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@PHDTHESIS{Frenzel:429201,
author = {Frenzel, Lara},
othercontributors = {Lehmkühler, Felix and Gruebel, Gerhard},
title = {{S}tructure and {D}ynamics of {C}omplex {L}iquids - {T}he
{P}hase {B}ehaviour of {S}ilica-{PNIPA}m {N}anogels},
school = {Universität Hamburg},
type = {Dissertation},
address = {Hamburg},
publisher = {Verlag Deutsches Elektronen-Synchrotron},
reportid = {PUBDB-2019-04870, DESY-THESIS-2019-032},
series = {DESY-THESIS},
pages = {101},
year = {2019},
note = {Dissertation, Universität Hamburg, 2019},
abstract = {In this thesis, the structure and dynamics of highly
concentrated core-shell nanogel particlescomposed of a
silica core and a poly(N-isoproylacrylamide) (PNIPAm) shell
suspendedin water are studied. The particles were
synthesised with dierent core-to-shell size ratiosand
prepared at various concentrations with volume fractions e
between approximately0:004 and 2. X-ray photon correlation
spectroscopy (XPCS) enables to follow the
dynamical,small-angle X-ray scattering (SAXS) the structural
changes of the thermo-responsivenanogel particles which
undergo a volume phase transition at a so-called lower
criticalsolution temperature (LCST) of 32C. All samples were
studied in a broad temperaturerange around the LCST with
approximately 15C < T < 45C and the main focus is
ondensely-packed systems.For a system with e = 0:55, the
structural relaxation time c was found to decreasewith
increasing temperature. Above the LCST, the structural
relaxation time initiallycontinues to decrease. The eect is
accompanied by a transition from stretched to
compressedexponential behaviour of the intensity
autocorrelation functions, which could bedetermined by
analysing the intensity autocorrelation functions. Upon
further heating asudden slowing down at a critical
temperature Tc 37C. In parallel, the q-dependenceof the
relaxation time shows an anomalous change from c / q3 to
c / q1. Theresults reveal a temperature-induced
transition from swollen repulsive particles with
polymerdriven dynamics at lower temperatures T < Tc towards
a colloidal gel composed ofcollapsed attractive particles.
The transition of structure and dynamics shows a
distinctdependency on the eective particle volume fraction.
Below a critical concentration notransition upon heating was
found.The de-swelling behaviour of the PNIPam nanogel was
inuenced with the additionof Trimethylamine N-oxide (TMAO)
to the concentrated particle suspension. With increasingTMAO
concentration, a shift of the LCST towards lower
temperatures and apreferential hydrophobic state could be
determined.With all results a full phase diagram of a
silica-PNIPAm core-shell system is presentedas a function of
temperature and concentration. It spans from dilute
suspensions toan eective volume fraction of more than ninety
percent covering two liquid phases, astructural
rearrangement phase and a colloidal gel phase.},
cin = {FS-CXS},
cid = {I:(DE-H253)FS-CXS-20130727},
pnm = {6215 - Soft Matter, Health and Life Sciences (POF3-621) /
6G3 - PETRA III (POF3-622)},
pid = {G:(DE-HGF)POF3-6215 / G:(DE-HGF)POF3-6G3},
experiment = {EXP:(DE-H253)P-P10-20150101 /
EXP:(DE-MLZ)External-20140101},
typ = {PUB:(DE-HGF)3 / PUB:(DE-HGF)29 / PUB:(DE-HGF)11},
doi = {10.3204/PUBDB-2019-04870},
url = {https://bib-pubdb1.desy.de/record/429201},
}