Carbon nanostructures are a wide field with many applications. The use of carbon nanostructures as support in heterogeneous catalysis is a key development that led together with the use of nanoparticles to a significant cost reduction of catalysts. Catalysts designed in this way are widely applied in fuel cell technologies. For portable devices especially low temperature fuel cells are desirable with low hazards for the user. One technology which fulfills these requirements is the direct formic acid fuel cell (DFAFC). DFAFC have many promising characteristics, such as high electromotive force and easy fuel handling. However, they still suffer from too low power output and lifetime for commercialization. This thesis focusses on two main aspects: the synthesis of carbon nanostructures by chemical vapor deposition (CVD) and their application as catalyst support. The materials are investigated by many different techniques ranging from transmission electron microscopy (TEM) to fuel cell tests. Different carbon nanostructures could be synthesized by catalytic CVD on palladium (Pd) nanoparticles. Multi-walled carbon nanotubes (MWCNTs), carbon nanofibers (CNFs) and helical carbon nanofibers (HCNFs) were grown, selectively, dependent on temperature, using acetylene as carbon precursor. Especially HCNF raised further interest due to their unique structure. A growth model for HCNFs was developed based on an anisotropic extrusion model. The synthesis conditions for HCNFs were optimized until an almost 100 % purity with very high efficiency was obtained. The unique helical but fiber-like structure made the material very interesting as support for heterogeneous catalysis. Several catalysts based on Pd nanoparticle decorated HCNFs were developed. The synthesis methods ranged from standard methods like the polyol method to phase-transfer methods. The catalysts showed very promising results for the electro-oxidation of methanol, ethanol and formic acid. This makes them highly attractive for fuel cell applications. The catalysts were tested in DFAFC. The superiority of HCNF-based catalysts is attributed to the good attachment of nanoparticles to the defect-rich and easy to functionalize surface of HCNFs in combination with adequate film forming properties during electrode preparation. / Nanostrukturerat kol är ett mycket brett fält med ett stort antal tillämpningar. Användning av kolnanostrukturer som support för heterogena katalysmaterial har tillsammans med utvecklingen av nanopartiklar lett till en avsevärd minskning av kostnaden för katalysatorer. Katalysatorer designade på detta sätt används frekvent i bränsleceller. För portabla tillämpningar är utvecklingen av säkra och miljövänliga lågtemperaturceller mycket viktig. En teknologi som uppfyller dessa kriterier är bränsleceller som drivs med myrsyra (DFAFC). Sådana bränsleceller har många önskvärda egenskaper, såsom en hög elektromotorisk kraft och en enkel hantering av bränslet. Trots dessa goda egenskaper har de också en del nackdelar som hindrar en full kommersialisering. De två mest problematiska är en för låg genererad effekt samt en för kort livslängd på katalysatorerna. Denna avhandling fokuserar på två huvudpunkter som adresserar dessa problem; tillverkning och karaktärisering av kolnanostrukturer producerade med CVD, och deras tillämpningar som support för katalysatorer. Materialen karaktäriseras med en rad olika tekniker, allt från transmission-elektronmikroskopi till bränslecellstester. Olika kolnanostrukturer har syntetiserats med katalytisk CVD på palladium (Pd) nanopartiklar. Produktionen av flerväggiga kolnanorör, kolfibrer och heliska kolnanofibrer har tillverkats med acetylen som kolkälla och genom att variera temperaturen kunde innehållet av olika typer av nanostrukturerat kol kontrolleras. Särskilt stort intresse har de heliska kolnanofibrerna rönt på grund av deras unika struktur. Vi beskriver en tillväxtmekanism baserad på en anisotrop diffusionsmodell. Genom att justera produktionsparametrarna visar vi att heliska kolnanofibrer kunde tillverkas med nära 100 %-ig renhet och hög effektivitet. Den unika heliska och fiberlika strukturen är mycket intressant for tillämpningar som support för heterogena katalysatorer. Ett flertal kompositer för katalytiska tillämpningar har utvecklats baserade på heliska kolnanofibrer, dekorerade med heterogena katalysatorer genom en rad olika kemiska/fysikaliska tekniker. De syntetiserade materialen visar mycket goda katalytiska egenskaper för att oxidera metanol, etanol och myrsyra. Därigenom blir de mycket attraktiva för användning i bränsleceller. Vi korrelerar de goda katalytiska egenskaperna med en bra vidhäftning av nanopartiklarna på de heliska kolnanofibrerna defekter, deras goda ledningsförmåga, bra egenskaper för att förbereda elektroder, samt deras stora yta i förhållande till deras volym och vikt.

It is well known that thin coatings can provide increased lifetime and reduced energy consumption for tools and components. During use, e.g. in sliding contact, mechanical and chemical reactions often lead to the formation of new surface layers, tribofilms, possessing different properties compared to the original surface, hence affecting the overall performance. In this work, analytical electron microscopy was applied to investigate the structure and composition of tribofilms. Concerning coatings, deposition parameter dependencies, stability and tribology were investigated. The carbon content of hydrogen-free TiCx coatings was shown to significantly influence the morphology. Low carbon content resulted in columnar grains with a strong texture while high carbon content led to the formation of randomly ordered TiCx crystals. The application of positive bias to the substrate as opposed to the normally used negative bias gave a fibrous structure of sputtered TiB2 and low residual stress with maintained hardness. Further, oxidation stability was examined on a (Ta,Al)C:C coating where oxidation led to partial oxidation and formation of AlTaO4 with an 8 nm interface. A focused ion beam instrument was used to extract samples from certain areas of worn specimens. Tribological contact was observed to result in phase changes and intermixing of materials present in the contact. Sliding contact involving a Co-alloy led to a phase change from fcc to hcp. A 30 nm Co-rich tribofilm was observed with basal planes parallel to the surface. Fully formulated oil was found to inflict considerable wear to a metal doped carbon film through chemical reaction with the metal dopant. WC/Co cemented carbide used for rock drilling exhibited intermixing of rock and Co binder phase after field tests. Chemical vapour deposited diamond worn in nitrogen and argon showed formation of wear debris with amorphous structure containing nitrogen and graphitic like structure, respectively.

Die vorliegende Dissertation beschäftigt sich mit der Optimierung und der Untersuchung der Materialeigenschaften des thermoelektrischen Materials Ag1-xPb18Sb1+yTe20 (englisch Lead-Antimony-Silver-Telluride: LAST). Bei LAST handelt es sich um Bleitellurid mit geringen Anteilen von Silber und Antimon, welche teilweise gelöst den Gitterplatz von Blei substituieren (Einbau in PbTe-Matrix) bzw. Fremdphasen auf m- und nm-Skala bilden. Seine hohe thermoelektrische Güte wird dabei hauptsächlich der geringen thermischen Gitterleitfähigkeit zugeschrieben, die in ersten Veröffentlichungen mit dem Auftreten nanoskaliger, Silber- und Antimonreicher Einschlüsse und deren Funktion als Phononenstreuer erklärt wurde. Das durch Schmelzsynthese hergestellte Bulkmaterial wurde im Rahmen der Arbeit durch Gefügeabbildung und Elementanalytik untersucht. In Kooperation mit den Projektpartnern sollte daraus eine Korrelation von Struktur- und Funktionseigenschaften abgeleitet, sowie eine reproduzierbare Syntheseroute entwickelt werden. Die elektronenmikroskopische Abbildung der Mikrostruktur erfolgte dabei auf zwei Größenskalen. Auf der µm-Skala wurde die Oberfläche des Bulkmaterials auf Homogenität und Zusammensetzung sowie Anteil des Fremdphasenbestands untersucht. Trotz des sehr komplexen Phasenbestandes aufgrund des quaternären Phasendiagramms und der Vielzahl relevanter Syntheseparameter konnte ein Zusammenhang zwischen Zusammensetzung (Regulierung des Silber- und Antimonanteils bzw. dessen Verhältnis), Temperbedingungen und thermoelektrischen Eigenschaften hergestellt werden. Mithilfe des detektierten Phasenbestandes konnte die Existenz einer Mischungslücke im quasibinären Phasendiagramm 2PbTe-AgSbTe2 nachgewiesen werden. Dabei bilden die Zusammensetzungen zwei der ermittelten Fremdphasen die Phasengrenzen. Die beobachtete spinodale Entmischung erzeugte eine extrem hohe Grenzflächendichte und kann somit ebenfalls einen Beitrag zur Senkung der Wärmeleitfähigkeit liefern. Für die Analyse der Mikrostruktur auf nm-Skala wurden aus der LAST-Matrix mithilfe der fokussierten Ionenstrahltechnik elektronentransparente Schnitte gefertigt. Abhängig von Temperbedingungen und dem Verhältnis von Silber und Antimon wurden auch hier fremdphasige Einschlüsse entdeckt. Dabei konnte ein optimaler Temperbereich von 500 bis 550 °C (bezogen auf einen hohen Gütewert) mit dem Auftreten dieser Einschlüsse korreliert werden. Eine allgemeine, direkte Zuordnung des Vorhandenseins von Nanostrukturen zu guten oder schlechten thermoelektrischen Eigenschaften konnte im Allgemeinen jedoch nicht nachgewiesen werden. Vielmehr wurden deutliche Hinweise gefunden, dass auch die Anordnung von Punktdefekten (Blei-Substitution durch Silber und Antimon) und ggf. Agglomerate aus Punktdefekten in der LAST-Matrix eine Rolle bei der Senkung der Wärmeleitfähigkeit spielen. Im hochaktuellen Entwicklungsgebiet selbstorganisierender Nanostrukturen mit Auswirkungen auf thermoelektrische Eigenschaften wurden substantielle Fortschritte bei der Entwicklung geeigneter, LAST-basierter Thermoelektrika für mittlere Einsatztemperaturen erzielt. Die gewonnenen Erkenntnisse dieser Arbeit zeigen Optionen zur Erzeugung hocheffizienter thermoelektrischer Bauelemente auf, wie unter anderem die bestätigte Stabilität bis zu relativ hohen Einsatztemperaturen (> 500 °C) zeigt.

Membrane proteins are involved in a number of disease pathologies and thus comprise a large number of drug targets. Determination of the high-resolution three-dimensional structure is essential for rational drug design, but several hurdles need to be overcome, primarily the over-expression and purification of said membrane proteins. Human leukotriene C4 synthase (hLTC4S), an 18 kDa integral membrane protein localized in the outer nuclear membrane of eosinophils and basophils, catalyzes the conjugation of LTA4 and reduced glutathione to produce LTC4. LTC4 and its metabolites LTD4 and LTE4 are the cysteinyl leukotrienes implicated in bronchoconstriction and inflammation pathways. The focus of my project involves optimizing the over-expression and purification of hLTC4S, which was heterologously expressed in Schizosaccharomyces pombe, purified by immobilized affinity chromatography, and finally "polished" with a buffer exchange step to remove excess co-purified lipids. The optimized protocol yielded ~1 mg of ~90% homogenous, pure protein per liter of cell culture. The finalized purified protein can then be used for further investigation of two-dimensional crystals by electron crystallography with the overall goal of structure determination.

EfPm-27 is a Protohistoric bison pound and processing site located in Fish Creek Park in Calgary, Alberta. The site exhibited the presence of metal tools and macroscopically deceptive cut marks suggesting the potential for the presence of both metal and stone cut marks. Moulds of selected cut marks from the assemblage were made and examined with the scanning electron microscope (SEM) to verify or negate the use of metal tools for butchery at the site. SEM images of the cut mark moulds reveal micromorphology that is similar to experimental and published stone tool cut mark SEM images. No evidence for the use of metal tools for butchering was identified. Protohistoric sites research could benefit from the use of SEM analysis of cut marks to distinguish between stone and metal tool use. This would provide important secondary evidence for metal trade items in scenarios where such artifacts may be beyond recovery. Conversely, the presence of metal artifacts at a site does not necessarily imply that they were used for butchery and this assertion must be verified by the presence of metal cut marks.

The research presented in this dissertation involves the synthesis, characterization, and application of novel anionic and cationic chiral molecular micelles in capillary electrophoresis (CE) for the separation of diverse chiral compounds. Chapter 1 presents brief overview of the surfactants, micelle polymer, CE and micellar electrokinetic chromatography (MEKC). Chapter 2 describes the simultaneous enantioseparation of eight single chiral center â-blockers using two novel leucine and isoleucine based polymeric surfactants. The simultaneous enantioseparation of multichiral center bearing â-blockers, nadolol and labetalol is described in chapter 3. A synergistic approach, using a combination of polysodium N-undecenoxycarbonyl-L-isoleucinate (poly-L-SUCIL) and sulfated â-CD showed dramatic enantioseparation of four stereoisomers of nadolol. On the other hand for labetalol, enantiomeric separation remains unaffected using the dual chiral selector system. Chapter 4 deals with the enantiomeric separation of the binaphthyl derivatives that was found to be influenced by pH, type and concentration of the background electrolyte as well as concentration of the polymeric surfactant. In chapter 5, characterization of five alkenoxy leucine-based surfactants with variations in chain length (C8-C11), polymerization concentration and degree of polymerization showed significant effects on the chiral resolution and efficiency of hydrophobic â-blockers. The synthesis and characterization of two positively charged amino acid derived chiral ionic liquids (ILs) and their corresponding polymers is presented in chapter 6. Chiral separation of two acidic analyte (difficult to resolve with anionic micelles) can be achieved with both monomers and polymers of ILs. In chapter 7, the synthesis and detailed characterization of three pH independent amino acids derived (L-leucinol, L-isoleucinol and L-valinol) sulfated chiral polymeric surfactants is presented. These chiral sulfated surfactants are thoroughly characterized and the morphological behavior of polymeric sulfated surfactants is revealed using cryogenic high-resolution electron microscopy. The work clearly demonstrates for the first time the superiority of chiral separation in MEKC coupled to mass spectrometry at low pH. Finally, in chapter 8, six amino acid derived chiral surfactants with carboxylate and sulfate head groups were compared for enantioseparation of broad range of structurally diverse racemic compounds at neutral and basic pH conditions.

The marginal glass-forming alloys have attracted much attention due to unique products of devitrification with a very high number density of nuclei up to 10^23 m^-3. Among these alloy systems, utmost interest is given to Al-RE and Al-TM-RE alloys with excellent lightweight mechanical (fracture strength close to 1 GPa) and chemical properties attributed to the presence of an extremely high density of nanocrystals embedded in an amorphous matrix. Classical nucleation theory fails in explaining this abnormal nucleation behavior, several other mechanisms have been proposed / however, there is still no agreement on the exact nucleation mechanism. Al-Tb system was investigated in liquid and solid amorphous states with a collective study of ab-initio MD and RMC simulations and state of art X-rays and e-beam techniques. Regions of pure Al clusters in the solid and liquid states were detected with the sizes extending up to 1-2 nm length. Al clusters interconnecting regions lead to formation of RE rich MRO structure which gave rise to the pre-peak in S(Q)-Q data in liquid and solid states. Specimens having MRO were crystallized within a controlled atmosphere and temperature and investigated using a combined study of TEM, HRTEM, SEM, XRD and DSC. HRTEM investigations and JMA results indicated different mechanism of nucleation. Therefore the kinetics of highly populated nuclei formation was found too complicated to be explained by well-known JMA approach. Mechanical tests were applied to determine the effects of morphology and populations of nanocrystals embedded in amorphous matrix. The tensile tests and the subsequent fracture surface analysis indicated brittle type of failure and the formation of shear bands, respectively. Relatively high hardness and tensile strength were detected by nanocrystallization.

Light emitting diodes (LEDs) and laser diodes (LDs) have many advantages over conventional light sources. Current commercial LEDs span the spectrum from IR to near- UV. There are a variety of applications for devices that extend into the deep-UV, including biological agent detection and optical storage. The nitride material system is a set of semiconducting compounds that have wavelengths that span a broad range, from yellow to deep-UV. AlGaN has a direct bandgap that extends into the deep-UV range; we will try to grow device-quality material, deposited epitaxially using metalorganic chemical vapor deposition on sapphire substrates.

Light emitting diodes (LEDs) and laser diodes (LDs) have many advantages over conventional light sources. Current commercial LEDs span the spectrum from IR to near- UV. There are a variety of applications for devices that extend into the deep-UV, including biological agent detection and optical storage. The nitride material system is a set of semiconducting compounds that have wavelengths that span a broad range, from yellow to deep-UV. AlGaN has a direct bandgap that extends into the deep-UV range; we will try to grow device-quality material, deposited epitaxially using metalorganic chemical vapor deposition on sapphire substrates.

No description available.