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@ARTICLE{Koizumi:873378,
author = {Koizumi, Satoshi and Annaka, Masahiko and Schwahn, Dietmar},
title = {{N}ecklace-like microstructure in shallow-quenched aqueous
solutions of poly( n -isopropylacrylamide), detected by
advanced small-angle neutron scattering methods},
journal = {Soft matter},
volume = {15},
number = {4},
issn = {1744-6848},
address = {London},
publisher = {Royal Soc. of Chemistry},
reportid = {FZJ-2020-00690},
pages = {671 - 682},
year = {2019},
abstract = {The microstructure of aqueous poly(N-isopropyl acrylamide)
(PNIPA) gel and solution was investigated by small-angle
neutron scattering (SANS) in the vicinity of the gel volume
phase transition at TV (= 34 °C). The SANS technique was
reinforced by refractive neutron lenses and perfect single
crystals in order to get access to μm length scales. At 31
°C SANS shows Ornstein–Zernike (OZ) type scattering in
the swollen gel which at 32 °C starts to deviate from the
OZ-formalism, exhibiting excess scattering and at the wave
number qc ≅ 5 × 10−3 Å−1 a crossover to Porod's
asymptotic q−4 power law. For shallow quenches of ΔT <
1.0 K above TV the excess scattering intensity is further
increasing whereas qc is shifting toward lower values. Based
on this observation and analysis of the SANS q-profiles, we
propose a necklace-like microstructure consisting of
PNIPA-rich globules of R ≅ 100 Å size which are connected
by swollen PNIPA chains and stabilized for more than a day
by pinning of chain connectivity. The formation of PNIPA
globules near TV is discussed in terms of partially
cooperative dehydration which is crucial to explain the
“miscibility square phase behavior” of aqueous PNIPA
solutions. Globule-like structure was also found in aqueous
PNIPA solution of size slightly larger than in gels. At
deeper quenches of gels above TV (ΔT > 1.0 K) the globules
are aggregating to larger objects of R ≅ 0.24 μm size as
determined from a strong intensity upturn in the small
q-region of USANS},
cin = {JCNS-FRM-II / JCNS-1 / MLZ},
ddc = {530},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 /
I:(DE-Juel1)JCNS-1-20110106 / I:(DE-588b)4597118-3},
pnm = {6G4 - Jülich Centre for Neutron Research (JCNS) (POF3-623)
/ 6G15 - FRM II / MLZ (POF3-6G15)},
pid = {G:(DE-HGF)POF3-6G4 / G:(DE-HGF)POF3-6G15},
experiment = {EXP:(DE-MLZ)KWS1-20140101},
typ = {PUB:(DE-HGF)16},
pubmed = {pmid:30623191},
UT = {WOS:000457329700009},
doi = {10.1039/C8SM02416B},
url = {https://juser.fz-juelich.de/record/873378},
}