Polylactide foaming materials with promising biocompatibility balance the lightweight and mechanical properties well, and thus they can be desirable candidates for biological scaffolds used in tissue engineering. However, the cells are likely to coalesce and collapse during the foaming process of polylactide (PLA) due to its intrinsic low melt strength. This work introduces a unique PLA stereocomplexation into the microcellular foaming of poly (l-lactide)/poly (butylene succinate) (PLLA/PBS) based on supercritical carbon dioxide. The rheological properties of PLA/PBS with 5 wt% or 10 wt% poly (d-lactide) (PDLA) present enhanced melt strength owing to the formation of PLA stereocomplex crystals (sc-PLA), which act as physical pseudo-cross-link points in the molten blends by virtue of the strong intermolecular interaction between PLLA and the added PDLA. Notably, the introduction of either PBS or PDLA into the PLLA matrix could enhance its crystallization, while introducing both in the blend triggers a decreasing trend in the PLA crystallinity, which it is believed occurs due to the constrained molecular chain mobility by formed sc-PLA. Nevertheless, the enhanced melt strength and decreased crystallinity of PLA/PBS/PDLA blends are favorable for the microcellular foaming behavior, which enhanced the cell stability and provided amorphous regions for gas adsorption and homogeneous nucleation of PLLA cells, respectively. Furthermore, although the microstructure of PLA/PBS presents immiscible sea-island morphology, the miscibility was improved while the PBS domains were also refined by the introduction of PDLA. Overall, with the addition of PDLA into PLA/10PBS blends, the microcellular average cell size decreased from 3.21 to 0.66 μm with highest cell density of 2.23 × 1010 cells cm−3 achieved, confirming a stable growth of cells was achieved and more cell nucleation sites were initiated on the heterogeneous interface.
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