture that prevented film formation. The result was a porous barrier, but a continuous film was later obtained by dissolving dried emulsion solids in ethanol. 

Starch is an abundant, inexpensive polysaccharide that is readily available from staple crops such as com or maize and is thus is mostly important as food. Industrially, starch is also widely used in papermaking, the production of adhesives or as additives in plastics. For a number of these applications, it is desirable to chemically modify the starch to increase its hydrophobicity. Starch modification can thus prevent retrodegradation improve gel texture, clarity and sheen improve film formation and stabilize emulsions [108], This may, for example, be achieved by partial acetylation, alkyl siliconation or esterification however, these methods typically require environmentally unfriendly stoichiometric reagents and produce waste. Catalytic modification, such as the palladium-catalyzed telomerization (Scheme 18), of starch may provide a green atom-efficient way for creating chemically modified starches. The physicochemical properties of thus modified starches are discussed by Bouquillon et al. [22]. 

New starch products might be derived from emulsion copolymerization with synthetic monomers and the replacement of all-synthetic polymers. Potential applications could be in flocculation, sizing, modified rheological characteristics, bonding to a wide range of substrates, film formation and in effluent treatment. A critical requirement will be the removal of hazardous residuals and Food and Drug Administration (FDA) approval for use in specific paper grades. 

The freeze/thaw (F/T) stability of a polymer emulsion serves as a macroscopic probe for investigating the properties of the average particle in a polymer emulsion. A review of the factors which contribute to this stability is included. A study of styrene-ethyl acrylate-methacrylic acid polymers shows the existence of a minimum in the plot of minimum weight percent acid required for F/T stability vs. the minimum film formation temperature (MFT) of the polymer. This is considered to be a function of both the amount of associated surfactant and the minimum acid content. Thus, both the type of surfactant and the copolymer ratio—i.e., MFT—play major roles. Chain transfer between radicals and polyether surfactant resulting in covalently bonded surfactant-polymer combinations is important in interpreting the results. 

Minimum Film Formation Temperature (MFT). Equipment described by Protzman and Brown (24) was built, calibrated, and used for all measurements. A series of 25% emulsions, adjusted to pH 9.5 with NH3, was used throughout unless otherwise indicated. 

In most cases, physical instabilities are consequences of previous chemical instabilities. Physical instabilities can arise principally from changes in uniformity of suspensions or emulsions, difficulties related to dissolution of ingredients, and volume changes [6], For instance, some cases where physical stability has been affected are cloudiness, flocculence, film formation, separation of phases, precipitation, crystal formation, droplets of fog forming on the inside of container, and swelling of the container [8],... 

By many properties emulsion aqueous films are analogous to foam films. There are several review articles dedicated to properties of emulsion aqueous films [e.g. 320,503-506]. The properties of microscopic emulsion aqueous films (kinetics of thinning, determination of equilibrium thickness, etc.) are studied employing devices quite similar to those used for foam films [503]. Analogous to foam films, stable (metastable) emulsion films are formed only in the presence of surfactants (emulsifiers) at concentrations higher than the critical concentration of formation of black spots C or the concentration, corresponding to... 

Comparison of the concentrations corresponding to formation of black spots for emulsion and foam films, obtained from solutions of the same surfactants, indicate that Cbi for foam films are considerably lower than Cbi.f for emulsion films. This means that stable foam films (usually black) form at lower surfactant concentrations than emulsion films even from apolar organic phase. With the increase in the polarity of the molecules of the organic phase Cbi.f for emulsion aqueous films increases [507] which is analogous to the increase in Cbi for hydrocarbon emulsion films [509],... 

The concentration of formation of black spots in emulsion films is close to the emulsifier concentration at which it is possible to disperse a small quantity of the organic phase in certain volume of the aqueous surfactant solution under definite conditions resulting in formation of stable emulsions. Kruglyakov et. al. [510] have compared the concentration of black spot formation in emulsion aqueous films and the minimum surfactant concentration Cmin needed to form stable heptane aqueous emulsion studying the NaDoS emulsifying ability vs. its concentration in the solution. They found that Cmin = 4.110 4 mol dm 3 in a solution containing 51 O 2 mol dm 3 NaCl and Cw = 3.5-4-10 4 mol dm 3, depending on the time of film formation. 

The process of expansion of an emulsion film is also quite similar to that of black spots in a foam film at low electrolyte concentrations the spots in the emulsion film expand slowly, at high concentrations the process is very fast (within a second or less) and ends up with the formation of a black film with large contact angle with the bulk phase (meniscus). In the process of transformation of the black spots into a black film, the emulsion film is very sensitive to any external effects (vibrations, temperature variations, etc.) in contrast to the equilibrium black foam film. 

Study of microscopic O/W films has been performed by Velev et. al. [514-516] and a new phenomenon spontaneous cyclic formation of a dimple (thicker lens-like formations) in O/W emulsion films stabilised by a non-ionic surfactant (Tween 20) was observed. This phenomenon was described as a diffusion dimple formation in contrast to the dimple created as a result of hydrodynamic resistance to thinning in liquid films [55,56,63,237,517], The dimple shifted from the centre to the periphery and periodically regenerated. Photos of the different periods of a dimple growth are shown in Fig. 3.115 and the process is schematically presented in Fig. 3.116. 

The methods developed recently for formation of monodisperse emulsions by applying a fractionated crystallisation process on an initial crude emulsion and creating large capillary (disjoining) pressures in them using osmotic stress techniques [520] are particularly suitable for the comparison of the properties of free emulsion films and films in emulsions. 

Analysing the data presented leads to the conclusion that the behaviour of aqueous asymmetric films is similar to that of foam and emulsion films (kinetics of thinning and formation of equilibrium thin films). At certain surfactant concentration in the water phase the... 

Recently a new method for formation of monodisperse emulsions that creates high capillary pressures, involving osmotic stress technique, has been introduced [73]. It proves to be most reliable for the purpose. Preliminary calculations showed that the emulsion films in such monodisperse systems rupture in a narrow range of critical disjoining pressure. For example, NaDoS emulsion films rupture in the range from 1 to 1.3-105 Pa, which is analogous to foam films from the same surfactant solution. Unfortunately, the foam film type has not been considered. 

Such a relationship between Cm and the state of the adsorption layer is also found for CBFs (see Chapter 3). However, no quantitative link between Cm and the stability of these films has been found. As far as in the formation of black spots the adsorption layers at film surface plays a significant role, the clarification of the decrease in surface tension Act with the surfactant concentration is also important. Being a characteristic of surfactants Cm is in agreement with the commonly used quantity Act but is also related to the film properties. It is also important that Cm is in correlation with foam stability and, thus, is a more precise, suitable and physically better grounded characteristic. Such a correlation has been found for aqueous emulsion films [69,70]. 

---