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@ARTICLE{Campanella:283343,
author = {Campanella, Antonella and Holderer, O. and Raftopoulos, K.
N. and Papadakis, C. M. and Staropoli, Mariapaola and
Appavou, M. S. and Müller-Buschbaum, P. and Frielinghaus,
H.},
title = {{M}ulti-stage freezing of {HEUR} polymer networks with
magnetite nanoparticles},
journal = {Soft matter},
volume = {12},
number = {13},
issn = {1744-6848},
address = {London},
publisher = {Royal Soc. of Chemistry},
reportid = {FZJ-2016-01771},
pages = {3214-3225},
year = {2016},
abstract = {We observe a change in the segmental dynamics of hydrogels
based on hydrophobically modified ethoxylated urethanes
(HEUR) when hydrophobic magnetite nanoparticles (MNPs) are
embedded in the hydrogels. The dynamics of the nanocomposite
hydrogels is investigated using dielectric relaxation
spectroscopy (DRS) and neutron spin echo (NSE) spectroscopy.
The magnetic nanoparticles within the hydrophobic domains of
the HEUR polymer network increase the size of these domains
and their distance. The size increase leads to a dilution of
the polymers close to the hydrophobic domain, allowing
higher mobility of the smallest polymer blobs close to the
“center”. This is reflected in the decrease of the
activation energy of the β-process detected in the DRS
data. The increase in distance leads to an increase of the
size of the largest hydrophilic polymer blobs. Therefore,
the segmental dynamics of the largest blobs is slowed down.
At short time scales, i.e. 10−9 s < τ < 10−3 s, the
suppression of the segmental dynamics is reflected in the
α-relaxation processes detected in the DRS data and in the
decrease of the relaxation rate Γ of the segmental motion
in the NSE data with increasing concentration of magnetic
nanoparticles. The stepwise (multi-stage) freezing of the
small blobs is only visible for the pure hydrogel at low
temperatures. On the other hand, the glass transition
temperature (Tg) decreases upon increasing the MNP loading,
indicating an acceleration of the segmental dynamics at long
time scales (τ ∼ 100 s). Therefore, it would be possible
to tune the Tg of the hydrogels by varying the MNP
concentration. The contribution of the static
inhomogeneities to the total scattering function Sst(q) is
extracted from the NSE data, revealing a more ordered gel
structure than the one giving rise to the total scattering
function S(q), with a relaxed correlation length ξNSE = (43
± 5) Å which is larger than the fluctuating correlation
length from a static investigation ξSANS = (17.2 ± 0.3)
Å.},
cin = {JCNS (München) ; Jülich Centre for Neutron Science JCNS
(München) ; JCNS-FRM-II / Neutronenstreuung ; JCNS-1},
ddc = {530},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106},
pnm = {6215 - Soft Matter, Health and Life Sciences (POF3-621) /
6G15 - FRM II / MLZ (POF3-6G15) / 6G4 - Jülich Centre for
Neutron Research (JCNS) (POF3-623)},
pid = {G:(DE-HGF)POF3-6215 / G:(DE-HGF)POF3-6G15 /
G:(DE-HGF)POF3-6G4},
experiment = {EXP:(DE-MLZ)J-NSE-20140101 / EXP:(DE-MLZ)KWS1-20140101 /
EXP:(DE-MLZ)TEM-MLZ-20151210},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000372795100011},
doi = {10.1039/C6SM00074F},
url = {https://juser.fz-juelich.de/record/283343},
}