Due to the effects of microphase separation and physical dimensions, confinement widely exists in the multi-component polymer systems (e.g., polymer blends, copolymers) and the polymers having nanoscale dimensions, such as thin films and nanofibers. Semicrystalline polymers usually show different crystallization kinetics, crystalline structure and morphology from the bulk when they are confined in the nanoscale environments; this may dramatically influence the physical performances of the resulting materials. Therefore, investigations on the crystalline and spherulitic morphology of semicrystalline polymers in confined systems are essential from both scientific and technological viewpoints; significant progresses have been achieved in this field in recent years. In this article, we will review the recent research progresses on the crystalline and spherulitic morphology of polymers crystallized in the nanoscale confined environments. According to the types of confined systems, crystalline, spherulitic morphology and morphological evolution of semicrystalline polymers in the ultrathin films, miscible polymer blends and block copolymers will be summarized and reviewed.

A novel thermogel exhibiting unique thermally-induced gel–sol–gel multiple phase transitions was obtained by controlling the compositions of PLA/PEG copolymers.

Physical hydrogels crosslinked by non-covalent interactions have attained increasing attention due to their good mechanical properties and processability. However, the use of feasible and controllable non-covalent interactions is highly essential for preparing such hydrogels. In this article, we report on stereocomplexed physical hydrogels prepared by simple casting and swelling of amphiphilic graft copolymers bearing a poly(acrylic acid) (PAA) backbone and poly(L-lactic acid) (PLLA) or poly(D-lactic acid) (PDLA) stereocomplexable side chains. The microstructure, swelling behavior, and mechanical and shape memory properties of the obtained hydrogels can be tuned by varying the copolymer composition and stereocomplex (SC) crystallization of PLLA/PDLA enantiomeric chains. The long PLLA or PDLA chains segregate to form hydrophobic, crystallized domains in water, serving as physical crosslinking junctions for hydrogels. SC crystallization between PLLA and PDLA further enhances the number density of physical crosslinkers of enantiomerically mixed hydrogels. The SC content increases as the PLLA/PDLA ratio approaches 1/1 in enantiomerically mixed hydrogels. The average distance between crosslinking junctions declines for the hydrogels with a high PLLA (or PDLA) mass fraction (M_PLA) and SC content, due to the increased number density of physical crosslinkers. Accordingly, the tensile strength and the Young's modulus increase but the swelling ratio and the elongation-at-break of the hydrogels decrease with an increase in M_PLA and SC content. The hydrogels exhibit shape memory behavior; the shape fixing ability is enhanced by the SC crystallization of PLLA/PDLA side chains in the hydrogels.

Adhesion-switchable ionogels with ultralow hysteresis are developed through moisture-mediated phase separation using opposite-affinity ionic components. These ionogels show great potential in smart adhesives for targeted object capture.