In miscible crystalline/amorphous polymer blends, the exclusion behaviors of the latter with various molecular weights during the crystallization of the former were investigated by the combination of SAXS and DSC by taking a PVDF/PMMA blend as an example. The ratio between internal crystallinity from SAXS and overall crystallinity of the entire blend from DSC was employed to characterize the exclusion of PMMA. Our results indicate that the molecular weight of the amorphous component produces a remarkable influence on the diffusion coefficient (D) and the crystal growth rate (G) of the crystalline component. There are both inter-lamellar and inter-fibrillar structures when PVDF blended with lower-molecular-weight PMMA. With increasing molecular weight of PMMA, the decrease in crystal growth rate (G) dominates the enhanced exclusion behaviors of PMMA, resulting in bigger pores after extraction. Our results are significant not only for the basic understanding of crystallization in polymer blends, but also for the fabrication and structure control of porous structures based on crystallization templates.

Superhydrophobic surfaces with switchable adhesive/anti-adhesive performances are highly desired but still challenging. Herein, by loading porous poly (vinylidene fluoride) (PVDF) spheres on a shape memory polylactic acid (PLLA) film, a quasi-superhydrophobic surface of composite film (PVDF@PLLA) with the ability to tailor its surface structures/composition and related adhesive behaviors was fabricated. The as-prepared surface is covered by porous PVDF spheres. The combination of hydrophobicity of PVDF and hierarchical roughness resulted from porous spheres contributing to the high contact angle and low sliding angle, corresponding to Cassie state and lotus leaves effect. Upon uniaxial or biaxial tension, the distance among hydrophobic spheres is so high that more and more hydrophilic defects (PLLA film) have been exposed to water droplets, accounting for the quasi-superhydrophobic surface with a higher sliding angle. This is the reason for the Wenzel state and rose petals effect. After heating, PLLA film recovers to its original state. The porous PVDF spheres cover the whole film again, leading to the enhanced mobility of water droplets on the surface. The transition between the rose petals effect and the lotus leaves effect is programmable and reversible. Our result provides a novel strategy to tailor adhesive behaviors by combining (quasi-)superhydrophobic surface with shape memory effect.