Stabilization, particle formation

Figure 9 The schematical representation of dispersion polymerization process, (a) initially homogeneous dispersion medium (b) particle formation and stabilizer adsorption onto the nucleated macroradicals (c) capturing of radicals generated in the continuous medium by the forming particles and monomer diffusion to the forming particles (d) polymerization within the monomer swollen latex particles, (e) latex particle stabilized by steric stabilizer and graft copolymer molecules (f) list of symbols.

The procedure chosen for the preparation of lipid complexes of AmB was nanoprecipitation. This procedure has been developed in our laboratory for a number of years and can be applied to the formulation of a number of different colloidal systems liposomes, microemulsions, polymeric nanoparticles (nanospheres and nanocapsules), complexes, and pure drug particles (14-16). Briefly, the substances of interest are dissolved in a solvent A and this solution is poured into a nonsolvent B of the substance that is miscible with the solvent A. As the solvent diffuses, the dissolved material is stranded as small particles, typically 100 to 400 nm in diameter. The solvent is usually an alcohol, acetone, or tetrahydrofuran and the nonsolvent A is usually water or aqueous buffer, with or without a hydrophilic surfactant to improve colloid stability after formation. Solvent A can be removed by evaporation under vacuum, which can also be used to concentrate the suspension. The concentration of the substance of interest in the organic solvent and the proportions of the two solvents are the main parameters influencing the final size of the particles. For liposomes, this method is similar to the ethanol injection technique proposed by Batzii and Korn in 1973 (17), which is however limited to 40 mM of lipids in ethanol and 10% of ethanol in final aqueous suspension. 

For the production of CLPs and VLPs with baculovirus infected insect cells the specific proteins that are required for particle formation should be chosen at an early step. The specific particle composition, along with the expression of other non-structural (NS) proteins often has a great impact on particle stability [11] or on particle localisation [12], i.e. - cell-associated or secreted to the supernatant. 

This chapter focuses on silica synthesis via the microemulsion-mediated alkoxide sol-gel process. The discussion begins with a brief introduction to the general principles underlying microemulsion-mediated silica synthesis. This is followed by a consideration of the main microemulsion characteristics believed to control particle formation. Included here is the influence of reactants and reaction products on the stability of the single-phase water-in-oil microemulsion region. This is an important issue since microemulsion-mediated synthesis relies on the availability of surfactant/ oil/water formulations that give stable microemulsions. Next is presented a survey of the available experimental results, with emphasis on synthesis protocols and particle characteristics. The kinetics of alkoxide hydrolysis in the microemulsion environment is then examined and its relationship to silica-particle formation mechanisms is discussed. Finally, some brief comments are offered concerning future directions of the microemulsion-based alkoxide sol-gel process for silica. 

If one chooses a chelating agent with a relatively high stability constant, such as EDTA, one may find some ideal separation of nucleation and growth stages as a decisive prerequisite for monodispersed particles formation, since a drastic change of supersaturation can be expected in a system with metal ions around the stoichio-... 

These stabilizers are added to the formulation in order to stabilize the emulsion formed during particle preparation. These stabilizers, however, can also influence the properties of the particles formed. The type and concentration of the stabilizer selected may affect the particle size. Being present at the boundary layer between the water phase and the organic phase during particle formation, the stabilizer can also be incorporated on the particle surface, modifying particle properties such as particle zeta potential and mucoadhesion (203). Other polymers have also been evaluated as stabilizers in earlier studies such as cellulosic derivatives methylcellu-lose (MC), hydroxyethylcellulose ( ), hydroxypropylcellulose (HPC), and hydroxypropylmethylcellulose (HPMC), as well as gelatin type A and B, carbomer and poloxamer (203). 

Thus the use amphiphilic macromonomers is another method to achieve the particle formation and their subsequent stabilization. Macromonomers can be pre-reacted to form graft copolymers, which are be introduced into the reaction medium afterwards. Macromonomers can also be copolymerized with classical monomers in situ to form graft copolymers. This is a simple and flexible method for producing monodisperse micron-sized polymer particles. Macromonomers can produce ion-free acrylic lattices with superior stability and film forming properties compared to conventional charge stabilized lattices. These non-con-... 

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. 

The mechanism of polystyrene and poly(methyl methacrylate) particle formation in the presence of PEO-MA macromonomer in the presence of conventional stabilizer (PVPo) and the graft copolymers (PSt-gra/f-PEO), respectively, was discussed [77]. At the beginning of dispersion polymerization (in methanol) of MMA (0-250 s) using PVPo, very small particles were formed (12-35 nm in diameter). The population of bigger particles was roughly stabilized at ca. 345 nm in diameter. In the dispersion polymerization of styrene, small particles... 

This model is based on the particle formation during polymerization where the polymer particles are sterically stabilized by graft-copolymerized PEO chains on the particle surface. In the later stage the polymer particles were supposed to grow in size mainly by copolymerization of monomers occluded in the particles which may favor the substrate monomer (styrene) over the macromonomer as compared to the composition in the continuous phase. 

In 1965 Dunn and Taylor confirmed the theory for vinyl acetate polymerization (15), and proposed, in the light of the presumed importance of rapid coagulation during the earliest stages of reaction, that the "DLVO" theory for colloid stability (16) be applied. Fitch proposed a kinetic basis for a quantitative theory and observed that for observation of particle formation kinetics, "fast" reaction techniques must be used because "particle formation occurs in a matter of seconds or even less (17)". 

The present review paper, therefore, refers firstly to the particle formation mechanism in emulsion polymerization, the complete understanding of which is indispensable for establishing a correct kinetic model, and then, deals with the present subject, that is, what type of reactor and operating conditions are the most suitable for a continuous emulsion polymerization process from the standpoint of increasing the volume efficiency and the stability of the reactors. 

The flocculation process is more clearly observed in experiments with high monomer contents (2.7 moles) and rather moderate SDS concentration (4 g). As shown in figure 10, most of the emulsifier is used to stabilize the particles, when droplets are still present, and at the same time particle average size tends to decrease, while their number rapidly increases. At a point where prac tically all the emulsifier has been used, which possibly incidental ly corresponds to disappearance of droplets, particle formation rate decreases to a lower value, particle size tends to increase, while a part of the emulsifier is desorbed. 

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