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Passive plant actuators have fascinated many researchers in the field of botany and structural biology since at least one century. Up to date, the most investigated tissue types in plant and artificial passive actuators are fibre-reinforced composites (and multilayered assemblies thereof) where stiff, almost inextensible cellulose microfibrils direct the otherwise isotropic swelling of a matrix. In addition, Nature provides examples of actuating systems based on lignified, low-swelling, cellular solids enclosing a high-swelling cellulosic phase. This is the case of the Delosperma nakurense seed capsule, in which a specialized tissue promotes the reversible opening of the capsule upon wetting. This tissue has a diamond-shaped honeycomb microstructure characterized by high geometrical anisotropy: when the cellulosic phase swells inside this constraining structure, the tissue deforms up to four times in one principal direction while maintaining its original dimension in the other. Inspired by the example of the Delosoperma nakurense, in this thesis we analyze the role of architecture of 2D cellular solids as models for natural hygromorphs. To start off, we consider a simple fluid pressure acting in the cells and try to assess the influence of several architectural parameters onto their mechanical actuation. Since internal pressurization is a configurational type of load (that is the load direction is not fixed but it “follows” the structure as it deforms) it will result in the cellular structure acquiring a “spontaneous” shape. This shape is independent of the load but just depends on the architectural characteristics of the cells making up the structure itself. Whereas regular convex tiled cellular solids (such as hexagonal, triangular or square lattices) deform isotropically upon pressurization, we show through finite element simulations that by introducing anisotropic and non-convex, reentrant tiling large expansions can be achieved in each individual cell. The influence of geometrical anisotropy onto the expansion behaviour of a diamond shaped honeycomb is assessed by FEM calculations and a Born lattice approximation. We found that anisotropic expansions (eigenstrains) comparable to those observed in the keels tissue of the Delosoperma nakurense are possible. In particular these depend on the relative contributions of bending and stretching of the beams building up the honeycomb. Moreover, by varying the walls’ Young modulus E and internal pressure p we found that both the eigenstrains and 2D elastic moduli scale with the ratio p/E. Therefore the potential of these pressurized structures as soft actuators is outlined. This approach was extended by considering several 2D cellular solids based on two types of non-convex cells. Each honeycomb is build as a lattice made of only one non-convex cell. Compared to usual honeycombs, these lattices have kinked walls between neighbouring cells which offers a hidden length scale allowing large directed deformations. By comparing the area expansion in all lattices, we were able to show that less convex cells are prone to achieve larger area expansions, but the direction in which the material expands is variable and depends on the local cell’s connectivity. This has repercussions both at the macroscopic (lattice level) and microscopic (cells level) scales. At the macroscopic scale, these non-convex lattices can experience large anisotropic (similarly to the diamond shaped honeycomb) or perfectly isotropic principal expansions, large shearing deformations or a mixed behaviour. Moreover, lattices that at the macroscopic scale expand similarly can show quite different microscopic deformation patterns that include zig-zag motions and radical changes of the initial cell shape. Depending on the lattice architecture, the microscopic deformations of the individual cells can be equal or not, so that they can build up or mutually compensate and hence give rise to the aforementioned variety of macroscopic behaviours. Interestingly, simple geometrical arguments involving the undeformed cell shape and its local connectivity enable to predict the results of the FE simulations. Motivated by the results of the simulations, we also created experimental 3D printed models of such actuating structures. When swollen, the models undergo substantial deformation with deformation patterns qualitatively following those predicted by the simulations. This work highlights how the internal architecture of a swellable cellular solid can lead to complex shape changes which may be useful in the fields of soft robotics or morphing structures.
LCST-type synthetic thermoresponsive polymers can reversibly respond to certain stimuli in aqueous media with a massive change of their physical state. When fluorophores, that are sensitive to such changes, are incorporated into the polymeric structure, the response can be translated into a fluorescence signal. Based on this idea, this thesis presents sensing schemes which transduce the stimuli-induced variations in the solubility of polymer chains with covalently-bound fluorophores into a well-detectable fluorescence output. Benefiting from the principles of different photophysical phenomena, i.e. of fluorescence resonance energy transfer and solvatochromism, such fluorescent copolymers enabled monitoring of stimuli such as the solution temperature and ionic strength, but also of association/disassociation mechanisms with other macromolecules or of biochemical binding events through remarkable changes in their fluorescence properties. For instance, an aqueous ratiometric dual sensor for temperature and salts was developed, relying on the delicate supramolecular assembly of a thermoresponsive copolymer with a thiophene-based conjugated polyelectrolyte. Alternatively, by taking advantage of the sensitivity of solvatochromic fluorophores, an increase in solution temperature or the presence of analytes was signaled as an enhancement of the fluorescence intensity. A simultaneous use of the sensitivity of chains towards the temperature and a specific antibody allowed monitoring of more complex phenomena such as competitive binding of analytes. The use of different thermoresponsive polymers, namely poly(N-isopropylacrylamide) and poly(meth)acrylates bearing oligo(ethylene glycol) side chains, revealed that the responsive polymers differed widely in their ability to perform a particular sensing function. In order to address questions regarding the impact of the chemical structure of the host polymer on the sensing performance, the macromolecular assembly behavior below and above the phase transition temperature was evaluated by a combination of fluorescence and light scattering methods. It was found that although the temperature-triggered changes in the macroscopic absorption characteristics were similar for these polymers, properties such as the degree of hydration or the extent of interchain aggregations differed substantially. Therefore, in addition to the demonstration of strategies for fluorescence-based sensing with thermoresponsive polymers, this work highlights the role of the chemical structure of the two popular thermoresponsive polymers on the fluorescence response. The results are fundamentally important for the rational choice of polymeric materials for a specific sensing strategy.
Within the course of this thesis, I have investigated the complex interplay between electron and lattice dynamics in nanostructures of perovskite oxides. Femtosecond hard X-ray pulses were utilized to probe the evolution of atomic rearrangement directly, which is driven by ultrafast optical excitation of electrons. The physics of complex materials with a large number of degrees of freedom can be interpreted once the exact fingerprint of ultrafast lattice dynamics in time-resolved X-ray diffraction experiments for a simple model system is well known. The motion of atoms in a crystal can be probed directly and in real-time by femtosecond pulses of hard X-ray radiation in a pump-probe scheme. In order to provide such ultrashort X-ray pulses, I have built up a laser-driven plasma X-ray source. The setup was extended by a stable goniometer, a two-dimensional X-ray detector and a cryogen-free cryostat. The data acquisition routines of the diffractometer for these ultrafast X-ray diffraction experiments were further improved in terms of signal-to-noise ratio and angular resolution. The implementation of a high-speed reciprocal-space mapping technique allowed for a two-dimensional structural analysis with femtosecond temporal resolution. I have studied the ultrafast lattice dynamics, namely the excitation and propagation of coherent phonons, in photoexcited thin films and superlattice structures of the metallic perovskite SrRuO3. Due to the quasi-instantaneous coupling of the lattice to the optically excited electrons in this material a spatially and temporally well-defined thermal stress profile is generated in SrRuO3. This enables understanding the effect of the resulting coherent lattice dynamics in time-resolved X-ray diffraction data in great detail, e.g. the appearance of a transient Bragg peak splitting in both thin films and superlattice structures of SrRuO3. In addition, a comprehensive simulation toolbox to calculate the ultrafast lattice dynamics and the resulting X-ray diffraction response in photoexcited one-dimensional crystalline structures was developed in this thesis work. With the powerful experimental and theoretical framework at hand, I have studied the excitation and propagation of coherent phonons in more complex material systems. In particular, I have revealed strongly localized charge carriers after above-bandgap femtosecond photoexcitation of the prototypical multiferroic BiFeO3, which are the origin of a quasi-instantaneous and spatially inhomogeneous stress that drives coherent phonons in a thin film of the multiferroic. In a structurally imperfect thin film of the ferroelectric Pb(Zr0.2Ti0.8)O3, the ultrafast reciprocal-space mapping technique was applied to follow a purely strain-induced change of mosaicity on a picosecond time scale. These results point to a strong coupling of in- and out-of-plane atomic motion exclusively mediated by structural defects.