Morphology development of polymeric microparticles in aqueous dispersions. I. Thermodynamic considerations

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Abstract
A thermodynamic analysis of polymer particle morphology highlights the role of interfacial tensions in controlling particle structure. The influence of the surfactant and the nature of the incompatible polymers is seen through their individual and collective effects upon these interfacial tensions. It has been found that by simply changing the type of surfactant used in the emulsion the particle morphology can change from core‐shell to hemispherical, in agreement with thermodynamic predictions. Several apparently different morphologies (hemispherical, sandwich, multiple lobes) have been found to coexist at the same time within a single emulsion, suggesting that they may be simply different states of phase separation and not thermodynamically stable, unique morphologies. The thermodynamic analyses are independent of particle size and method of emulsion processing. Experimental evidence shows that the morphology of particles formed via in situ polymerization (as in a synthetic latex) is controlled by interfacial tensions in the same manner as those particles formed via solvent evaporation from a solution of an incompatible polymer pair (as in an artificial latex or microencapsulation).