Role of the Branched PEG‑<i>b</i>‑PLLA Block Chain in Stereocomplex Crystallization and Crystallization Kinetics for PDLA/MPEG‑<i>b</i>‑PLLA‑<i>g</i>‑glucose Blends with Different Architectures

The isothermal crystallization behavior and corresponding morphology evolution of poly(d-lactic acid) (PDLA) blends with PLLA6.7k or MPEG-b-PLLA6.7k-g-glucose with different architectures and different PLLA-grafted copolymer contents were investigated. The formation of stereocomplexes (SCs) in between the chain branched structure of MPEG-b-PLLA6.7k-g-glucose and PDLA chains acting as the physical crosslinking points slows down the motion of PDLA chains, but the SCs could act as a heterogeneous nucleating agent for the late formation of homocrystals (HCs) in the blend system, accelerating the crystallization kinetics of HCs through enhancing the nucleation density. For PDLA/MPEG-b-PLLA6.7k-g-glucose blends, the mobility of SCs in the blend system and the nucleation density of SCs in the blends exhibit oppositional behavior during the isothermal crystallization at a Tc of 130 °C. The evolution of the crystal growth and structure during the isothermal crystallization process by rheometry has revealed the interesting role of the branched chains of MPEG-b-PLLA6.7k-g-glucose in the mechanism of the crystallization in PDLA blends

Design of Heterogeneous Nuclei Composed of Uniaxial Cellulose Nanocrystal Assemblies for Epitaxial Growth of Poly(ε-caprolactone)

Epitaxial crystallization is the most prominent approach to achieving oriented thin films composed of semicrystalline polymers (SCPs). Nevertheless, current templates remain limited in fulfilling oriented SCPs with high-throughput coating processes. Herein, we report the first template for the epitaxial crystallization of SCPs based on a uniaxial assembly of shape-anisotropic nanocrystalscellulose nanocrystals (CNCs). The template was fabricated via a dip-coating method, leading to a uniaxial thin coating on both planar and nonplanar substrates. Such a thin coating functioned similarly to a laterally oriented SCP thin film in regulating the crystallization behaviors of poly­(ε-caprolactone) (PCL). The orientational relationship between the CNC thin coating and the PCL overlayer was studied systematically by employing multiple characterization tools including scattering, diffraction, and microscopy. Moreover, the epitaxial match based on the crystallography-regulated hydrogen-bonding networks between the two layers was confirmed by molecular modeling, in agreement with the experimental results. Besides the orientational regulation, CNCs also promoted the crystallization kinetics of PCL effectively due to the nanoepitaxial effect provided by each CNC particle. We highlight this facile assembly approach to heterogeneous nuclei for the epitaxial crystallization of SCPs and its extendability of achieving thin coatings composed of 3D-oriented SCPs on ambient substrates

Design of Heterogeneous Nuclei for Lateral Crystallization via Uniaxial Assembly of Cellulose Nanocrystals

Semicrystalline polymers (SCPs) represent a group of cheap heterogeneous nuclei for crystallization. Nevertheless, cellulose, the most abundant biogenic SCP, is notorious for its poor processability. This limits its application as the orientational guiding agent in crystallization of functional compounds. Different from current polymer engineering approaches to uniaxial SCP thin films, we explored a novel approach to the uniaxial cellulose thin film via the oriented assembly of cellulose nanocrystals (CNCs) by means of a simple dip-coating technique. This thin film successfully guides the lateral crystallization of two drug compounds, which in turn reflects the uniformity of the uniaxial CNC alignment on the macroscopic scale. Furthermore, unlike traditional SCP thin films, the assembly route driven by different external forces can lead to CNC thin films with distinct orientational characters for fabrication of patterned drug thin films. The emerging colloidal assembly route to a uniaxial SCP substrate leads to unprecedented access to design heterogeneous nuclei for oriented crystallization of functional hybrids