Effect of interfacial free energy on the formation of polymer microcapsules by emulsification/freeze-drying.

Hollow polymer microparticles with a single opening on the surface were formed by freeze-drying aqueous polymer colloids swollen with solvent. The results show that the particle morphology is due to phase separation in the polymer emulsion droplets upon freezing in liquid nitrogen, and that morphological changes are driven largely by lowering interfacial free energy. The effects of added surfactant, volume fraction of solvent, type of solvent, and processing conditions on the particle morphology were examined and compared to theoretical predictions. The dried hollow particles were resuspended in a dispersing media and exposed to a second swelling solvent to close the surface opening and form microcapsules. The interfacial free energy difference between the inside and outside surfaces is the driving force for closing the hole on the surface. The emulsification/freeze-drying technique can be used to encapsulate hydrophilic additives in the core of the microcapsules, demonstrating the potential of the technique in controlled-release applications.