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Title: Multiple nucleation events and local dynamics of poly(epsilon-caprolactone) (PCL) confined to nanoporous alumina
Authors: Suzuki, Yasuhito
Duran, Hatice
Akram, Wajiha
Steinhart, Martin
Floudas, George
Butt, Hans-Juergen
Keywords: [No Keywords]
Issue Date: 2013
Publisher: Royal Soc Chemistry
Abstract: The crystallization and local dynamics of poly(epsilon-caprolactone) (PCL) confined to self-ordered nanoporous alumina (AAO) were studied as a function of pore size, pore surface functionality, molecular weight and cooling/heating rate by differential scanning calorimetry (DSC), wide-angle X-ray diffraction and dielectric spectroscopy. In contrast to the bulk, PCL located inside nanoporous alumina crystallizes via several distinct nucleation mechanisms. All mechanisms display pronounced rate dependence. At low undercoolings, the usual heterogeneous nucleation of bulk PCL was suppressed at the expense of two additional mechanisms attributed to heterogeneous nucleation initiated at the pore walls. At higher undercoolings a broad peak was observed in DSC which we attribute to crystallization initiated by homogeneous nucleation. At high cooling rates, the critical nucleus size is smaller than the smallest diameter of pores. Thus, PCL is able to crystallize within the smallest pores, despite the lower degree of crystallinity. Inevitably, homogeneous nucleation is strongly coupled to the local viscosity and hence to the local segmental dynamics. Dielectric spectroscopy revealed that confinement affected both the rate of segmental motion with a lowering of the glass temperature as well as a broader distribution of relaxation times.
ISSN: 1744-683X
Appears in Collections:Malzeme Bilimi ve Nanoteknoloji Mühendisliği Bölümü / Department of Material Science & Nanotechnology Engineering
Scopus İndeksli Yayınlar Koleksiyonu / Scopus Indexed Publications Collection
WoS İndeksli Yayınlar Koleksiyonu / WoS Indexed Publications Collection

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