Roozemond Peter C, van Drongelen Martin, Ma Zhe, Spoelstra Anne B, Hermida-Merino Daniel, Peters Gerrit W M
Department of Mechanical Engineering, Eindhoven University of Technology, P.O. Box 513, 5600MB, Eindhoven, The Netherlands.
Macromol Rapid Commun. 2015 Feb;36(4):385-90. doi: 10.1002/marc.201400505. Epub 2014 Dec 17.
Flow-induced structure formation is investigated with in situ wide-angle X-ray diffraction with high acquisition rate (30 Hz) using isotactic polypropylene in a piston-driven slit flow with high wall shear rates (up to ≈900 s(-1) ). We focus on crystallization within the shear layers that form in the high shear rate regions near the walls. Remarkably, the kinetics of the crystallization process show no dependence on either flow rate or flow time; the crystallization progresses identically regardless. Stronger or longer flows only increase the thickness of the layers. A conceptual model is proposed to explain the phenomenon. Above a certain threshold, the number of shish-kebabs formed affects the rheology such that further structure formation is halted. The critical amount is reached already within 0.1 s under the current flow conditions. The change in rheology is hypothesized to be a consequence of the "hairy" nature of shish. Our results have large implications for process modelling, since they suggest that for injection molding type flows, crystallization kinetics can be considered independent of deformation history.
采用全同立构聚丙烯,在具有高壁面剪切速率(高达约900 s⁻¹)的活塞驱动狭缝流中,利用高采集速率(30 Hz)的原位广角X射线衍射研究流动诱导结构形成。我们关注在壁面附近高剪切速率区域形成的剪切层内的结晶情况。值得注意的是,结晶过程的动力学与流速或流动时间均无关;无论如何,结晶过程都是相同的。更强或更长时间的流动只会增加层的厚度。提出了一个概念模型来解释这一现象。超过一定阈值后,形成的串晶数量会影响流变学,从而使进一步的结构形成停止。在当前流动条件下,在0.1 s内就已达到临界数量。流变学的变化被假定为串晶“多毛”性质的结果。我们的结果对过程建模有重大影响,因为它们表明对于注塑成型类流动,结晶动力学可被视为与变形历史无关。