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Tensile Deformation of Oriented Poly(ε-caprolactone) and Its Miscible Blends with Poly(vinyl methyl ether)
Jiang, Z. Wang, Y. Fu, L. Whiteside, Benjamin R. Wyborn, John Norris, Keith Wu, Z. Men, Y.
Jiang, Z.
Wang, Y.
Fu, L.
Whiteside, Benjamin R.
Wyborn, John
Norris, Keith
Wu, Z.
Men, Y.
Publication Date
2013-09-10
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© 2013 American Chemical Society. Full-text reproduced in accordance with the publisher’s self-archiving policy.
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Macromolecules, copyright © American Chemical Society after peer-review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/ma401052x.
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Abstract
The structural evolution of micromolded poly(ε‑caprolactone) (PCL) and its miscible blends with noncrystallizable poly(vinyl methyl ether) (PVME) at the nanoscale was investigated as a function of deformation ratio and blend composition using in situ synchrotron small‑angle X‑ray scattering (SAXS) and scanning SAXS techniques. The deformation mechanism of the oriented samples follows a general scheme: at small deformations, crystal block slip occurs within the lamellae, followed at a critical strain by stress‑induced fragmentation and recrystallization along the drawing direction, during which the average crystalline lamellar thickness remains essentially constant. The value of this critical strain depends on the amount of amorphous component incorporated into the blends, attributable to the lower modulus of the entangled amorphous phase and the resulting reduction in network stress acting on the crystallites upon PVME addition. Beyond the critical strain, slippage of fibrils—stacks of newly formed lamellae—past one another leads to relaxation of stretched interlamellar amorphous chains. In highly oriented blends, deformation‑induced incorporation of amorphous PVME into interfibrillar regions strengthens interactions between fibrils during further stretching, thereby impeding fibril sliding and ultimately resulting in reduced contraction of the interlamellar amorphous layers compared to pure PCL.
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Jiang Z, Wang Y, Fu L, Whiteside B et al (2013) Tensile Deformation of Oriented Poly(ε-caprolactone) and Its Miscible Blends with Poly(vinyl methyl ether). Macromolecules. 46(17): 6981-6990.
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