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    Crystalline Carbosilane-Based Block Copolymers: Synthesis by Anionic Polymerization and Morphology Evaluation in the Bulk State
    (Weinheim : Wiley-VCH, 2022) Hübner, Hanna; Niebuur, Bart‐Jan; Janka, Oliver; Gemmer, Lea; Koch, Marcus; Kraus, Tobias; Kickelbick, Guido; Stühn, Bernd; Gallei, Markus
    Block copolymers (BCPs) in the bulk state are known to self-assemble into different morphologies depending on their polymer segment ratio. For polymers with amorphous and crystalline BCP segments, the crystallization process can be influenced significantly by the corresponding bulk morphology. Herein, the synthesis of the amorphous-crystalline BCP poly(dimethyl silacyclobutane)-block-poly(2vinyl pyridine), (PDMSB-b-P2VP), by living anionic polymerization is reported. Polymers with overall molar masses ranging from 17 400 g to 592 200 g mol−1 and PDMSB contents of 4.8–83.9 vol% are synthesized and characterized by size-exclusion chromatography and NMR spectroscopy. The bulk morphology of the obtained polymers is investigated by means of transmission electron microscopy and small angle X-ray scattering, revealing a plethora of self-assembled structures, providing confined and nonconfined conditions. Subsequently, the influence of the previously determined morphologies and their resulting confinement on the crystallinity and crystallization behavior of PDMSB is analyzed via differential scanning calorimetry and powder X-ray diffraction. Here, fractionated crystallization and supercooling effects are observable as well as different diffraction patterns of the PDMSB crystallites for confined and nonconfined domains.
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    Crystallization behavior of poly(lactic acid)/titanium dioxide nanocomposites
    (Bangkok : King Mongkut’s University of Technology, 2015) Nomai, Jiraporn; Suksut, Buncha; Schlarb, Alois K
    In this study, a poly(lactic acid) (PLA) with various titanium dioxide (TiO2) nanoparticles loading were prepared by a manual laboratory mixing method. The effect of TiO2 nanoparticles on the non-isothermal and the isothermal crystallization behavior of PLA was investigated by polarized optical microscopy (POM) and differential scanning calorimetry (DSC). The presence of TiO2 nanoparticles decreased the spherulite growth rate of PLA, whereas it initiated faster crystallization through the heterogeneous nucleation process as observed by optical microscopy. The results of DSC analyzes confirmed that the TiO2 nanoparticles act as an efficient nucleating agent for PLA crystallization. The cold crystallization temperature and crystallization half-time of PLA decreased, while the degree of crystallinity of PLA increased in relation to increases of TiO2 nanoparticles.
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    Enantiomer-selective magnetization of conglomerates for quantitative chiral separation
    (Berlin : Springer Nature, 2019) Ye, X.; Cui, J.; Li, B.; Li, N.; Wang, R.; Yan, Z.; Tan, J.; Zhang, J.; Wan, X.
    Selective crystallization represents one of the most economical and convenient methods to provide large-scale optically pure chiral compounds. Although significant development has been achieved since Pasteur’s separation of sodium ammonium tartrate in 1848, this method is still fundamentally low efficient (low transformation ratio or high labor). Herein, we describe an enantiomer-selective-magnetization strategy for quantitatively separating the crystals of conglomerates by using a kind of magnetic nano-splitters. These nano-splitters would be selectively wrapped into the S-crystals, leading to the formation of the crystals with different physical properties from that of R-crystals. As a result of efficient separation under magnetic field, high purity chiral compounds (99.2 ee% for R-crystals, 95.0 ee% for S-crystals) can be obtained in a simple one-step crystallization process with a high separation yield (95.1%). Moreover, the nano-splitters show expandability and excellent recyclability. We foresee their great potential in developing chiral separation methods used on different scales. © 2019, The Author(s).