伸长的polymer溶液的构象演化对有机纳米纤维的光发射偏振的调节
The conformational evolution of elongated polymer solutions tailors the polarization of light-emission from organic nanofibers
摘要：
聚合物纤维目前被用于非常重要的技术中。它们的创新性能主要由聚合物大分子在外部机械力或静电力诱导的伸长下的行为决定，表征纤维拉伸过程。虽然在强拉伸条件下生产的聚合物纤维中观察到增强的物理性能，但对聚合物分子的工艺诱导的纳米级组织的研究不可用，并且大多数纤维性能仍然是在经验基础上获得的。在这里，我们揭示了电纺纳米纤维中半柔性聚合物的取向特性，这使得活性纤维的偏振特性得到精细控制。在静电伸长的半稀释液的解决方案的聚合物链的构象演化的建模和模拟表明，分子几乎完全拉伸从喷射开始不到1毫米内，增加在喷射中心的聚合物轴向取向。通过偏振近场光学显微镜对单个纤维的局部二向色性的纳米尺度映射首次揭示了分子顺序的内部空间变化的存在，即存在具有轴向排列的分子的芯和具有几乎径向取向的分子的鞘。这些结果允许操纵和定制重要和特定的光纤特性，如这里所示的发射光的偏振。
英文摘要：
Polymer fibers are currently exploited in tremendously important technologies. Their innovative properties are mainly determined by the behavior of the polymer macromolecules under the elongation induced by external mechanical or electrostatic forces, characterizing the fiber drawing process. Although enhanced physical properties were observed in polymer fibers produced under strong stretching conditions, studies of the process-induced nanoscale organization of the polymer molecules are not available, and most of fiber properties are still obtained on an empirical basis. Here we reveal the orientational properties of semiflexible polymers in electrospun nanofibers, which allow the polarization properties of active fibers to be finely controlled. Modeling and simulations of the conformational evolution of the polymer chains during electrostatic elongation of semidilute solutions demonstrate that the molecules stretch almost fully within less than 1 mm from jet start, increasing polymer axial orientation at the jet center. The nanoscale mapping of the local dichroism of individual fibers by polarized near-field optical microscopy unveils for the first time the presence of an internal spatial variation of the molecular order, namely the presence of a core with axially aligned molecules and a sheath with almost radially oriented molecules. These results allow important and specific fiber properties to be manipulated and tailored, as here demonstrated for the polarization of emitted light.
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