Titanium diboride was produced both by volume combustion synthesis (VCS) and by mechanochemical synthesis through the reaction of TiO2, B2O3 and metallic Mg. Reaction products were expected to be composed of TiB2 and MgO. However, side products such as Mg2TiO4, Mg3B2O6, MgB2 and TiN were also present in the products obtained by volume combustion synthesis. Formation of TiN could be prevented by conducting the volume combustion synthesis under argon atmosphere. Mg2TiO4 did not form when 40% excess Mg was used. Wet ball milling of the products before leaching was found to be effective in removal of Mg3B2O6 during leaching in 1M HCl. When stoichiometric starting mixtures were used, all of the side products could be removed after wet ball milling in ethanol and leaching in 5 M HCl. Thus, pure TiB2 was obtained with a molar yield of 30%. Pure TiB2 could also be obtained at a molar yield of 45.6% by hot leaching of VCS products at 75oC in 5 M HCl, omitting the wet ball milling step. By mechanochemical processing, products containing only TiB2 and MgO were obtained after 15 hours of ball milling. Leaching in 0.5 M HCl for 3 minutes was found to be sufficient for elimination of MgO. Molar yield of TiB2 was 89.6%, much higher than that of TiB2 produced by volume combustion synthesis. According to scanning electron microscope analyses, produced TiB2 had average particle size of 0.27&plusmn / 0.08 &amp / #956 / m.

Die vorliegende Arbeit zielte auf die Erarbeitung der verfahrens- und legierungstechnischen Grundlagen zur Randschichtbehandlung von TiAl6V4 durch Dispergieren/Legieren mit Diboriden ab. Für die Untersuchungen zum Dispergieren/Legieren wurden sowohl unterschiedliche Lasersysteme (CO2, CO2-Slab, diodengepumpter Nd:YAG, Diodenlaser) als auch der Elektronenstrahl gewählt. Das Konzept für die Vorbehandlung und die Prozessgestaltung wurde entwickelt und erfolgreich getestet. Anhand von Untersuchungen zum Dispergieren/Legieren wurde das Prozessparameterfeld erarbeitet, wobei sich die nachfolgend aufgeführten Einflussgrößen als wesentlich erwiesen: • Pulverkorngröße (Kornfraktion 5 - 125 µm), • Pulvereintragsmenge (Förderparameter, Förderrate, Pulvervor-/-nachlauf, Pastenschichtdicke), • Prozessparameter (Strahlleistung, Defokussierung, Streckenenergie, Ablenkfigur). Zusammenfassend wurde die gute Eignung des Dispergierens/Legierens mittels Hochleistungsstrahlquellen für die Erzeugung boridverstärkter Randschichten an Bauteilen aus TiAl6V4 nachgewiesen.

Specimens of ZrB2 containing various concentrations of B4C, SiC, TaB2, and TaSi2 were pressureless-sintered and post-hot isostatic pressed to their theoretical densities. Oxidation resistances were studied by scanning thermogravimetry over the range 1150 - 1550 degree C. SiC additions improved oxidation resistance over a broadening range of temperatures with increasing SiC content. Tantalum additions to ZrB2-B4C-SiC in the form of TaB2 and/or TaSi2 increased oxidation resistance over the entire evaluated spectrum of temperatures. TaSi2 proved to be a more effective additive than TaB2. Silicon-containing compositions formed a glassy surface layer, covering an interior oxide layer. This interior layer was less porous in tantalum-containing compositions. The oxidation resistances of ZrB2 containing SiC, TaB2, and TaSi2 additions of various concentrations was studied using isothermal thermogravimetry at 1200, 1400, and 1500 degree C, and specimens were further characterized using x-ray diffraction and electron microscopy. Increasing SiC concentration resulted in thinner glassy surface layers as well as thinner ZrO2 underlayers deficient in silica. This silica deficiency was argued to occur by a wicking process of interior-formed borosilicate liquid to the initially-formed borosilicate liquid at the surface. Small (3.32 mol%) concentrations of TaB2 additions were more effective at increasing oxidation resistance than equal additions of TaSi2. The benefit of these additives was related to the formation of zirconium-tantalum boride solid solution during sintering, which during oxidation, fragmented into fine particles of ZrO2 and TaC. These particles resisted wicking of their liquid/glassy borosilicate encapsulation, which increased overall oxidation resistance. With increasing TaB2 or TaSi2 concentration, oxidation resistance degraded, most egregiously with TaB2 additions. In these cases, zirconia dendrites appeared to grow through the glassy layers, providing conduits for oxygen migration.

Thesis (Ph.D.)--University of Wollongong, 2008. / Typescript. Includes bibliographical references: leaf [162]-180.

Made available in DSpace on 2014-06-11T19:23:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-05-20Bitstream added on 2014-06-13T18:09:41Z : No. of bitstreams: 1 murad_or_me_bauru.pdf: 1607364 bytes, checksum: a13c081e60319e997b56935fa0771793 (MD5) / O presente trabalho teve como objetivo estudar as propriedades magnéticas e de transporte elétrico de filmes finos de MGBIND.2', de espessura, rescidos pelo método de Pulsed Laser Deposition, diante de variações de conformidade microestrutural. Para efeito de comparação, foram utilizados filmes finos com 100 e 400nm de espessura crescidos pelo método Chemical Vapor Deposition. O trabalho foi possível graças ao desenvolvimento de um sistema de fixação de amostras que mostrou ser eficaz nos casos onde a deposição de terminais com epóxi prata inutiliza as amostras para estudos posteriores devido à contaminação. Foram realizados ensaios de magneto-transporte, magnetização e susceptibilidade magnética utilizando o Physical Property Measurement System (PPMS). Os resultados de magneto-transporte foram modelados matematicamente por meio do modelo de Bloch-Grüneisen, mediante o uso do software Mathematica. A análise dos resultados mostrou que diferenças microestruturais conduzem a um comportamento de resistividade no estado normal diferenciado. A possível existência de uma microestrutura diferenciada, onde há dificuldade em se definir um contorno de grão, e praticamente a inexistência de material intragranular, podem ser a chave para o entendimento de medidas de transporte elétrico e magnéticas tão singulares, onde não há evidências de comportamento inter e intragranular, como ocorre geralmente nos supercondutores cerâmicos. Por último, o modelamento da resistividade permitiu validar todo o sistema de medidas utilizado, pois os resultados obtidos estão em acordo com a literatura. / In this work it was studied magnetic and electrical transport properties of MGB IND.2' thin films, with 200nm of thick, grown by the method of Pulsed Laser Deposition, in front of microstructure variation. For comparison, were also analyzed thin films with 100 and 400nm of thickness grown by Chemical Vapor Deposition method. This study was possible since the development of sample fixing system that showed be effective in the cases that the terminals depositions with silver epoxy make samples useless for the future studies due to contamination. Magnetic-transport, magnetization and magnetic susceptibility were performed using the Physical Property Measurement System (PPMS). The results of magnetictransport measurements were modeled by the Bloch-Grüneisen model through the Mathematica Software. Analysis of the results showed that microstructural differences of the samples make different the value of resistivity in the normal state. Possible existence of the different microstructural where have difficult to define the grain boundary and absent of intergranular material, factors that can the key for the understanding of electrical transport and magnectic measurements how individuals, where no have evidences of inter and intragranular behavior, how exist in the ceramic superconductors. At last, the resistivity model permitted validates all the measurement system utilized, because the results obtained are in agreement with the literature.

abstract: Ultrasonication-mediated liquid-phase exfoliation has emerged as an efficient method for producing large quantities of two-dimensional materials such as graphene, boron nitride, and transition metal dichalcogenides. This thesis explores the use of this process to produce a new class of boron-rich, two-dimensional materials, namely metal diborides, and investigate their properties using bulk and nanoscale characterization methods. Metal diborides are a class of structurally related materials that contain hexagonal sheets of boron separated by metal atoms with applications in superconductivity, composites, ultra-high temperature ceramics and catalysis. To demonstrate the utility of these materials, chromium diboride was incorporated in polyvinyl alcohol as a structural reinforcing agent. These composites not only showed mechanical strength greater than the polymer itself, but also demonstrated superior reinforcing capability to previously well-known two-dimensional materials. Understanding their dispersion behavior and identifying a range of efficient dispersing solvents is an important step in identifying the most effective processing methods for the metal diborides. This was accomplished by subjecting metal diborides to ultrasonication in more than thirty different organic solvents and calculating their surface energy and Hansen solubility parameters. This thesis also explores the production and covalent modification of pristine, unlithiated molybdenum disulfide using ultrasonication-mediated exfoliation and subsequent diazonium functionalization. This approach allows a variety of functional groups to be tethered on the surface of molybdenum disulfide while preserving its semiconducting properties. The diazonium chemistry is further exploited to attach fluorescent proteins on its surface making it amenable to future biological applications. Furthermore, a general approach for delivery of anticancer drugs using pristine two-dimensional materials is also detailed here. This can be achieved by using two-dimensional materials dispersed in a non-ionic and biocompatible polymer, as nanocarriers for delivering the anticancer drug doxorubicin. The potency of this supramolecular assembly for certain types of cancer cell lines can be improved by using folic-acid-conjugated polymer as a dispersing agent due to strong binding between folic acid present on the nanocarriers and folate receptors expressed on the cells. These results show that ultrasonication-mediated liquid-phase exfoliation is an effective method for facilitating the production and diverse application of pristine two-dimensional metal diborides and transition metal dichalcogenides. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2018

Made available in DSpace on 2014-06-11T19:23:08Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-08-10Bitstream added on 2014-06-13T20:50:08Z : No. of bitstreams: 1 silva_mr_me_bauru_prot.pdf: 5425736 bytes, checksum: c0025dd94306d704e10c08b2a6628b66 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A descoberta da supercondutividade no MgB2 (diaboreto de magnésio) foi de grande importância para a comunidade de Física do Estado Sólido, pois este material é um dos poucos compostos intermetálicos binários conhecidos atualmente com uma das maiores temperaturas críticas (39 K) para um não óxido e não pertencente à família dos compostos baseados em C60. Por ser um composto granular, é de fundamental importância a compreensão de mecanismos de interação de defeitos e a rede cristalina do material, além de eventuais processos envolvendo os contornos dos grãos que compõem o material. Neste sentido, as medidas de especgroscopia mecânica constituem uma ferramenta bastante poderosa para este estudo, pois por intermédio delas podemos obter importantes informações a respeito de transições e de fase e do comportamento de elementos intersticiais, substitucionais, discordâncias, contornos de grãos, difusão, instabilidades e outras imperfeições da rede. Estudos anelásticos em amostras de MgB2 são bastante escassos, porém, trabalhos recentes em magnésio puro e ligas especiais a base de magnésio mostram a ocorrência de diversos processos de relaxação associados à discordâncias, contornos de grãos e interações entre elementos intersticiais e outras imperfeições da rede. Neste trabalho, as amostras foram preparadas pelo método powder-in-tube (PIT) e forma caracterizadas por medidas de densidade, difração de raios X, microscopia eletrônica de varredura, espectrometria por dispersão de energia, resistividade elétrica e magnetização. As medidas de espectroscopia mecânica mostraram espectros bastante complexos, onde foram identificados oito processos de relaxação devido a movimentos de discordâncias, interação entre elementos intersticiais e discordâncias, auto-difusão e movimento de contornos de grãos. / The discovery of the superconductivity in the MgB2 (magnesium diaboride) was of great importance for the community of the solid state physics, therefore this material is one of few binary intermetallic composites known currently with the one of the biggest critical temperatures (39 K) for a non-oxide and not pertainig to C60 composites based family. Due its granular composition, it is of great importance the understanding of mechanisms of interaction of defects and the crystalline lattice of the material, beyond eventual processes involving the grains boundaries that compose the material. In this sense, the mechanical spectroscopy measurements constitute a powerful tool for this study, therefore by them we can get important information regarding phase transitions and the behavior of intersistial or substitutional elements, dislocations, grain boundaries, diffusion, instabilities and other imperfections of the lattice. Anelastic studies in MgB2 samples are very poor, but, recent researches made in pure magnesium and magnesium based alloys shown the occurrence of several relaxation processes associated to dislocations, grain boundaries and interaction of interstitial elements and another lattice imperfections. In this research, the samples were prepared by powder-in-tube (PIT) method and were characterized by density, x-ray diffraction, scanning electron microscopy, energy diepersive x-ray spectroscopy, electrical resistivity and magnetization measurements. The mechanical spectroscopy measurements shown sufficiently complex spectra, where identified eight relaxation processes due to the dislocation motion, interaction between interstitials elements and dislocations, self-diffusion and grain boundaries motion

In this thesis, growth of ZrB2 thin films by direct current magnetron sputtering is investigatedusing a high vacuum industrial scale deposition system and an ultra-high vacuum laboratory scalesystem. The films were grown from ZrB2 compound targets at temperatures ranging from ambient (without external heating) to 900 °C and with substrate biases from -20 to -120 V. Short deposition times of typically 100 or 300 s and high growth rates of 80-180 nm/min were emphasized to yield films with thicknesses of 300-400 nm. The films were characterized by thinfilm X-ray diffraction with the techniques θ/2θ and ω scans, pole figure measurements andreciprocal space mapping, scanning and transmission electron microscopy, elastic recoil detection analysis and four point probe measurements. The substrates applied were Si(100), Si(111),4H-SiC(0001) and GaN(0001) epilayers grown on 4H-SiC. The Si(111), 4H-SiC(0001) substrates and GaN(0001) epilayers were chosen given their small lattice mismatches to ZrB2 making them suitable for epitaxial growth.The films deposited in the industrial system were found to be close to stoichiometric with a low degree of contaminants, with O being the most abundant at a level of < 1 at.%. Furthermore, the structure of the films is temperature dependent as films deposited in this system without external heating are fiber textured with a 0001-orientation while the films deposited at 550 °C exhibitrandom orientation. In contrast, epitaxial growth was demonstrated in the laboratory scale system on etched 4H-SiC(0001) and Si(111) deposited at 900 °C following outgassing of the substrates at 300 °C and in-situ heat treatment at the applied growth temperature to remove the native oxides. However, films grown on GaN(0001) were found to be 0001 textured at the applied deposition conditions, which make further studies necessary to enable epitaxial growth on this substrate material. Four point probe measurements on the films deposited in the industrial system show typical resistivity values ranging from ˜95 to 200 μΩcm with a trend to lower values for the films deposited at higher temperatures and at higher substrate bias voltages.

In multiband superconductors, different bands at the Fermi surface contribute to the superconductivity with different magnitudes of superconducting gaps on different portions of the Fermi surface. Each band in a multiband superconductor has a condensate with an amplitude and phase that weakly interacts with the other bands’ condensate. The coupling strength between the bands determines whether one or two superconducting transition temperatures are observed, and it is the key to many peculiar properties. In general, if there are two gaps of different magnitude, there are two different length scales associated with the suppression of these gaps in applied magnetic fields, for example. Therefore, effects of multigap superconductivity can be observed in superconducting vortices, which are twirls of supercurrents that are generated when a superconductor is placed in a magnetic field. Furthermore, the two superconducting order parameters in different bands are characterized by a magnitude and phase. In multiband superconductors, there are collective excitations corresponding to fluctuations of the relative phase of two order parameters, so-called the Leggett mode. The first material identified as multiband superconductor is Magnesium Diboride (MgB2) in 2001 with a critical temperature Tc of 39 K. MgB2 is a superconducting material with the highest transition temperature among all conventional BCS superconductors. It has two superconducting gaps \Delta_\pi ~ 2 meV and \Delta_\sigma\ ~ 7 meV and they arise from the existence of two bands \pi and \sigma bands of boron electrons. The discovery of superconductivity in MgB2 renewed interest in the field of multiband superconductivity. MgB2 has attracted many scientists’ attention both for the fundamental importance of understanding the multiband superconductivity and possible applications such as magnets, power cables, bolometers, Josephson junction-based electronic devices, and radio-frequency cavities. Afterward, other materials have been identified as multiband superconductors such as NbSe2, the family of iron-based superconductors, heavy fermion superconductors, multilayer cuprates, borocarbides, etc. This dissertation uses tunneling experiments to highlight multiband superconductivity features in two systems, namely MgB2 thin films and ultrathin films of Pb. Further, we use multiple techniques to study a superconducting material, nitrogen-doped niobium, used for superconducting radio-frequency cavities. For the project on MgB2, MgB2/Native-Oxide/Ag planar junctions are fabricated and characterized down to 2.1 K and in the magnetic field parallel to the sample surface up to 6 Tesla. This work investigates how pairbreaking affects the magnitude and phase of the order parameter in a multiband superconductor. The tunneling spectra are analyzed in the framework of a two-band model developed by our theory collaborator Prof. Alex Gurevich, Old Dominion University. The model allows the extraction of the pair-breaking parameters among other quantities. The analysis shows that the order parameter in the ? band is quickly suppressed in the field, the ? band is cleaner than the ? band. The ratio of pairbreaking parameter in the ? band to the ? band rapidly increases at fields higher than ~0.1 T and then plateau at higher fields. This transition around 0.1 T magnetic field suggests a phase decoupling in the two bands of MgB2. Below the transition, the two bands are phase-locked, so mostly, the superconductivity in the ? band is affected, and after phase decoupling, both bands are affected by the applied field. These results are important for a basic understanding of multiband superconductors and the application implications of this material. This phase decoupling has a new and profound consequence on the superconducting state of a multiband superconductor that has been theoretically predicted and never observed experimentally. For the Pb project, ultrathin films of Pb in ultrahigh vacuum conditions are deposited by e-beam evaporation and characterized with low-temperature scanning tunneling microscopy and spectroscopy (STM/STS). The STM/STS allows measuring the electronic density of states with the highest spatial resolution down to atomic scale. The shape of a superconducting vortex core is determined by the superconducting gap and the Fermi velocity, and the STM allows to map anisotropies of these quantities spatially. The vortex cores of Pb film show a complex shape that evolves from triangular at short distances from the center to a six-fold symmetric star shape farther away from the center. These details are very subtle, and they can be highlighted only if one works within the clean limit (to avoid the averaging effect of the scattering) and by fabricating the heterostructure that pins the vortices spatially. The complex vortex core shape reflects the anisotropy of the two bands that contribute to superconductivity in this material. For the project on Niobium, cold and hot spots from nitrogen-doped Nb cutouts are characterized by low temperature scanning tunneling microscopy and spectroscopy (STM/STS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The radiofrequency (RF) measurements of the quality factor and temperature mapping on an N-doped Nb superconducting resonator cavity are carried out at Jefferson Laboratory before cutting out the samples. This work aims to identify possible sources of excess dissipation in hot spots and relate them to the surface chemical composition and superconducting properties. The temperature mapping revealed a strong effect of the cavity cooldown rate on the intensities of hot spots and their spatial distribution, which indicates a significant contribution of trapped vortices to the RF dissipation. SEM images acquired on the cold and hot spots using a secondary electron detector show absence of residual hydride scars and niobium nitrides on their surface. Angle-resolved XPS measurements on the native surface of these samples revealed higher oxidized Nb 3d states on the N-doped Nb cold spots, which is supported by XPS depth profiles done on the samples by Argon ion sputtering. Argon ion sputtering of oxidized Nb removes oxygen preferentially from Nb2O5 and diffuses to bulk, thickening the lower oxidation state layers. The proximity theory framework’s tunneling spectra analysis suggests hot spots have stronger pairbreaking due to a weakly reduced pair potential, a thicker metallic suboxide layer, and a wide distribution of the contact resistance. STM imaging of vortex cores shows a triangular vortex lattice in both samples, and the coherence length is nearly the same in hot and cold spots. The experimental data analysis suggests weakly degraded superconducting properties at the surface of hot spot regions are not the primary sources of RF losses. Instead, they are the regions where vortices nucleate first and get trapped during cooling down. These experimental techniques and findings will be crucial in helping to qualify new recipes for SRF cavity production and to boost their performance. / Physics

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