1 DEPARTMENT OF PHYSICS, UNIVERSITY OF IOANNINA, 45110 IOANNINA, GREECE
2 INSTITUT FÜR CHEMIE NEUER MATERIALIEN, UNIVERSITÄT OSNABRÜCK, D-49069 OSNABRÜCK, GERMANY
The effect of confinement on polymer dynamics and the associated liquid-to-glass temperature, T g , has been an issue of great interest in polymer physics. In this study, we investigate the effect of confinement in the nanometer scale on the dynamics of cis- 1,4-polyisoprene with molecular weights in the vicinity and over the entanglement limit ( M w =8500-100000 g/mol), confined in self-ordered nanoporous alumina (AAO) with diameters, d , ranging from 400 nm to 25 nm. An earlier study  investigated the effect of confinement in PI with M < M e and found an unaffected T g under confinement with respect to the bulk. Another study  reported on the effect of interfacial energy on the segmental dynamics for different polymers confined in AAO. Broadband Dielectric Spectroscopy (BDS) and Temperature-Modulated Differential Scanning Calorimetry (TMDSC) measurements were employed to examine the effect of confinement on molecular dynamics and the thermodynamic T g , respectively. For molecular weights higher than the entanglement limit (M w >10000 g/mol), BDS measurements revealed consistently faster segmental dynamics under confinement with respect to the bulk, leading to a decrease in T g with increasing degree confinement (2 R g / d ). In addition, we provide evidence for an intermediate process with an Arrhenius temperature dependence whose dielectric strength increases with increasing degree of confinement. This is attributed to a “dead layer” consisting of partially immobilized chains next to the interface, discussed in recent imbibition studies of polymers in nanopores and confirmed by theory ,  . We further report on the effects of annealing and quenching on the thermodynamics and dynamics  .
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 Alexandris, S.; Papadopoulos, P.; Sakellariou, G.; Steinhart, M.; Butt, H.-J.; Floudas, G. Interfacial Energy and Glass Temperature of Polymers Confined to Nanoporous Alumina Macromolecules 2016, 49, 7400-7414.
 Yao, Y.; Alexandris, S.; Henrich, F.; Auernhammer G.; Steinhart, M.; Butt, H.-J.; Floudas, G. Complex dynamics of capillary imbibition of poly(ethylene oxide) melts in nanoporous alumina. J. Chem. Phys. 2017, 146, 203320.
 Yao, Y.; Butt, H.-J.; Zhou, J.; Doi, M.; Floudas, G. Capillary Imbibition of Polymer Mixtures in Nanopores Macromolecules 2018 51, 3059-3065.
 Politidis, C.; Alexandris, S.; Steinhart, M.; Floudas, G. High molecular weight cis-1,4-polyisoprene confined in nanoporous alumina: Dynamics over the entanglement limit (In preparation).