Film formation, from emulsions

Poly(vinyl acetate) (PVAc), -[CH2-CH(OCOCH3) , is also prepared as an emulsion for adhesive applications, and is familiar to users as white glue. As mentioned already, the Tg of PVAc is above room temperature, which makes the polymer rigid and brittle at room temperature. For adhesive application, therefore, an external plasticizer, such as dibutyl phthalate, is added to lower the Tg below room temperature and to facilitate film formation from emulsions. 

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. 

In the specific case of film formation from latexes the terminal stage is characterized by the removal of interstitial solvent and the deformation of the dispersed spheres into polyhedra (1). The continuum can be represented by a closed array of hexagons each of which has been deformed radially (2). In practice one formulates an emulsion so as to minimize the stresses accompanying this type of deformation otherwise film integrity would be lost. 

One feature which distinguishes latex film formation from other polymer sintering processes is that latex microspheres have polar groups at the particle surface. These groups are introduced during the emulsion polymerization process used to prepare the particles, and they serve to provide colloidal stability for the particle dispersion. When the dispersion... 

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. 

Rust inhibitors usually are corrosion inhibitors that have a high polar attraction toward metal surfaces and that form a tenacious, continuous film which prevents water from reaching the metal surface. Typical mst inhibitors are amine succinates and alkaline-earth sulfonates. Rust inhibitors can be used in most types of lubricating oils, but factors of selection include possible corrosion of nonferrous metals or formation of emulsions with water. Because mst inhibitors are adsorbed on metal surfaces, an oil can be depleted of its mst inhibitor. In certain cases, it is possible to correct the depletion by adding more inhibitor. 

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... 

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. 

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. 

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],... 

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],... 

In the solvent method the separation of the solubilised or dispersed material from the solvent phase can be explained by precipitation or phase change induced by solvent evaporation, addition of electrolyte, pH modification or heat treatment (Krochta and McHugh 1997). Such treatments can be adjusted to enhance film formation or specific properties. For composite emulsion-based films or coatings a lipid material and most likely a surfactant, is added to the solution, which is then heated above the lipid melting point and homogenised. The prepared solution is then applied on an appropriate support and the solvent evaporates. 

The formation of emulsions or microemulsions is conneeted with several dynamic processes the time dependence of surface tensions due to the kinetics of adsorption, the dynamic contact angle, the elasticity of adsorption layers as a mechanic surface property influencing the thiiming of the liquid films between oil droplets, the mass transfer across interfaces and so on. Kahlweit et al. (1990) have recently extended Widom s (1987) concept of wetting or nonwetting of an oil-water interface of the middle phase of weakly-structured mixtures and microemulsions. They pointed out that the phase behaviour of microemulsions does not differ from that of other ternary mixtures, in particular of mixtures of short-chain amphiphiles (cf for example Bourrell Schechter (1988). 

Following a related approach, Castelvetro et al. reported the formation and properties of hybrid latex films resulting from the coalescence of low 7 poly(BA-co-MMA-co-MPTMS) terpolymer latex particles coated by a silica shell [78], The latex was synthesized at neutral pH by semi-continuous emulsion polymerization under starved-feed conditions in order to protect the MPTMS monomer from premature hydrolysis and condensation reactions. A substantial amount of free silanols were therefore available for further reaction with the silica precursor. In order to avoid the formation of a densely crosslinked silica network around the latex core, which may significantly alter film formation, the pH was kept at around 2 (at this pH, hydrolysis is promoted and condensation is significantly retarded). TEM and AFM studies of the nanocomposite film indicated that the silica shell formed a continuous percolating network throughout the polymer matrix. A porous film of interconnected hollow silica spheres was next elaborated by thermo-oxidative decomposition of the organic phase. 

It was, therefore, concluded that the internal polymeric emulsifier controls the release rates both by improving the film formation on the interface and by restricting the formation of reverse micelles in the oil phase. It is assumed that the presence of the two emul sifiers (Span 80 and silicone lipophilic emulsifier) form reverse hemimicelles. These structures are capable of solubilizing less water and, therefore, less marker, a fact that leads to slower release and the ability to con trol better the release rates. Emulsions prepared from polymeric emulsifiers and without the lipophilic monomeric emulsifier remained stable on the shelf for over 6 months and did not show any leaking of the marker upon storage. Once the monomeric emulsifier was added drop-... 

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