@phdthesis{Koelsch2005,
  author    = {K{\"o}lsch, Patrick},
  title     = {Static and dynamic properties of soluble surfactants at the air/water interface},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus-5716},
  school      = {Universit{\"a}t Potsdam},
  year      = {2005},
  abstract  = {Amphiphilic molecules contain a hydrophilic headgroup and a hydrophobic tail. The headgroup is polar or ionic and likes water, the tail is typically an aliphatic chain that cannot be accommodated in a polar environment. The prevailing molecular asymmetry leads to a spontaneous adsorption of amphiphiles at the air/water or oil/water interfaces. As a result, the surface tension and the surface rheology is changed. Amphiphiles are important tools to deliberately modify the interfacial properties of liquid interfaces and enable new phenomena such as foams which cannot be formed in a pure liquid. In this thesis we investigate the static and dynamic properties of adsorption layers of soluble amphiphiles at the air/water interface, the so called Gibbs monolayers. The classical way for an investigation of these systems is based on a thermodynamic analysis of the equilibrium surface tension as a function of the bulk composition in the framework of Gibbs theory. However, thermodynamics does not provide any structural information and several recent publications challenge even fundamental text book concepts. The experimental investigation faces difficulties imposed by the low surface coverage and the presence of dissolved amphiphiles in the adjacent bulk phase. In this thesis we used a suite of techniques with the sensitivity to detect less than a monolayer of molecules at the air-water interface. Some of these techniques are extremely complex such as infrared visible sum frequency generation (IR-VIS SFG) spectroscopy or second harmonic generation (SHG). Others are traditional techniques, such as ellipsometry employed in new ways and pushed to new limits. Each technique probes selectively different parts of the interface and the combination provides a profound picture of the interfacial architecture. The first part of the thesis is dedicated to the distribution of ions at interfaces. Adsorption layers of ionic amphiphiles serve as model systems allowing to produce a defined surface charge. The charge of the monolayer is compensated by the counterions. As a result of a complex zoo of interactions there will be a defined distribution of ions at the interface, however, its experimental determination is a big scientific challenge. We could demonstrate that a combination of linear and nonlinear techniques gives direct insights in the prevailing ion distribution. Our investigations reveal specific ion effects which cannot be described by classical Poisson-Boltzmann mean field type theories. Adsorption layer and bulk phase are in thermodynamic equilibrium, however, it is important to stress that there is a constant molecular exchange between adsorbed and dissolved species. This exchange process is a key element for the understanding of some of the thermodynamic properties. An excellent way to study Gibbs monolayers is to follow the relaxation from a non-equilibrium to an equilibrium state. Upon compression amphiphiles must leave the adsorption layer and dissolve in the adjacent bulk phase. Upon expansion amphiphiles must adsorb at the interface to restore the equilibrium coverage. Obviously the frequency of the expansion and compression cycles must match the molecular exchange processes. At too low frequencies the equilibrium is maintained at all times. If the frequency is too fast the system behaves as a monolayer of insoluble surfactants. In this thesis we describe an unique variant of an oscillating bubble technique that measures precisely the real and imaginary part of the complex dilational modulus E in a frequency range up to 500 Hz. The extension of about two decades in the time domain in comparison to the conventional method of an oscillating drop is a tremendous achievement. The imaginary part of the complex dilational modulus E is a consequence of a dissipative process which is interpreted as an intrinsic surface dilational viscosity. The IR-VIS SFG spectra of the interfacial water provide a molecular interpretation of the underlying dissipative process.},
  subject      = {Nichtlineare Optik},
  language  = {en}
}