Structural Basis for Unique Hierarchical Cylindrites Induced by Ultrahigh Shear Gradient in Single Natural Fiber Reinforced Poly(lactic acid) Green Composites
2014 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 15, no 5, 1676-1686 p.Article in journal (Refereed) Published
A local shear flow field was feasibly generated by pulling the ramie fiber in single fiber reinforced poly(lactic acid) (PLA) composites. This was featured by an ultrahigh shear gradient with a maximum shear rate up to 1500 s(-1), a level comparable to that frequently occurring during the practical polymer processing. To distinguish shear-induced self-nucleation and ramie fiber-induced heterogeneous nucleation, the shear history was classified by pulling the fiber for 5 s (pulled sample) and pulling out the fiber during 10 s (pulled-out sample), while the static fiber-induced crystallization was carried out as the counterpart. As a result of the ultrahigh shear gradient, the combination of primary shear-induced nucleation in the central region and secondary nucleation in the outer layer assembled the unique hierarchical superstructures. By comparing the architectural configurations of interphases formed in the static, pulled, and pulled-out samples, it was shown that the hierarchical cylindrites underwent the process of self-nucleation driven by the applied shear flow, very different from the formation of fiber-induced transcrystallinity (TC) triggered by the heterogeneous nucleating sites at the static fiber surface. The twisting of transcrystallized lamellae may take place due to the spatial hindrance induced by the incredibly dense nuclei under the intense shearing flow, as observed in the synchrotron X-ray diffraction patterns. The influence of chain characteristics on the crystalline morphology was further explored by adding a small amount of poly(ethylene glycol) (PEG) to enhance the molecular mobility of PLA. It was of interest to find that the existence of PEG not only facilitated the growth rates of TC and cylindrites but also improved the preferential orientation of PLA chains and thus expanded the ordered regions. We unearthed lamellar units that were composed of rich fibrillar extended chain crystals (diameter of 50-80 nm). These results are of importance to shed light on tailoring crystalline morphology for natural fibers reinforced green composite materials. Of immense practical significance, too, is the crystalline evolution that has been tracked in the simple model penetrated with an ultrahigh shear gradient, which researchers have so far been unable to replicate during the practical melt processing, such as extrusion and injection molding.
Place, publisher, year, edition, pages
2014. Vol. 15, no 5, 1676-1686 p.
Crystalline evolution, Crystalline morphologies, Extended chain crystals, Heterogeneous nucleation, Natural fiber reinforced, Preferential orientation, Secondary nucleation, Synchrotron x ray diffraction, Chains, Crystalline materials, Hemp, Lactic acid, Morphology, Natural fibers, Nucleation, Polyethylene glycols
Biochemistry and Molecular Biology Polymer Chemistry
IdentifiersURN: urn:nbn:se:kth:diva-146553DOI: 10.1021/bm500100zISI: 000335939800014ScopusID: 2-s2.0-84900405478OAI: oai:DiVA.org:kth-146553DiVA: diva2:724243
QC 201406122014-06-122014-06-122014-06-12Bibliographically approved