Emulsions model systems

One concludes that modeling of concentrated emulsions becomes possible by combining experimental investigation of the simplest emulsion model system with computer simulation accounting for the characteristics of a concentrated emulsion (high droplet-volume fraction, etc.). 

An important step in tire progress of colloid science was tire development of monodisperse polymer latex suspensions in tire 1950s. These are prepared by emulsion polymerization, which is nowadays also carried out industrially on a large scale for many different polymers. Perhaps tire best-studied colloidal model system is tliat of polystyrene (PS) latex [9]. This is prepared with a hydrophilic group (such as sulphate) at tire end of each molecule. In water tliis produces well defined spheres witli a number of end groups at tire surface, which (partly) ionize to... 

Continuous emulsion polymerization systems are studied to elucidate reaction mechanisms and to generate the knowledge necessary for the development of commercial continuous processes. Problems encountered with the development of continuous reactor systems and some of the ways of dealing with these problems will be discussed in this paper. Those interested in more detailed information on chemical mechanisms and theoretical models should consult the review papers by Ugelstad and Hansen (1), (kinetics and mechanisms) and by Poehlein and Dougherty (2, (continuous emulsion polymerization). 

DetaUed Modeling of Multicomponent Emulsion Polymerization Systems... 

The majority of RDC studies have concentrated on the measurement of solute transfer resistances, in particular, focusing on their relevance as model systems for drug transfer across skin [14,39-41]. In these studies, isopropyl myristate is commonly used as a solvent, since it is considered to serve as a model compound for skin lipids. However, it has since been reported that the true interfacial kinetics cannot be resolved with the RDC due to the severe mass transport limitations inherent in the technique [15]. The RDC has also been used to study more complicated interfacial processes such as kinetics in a microemulsion system [42], where one of the compartments contains an emulsion. 

Two of the most comprehensive discussions of these models were presented by Min and Ray (5) and by Poehlein and Dougherty (6). Min and Ray (5) gave a very general model framework which should be capable of modelling most emulsion polymerization systems. Of course, decisions must be made on the relative importance of the various phenomena occurring in a particular system. Other, more recent efforts on the modelling of emulsion reactors include the ones of Table I. Further details can also be found in (30). 

H.M. Princen Rheology of Foams and Highly Concentrated Emulsions I. Elastic Properties and Yield Stress of a Cyhndrical Model System. J. Colloid Interface Sci. 91, 160 (1983). 

The model system used by Mabille et al. [149, 150] was a set of monodisperse dilute (2.5 wt% of dispersed oil) emulsions of identical composition, whose mean size ranged from 4 p.m to 11 p.m. A sudden shear of 500 s was applied by means of a strain-controlled rheometer for durations ranging from 1 to 1500 s. All the resulting emulsions were also monodisperse. At such low oil droplet fraction, the emulsion viscosity was mainly determined by that of the continuous phase (it was checked that the droplet size had no effect on the emulsion viscosity). The viscosity ratio p = t]a/t]c = 0.4 and the interfacial tension yi t = 6 mN/m remained constant. 

The observations of model systems made of monodisperse dilute emulsions can be generalized to polydisperse and concentrated emulsions. 

But the droplets are fragile, and must be lucidly protected. Formulating an industrial emulsion implies numerous conditions stability, efficiency, easy delivery, price,. .. This is an art, and like all forms of art it requires experience and imagination. The present book provides both. It describes basic experiments on realistic model systems. I like this matter of fact approach. For instance, instead of beginning by formal discussions on interaction energies, the book starts with methods offabrication. And, all along the text, the theoretical aspects are restricted to basic needs. 

Fat attraction. These are methods originally designed for only a two phase system, that is, the material and the oil. They now include the model systems inritating solid emulsions that contain large quantities of water and aqueous particulates ( -55). 

Whey protein concentrates (WPC), which are relatively new forms of milk protein products available for emulsification uses, have also been studied (4,28,29). WPC products prepared by gel filtration, ultrafiltration, metaphosphate precipitation and carboxymethyl cellulose precipitation all exhibited inferior emulsification properties compared to caseinate, both in model systems and in a simulated whipped topping formulation (2. However, additional work is proceeding on this topic and it is expected that WPC will be found to be capable of providing reasonable functionality in the emulsification area, especially if proper processing conditions are followed to minimize protein denaturation during their production. Such adverse effects on the functionality of WPC are undoubtedly due to their Irreversible interaction during heating processes which impair their ability to dissociate and unfold at the emulsion interface in order to function as an emulsifier (22). 

Model systems that simulate the photographic emulsion have been used extensively as simpler systems for mechanistic studies. These include macroscopic sheet crystals grown from the melt (55-58), "evaporated layers" formed by evaporating silver... 

Sensitization of Model Systems. Silver bromide sheet crystals can be sulfur-sensitized easily, and have been studied extensively (56-58). Evaporated silver halide layers and sprayed emulsions likewise can be sulfur-sensitized. 

Model systems have been used to demonstrate that S-sensitization is important in determining the location of the latent image centers. Moisar s experiments with core/shell emulsions showed that, when the surface of the core was sulfur-sensitized, the latent image formed by exposure of the core/shell grains was situated predominantly at or very close to the core/shell interface (124). 

Monodispersed sols containing spherical polymer particles (e.g. polystyrene latexes22"24, 135) can be prepared by emulsion polymerisation, and are particularly useful as model systems for studying various aspects of colloidal behaviour. The seed sol is prepared with the emulsifier concentration well above the critical micelle concentration then, with the emulsifier concentration below the critical micelle concentration, subsequent growth of the seed particles is achieved without the formation of further new particles. 

The majority of the recipes described in the literature are based on the anionic sodium dodecylsulfate (SDS) as a model system. The possibility of using cationic surfactants such as octadecyl pyridinium bromide for the preparation of miniemulsions was first exploited in 1976. However, the emulsions were prepared by stirring and the resulting emulsions showed broadly distributed droplet sizes [2,39,50]. Recent work on steady-state miniemulsions showed that cationic and nonionic surfactants form well-defined miniemulsions for further miniemulsion polymerization processes, resulting in narrow size distributed stable cationic and nonionic latex particles [51]. Similar molecular amounts of the simple cationic surfactant, cetyltrimethylammonium bromide or chloride... 

In this article we have shown how a capillary instability may generate a well-defined characteristic size. The materials that derive are essentially emulsions made of liquid or crystallizable droplets. The monodispersity make it possible to obtain materials with perfectly controlled and reproducible properties, which certainly cannot be achieved in presence of polydisperse emulsions. This is why monodisperse emulsions are not only model systems for fundamental science but also materials with commercial applications. 

Experimce has shown that each monomer has its own specific features hi emulsion polymerization and requires a specific techncdogy. To a certain extent this is also true of other components in the reaction sy em, e.g., the emulsifier and the initiator. Attempts to fit various emulsion reaction systems into one physicochemical model or theoretical scheme have therefore failed. 

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