@phdthesis{Kurpiers2019,
  author    = {Kurpiers, Jona},
  title     = {Probing the pathways of free charge generation and recombination in organic solar cells},
  doi       = {10.25932/publishup-42909},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-429099},
  school      = {Universit{\"a}t Potsdam},
  pages     = {VI, 128, xxi},
  year      = {2019},
  abstract  = {Organic semiconductors are a promising class of materials. Their special properties are the particularly good absorption, low weight and easy processing into thin films. Therefore, intense research has been devoted to the realization of thin film organic solar cells (OPVs). Because of the low dielectric constant of organic semiconductors, primary excitations (excitons) are strongly bound and a type II heterojunction needs to be introduced to split these excitations into free charges. Therefore, most organic solar cells consist of at least an electron donor and electron acceptor material. For such donor acceptor systems mainly three states are relevant; the photoexcited exciton on the donor or acceptor material, the charge transfer state at the donor-acceptor interface and the charge separated state of a free electron and hole. The interplay between these states significantly determines the efficiency of organic solar cells. Due to the high absorption and the low charge carrier mobilities, the active layers are usually thin but also, exciton dissociation and free charge formation proceeds rapidely, which makes the study of carrier dynamics highly challenging. Therefore, the focus of this work was first to install new experimental setups for the investigation of the charge carrier dynamics in complete devices with superior sensitivity and time resolution and, second, to apply these methods to prototypical photovoltaic materials to address specific questions in the field of organic and hybrid photovoltaics. Regarding the first goal, a new setup combining transient absorption spectroscopy (TAS) and time delayed collection field (TDCF) was designed and installed in Potsdam. An important part of this work concerned the improvement of the electronic components with respect to time resolution and sensitivity. To this end, a highly sensitive amplifier for driving and detecting the device response in TDCF was developed. This system was then applied to selected organic and hybrid model systems with a particular focus on the understanding of the loss mechanisms that limit the fill factor and short circuit current of organic solar cells. The first model system was a hybrid photovoltaic material comprising inorganic quantum dots decorated with organic ligands. Measurements with TDCF revealed fast free carrier recombination, in part assisted by traps, while bias-assisted charge extraction measurements showed high mobility. The measured parameters then served as input for a successful description of the device performance with an analytical model. With a further improvement of the instrumentation, a second topic was the detailed analysis of non-geminate recombination in a disordered polymer:fullerene blend where an important question was the effect of disorder on the carrier dynamics. The measurements revealed that early time highly mobile charges undergo fast non-geminate recombination at the contacts, causing an apparent field dependence of free charge generation in TDCF experiments if not conducted properly. On the other hand, recombination the later time scale was determined by dispersive recombination in the bulk of the active layer, showing the characteristics of carrier dynamics in an exponential density of state distribution. Importantly, the comparison with steady state recombination data suggested a very weak impact of non-thermalized carriers on the recombination properties of the solar cells under application relevant illumination conditions. Finally, temperature and field dependent studies of free charge generation were performed on three donor-acceptor combinations, with two donor polymers of the same material family blended with two different fullerene acceptor molecules. These particular material combinations were chosen to analyze the influence of the energetic and morphology of the blend on the efficiency of charge generation. To this end, activation energies for photocurrent generation were accurately determined for a wide range of excitation energies. The results prove that the formation of free charge is via thermalized charge transfer states and does not involve hot exciton splitting. Surprisingly, activation energies were of the order of thermal energy at room temperature. This led to the important conclusion that organic solar cells perform well not because of predominate high energy pathways but because the thermalized CT states are weakly bound. In addition, a model is introduced to interconnect the dissociation efficiency of the charge transfer state with its recombination observable with photoluminescence, which rules out a previously proposed two-pool model for free charge formation and recombination. Finally, based on the results, proposals for the further development of organic solar cells are formulated.},
  language  = {en}
}
@phdthesis{Kerutt2019,
  author    = {Kerutt, Josephine Victoria},
  title     = {The high-redshift voyage of Lyman alpha and Lyman continuum emission as told by MUSE},
  doi       = {10.25932/publishup-47881},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-478816},
  school      = {Universit{\"a}t Potsdam},
  pages     = {152},
  year      = {2019},
  abstract  = {Most of the matter in the universe consists of hydrogen. The hydrogen in the intergalactic medium (IGM), the matter between the galaxies, underwent a change of its ionisation state at the epoch of reionisation, at a redshift roughly between 6>z>10, or ~10^8 years after the Big Bang. At this time, the mostly neutral hydrogen in the IGM was ionised but the source of the responsible hydrogen ionising emission remains unclear. In this thesis I discuss the most likely candidates for the emission of this ionising radiation, which are a type of galaxy called Lyman alpha emitters (LAEs). As implied by their name, they emit Lyman alpha radiation, produced after a hydrogen atom has been ionised and recombines with a free electron. The ionising radiation itself (also called Lyman continuum emission) which is needed for this process inside the LAEs could also be responsible for ionising the IGM around those galaxies at the epoch of reionisation, given that enough Lyman continuum escapes. Through this mechanism, Lyman alpha and Lyman continuum radiation are closely linked and are both studied to better understand the properties of high redshift galaxies and the reionisation state of the universe. Before I can analyse their Lyman alpha emission lines and the escape of Lyman continuum emission from them, the first step is the detection and correct classification of LAEs in integral field spectroscopic data, specifically taken with the Multi-Unit Spectroscopic Explorer (MUSE). After detecting emission line objects in the MUSE data, the task of classifying them and determining their redshift is performed with the graphical user interface QtClassify, which I developed during the work on this thesis. It uses the strength of the combination of spectroscopic and photometric information that integral field spectroscopy offers to enable the user to quickly identify the nature of the detected emission lines. The reliable classification of LAEs and determination of their redshifts is a crucial first step towards an analysis of their properties. Through radiative transfer processes, the properties of the neutral hydrogen clouds in and around LAEs are imprinted on the shape of the Lyman alpha line. Thus after identifying the LAEs in the MUSE data, I analyse the properties of the Lyman alpha emission line, such as the equivalent width (EW) distribution, the asymmetry and width of the line as well as the double peak fraction. I challenge the common method of displaying EW distributions as histograms without taking the limits of the survey into account and construct a more independent EW distribution function that better reflects the properties of the underlying population of galaxies. I illustrate this by comparing the fraction of high EW objects between the two surveys MUSE-Wide and MUSE-Deep, both consisting of MUSE pointings (each with the size of one square arcminute) of different depths. In the 60 MUSE-Wide fields of one hour exposure time I find a fraction of objects with extreme EWs above EW_0>240A of ~20\%, while in the MUSE-Deep fields (9 fields with an exposure time of 10 hours and one with an exposure time of 31 hours) I find a fraction of only ~1\%, which is due to the differences in the limiting line flux of the surveys. The highest EW I measure is EW_0 = 600.63 +- 110A, which hints at an unusual underlying stellar population, possibly with a very low metallicity. With the knowledge of the redshifts and positions of the LAEs detected in the MUSE-Wide survey, I also look for Lyman continuum emission coming from these galaxies and analyse the connection between Lyman continuum emission and Lyman alpha emission. I use ancillary Hubble Space Telescope (HST) broadband photometry in the bands that contain the Lyman continuum and find six Lyman continuum leaker candidates. To test whether the Lyman continuum emission of LAEs is coming only from those individual objects or the whole population, I select LAEs that are most promising for the detection of Lyman continuum emission, based on their rest-frame UV continuum and Lyman alpha line shape properties. After this selection, I stack the broadband data of the resulting sample and detect a signal in Lyman continuum with a significance of S/N = 5.5, pointing towards a Lyman continuum escape fraction of ~80\%. If the signal is reliable, it strongly favours LAEs as the providers of the hydrogen ionising emission at the epoch of reionisation and beyond.},
  language  = {en}
}
@phdthesis{Kegelmann2019,
  author    = {Kegelmann, Lukas},
  title     = {Advancing charge selective contacts for efficient monolithic perovskite-silicon tandem solar cells},
  doi       = {10.25932/publishup-42642},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-426428},
  school      = {Universit{\"a}t Potsdam},
  pages     = {v, 155},
  year      = {2019},
  abstract  = {Hybrid organic-inorganic perovskites are one of the most promising material classes for photovoltaic energy conversion. In solar cells, the perovskite absorber is sandwiched between n- and p-type contact layers which selectively transport electrons and holes to the cell's cathode and anode, respectively. This thesis aims to advance contact layers in perovskite solar cells and unravel the impact of interface and contact properties on the device performance. Further, the contact materials are applied in monolithic perovskite-silicon heterojunction (SHJ) tandem solar cells, which can overcome the single junction efficiency limits and attract increasing attention. Therefore, all contact layers must be highly transparent to foster light harvesting in the tandem solar cell design. Besides, the SHJ device restricts processing temperatures for the selective contacts to below 200°C. A comparative study of various electron selective contact materials, all processed below 180°C, in n-i-p type perovskite solar cells highlights that selective contacts and their interfaces to the absorber govern the overall device performance. Combining fullerenes and metal-oxides in a TiO2/PC60BM (phenyl-C60-butyric acid methyl ester) double-layer contact allows to merge good charge extraction with minimized interface recombination. The layer sequence thereby achieved high stabilized solar cell performances up to 18.0\% and negligible current-voltage hysteresis, an otherwise pronounced phenomenon in this device design. Double-layer structures are therefore emphasized as a general concept to establish efficient and highly selective contacts. Based on this success, the concept to combine desired properties of different materials is transferred to the p-type contact. Here, a mixture of the small molecule Spiro-OMeTAD [2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluoren] and the doped polymer PEDOT [poly(3,4-ethylenedioxythiophene)] is presented as a novel hole selective contact. PEDOT thereby remarkably suppresses charge recombination at the perovskite surface, allowing an increase of quasi-Fermi level splitting in the absorber. Further, the addition of Spiro-OMeTAD into the PEDOT layer is shown to enhance charge extraction at the interface and allow high efficiencies up to 16.8\%. Finally, the knowledge on contact properties is applied to monolithic perovskite-SHJ tandem solar cells. The main goal is to optimize the top contact stack of doped Spiro-OMeTAD/molybdenum oxide(MoOx)/ITO towards higher transparency by two different routes. First, fine-tuning of the ITO deposition to mitigate chemical reduction of MoOx and increase the transmittance of MoOx/ITO stacks by 25\%. Second, replacing Spiro-OMeTAD with the alternative hole transport materials PEDOT/Spiro-OMeTAD mixtures, CuSCN or PTAA [poly(triaryl amine)]. Experimental results determine layer thickness constrains and validate optical simulations, which subsequently allow to realistically estimate the respective tandem device performances. As a result, PTAA represents the most promising replacement for Spiro-OMeTAD, with a projected increase of the optimum tandem device efficiency for the herein used architecture by 2.9\% relative to 26.5\% absolute. The results also reveal general guidelines for further performance gains of the technology.},
  language  = {en}
}
@phdthesis{Kav2019,
  author    = {Kav, Batuhan},
  title     = {Membrane adhesion mediated via lipid-anchored saccharides},
  doi       = {10.25932/publishup-42879},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-428790},
  school      = {Universit{\"a}t Potsdam},
  pages     = {125},
  year      = {2019},
  abstract  = {Membrane adhesion is a fundamental biological process in which membranes are attached to neighboring membranes or surfaces. Membrane adhesion emerges from a complex interplay between the binding of membrane-anchored receptors/ligands and the membrane properties. In this work, we study membrane adhesion mediated by lipid-anchored saccharides using microsecond-long full-atomistic molecular dynamics simulations. Motivated by neutron scattering experiments on membrane adhesion via lipid-anchored saccharides, we investigate the role of LeX, Lac1, and Lac2 saccharides and membrane fluctuations in membrane adhesion. We study the binding of saccharides in three different systems: for saccharides in water, for saccharides anchored to essentially planar membranes at fixed separations, and for saccharides anchored to apposing fluctuating membranes. Our simulations of two saccharides in water indicate that the saccharides engage in weak interactions to form dimers. We find that the binding occurs in a continuum of bound states instead of a certain number of well-defined bound structures, which we term as "diffuse binding". The binding of saccharides anchored to essentially planar membranes strongly depends on separation of the membranes, which is fixed in our simulation system. We show that the binding constants for trans-interactions of two lipid-anchored saccharides monotonically decrease with increasing separation. Saccharides anchored to the same membrane leaflet engage in cis-interactions with binding constants comparable to the trans-binding constants at the smallest membrane separations. The interplay of cis- and trans-binding can be investigated in simulation systems with many lipid-anchored saccharides. For Lac2, our simulation results indicate a positive cooperativity of trans- and cis-binding. In this cooperative binding the trans-binding constant is enhanced by the cis-interactions. For LeX, in contrast, we observe no cooperativity between trans- and cis-binding. In addition, we determine the forces generated by trans-binding of lipid-anchored saccharides in planar membranes from the binding-induced deviations of the lipid-anchors. We find that the forces acting on trans-bound saccharides increase with increasing membrane separation to values of the order of 10 pN. The binding of saccharides anchored to the fluctuating membranes results from an interplay between the binding properties of the lipid-anchored saccharides and membrane fluctuations. Our simulations, which have the same average separation of the membranes as obtained from the neutron scattering experiments, yield a binding constant larger than in planar membranes with the same separation. This result demonstrates that membrane fluctuations play an important role at average membrane separations which are seemingly too large for effective binding. We further show that the probability distribution of the local separation can be well approximated by a Gaussian distribution. We calculate the relative membrane roughness and show that our results are in good agreement with the roughness values reported from the neutron scattering experiments.},
  language  = {en}
}
@phdthesis{Haase2019,
  author    = {Haase, Nadin},
  title     = {The nascent peptide chain in the ribosomal exit tunnel},
  school      = {Universit{\"a}t Potsdam},
  pages     = {105},
  year      = {2019},
  language  = {en}
}
@phdthesis{Gong2019,
  author    = {Gong, Chen Chris},
  title     = {Synchronization of coupled phase oscillators},
  doi       = {10.25932/publishup-48752},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-487522},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xvii, 115},
  year      = {2019},
  abstract  = {Oscillatory systems under weak coupling can be described by the Kuramoto model of phase oscillators. Kuramoto phase oscillators have diverse applications ranging from phenomena such as communication between neurons and collective influences of political opinions, to engineered systems such as Josephson Junctions and synchronized electric power grids. This thesis includes the author's contribution to the theoretical framework of coupled Kuramoto oscillators and to the understanding of non-trivial N-body dynamical systems via their reduced mean-field dynamics. The main content of this thesis is composed of four parts. First, a partially integrable theory of globally coupled identical Kuramoto oscillators is extended to include pure higher-mode coupling. The extended theory is then applied to a non-trivial higher-mode coupled model, which has been found to exhibit asymmetric clustering. Using the developed theory, we could predict a number of features of the asymmetric clustering with only information of the initial state provided. The second part consists of an iterated discrete-map approach to simulate phase dynamics. The proposed map --- a Moebius map --- not only provides fast computation of phase synchronization, it also precisely reflects the underlying group structure of the dynamics. We then compare the iterated-map dynamics and various analogous continuous-time dynamics. We are able to replicate known phenomena such as the synchronization transition of the Kuramoto-Sakaguchi model of oscillators with distributed natural frequencies, and chimera states for identical oscillators under non-local coupling. The third part entails a particular model of repulsively coupled identical Kuramoto-Sakaguchi oscillators under common random forcing, which can be shown to be partially integrable. Via both numerical simulations and theoretical analysis, we determine that such a model cannot exhibit stationary multi-cluster states, contrary to the numerical findings in previous literature. Through further investigation, we find that the multi-clustering states reported previously occur due to the accumulation of discretization errors inherent in the integration algorithms, which introduce higher-mode couplings into the model. As a result, the partial integrability condition is violated. Lastly, we derive the microscopic cross-correlation of globally coupled non-identical Kuramoto oscillators under common fluctuating forcing. The effect of correlation arises naturally in finite populations, due to the non-trivial fluctuations of the meanfield. In an idealized model, we approximate the finite-sized fluctuation by a Gaussian white noise. The analytical approximation qualitatively matches the measurements in numerical experiments, however, due to other periodic components inherent in the fluctuations of the mean-field there still exist significant inconsistencies.},
  language  = {en}
}
@phdthesis{Eckert2019,
  author    = {Eckert, Sebastian},
  title     = {Accessing active sites of molecular proton dynamics},
  doi       = {10.25932/publishup-42587},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-425870},
  school      = {Universit{\"a}t Potsdam},
  pages     = {xviii, 193},
  year      = {2019},
  abstract  = {The unceasing impact of intense sunlight on earth constitutes a continuous source of energy fueling countless natural processes. On a molecular level, the energy contained in the electromagnetic radiation is transferred through photochemical processes into chemical or thermal energy. In the course of such processes, photo-excitations promote molecules into thermally inaccessible excited states. This induces adaptations of their molecular geometry according to the properties of the excited state. Decay processes towards energetically lower lying states in transient molecular geometries result in the formation of excited state relaxation pathways. The photo-chemical relaxation mechanisms depend on the studied system itself, the interactions with its chemical environment and the character of the involved states. This thesis focuses on systems in which photo-induced deprotonation processes occur at specific atomic sites. To detect these excited-state proton dynamics at the affected atoms, a local probe of molecular electronic structure is required. Therefore, site-selective and orbital-specific K-edge soft X-ray spectroscopy techniques are used here to detect photo-induced proton dynamics in gaseous and liquid sample environments. The protonation of nitrogen (N) sites in organic molecules and the oxygen (O) atom in the water molecule are probed locally through transitions between 1s orbitals and the p-derived molecular valence electronic structure. The used techniques are X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). Both yield access to the unoccupied local valence electronic structure, whereas the latter additionally probes occupied states. We apply these probes in optical pump X-ray probe experiments to investigate valence excited-state proton transfer capabilities of aqueous 2-thiopyridone. A characteristic shift of N K-edge X-ray absorption resonances as well as a distinct X-ray emission line are established by us as spectral fingerprints of N deprotonation in the system. We utilize them to identify photo-induced N deprotonation of 2-thiopyridone on femtosecond timescales, in optical pump N K-edge RIXS probe measurements. We further establish excited state proton transfer mechanisms on picosecond and nanosecond timescales along the dominant relaxation pathways of 2-thiopyridone using transient N K-edge XAS. Despite being an excellent probe mechanism for valence excited-state proton dynamics, the K-edge core-excitation itself also disturbs the electronic structure at specific sites of a molecule. The rapid reaction of protons to 1s photo-excitations can yield directional structural distortions within the femtosecond core-excited state lifetime. These directional proton dynamics can change the energetic separation of eigenstates of the system and alter probabilities for radiative decay between them. Both effects yield spectral signatures of the dynamics in RIXS spectra. Using these signatures of RIXS transitions into electronically excited states, we investigate proton dynamics induced by N K-edge excitation in the amino-acid histidine. The minor core-excited state dynamics of histidine in basic and neutral chemical environments allow us to establish XAS and RIXS spectral signatures of different N protonation states at its imidazole N sites. Based on these signatures, we identify an excitation-site-independent N-H dissociation for N K-edge excitation under acidic conditions. Such directional structural deformations, induced by core-excitations, also make proton dynamics in electronic ground states accessible through RIXS transitions into vibrationally excited states. In that context, we interpret high resolution RIXS spectra of the water molecule for three O K-edge resonances based on quantum-chemical wave packet propagation simulations. We show that highly oriented ground state vibrational modes of coupled nuclear motion can be populated through RIXS processes by preparation of core-excited state nuclear wave packets with the same directionality. Based on that, we analytically derive the possibility to extract one-dimensional directional cuts through potential energy surfaces of molecular systems from the corresponding RIXS spectra. We further verify this concept through the extraction of the gas-phase water ground state potential along three coordinates from experimental data in comparison to quantum-chemical simulations of the potential energy surface. This thesis also contains contributions to instrumentation development for investigations of photo-induced molecular dynamics at high brilliance X-ray light sources. We characterize the setup used for the transient valence-excited state XAS measurements of 2-thiopyridone. Therein, a sub-micrometer thin liquid sample environment is established employing in-vacuum flat-jet technology, which enables a transmission experimental geometry. In combination with a MHz-laser system, we achieve a high detection sensitivity for photo-induced X-ray absorption changes. Additionally, we present conceptual improvements for temporal X-ray optical cross-correlation techniques based on transient changes of multilayer optical properties, which are crucial for the realization of femtosecond time-resolved studies at synchrotrons and free-electron lasers.},
  language  = {en}
}
@phdthesis{Cecchini2019,
  author    = {Cecchini, Gloria},
  title     = {Improving network inference by overcoming statistical limitations},
  doi       = {10.25932/publishup-42670},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-426705},
  school      = {Universit{\"a}t Potsdam},
  pages     = {124},
  year      = {2019},
  abstract  = {A reliable inference of networks from data is of key interest in many scientific fields. Several methods have been suggested in the literature to reliably determine links in a network. These techniques rely on statistical methods, typically controlling the number of false positive links, but not considering false negative links. In this thesis new methodologies to improve network inference are suggested. Initial analyses demonstrate the impact of falsepositive and false negative conclusions about the presence or absence of links on the resulting inferred network. Consequently, revealing the importance of making well-considered choices leads to suggest new approaches to enhance existing network reconstruction methods. A simulation study, presented in Chapter 3, shows that different values to balance false positive and false negative conclusions about links should be used in order to reliably estimate network characteristics. The existence of type I and type II errors in the reconstructed network, also called biased network, is accepted. Consequently, an analytic method that describes the influence of these two errors on the network structure is explored. As a result of this analysis, an analytic formula of the density of the biased vertex degree distribution is found (Chapter 4). In the inverse problem, the vertex degree distribution of the true underlying network is analytically reconstructed, assuming the probabilities of type I and type II errors. Chapters 4-5 show that the method is robust to incorrect estimates of α and β within reasonable limits. In Chapter 6, an iterative procedure to enhance this method is presented in the case of large errors on the estimates of α and β. The investigations presented so far focus on the influence of false positive and false negative links on the network characteristics. In Chapter 7, the analysis is reversed - the study focuses on the influence of network characteristics on the probability of type I and type II errors, in the case of networks of coupled oscillators. The probabilities of α and β are influenced by the shortest path length and the detour degree, respectively. These results have been used to improve the network reconstruction, when the true underlying network is not known a priori, introducing a novel and advanced concept of threshold.},
  language  = {en}
}
@phdthesis{Bartel2019,
  author    = {Bartel, Melanie},
  title     = {Kernresonanz-Strukturuntersuchungen an alternativen Precursoren und deren Zwischenprodukten f{\"u}r die Herstellung von Carbonfasern f{\"u}r den Massenmarkt},
  doi       = {10.25932/publishup-46930},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-469301},
  school      = {Universit{\"a}t Potsdam},
  pages     = {XII, 101, XXV},
  year      = {2019},
  abstract  = {Carbonfasern haben sich in der Luft- und Raumfahrt etabliert und gewinnen in Alltagsanwendungen wie dem Automobilbereich, Windkraft- und Sportbereich durch ihre hohen Zugfestigkeiten, insbesondere ihrer hohen E-Moduli, und ihrer geringen Dichte immer mehr an Bedeutung. Auf Grund ihrer hohen Kosten, welche sich zur H{\"a}lfte aus der Precursorherstellung, inklusive seiner Synthese und seinem Verspinnprozess, dem L{\"o}sungsspinnverfahren, ergeben, erhalten zunehmend alternative und schmelzspinnbare Precursoren Interesse. F{\"u}r die Carbonfaserherstellung wird fast ausschließlich Polyacrylnitril (PAN) verwendet, das vor dem Schmelzen irreversible exotherme Zyklisierungsreaktionen aufweist, welchen sich seine Zersetzung anschließt. Eine M{\"o}glichkeit der Reduzierung der Schmelztemperatur von Polymeren ist die Einbringung von Comonomeren zur Erh{\"o}hung des freien Volumens und die Reduzierung der intermolekularen Wechselwirkungen als interne Weichmacher. Wie am Fraunhofer IAP gezeigt wurde, kann mittels 2-Methoxyethylacrylat (MEA) die Schmelztemperatur zu neuartigen PAN-basierten Precursoren verringert werden. Um den PAN-co-MEA-Precursor f{\"u}r die nachfolgenden Prozessschritte der Carbonfaserherstellung zu verwenden, m{\"u}ssen die thermoplastischen Fasern in thermisch stabile Fasern ohne thermoplastisches Verhalten {\"u}berf{\"u}hrt werden. Es wurde ein neuer Prozessschritt (Pr{\"a}stabilisierung) eingef{\"u}hrt, welcher unter alkalischen Bedingungen zur Abspaltung der Comonomerseitenkette f{\"u}hrt. Neben der Esterhydrolyse finden Reaktionen statt, welche an diesem Material noch nicht hinreichend untersucht wurden. Weiterhin stellt sich die Frage nach der Kinetik der Pr{\"a}stabilisierung und der Ermittlung einer geeigneten Prozessf{\"u}hrung. Hierzu wurde die Pr{\"a}stabilisierung in den Labormaßstab {\"u}berf{\"u}hrt und die m{\"o}glichen Zusammensetzungen des aus DMSO und einer KOH-L{\"o}sung bestehenden Reaktionsmediums evaluiert. Weiterhin wurde die Behandlung bei verschiedenen Pr{\"a}stabilisierungszeiten von maximal 30 min und Temperaturen von 40, 50 und 60 °C durchgef{\"u}hrt, um prim{\"a}r mittels NMR-Spektroskopie die chemischen Struktur{\"a}nderungen aufzukl{\"a}ren. Die Esterhydrolyse des Comonomers, welche zur Abspaltung des 2-Methoxyethanols f{\"u}hrt, wurde mittels 1H-NMR-spektroskopischer Untersuchungen detektiert. Es wurde ein Modell aufgestellt, das die chemisch-physikalischen Struktur{\"a}nderungen w{\"a}hrend der Pr{\"a}stabilisierung aufzeigt. Die zuerst ablaufende Reaktion ist die Esterhydrolyse am Comonomer, welche vom Faserrand nach innen verl{\"a}uft und durch die Pr{\"a}senz des DMSO in Kombination mit der KOH-L{\"o}sung (Superbase) initiiert wird. Der zeitliche Reaktionsverlauf der Esterhydrolyse kann in drei Bereiche eingeteilt werden. Der erste Bereich ab dem Pr{\"a}stabilisierungsbeginn wird durch die Diffusion der basischen Anionen in die Faser, der zweite Bereich durch die Reaktion an der Estergruppe des Comonomers und der dritte Bereich durch letzte Reaktionen im Faserinneren und diffusiven Prozessen der Produkte und Edukte charakterisiert. Der zweite Bereich kann mit einer Reaktion pseudo 1. Ordnung abgebildet werden, da in diesem Bereich bereits eine ausreichende Diffusion der Edukte in die Faser stattgefunden hat. Bei 50 °C spielt die Diffusion im ersten Bereich im Vergleich zur Reaktion eine untergeordnete Rolle. Mit Erh{\"o}hung der Temperatur auf 60 °C kann eine im Verh{\"a}ltnis geringere Diffusions- als Reaktionsgeschwindigkeit beobachtet werden. Die Nebenreaktionen wurden mittels 13C-CP/MAS-NMR-spektroskopischen, elementaranlaytischen Untersuchungen sowie Doppelbrechungsmessungen charakterisiert. W{\"a}hrend der alkalischen Esterhydrolyse beginnt die Reduzierung der Nitrilgruppen unter der Bildung von prim{\"a}ren Carbons{\"a}ureamiden und Carbons{\"a}uren. Zur Beschreibung dieser Umsetzung wurde eine Methode entwickelt, welche die Addition von 13C-CP/MAS-NMR-Spektren der Modellsubstanzen PAN, PAM und PAA beinhaltet. Weitere stattfindende Reaktionen sind die Bildung von konjugierten Doppelbindungen, welche insbesondere auf eine Zyklisierung der Nitrile hinweisen. Die nasschemisch initiierte Zyklisierung der Nitrilgruppen kann zu k{\"u}rzeren Stabilisierungszeiten und einem besser kontrollierbaren Stabilisierungsprozess durch geringere W{\"a}rmefreisetzung und schlussendlich zu einer Kostenersparnis des gesamten Verfahrens f{\"u}hren. Die Umsetzung der Nitrilgruppen konnte mit einer Reaktion pseudo 1. Ordnung gut abgebildet werden. DMSO initiiert die Esterhydrolyse, wobei die KOH-Konzentration einen h{\"o}heren Einfluss auf die Reaktionsgeschwindigkeit der Ester- und Nitrilhydrolyse als die DMSO-Konzentration besitzt. Beide Reaktionen zeigen eine vergleichbare Abh{\"a}ngigkeit von der Temperatur. Die Erh{\"o}hung der Pr{\"a}stabilisierungszeit und der KOH- bzw. DMSO-Konzentration f{\"u}hrt zur Migration niedermolekularer Bestandteile des Fasermaterials an die Oberfl{\"a}che und der Bildung punktueller Ablagerungen bis hin zu miteinander verbundenen Einzelfasern. Eine weitere Erh{\"o}hung der Pr{\"a}stabilisierungszeit bzw. der Konzentration f{\"u}hrt zu einem steigenden Carbons{\"a}ureanteil und zur Quellung des Fasermaterials, wodurch die Ablagerungen in das Reaktionsmedium diffundieren. Die Ablagerungen enthalten Chlor, welches durch den Waschvorgang mit HCl in das Materialsystem gelangt ist und durch Parameteranpassungen reduziert wurde. Die schmelzbaren Fasern konnten durch die Pr{\"a}stabilisierung erfolgreich {\"u}ber eine Kern-Mantel-Struktur in nicht-thermoplastische Fasern {\"u}berf{\"u}hrt werden. Zur Ermittlung eines geeigneten Prozessfensters f{\"u}r nachfolgende thermische Beanspruchungen der pr{\"a}stabilisierten Fasern wurden drei Kriterien identifiziert, anhand welcher die Evaluation erfolgte. Das erste Kriterium beinhaltet die Notwendigkeit der vollst{\"a}ndigen Aufhebung der thermoplastischen Eigenschaft der Fasern. Als zweites Kriterium diente die Fasermorphologie. Anhand von REM-Aufnahmen wurden Faserb{\"u}ndel mit separierten Einzelfasern ohne Ablagerungen f{\"u}r die nachfolgende Stabilisierung ausgew{\"a}hlt. Das dritte Kriterium bezieht sich auf eine m{\"o}glichst geringe Umsetzung der Nitrilgruppen, um Pr{\"a}stabilisierungsbedingungen mit Nebenreaktionen zu vermeiden. Aus den Untersuchungen konnte eine Pr{\"a}stabilisierungstemperatur von 60 °C als geeignet identifiziert werden. Weiterhin f{\"u}hren hoch alkalische Zusammensetzungen des Reaktionsmediums mit KOH-Konzentrationen von 1, 1,5 und 2 M, vorzugsweise 1,5 M und 50 vol\% DMSO mit Reaktionszeiten von unter 10 min zu geeigneten Fasern. Ein MEA-Anteil unterhalb von 2 mol\% bewirkt eine {\"U}berf{\"u}hrung in die Unschmelzbarkeit. Thermisch stabile und f{\"u}r die nachfolgende Stabilisierung geeignete Fasern besitzen weiterhin 68 - 80 mol\% Nitrilgruppen, 20 - 25 mol\% Carbons{\"a}uren, bis zu 15 mol\% prim{\"a}re Carbons{\"a}ureamide und zyklisierte Strukturen.},
  language  = {de}
}
@phdthesis{Bachmann2019,
  author    = {Bachmann, Felix},
  title     = {Non-linearity of magnetic micropropellers},
  school      = {Universit{\"a}t Potsdam},
  pages     = {120},
  year      = {2019},
  language  = {en}
}
@phdthesis{Aretz2019,
  author    = {Aretz, Sarah},
  title     = {Entwicklung und Evaluation eines Testinstruments zur Untersuchung von Vorkenntnissen und Pr{\"a}konzepten in der Kosmologie},
  doi       = {10.25932/publishup-42542},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-425421},
  school      = {Universit{\"a}t Potsdam},
  pages     = {x, 133},
  year      = {2019},
  abstract  = {Kosmologie beschreibt die Entwicklung des Universums als Ganzes. Kosmologische Entdeckungen in Theorie und Praxis haben daher unser modernes wissenschaftliches Weltbild entscheidend ge­pr{\"a}gt. Die Vermittlung eines modernen Weltbildes durch Unterricht ist ein h{\"a}ufiger Wunsch in der naturwissenschaftlichen Bildungsdiskussion. Dennoch exis­tieren weiterhin Forschungs- und Entwicklungsbedarfe. Kosmologische Themen finden sich h{\"a}ufig in den Medien und sind gleichzeitig weiter vom Alltag entfernt, so dass sich hier besonders leicht wissenschaftlich inkorrekte Vorstellungen entwickeln k{\"o}nnen, die zu Problemen im Unterricht f{\"u}hren k{\"o}nnen. Das Ziel dieser wissenschaftlichen Arbeit ist es, zu diesem Forschungsgebiet beizutragen und die Voraussetzungen hinsichtlich vorhandener Vorkenntnisse und Pr{\"a}konzepte in Kosmologie, mit denen Sch{\"u}lerinnen und Sch{\"u}ler in den Unterricht kommen, zu untersuchen und anschließend mit denen anderer L{\"a}nder zu vergleichen. Dies erfolgt anhand einer qualitativen Inhaltsanalyse eines offenen Fragebogens. Auf dieser Grundlage wird schließlich ein Multiple-Choice Frage­bogen entwickelt, angewendet und evaluiert. Die Ergebnisse zeigen große Wissensl{\"u}cken im Bereich der Kosmologie auf und geben erste Hin­weise auf vorhandene Unterschiede zwischen den L{\"a}ndern. Es existieren ebenfalls einige teils weit verbreitete wissenschaftlich inkorrekte Vorstellungen wie beispiels­weise die Assoziation des Urknalls mit einer Explosion, der Urknall verursacht durch eine Kollision von Teilchen oder gr{\"o}ßeren Objekten, oder die Vorstellung der Ausdehnung des Universums als neue Entdeckungen und/oder Wissen. Des Weiteren gab nur etwa jeder F{\"u}nfte das korrekte Alter des Universums oder die Ausdehnung des Universums als einen der drei Belege der Urknalltheorie an, w{\"a}hrend fast 40\% keinen einzigen Beleg nennen konn­ten. F{\"u}r den geschlossenen Fragebogen konnten gute Hinweise f{\"u}r verschiedene Validit{\"a}tsa­spekte herausgearbeitet werden und es existieren erste Hinweise darauf, dass der Fragebogen Wissenszu­wachs messen kann und damit wahrscheinlich zur Unter­suchung der Wirksamkeit von Lerneinhei­ten eingesetzt werden kann. Auch ein entsprechendes Modell zur Verst{\"a}ndnisentwicklung der Aus­dehnung des Universums zeigte sich vielversprechend. Diese Arbeit liefert insgesamt einen Forschungsbeitrag zum Sch{\"u}lervorwissen und Vorstellungen in der Kosmologie und deren Large Scale Assessment. Dies er{\"o}ffnet die M{\"o}glichkeit zuk{\"u}nftiger For­schungen im Bereich von Gruppenvergleichen insbesondere hinsichtlich objektiver L{\"a}nderverglei­che sowie der Untersuchungen der Wirksamkeit von einzelnen Ler­neinheiten als auch Vergleiche verschiedener Lerneinheiten untereinander.},
  language  = {de}
}