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@PHDTHESIS{Prause:1018701,
author = {Prause, Albert},
title = {{S}tructural {I}nvestigation of {H}ydrophobically
{M}odified {T}hermoresponsive {P}olymers and{T}heir
{I}nfluence on the {R}heology of {M}icroemulsions},
school = {TU Berlin},
type = {Dissertation},
reportid = {FZJ-2023-04995},
pages = {182p},
year = {2023},
note = {Dissertation, TU Berlin, 2023},
abstract = {A library of nonsymmetrical thermosensitive BAB* block
copolymers was investigated in terms of their aggregation
behavior and rheological properties as a function of
temperature in aqueous solutions. Additionally, these block
copolymers were used to study the modification of
temperature-dependent rheological properties of
microemulsions. The block copolymers comprise a permanently
hydrophilic poly(N,N -dimethylacrylamide) (pDMAm) block
“A”, a permanently hydrophobic n-dodecyl (C12) chain as
end-group “B”, and a ther-moresponsive (TR) block
“B*” featuring a lower critical solution temperature
(LCST). To vary the chemical nature and LCST behavior,
different polyacrylamides, i. e., poly(N
-n-propylacrylamide) (pNPAm), poly(N,N -diethylacrylamide)
(pDEAm), poly(N -isopropyl-acrylamide) (pNiPAm), and poly(N
-acryloylpyrrolidine) (pNAP), were introduced as TR blocks.
Additionally, the length of the TR block was varied
systematically as well as the architecture of the block
copolymer, for which three types were employed, i. e., BAB*,
B2AB*, and B(AB*)2.The influence of the length of the TR
block on the aggregation behavior and temperature response
was studied via light and neutron scattering (SLS, DLS, and
SANS). For TR blocks with more than 40 monomer units, a
marked hydrophobic interaction occurs above the LCST,
leading to ordered, well-structured clusters of micellar
aggregates. Thus, the temperature-dependent mesoscopic
organization of aggregates can be tuned by the length and
type of the TR block.The temperature response of rheological
properties was investigated and compared for the various
copolymer architectures. Depending on the TR block and the
copolymer archi-tecture, their solution’s viscosity can
increase significantly with rising temperature. These
results are well in line with the observed mesoscopic
organization obtained by SLS, DLS, and SANS experiments.
Additionally, fluorescence experiments using the
solvatochromic probe Prodan revealed a direct relationship
between the increased viscosity and the for-mation of
additional hydrophobic domains of TR blocks. Consequently,
the viscoelastic properties of aqueous solutions can be
tuned temperature dependently by carefully designing these
copolymers.Following this, the viscoelastic properties of
low-viscous oil-in-water (O/W) microemul-sions (MEs) can
also be adjusted. For a properly chosen ME concentration,
these block copolymers lead to a viscosity increase with
rising temperature. At a polymer concentration of about 22 g
L−1, the most pronounced enhancement was observed for the
pNPAm-based systems, with factors up to about 3, 5, and 8
for BAB*, B2AB*, and B(AB*)2, respectively. The enhancement
is caused by the formation of a transient net-work mediated
by TR blocks, as evidenced by the direct correlation between
the viscosity enhancement and the attraction strength. This
kind of tailored temperature-dependent viscosity control of
surfactant-based systems could therefore be advantageous for
applications requiring a high hydrophobic payload, which is
accomplished by the droplet microemulsion.},
cin = {JCNS-FRM-II / MLZ},
cid = {I:(DE-Juel1)JCNS-FRM-II-20110218 / I:(DE-588b)4597118-3},
pnm = {6G4 - Jülich Centre for Neutron Research (JCNS) (FZJ)
(POF4-6G4)},
pid = {G:(DE-HGF)POF4-6G4},
experiment = {EXP:(DE-MLZ)KWS1-20140101},
typ = {PUB:(DE-HGF)11},
doi = {10.34734/FZJ-2023-04995},
url = {https://juser.fz-juelich.de/record/1018701},
}