Droplet size Ostwald ripening

Stability of a macroemulsion is an important factor as this determines its extent of usability for particle preparation or various other applications. Instability is basically coalescence of the dispersed phase droplets or Ostwald ripening (growth of large droplets at the expense of much smaller ones). When this process goes on, the emulsion eventually breaks into two layers. Other processes related to stability but considered less important [3] are (a) creaming or sedimentation, the rate of which is dependent on the difference in density between the continuous and dispersed phases, droplet size, viscosity of the continuous phase and interdroplet interaction and (b) flocculation, dependent on colloidal interactions between the droplets [8, 12]. Several factors determine the stability of macroemulsions these are discussed here in brief. This discussion is largely derived from Rosen [3] and some subsequent investigations [e.g. 6, 7, 13-15]. 

Note 2 Representative mechanisms for coarsening at the late stage of phase separation are (1) material flow in domains driven by interfacial tension (observed in a co-continuous morphology), (2) the growth of domain size by evaporation from smaller droplets and condensation into larger droplets, and (3) coalescence (fusion) of more than two droplets. The mechanisms are usually called (1) Siggia s mechanism, (2) Ostwald ripening (or the Lifshitz-Slyozov mechanism), and (3) coalescence. 

The rate of Ostwald ripening depends on the size, the polydispersity, and the solubility of the dispersed phase in the continuous phase. This means that a hydrophobic oil dispersed as small droplets with a low polydispersity already shows slow net mass exchange, but by adding an ultrahydrophobe , the stability can still be increased by additionally building up a counteracting osmotic pressure. This was shown for fluorocarbon emulsions, which were based on perfluo-rodecaline droplets stabilized by lecithin. By adding a still less soluble species, e.g., perfluorodimorphinopropane, the droplets stability was increased and could be introduced as stable blood substitutes [6,7]. 

Stability of emulsions refers to the resistance to the formation of two separate phases [13,14]. Coalescence of the droplets is responsible for the phase separation. Ostwald ripening constitutes an additional mechanism by which the large droplets grow in size at the expense of the smaller ones, which decrease in size. 

Polymeric materials are not costabilizers in the sense that costabihzers cause superswelling. Rather, they slow the onset of Ostwald ripening and preserve the number of monomer droplets, if not their size. However, this review will take a functional, rather than thermodynamic definition of a costabilizer, and include a discussion of the use of polymers as agents to enhance droplet nuclea-tion under the heading of costabihzers. 

Mouran et al. [105] polymerized miniemulsions of methyl methacrylate with sodium lauryl sulfate as the surfactant and dodecyl mercaptan (DDM) as the costabilizer. The emulsions were of a droplet size range common to miniemulsions and exhibited long-term stability (of greater than three months). Results indicate that DDM retards Ostwald ripening and allows the production of stable miniemulsions. When these emulsions were initiated, particle formation occurred predominantly via monomer droplet nucleation. The rate of polymerization, monomer droplet size, polymer particle size, molecular weight of the polymer, and the effect of initiator concentration on the number of particles all varied systematically in ways that indicated predominant droplet nucleation. 

The destabilization processes are not independent and each may influence or be influenced by fhe ofhers. For example, the increased droplet sizes after coalescence or Ostwald ripening will enhance the rate of creaming, as will the formation of large floccules which behave as single entities. In practice, creaming, flocculation, and Ostwald ripening may proceed simultaneously or in any order followed by coalescence. 

The term microemulsion, which implies a close relationship to ordinary emulsions, is misleading because the microemulsion state embraces a number of different microstructures, most of which have little in common with ordinary emulsions. Although microemulsions may be composed of dispersed droplets of either oil or water, it is now accepted that they are essentially stable, single-phase swollen micellar solutions rather than unstable two-phase dispersions. Microemulsions are readily distinguished from normal emulsions by their transparency, their low viscosity, and more fundamentally their thermodynamic stability and ability to form spontaneously. The dividing line, however, between the size of a swollen micelle ( 10-140 nm) and a fine emulsion droplet ( 100-600 nm) is not well defined, although microemulsions are very labile systems and a microemulsion droplet may disappear within a fraction of a second whilst another droplet forms spontaneously elsewhere in the system. In contrast, ordinary emulsion droplets, however small, exist as individual entities until coalescence or Ostwald ripening occurs. 

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