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Henning Rohwer wird im Dorf Esau genannt, weil sein Vater sich dazu entschieden hat, die Erbfolge zu durchbrechen und seinen Bauernhof nicht dem erstgeborenen Henning zu übertragen, sondern dem zweiten geeigneteren Sohn Fritz. Fritz soll Anna Harder heiraten. Henning versucht, durch Anritzen des Pferdegeschirrs die Brautfahrt der beiden mit einem tödlichen Unfall enden zu lassen und sich auf diese Weise den Hof zurückzuerobern. Diese Geschichte, die in der 1975 posthum publizierten Baasdörper Krönk andeutungsweise enthalten ist, wurde von F.E. Peters zu Lebzeiten auf Hochdeutsch veröffentlicht. Sie erzählt von dem sozialen Abstieg eines Verstoßenen und den archaischen Selektionsmechanismen und Abwehrstrategien einer Dorfgemeinschaft, die Verstöße ihrer Mitglieder gegen den bäuerlichen Sitten- und Ehrenkodex hart ahndet.
The potential increase in frequency and magnitude of extreme floods is currently discussed in terms of global warming and the intensification of the hydrological cycle. The profound knowledge of past natural variability of floods is of utmost importance in order to assess flood risk for the future. Since instrumental flood series cover only the last ~150 years, other approaches to reconstruct historical and pre-historical flood events are needed. Annually laminated (varved) lake sediments are meaningful natural geoarchives because they provide continuous records of environmental changes > 10000 years down to a seasonal resolution. Since lake basins additionally act as natural sediment traps, the riverine sediment supply, which is preserved as detrital event layers in the lake sediments, can be used as a proxy for extreme discharge events. Within my thesis I examined a ~ 8.50 m long sedimentary record from the pre-Alpine Lake Mondsee (Northeast European Alps), which covered the last 7000 years. This sediment record consists of calcite varves and intercalated detrital layers, which range in thickness from 0.05 to 32 mm. Detrital layer deposition was analysed by a combined method of microfacies analysis via thin sections, Scanning Electron Microscopy (SEM), μX-ray fluorescence (μXRF) scanning and magnetic susceptibility. This approach allows characterizing individual detrital event layers and assigning a corresponding input mechanism and catchment. Based on varve counting and controlled by 14C age dates, the main goals of this thesis are (i) to identify seasonal runoff processes, which lead to significant sediment supply from the catchment into the lake basin and (ii) to investigate flood frequency under changing climate boundary conditions. This thesis follows a line of different time slices, presenting an integrative approach linking instrumental and historical flood data from Lake Mondsee in order to evaluate the flood record inferred from Lake Mondsee sediments. The investigation of eleven short cores covering the last 100 years reveals the abundance of 12 detrital layers. Therein, two types of detrital layers are distinguished by grain size, geochemical composition and distribution pattern within the lake basin. Detrital layers, which are enriched in siliciclastic and dolomitic material, reveal sediment supply from the Flysch sediments and Northern Calcareous Alps into the lake basin. These layers are thicker in the northern lake basin (0.1-3.9 mm) and thinner in the southern lake basin (0.05-1.6 mm). Detrital layers, which are enriched in dolomitic components forming graded detrital layers (turbidites), indicate the provenance from the Northern Calcareous Alps. These layers are generally thicker (0.65-32 mm) and are solely recorded within the southern lake basin. In comparison with instrumental data, thicker graded layers result from local debris flow events in summer, whereas thin layers are deposited during regional flood events in spring/summer. Extreme summer floods as reported from flood layer deposition are principally caused by cyclonic activity from the Mediterranean Sea, e.g. July 1954, July 1997 and August 2002. During the last two millennia, Lake Mondsee sediments reveal two significant flood intervals with decadal-scale flood episodes, during the Dark Ages Cold Period (DACP) and the transition from the Medieval Climate Anomaly (MCA) into the Little Ice Age (LIA) suggesting a linkage of transition to climate cooling and summer flood recurrences in the Northeastern Alps. In contrast, intermediate or decreased flood episodes appeared during the MWP and the LIA. This indicates a non-straightforward relationship between temperature and flood recurrence, suggesting higher cyclonic activity during climate transition in the Northeast Alps. The 7000-year flood chronology reveals 47 debris flows and 269 floods, with increased flood activity shifting around 3500 and 1500 varve yr BP (varve yr BP = varve years before present, before present = AD 1950). This significant increase in flood activity shows a coincidence with millennial-scale climate cooling that is reported from main Alpine glacier advances and lower tree lines in the European Alps since about 3300 cal. yr BP (calibrated years before present). Despite relatively low flood occurrence prior to 1500 varve yr BP, floods at Lake Mondsee could have also influenced human life in early Neolithic lake dwellings (5750-4750 cal. yr BP). While the first lake dwellings were constructed on wetlands, the later lake dwellings were built on piles in the water suggesting an early flood risk adaptation of humans and/or a general change of the Late Neolithic Culture of lake-dwellers because of socio-economic reasons. However, a direct relationship between the final abandonment of the lake dwellings and higher flood frequencies is not evidenced.
Assuming that liquid iron alloy from the outer core interacts with the solid silicate-rich lower mantle the influence on the core-mantle reflected phase PcP is studied. If the core-mantle boundary is not a sharp discontinuity, this becomes apparent in the waveform and amplitude of PcP. Iron-silicate mixing would lead to regions of partial melting with higher density which in turn reduces the velocity of seismic waves. On the basis of the calculation and interpretation of short-period synthetic seismograms, using the reflectivity and Gauss Beam method, a model space is evaluated for these ultra-low velocity zones (ULVZs). The aim of this thesis is to analyse the behaviour of PcP between 10° and 40° source distance for such models using different velocity and density configurations. Furthermore, the resolution limits of seismic data are discussed. The influence of the assumed layer thickness, dominant source frequency and ULVZ topography are analysed. The Gräfenberg and NORSAR arrays are then used to investigate PcP from deep earthquakes and nuclear explosions. The seismic resolution of an ULVZ is limited both for velocity and density contrasts and layer thicknesses. Even a very thin global core-mantle transition zone (CMTZ), rather than a discrete boundary and also with strong impedance contrasts, seems possible: If no precursor is observable but the PcP_model /PcP_smooth amplitude reduction amounts to more than 10%, a very thin ULVZ of 5 km with a first-order discontinuity may exist. Otherwise, if amplitude reductions of less than 10% are obtained, this could indicate either a moderate, thin ULVZ or a gradient mantle-side CMTZ. Synthetic computations reveal notable amplitude variations as function of the distance and the impedance contrasts. Thereby a primary density effect in the very steep-angle range and a pronounced velocity dependency in the wide-angle region can be predicted. In view of the modelled findings, there is evidence for a 10 to 13.5 km thick ULVZ 600 km south-eastern of Moscow with a NW-SE extension of about 450 km. Here a single specific assumption about the velocity and density anomaly is not possible. This is in agreement with the synthetic results in which several models create similar amplitude-waveform characteristics. For example, a ULVZ model with contrasts of -5% VP , -15% VS and +5% density explain the measured PcP amplitudes. Moreover, below SW Finland and NNW of the Caspian Sea a CMB topography can be assumed. The amplitude measurements indicate a wavelength of 200 km and a height of 1 km topography, previously also shown in the study by Kampfmann and Müller (1989). Better constraints might be provided by a joined analysis of seismological data, mineralogical experiments and geodynamic modelling.
This thesis is focussed on the electronic properties of the new material class named topological insulators. Spin and angle resolved photoelectron spectroscopy have been applied to reveal several unique properties of the surface state of these materials. The first part of this thesis introduces the methodical background of these quite established experimental techniques.
In the following chapter, the theoretical concept of topological insulators is introduced. Starting from the prominent example of the quantum Hall effect, the application of topological invariants to classify material systems is illuminated. It is explained how, in presence of time reversal symmetry, which is broken in the quantum Hall phase, strong spin orbit coupling can drive a system into a topologically non trivial phase. The prediction of the spin quantum Hall effect in two dimensional insulators an the generalization to the three dimensional case of topological insulators is reviewed together with the first experimental realization of a three dimensional topological insulator in the Bi1-xSbx alloys given in the literature.
The experimental part starts with the introduction of the Bi2X3 (X=Se, Te) family of materials. Recent theoretical predictions and experimental findings on the bulk and surface electronic structure of these materials are introduced in close discussion to our own experimental results. Furthermore, it is revealed, that the topological surface state of Bi2Te3 shares its orbital symmetry with the bulk valence band and the observation of a temperature induced shift of the chemical potential is to a high probability unmasked as a doping effect due to residual gas adsorption.
The surface state of Bi2Te3 is found to be highly spin polarized with a polarization value of about 70% in a macroscopic area, while in Bi2Se3 the polarization appears reduced, not exceeding 50%. We, however, argue that the polarization is most likely only extrinsically limited in terms of the finite angular resolution and the lacking detectability of the out of plane component of the electron spin. A further argument is based on the reduced surface quality of the single crystals after cleavage and, for Bi2Se3 a sensitivity of the electronic structure to photon exposure.
We probe the robustness of the topological surface state in Bi2X3 against surface impurities in Chapter 5. This robustness is provided through the protection by the time reversal symmetry. Silver, deposited on the (111) surface of Bi2Se3 leads to a strong electron doping but the surface state is observed up to a deposited Ag mass equivalent to one atomic monolayer. The opposite sign of doping, i.e., hole-like, is observed by exposing oxygen to Bi2Te3. But while the n-type shift of Ag on Bi2Se3 appears to be more or less rigid, O2 is lifting the Dirac point of the topological surface state in Bi2Te3 out of the valence band minimum at $\Gamma$. After increasing the oxygen dose further, it is possible to shift the Dirac point to the Fermi level, while the valence band stays well beyond. The effect is found reversible, by warming up the samples which is interpreted in terms of physisorption of O2.
For magnetic impurities, i.e., Fe, we find a similar behavior as for the case of Ag in both Bi2Se3 and Bi2Te3. However, in that case the robustness is unexpected, since magnetic impurities are capable to break time reversal symmetry which should introduce a gap in the surface state at the Dirac point which in turn removes the protection. We argue, that the fact that the surface state shows no gap must be attributed to a missing magnetization of the Fe overlayer. In Bi2Te3 we are able to observe the surface state for deposited iron mass equivalents in the monolayer regime. Furthermore, we gain control over the sign of doping through the sample temperature during deposition.
Chapter6 is devoted to the lifetime broadening of the photoemission signal from the topological surface states of Bi2Se3 and Bi2Te3. It is revealed that the hexagonal warping of the surface state in Bi2Te3 introduces an anisotropy for electrons traveling along the two distinct high symmetry directions of the surface Brillouin zone, i.e., $\Gamma$K and $\Gamma$M. We show that the phonon coupling strength to the surface electrons in Bi2Te3 is in nice agreement with the theoretical prediction but, nevertheless, higher than one may expect. We argue that the electron-phonon coupling is one of the main contributions to the decay of photoholes but the relatively small size of the Fermi surface limits the number of phonon modes that may scatter off electrons. This effect is manifested in the energy dependence of the imaginary part of the electron self energy of the surface state which shows a decay to higher binding energies in contrast to the monotonic increase proportional to E$^2$ in the Fermi liquid theory due to electron-electron interaction.
Furthermore, the effect of the surface impurities of Chapter 5 on the quasiparticle life- times is investigated. We find that Fe impurities have a much stronger influence on the lifetimes as compared to Ag. Moreover, we find that the influence is stronger independently of the sign of the doping. We argue that this observation suggests a minor contribution of the warping on increased scattering rates in contrast to current belief. This is additionally confirmed by the observation that the scattering rates increase further with increasing silver amount while the doping stays constant and by the fact that clean Bi2Se3 and Bi2Te3 show very similar scattering rates regardless of the much stronger warping in Bi2Te3.
In the last chapter we report on a strong circular dichroism in the angle distribution of the photoemission signal of the surface state of Bi2Te3. We show that the color pattern obtained by calculating the difference between photoemission intensities measured with opposite photon helicity reflects the pattern expected for the spin polarization. However, we find a strong influence on strength and even sign of the effect when varying the photon energy. The sign change is qualitatively confirmed by means of one-step photoemission calculations conducted by our collaborators from the LMU München, while the calculated spin polarization is found to be independent of the excitation energy. Experiment and theory together unambiguously uncover the dichroism in these systems as a final state effect and the question in the title of the chapter has to be negated: Circular dichroism in the angle distribution is not a new spin sensitive technique.
Ein viel diskutiertes Thema unserer Zeit ist die Zukunft der Energiegewinnung und Speicherung. Dabei nimmt die Nanowissenschaft eine bedeutende Rolle ein; sie führt zu einer Effizienzsteigerung bei der Speicherung und Gewinnung durch bereits bekannte Materialien und durch neue Materialien. In diesem Zusammenhang ist die Chemie Wegbereiter für Nanomaterialien. Allerdings führen bisher die meisten bekannten Synthesen von Nanopartikeln zu undefinierten Partikeln. Eine einfache, kostengünstige und sichere Synthese würde die Möglichkeit einer breiten Anwendung und Skalierbarkeit bieten. In dieser Arbeit soll daher die Darstellung der einfachen Synthese von Mangannitrid-, Aluminiumnitrid-, Lithiummangansilicat-, Zirkonium-oxinitrid- und Mangancarbonatnanopartikel betrachtet werden. Dabei werden die sogenannte Harnstoff-Glas-Route als eine Festphasensynthese und die Solvothermalsynthese als typische Flüssigphasensynthese eingesetzt. Beide Synthesewege führen zu definierten Partikelgrößen und interessanten Morphologien und ermöglichen eine Einflussnahme auf die Produkte. Im Falle der Synthese der Mangannitridnanopartikel mithilfe der Harnstoff-Glas-Route führt diese zu Nanopartikeln mit Kern-Hülle-Struktur, deren Einsatz als Konversionsmaterial erstmalig vorgestellt wird. Mit dem Ziel einer leichteren Anwendung von Nanopartikeln wird eine einfache Beschichtung von Oberflächen mit Nanopartikeln mithilfe der Rotationsbeschichtung beschrieben. Es entstand ein Gemisch aus MnN0,43/MnO-Nanopartikeln, eingebettet in einem Kohlenstofffilm, dessen Untersuchung als Konversionsmaterial hohe spezifische Kapazitäten (811 mAh/g) zeigt, die die von dem konventionellen Anodenmaterial Graphit (372 mAh/g) übersteigt. Neben der Synthese des Anodenmaterials wurde ebenfalls die des Kathodenmaterials Li2MnSiO4-Nanopartikeln mithilfe der Harnstoff-Glas-Route vorgestellt. Mithilfe der Synthese von Zirkoniumoxinitridnanopartikeln Zr2ON2 kann eine einfache Einflussnahme auf das gewünschte Produkt durch die Variation derReaktionsbedingungen, wie Harnstoffmenge oder Reaktionstemperatur, bei der Harnstoff-Glas-Route demonstriert werden. Der Zusatz von kleinsten Mengen an Ammoniumchlorid vermeidet, dass sich Kohlenstoff im Endprodukt bildet und führt so zu gelben Zr2ON2-Nanopartikeln mit einer Größe d = 8 nm, die Halbleitereigen-schaften besitzen. Die Synthese von Aluminiumnitridnanopartikeln führt zu kristallinen Nanopartikeln, die in eine amorphe Matrix eingebettet sind. Die Solvothermalsynthese von Mangancarbonatnanopartikel lässt neue Morphologien in Form von Nanostäbchen entstehen, die zu schuppenartigen sphärischen Überstrukturen agglomeriert sind.
Heine Steenhagen erzählt die Geschichte von Aufstieg und Fall eines unehelichen Kindes, das in einem holsteinischen Dorf der Jahrhundertwende, dem fiktiven Vollstedt, aufwächst und als Ausgleich für die in der Jugend erlittenen Demütigungen eine militärische Karriere anstrebt, mit der er es seinem Heimatdorf zeigen will („Ik wöll ju dat woll wiesen!“). Als er beginnt, die Sprossen der sozialen Leiter zu erklimmen, wird sein Jugendfeind Jürgen Grootholm zu einem Hindernis auf dem Weg nach oben. Um ihn zu „überholen“, sich an den Vollstedtern zu rächen und die berechnende Margot Kandelhardt heiraten zu können, denunziert Heinrich Steinhagen den Konkurrenten wegen einer Urlaubsüberschreitung in der Hoffnung, dessen Beförderung zu vereiteln und leitet damit sein eigenes tragisches Ende ein.
Data dependencies, or integrity constraints, are used to improve the quality of a database schema, to optimize queries, and to ensure consistency in a database. In the last years conditional dependencies have been introduced to analyze and improve data quality. In short, a conditional dependency is a dependency with a limited scope defined by conditions over one or more attributes. Only the matching part of the instance must adhere to the dependency. In this paper we focus on conditional inclusion dependencies (CINDs). We generalize the definition of CINDs, distinguishing covering and completeness conditions. We present a new use case for such CINDs showing their value for solving complex data quality tasks. Further, we define quality measures for conditions inspired by precision and recall. We propose efficient algorithms that identify covering and completeness conditions conforming to given quality thresholds. Our algorithms choose not only the condition values but also the condition attributes automatically. Finally, we show that our approach efficiently provides meaningful and helpful results for our use case.
Goethe in Vicenza 1952
(2012)
"O du fröhliche ..."
(2012)
Der Begriff „Kindjees“ (Kind Jesus) bezeichnete lange Zeit in ländlichen Gegenden Norddeutschlands den Weihnachtsmann. Peters erinnert sich hier an die Weihnachtsbräuche seiner Kindheit und schildert gleichzeitig die eigene Entwicklung von dem blind der Macht des Kindjees vertrauenden Knaben zu dem Friedrich Schiller verehrenden Vierzehnjährigen, der selbst für die Kleineren die Rolle des Kindjees übernimmt. Die Schönheit der in der Schule gesungenen Kirchenlieder von Gerhard Tersteegen, die Faszination der Kinder für die Neuruppiner Bilderbogen (plattdeutsch: Lex) tragen viel zu der märchenhaften Stimmung bei, in der die Weihnachtsvorbereitungen in Luhnstedt, dem Heimatdorf des Dichters, stattfinden: „Überhaupt kam es vor Weihnachten sehr darauf an, alles, auch das Geringste, in der vertrauten Form wiederkehren zu lassen, Tradition zu schaffen. Die periodische, unbedingt gleichförmige Wiederkehr äußerer Ereignisse ist eine Quelle der Poesie.“
Jochen Pahl un de Subrekter
(2012)
Detlev von Liliencron
(2012)
Charakterisierung und Bewertung des Schaffens Detlevs von Liliencron und Überlegungen zu dessen Rezeption. Es werden Liliencrons Liebe zu Schleswig-Holstein, die Unmöglichkeit, ihn einer Schule zuzuordnen sowie die synästhetischen Qualitäten seines innovativen Werkes von dem Synästhetiker Peters hervorgehoben. Auch Humor und Menschlichkeit Liliencrons finden Erwähnung.
Am alten Markt
(2012)
Weihnacht 1914 in Issoudun
(2012)
F. E. Peters wurde 1914 als junger Lehrer eingezogen und an der Marne von den Franzosen gefangengenommen. In seinen Kriegserinnerungen ("Kriegsgefangener in Frankreich (1914-1920)")beschreibt er die Zeit seiner Gefangenschaft und auch seine Freundschaft mit dem Schauspieler Willi Lohmann. In dieser Erzählung organisieren Kriegsgefangene ein Weihnachtsfest wider den Willen der Franzosen.
Der Herr Major
(2012)
Ein alter Major stößt zu einer Reisegesellschaft, die sich auf einem Dampfer nach Hallig Hooge befindet. Durch seine verbalen Ausfälle und seine Trunksucht verspielt der Major allmählich die Achtung, die ihm anfangs entgegengebracht wurde. Eine genaue Beobachtung von gesellschaftlicher Gruppendynamik und unterschiedlichen Rollenverhalten in der Konfrontation mit einem Außenseiter.
Der Gewaltige und der Poet
(2012)
Das Opfer
(2012)
Der alte Timm Wieben sieht die natürliche gottgewollte Ordnung durch den Fortschritt, d. h. den Bau eines Bahndammes in seinem Dorf, gefährdet. Er prophezeit die Notwendigkeit eines Menschenopfers, das die Erde besänftigen soll: "Es muss etwas Lebiges in die Grund". Daraufhin ereignet sich ein schwerer Unfall. Der aus dem Nachlass veröffentlichte Text gehört eindeutig zu dem Umfeld der "Baasdörper Krönk". Er kontrastiert Aberglaube und aufgeklärtes Denken, , ohne in Schwarz-Weiß-Malerei zu verfallen. In Peters' Autobiographie Preis der guten Mächte (1940) erscheint der Großvater als ein Fürsprecher des Rationalismus und, wie Hans Lohse in der Erzählung, als ein Gegenentwurf zu Timm Wieben ("Dat geiht all natürlich to"). Aber auch er erkennt trotz allem die Macht des Übernatürlichen an. Für Peters löst sich der Gegensatz zwischen Licht und Dunkel, Aufklärung und Dämonie in der Religion auf: "Und wenn wir auch den beschränkten Geltungsbereich unserer Leuchte erkennen, so haben wir dennoch die Pflicht, sie ins Dunkel hinauszutragen bis an den alleräußersten Rand unseres Vermögens. Wer aber vor dem letzten, undurchleuchtbaren Dunkel steht, der suche seine Zuflucht nicht bei verdächtigen Mächten des Zaubers, sondern fasse die Hand Gottes, die sich ihm aus der deutschen Bibel Martin Luthers hilfreich entgegenstreckt." (Ausgewählte Werke, Bd II, Hamburg, Hoffmann und Campe, S. 111)
"Hinnerk Pick und der Steernkieker" ist ein poetischer Text, der sich mit dem Astronomen J. J. Sievers, der an der Altonaer Sternwarte tätig war, befasst. J. J. Sievers (1804-1881) stammte aus Stafstedt (Kreis Rendsburg-Eckernförde), einem Dorf in der Nähe von Luhnstedt, dem Heimatdorf von F. E. Peters. Er wird beschrieben als märchenhaft geheimnisvolle Gestalt und zugleich liebenswerter Sonderling, in dessen Augen sich eine Pascalsche Scheu vor der Unendlichkeit des Raumes widerspiegelt. "Immer aber wird mir der Steernkieker teuer bleiben als ein Zeugnis dafür, dass aus der Enge eines holsteinischen Dorfes zum Geist geführt werden kann, wen der Geist gerufen hat. Am Ende ist eines Menschen Drang ins Weite doch vergeblich, wenn er sie nach unruhigen Jahren des Suchens nicht findet in sich selbst." In den Mund des Astronomen Sievers ("de ool Steernkieker", "de ool Klooksnacker") legt Peters am Anfang der "Baasdörper Krönk" die berühmte Beschreibung von Baasdorp und der Anlage des Dorfes in drei sozial definierte konzentrische Kreise (reiche Bauern; Halbhufner und kleine Bauern; schließlich Handwerker und Katenbauern).
The present work is devoted to establishing of a new generation of self-healing anti-corrosion coatings for protection of metals. The concept of self-healing anticorrosion coatings is based on the combination of the passive part, represented by the matrix of conventional coating, and the active part, represented by micron-sized capsules loaded with corrosion inhibitor. Polymers were chosen as the class of compounds most suitable for the capsule preparation. The morphology of capsules made of crosslinked polymers, however, was found to be dependent on the nature of the encapsulated liquid. Therefore, a systematic analysis of the morphology of capsules consisting of a crosslinked polymer and a solvent was performed. Three classes of polymers such as polyurethane, polyurea and polyamide were chosen. Capsules made of these polymers and eight solvents of different polarity were synthesized via interfacial polymerization. It was shown that the morphology of the resulting capsules is specific for every polymer-solvent pair. Formation of capsules with three general types of morphology, such as core-shell, compact and multicompartment, was demonstrated by means of Scanning Electron Microscopy. Compact morphology was assumed to be a result of the specific polymer-solvent interactions and be analogues to the process of swelling. In order to verify the hypothesis, pure polyurethane, polyurea and polyamide were synthesized; their swelling behavior in the solvents used as the encapsulated material was investigated. It was shown that the swelling behavior of the polymers in most cases correlates with the capsules morphology. Different morphologies (compact, core-shell and multicompartment) were therefore attributed to the specific polymer-solvent interactions and discussed in terms of “good” and “poor” solvent. Capsules with core-shell morphology are formed when the encapsulated liquid is a “poor” solvent for the chosen polymer while compact morphologies are formed when the solvent is “good”. Multicompartment morphology is explained by the formation of infinite networks or gelation of crosslinked polymers. If gelation occurs after the phase separation in the system is achieved, core-shell morphology is present. If gelation of the polymer occurs far before crosslinking is accomplished, further condensation of the polymer due to the crosslinking may lead to the formation of porous or multicompartment morphologies. It was concluded that in general, the morphology of capsules consisting of certain polymer-solvent pairs can be predicted on the basis of polymer-solvent behavior. In some cases, the swelling behavior and morphology may not match. The reasons for that are discussed in detail in the thesis. The discussed approach is only capable of predicting capsule morphology for certain polymer-solvent pairs. In practice, the design of the capsules assumes the trial of a great number of polymer-solvent combinations; more complex systems consisting of three, four or even more components are often used. Evaluation of the swelling behavior of each component pair of such systems becomes unreasonable. Therefore, exploitation of the solubility parameter approach was found to be more useful. The latter allows consideration of the properties of each single component instead of the pair of components. In such a manner, the Hansen Solubility Parameter (HSP) approach was used for further analysis. Solubility spheres were constructed for polyurethane, polyurea and polyamide. For this a three-dimensional graph is plotted with dispersion, polar and hydrogen bonding components of solubility parameter, obtained from literature, as the orthogonal axes. The HSP of the solvents are used as the coordinates for the points on the HSP graph. Then a sphere with a certain radius is located on a graph, and the “good” solvents would be located inside the sphere, while the “poor” ones are located outside. Both the location of the sphere center and the sphere radius should be fitted according to the information on polymer swelling behavior in a number of solvents. According to the existing correlation between the capsule morphology and swelling behavior of polymers, the solvents located inside the solubility sphere of a polymer give capsules with compact morphologies. The solvents located outside the solubility sphere of the solvent give either core-shell or multicompartment capsules in combination with the chosen polymer. Once the solubility sphere of a polymer is found, the solubility/swelling behavior is approximated to all possible substances. HSP theory allows therefore prediction of polymer solubility/swelling behavior and consequently the capsule morphology for any given substance with known HSP parameters on the basis of limited data. The latter makes the theory so attractive for application in chemistry and technology, since the choice of the system components is usually performed on the basis of a large number of different parameters that should mutually match. Even slight change of the technology sometimes leads to the necessity to find the analogue of this or that solvent in a sense of solvency but carrying different chemistry. Usage of the HSP approach in this case is indispensable. In the second part of the work examples of the HSP application for the fabrication of capsules with on-demand-morphology are presented. Capsules with compact or core-shell morphology containing corrosion inhibitors were synthesized. Thus, alkoxysilanes possessing long hydrophobic tail, combining passivating and water-repelling properties, were encapsulated in polyurethane shell. The mechanism of action of the active material required core-shell morphology of the capsules. The new hybrid corrosion inhibitor, cerium diethylhexyl phosphate, was encapsulated in polyamide shells in order to facilitate the dispersion of the substance and improve its adhesion to the coating matrix. The encapsulation of commercially available antifouling agents in polyurethane shells was carried out in order to control its release behavior and colloidal stability. Capsules with compact morphology made of polyurea containing the liquid corrosion inhibitor 2-methyl benzothiazole were synthesized in order to improve the colloidal stability of the substance. Capsules with compact morphology allow slower release of the liquid encapsulated material compared to the core-shell ones. If the “in-situ” encapsulation is not possible due to the reaction of the oil-soluble monomer with the encapsulated material, a solution was proposed: loading of the capsules should be performed after monomer deactivation due to the accomplishment of the polymerization reaction. Capsules of desired morphologies should be preformed followed by the loading step. In this way, compact polyurea capsules containing the highly effective but chemically active corrosion inhibitors 8-hydroxyquinoline and benzotriazole were fabricated. All the resulting capsules were successfully introduced into model coatings. The efficiency of the resulting “smart” self-healing anticorrosion coatings on steel and aluminium alloy of the AA-2024 series was evaluated using characterization techniques such as Scanning Vibrating Electron Spectroscopy, Electrochemical Impedance Spectroscopy and salt-spray chamber tests.
Zwischen Morgen und Abend
(2012)
Diese tragische Geschichte von einem Jagdunfall, bei dem ein dreizehnjähriger Junge, einziger Sohn seiner Eltern, ums Leben kommt, ist die bekannteste Episode aus der 1975 posthum veröffentlichten Baasdörper Krönk. F.E. Peters hat sie zu Lebzeiten auf Hochdeutsch veröffentlicht. Die Erzählung variiert den Freischütz-Stoff.