An-Najah Staff

Polylactide microspheres were prepared by pre-mix membrane emulsification and subsequent extraction of solvent in a coagulation bath, and ultimately to the gas phase. The polymer was dissolved in dichloromethane and emulsified with water or water–methanol mixtures by repeated passage through a glass membrane. During and after emulsification, the droplets are exposed to a bath consisting of a mixture of water and methanol. Transfer of dichloromethane takes place into the bath and (subsequently) to the gas phase. Compared to water, the solubility of dichloromethane is increased when using water–methanol mixtures; the continuous phase can quickly dissolve a significant amount of the solvent, while transfer to the gas phase is strongly enhanced as well. This was observed experimentally and by computer simulation, using a combined model based on the Maxwell–Stefan theory for non-ideal, multi-component mass transfer. With increasing methanol concentration, the size and span of the microspheres became smaller, and was approximately 1 μm at 30% methanol. The surface morphology of these particles was solid and smooth, whereas holes were observed in those prepared in pure water. At methanol concentrations higher than 30%, the size of the microspheres increased again. This is probably due to the swelling of the particles because of the high in-diffusion of methanol which increases the porosity of the particles. Our main conclusion is that particles of defined size and size distribution can be produced by simply adjusting the non-solvent composition of the pre-mix.

Hollow polylactide microcapsules that can be used as ultrasound contrast agents were prepared using premix membrane emulsification. Polylactide/dichloromethane and dodecane solutions were emulsified together with a nonsolvent phase (water or a water–alcohol mixture) by repeated passage through a glass fibre membrane. The solvent, dichloromethane, diffuses out of the droplets and the polylactide solidifies around a droplet of dodecane. To investigate the effect of the nonsolvent properties on the size and span of the microcapsules, different methanol–water, ethanol–water and 2-propanol–water mixtures were used as nonsolvents. The alcohol lowers the interfacial tension and increases the viscosity of the nonsolvent, and therewith it decreases the size and the span of the microcapsules. It was remarkable that 2-propanol yields the smallest size (0.35 μm) followed by ethanol (0.8 μm) and methanol (1.4 μm). In contrast, the smallest span was obtained with methanol (0.7), whereas 2-propanol gave the largest span (1.5). The results further show that the size and the span of the microcapsules decreases with increasing number of emulsification passes and transmembrane flux. The presence of alcohol in the nonsolvent phase increases the efficiency of the emulsification process and decreases the optimum number of passes required to obtain the minimum average size of the droplets. A three-parameter correlation was defined that could quantitatively describe the effects of all the aforementioned parameters on the size of the microcapsules.