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@PHDTHESIS{Kyrey:872595,
      author       = {Kyrey, Tetyana},
      title        = {{I}nternal structure and dynamics of {PNIPAM} based
                      microgels in bulk and adsorbed state at different internal
                      crosslinker distributions},
      school       = {TU Darmstadt},
      type         = {Dissertation},
      address      = {Darmstadt},
      publisher    = {TU Darmstadt},
      reportid     = {FZJ-2020-00093},
      pages        = {135p.},
      year         = {2019},
      note         = {Dissertation, TU Darmstadt, 2019},
      abstract     = {Stimuli-responsive microgels are a unique class of polymer
                      structures which can undergo a fast response to an external
                      trigger such as light, temperature or pH. It provides a wide
                      potential application spectrum in optical devices, smart
                      surface coatings, emulsion stabilisation etc. The most
                      prominent example of these microgels are
                      poly(N-isopropylacrylamide)(PNIPAM) microgels. During the
                      last decades PNIPAM-based microgels were widely studied and
                      serve nowadays as model systems for the investigation of the
                      basic properties of microgels and the principles of
                      supported transport of active substances, e.g. drug
                      delivery. The responsive behaviour of the microgels is
                      governed by the polymer network structure, i.e. the
                      crosslinking of the polymer chains has a considerable
                      influence on the physico-chemical and mechanical properties
                      of the microgels. Especially the amount and the crosslinker
                      distribution within a single microgel have a high relevance
                      for the application as well as for the understanding of the
                      microgel nature. This thesis focuses on a detailed analysis
                      of microgels in solution and at interfaces with scattering
                      experiments. Neutron and X-ray scattering provide a unique
                      insight into the structure and dynamics of microgels,
                      especially at the interface with grazing incidence small
                      angle neutron scattering and neutron spin-echo spectroscopy
                      (GISANS and GINSES). New insights into the inner structure
                      and dynamics have been gained with improved experimental
                      conditions and data analysis. This thesis is divided into
                      the two main parts. In order to characterise the internal
                      structure and dynamics of the PNIPAM microgels with respect
                      to the crosslinker (N,N'-methylenebis(acrylamide), BIS)
                      distribution, sophisticated analysis of the internal
                      microgel (domain-like) structure and studies of its
                      influence on the polymer dynamics in nanometer and
                      nanosecond scales are presented in the first part of the
                      thesis. In the context of smart polymer coatings, the
                      influence of the confinement to the solid surface on the
                      internal architecture and the thermoresponsiveness of the
                      adsorbed PNIPAM microgels is investigated. It is shown that
                      in contrast to the atomic force microscopy, the
                      inhomogeneities of the polymer network of the adsorbed soft
                      microgels can be achieved with surface sensitive neutron
                      reflectometry and GISANS. The second part of the thesis aims
                      at the peculiarities of the scattering experiments of thin
                      polymer layers under grazing incidence conditions.
                      Simulation of the scattering signal within the Distorted
                      Wave Born Approximation is presented in order to improve the
                      analysis of the GINSES data and to simplify the initial
                      planing and performance of the grazing incidence
                      experiments. The main impacts of this thesis are (i) an
                      extended description of the complex internal structure,
                      dynamics and the thermoresponsiveness of the PNIPAM microgel
                      before and after adsorption onto a solid surface and (ii)
                      demonstration the advantages of the investigation of the
                      polymer systems at grazing incidence conditions in
                      combination with numerical simulations.},
      cin          = {JCNS-FRM-II / MLZ / JCNS-1},
      cid          = {I:(DE-Juel1)JCNS-FRM-II-20110218 / I:(DE-588b)4597118-3 /
                      I:(DE-Juel1)JCNS-1-20110106},
      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 / EXP:(DE-MLZ)KWS2-20140101 /
                      EXP:(DE-MLZ)KWS3-20140101 / EXP:(DE-MLZ)J-NSE-20140101 /
                      EXP:(DE-MLZ)MARIA-20140101},
      typ          = {PUB:(DE-HGF)11},
      urn          = { 	urn:nbn:de:tuda-tuprints-94781},
      urn          = {urn:nbn:de:tuda-tuprints-94781},
      doi          = {10.25534/TUPRINTS-00009478},
      url          = {https://juser.fz-juelich.de/record/872595},
}