Hamburg, Universiẗat, Diss., 1999. / Dateiformat: zip, Dateien im PDF-Format.

Freiburg i. Br., Univ., Diss., 2008.

Thesis (M.S.)--Oregon Graduate Center, 1985.

Techn. Universiẗat, Diss., 2004--Dresden.

Over the last two decades there has been an increased interest in understanding the influence of trace boron additions in Ti alloys. These additions refine the prior β grain size in as-cast Ti alloys along with increasing their modulus and yield strength due to the precipitation of TiB. TiB also acts as a heterogeneous nucleation site for α precipitation and has been shown to influence the α phase morphology. B is completely soluble in liquid Ti but has a negligible solubility in both body centered cubic β and hexagonal close packed α phases of Ti. Thus, during solidification of hypoeutectic B containing alloys, B is rejected from β into the liquid where it reacts with Ti to form pristine single crystal whiskers of TiB. Despite a substantial amount of reported experimental work on the characterization of TiB precipitates, its formation mechanism and influence on α phase precipitation are still not clear. The current work is divided into two parts – (i) understanding the mechanism of TiB formation using first principles based density functional theory (DFT) calculations and (ii) elucidating how TiB influences the α phase morphology and crystallography in titanium alloys using electron microscopy techniques. TiB exhibits anisotropic growth morphology with [010] direction as its predominant growth direction and displays a hexagonal cross section with (100), (101), and (10) as the bounding planes. A high density of stacking faults has been experimentally observed on the (100) plane. The present study, by using DFT based nudged elastic band (NEB) calculations, elucidates for the first time that the diffusion of B through TiB is via an interstitial-assisted mechanism as opposed to vacancy-assisted mechanism hypothesized in literature. This one dimensional interstitial-assisted diffusion results in the anisotropic growth of TiB. In addition, the energetics of TiB- α interfaces was calculated to understand the hexagonal cross-section of TiB. The intimate mixing of B27 and Bf structures and their co-existence with stacking faults has been explained by calculating the interfacial energy of B27/Bf interfaces along with stacking fault formation energy. The boride precipitates have also been shown to modify the morphology of α phase from lath like to more equiaxed like. However, the influence of TiB on the crystallography of α precipitation has not been explored in great detail. The present study will clearly demonstrate, for the first time, the influence of various alloying elements present in the titanium alloy, on the resulting effect of B addition on α morphology and its crystallography in Ti alloys. Thus, the influence of B addition on α precipitation in two classes of commercial Ti alloys, i.e. β alloys and α + β alloys have been explored. It has been found that TiB nucleated α can either become equiaxed by a loss of Burgers orientation relationship (OR) with β or can retain the lath morphology in case of alloys containing a combination of Ti, Al and Mo.

Techn. Universiẗat, Diss., 2004--Chemnitz.

Durch Untersuchungen zur Reaktivität von Boryl- und Boridverbindungen konnten deren Bindungssituationen aufgeklärt und neuartige Koordinationsmotive von Übergangsmetall-Bor-Verbindungen erhalten werden. Die erhaltenen Verbindungen wurden mittels NMR-Spektroskopie, IR-Spektroskopie, Elementaranalyse und Röntgendiffraktometrie untersucht und zusätzlich wurden DFT-Rechnungen angefertigt. An verschieden substituierten Eisenborylkomplexen wurden Reaktivitätsuntersuchungen gegenüber Halogenidabstraktionsmitteln und Reduktionsmitteln durchgeführt und im Falle der Boridkomplexe wurden Verbindungen mit bis dato unbekanntem Strukturmotiv erhalten. / Investigations into the reactivities of boryl and boride complexes provided insight into their bonding and led to previously unknown coordination motifs for transition-metal-boron complexes. The resulting compounds were analyzed via NMR spectroscopy, IR spectroscopy, elemental analyses and crystal structure analyses. Their electronic structures were investigated by theoretical calculations using DFT methods. The reactivities of substituted iron boryl complexes toward halogenide abstracting and reducing reagents were studied and, in case of the boride complexes, novel structural motifs were dentified.

Hard and ultra-incompressible materials are of great interest due to their important applications in industry. A common route to design hard materials is combining transition metals with light and small covalent elements. Light elements such as carbon, oxygen, nitrogen and boron have been considered as good candidates. This study includes the synthesis of ReB2, OsB2 and another higher boride AlMgB14. Most of the techniques used for ReB2 synthesis reported 1:2.5 Re to B ratio because of the loss of the B during high temperature synthesis. However, as a result of B excess, the amorphous boron, located along the grain boundaries of polycrystalline ReB2, would degrade the ReB2 properties. Therefore, techniques which could allow synthesizing the stoichiometric ReB2 preferably at room temperature are in high demand. This thesis reported the synthesis of ReB2 powders using mechanochemical route by milling elemental crystalline Re and amorphous B powders in the SPEX 8000 high energy ball mill for 80 hours. The formation of boron and perrhenic acids are also reported after ReB2 powder was exposed to the moist air environment for a twelve months period of time. The synthesized ReB2 powder was characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, secondary ion mass spectrometry and Raman spectroscopy. OsB2 also shows its attractive properties. The hardness of orthorhombic OsB2 was reported to be 37 GPa, when the applied load is lowered to 0.245N. However, only one of the three predicted phases has been synthesized. In this study, the hexagonal OsB2 has been synthesized by the mechanochemical method. The lattice parameters of the Hex-OsB2 are iv α=β=90°, γ=120°; a=b=2.9047 Å, c=7.4500 Å. The synthesized OsB2 powder was annealed at 1050°C for 6 days, but no phase change was found. This shows that the Hex-OsB2 is very stable. Another promising hard material, AlMgB14, was also studied in this thesis. The AlMgB14 was synthesized at 1050 °C under normal pressure. Several different routes were tried and compared. It shows AlMgB14 cannot be synthesized merely by ball milling, which can bring the risk of oxidization. Magnesium metal is preferred to use as one of the raw materials.

Neste trabalho, camadas de elevadas durezas e resistentes ao desgaste, constituídas de NbC, VC ou Fe-B, foram produzidas nos aços AISI H13 e D2, por meio de tratamentos termo-reativos em banhos de bórax, com adição de Fe-Nb, Fe-V, Fe-Ti e Al. As amostras foram caracterizadas por meio de microscopias ótica e eletrônica de varredura com EDS (espectroscopia de dispersão de energia), difração de raios-X, GDOS (“Glow discharge optical spectroscopy"), microdureza Vickers, e ensaios de adesividade e desgaste em micro-escala. Para os banhos contendo Fe-Nb/Al, foram obtidas camadas de NbC nos dois aços, com espessuras médias de 6,2 mícrons, quando produzida no aço AISI H13, e 15,6 mícrons para o aço AISI D2. No caso do banho com adição de Fe-V/Al, produziram-se camadas de VC, com espessuras médias de 5,8 e 14,2 mícrons, para os aços AISI H13 e D2, respectivamente. As durezas das camadas de NbC e VC situaram-se na faixa de 2338 a 2471HV. No caso dos banhos contendo Fe-Ti e Al ou apenas Al, foram produzidas camadas de boretos, principalmente FeB e Fe2B, com espessuras variando de 30 a 130 mícrons, e durezas médias na faixa de 1583 a 1742HV. Os ensaios de adesividade evidenciaram as excelentes aderências das camadas com os substratos. Todas as camadas apresentaram resistências ao desgaste muito superiores as dos substratos, destacando-se as camadas de NbC e VC. Os ensaios de desgaste em micro-escala foram realizados sob carga elevada e sem uso de abrasivo, simulando condições de desgaste adesivo-abrasivo, uma vez que inexistem dados a respeito desse comportamento. Com o decorrer do ensaio, o modo de desgaste passou de adesivo para abrasivo, o que foi registrado pela presença de sulcos paralelos e de superfícies polidas nas calotas de desgaste. / In the present work, hard and wear resistant layers, consisting of NbC, VC or Fe-B, were produced on AISI H13 and D2 steels, by thermo-reactive treatments in borax baths, added with Fe-Nb, Fe-V, Fe-Ti and Al. Samples were characterized by optical and scanning electron microscopy, energy dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD), Glow discharge optical spectroscopy (GDOS), Vickers microhardness, and adhesion and micro-scale wear tests. For the baths containing Fe-Nb/Al, the layers obtained on both steels consisted of NbC, with an average thickness of 6.2 micrometers, when formed on AISI H13 steel, and 15.6 micrometers for the AISI D2 steel. In the case of borax bath added with Fe-V/Al, the produced layers contained VC, which had average thicknesses of 5.8 and 14.2 micrometers, for the AISI H13 and D2 steels, respectively. The hardness of the NbC and VC layers varied from 2338 to 2471HV. In the case of the borax bath containing Fe-Ti and Al or only Al, boride layers were produced, mainly FeB and Fe2B, with depths ranging from 30 to 130 micrometers, and average hardnesses varying from 1583 to 1742HV. The obtained layers presented excellent adhesion to the substrates. All layers presented wear resistance superior to the substrates, mainly the NbC and VC layers. The micro-scale wear tests were performed under high applied loads and without addition of abrasive, thus simulating adhesive-abrasive wear conditions, as there is no existing data concerning this wear behavior. During the micro-scale wear test, the wear mode changed from adhesive wear to abrasive wear, which was verified by the presence of parallel grooves and smooth surfaces in the wear craters.

Os aços AISI 8620, 15B30, 8640 e 52100 são amplamente usados como componentes em rolamentos, engrenagens, pistões e discos de arado, estando sujeitos a constante contato relativo e, consequentemente, sobre diferentes formas de desgaste tribológico. O uso de tratamentos que produzam camadas duras e resistente ao desgaste podem aumentar significativamente o tempo em uso e reduzir custos operacionais. Neste trabalho, tais aços, foram submetidos a tratamentos de Boretação e Deposição termorreativa (TRD) e caracterizados por meio de ensaios de dureza, desgaste microadesivo e difração de raios - X. A dureza das camadas foram determinadas, ocorrendo aumento dessa propriedade para valores de 1650 a 1750 HK0.2 e 2000 a 2400 HK0.2 respectivamente para as camadas de boretos e carbonetos, já em relação ao desgaste microadesivo, as camadas de boretos, VC e NbC formadas apresentaram maior resistência ao desgaste quando comparadas aos seus respectivos substratos protegidos. / The AISI 8620, 15B30, 8640 and 52100 steels are widely used as components in bearings, gears, pistons and plow discs, being subject to constant relative contact and, consequently, to different forms of tribological wear. The use of treatments that produce hard layers and wear resistant can significantly increase the time in use and reduce operating costs. In this work, these steels were submitted to Boride and Thermorreative Deposition (TRD) treatments and characterized by tests of hardness, microadhesive wear and X - ray diffraction. The hardness of the layers was determined, increasing this property to values of 1650 to 1750 HK0.2 and 2000 to 2400 HK0.2 respectively for the layers of borides and carbides, already in relation to the microadhesive wear, the boride layers, VC and NbC formed presented higher resistance to wear when compared to their respective protected substrates.