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剪切流和碳纳米管协同诱导聚乳酸的非等温结晶及其在注塑成型中的应用。

Shear flow and carbon nanotubes synergistically induced nonisothermal crystallization of poly(lactic acid) and its application in injection molding.

机构信息

College of Polymer Science and Engineering, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, 610065, Sichuan, People's Republic of China.

出版信息

Biomacromolecules. 2012 Nov 12;13(11):3858-67. doi: 10.1021/bm3013617. Epub 2012 Oct 22.

Abstract

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.

摘要

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。

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