Depressurization-Induced Nucleation in the “Polylactide-Carbon Dioxide” System: Self-Similarity of the Bubble Embryos Expansion

Abstract

Self-similar expansion of bubble embryos in a plasticized polymer under quasi-isothermal depressurization is examined using the experimental data on expansion rates of embryos in the CO2-plasticized d,l-polylactide and modeling the results. The CO2 initial pressure varied from 5 to 14 MPa, and the depressurization rate was 5 × 10−3 MPa/s. The constant temperature in experiments was in a range from 310 to 338 K. The initial rate of embryos expansion varied from ≈0.1 to ≈10 µm/s, with a decrease in the current external pressure. While modeling, a non-linear behavior of CO2 isotherms near the critical point was taken into account. The modeled data agree satisfactorily with the experimental results. The effect of a remarkable increase in the expansion rate at a decreasing external pressure is interpreted in terms of competing effects, including a decrease in the internal pressure, an increase in the polymer viscosity, and an increase in the embryo radius at the time of embryo formation. The vanishing probability of finding the steadily expanding embryos for external pressures around the CO2 critical pressure is interpreted in terms of a joint influence of the quasi-adiabatic cooling and high compressibility of CO2 in the embryos.