Foaming strategies for bioabsorbable polymers in supercritical fluid mixtures. Part I. Miscibility and foaming of poly( l-lactic acid) in carbon dioxide + acetone binary fluid mixtures

Abstract

Miscibility and foaming of poly( l-lactic acid) (PLLA) in carbon dioxide + acetone mixtures have been explored over the temperature and pressure ranges from 60 to 180 °C and 14 to 61 MPa. Liquid–liquid phase boundaries were determined in a variable-volume view-cell for polymer concentrations up to 25 wt% PLLA and fluid mixtures containing 67–93 wt% CO 2 over a temperature range from 60 to 180 °C. Even though not soluble in carbon dioxide at pressures tested, the polymer could be completely solubilized in mixtures of carbon dioxide and acetone at modest pressures. Foaming experiments were carried out in different modes. Free-expansions were carried out by exposure and swelling in pure carbon dioxide in a view-cell followed by depressurization. Foaming experiments were also carried out within the confinement of specially designed molds with porous metal surfaces as boundaries to direct the fluid escape path and to generate foams with controlled overall shape and dimensions. These experiments were conducted in pure carbon dioxide and also in carbon dioxide + acetone fluid mixtures over a wide range of temperatures and pressures. Foaming in carbon dioxide + acetone mixtures was limited to 1 and 4 wt% acetone cases. Microstructures were examined using an environmental scanning electron microscope (ESEM). Depending upon the conditions employed, pore diameters ranging from 5 to 400 μm were generated. At a given temperature, smaller pores were promoted when foaming was carried out by depressurization from higher pressures. At a given pressure, smaller pores were generated from expansions at lower temperatures. Foams with larger pores were produced in mixtures of carbon dioxide with acetone.