Hierarchical Structural Change in the Stress-Induced Phase Transition of Poly(tetramethylene terephthalate) As Studied by the Simultaneous Measurement of FTIR Spectra and 2D Synchrotron Undulator WAXD

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• 作者：Kohji Tashiro ; Hiroko Yamamoto ; Taiyo Yoshioka ; Tran Hai Ninh ; Masafumi Tasaki ; Shigeru Shimada ; Takeshi Nakatani ; Hiroyuki Iwamoto ; Noboru Ohta ; Hiroyasu Masunaga
• 刊名：Macromolecules
• 出版年：2014
• 出版时间：March 25, 2014
• 年：2014
• 卷：47
• 期：6
• 页码：2052-2061
• 全文大小：649K
• 年卷期：v.47,no.6(March 25, 2014)
• ISSN：1520-5835

文摘

The simultaneous measurement of Fourier transform infrared (FTIR) transmission spectra and 2-dimensional wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) patterns has been performed successfully to investigate the hierarchical structure changes occurring in the stress-induced phase transition phenomenon of uniaxially oriented poly(tetramethylene terephthalate) film. The molar fraction of the 尾-crystal form, evaluated from the IR and WAXD data analyses, increased steeply in the plateru region of the stress鈥搒train curve as already known well. The 2D SAXS data have revealed the remarkable and reversible change in the stacked lamellar structure just after the 伪-to-尾 phase transition was completed, where the tilting angle of the stacked lamellae measured from the draw axis of the oriented sample became zero, and the lamellar thickness increased due to the inclusion of amorphous region located in the boundary part of the crystalline lamellae. In parallel, the X-ray reflection spots in a wider diffraction angle region became diffuse in the observed WAXD pattern of the 尾 form, indicating the packing disorder of the mechanically stressed chains. In this way, the simultaneous combination of the 3 different types of equipments has allowed us to deduce the detailed structural change from the various levels: the stress-induced 伪鈥撐?transition was found to occur not only with the remarkable changes in the molecular chain conformation and chain packing mode in the crystal lattice, but also with the large and reversible change in the lamellar stacking structure. The stress-induced changes in lamellar thickness and long period were simulated using a mechanical model with these hierarchical structure changes taken into account, giving relatively good reproduction of the observed data.