Interdisciplinary Center for Transfer-Oriented Research in Natural Sciences (IWE TFN), Martin Luther University Halle-Wittenberg, 06099, Halle/Saale, Germany.
University of Rostock, Institute of Physics & Competence Centre CALOR, 18051, Rostock, Germany.
Macromol Rapid Commun. 2024 Sep;45(18):e2400273. doi: 10.1002/marc.202400273. Epub 2024 Jun 28.
Poly(butylene succinate) (PBS) forms small and imperfect crystals of low melting temperature at high supercooling of the melt. Slow heating allows reorganization of the obtained semicrystalline structure with the changes of the crystallinity and of the size and perfection of crystals analyzed by differential scanning calorimetry (DSC) and temperature-resolved X-ray scattering techniques. Crystals generated at 20 °C begin to melt and reorganize at a few K higher temperature with their initial imperfection and thickness unchanged upon heating to 70-80 °C. Slow heating to temperatures higher than 70-80 °C yields a distinct exothermic peak in the DSC scan, paralleled by detection of crystals of larger size/higher perfection, beginning to melt at ≈100 °C. These observations suggest that below 70-80 °C, reorganization of the semicrystalline morphology is constrained such that only minor and local improvement of the structure of crystals are possible. The formation of both perfect and thicker crystal lamellae at higher temperature proceeds via melting of imperfect crystals followed by melt-recrystallization as for PBS solid-state thickening is impossible. The study shows the limit of low-temperature reorganization processes when not involving both complete melting of crystals and rearrangement of the lamellar-stack structure.
聚丁二酸丁二醇酯(PBS)在熔体高过冷度下形成小而不完善的低熔点晶体。缓慢加热允许通过差示扫描量热法(DSC)和温度分辨 X 射线散射技术分析的结晶度以及晶体尺寸和完善度的变化来重新组织所获得的半晶结构。在 20°C 下生成的晶体在稍高几度的温度下开始熔化和重组,其初始不完整性和厚度在加热至 70-80°C 时保持不变。缓慢加热至高于 70-80°C 的温度会在 DSC 扫描中产生明显的放热峰,同时检测到大尺寸/更高完善度的晶体开始在 ≈100°C 熔化。这些观察结果表明,在 70-80°C 以下,半晶形态的重组受到限制,因此晶体结构的微小和局部改善是可能的。在较高温度下形成完美和较厚的晶体层片是通过不完善晶体的熔化以及熔体再结晶进行的,因为 PBS 固态增稠是不可能的。该研究表明,当不涉及晶体完全熔化和层片堆积结构的重新排列时,低温重组过程的极限。