Zur Halogenaktivierung im Aerosol und in Salzpfannen
- Diese Arbeit zeigt die weltweit ersten Messungen der Halogenaktivierung mit direkter Beobachtung der Halogenoxide BrO, ClO und OClO unter kontrollierten Bedingungen eines Laboratoriums. Dazu wurde die an Forschungsstelle für atmosphärische Chemie vorhandene Teflon-Umweltkammer mit einem Sonnensimulator für troposphärisches Licht und diverser Sensorik ausgestattet. Zusätzlich wurde in Zusammenarbeit mit der Universität Heidelberg ein Langpfad-DOAS (Differential Optical Absorption Spectroscopy) installiert. In diesem Aufbau wurden zwei Arten von Experimenten durchgeführt: mit künstlichem Meerwasseraerosol und mit Salzpfannen. Nachgewiesen wurde ein starker Einfluss der Stickoxide auf die Aktivierung der Halogene, so dass in Extremfällen das Bromid und das Chlorid komplett freigesetzt wurde, was Mischungsverhältnisses von bis zu 17 ppb OClO, 6 ppm ClO und 1.5 ppb BrO führte. Zur eingehenden Untersuchung der Resultate wurden Modelle eingesetzt: das eigens für die Salzpfannenexperimente erstellte HaloBox-Modell und das CAABA/MECCA-Modell für Aerosolexperimente. Durch die Anpassung des CAABA/MECCA-Modells an die Rahmenbedingungen der Umweltkammer, kann dieses nun die Beobachtungen hinreichend wiedergeben und über unbekannte Größen wie pH-Wert oder die Konzentration von Halogenionen Aufschluss geben. In den Experimenten mit Salzpfannen wurden Mischungsverhältnisse von bis zu 6 ppb BrO beobachtet. Dort wurde eine Korrelation der Bromaktivierung zur relativen Luftfeuchte nachgewiesen. Untersucht wurden auch die einleitende Mechanismen der Aktivierung, die bereits bei Dunkelheit ablaufen. Hier wirkt Ozon als auslösende Spezies.
Energy-domain synchrotron radiation Mössbauer source for physics under extreme conditions
- Iron is one of the most abundant elements on Earth, and it is an important component in minerals. Electronic and magnetic properties of iron-bearing materials significantly affect processes occurring in the deep interior of the Earth. In the materials that make up the Earth’s lower mantle iron may exist in different valence, spin states and crystallographic environments. Most of the existing experimental techniques either do not allow to separately follow evolution of different iron sites or are not suitable for measurements under high-pressure/high-temperature conditions. This makes studies of iron electronic structure under such conditions extremely challenging.
The current Ph.D. thesis is divided into two major parts. The first part is dedicated to the development of a Synchrotron Mössbauer Source (SMS). This device allows energy domain Mossbauer spectroscopy to be performed on a sample under pressures above 100 GPa in laser heated diamond anvil cells. The second part is dedicated to studying the behavior of iron in iron/alumina-bearing silicate perovskite under conditions of the Earth’s lower mantle.
1. Synchrotron Mössbauer Source
There are several techniques that allow magnetic and electronic properties of materials under extreme conditions to be probed: X-ray Emission Spectroscopy (XES), X-ray absorption near edge structure (XANES), Nuclear Resonance Spectroscopes, etc. For elements in which observation of Mössbauer effect is possible the most mature, sensitive, and suitable technique for studies of magnetic and electronic properties is energy-domain Mössbauer spectroscopy.
However, due to low brilliance of utilized radioactive sources and low natural abundance of iron in lower mantle minerals measurements using conventional energy- resolved Mössbauer spectroscopy require very long time and usually are limited to moderate pressures. The problem can be solved by combining the outstanding properties of synchrotron radiation (high brilliance, possibility for extreme focusing) with the energy-resolved approach. In brief, what is needed is a synchrotron source of Mössbauer radiation. Construction of such source was the primary task of my PhD work. The possibility to develop such a source was demonstrated at the Nuclear Resonance beamline ID18 at the European Synchrotron Radiation Facility (ESRF) by Smirnov et al. (1997). The source is based on pure nuclear reflections existing in antiferromagnetic 57FeBO3 crystals.
￼The major technical goals of my PhD work were to (a) construct a device that would be permanently ready for operation, and (b) optimize it to have the best possible resolution and highest possible intensity. In order to achieve these goals theoretical calculations were first conducted to understand how to best improve the performance. Second, several experiments were performed to confirm the theoretically predicted results. Third, several optical schemes of the SMS were tested in order to determine the optimal setup.
As a result of the research and development program a powerful Synchrotron Mössbauer Source (SMS) for high-pressure applications was constructed at the Nuclear Resonance beamline (ID18) of the ESRF. Using results obtained in the combined theoretical/experimental study of angular dependence of energy and temporal distributions of the pure nuclear reflections of iron borate crystal, the SMS was optimized for the highest possible intensity and best possible resolution. The bandwidth of radiation provided by the SMS is between 10-15 neV (2-3 Γ0, where Γ0 is a natural linewidth of Mössbauer resonance for Iron), the intensity is ~2.5×104 photons/s and the typical scanning velocity range is about ±12 mm/s (±0.6 μeV). In contrast to conventional radioactive sources, the SMS gives the possibility to focus the beam to tens of microns. SMS is the in-line monochromator, permanently located in the optics hutch and operational immediately after moving it into the incident beam position. The source can be used with all existing sample environments in the experimental hutches downstream of the beamline.
The implementation of this device opens the possibility for studying systems with complex hyperfine structure utilizing energy-resolved approach under various extreme conditions, for example at high-pressure. Furthermore, the SMS allows for very short collection times of only a few minutes, which enables data to be collected during laser heating. Several high-pressure and high-pressure/high-temperature studies that have already been performed are described in the second part of this Ph.D. thesis. The almost 100% recoilless resonant radiation delivered by the source and its high brightness allow a broad field of SMS applications. The SMS can be utilized in any mode of synchrotron storage ring operation.
2. Study of the spin state of Fe3+ ions in perovskite
Silicate perovskite (Mg,Fe)(Si,Al)O3 is the most abundant phase in the Earth’s lower mantle. Knowledge of its properties is indispensable for understanding lower mantle behavior. Dynamic, thermodynamic, and transport properties of silicate perovskite can be significantly affected by the valence and spin state of iron. Silicate perovskite with 5-10 mol% of Fe (where Fe3+/ΣFe ~50–75% (McCammon et al., ￼1997)) and Al, is dominant phase in Earth lower mantle (~75 vol%) (Zhang et al., 2006; Stackhouse et al., 2007). The behavior of Fe electronic properties under conditions close to those of the Earths lower mantle remains strongly controversial.
The second part of my Ph.D. work is dedicated to an investigation of the spin state of iron in Fe3+- rich silicate perovskite at high pressure. Four different silicate perovskite samples with different stoichiometry were studied using the Synchrotron Mössbauer Source. SMS spectra were collected at room temperature and pressures up to 122 GPa using diamond anvil cells, with or without laser annealing of the samples.
The hyperfine parameters, i.e., centre shift and quadrupole splitting, for the same phases, which were extracted from measured spectra for all perovskite samples studied in this work, are the same at each pressure within experimental error. Moreover, there is no change in Fe3+/ΣFe for individual samples over the entire pressure range of the experiment. The hyperfine parameters of the Fe3+ doublet are consistent with the high-spin state (Gütlich et al., 2011), and their smooth variation with pressure indicates that Fe3+ does not undergo spin crossover within the entire pressure range. All observed changes in the spectra are associated with abrupt changes in the electronic state of Fe2+. The hyperfine parameters of the low QS Fe2+ doublet correspond to the high-spin state (McCammon et al., 2008), while the doublet with high quadrupole splitting, whose intensity grows with pressure at the expense of the Fe2+ high-spin state, corresponds either to intermediate-spin (IS) Fe2+ (McCammon et al., 2008) or a distortion of the site occupied by high-spin Fe2+ (Hsu et al., 2010). Based on results presented in a work of Narygina (2010), we indentify changes in Fe2+ electronic structure as high-spin to intermediate spin transition. Irrespective of the interpretation of the Fe2+ spin state, conclusions regarding the absence of spin crossover in Fe3+ remain valid.
These results show that the previously reported spin crossover of Fe3+ ions does not occur when Fe3+ occupies the A-site. In both alumina-containing and alumina-free silicate perovskites Fe3+ ions remain in the high-spin state up to at least 122 GPa, i.e., almost up to the pressure corresponding to the lower mantle - outer core boundary. The results also indicate that Fe3+ ions do not diffuse from the A-site to the B-site in perovskite after high-temperature annealing at high pressure, Mössbauer spectra of before and after annealing are identical. There is also no evidence for high-spin to low-spin crossover of Fe3+ ions due to site change. In contrast, the results confirm that Fe2+ ions undergo a transition from a high-spin to an intermediate spin state, without reaching a low-spin state within the studied pressure range at room temperature. These results suggest that the seismic velocity anomalies in the lower mantle cannot be attributed to spin crossover in Fe3+.
Synthesis and investigation of boron phases at high pressures and temperatures
- Boron, discovered as an element in 1808 and produced in pure form in 1909, still remains one of the most complicated light elements full of surprises. Even the number of pure boron polymorphs is a subject of intensive discussions. It is proven the existence of α-, β- and γ-boron phases. Structural details of the most common boron phase (β-B) are still not fully revealed. For decades boron remained the last stable element in the periodic table, whose ground state was not determined. It has been a subject of a longstanding controversy, whether α-B or β-B is the thermodynamically stable phase at ambient pressure and temperature.
The existence of the α-tetragonal boron phase T-50 has been an open question since its first discovery. It was not clear if T-50 could be synthesized as a pure boron phase or its structure must be stabilized by the presence of carbon or nitrogen. Theorists claimed that T-50 could not exist at all because of its unstable electronic configuration.
We have developed a method of synthesis of single crystals of α-boron. They were crystallized from a boron-platinum melt at high pressures (6-11 GPa) and high temperatures (1450-1875 K). An average size of the as-grown isometric crystals was 60 μm to 80 μm in maximum dimension. The crystal structure is in good agreement with the literature data. Detailed investigation of single crystals of α-boron using Raman spectroscopy was performed under elevated pressures and temperatures. The behaviour of the Raman modes under pressure was studied both theoretically and experimentally. Single crystals of β-boron were grown at temperatures above 1550 K and pressures up to 11 GPa using the similar methodology like that worked out for synthesis of α-boron.
In a series of experiments above 8 GPa we synthesized single crystals of tetragonal δ-boron (also known in literature as α-tetragonal boron or T-50) and refined the crystal structure of this phase based on synchrotron X-ray diffraction data. The purity of δ-boron was confirmed by means of the microprobe analysis and the electron energy loss spectroscopy (EELS).
A new, so far unknown boron phase, ε-boron, was synthesized at pressures of 8-10 GPa and temperatures between 2000-2250 K. The microprobe analysis and EELS revealed that the samples were not contaminated. The crystal structure of the new phase was determined by means of single crystal X-ray diffraction. ε-boron crystallizes in a R-3m space group with the unit cell parameters a = 5.5940(7) Å and c = 12.0756(16) Å (in hexagonal setting). The unit cell contains 15 boron atoms. The structure can be presented by the network of B12 icosahedra with a group of three boron atoms in the inter-icosahedra space. This phase is isostructural to boron carbide B13C2 (if carbon atoms are substituted by boron ones). Measured hardness is ~60 GPa which places ε-boron in the family of superhard materials.
We have demonstrated that δ-boron and ε-boron are metastable polymorphs because (a) they were found only together with other stable boron phases (α-, β-, or γ-B), and (b) upon heating at high pressure, both δ-B and ε-B transform to β- or γ-B, if the PT conditions correspond to the fields of stability of the latter.
Summarising, in the course of the present work the high-pressure high-temperature synthesis of the five boron polymorphs was established as a reproducible, verifiable and well-documented process. Following the synthesis prescription one can grow single crystals of α-B, β-B, γ-B, δ-B, and ε-B phases. Based on results of numerous HPHT experiments, the phase boundaries between the stable boron phases (α-B, β-B, γ-B) were found. Thus, our serial exploration of the pressure-temperature field using the large volume press synthesis technique resulted in establishing the phase diagram of boron (showing also the PT fields of the appearance of its two metastable phases, δ-B and ε-B) in the pressure interval of 3 GPa to 18 GPa at temperatures between 1073 K and 2423 K. Based on our experimental data and linear extrapolation of the α/β phase boundary down to ambient pressure we could resolve a longstanding controversy on the ground state of boron in favour of the α-B phase.
Greenhouse gas metabolizing prokaryotes in peatlands
- Peatlands in the northern hemisphere store substantial amounts of carbon and nitrogen, and are predicted to react sensitively to global warming. The main objective of the study was to study microbial processes involved in the fluxes of the greenhouse gases methane (CH4) and nitrous oxide (N2O) from peatlands. Five model peatlands with contrasting features (e.g., nitrate content, mean annual temperature, pH) were assessed.
A pH-neutral fen produced CH4 in situ as well as in unsupplemented anoxic microcosms. Supplemental N-Acetylglucosaminestimulated formation of fermentation products and CH4 and lead to increased accumulation of fermentation products when methanogenesis was inhibited by Bromoethanesulfonate. Supplemental H2/CO2 and formate greatly stimulated methanogenesis, while acetate and methanol stimulated methanogenesis to a much lesser extent. A high family-level diversity of bacterial 16S rRNA genes was detected. Within the detected families, genera known for syntrophic interactions with methanogens were found. Diversity of methanogens was lower than bacterial diversity, as only hydrogenotrophic Methanomicrobiales and Methanocellales were detected. Both process data and molecular data suggest that (i) hydrogenotrophic methanogenesis is the main process of CH4 formation in pH-neutral fen soil, and (ii) a high diversity of bacterial families are likely involved in diverse fermentations, providing substrates for methanogens.
Denitrification and N2O consumption potentials as well as denitrifier community composition were assessed in all five northern peatlands. In situ N2O emissions range from < 0.01 to 10 mg N2O*m-2*d-1,and were positively and negatively correlated with soil nitrate and ammonia contents, respectively. All soils produced and consumed N2O in anoxic microcosms without apparent delay. N2O production capacities and apparent affinities for nitrate were likewise positively correlated with soil nitrate content. Phylogenetic analyses of the nitrate reduction- and denitrification-associated genes narG, nirK/nirS, and nosZ indicated that the diversity of the denitifier community was highest in pH-neutral fen soil and positively correlated with pH. Detected narG affiliated mainly with Betaproteobacterial and Actinobacterial narG. . The number and the identity of observed operational taxonomic units (OTUs) of nirK, nirS, and nosZ in pH-neutral fen soil was clearly distinct from those of the more acidic soils, and indicated Alpha-, Beta-, and Gammaproteobacterial denitrifiers in all peatlands. Permafrost-affected soils mainly clustered together in the canonical correspondence analysis plots of the analyzed genes. pH was the most important factor determining community composition of nitrate reducers and denitrifiers.Significant influences of soil carbon content, precipitation, or temperature were also detected. The occurrence of certain OTUs of nirK and nirS was positively correlated with N2O emissions. The collective data indicate that (i) denitrification is an ongoing process in different types of pristine peatland soils, (ii) source and sink function of peatland denitrifiers for N2O are influenced by soil nitrate content and denitrifier community composition, and (iii) nitrate reducer and denitrifier community composition are affected by pH, temperature, precipitation, and soil carbon content.
Global warming is predicted to increase the frequency of extreme weather events, affecting on the water table level in peatlands and on the microbial communities involved in the production of CH4 and N2O. Thus, the influence of short-term water table manipulations including application of artificial drought conditions or excessive flooding was assessed in the acidicfen. Fermentative, methanogenic and denitrifying potentials in anoxic microcosm studies revealed that the potential activity of methanogens and denitrifiers was affected by changing water tables, whereas the potential activity of fermenters was largely unaffected. Changes in the copy numbers of mcrA, narG, and nosZ detected by quantitative PCR were rather small when compared to the observed changes in potential activity. Community composition of methanogens, nitrate and N2O-reducers was similar at all sampled timepoints of the manipulation experiments. The collective data indicate a stable microbial community in fen soil that is able to adapt its activity to the changing conditions quite rapidly.
Flüssigkristalline supramolekulare Systeme
- Diese Arbeit liefert einen umfassenden und systematischen Vergleich der thermischen Eigenschaften, des Phasenverhaltens und der Mesophasenstrukturen einer breiten Auswahl von 1,3,5-Benzol- und 1,3,5-Cyclohexantricarboxamiden mit linearen und verzweigten Alkylsubstituenten. Dadurch konnte ein tiefer Einblick in die Struktur-Eigenschaftsbeziehungen erhalten werden. Die Benzoltricarboxamide mit linearen Alkylsubstituenten zeigen hexagonale Mesophasen mit plastischkristalliner Ordnung (Colhp, 5 bis 6 C-Atome) bzw. mit flüssigkristalliner Ordnung (Colho, 6 bis 10 C-Atome). Der thermische Stabilitätsbereich der flüssigkristallinen Phase wird mit steigender Kettenlänge breiter. Der Kolumnenabstand wächst linear mit steigender Länge der Seitenketten. Bei den Benzoltricarboxamiden mit verzweigten Seitenketten werden in etlichen Fällen nacheinander eine Colhp- und eine Colho-Phase durchlaufen. Außerdem wurden höhere Übergangstemperaturen in die flüssigkristalline Phase (sofern vorhanden) und in die isotrope Schmelze gefunden, als bei den linear substituierten Verbindungen. Für die Überganstemperaturen gilt außerdem: Eine Verzweigung in der Nähe der Amidgruppe führt zu einer höheren Überganstemperatur. Der Kolumnenabstand ist durch die Verzweigungen größer bezogen auf die Anzahl der C-Atome in der längsten Seitenkette, aber kleiner bezogen auf die Gesamtzahl der C-Atome. Die Übergangstemperaturen der Cyclohexantricarboxamide liegen allgemein höher als die entsprechenden Temperaturen der Benzoltricarboxamide. Die andere Packung der Moleküle führt zu einem größeren Interdiskabstand aber zu einem kleineren Kolumnenabstand im Vergleich zu den Benzoltricarboxamiden. Die Cyclohexantricarboxamide mit linearen Alkylsubstituenten bilden wegen ihrer Geometrie keine hexagonalen, sondern rektangulare Mesophasen (Colrp). In einigen Fällen wurden außerdem noch kolumnar nematische (NC) Phasen gefunden. Im Rahmen dieser Arbeit wurde zum ersten Mal eine NC Phase bei einem niedermolekularen Einkomponentensystemen gefunden. Generell wurde gezeigt, dass die thermische Ausdehnung der Tricarboxamide nur in den zwei Raumrichtungen senkrecht zur Säulenachse stattfindet. Der Übergang in die isotrope Schmelze wurde mittels temperaturabhängiger IR Spektroskopie untersucht. Dabei wurde erstmals experimentell gezeigt, dass in dieser optisch isotropen Phase immer noch kolumnare Aggregate statt Einzelmoleküle vorhanden sind. Dies konnte auch mittels Röntgendiffraktometrie bestätigt werden. Diese optisch isotrope Phase ist also ein Zwischenzustand zwischen der anisotropen NC-Phase und der molekular aufgebauten isotropen Phase, in der ungeordnete Einzelmoleküle vorliegen. Nur bei sehr starken intrakolumnaren Wechselwirkungen überschreiten die gebildeten Aggregate die kritische Länge zur Bildung kolumnar nematischer Phasen. Sind die intrakolumnaren Wechselwirkungen weniger stark, brechen die Säulen in kleinere Stücke, sobald die stabilisierenden Wechselwirkungen zwischen den Säulen überwunden worden sind.
Neben den Ordnungsmerkmalen im Reinstoff wurde auch das Verhalten ausgewählter Tricarboxamide in organischen Lösemitteln untersucht. Wenn die Wechselwirkungen zwischen den Molekülen hinreichend stark sind, können auch im Lösemittel dreidimensionale Überstrukturen gebildet werden, die zur Bildung von Physikalischen Gelen führen können. Insbesondere das Cyclohexantricarboxamid mit Decylsubstituenten (N,N',N"-Tris(decyl)-cis,cis-1,3,5-cyclohexantricarboxamid) hat sich als hervorragender Gelator für organische Flüssigkeiten erwiesen, und wurde bisher noch nicht in der Literatur beschrieben. Besonders feste und klare Gele wurden aus Toluol, Xylol und Decalin erhalten, wobei bezogen auf ein Molekül Gelator mehr als 5900 Moleküle Toluol geliert werden können.
Zur Gelierung nematischer Flüssigkeiten wurde eine andere Verbindungsklasse gefunden. Phenylenbisamide und deren Amid/Harnstoffderivate sind als Gelatoren für organische Lösemittel bekannt und konnten auch erfolgreich zur Gelierung nematischer Flüssigkeiten eingesetzt werden. Es wurde gezeigt, dass diese Verbindungen zwar selbst keine Mesophasen bilden, aber in der Lage sind, flüssigkristalline Gele aus nematischen Flüssigkeiten zu erzeugen. Mit einer besonders empfindlichen Mikro-DSC konnte die Netzwerkbildung im Gel kalorimetrisch verfolgt werden. Die Änderungen der elastischen und viskosen Eigenschaften am Gel-Sol-Übergang wurden auch rheologisch bestimmt. Schließlich wurde die Netzwerkstruktur auch elektronenmikroskopisch abgebildet. Es wurden optische und elektrische Methoden eingesetzt, um den im elektrischen Feld induzierten Fréedericksz-Effekt zu untersuchen, der die Grundlage für die Anwendung in Flüssigkristallanzeigen bildet. Es wurde gezeigt, dass der Gelator einen Anstieg der Fréedericksz-Schwellspannung verursacht, was mit den mechanischen Eigenschaften des Gels zu erklären ist. Diese Schwellspannung kann durch Wahl der Probentemperatur in einem weiten Bereich eingestellt werden.
Crystalline-core micelles based on triblock terpolymers with polyethylene middle blocks
- This thesis is focused on the crystallization-induced structure formation of polyethylene containing triblock terpolymers in organic solvents to surface-compartmentalized worm-like crystalline-core micelles (wCCMs). Obtaining profound knowledge of the parameters controlling the self-assembly process allowed the production of a variety of complex one-dimensional micellar architectures with many potential applications, such as adaptive surfactants.
At first, the basic parameters that control the crystallization-induced self-assembly were explored using symmetric polystyrene-block-polyethylene-block-poly(methyl methacrylate) (PS-b-PE-b-PMMA) triblock terpolymers and a PS-b-PE-b-PS triblock copolymer. In good solvents for the PE block, e.g. THF and toluene, the selective formation of wCCMs was observed over a wide range of concentration, applied crystallization temperature and polymer composition. Whereas wCCMs produced by PS-b-PE-b-PS showed a homogeneous PS corona, a patch-like compartmentalization of the corona was observed if the micelles were formed by PS-b-PE-b-PMMA. As THF shows equal solvent quality for both corona blocks, wCCMs with almost alternating PS and PMMA compartments of about 15 nm were observed in this solvent. However, if structure formation was conducted in bad solvents for PE, such as dioxane or dimethylacetamide, spherical micelles with amorphous PE cores were formed already before crystallization. Hence, the subsequent crystallization of PE resulted in spherical CCMs with a patchy or a homogeneous corona depending on the used triblock. These findings allow the highly selective production of stable spherical or worm-like CCMs from the same polymer.
As the corona structure of the patchy micelles self-assembled from triblock terpolymers was mainly deduced from transmission electron microscopy (TEM) performed on dried samples, a small-angle neutron scattering (SANS) study was performed in order to elucidate the morphology in solution. Therefore a partly deuterated triblock terpolymer was synthesized and measured at different contrasts to allow the selective detection of the different corona compartments. The resulting SANS curves could be interpreted using a form factor model for core-shell cylinders with alternating PS and PMMA hemishells including interparticle interactions, thus validating the TEM observations. Notably, Janus-type and patchy cylinders can be clearly distinguished using the applied form factor model.
Moreover, the controlled formation of wCCMs with tunable corona composition and structure was achieved using the cocrystallization of different triblock copolymers. Via random cocrystallization of PS-b-PE-b-PMMA and PS-b-PE-b-PS the corona morphology could be tuned continuously from a mixed corona at low PMMA content over spherical PMMA patches of increasing number and size to alternating PS and PMMA patches. This approach allows to manufacture wCCMs with predefined corona structure omitting the need to synthesize a new tailor-made triblock terpolymer for every desired morphology.
By establishing the controlled crystallization-driven self-assembly of triblock terpolymers with PE middle blocks, it was further possible to prepare wCCMs with predefined average lengths up to 500 nm and length polydispersities as low as Lw/Ln = 1.1. Here, self-assembled spherical CCMs of PS-b-PE-b-PS were used as seeds for the controlled growth of PS-b-PE-b-PS unimers. Upon further addition of PS-b-PE-b-PMMA unimers these grew epitaxially onto the preexisting wCCMs, resulting in triblock co-micelles that consisted of middle blocks with a homogeneous PS corona and outer blocks with alternating PS/PMMA compartments. These structures represent not only the first block co-micelles including blocks with a patchy corona, but also the first ones produced from purely organic block copolymers.
In view of application, the ability of patchy wCCMs formed by PS-b-PE-b-PMMA to stabilize interfaces was investigated using pendant-drop tensiometry. The observed reduction of the interfacial tension at the toluene/water interface was significantly higher than that of comparable triblock terpolymer single chains and that of wCCMs with a homogeneous PS corona. Interestingly, the obtained equilibrium interfacial tension equaled that of Janus cylinders with similar dimensions. To explain this unexpected finding the corona chains were proposed to adapt to the interface via selective collapse and shielding of the incompatible part of the corona chains. Studying wCCMs formed by several triblock terpolymers with different compositions, the interfacial activity was found to increase with increasing overall length of the corona chains, and to a certain extent with the molar fraction of PS units in the corona.
Light Harvesting using Metal-Organic and Organic Sensitizers in Hybrid Solar Cells: Synthesis, Characterisation and Application
- This thesis addresses the question how to improve light harvesting with novel tailor-made metal-organic and organic sensitizers for solid-state hybrid solar cell applications. Two approaches are in the focus: 1) the design and synthesis of sensitizers featuring high extinction coefficients over a broad wavelength range and 2) modern device concepts to further enhance or extend the absorption by the combination of two sensitizers. In short: The primary goal was to broaden and boost the optical density of hybrid solar cells. To reach this, novel sensitizer with extended conjugated π-system providing excellent optical properties had to be designed and synthesised in complex multi-step reaction sequences. For ideal sensitizers, further aspects had to be taken into account such as structural demands, electronic properties, and the tendency towards aggregation.
The first part of this thesis deals with the synthesis, characterisation and application of a series of metal-organic ruthenium(II) donor-antenna complexes. In addition to the typically broad absorption of Ru(II)bis(bipyridyl)(NCS)2 complexes in the blue-green region arising from MLCT, these dyes feature much higher extinction coefficients in comparison to a commercially available reference dye lacking any donor-antenna groups. By the application of these Ru(II) complexes in solid-state dye-sensitized solar cells, we found a clear structure-property relationship. The performance - especially the photocurrent density - was significantly improved with increasing extension of the delocalized system of the donor-antenna groups.
To further boost the optical density in hybrid solar cells sensitized with a donor-antenna ruthenium dye (Ru-TPA-NCS), we developed an innovative and technically relevant concept for multichromophore sensitization involving a second sensitizer (TPD-dye). The latter absorbs in a region where Ru-TPA-NCS absorbs weakly. The solar cells were fabricated according to a novel method developed by us. However, the power conversion efficiencies of multichromophore hybrid blend solar cells were initially low due the weak interconnectivity of the TiO2 particles. This issue was addressed by an optimization of the TiO2:spiro-OMeTAD ratio and the addition of PCBM
A further concept dealing with the combination of two sensitizers in solid-state dye-sensitized solar cell was accomplished by co-sensitization of a triphenyldiamine-based dye (TPD-dye) absorbing in the blue region and squaraine dye (SQ-dye) mainly absorbing the red part of the visible spectrum. In this way, the optical response of the device was extended up to 700 nm. Under optimized conditions, a conversion efficiency of 2.41 % could be reached.
To accomplish the desired panchromaticity or even an extension of the absorption up to the NIR region with a single sensitizer, novel BODIPY dyes with excellent optical properties were designed and synthesised. We prepared BODIPYs with donor-groups to extend the delocalized system and integrated a meso-ethynyl bridge between the BODIPY core and the anchoring group to improve the electronic connection between them. For comparison, we synthesised the corresponding BODIPYs without donor-moieties and without ethynyl bridge. The multi-step synthetic routes were optimized, the mechanism of the donor-attachment was clarified and the introduction of the ethynylphenyl group in the meso-position was accomplished for the first time. The optical characterisation of the compounds disclosed an impressively broad and intensive spectral response, especially for a meso-ethynylphenyl BODIPY with donor-groups. This dye absorbs up to 1030 nm with high extinction coefficients. This makes suitable functionalised BODIPYs promising candidates for solar cell applications.
The next part took advantage of the excellent optical properties of BODIPYs and expanded the topic towards the concept of energy transfer. Here, an unattached energy donor dye provides additional adsorption and transfers the energy to a sensitizing acceptor dye. Indeed, for appropriate combinations an additional contribution to the external quantum efficiency was found in the absorption region of the energy donor dye.
Furthermore, a review chapter covering all aspects of dye-sensitized solar cells and the sensitizers is added as appendix.
In summary, this thesis presents the successful design, synthesis and characterisation of both metal-organic and organic sensitizers including ruthenium complexes, triphenyldiamine-based dyes, a squaraine sensitizer and BODIPY dyes. The sensitizers (either individually or in combination with complementary sensitizers) provide excellent optical properties for the application in solar cells. The applicability of these sensitizers was successfully demonstrated in standard solid-state dye-sensitized solar cells, in newly developed multichromophore hybrid blend solar cells, co-sensitized solar cells and in solid-state dye-sensitized solar cells taking advantage of energy transfer.
The origins of olivine fabric transitions and their effects on seismic anisotropy in the upper mantle
- Convecting mantle plays a central role in the thermal and geochemical evolution of the Earth. It provides the principal force responsible for major geological features such as mountains and ocean basins. Plate tectonics and its violent consequences such as earthquakes and volcanoes are all manifestations of the dynamics of the convective mantle. Shearing forces generated by mantle convection leads to lattice preferred orientation (LPO) of the major upper mantle mineral phases. LPO that develops in this way is thought to be the principal cause behind seismic anisotropy in the upper mantle, which can consequently be used to chart convective flow of the mantle.
Strong changes in seismic anisotropy occur in the top 300 km of the upper mantle where olivine is the principal mineral. In this study a solid media high pressure deformation apparatus, called the deformation-DIA or D-DIA, has been used to deform aggregates of San Carlos olivine in simple shear geometry at pressures between 3 and 8.5 GPa and temperatures from 1300-1500°C. As part of this project a high pressure and temperature solid-media cubic assembly was developed to facilitate these experiment that employed alumina pistons cut at 45° to shear the sample but minimized cold deformation of the sample by employing initially porous alumina in the sample column. Once stable high pressures and temperature were reached the cubic assembly was deformed by compressing two vertically oriented anvils of the D-DIA, while the four horizontally oriented anvils were maintained at a constant loading force. This assembly shortening led to shearing of the olivine sample. Recovered samples were analyzed for fabric development employing electron backscattered diffraction (EBSD) and microstructure was observed using transmission electron microscopy (TEM).
Experiments were performed at each pressure and temperature as a function of strain rate and H2O content. In dry olivine deformation experiments performed at slower strain rates an A-type fabric dominated at all pressures and temperatures, implying deformation by dislocation glide through the (010) slip system. At higher strain rates evidence for the B-type fabric was observed, suggesting increased activity of the (010) slip system at higher stresses. Recrystallization grains size and dislocation densities were used to estimate stresses in the samples and a good correlation was observed between strain rate and estimated flow stresses. Dry experiments from 8.5 GPa and 1500°C exhibited no LPO, which may be an indication for deformation through diffusion accommodated grain boundary sliding at these conditions. No indication was found that pressure influences the dominant slip system in olivine, in contrast to previous studies. It is considered that previously reported incidences of pressure effects can in fact be attributed to the development of higher stresses in experiments performed at higher pressures.
Fabrics in H2O bearing olivine deformed at similar conditions revealed the overriding dominance of the C-type fabric, developed through action of the (100) slip system. Variations in pressure, temperature and strain rate had little influence on this fabric development. TEM observations confirmed the presence of dislocations with slip systems consistent with the development of the macroscopic fabrics. Viscoplastic self consistent modeling was employed to understand the development of fabric in the samples and to estimate the relative contributions of variations slip systems to the developed fabrics.
These results are used to construct an olivine fabric map which is found to be consistent with some previous studies at lower pressures. It is argued that the decrease in seismic anisotropy observed in the top 300 km of the upper mantle cannot originate from a pressure induced change in the dominant olivine deformation fabric. Instead it is argued that changes in the H2O content of olivine with depth cause a shift in the dominant fabric from A-type to C-type, with a possible excursion through the E-type fabric, dominant slip system (001), which was, however, not observed in this study. Modeling is used to show that this variation in fabric with depth can cause the observed weakening the seismic anisotropy in the upper mantle if the olivine H2O content increases from below 100 ppm at 50 km to 250 ppm at 300 km. Rather than implying an increased in the H2O content of the mantle with depth, however, it is argued that this change in olivine H2O content can be caused by changes in the H2O olivine-pyroxene partition coefficients with depth, for a fixed bulk mantle H2O content of 200 ppm.
Similar deformation experiments performed on a peridotite assemblage at 8.5 GPa and 1300°C indicate identical olivine fabrics to those observed in monomineralic experiments at the same conditions. Fabrics for diopside and enstatite were found to be similar to those found in previously performed lower pressure experiments.
Experiments on a piezoelectric single crystal of GaPO4 were performed in the D-DIA and 6-ram MAVO press at high pressures in order to measure charge on the crystal developed through the application of deviatoric stresses. Electrical charges were measured through the use of an operational amplifier. Experiments performed at room temperature using a developed cubic assembly were successful in measuring quantifiable electrical charges resulting from the advancement of the deformation anvils by as little as 0.5 µm. Although the piezoelectric constant for this material is not yet calibrated at high pressures, stresses were estimated from the measured charges and measureable values were in the range 4-350 MPa.
Synthesis and Combinatorial Optimization of Novel Star-Shaped Resist Materials for Lithographic Applications
- Gordon Earle Moore predicted in the mid-1960s the cost-efficient doubling of transistors’ number on integrated circuits every two years – known as Moore’s Law. Leading companies orientates by the development of integrated circuits on this Moore’s Law and contributed to this prediction to come true up to the present. In so doing, the semiconductor industry drafts every two years aims to fulfill this prediction summarized in the so-called International Technology Roadmap for Semiconductors (ITRS). The ITRS lists guidelines for cost-effective progresses in performance of integrated circuits, e.g. design of integrated circuits, advancements of exposure tools and exposure techniques, and closely correlated resist materials. This thesis deals with the development of new resist materials and their combinatorial investigation concerning the performance in lithographic patterning.
The lithographic patterning procedure is a sequence of multiple processing steps and thus this procedure involves many processing variables interacting strongly with each other. For understanding and comprehensive investigation of such multi-variable dependent systems the development and implementation of combinatorial approaches were in the focus of this thesis. Furthermore this thesis is focused on the synthesis of new tailored resist materials for lithographic patterning. Star topology was the selected polymer architecture of this new resist material realized via the core-first atom transfer radical polymerization (ATRP) technique. The lithographic performance of electron beam lithography patterning was investigated for the resulting randomly distributed star terpolymers and star block copolymers by combinatorial libraries in view of features’ quality.
The first chapter deals with developed, adapted, and improved combinatorial techniques for thin film investigations in general and utilized for lithographic patterning investigations in particular. The lithographic patterning procedure of chemically amplified resist systems consists of various steps: film preparation, post apply bake (PAB) to remove residual solvent, exposure, post exposure bake (PEB) to activate the catalytic reaction, and development. For this rather complex process variable gradients were developed and adapted for each processing step to investigate and optimize the performance of especially new resist systems. For the film preparation a method was developed to prepare an internal material composition gradient. This was realized by a gradient extrudate prepared using two individual controllable syringe pumps and subsequent doctor-blading. The material composition gradient was verified by high performance liquid chromatography. The second (PAB) and also the fourth (PEB) processing step are both annealing processes of the resist film although they serve different purposes. For the investigation of such annealing processes temperature gradients were prepared adjustable in temperature range and temperature slope. This adjustability is ensured by the active heating and the active cooling source and also by the gap and the type of metal plate. For the third step exposure methods were developed to realize defined exposure dose gradients in very small areas of the resist film. Different exposure dose gradients were designed for photolithography as well as for electron beam lithography. For the latter case this dose gradient was programmed in the pattern design using the software which controls the electron beam during the exposure process. The dose gradient for photolithography investigations was realized by a special designed shadow mask. For the last processing step development a preliminary screening of the dissolubility conditions of the resist film was established utilizing quartz crystal microbalances. Based on this measured dissolubility behavior the time frame was set for development time gradients performed by a stepwise or continuously immersion of the resist films. Lastly two to three variable gradients were combined to binary or ternary combinatorial libraries, respectively. The ternary combinatorial libraries allow the investigation of three variables of the lithographic patterning process in one experiment. Thus it is possible to optimize a resist material system fast and efficiently in respect to resist performance.
In the second chapter a star-shaped teroligomer is reported as new high potential resist type for lithographic patterning purposes. The polymerization was carried out via the core-first ATRP route using a functionalized saccharose with eight initiating sites as core. Four star-shaped teroligomers were synthesized with varying target arm lengths. In addition a saccharose molecule was synthesized with an average number of 3.5 initiating sites and thus a star oligomer was realized with a reduced arm number but an identical core and similar arm length. As reference resist material a linear model oligomer was synthesized using ethyl 2-bromoisobutyrate as initiator. For all polymers narrow monomodal distributions were detected with polydispersity index values of lower than 1.1. Based on calibration polymerizations runs the monomer feed of the three used monomers was adapted to achieve targeted monomer incorporations for all teroligomers. The targeted monomer incorporation was copied from a currently industrially used linear teroligomer. One star oligomer was selected as proof of principle for the utilization of the star architecture for lithographic purposes. This new resist material was combinatorial investigated in a ternary library and thus optimized in one experiment concerning exposure dose, PEB temperature, and development time. The optimized patterns with a feature size of 100 nm and an excellent line edge roughness (LER) value of 3.1 nm were observed.
The last chapter of this thesis demonstrates the straight forward advancement of the star-shaped resist material reported in chapter two. The statistical monomer incorporation was exchanged by the introduction of the tailored star block copolymer architecture. This architecture was synthesized for the first time via the core-first ATRP route by full conversion of a first polar monomer and in-situ polymerization of additionally added nonpolar monomer. The successful syntheses were indicated by contact angle measurements showing increased hydrophobicity of star block copolymers in contrast to random star copolymers with the same monomer incorporation. The star block copolymers exhibited also enhanced dissolubility behavior characterized by quartz crystal microbalance measurements. Furthermore they demonstrated an up to eight times increased sensitivity at their lithographic application in contrast to the synthesized reference linear copolymer. The most promising star block copolymer was selected to investigate its lithographic performance. The optimization was performed in a ternary combinatorial library based on the gradient variables exposure dose and feature size, PEB temperature, and development time. The optimized pattern of clear lines and a feature size of 66 nm was observed with a LER value of 6 nm.
To conclude, different tailored star-shaped terpolymers were synthesized using the ATRP core-first route and successfully applied in the lithographic patterning process for the first time. In addition the combinatorial optimization offers the absolutely promising potential of utilizing these star shaped resist materials by the demonstrated brilliant LER values, the achieved extremely high sensitivity, and the fast and efficient development of clear 66 nm lines.
Umweltbildung zum Thema Klimawandel im botanischen Garten: Wissen, Einstellungen und Konzepte von Jugendlichen
- Das Thema Klimawandel ist eines der wichtigsten sozio-wissenschaftlichen Themen unserer Zeit (Klosterman & Sadler, 2010) und sicherlich auch eine der größten Bedrohungen für unsere Ökosysteme (Fischlin et al., 2007). Dementsprechend groß ist das Interesse sowohl in der Wissenschaft als auch in der Öffentlichkeit. Die Komplexität des Phänomens, seine vielfältigen lokalen und globalen Auswirkungen sowie die Flut an, teilweise inkorrekten, Informationen, mit denen (nicht nur) Jugendliche konfrontiert werden (Weingart et al., 2000), führen zu Unsicherheiten (Fortner et al., 2000) und erschweren ein Verstehen des Klimawandels zusätzlich. Entsprechende Umfragen zeigen Jugendliche durchaus bereit, im Klimaschutz aktiv zu werden, sie dokumentieren häufig aber auch eine individuelle Hilflosigkeit angesichts des globalen Charakters des Klimawandels (Emnid, 2009; forsa, 2009). Durch oft widersprüchliche Informationen entstehen häufig Alltagsvorstellungen über den Klimawandel, die mit der wissenschaftlichen Sichtweise nicht übereinstimmen (z. B. Andersson & Wallin, 2000; Lombardi & Sinatra, 2010; Shepardson et al., 2009). Das Thema Klimawandel bedarf daher einer Kommunikationsstrategie, die gängige Alltagsvorstellungen mit der wissenschaftlichen Sichtweise auf einen gemeinsamen Nenner bringen kann, aber auch Handlungsoptionen vermittelt, um die vorhandene Aktionsbereitschaft zu aktivieren (Bord et al., 2000).
Die vorliegende Studie zieht konsequent die Prinzipien der Umweltbildung als Basis für eine Bildung zum Thema Klimawandel heran, also die Wissensvermittlung zu umweltrelevanten Themen, die Förderung von umweltfreundlichen Einstellungen sowie die Unterstützung einer besseren Naturverbundenheit (Stern et al., 2008). Zum Erreichen dieser Ziele bieten sich außerschulische Lernorte für Umweltbildungsprogramme besonders an, da sie direkte Erlebnisse mit der Natur ermöglichen und so neben kognitiven auch affektive Domänen ansprechen. Die vorliegende Studie wurde ganz bewusst am außerschulischen Lernort botanischer Garten durchgeführt, weil hier ausgewählte Pflanzenarten aus nahezu allen Ökosystemen der Welt vertreten sind. Dadurch steht Kindern und Jugendlichen sozusagen ein „Fenster zur botanischen Welt“ zur Verfügung, welches globale Auswirkungen des Klimawandels hervorragend veranschaulichen kann.
Alle vier vorgestellten Studien beleuchten das kognitive Wissen und Vorstellungen von Jugendlichen zwischen 14 und 19 Jahren zum Thema Klimawandel; sie beschreiben ihre Naturverbundenheit und Umwelteinstellungen und deren positive Beeinflussung durch ein speziell abgestimmtes Umweltbildungsprogramm in einem botanischen Garten. Darüber hinaus werden gezielte Implikationen für die Entwicklung und Durchführung ähnlicher Programme vorgeschlagen.
Teilstudie A bezieht sich auf die Veränderung von Schülervorstellungen in Abhängigkeit von der Gestaltung von Unterrichtsmaterialien. Beispielsweise konnte durch ein gezieltes Eingehen auf typische Alltagsvorstellungen eine höhere Rate an Veränderungen hin zu wissenschaftlichen Konzepten erreicht werden. Teilstudie B beschreibt Alltagskonzepte von Jugendlichen und deren Beeinflussung durch ein Umweltbildungsprogramm hin zu den wissenschaftlich korrekten Konzepten zum Thema Klimawandel. Dabei wird speziell eine Methode zur Erfassung solcher Veränderungen der Schülervorstellungen dargelegt, die auch im Unterrichtsalltag leicht und ohne großen Zeitaufwand einzusetzen ist. Teilstudie C zeigt das kognitive Wissen der teilnehmenden Jugendlichen sowohl direkt nach dem Programm als auch vier bis sechs Wochen später als signifikant höher als vor einer Programmteilnahme. Schließlich weist Teilstudie D direkt nach einer Programmteilnahme erhöhte Umwelteinstellungen und erhöhte Naturverbundenheit nach, die allerdings über den längeren Zeitraum von vier bis sechs Wochen betrachtet nur bezüglich der Ausnutzung der Natur bestehen blieb; der Grad der Naturverbundenheit sowie die positivere Einstellung zum Naturschutz fielen wieder auf das Ausgangniveau zurück, bedürfen demnach einer wiederholten Intervention.
In der Zusammenfassung bleibt also festzuhalten, dass kurzfristige Umweltbildungsprogramme zum Thema Klimawandel durchaus effektiv und langfristig das kognitive Wissen der Schülerinnen und Schüler erhöhen können; dies gilt ebenso für die Einstellung bezüglich der Ausnutzung der Natur, nicht aber für die Naturverbundenheit oder Umweltschutzeinstellungen. Letztere zeigten nur kurzfristig eine positive Veränderung. Eine längere Programmdauer und wiederholte Naturerlebnisse könnten hier Abhilfe schaffen. Darüber hinaus wird der Vorteil einer unterrichtlichen Einbindung von Alltagsvorstellungen erfolgreich aufgezeigt, konsequenteres Eingehen auf bestehende Vorstellungen im Unterricht wirkt sich direkt auf die Effektivität aus. Künftige vergleichbare Lerneinheiten sollten dies berücksichtigen.