College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, 610065, Sichuan, People's Republic of China.
Biomacromolecules. 2012 Nov 12;13(11):3858-67. doi: 10.1021/bm3013617. Epub 2012 Oct 22.
The effect of shear flow and carbon nanotubes (CNTs), separately and together, on nonisothermal crystallization of poly(lactic acid) (PLA) at a relatively large cooling rate was investigated by time-resolved synchrotron wide-angle X-ray diffraction (WAXD) and polarized optical microscope (POM). Unlike flexible-chain polymers such as polyethylene, and so on, whose crystallization kinetics are significantly accelerated by shear flow, neat PLA only exhibits an increase in onset crystallization temperature after experiencing a shear rate of 30 s(-1), whereas both the nucleation density and ultimate crystallinity are not changed too much because PLA chains are intrinsically semirigid and have relatively short length. The breaking down of shear-induced nuclei into point-like precursors (or random coil) probably becomes increasingly active after shear stops. Very interestingly, a marked synergistic effect of shear flow and CNTs exists in enhancing crystallization of PLA, leading to a remarkable increase of nucleation density in PLA/CNT nanocomposite. This synergistic effect is ascribed to extra nuclei, which are formed by the anchoring effect of CNTs' surfaces on the shear-induced nuclei and suppressing effect of CNTs on the relaxation of the shear-induced nuclei. Further, this interesting finding was deliberately applied to injection molding, aiming to improve the crystallinity of PLA products. As expected, a remarkable high crystallinity in the injection-molded PLA part has been achieved successfully by the combination of shear flow and CNTs, which offers a new method to fabricate PLA products with high crystallinity for specific applications.
研究了剪切流和碳纳米管(CNTs)分别和共同作用对聚乳酸(PLA)在相对较大冷却速率下的非等温结晶的影响,采用时间分辨同步加速器广角 X 射线衍射(WAXD)和偏光显微镜(POM)进行研究。与聚乙烯等柔性链聚合物不同,其结晶动力学因剪切流而显著加速,纯 PLA 仅在经历 30 s(-1)的剪切速率后才表现出起始结晶温度的升高,而由于 PLA 链本质上是半刚性的并且相对较短,因此成核密度和最终结晶度变化不大。剪切诱导核的分解成点状前体(或无规卷曲)在剪切停止后可能变得越来越活跃。非常有趣的是,剪切流和 CNTs 的协同作用在增强 PLA 的结晶方面非常显著,导致 PLA/CNT 纳米复合材料中成核密度显著增加。这种协同效应归因于 CNT 表面对剪切诱导核的锚定效应和 CNT 对剪切诱导核松弛的抑制效应形成的额外核。此外,这一有趣的发现被故意应用于注塑成型,旨在提高 PLA 产品的结晶度。不出所料,通过剪切流和 CNTs 的结合成功地在注塑 PLA 零件中实现了高结晶度,为特定应用制备高结晶度 PLA 产品提供了一种新方法。