Abstract Densification and mechanical properties (hardness, fracture toughness and flexural strength) of the SiC-TiB2 composite were studied. Pressureless sintering experiments were carried out on samples containing 0 to 50 vol % of TiB2 created by an in-situ reaction between TiO2 and C: 2TiO2 + B4C + 3C 2TiB2 + 4CO Al2O3 and Y2O3 were used as sintering additives to create a liquid phase and promote densification at sintering temperatures ranging from 1820 to 1940oC. The sintered samples were subsequently heat-treated at temperatures ranging from 1850 to 1970oC It was found that the presence of TiB2 formed by the above reaction serves as an effective obstacle to crack propagation thus increasing both the strength and fracture toughness of SiC while maintaining high a hardness of the sintered samples. Densities higher than 98 % TD were achieved depending on both the sintering temperature and heat treatment conditions. From a density viewpoint, the optimum volume fraction of TiB2 was from 12 to 24 vol %. Typical microstructures for samples with this volume fraction of TiB2 consist of TiB2 particles (< 5m) uniformly dispersed in a matrix of elongated SiC plates. The presence of TiB2 particles in the matrix of SiC inhibited exaggerated grain growth of the SiC grains and activated additional toughening mechanisms. The subsequent heat treatment of the sintered samples improved mechanical properties. The optimum sintering and heat treatment temperatures were 1940 and 1970oC, respectively. The maximum flexural strength of 593 MPa was obtained in sample with 12 vol % TiB2. A maximum fracture toughness of 6.6 MPa•m1/2 was measured in samples containing 24 vol % TiB2. While both fracture toughness and strength increased with the presence of TiB2 particles, hardness on the other hand decreased from ~18 GPa in samples without TiB2 to 16.4 and 15.9 GPa in samples with 12 and 24 vol % TiB2, respectively. A theoretical analysis was conducted to model the effect of microstructure on the fracture toughness of SiC-TiB2 composites and was experimentally verified. / Thesis (Ph.D, Mechanical and Materials Engineering) -- Queen's University, 2009-09-30 23:04:32.565

This research deals with the synthesis and characterization of titanium diboride (TiB2) from novel carbon coated precursors. This work provides information on using different boron sources and their effect on the resulting powders of TiB2.The process has two steps in which the oxide powders were first coated with carbon by cracking of a hydrocarbon gas, propylene (C3H6) and then, mixed with boron carbide and boric acid powders in a stoichiometric ratio. These precursors were treated at temperatures in the range of 1200-1400° C for 2 h in flowing Argon atmosphere to synthesize TiB2.The process utilizes a carbothermic reduction reaction of novel carbon coated precursor that has potential of producing high-quality powders (sub-micrometer and high purity). Single phase TiB2 powders produced, were compared with commercially available titanium diboride using X-ray diffraction and Transmission electron microscopy obtained from boron carbide and boric acid containing carbon coated precursor.

AN ABSTRACT OF THE THESIS OF Lisa Rajan, for the Master of Science degree in Mechanical Engineering, presented on April 1, 2011, at Southern Illinois University Carbondale. TITLE: THEORETICAL AND EXPERIMENTAL STUDIES ON THE FORMATION OF METAL BORIDES MAJOR PROFESSOR: Dr. Rasit Koc Formation studies were done on six metal borides, TiB2, ZrB2, HfB2, AlB2, CaB6, and LaB6. The goal of this research is to research materials used for coatings on bipolar plates used in polymer electrolyte, PE, fuel cells. Theoretical calculations were done with formation equations from these six materials. Software used was HSC Chemistry version 5.0. Each equation was fully entered, and the range of formation temperature was narrowed till a value was obtained. Experimental work was done on TiB2 using thermogravimetric analysis and x-ray diffraction. Studies were done on carbon coated TiO2 precursors mixed with B4C and mixed carbon and TiO2 precursors mixed with B4C. The studies show that TiB2 is a very excellent material and easy to make. ZrB2, HfB2 and CaB6 are also easily processed and available for use in the market. AlB2 needs more research so that effective conclusions can be made about its formation temperature and suitable methods of production. Although made by methods uncommon to those studied in this work, LaB6 is already in commercial production and used in electron microscopes. Examination of previous experimental studies shows that the reduction reaction methods and formation of powders in an autoclave are the most consistent methods of metal boride formation. Calculations in the HSC 5.0 software confirmed that. When reactions for these methods were done, they consistently produced precise formation temperatures. Several variations of the combined reduction reaction were found in the literature, and all produced the same theoretical formation temperature. Molar amounts did not affect this temperature. Each method produced submicron particle powders. Thermodynamic data was useful in determining the certainty of each reaction being done experimentally. Most reactions were thermodynamically possible with a few exceptions. Change in enthalpy, ∆H, change in entropy, ∆S, change in Gibb's free energy, ∆G, and the formation constant K were all factors that were calculated and used to describe metal boride formation. The experimental studies showed that coated precursors have a lower temperature at which the reaction begins. The process is more gradual for coated precursors, although both coated and mixed precursors reach a pure TiB2 phase by 1400°C. The mixed precursor had a higher phase of purity than the coated precursor at 1400°C.

Untersuchungen der Hochtemperaturbenetzung und Grenzfächeninteraktionen in Flüssigmetall/Übergangsmetall-Diborid-Systemen werden durch die technologische Nachfrage nach qualitative hochwertigen Metall-Matrix-Kompositen und verläßlichen Verbindungen von Ultrahochtemperaturkeramiken für aggressive chemische und/oder thermische Umgebungen angetrieben. Die physikalischen und chemischen Charakteristika der Metall/Keramik-Grenzflächen (z.B. die Benetzungskinetik, Grenzflächenreaktionen und die Phasenbildung) sind unerläßlich um die fundamentalen Mechanismen, die kontrollierenden technologischen Parameter, sowie die definierenden Eigenschaften und die Qualität des Endprodukts zu verstehen. Die Methode des liegenden Tropfens (engl. sessile drop method) ist die am häufigsten verwendete Verfahren für die quantitative Charakterisierung der Benetzungseigenschaften und für die direkte Untersuchung von Grenzflächeninteraktionen zwischen Flüssigmetall und festen Substraten unter Zuhilfenahme von Mikroskopie. Der Fokus dieser Arbeit liegt auf der Hochtemperaturbenetzung und den Grenzflächeninteraktionen von geschmolzenen reinem Al und Ti-Al, Ni-Al und Ni-B Schmelzen mit der TiB2 Ultrahochtemperaturkeramik. Die über die Methode des liegenden Tropfens hergestellten Metall/Keramik Verbunde werden hauptsächlich mittels Rasterelektronenmikroskopie gekoppelt mit energiedispersiver Röntgenspektroskopie sowie Röntgenbeugung untersucht. Die temperatur- und zeitabhängige Benetzung von flüssigem Al auf der TiB2 Keramik wurde mittels der klassischen Technik des liegenden Tropfens und der sogenannten dispensed drop technique (engl.) über einen weiten Temperaturbereich untersucht. Die Ergebnisse zeigen, dass mit ansteigender Temperatur die Benetzung bedeutend schneller abläuft. Die beiden Methoden liefern einen Unterschied in der Benetzungstemperatur von etwa 300°C aufgrund der nativen Oxidschicht auf der Al-Oberfläche bei dem klassischen Sessile-drop Versuch. Beginnend bei 1000°C füllt das flüssige Al entweder die intergranularen Poren auf oder dringt entlang der Korngrenzen in das TiB2 Substrat ein. Es wurde keine Reaktion im Al/TiB2 System beobachtet. Die Grenzflächeninteraktionen zwischen Ti-Al Schmelzen und der TiB2 Keramik wurden mit der klassischen Technik des liegenden Tropfens untersucht, da ein passender Tiegel für flüssiges Ti und Ti-haltige Schmelzen nicht vorhanden war. Für reines Ti auf TiB2 setzt das Schmelzen bei etwa 120 °C unter seinem Schmelzpunkt ein, wie aus Untersuchungen der Form und Struktur der erstarrten Ti/TiB2 Proben hervorgeht. Dies wird durch Festkörperdiffusion von B aus dem Substrat in die Ti Probe hinein und einer Verschiebung der Zusammensetzung von reinem Ti zu einer Ti-B Legierung in der substratnahen Region verursacht. Die Rolle von Al scheint für das Eindringen von Ti-Al Schmelzen entlang von Krongrenzen in das Keramiksubstrat von größerer Bedeutung zu sein als die Rolle der Temperatur. Die Benetzung und Grenzflächeninteraktionen zwischen Ni-Al Schmelzen und TiB2 wurden mit dem dispensed drop Verfahren untersucht. Flüssige Ni-Al Legierungen zeigen deutlich unterschiedliche Benetzungsverhalten auf dem TiB2 Substrat in Abhängigkeit von Legierungszusammensetzung und Testbedingungen. Das Verhalten von Ni-Al Schmelzen auf TiB2 Keramik verändert sich von einem auflösenden, reaktiven Benetzen (engl. dissolutive, reactive wetting) auf der Ni-reichen Seite zu einem nicht-reaktiven Benetzen auf der Al-reichen Seite. Die Ergebnisse deuten darauf hin, dass der Ni-Gehalt in Ni-Al Legierungen eine Hauptursache für die Veränderungen der Substratauflösung und der geometrischen Konfiguration an der Metall/Keramik Grenzfläche ist. Um den Einfluss des Ni-Gehalts auf die Auflösung von TiB2 zu verstehen wurde das Schmelzen und Benetzen von Ni83B17 und Ni50B50 Legierungen auf der TiB2 Keramik mittels der klassischen Technik des liegenden Tropfens im Hinblick auf mögliches fügen von TiB2 Keramiken untersucht. Basierend auf den Benetzungstest wurden Zwischenschichten der Ni50B50 Legierung verwendet um TiB2 Keramiken zu Verbinden. In dieser Arbeit wurde die Technik des liegenden Tropfens erfolgreich angewandt um die Hochtemperaturbenetzung und die Grenzflächeninteraktionen zwischen flüssigen Al, Ti-Al, Ni-Al und Ni-B Legierungen und keramischem TiB2 zu untersuchen. Die in dieser Arbeit erhaltenen Ergebnisse ermöglichen ein besseres Verständis der Interaktionsmechanismen zwischen flüssigen Al, Ti-Al, Ni-Al und Ni-B Legierungen und TiB2 keramik in diesen Systemen ermöglichen und Erstellung von Richtlinien für die Herstellung von Metall-Matrix-Verbunden und/oder Keramik-Matrix-Verbunden sowie für die Verbindung von keramischen TiB2 Teilen für strukturelle Hochtemperaturanwendungen dar. / Investigations of high-temperature wetting and interfacial interactions in liquid metal/transition-metal diboride systems are driven by technological demand in obtaining high-quality metal matrix composites and reliable joining of ultrahigh-temperature ceramics for aggressive chemical and/or thermal environments. The physical and chemical characteristics of metal/ceramic interface (e.g. wetting kinetics, interfacial reactions and phase formation) are indispensable for understanding the fundamental mechanisms, controlling technological parameters, and defining the properties and quality of final products. The sessile drop method is the most commonly used for quantitative characterization of the wetting properties and direct investigations of the interfacial interactions between a liquid metal and a solid substrate with the help of microscopy. This thesis is focused on the high-temperature wetting and interfacial interactions of molten pure Al and Ti-Al, Ni-Al and Ni-B alloys with TiB2 ultra-high-temperature ceramic. The metal/ceramic couples after the sessile drop tests are mainly characterized using scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and X-ray diffraction. The temperature- and time-dependent wetting between the liquid Al and TiB2 ceramic over a wide temperature range was investigated using the classical sessile drop and dispensed drop techniques. The results showed that the wetting was significantly accelerated with increasing temperature. A difference of the wetting temperature by these two techniques was about 300 °C, due to the native oxide film present on the Al surface in the classical sessile drop tests. Starting from 1000 °C, liquid Al either filled the inter-grain pores or penetrated along the grain boundaries of the TiB2 substrate but there was no reaction observed in the Al/TiB2 system. The interfacial interactions between Ti-Al melts and TiB2 ceramic were studied by the classical sessile drop technique due to the absence of appropriate crucible for liquid Ti and Ti-containing melts. Pure Ti on TiB2 exhibited an incipient melting at about 120 °C below its melting point in view of the shape and structure of the solidified Ti/TiB2 couple. It was caused by the solid state diffusion of boron from the substrate into the Ti sample and a composition shift from pure Ti to a Ti-B alloy in the near-substrate region. In comparison to pure Ti, the role of Al in the penetration of Ti-Al melts penetration along the grain boundaries in the ceramic seemed to be more important than that of temperature in this study. The wetting and interfacial interactions between Ni-Al molten alloys and TiB2 were investigated using the dispensed drop technique. Liquid Ni-Al alloys showed a strong dependence of the wetting behavior on the TiB2 substrates, both on the alloy composition and testing conditions. It changed from a dissolutive, reactive wetting on the Ni-rich side to a non-reactive wetting on the Al-rich side. The results suggest that Ni content in Ni-Al alloys plays a major role in the changes of substrate dissolution and geometrical configuration at the metal/ceramic interface. To understand the effect of the Ni content on TiB2 dissolution, the melting and wetting of Ni83B17 and Ni50B50 alloys on TiB2 ceramic were investigated using the classical sessile drop technique in view of possible joining of TiB2 ceramics. Based on the wetting tests, TiB2 ceramics have been joined using Ni50B50 melt-spun ribbon as an interlayer. The results obtained in this work provide a better understanding of the interaction mechanisms in between liquid Al, Ti-Al, Ni-Al and Ni-B alloys and TiB2 ceramic and make basis for development of guidelines for the preparation of metal matrix composites and/or ceramic matrix composites and joining of TiB2 ceramic parts for high-temperature structural applications.

<div> <p>TiB₂particulate reinforced aluminum matrix composites (TiB₂/Al-MMCs) have received extensive attention due to a great potential in a wide variety of applications. Nano-TiB₂/Al-MMCs have also received attention from scholars with the development of nanotechnology in recent years. However, obstacles like agglomeration of nanoparticles in the matrix, and the difficulty of preparation of nanoparticulate reinforced metal matrix composites (PRMMNCs) still need to be resolved. This study summarizes the research progress of Al-matrix composites (Al-MMCs) in recent years and exemplifies the common preparation methods. Experiments were designed to study the common problems in the preparation of composite materials.</p> <p> </p> <p>Two experiments were designed and completed in this study. First, TiB₂/Al-4.5Cu composites were synthesized through a mixed salt reaction method. The distribution of reinforcing particle in the aluminum matrix was observed. The predictive model of particle behavior in Al-4.5wt. %Cu matrix based on thermodynamic laws was re-examined. The experiment results are inconsistent with the prediction from a classic prediction model. Regardless of the rate of solidification and critical velocity (V_C), the most of the particles are rejected by advancing solid-liquid interface. Through review of classic particle pushing theory, this study attempts to derive a new boundary condition used to predict the behavior of reinforcing particles in a metal matrix during solidification based on the diffusion convection equations. </p> <p> </p> <p>Second, nano-TiB₂/Al composites with a variety of volume fractions were synthesized by ultrasound assistance in a stirring method. The research has focused on optimization and improvement of preparation methods. High-energy ball milling (HEBM) and high-intensity ultrasound (HIU) were introduced into the fabrication process. Furthermore, a forging post-treatment process is used to process as-cast samples prepared by the experiment, so that the reinforcing particles in the composite material can be redistributed. The experiment results show that HEBM facilitates the mixing of nano-TiB₂ particles with salts. HIU helps distribute particles evenly throughout the matrix. The Vickers hardness and tensile strength of the composites were tested. The results indicated that the forging treatment has great influence on the mechanical properties of composite materials.</p> </div> <b><br></b>

Al alloys have been extensively used for producing structural and functional products. It is well known that a grain-refined as cast microstructure generally facilitates high quality finished products in the downstream processing stages. Chemical inoculation by Al-Ti-B grain refiners was widely used in the industry to refine Al alloys. However, the corresponding grain refining mechanism is still under dispute. In this study, the influence of solute elements on the grain refining of Al alloys in the presence of potent TiB2 inoculants was investigated in order to understand the grain refining mechanism of Al alloys by Al-Ti-B grain refiners. Firstly, an effective Al-Ti-B grain refiner, which contains potent TiB2 particles and negligible impurities (particularly Ti), was obtained by a settling experiment. The effectiveness of the grain refiner was verified by its inoculation in commercial purity Al (CP-Al) due to the significantly refined microstructure. Based on its compositional analysis, the grain refiner was found to contain little free Ti (only 600ppm) and other impurities (100ppm Fe, < 100ppm Si), and this refiner was referred to as Al-1.54TiB2. Secondly, with fixed addition of the Al-1.54TiB2 grain refiner, the effect of individual solute elements including Ti, Si, Fe, Sn, Zn, Cu, Mg, Mn, Cr and Zr, and the combined effects of Fe-Si, Fe-Cu and Fe-Ti on the grain structures of high purity Al (HP-Al) were investigated. It was found that, there is no direct correlation between the growth restriction parameter Q and the grain size when a fixed addition of Al-1.54TiB2 is present. The effects of solute elements on the grain structures of a final casting should consider both solidification kinetics and thermodynamic conditions. A theoretical columnar-equiaxed transition (CET) prediction model based on the analysis of a newly-established growth restriction coefficient β, which has considerations on both the thermodynamic and kinetic conditions, is presented for grain structure prediction. Finally, a poisoning (i.e., grain size coarsening) mechanism by Zr or Si addition in Al alloys containing TiB2 particles was studied. It was found that, for Al-Zr samples, a Zr-rich atomic mono-layer exists at the TiB2/Al interface to replace the originally present Al3Ti atomic monolayer. This was suggested to be the reason for Zr poisoning. For Al-Si samples, the Al3Ti atomic monolayer, which originally existed at the TiB2/Al interface, was found to have apparently disappeared, and this was likely to be the reason for Si poisoning.

Untersuchungen der Hochtemperaturbenetzung und Grenzfächeninteraktionen in Flüssigmetall/Übergangsmetall-Diborid-Systemen werden durch die technologische Nachfrage nach qualitative hochwertigen Metall-Matrix-Kompositen und verläßlichen Verbindungen von Ultrahochtemperaturkeramiken für aggressive chemische und/oder thermische Umgebungen angetrieben. Die physikalischen und chemischen Charakteristika der Metall/Keramik-Grenzflächen (z.B. die Benetzungskinetik, Grenzflächenreaktionen und die Phasenbildung) sind unerläßlich um die fundamentalen Mechanismen, die kontrollierenden technologischen Parameter, sowie die definierenden Eigenschaften und die Qualität des Endprodukts zu verstehen. Die Methode des liegenden Tropfens (engl. sessile drop method) ist die am häufigsten verwendete Verfahren für die quantitative Charakterisierung der Benetzungseigenschaften und für die direkte Untersuchung von Grenzflächeninteraktionen zwischen Flüssigmetall und festen Substraten unter Zuhilfenahme von Mikroskopie. Der Fokus dieser Arbeit liegt auf der Hochtemperaturbenetzung und den Grenzflächeninteraktionen von geschmolzenen reinem Al und Ti-Al, Ni-Al und Ni-B Schmelzen mit der TiB2 Ultrahochtemperaturkeramik. Die über die Methode des liegenden Tropfens hergestellten Metall/Keramik Verbunde werden hauptsächlich mittels Rasterelektronenmikroskopie gekoppelt mit energiedispersiver Röntgenspektroskopie sowie Röntgenbeugung untersucht. Die temperatur- und zeitabhängige Benetzung von flüssigem Al auf der TiB2 Keramik wurde mittels der klassischen Technik des liegenden Tropfens und der sogenannten dispensed drop technique (engl.) über einen weiten Temperaturbereich untersucht. Die Ergebnisse zeigen, dass mit ansteigender Temperatur die Benetzung bedeutend schneller abläuft. Die beiden Methoden liefern einen Unterschied in der Benetzungstemperatur von etwa 300°C aufgrund der nativen Oxidschicht auf der Al-Oberfläche bei dem klassischen Sessile-drop Versuch. Beginnend bei 1000°C füllt das flüssige Al entweder die intergranularen Poren auf oder dringt entlang der Korngrenzen in das TiB2 Substrat ein. Es wurde keine Reaktion im Al/TiB2 System beobachtet. Die Grenzflächeninteraktionen zwischen Ti-Al Schmelzen und der TiB2 Keramik wurden mit der klassischen Technik des liegenden Tropfens untersucht, da ein passender Tiegel für flüssiges Ti und Ti-haltige Schmelzen nicht vorhanden war. Für reines Ti auf TiB2 setzt das Schmelzen bei etwa 120 °C unter seinem Schmelzpunkt ein, wie aus Untersuchungen der Form und Struktur der erstarrten Ti/TiB2 Proben hervorgeht. Dies wird durch Festkörperdiffusion von B aus dem Substrat in die Ti Probe hinein und einer Verschiebung der Zusammensetzung von reinem Ti zu einer Ti-B Legierung in der substratnahen Region verursacht. Die Rolle von Al scheint für das Eindringen von Ti-Al Schmelzen entlang von Krongrenzen in das Keramiksubstrat von größerer Bedeutung zu sein als die Rolle der Temperatur. Die Benetzung und Grenzflächeninteraktionen zwischen Ni-Al Schmelzen und TiB2 wurden mit dem dispensed drop Verfahren untersucht. Flüssige Ni-Al Legierungen zeigen deutlich unterschiedliche Benetzungsverhalten auf dem TiB2 Substrat in Abhängigkeit von Legierungszusammensetzung und Testbedingungen. Das Verhalten von Ni-Al Schmelzen auf TiB2 Keramik verändert sich von einem auflösenden, reaktiven Benetzen (engl. dissolutive, reactive wetting) auf der Ni-reichen Seite zu einem nicht-reaktiven Benetzen auf der Al-reichen Seite. Die Ergebnisse deuten darauf hin, dass der Ni-Gehalt in Ni-Al Legierungen eine Hauptursache für die Veränderungen der Substratauflösung und der geometrischen Konfiguration an der Metall/Keramik Grenzfläche ist. Um den Einfluss des Ni-Gehalts auf die Auflösung von TiB2 zu verstehen wurde das Schmelzen und Benetzen von Ni83B17 und Ni50B50 Legierungen auf der TiB2 Keramik mittels der klassischen Technik des liegenden Tropfens im Hinblick auf mögliches fügen von TiB2 Keramiken untersucht. Basierend auf den Benetzungstest wurden Zwischenschichten der Ni50B50 Legierung verwendet um TiB2 Keramiken zu Verbinden. In dieser Arbeit wurde die Technik des liegenden Tropfens erfolgreich angewandt um die Hochtemperaturbenetzung und die Grenzflächeninteraktionen zwischen flüssigen Al, Ti-Al, Ni-Al und Ni-B Legierungen und keramischem TiB2 zu untersuchen. Die in dieser Arbeit erhaltenen Ergebnisse ermöglichen ein besseres Verständis der Interaktionsmechanismen zwischen flüssigen Al, Ti-Al, Ni-Al und Ni-B Legierungen und TiB2 keramik in diesen Systemen ermöglichen und Erstellung von Richtlinien für die Herstellung von Metall-Matrix-Verbunden und/oder Keramik-Matrix-Verbunden sowie für die Verbindung von keramischen TiB2 Teilen für strukturelle Hochtemperaturanwendungen dar. / Investigations of high-temperature wetting and interfacial interactions in liquid metal/transition-metal diboride systems are driven by technological demand in obtaining high-quality metal matrix composites and reliable joining of ultrahigh-temperature ceramics for aggressive chemical and/or thermal environments. The physical and chemical characteristics of metal/ceramic interface (e.g. wetting kinetics, interfacial reactions and phase formation) are indispensable for understanding the fundamental mechanisms, controlling technological parameters, and defining the properties and quality of final products. The sessile drop method is the most commonly used for quantitative characterization of the wetting properties and direct investigations of the interfacial interactions between a liquid metal and a solid substrate with the help of microscopy. This thesis is focused on the high-temperature wetting and interfacial interactions of molten pure Al and Ti-Al, Ni-Al and Ni-B alloys with TiB2 ultra-high-temperature ceramic. The metal/ceramic couples after the sessile drop tests are mainly characterized using scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and X-ray diffraction. The temperature- and time-dependent wetting between the liquid Al and TiB2 ceramic over a wide temperature range was investigated using the classical sessile drop and dispensed drop techniques. The results showed that the wetting was significantly accelerated with increasing temperature. A difference of the wetting temperature by these two techniques was about 300 °C, due to the native oxide film present on the Al surface in the classical sessile drop tests. Starting from 1000 °C, liquid Al either filled the inter-grain pores or penetrated along the grain boundaries of the TiB2 substrate but there was no reaction observed in the Al/TiB2 system. The interfacial interactions between Ti-Al melts and TiB2 ceramic were studied by the classical sessile drop technique due to the absence of appropriate crucible for liquid Ti and Ti-containing melts. Pure Ti on TiB2 exhibited an incipient melting at about 120 °C below its melting point in view of the shape and structure of the solidified Ti/TiB2 couple. It was caused by the solid state diffusion of boron from the substrate into the Ti sample and a composition shift from pure Ti to a Ti-B alloy in the near-substrate region. In comparison to pure Ti, the role of Al in the penetration of Ti-Al melts penetration along the grain boundaries in the ceramic seemed to be more important than that of temperature in this study. The wetting and interfacial interactions between Ni-Al molten alloys and TiB2 were investigated using the dispensed drop technique. Liquid Ni-Al alloys showed a strong dependence of the wetting behavior on the TiB2 substrates, both on the alloy composition and testing conditions. It changed from a dissolutive, reactive wetting on the Ni-rich side to a non-reactive wetting on the Al-rich side. The results suggest that Ni content in Ni-Al alloys plays a major role in the changes of substrate dissolution and geometrical configuration at the metal/ceramic interface. To understand the effect of the Ni content on TiB2 dissolution, the melting and wetting of Ni83B17 and Ni50B50 alloys on TiB2 ceramic were investigated using the classical sessile drop technique in view of possible joining of TiB2 ceramics. Based on the wetting tests, TiB2 ceramics have been joined using Ni50B50 melt-spun ribbon as an interlayer. The results obtained in this work provide a better understanding of the interaction mechanisms in between liquid Al, Ti-Al, Ni-Al and Ni-B alloys and TiB2 ceramic and make basis for development of guidelines for the preparation of metal matrix composites and/or ceramic matrix composites and joining of TiB2 ceramic parts for high-temperature structural applications.

Made available in DSpace on 2017-07-21T20:42:42Z (GMT). No. of bitstreams: 1 Cristiano da Silva.pdf: 5271302 bytes, checksum: 25a5bdf4a3671c9a497d93fa788662df (MD5) Previous issue date: 2014-01-30 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work aims at verifying the influence of processing by high energy ball milling of titanium diboride (TiB2), to increase the effect of grain refining of high-purity aluminum. Various mills were carried out by varying the ratio of the initial TiB2 and aluminum charges. After obtaining the milling products, they were compressed in a cylindrical array as a uniaxial compressive stress of 100MPa, some were later sintered at 600°C for 30 minutes. The tablets were introduced in the metal bath of aluminum and castings at 800°C in thermal analysis cups. In metal baths, experiments with and without the presence of titanium as a solute, in addition to the variation of the content of TiB2 (0.15 and 0.30 wt%) can be observed. The results indicate a significant reduction in grain size, especially in the samples were nucleated with pellets which were sintered before being added to the bath. / Este trabalho, tem por objetivo, verificar a influência do processamento por moagem de alta energia em moinho de bolas, do diboreto de titânio (TiB2), visando aumentar o efeito de refino de grãos do alumínio de alta pureza. Várias moagens foram realizadas, variando-se a razão de alumínio e TiB2 das cargas iniciais. Após a obtenção dos produtos de moagem, os mesmos foram compactados em uma matriz cilíndrica uniaxial como uma tensão de compressão de 100MPa, algumas posteriormente foram sinterizadas à 600°C por 30 minutos. As pastilhas foram introduzidas no banho metálico de alumínio e vazadas à 800°C em copos para análise térmica. Nos banhos metálicos, experimentos sem e com a presença de titânio como soluto, além da variação do teor de TiB2 (0,15 e 0,30%p) também podem ser observados. Os resultados indicam uma redução significativa no tamanho de grão, especialmente nas amostras que foram nucleadas por pastilhas que foram sinterizadas antes de serem adicionadas ao banho.

Les effets des nanoparticules (cisaillables et non-cisaillables) sur l’évolution microstructurale et l'évolution de la texture cristallographique des deux alliages à base d’aluminium après laminage à froid ont été étudiés dans cette thèse. Un alliage Al-Sc contenant des nanoparticules cisaillables de Al3Sc et un composite Al-TiB2 contenant des nanoparticules non-cisaillables TiB2 sont étudiés. La microscopie électronique en transmission (MET), la diffraction d'électrons rétrodiffusés (EBSD) et l’analyse de la texture par la diffraction de neutrons sont utilisées pour caractériser le développement de la microstructure et la texture cristallographique lors du laminage à froid des 2 alliages.La restauration dynamique pendant laminage a été inhibée dans la matrice contenant des Al3Sc nanoparticules cisaillables et TiB2 non-cisaillables. Par conséquent, peu de cellules de dislocation ont été générées dans la matrice, ce qui limite la diminution de la taille des grains.Le développement de la texture de laminage est retardé par les nanoparticules cisaillables ou les particules non-cisaillables. Des bandes d’orientation de cube résiduelles se trouvent dans les matériaux contenant des particules cisaillables dans une matrice très déformée en raison de la limitation du glissement croisé. La réduction de la proption volumique des composantes de texture du laminage se produit dans les matériaux contenant de grandes particules non-cisaillables (de l’ordre d’un micromètre) en raison de la recristallisation dans les PDZs (Particle Deformation Zones), ce qui contribue également à la diminution des grains.De plus, le cisaillement de nanoparticules favorise le glissades en plan, ce qui conduit à une forte localisation des déformations et à l'apparition de bandes de cisaillement. La génération de bandes de cisaillement dépend de l'orientation et est dû au changement soudain des chemins de déformation et et de l'inhibition de la récupération dynamique. Les nanoparticules non cisaillables ont probablement pivoté avec la matrice environnante, ce qui pourrait constituer un nouveau mécanisme de déformation. / The effects of shearable and non-shearable nanoparticles on the microstructure and crystallographic texture evolution of two Al-based alloys after cold rolling have been studied in this thesis. An Al-Sc alloy containing shearable Al3Sc nanoprecipitates and Al-TiB2 composite containing non-shearable TiB2 nanoparticles are investigated, respectively. Transmission electron microscopy (TEM), electron backscatter diffraction (EBSD) and neutron diffraction texture analysis are employed to characterize the microstructure and texture development of the two alloys during cold rolling.Dynamic recovery has been inhibited in the matrix containing both shearable (Al3Sc) and non-shearable (TiB2) nanoparticles due to the pinning effects. Hence, few dislocation cells are generated in these matrices that impedes the grain refinement.The development of rolling texture is retarded by either shearable nanoprecipitates or non-shearbale particles. Obvious residual Cube orientation bands are found in materials containing shearable precipitates at the deformed states due to the limitation of cross-slip. Volume reduction of rolling texture components occurs in materials containing large non-shearable particles (about 1 micrometer) due to the recrystallization at PDZs (Particle Deformation Zones), which contributes to grain refinement.In addition, the shearing of nanoprecipitates promotes planar slip leading to strong strain localization and the occurrence of shearbands. The generation of shearbands is orientation dependent and results from the sudden change of deformation paths and inhibition of dynamic recovery. The non-shearable nanoparticles probably have rotated together with the surrounding matrix, which could be a new deformation mechanism.

<p>The aim of this thesis was to develop wear resistant physical vapour deposited coatings of TiB₂ as well as multilayers of Cr/CrN. The correlation between deposition parameters and fundamental coating properties such as microstructure, composition, residual stress and hardness has been investigated. Finally, the influence of these properties on the coating behaviour in tribological applications has been evaluated.</p><p>It is shown that the use of electron bombardment of the growing coating during d.c. magnetron sputtering is beneficial for the growth of superhard TiB₂ coatings. Furthermore, electron bombardment results in TiB₂ coatings with significantly lower residual stresses than coatings deposited using ion bombardment. The low stresses in these coatings open up the possibility to deposit thicker PVD coatings, as confirmed in this thesis.</p><p>In addition, the use of TiB₂ coatings in tribological contacts against aluminium proved to be superior to many other commercial coatings used today, with respect to wear resistance, anti galling properties and a low friction.</p><p>Finally, a model is proposed which explains the observation that the abrasive wear resistance of multilayered Cr/CrN coatings can outperform that of the individual constituents. The model was found to satisfactory predict experimental data.</p>