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- Institut für Integrierte Naturwissenschaften, Abt. Physik (4) (remove)
The three biodegradable polymers polylactic acid (PLA), polyhydroxybutyrate (PHB) and polybutylene adipate terephthalate (PBAT) were coated with hydrogenated amorphous carbon layers (a-C:H) in the context of this thesis. A direct alignment of the sample surface to the source was chosen, resulting in the deposition of a robust, r-type a-C:H. At the same time, a partly covered silicon wafer was placed together with the polymers in the coating chamber and was coated. Silicon is a hard material and serves as a reference for the applied layers. Due to the hardness of the material, no mixed phase occurs between the substrate and the applied layer (no interlayer formation). In addition, the thickness of the applied layer can be estimated with the help of the silicon sample.
The deposition of the layer was realized by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). For the coating the samples were pre-treated with an oxygen plasma. Acetylene was used as precursor gas for the plasma coating. Coatings with increasing thickness in 50 nm steps from 0-500 nm were realised.
The surface analysis was performed using several techniques: The morphology and layer stability were analyzed with scanning electron microscopy (SEM) measurements. The wettability was determined by contact angle technique. In addition, the contact angles provide macroscopic information about the bond types of the carbon atoms present on the surface. For microscopic analysis of the chemical composition of the sample and layer surfaces, diffuse reflectance Fourier transform infrared spectroscopy (DRIFT) as well as synchrotron based X-ray photon spectroscopy (XPS) and near edge X-ray absorption fine structure spectroscopy (NEXAFS) were used.
All coated polymers showed several cases of layer failure due to internal stress in the layers. However, these were at different layer thicknesses, so there was a substrate effect. In addition, it is visible in the SEM images that the coatings of PLA and PHB can cause the applied layer to wave, the so-called cord buckling. This does not occur with polymer PBAT, which indicates a possible better bonding of the layer to the polymer. The chemical analyses of the layer surfaces show for each material a layer thickness dependent ratio of sp² to sp³ bonds of carbon, which alternately dominate the layer. In all polymers, the sp³ bond initially dominates, but the sp² to sp³ ratio changes at different intervals. Although the polymers were coated in the same plasma, i.e. the respective layer thicknesses (50 nm, 100 nm, ...) were applied in the same plasma process, the respective systems differed considerably from each other. A substrate effect is therefore demonstrably present. In addition, it was found that a change in the dominant bond from sp³ to sp² is an indication ofan upcoming layer failure of the a-C:H layer deposited on the polymer. In the case of PLA, this occurs immediately with change to sp² as the dominant bond; in the case of PHB and PBAT, this occurs with different delay to increased layer thicknesses (at PHB 100 nm, at PBAT approx. 200 nm.
Overall, this thesis shows that there is a substrate effect in the coating of the biodegradable polymers PLA, PHB and PBAT, since despite the same coating there is a different chemical composition of the surface at the respective layer thicknesses. In addition, a layer failure can be predicted by analyzing the existing bond.
Spektroskopie zweiatomiger Moleküle bei Einstrahlung ultrakurzer Laserpulse und ihre Anwendung
(2020)
Even with moderate pulse energies and average powers, ultrashort pulse lasers achieve very high peak powers, whose effect on matter is fundamentally different from that of other light sources. The high electric field strength does not only cause an increase of optically nonlinear effects such as second harmonic generation, but it is also responsible for the “cold“ ablation, which leads to colder plasmas. An investigation of these two circumstances in terms of a simplification of the pulse duration measurement and an improvement of the molecular formation in cooling plasmas is the topic of this work. In this context, it is shown that when selecting suitable process parameters, especially when purposefully defocusing the medium, the use of ultrashort pulse lasers improves the spectroscopy of several emitting molecules such as aluminum oxide. Therefore, their detection is possible even without the time-resolving spectrometers required in literature. In addition, ultrashort pulses enable spatially resolved crystallization of zinc oxide on zinc surfaces prepared by basic means. The resulting wurtzites usually align their c-axis approximately perpendicular to the underlying surface and can be used to generate scattered second harmonics. Fiber-based femtosecond lasers with pulse energies in the microjoule range, pulse durations of a few 100fs and very low maintenance requirements have proven to be a powerful instrument for these purposes. For measuring the pulse duration, the high pulse energy also enables the usage of frequency doublers with much lower conversion eciencies. Despite nonuniform crystal axes, the scattering second harmonic generating aluminum nitride has proven to be particularly suitable for optical autocorrelation. Compared to the commonly used monocrystalline beta-barium borate, the sintered aluminum nitride ceramic plates facilitate the adjustment, simplify the material handling and reduce the expenses by two to three orders of magnitude. The method developed in this work is therefore also suitable for confirmatory measurements of the pulse duration during the production process of such systems – especially when the occurring pulse energies are high or rather too high for beta-barium borate.
This dissertation presents the application of the molecular LIBS method, a novelapproach of Laser-Induced Breakdown Spectroscopy (LIBS), to optimize the detection of pitting chlorides in concrete structures, which are e.g. contaminated bydeicing salt in winter. Potentiometric titration as the standard method for chloride determination in building material analysis is costly and time-consuming. Ithas the decisive disadvantage that the determination of chloride concentrationis based on the total mass of the concrete and not on the cement content asrequired by the European standard EN 206. The imaging capabilities of LIBS forphase separation of the concrete meet this requirement. LIBS was already usedby BAM in 1998 in building material analysis, but the detection of chlorides withLIBS requires expensive helium purging and spectrometers outside the visiblespectral range to detect emissions of atomic chlorine. The approach of molecular LIBS is to quantify the emission of chloride-containing molecular radicalsformed during the cooling phase of the laser-induced plasma. The advantagescompared to conventional LIBS method are the emission in the visible spectralrange and the applicability without noble gas purging. In this thesis the influenceof the experimental components on the time behaviour of the relevant molecularemission bands is investigated, signal deviations due to plasma fluctuations aresignificantly reduced and for plasma analysis the molecular formation is simulated on atomistic scales and compared with standard methods. In simultaneousmeasurements, atomic and molecular Cl emission are directly compared and the quantification is optimized by data combination. Molecular LIBS will be extended to a quantifying and imaging method that can detect chlorides withoutnoble gas purging.
The analysis of three-dimensional and complex motion sequences
of human gait and therefore the most important question
of kenesiology ”why are we falling?” is the essence of this
paper. The gerontology and its science of movement is currently
limited to simple and one-dimensional methods and models. An
extensive literature research shows the latest state of research of
the three common methods to determine the stability of human
gait. To assess the margin of stability, local stability and orbital
stability it is shown, how those methods are applicable to evaluate
the subject’s ability to recover from any disturbences of
the subject’s gait. Based on this assessment and the method’s
advantages and disadvantages a new method will be derived
that allows spatial analysis of dynamic instability of linear and
non-linear human gait. A motion capture system and the timed
up and go test serve as a basis for this new method and will be
explained. A numerical approximation to optimise the number
of markers within a marker-set of a motion capture analysis
and its maximum correlation with the full-body-marker-set will
be given. This simplification is very helpful for further clinical
or scientific research. To validate the new method a trial
with subjects will be shown and discussed. New appreciable
variables and snapshots of specific situations during the gait
offer new and different interpretations of the human gait. The
new method is the most applicable and appropriate assessment
of human gait and the individual development of the human
gait while aging, as well as to detect and prevent falling and
associated injuries. Especially directional change of a non-linear
gait become assessable with the new method.