Jesse Kuebler, Sunil Dhapola and Lucia Fernandez-Ballester*,
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引用次数: 0
摘要
通过去除聚（3-己基噻吩）（P3HT）薄膜中的空气-聚合物界面，可获得大块结晶形态，在 T ≫ TC,BULK 时，高吸收性 "大块物体 "在整个薄膜厚度上生长，并且不显示优先结晶取向。与此相反，具有自由表面的薄膜在 T ≫ TC,BULK 时会在空气-聚合物界面形成高度边缘取向的二维球状体（"环状体"），然后在 TC,BULK 附近的底层促进边缘取向的无特征结晶。有趣的是，尽管两种形态都由相同的晶体构成，但在链流动性预计不会主导生长速度的温度下，环状晶体的线性生长速度比块状物体快 10 倍，这表明可能有另一种机制在起作用。总之，这些结果让我们深入了解了自由表面在结晶过程中的作用，并表明空气-聚合物界面的存在与否可用于控制 P3HT 薄膜的半结晶形态和取向。
Selecting for Surface-Induced vs Bulk Crystallization in P3HT Thin Films: Distinct Morphology, Orientation, and Linear Growth Rates
By removal of the air–polymer interface in poly(3-hexylthiopene) (P3HT) thin films, bulk crystallization morphology is attained, where highly absorbing “bulk objects” grow throughout the film thickness at T ∼ TC,BULK and exhibit no preferential crystalline orientation. In contrast, films with a free surface develop highly edge-on oriented 2D spherulites (“circulites”) at the air–polymer interface at T ≫ TC,BULK, which then promote edge-on oriented, featureless crystallization in the underlayer near TC,BULK. Interestingly, circulites exhibit ∼10× faster linear growth rates than bulk objects─despite both morphologies consisting of the same crystal form─at temperatures where chain mobility is not expected to dominate growth rates, suggesting that another mechanism may be at play. Overall, these results provide insight into the role of the free surface in the crystallization process and indicate that the presence or absence of an air–polymer interface can be used to control the semicrystalline morphology and orientation of P3HT thin films.
期刊介绍：
Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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