4.7 Article

Rapid Melt Crystallization of Bisphenol-A Polycarbonate Jointly Induced by Pressure and Flow

期刊

MACROMOLECULES
卷 54, 期 5, 页码 2383-2393

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.macromol.0c02208

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资金

  1. National Key R&D Program of China [2018YFB0704200]
  2. National Natural Science Foundation of China [52033005, 51761145112, 51773136, 51803138]

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This study reports on the rapid melt crystallization of Bisphenol-A polycarbonate induced by pressure and shear flow, achieving a crystallinity of up to 25% in 60 minutes, which is 500 times faster than quiescent melt crystallization under ordinary pressure. The synergistic effect of pressure and flow in promoting crystallization kinetics of PC is highlighted, reducing the critical shear rate for nucleation effectively. A critical specific work of flow is identified, above which PC can crystallize, potentially revolutionizing our understanding of crystallization in similar polymers with rigid chains.
Bisphenol-A polycarbonate (PC) is an intrinsically crystallizable polymer. Its industrial parts, however, invariably remain in an amorphous state due to its extremely slow crystallization kinetics. In the current study, we reported rapid melt crystallization of bulk PC jointly induced by pressure and shear flow. The crystallinity of pure bulk PC reached up to similar to 25% when crystallized at 100 MPa and 42.8 s(-1) for only 60 min, ca. 500 times faster than quiescent melt crystallization under ordinary pressure. In consideration of no crystallization by applying pressure or shear flow alone, a synergistic effect of pressure and flow on promoting crystallization kinetics of PC clearly existed. The spinodal decomposition induced by pressure and flow activated the conformation ordering prior to nucleation, and furthermore, the flow-induced chain orientation facilitated nucleation via reducing the energy barrier. The critical shear rate for nucleation was reduced effectively by increasing the applied pressure. A formula of the modified specific work of flow was proposed to quantify the contribution of pressure and flow to the rapid crystallization of PC. There existed a critical specific work of flow, w(c(T,P)) = (3.9 +/- 0.3) x 10(8) J.m(-3), only above which the PC could crystallize. The findings in this work may revolutionize our understanding of the crystallization of PC and other similar polymers with rigid chains.

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