Polymer nanocomposites are promising materials for dielectrical use in high voltage applications and insulations. This work presents a study of nanocomposites based on poly(ethylene-co-butyl acrylate) with two different comonomer compositions and two different aluminium oxide nanoparticles. The nanoparticles were either untreated, or surface-treated with two different silanes, aminopropyl triethoxy silane and octyltriethoxy silane. The best level of dispersion was found for the polymer with 13 wt. % of butyl acrylate (EBA-13) whereas the low melt viscosity of the polymer with 28 wt. % of butyl acrylate (EBA-28) resulted in insufficient mixing with uneven dispersion as a result. Octyltriethoxy silane-treated particles were best dispersed in the polymer. The nanoparticles acted as nucleation agents in EBA-28, increasing the crystallization temperature by several degrees. Studies of the water uptake in the nanocomposite materials showed the effect of the enormous interfacial surfaces and great number of polar groups present on the nanoparticle surfaces. For the well-dispersed nanomaterials, the water sorption data could be modeled by a single Fickian equation, whereas materials that contained a sizeable fraction of large nanoparticle agglomerates showed a two stage sorption process, first a fast process associated with the saturation of the polymer phase and second, a slow diffusion process due to water sorption of large particle agglomerates. The long-term performance and interaction between the nanoparticles and the phenolic antioxidant (Irganox 1010) was investigated by differential scanning calorimetry in order to assess the oxidation induction time (OIT); the latter being proportional to the concentration of efficient antioxidant. It was found that the stabilizer was adsorbed to the untreated Al2O3 nanoparticles, resulting in a significant reduction in OIT. However, silanization of the nanoparticles resulted in an increase in OIT, compared to the materials containing untreated particles. Furthermore, it was shown that the stabilizer was not irreversibly adsorbed to the particles, allowing a gradual release of stabilizer with ageing time. / Polymera nanokompositer är lovande material för användning som dielektriskt material inom högspänningsområdet. I detta arbete studeras nanokompositer framställda av två olika sampolymerer av eten och butylakrylat (EBA-13 med 13 vikt% butylakrylat samt EBA-28 med 28 vikt% och två olika typer av nanopartiklar av Al2O3. Nanopartiklarna användes antingen som obehandlade eller efter silanisering med aminopropyltrietoxysilan- eller oktyltrietoxysilan. Den bästa partikeldispergeringen observerades för de material som baserats på EBA-13 medan den låga smältviskositeten hos EBA-28 resulterade i låga skjuvkrafter under kompounderingen och en observerat ojämn dispergering och förekomst av mikrometerstora agglomerat. Partiklar som silaniserats med oktyltrietoxysilan var lättast att dispergera. Nanopartiklarna fungerade som kärnbildare i EBA-28 vilket medförde en höjning av kristallisationstemperaturen. Vattensorptionsstudier demonstrerade dels effekten av den stora specifika gränsytan mellan partikel och matris och dels av förekomst av polära grupper lokaliserade till nämnda gränsyta. Kompositer med väldispergerade partiklar uppvisade en enkel Ficksk sorptionsprocess medan de material som innehöll en betydande mängd stora agglomerat påvisade en tvådelad process. Den första processen var kopplad till mättningen av polymermatrisen och den andra kunde länkas till vattenupptaget i de stora agglomeraten. Vidare undersöktes långtidsegenskaperna hos nanokompositerna, samt om det fanns någon växelverkan mellan nanopartiklar och en fenolbaserade antioxidant (Irganox 1010). DSC användes för att bestämma induktionstiden för oxidation (OIT) vilket är ett mått på koncentrationen av aktiv fenolisk antioxidant. Det framgick det att Irganox 1010 adsorberades på nanopartiklarna, vilket ledde till en minskning av OIT. Det framgick även att de material som innehöll silaniserade nanopartiklar hade högre OIT jämfört material med obehandlade partiklar. Antioxidanten var däremot inte irreversibelt bunden till nanopartiklarna, utan frigjordes från deras ytor och blev aktiv under åldringen. / QC 20110128

Solar absorber coatings are one of the key components in concentrated solar power (CSP) plants. Currently operating at temperatures up to 565°C and suffering from emissive losses, their energy conversion efficiency could be improved by applying high-temperature stable materials with solar selective properties, i.e. high absorptivity and low emissivity. In this work, the transparent conductive oxide (TCO) SnO2:Ta is developed as a solar selective coating (SSC) for CSP absorbers. Starting with simulations covering basic requirements for SSCs, the deposition process of SnO2:Ta is optimized and extensive optical characterization and modelling are performed. It is shown that upon covering with a SiO2 antireflective layer, a calculated absorptivity of 95% and an emissivity of 30% are achieved for the model configuration of SnO2:Ta on top of a perfect black body (BB). High-temperature stability of the developed TCO up to 800 °C is shown in situ by spectroscopic ellipsometry and Rutherford backscattering spectrometry. The universality of the concept is then demonstrated by transforming silicon and glassy carbon from non-selective into solar selective absorbers by depositing the TCO on top of them. Finally, the energy conversion efficiencies ηCSP of SnO2:Ta on top of a BB and an ideal non-selective BB absorber are compared as a function of solar concentration factor C and absorber temperature TH.

Polymer-based drug delivery systems represent one of the promising strategies for successful tumor treatment. Conjugation of a low-molecular-weight drug to a syn- thetic polymer carrier enables targeted drug delivery to tumor tissue/cells and limited systemic toxicity of the drug. The conjugates show extended circulation time, and preferentially accumulate in tumor tissue due to the Enhanced Permeability and Re- tention (EPR) effect. The EPR effect depends on a structural anomaly in tumor neovasculature, and vasodilators were shown to enhance the EPR effect via an in- crease of blood supply in the tumor. Polymer drug carriers based on water-soluble N-(2-hydroxypropyl)methacrylamide (HPMA) benefit from variable architecture, drug loading and controlled release. HPMA-based conjugates with cancerostatics have al- ready proved high anti-tumor activity, inducing complete tumor regression followed by resistance to a second tumor challenge in experimental murine models. Three HPMA-based conjugates with organic nitrates (labeled 1, 2, and 3) were pre- pared as polymer donors of nitric oxide (NO) with the aim to intensify the EPR effect, thereby enhancing accumulation of co-administered macromolecular cancerostatics in the tumor. In this study, the conjugates were non-toxic to cancer cells and did not potentiate...

Die vorliegende Arbeit widmet sich der Untersuchung von 4 Modellsystemen der Oberflächenforschung. Die verwendeten experimentellen Methoden sind Summenfrequenzerzeugungsspekroskopie (SFG), Thermische Desorptionsspektroskopie (TDS), Beugung niederenergetischer Elektronen (LEED), Augerelektronenspektroskopie (AES), Infrarotadsorptionsspektrokopie (IRAS) und Rastertunnelmikroskopie (STM). Durch die Verwendung von SFG waren Messungen bis zu 50 mbar möglich. Die untersuchten Systeme sind: CO auf Pt(111), Wasser auf Ag(001) und MgO/Ag(001), CO auf Au/MgO/Ag(001) und CO auf Au-Pd/MgO/Ag(001). Bei den Messungen von CO auf Pt(111) tritt unter bestimmten Druck- und Temperaturbedingungen eine bisher nicht näher untersuchte Doppelpeakstruktur auf, die genauer charakterisiert wurde. Die Untersuchungen von Wasser auf MgO/Ag(001) und Ag(001) zeigen, dass sich auf MgO/Ag(001) zuerst eine Monolage Wasser mit einer darauffolgenden Multilage ausbildet, wohingegen es auf Ag(001) von Beginn an in einer Multilagenschicht wächst. Die Monolage kann unter der Multilage gemessen werden und einige Resonanzen identifiziert werden. Für Au/MgO/Ag(001) zeigte sich mittels STM eine Abhängigkeit des Au-Wachstums von der Schichtdicke, die allerdings nicht spektroskopisch in Erscheinung tritt. Bei den Messungen an gemischten Au-Pd-Teilchen auf MgO/Ag(001) zeigen sich Unterschiede im Adsorptionsverhalten zwischen reinen Metallteilchen und gemischten Teilchen, die auf eine Wechselwirkung zwischen den beiden Metallen zurückzuführen ist. Nach Heizschritten auf 600 K reichern sich die Au-Atome im Mantel des Teilchens an, das Pd bildet den Kern. Die Ergebnisse aller Messungen werden unter Berücksichtigung neuer Veröffentlichungen diskutiert. / This thesis focuses on 4 different model systems of surface science. The experimental techniques used for the measurements include sum frequency generation (SFG), thermal desorption spectroscopy (TDS), low energy electron diffraction (LEED), Auger electron spectroscopy (AES), infrared adsorption spectrosocopy (IRAS) and scanning tunneling microscopy (STM). By using SFG, measurements could be performed up to a pressure of 50 mbar. The systems under investigation were: CO on Pt(111), water on Ag(001) and on MgO/Ag(001), CO on Au/MgO/Ag(001), and CO on Au-Pd/MgO/Ag(001). The system of CO on Pt(111) exhibits a two peak-pattern under certain pressure and temperature conditions which has not been studied so far. Various experiments helped to elucidate the origin of this distinct behaviour. The measurements of water on Ag(001) and MgO/Ag(001) show that on MgO, water first adsorbs as a monolayer with a following multilayer, whereas on Ag(001) it adsorbs as a multilayer from the beginning. The monolayer can be studied below the multilayer and some resonances can be identified. For the case of Au/MgO/Ag(001), STM shows that the growth mode of Au depends on the thickness of the supporting MgO film, which can not be seen with spectroscopic methods. For mixed Au-Pd particles on MgO/Ag(001) a clear difference in the adsorption behaviour between pure metal particles and mixed particles can be seen, which is explained by an interaction between these metals. Annealing the mixed particles to 600 K leads to a segregation of the metals, where the Au atoms diffuse to the shell and the Pd atoms make up the core. The results of all these measurements are discussed in the light of recent publications.

5 Abstract Tobacco mature pollen rehydrates in vivo on a stigma tissue, and develops into the rapidly-growing pollen tube. This rehydration process is accompanied by the de-repression of stored mRNA transcripts, resulting in the synthesis of novel proteins. Furthermore, such metabolic switch is also likely to be regulated on the level of post-translational modifications of the already-present proteins, namely via phosphorylation, since it was shown to play a significant regulatory role in numerous cellular processes. Since only a minor part of proteins is phosphorylated in a cell at a time, the employment of various enrichment techniques is usually of key importance. In this diploma project, metal oxide/hydroxide affinity chromatography (MOAC) with aluminium hydroxide matrix was applied in order to enrich phosphoproteins from the mature pollen and the 30-minute in vitro activated pollen crude protein extracts. The enriched fraction was separated by both 2D-GE and gel-free liquid chromatography (LC) approaches with subsequent mass spectrometric analyses. Collectively, 139 phosphoprotein candidates were identified. Additionally, to broaden the number of phosphorylation sites identified, titanium dioxide phosphopeptide enrichment of trypsin-digested mature pollen crude extract was performed. Thanks to the...

In der vorliegenden Arbeit werden Möglichkeiten der Stabilisierung und die photokatalytische Aktivität von Polymorphen des Bismut(III)-oxids, synthetisiert ausgehend von nanoskaligen, polynuklearen Bismutoxidoclustern, beschrieben. Hydrolyse- und Kondensationsstudien werden mit dem Ziel der Aufklärung von Bildungsprozessen von Bismutoxidoclustern ausgehend von bismutnitrat- und bismutsilanolathaltigen Lösungen durchgeführt. Basierend auf polynuklearen Modellverbindungen wird durch deren Hydrolyse und anschließende thermische Behandlung die Darstellung von Nanopartikeln von verschiedenen Polymorphen des Bismut(III)-oxids erreicht. Die Reaktivität der synthetisierten β Bi2O3 Nanopartikel wird zur Synthese von Verbindungen vom Sillenit-Strukturtyp ausgenutzt. Diese Verbindungen sind isostrukturell zum metastabilen γ-Bi2O3. Die isolierten oxidischen Materialien weisen eine hohe photokatalytische Aktivität gegenüber wässrigen Rhodamin B Lösungen bei der Bestrahlung mit sichtbarem Licht auf. Für die β Bi2O3 Nanopartikel wird ebenso die photokatalytische Aktivität gegenüber wässrigen Farbstofflösungen von Indigokarmin, Orange G, Methylorange und Methylenblau sowie wässrigen Schadstofflösungen von Phenol, 4-Chlorphenol, 2,4-Dichlorphenol, 4-Nitrophenol, Triclosan und Ethinylestradiol beschrieben. Die Charakterisierung der synthetisierten Verbindungen erfolgte unter anderem mittels Einkristall-Röntgenstrukturanalyse, Röntgenpulverdiffraktometrie, NMR-Spektroskopie, FTICR-ESI-Massenspektrometrie, UV/Vis-, Infrarot- und Ramanspektroskopie sowie thermischen Analysemethoden. / The present essay describes the stabilization and photocatalytic activity of different polymorphs of bismuth(III) oxide which were prepared starting from nanoscaled, polynuclear bismuth oxido clusters. Hydrolysis and condensation processes of bismuth nitrate as well as bismuth silanolates in solution were performed to provide an insight into the formation process of bismuth oxido clusters. Nanoparticles of different polymorphs of bismuth(III) oxide were obtained by hydrolysis, followed by annealing steps at temperatures of 370 °C and 600 °C starting from polynuclear bismuth compounds, respectively. The high reactivity of the as-prepared β-Bi2O3 nanoparticles was used to synthesize sillenite-type compounds at rather low temperatures which are isostructural to metastable γ-Bi2O3. The isolated oxidic materials show promising photocatalytic activities exemplified by the degradation of aqueous Rhodamine B solutions under visible light irradiation. Additionally, the β- Bi2O3 nanoparticles were tested in photodegradation processes of aqueous solutions containing different dyes such as indigo carmine, orange G, methyl orange and methylene blue as well as typical organic pollutants such as phenol, 4-chlorophenol, 2,4-dichlorophenol, 4-nitrophenol, triclosan and ethinyl estradiol. The characterization of the as-prepared materials was performed using single crystal X-ray diffraction, powder X-ray diffraction analysis, NMR spectroscopy, FTICR- electrospray ionization mass spectrometry, UV/Vis-, IR- and Raman spectroscopy, electron microscopy, nitrogen physisorption as well as thermal analyses.

The main goal of this dissertation was to show that the principle of atomic layer deposition (ALD) can be applied to “endless” fibers. A reactor of atomic layer deposition has been designed, especially for coating depositions onto meter long bundles of fibers. Aluminum oxide (alumina), titanium oxide (titania), double layers of alumina and titania, as well as aluminium phosphate have been deposited onto bundles of carbon fibers using the home-built reactor. Scanning electron microscopic (SEM) and transmission electron microscopic (TEM) images indicate that the coatings were uniform and conformal onto fiber surface. There was a good adhesion of the coatings to the fibers. Alumina has been deposited using two separate aluminum sources (aluminum trichloride and trimethylaluminum), and water as a source of oxygen. In case of alumina deposition using aluminum trichloride and water, initial deposition temperature was 500 °C. In these conditions, a part of the fiber bundle has been damaged. Thus, the deposition temperature was decreased to 300 °C and the fibers were unaffected. In addition, during this process hydrochloric acid is formed as a byproduct which is a corrosive substance and affects the reactor and there was a chloride impurity in the coatings. Thus, aluminum trichloride precursor was replaced by trimethylalumium. Alumina deposition onto carbon fibers using trimethylaluminum and water was carried out at a temperature of 77 °C. SEM images revealed that the fibers were unaffected and the coatings were uniform and conformal. Oxidation resistance of the carbon fibers was improved slightly after alumina deposition. Oxidation onset temperature of the uncoated fibers was about 630 °C. The resistance was linearly increased with the coating thickness (up to 660 °C) and getting saturated over a thickness of 120 nm. Titania coatings have been deposited using titanium tetrachloride and water. The physical appearances of the titania coatings were similar to the alumina coatings. The oxidation onset temperature of the titania coated carbon fibers was similar to the uncoated fibers but the rate of oxidation was decreased than the uncoated fibers. Two double layer coatings were deposited, alumina followed by titania (alumina/titania), and titania followed by alumina (titania/alumina). If the fibers were coated with the double layer of alumina/titania, they had almost same oxidation onset as alumina coated fibers but the rate of oxidation was decreased significantly compared to alumina coated fibers. This feature is independent of the thickness of the titania layers, at least in the regime investigated (50 nm alumina followed by 13 nm and 40 nm titania). On the other hand, the oxidation onset temperature of fibers coated with titania/alumina (20 nm titania /30 nm alumina) was approximately 750 °C. The fibers were burned completely when temperature was further increased to 900 °C and held another 60 minutes at 900 °C. This is significantly better than any other coating used in this dissertation. ALD of titania and alumina in principle was known beforehand, this dissertation here applies this knowledge for the first time to endless fibers. Furthermore, this dissertation shows for the first time that one can deposit aluminum phosphate via ALD (planar surface as well as fibers). Aluminum phosphate might be special interest in the fiber coating because it is a rather soft material and thus might be used to obtain a weak coupling between fiber and matrix in composites. Aluminum phosphate was deposited using trimethylaluminum and triethylphosphate as precursors. Energy dispersive X-ray spectroscopy and solid state nuclear magnetic resonance spectra confirmed that the coating comprises aluminum phosphate (orthophosphate as well as other stoichiometries). Scanning electron microscopic images revealed that coatings are uniform and conformal. In cases of alumina and titania, it was observed that the coatings were delaminated from the ends of cut fibers and thus formed of clear steps. On the other hand, for aluminum phosphate coating it was observed that the border between coating and underlying fiber often being smeared out and thus formed an irregular line. It seems in case aluminum phosphate cohesion is weaker than adhesion, thus it might be act a weak interface between fiber and matrix. Alumina, titania, and double layer microtubes have been obtained after selective removal of the underlying carbon fibers. The carbon fibers were selectively removed via thermal oxidation in air at temperatures exceeding 550 °C. SEM and TEM images indicate that the inner side of the tube wall has the same morphology like the fibers. In addition, it was observed that the individual microtubes were separated from their neighbors and they had almost uniform wall thicknesses. The longest tubes had a length of 30 cm. / Das Hauptziel dieser Dissertation bestand darin nachzuweisen, dass die Atomlagenabscheidung (engl. atomic layer deposition (ALD)) auf „endlose“ Fasern angewendet werden kann. Es wurde ein Reaktor zur Atomlagenabscheidung gestaltet, der speziell für die Beschichtung meterlanger Faserbündel geeignet ist. Aluminiumoxid, Titanoxid, Doppelschichten aus Aluminiumoxid und Titanoxid sowie Aluminiumphosphat wurden mit Hilfe des selbstgebauten Reaktors auf Kohlefaserbündel abgeschieden. Rasterelektronenmikroskopische (REM) und transmissionselektronenmikroskopische (TEM) Aufnahmen zeigten, dass die Beschichtung auf den Fasern einheitlich und oberflächentreu war. Des Weiteren wurde eine gute Adhäsion zwischen Beschichtung und Fasern beobachtet. Das Prinzip der Beschichtung mit Titanoxid und Aluminiumoxid mit Hilfe der ALD war bereits vorher bekannt und im Rahmen dieser Dissertation jedoch erstmals auf "endlose" Fasern angewendet. Des Weiteren wird in dieser Dissertation erstmals gezeigt, dass es möglich ist, Aluminiumphosphat mittels ALD abzuscheiden (sowohl auf planaren Oberflächen als auch auf Fasern). Aluminiumphosphat könnte von besonderem Interesse in der Faserbeschichtung sein, da es ein relativ weiches Material ist und könnte daher als eine Art „schwacher“ Verbindung zwischen Faser und Matrix in Kompositen dienen. Die Oxidationsbeständigkeit von beschichten Kohlefasern wurde im Vergleich zu unbeschichteten Fasern bis zu einem gewissen Grad erhöht. Monoschichten von Aluminiumoxid und Titanoxid waren dafür wenig effektiv. Aluminiumphosphatbeschichtete Fasern waren deutlich besser geeignet als die beiden anderen. Eine Doppelschicht aus Titanoxid gefolgt von Aluminiumoxid verbesserte die Oxidationsbeständigkeit nochmals deutlich gegenüber allen anderen Beschichtungen, die in dieser Dissertation verwendet wurden. Mikroröhren aus Aluminiumoxid, Titanoxid und Doppelschichten wurden durch die selektive Entfernung der zugrunde liegenden Kohlefasern erhalten. Einzelne Mikroröhren waren von benachbarten Röhren getrennt und sie weisen eine nahezu einheitliche Wanddicke auf.

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Hierarchically porous nitrogen-doped graphene frameworks (N-GFs) are fabricated through the ice-templating of GO with polyethylenimine and the thermal treatment of the resultant hybrids. As cathode materials in lithium ion batteries (LIBs), the obtained N-GFs exhibit an outstanding specific capacity of 379 mA h g−1 at 0.5 A g−1 for 2500 cycles. Even at an ultrahigh current density of 5 A g−1, the N-GFs maintain a capacity of 94 mA h g−1, superior to that of most reported LIB cathode materials. The experimental results and quantum mechanics calculations suggest that pyridinic-like N and pyridinic N-oxide in graphene are responsible for the excellent cathodic performance of the bipolar N-GFs by providing fast surface faradaic reactions with both p- and n-doped states.

Hierarchically porous nitrogen-doped graphene frameworks (N-GFs) are fabricated through the ice-templating of GO with polyethylenimine and the thermal treatment of the resultant hybrids. As cathode materials in lithium ion batteries (LIBs), the obtained N-GFs exhibit an outstanding specific capacity of 379 mA h g−1 at 0.5 A g−1 for 2500 cycles. Even at an ultrahigh current density of 5 A g−1, the N-GFs maintain a capacity of 94 mA h g−1, superior to that of most reported LIB cathode materials. The experimental results and quantum mechanics calculations suggest that pyridinic-like N and pyridinic N-oxide in graphene are responsible for the excellent cathodic performance of the bipolar N-GFs by providing fast surface faradaic reactions with both p- and n-doped states.