Confined Glassy Dynamics
in a Star-Shaped Polymer Induced
by Crystallization: Case Study
of Polyhedral Oligomeric
Polysilesquioxane—Isotactic Polystyrene
(POSS-iPS)
Martin Tress, Arthur Markus Anton, Maximilian Vielhauer, Pierre Lutz,
Rolf Mülhaupt, and Friedrich Kremer
Abstract The crystallites in semi-crystalline polymers typically constrain the
segmental motion of the protruding chains in close proximity. While segments far
away from the crystallites have the same (unperturbed) dynamics as the purely
amorphous state (mobile amorphous fraction), the segments in the transition regions
around the crystallites relax significantly slower (rigid amorphous fraction). Here,
we present a study combining broadband dielectric spectroscopy (BDS) and Fourier
transform infrared spectroscopy (FTIR) which reveals a further type of perturbation
of contrary impact on the dynamics. In a star-shaped polymer—based on a polyhedral oligomeric silesquioxane (POSS) molecule as center and isotactic polystyrene
arms—we demonstrate for the first time that in the semi-crystalline state remaining
amorphous segments can exhibit a faster mean relaxation rate than in the purely
M. Tress (B) · A. M. Anton · F. Kremer
Leipzig University, Leipzig, Germany
e-mail: martin.tress@uni-leipzig.de
A. M. Anton
e-mail: arthur.anton@sheffield.ac.uk
F. Kremer
e-mail: friedrich.kremer@physik.uni-leipzig.de
A. M. Anton
The University of Sheffield, Sheffield, UK
M. Vielhauer · R. Mülhaupt
University Freiburg, Freiburg, Germany
e-mail: maximilian.vielhauer@fmf.uni-freiburg.de
R. Mülhaupt
e-mail: rolf.muelhaupt@makro.uni-freiburg.de
P. Lutz
University Strasbourgh, Strasbourgh, France
e-mail: lutz@ics.u-strasbg.fr
© Springer Nature Switzerland AG 2020
T. A. Ezquerra and A. Nogales (eds.), Crystallization as Studied
by Broadband Dielectric Spectroscopy, Advances in Dielectrics,
https://doi.org/10.1007/978-3-030-56186-4_11
267
in a Star-Shaped Polymer Induced
by Crystallization: Case Study
of Polyhedral Oligomeric
Polysilesquioxane—Isotactic Polystyrene
(POSS-iPS)
Martin Tress, Arthur Markus Anton, Maximilian Vielhauer, Pierre Lutz,
Rolf Mülhaupt, and Friedrich Kremer
Abstract The crystallites in semi-crystalline polymers typically constrain the
segmental motion of the protruding chains in close proximity. While segments far
away from the crystallites have the same (unperturbed) dynamics as the purely
amorphous state (mobile amorphous fraction), the segments in the transition regions
around the crystallites relax significantly slower (rigid amorphous fraction). Here,
we present a study combining broadband dielectric spectroscopy (BDS) and Fourier
transform infrared spectroscopy (FTIR) which reveals a further type of perturbation
of contrary impact on the dynamics. In a star-shaped polymer—based on a polyhedral oligomeric silesquioxane (POSS) molecule as center and isotactic polystyrene
arms—we demonstrate for the first time that in the semi-crystalline state remaining
amorphous segments can exhibit a faster mean relaxation rate than in the purely
M. Tress (B) · A. M. Anton · F. Kremer
Leipzig University, Leipzig, Germany
e-mail: martin.tress@uni-leipzig.de
A. M. Anton
e-mail: arthur.anton@sheffield.ac.uk
F. Kremer
e-mail: friedrich.kremer@physik.uni-leipzig.de
A. M. Anton
The University of Sheffield, Sheffield, UK
M. Vielhauer · R. Mülhaupt
University Freiburg, Freiburg, Germany
e-mail: maximilian.vielhauer@fmf.uni-freiburg.de
R. Mülhaupt
e-mail: rolf.muelhaupt@makro.uni-freiburg.de
P. Lutz
University Strasbourgh, Strasbourgh, France
e-mail: lutz@ics.u-strasbg.fr
© Springer Nature Switzerland AG 2020
T. A. Ezquerra and A. Nogales (eds.), Crystallization as Studied
by Broadband Dielectric Spectroscopy, Advances in Dielectrics,
https://doi.org/10.1007/978-3-030-56186-4_11
267