@phdthesis{Knauf2020,
  author    = {Knauf, Jan},
  title     = {Synthesis of highly fluorinated precursors and their deposition conditions for self-assembled monolayers with defined small-scale surface structures as templates for the manipulation of wetting behavior},
  doi       = {10.25932/publishup-47380},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-473804},
  school      = {Universit{\"a}t Potsdam},
  pages     = {X, 204},
  year      = {2020},
  abstract  = {"How Wenzel and Cassie were wrong" - this was the eye-catching title of an article published by Lichao Gao and Thomas McCarthy in 2007, in which fundamental interpretations of wetting behavior were put into question. The authors initiated a discussion on a subject, which had been generally accepted a long time ago and they showed that wetting phenomena were not as fully understood as imagined. Similarly, this thesis tries to put a focus on certain aspects of liquid wetting, which so far have been widely neglected in terms of interpretation and experimental proof. While the effect of surface roughness on the macroscopically observed wetting behavior is commonly and reliably interpreted according to the well-known models of Wenzel and Cassie/Baxter, the size-scale of the structures responsible for the surface's rough texture has not been of further interest. Analogously, the limits of these models have not been described and exploited. Thus, the question arises, what will happen when the size of surface structures is reduced to the size of the contacting liquid molecules itself? Are common methods still valid or can deviations from macroscopic behavior be observed? This thesis wants to create a starting point regarding these questions. In order to investigate the effect of smallest-scale surface structures on liquid wetting, a suitable model system is developed by means of self-assembled monolayer (SAM) formation from (fluoro)organic thiols of differing lengths of the alkyl chain. Surface topographies are created which rely on size differences of several {\AA}ngstr{\"o}ms and exhibit surprising wetting behavior depending on the choice of the individual precursor system. Thus, contact angles are experimentally detected, which deviate considerably from theoretical calculations based on Wenzel and Cassie/Baxter models and confirm that sub-nm surface topographies affect wetting. Moreover, experimentally determined wetting properties are found to correlate well to an assumed scale-dependent surface tension of the contacting liquid. This behavior has already been described for scattering experiments taking into account capillary waves on the liquid surface induced by temperature and had been predicted earlier by theoretical calculations. However, the investigation of model surfaces requires the provision of suitable precursor molecules, which are not commercially available and opens up a door to the exotic chemistry of fluoro-organic materials. During the course of this work, the synthesis of long-chain precursors is examined with a particular focus put on oligomerically pure semi-fluorinated n-alkyl thiols and n-alkyl trichlorosilanes. For this, general protocols for the syntheses of the desired compounds are developed and product mixtures are assayed to be separated into fractions of individual chain lengths by fluorous-phase high-performance liquid chromatography (F-HPLC). The transition from model systems to technically more relevant surfaces and applications is initiated through the deposition of SAMs from long-chain fluorinated n-alkyl trichlorosilanes. Depositions are accomplished by a vapor-phase deposition process conducted on a pilot-scale set-up, which enables the exact control of relevant process parameters. Thus, the influence of varying deposition conditions on the properties of the final coating is examined and analyzed for the most important parameters. The strongest effect is observed for the partial pressure of reactive water vapor, which directly controls the extent of precursor hydrolysis during the deposition process. Experimental results propose that the formation of ordered monolayers rely on the amount of hydrolyzed silanol species present in the deposition system irrespective of the exact grade of hydrolysis. However, at increased amounts of species which are able to form cross-linked molecules due to condensation reactions, films deteriorate in quality. This effect is assumed to be caused by the introduction of defects within the film and the adsorption of cross linked agglomerates. Deposition conditions are also investigated for chain extended precursor species and reveal distinct differences caused by chain elongation.},
  language  = {en}
}
@phdthesis{Lazar2005,
  author    = {Lazar, Paul},
  title     = {Transport mechanisms and wetting dynamics in molecularly thin films of long-chain alkanes at solid/vapour interface : relation to the solid-liquid phase transition},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-5275},
  school      = {Universit{\"a}t Potsdam},
  year      = {2005},
  abstract  = {Wetting and phase transitions play a very important role our daily life. Molecularly thin films of long-chain alkanes at solid/vapour interfaces (e.g. C30H62 on silicon wafers) are very good model systems for studying the relation between wetting behaviour and (bulk) phase transitions. Immediately above the bulk melting temperature the alkanes wet partially the surface (drops). In this temperature range the substrate surface is covered with a molecularly thin ordered, solid-like alkane film ("surface freezing"). Thus, the alkane melt wets its own solid only partially which is a quite rare phenomenon in nature. The thesis treats about how the alkane melt wets its own solid surface above and below the bulk melting temperature and about the corresponding melting and solidification processes. Liquid alkane drops can be undercooled to few degrees below the bulk melting temperature without immediate solidification. This undercooling behaviour is quite frequent and theoretical quite well understood. In some cases, slightly undercooled drops start to build two-dimensional solid terraces without bulk solidification. The terraces grow radially from the liquid drops on the substrate surface. They consist of few molecular layers with the thickness multiple of all-trans length of the molecule. By analyzing the terrace growth process one can find that, both below and above the melting point, the entire substrate surface is covered with a thin film of mobile alkane molecules. The presence of this film explains how the solid terrace growth is feeded: the alkane molecules flow through it from the undercooled drops to the periphery of the terrace. The study shows for the first time the coexistence of a molecularly thin film ("precursor") with partially wetting bulk phase. The formation and growth of the terraces is observed only in a small temperature interval in which the 2D nucleation of terraces is more likely than the bulk solidification. The nucleation mechanisms for 2D solidification are also analyzed in this work. More surprising is the terrace behaviour above bulk the melting temperature. The terraces can be slightly overheated before they melt. The melting does not occur all over the surface as a single event; instead small drops form at the terrace edge. Subsequently these drops move on the surface "eating" the solid terraces on their way. By this they grow in size leaving behind paths from were the material was collected. Both overheating and droplet movement can be explained by the fact that the alkane melt wets only partially its own solid. For the first time, these results explicitly confirm the supposed connection between the absence of overheating in solid and "surface melting": the solids usually start to melt without an energetic barrier from the surface at temperatures below the bulk melting point. Accordingly, the surface freezing of alkanes give rise of an energetic barrier which leads to overheating.},
  subject      = {Benetzung},
  language  = {en}
}
@phdthesis{Heinig2003,
  author    = {Heinig, Peter},
  title     = {The geometry of interacting liquid domains in Langmuir monolayers},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-0000814},
  school      = {Universit{\"a}t Potsdam},
  year      = {2003},
  abstract  = {Es werden die Strukturbildung und Benetzung zweidimensionaler (2D) Phasen von Langmuir-Monolagen im lokalen thermodynamischen Gleichgewicht untersucht. Eine Langmuir-Monolage ist ein isoliertes 2D System von Surfaktanten an der Wasser/Luft-Grenzfl{\"a}che, in dem kristalline, fl{\"u}ssigkristalline, fl{\"u}ssige oder gasf{\"o}rmige Phasen auftreten, die sich in Positionsordnung und/oder Orientierungsordnung unterscheiden. Permanente elektrische Dipolmomente der Surfaktanten f{\"u}hren zu einer langreichweitigen repulsiven Selbstwechselwirkung der Monolage und zur Bildung mesoskopischer Strukturen. Es wird ein Wechselwirkungsmodell verwendet, das die Strukturbildung als Wechselspiel kurzreichweitiger Anziehung (nackte Linienspannung) und langreichweitiger Abstoßung (Oberfl{\"a}chenpotential) auf einer Skala Delta beschreibt. Physikalisch trennt Delta die beiden L{\"a}ngenskalen der lang- und kurzreichweitigen Wechselwirkung. In dieser Arbeit werden die thermodynamischen Stabilit{\"a}tsbedingungen f{\"u}r die Form einer Phasengrenzlinie (Young-Laplace-Gleichung) und Dreiphasenkontaktpunkt (Young-Bedingung) hergeleitet und zur Beschreibung experimenteller Daten genutzt: Die Linienspannung benetzender 2D Tropfen wird mit Hilfe h{\"a}ngender-Tropfen-Tensiometrie gemessen. Die Blasenform und -gr{\"o}ße von 2D Sch{\"a}umen wird theoretisch modelliert und mit experimentellen 2D Sch{\"a}umen verglichen. Kontaktwinkel werden durch die Anpassung von experimentellen Tropfen mit numerischen L{\"o}sungen der Young-Laplace-Gleichung auf Mikrometerskalen gemessen. Das Skalenverhalten des Kontaktwinkels erm{\"o}glicht die Bestimmung einer unteren Schranke von Delta. Weiterhin wird diskutiert, inwieweit das Schalten von 2D Benetzungsmodi in biologischen Membranen zur Steuerung der Reaktionskinetik ein Rolle spielen k{\"o}nnte. Hierzu werden Experimente aus unserer Gruppe, die in einer Langmuir-Monolage durchgef{\"u}hrt wurden, herangezogen. Abschließend wird die scheinbare Verletzung der Gibbs\′schen Phasenregel in Langmuir-Monolagen (nicht-horizontales Plateau der Oberfl{\"a}chendruck-Fl{\"a}che Isotherme, ausgedehntes Dreiphasengebiet in Einkomponentensystemen) quantitativ untersucht. Eine Verschmutzung der verwendeten Substanzen ist demnach die wahscheinlichste Erkl{\"a}rung, w{\"a}hrend Finite-Size-Effekte oder der Einfluss der langreichweitigen Elektrostatik die Gr{\"o}ßenordnung des Effektes nicht beschreiben k{\"o}nnen.},
  language  = {en}
}