@phdthesis{Jensen2018, author = {Jensen, Anders Christian Solberg}, title = {Structure and dynamics of amorphous carbonates related to biomineralization}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-421691}, school = {Universit{\"a}t Potsdam}, pages = {138}, year = {2018}, abstract = {Amorphous calcium carbonate(ACC) is a wide spread biological material found in many organisms, such as sea Urchins and mollusks, where it serves as either a precursor phase for the crystalline biominerals or is stabilized and used in the amorphous state. As ACC readily crystallizes, stabilizers such as anions, cations or macromolecules are often present to avoid or delay unwanted crystallization. Furthermore, additives often control the properties of the materials to suit the specific function needed for the organism. E.g. cystoliths in leaves that scatter light to optimize energy uptake from the sun or calcite/aragonite crystals used in protective shells in mussels and gastropods. Lifetime of the amorphous phase is controlled by the kinetic stability against crystallization. This has often been linked to water which plays a role in the mobility of ions and hence the probability of forming crystalline nuclei to initiate crystallization. However, it is unclear how the water molecules are incorporated within the amorphous phase, either as liquid confined in pores, as structural water binding to the ions or as a mixture of both. It is also unclear how this is perturbed when additives are added, especially Mg2+, one the most common additives found in biogenic samples. Mg2+ are expected to have a strong influence on the water incorporated into ACC, given the high energy barrier to dehydration of magnesium ions compared to calcium ions in solution. During the last 10-15 years, there has been a large effort to understand the local environment of the ions/molecules and how this affects the properties of the amorphous phase. But only a few aspects of the structure have so far been well-described in literature. The reason for this is partly caused by the low stability of ACC if exposed to air, where it tends to crystallize within minutes and by the limited quantities of ACC produced in traditional synthesis routes. A further obstacle has been the difficulty in modeling the local structure based on experimental data. To solve the problem of stability and sample size, a few studies have used stabilizers such as Mg2+ or OH- and severely dehydrated samples so as to stabilize the amorphous state, allowing for combined neutron and x-ray analysis to be performed. However, so far, a clear description of the local environments of water present in the structure has not been reported. In this study we show that ACC can be synthesized without any stabilizing additives in quantities necessary for neutron measurements and that accurate models can be derived with the help of empirical-potential structural refinement. These analyses have shown that there is a wide range of local environments for all of the components in the system suggesting that the amorphous phase is highly inhomogeneous, without any phase separation between ions and water. We also showed that the water in ACC is mainly structural and that there is no confined or liquid-like water present in the system. Analysis of amorphous magnesium carbonate also showed that there is a large difference in the local structure of the two cations and that Mg2+ surprisingly interacts with significantly less water molecules then Ca2+ despite the higher dehydration energy. All in all, this shows that the role of water molecules as a structural component of ACC, with a strong binding to cat- and anions probably retard or prevents the crystallization of the amorphous phase.}, language = {en} } @phdthesis{Gidion2018, author = {Gidion, Gunnar}, title = {Akustische Resonatoren zur Analyse und Kontrolle von schwingungsf{\"a}higen Systemen am Beispiel von Streichinstrumenten und Dielektrischen Elastomeraktoren}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-411772}, school = {Universit{\"a}t Potsdam}, pages = {190}, year = {2018}, abstract = {Die Klangeigenschaften von Musikinstrumenten werden durch das Zusammenwirken der auf ihnen anregbaren akustischen Schwingungsmoden bestimmt, welche sich wiederum aus der geometrischen Struktur des Resonators in Kombination mit den verwendeten Materialien ergeben. In dieser Arbeit wurde das Schwingungsverhalten von Streichinstrumenten durch den Einsatz minimal-invasiver piezoelektrischer Polymerfilmsensoren untersucht. Die studierten Kopplungsph{\"a}nomene umfassen den sogenannten Wolfton und Schwingungstilger, die zu dessen Abschw{\"a}chung verwendet werden, sowie die gegenseitige Beeinflussung von Bogen und Instrument beim Spielvorgang. An Dielektrischen Elastomeraktormembranen wurde dagegen der Einfluss der elastischen Eigenschaften des Membranmaterials auf das akustische und elektromechanische Schwingungsverhalten gezeigt. Die Dissertation gliedert sich in drei Teile, deren wesentliche Ergebnisse im Folgenden zusammengefasst werden. In Teil I wurde die Funktionsweise eines abstimmbaren Schwingungstilgers zur D{\"a}mpfung von Wolft{\"o}nen auf Streichinstrumenten untersucht. Durch Abstimmung der Resonanzfrequenz des Schwingungstilgers auf die Wolftonfrequenz kann ein Teil der Saitenschwingungen absorbiert werden, so dass die zu starke Anregung der Korpusresonanz vermieden wird, die den Wolfton verursacht. Der Schwingungstilger besteht aus einem „Wolft{\"o}ter", einem Massest{\"u}ck, welches auf der Nachl{\"a}nge der betroffenen Saite (zwischen Steg und Saitenhalter) installiert wird. Hier wurde gezeigt, wie die Resonanzen dieses Schwingungstilgers von der Masse des Wolft{\"o}ters und von dessen Position auf der Nachl{\"a}nge abh{\"a}ngen. Aber auch die Geometrie des Wolft{\"o}ters stellte sich als ausschlaggebend heraus, insbesondere bei einem nicht-rotationssymmetrischen Wolft{\"o}ter: In diesem Fall entsteht - basierend auf den zu erwartenden nicht-harmonischen Moden einer massebelasteten Saite - eine zus{\"a}tzliche Mode, die von der Polarisationsrichtung der Saitenschwingung abh{\"a}ngt. Teil II der Dissertation befasst sich mit Elastomermembranen, die als Basis von Dielektrischen Elastomeraktoren dienen, und die wegen der Membranspannung auch akustische Resonanzen aufweisen. Die Ansprache von Elastomeraktoren h{\"a}ngt unter anderem von der Geschwindigkeit der elektrischen Anregung ab. Die damit zusammenh{\"a}ngenden viskoelastischen Eigenschaften der hier verwendeten Elastomere, Silikon und Acrylat, wurden einerseits in einer frequenzabh{\"a}ngigen dynamisch-mechanischen Analyse des Elastomers erfasst, andererseits auch optisch an vollst{\"a}ndigen Aktoren selbst gemessen. Die h{\"o}here Viskosit{\"a}t des Acrylats, das bei tieferen Frequenzen h{\"o}here Aktuationsdehnungen als das Silikon zeigt, f{\"u}hrt zu einer Verminderung der Dehnungen bei h{\"o}heren Frequenzen, so dass {\"u}ber etwa 40 Hertz mit Silikon gr{\"o}ßere Aktuationsdehnungen erreicht werden. Mit den untersuchten Aktoren konnte die Gitterkonstante weicher optischer Beugungsgitter kontrolliert werden, die als zus{\"a}tzlicher Film auf der Membran installiert wurden. {\"U}ber eine Messung der akustischen Resonanzfrequenz von Elastomermebranen aus Acrylat in 1Abh{\"a}ngigkeit von ihrer Vorstreckung konnte in Verbindung mit einer Modellierung des hyperelastischen Verhaltens des Elastomers (Ogden-Modell) der Schermodul bestimmt werden. Schließlich wird in Teil III die Untersuchung von Geigen und ihrer Streichanregung mit Hilfe minimal-invasiver piezoelektrischer Polymerfilme geschildert. Es konnten am Bogen und am Steg von Geigen - unter den beiden F{\"u}ßen des Stegs - jeweils zwei Filmsensoren installiert werden. Mit den beiden Sensoren am Steg wurden Frequenzg{\"a}nge von Geigen gemessen, welche eine Bestimmung der frequenzabh{\"a}ngigen Stegbewegung erlaubten. Diese Methode erm{\"o}glicht damit auch eine umfassende Charakterisierung der Signaturmoden in Bezug auf die Stegdynamik. Die Ergebnisse der komplement{\"a}ren Methoden von Impulsanregung und nat{\"u}rlichem Spielen der Geigen konnten dank der Sensoren verglichen werden. F{\"u}r die Nutzung der Sensoren am Bogen - insbesondere f{\"u}r eine Messung des Bogendrucks - wurde eine Kalibrierung des Bogen-Sensor-Systems mit Hilfe einer Materialpr{\"u}fmaschine durchgef{\"u}hrt. Bei einer Messung w{\"a}hrend des nat{\"u}rlichen Spielens wurde mit den Sensoren am Bogen einerseits die {\"U}bertragung der Saitenschwingung auf den Bogen festgestellt. Dabei konnten außerdem longitudinale Bogenhaarresonanzen identifiziert werden, die von der Position der Saite auf dem Bogen abh{\"a}ngen. Aus der Analyse dieses Ph{\"a}nomens konnte die longitudinale Wellengeschwindigkeit der Bogenhaare bestimmt werden, die eine wichtige Gr{\"o}ße f{\"u}r die Kopplung zwischen Saite und Bogen ist. Mit Hilfe des Systems aus Sensoren an Bogen und Steg werden auf Grundlage der vorliegenden Arbeit Studien an Streichinstrumenten vorgeschlagen, in denen die Bespielbarkeit der Instrumente zu den jeweils angeregten Steg- und Bogenschwingungen in Beziehung gesetzt werden kann. Damit k{\"o}nnte nicht zuletzt auch die bisher nicht vollst{\"a}ndig gekl{\"a}rte Rolle des Bogens f{\"u}r Klang und Bespielbarkeit besser beurteilt werden}, language = {de} } @phdthesis{Pavlenko2016, author = {Pavlenko, Elena}, title = {Hybrid nanolayer architectures for ultrafast acousto-plasmonics in soft matter}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-99544}, school = {Universit{\"a}t Potsdam}, pages = {85}, year = {2016}, abstract = {The goal of the presented work is to explore the interaction between gold nanorods (GNRs) and hyper-sound waves. For the generation of the hyper-sound I have used Azobenzene-containing polymer transducers. Multilayer polymer structures with well-defined thicknesses and smooth interfaces were built via layer-by-layer deposition. Anionic polyelectrolytes with Azobenzene side groups (PAzo) were alternated with cationic polymer PAH, for the creation of transducer films. PSS/PAH multilayer were built for spacer layers, which do not absorb in the visible light range. The properties of the PAzo/PAH film as a transducer are carefully characterized by static and transient optical spectroscopy. The optical and mechanical properties of the transducer are studied on the picosecond time scale. In particular the relative change of the refractive index of the photo-excited and expanded PAH/PAzo is Δn/n = - 2.6*10-4. Calibration of the generated strain is performed by ultrafast X-ray diffraction calibrated the strain in a Mica substrate, into which the hyper-sound is transduced. By simulating the X-ray data with a linear-chain-model the strain in the transducer under the excitation is derived to be Δd/d ~ 5*10-4. Additional to the investigation of the properties of the transducer itself, I have performed a series of experiments to study the penetration of the generated strain into various adjacent materials. By depositing the PAzo/PAH film onto a PAH/PSS structure with gold nanorods incorporated in it, I have shown that nanoscale impurities can be detected via the scattering of hyper-sound. Prior to the investigation of complex structures containing GNRs and the transducer, I have performed several sets of experiments on GNRs deposited on a small buffer of PSS/PAH. The static and transient response of GNRs is investigated for different fluence of the pump beam and for different dielectric environments (GNRs covered by PSS/PAH). A systematic analysis of sample architectures is performed in order to construct a sample with the desired effect of GNRs responding to the hyper-sound strain wave. The observed shift of a feature related to the longitudinal plasmon resonance in the transient reflection spectra is interpreted as the event of GNRs sensing the strain wave. We argue that the shift of the longitudinal plasmon resonance is caused by the viscoelastic deformation of the polymer around the nanoparticle. The deformation is induced by the out of plane difference in strain in the area directly under a particle and next to it. Simulations based on the linear chain model support this assumption. Experimentally this assumption is proven by investigating the same structure, with GNRs embedded in a PSS/PAH polymer layer. The response of GNRs to the hyper-sound wave is also observed for the sample structure with GNRs embedded in PAzo/PAH films. The response of GNRs in this case is explained to be driven by the change of the refractive index of PAzo during the strain propagation.}, language = {en} } @phdthesis{Bojahr2016, author = {Bojahr, Andre}, title = {Hypersound interaction studied by time-resolved inelastic light and x-ray scattering}, url = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-93860}, school = {Universit{\"a}t Potsdam}, pages = {xxiii, 201}, year = {2016}, abstract = {This publications-based thesis summarizes my contribution to the scientific field of ultrafast structural dynamics. It consists of 16 publications, about the generation, detection and coupling of coherent gigahertz longitudinal acoustic phonons, also called hypersonic waves. To generate such high frequency phonons, femtosecond near infrared laser pulses were used to heat nanostructures composed of perovskite oxides on an ultrashort timescale. As a consequence the heated regions of such a nanostructure expand and a high frequency acoustic phonon pulse is generated. To detect such coherent acoustic sound pulses I use ultrafast variants of optical Brillouin and x-ray scattering. Here an incident optical or x-ray photon is scattered by the excited sound wave in the sample. The scattered light intensity measures the occupation of the phonon modes. The central part of this work is the investigation of coherent high amplitude phonon wave packets which can behave nonlinearly, quite similar to shallow water waves which show a steepening of wave fronts or solitons well known as tsunamis. Due to the high amplitude of the acoustic wave packets in the solid, the acoustic properties can change significantly in the vicinity of the sound pulse. This may lead to a shape change of the pulse. I have observed by time-resolved Brillouin scattering, that a single cycle hypersound pulse shows a wavefront steepening. I excited hypersound pulses with strain amplitudes until 1\% which I have calibrated by ultrafast x-ray diffraction (UXRD). On the basis of this first experiment we developed the idea of the nonlinear mixing of narrowband phonon wave packets which we call "nonlinear phononics" in analogy with the nonlinear optics, which summarizes a kaleidoscope of surprising optical phenomena showing up at very high electric fields. Such phenomena are for instance Second Harmonic Generation, four-wave-mixing or solitons. But in case of excited coherent phonons the wave packets have usually very broad spectra which make it nearly impossible to look at elementary scattering processes between phonons with certain momentum and energy. For that purpose I tested different techniques to excite narrowband phonon wave packets which mainly consist of phonons with a certain momentum and frequency. To this end epitaxially grown metal films on a dielectric substrate were excited with a train of laser pulses. These excitation pulses drive the metal film to oscillate with the frequency given by their inverse temporal displacement and send a hypersonic wave of this frequency into the substrate. The monochromaticity of these wave packets was proven by ultrafast optical Brillouin and x-ray scattering. Using the excitation of such narrowband phonon wave packets I was able to observe the Second Harmonic Generation (SHG) of coherent phonons as a first example of nonlinear wave mixing of nanometric phonon wave packets.}, language = {en} }