Thesis (M.Eng.)--University of Wollongong, 2004. / Typescript. Includes bibliographical references: leaf 104-108.

Orientador: Carlos Roberto Grandini / Banca: Paulo Noronha Lisboa Filho / Banca: Durval Rodrigues Júnior / Resumo: 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. / Abstract: 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 / Mestre

Orientador: Paulo Noronha Lisboa Filho / Banca: Carlos Roberto Grandini / Banca: Rubens de Andrade Júnior / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: O presente trabalho teve como objetivo estudar as propriedades magnéticas e de transporte elétrico de filmes finos de MG"BIND.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. / Abstract: In this work it was studied magnetic and electrical transport properties of MG"B 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. / Mestre

The stoichiometric Self-propagating High-temperature Synthesis (SHS) thermite reaction involving magnesium oxide (MgO), titanium dioxide (TiO₂), and boron oxide (B₂O₃) forms titanium diboride (TiB₂) and MgO as final products. Selective acid leaching is used to remove the MgO leaving high purity TiB₂ powder. The SHS method to produce TiB₂ is attractive because of the relatively low temperature required to initiate the reaction, fast reaction time, and product purity. This study investigates the acid leaching of SHS produced MgO/TiB2 and a stoichiometric mixture of commercial MgO and TiB₂ powders. Leaching was conducted at 90° C, 60° C, and 30° C at pH levels of 4.0, 2.5, and 1.0 by introduction of concentrated aliquots of HNO₃. This method maintains a minimum pH target throughout the leaching process, thereby sustaining a dynamic concentration to remove the oxide. The optimal leaching conditions were determined to be at 90° C at a minimum pH target of 2.5 for the SHS produced product. At these conditions, conversion percentages of 83%-84% of MgO were measured with only trace amounts of TiB2 measured in the solution (less than 100 ppm). Conversion percentages for each leaching condition and dissolution mass of solid MgO and TiB₂ at each pH are also reported. Results from powder XRD confirm the removal of MgO and minimal dissolution of TiB₂, and indicate the formation of unidentified compounds. Inductively coupled plasma mass spectrometry (ICP) was used to analyze the ionic composition and extent of leaching. Scanning electron microscopy (SEM) was used to observe the particle morphology of the leached powders. / Master of Science

Reaction synthesis is a processing technique where the thermal activation energy needed to form a compound is provided by the exothermic heat of formation of the thermodynamically stable product. This type of synthesis has been used to form a variety of ceramics, intermetallics, and in-situ composites. In this work, the effects of changing the stoichiometry of the titanium aluminide matrix, and the effects of extrinsic reaction variables on the behavior of the reaction were studied and compared to theoretical predictions. It was shown that changing the stoichiometry of the titanium aluminide did have an effect on the measured heat of reaction; however this did not match the prediction. Changing the extrinsic variables of titanium and aluminum particle sizes also showed a significant effect on the behavior of the reaction. / Master of Science

The aim of this study was to understand the processing – structure – property relationships in spark plasma sintered (SPS) boron carbide (B4C) and B4C-titanium diboride (TiB2) ceramic composites. SPS allowed for consolidation of both B4C and B4C-TiB2 composites without sintering additives, residual phases, e.g., graphite, and excessive grain growth due to long sintering times. A selection of composite compositions in 20% TiB2 feedstock powder increments from 0% to 100%, was sintered at 1900°C for 25 minutes hold time. A homogeneous B4C-TiB2 composite microstructure was determined with excellent distribution of TiB2 phase, while achieving ~99.5% theoretical density. An optimum B4C-23 vol.% TiB2 composite composition with low density of ~3.0 g/cm3 was determined that exhibited ~30-35% increase in hardness, fracture toughness, and flexural bend strength compared to commercial armor-grade B4C. This is a result of a) no residual graphitic carbon in the composites, b) interfacial microcrack toughening due to thermal expansion coefficient differences placing the B4C matrix in compression and TiB2 phase in tension, and c) TiB2 phase aids in crack deflection thereby increasing the amount of intergranular fracture. Collectively, the addition of TiB2 serves as a strengthening and toughening agent, and SPS shows promise for the manufacture of hybrid ceramic composites.

[pt] O presente trabalho teve como objetivo central o estudo das modificações nas propriedades estruturais, mecânicas e tribológicas causadas pela incorporação de nitrogênio em filmes de diborato de titânio (TiB2) crescidos pela técnica de erosão catódica assistida por um campo magnético. Os revestimentos de Ti-B-N com diferentes conteúdos de nitrogênio foram depositados em substratos de silício cristalino (100) a partir da erosão de um alvo de diborato de titânio mediante o uso da técnica de erosão catódica em uma atmosfera de argônio e nitrogênio e com tensões de polarização variando entre +100V e - 100V. Os efeitos do conteúdo de nitrogênio e a influência da tensão de polarização na estrutura e no comportamento tribológico foram investigados com o uso da técnica nuclear de retroespalhamento Rutherford (RBS), espectroscopia de fotoelétrons induzida por raios-x (XPS), difração por raios-x (XRD), perfilometria (medidas de tensão interna), microscopia de força atômica (AFM) e de ângulo de contato. Os resultados do presente trabalho mostraram que a incorporação de nitrogênio produz filmes com tensões internas cada vez mais compressivas. No entanto a mudança da tensão de autopolarização a valores positivos provocou uma relaxação na tensão interna. Nesses casos, foi observada uma melhor adesão dos filmes aos substratos de silício. Os resultados de XPS mostraram que as fases, TiB2, BN e TiN, estão presentes nos filmes de Ti-B-N e a caracterização por XRD determinou a estrutura nanocristalina desses revestimentos. Medidas de AFM indicaram valores de rugosidade superficial entre 1 e 2nm. / [en] The main purpose of the present work was the study of the effects on the structural, mechanical and tribological properties of the incorporation of nitrogen in titanium diboride films (TiB2) grown by reactive dc magnetron sputtering. Ti-BN coatings with different N contents were deposited on Si (100) substrates from a TiB2 target. The sputtering was carried out in an Ar-N2 gas mixture with a substrate bias voltage in the range between +100V e -100V. The effects of the nitrogen content and the influence of substrate bias voltage on the coatings properties were studied by Rutherford Backscattering Spectrometry (RBS), XRay photoelectron spectroscopy (XPS), X-Ray diffraction (XRD), profilometry (internal stress measurements), atomic force microscopy (AFM) and contact angle measurements. The results of the present work show that nitrogen incorporation produces films with higher compressive internal stress. However, a positive substrate bias reduces the compressive stress, thus resulting in a better adhesion to the substrate. The XPS results showed that the TiB2, TiN and BN phases are present in the Ti-B-N films. Characterization by XRD determined the nanocrystalline structure of Ti-B-N coatings. Measurements by AFM revealed low surface roughness values.

A descoberta da supercondutividade no diboreto de magnésio (MgB2) em 2001 com temperatura crítica (Tc) de 39 K e campo magnético crítico superior (Hc2) (H?c2 (0)) _ 40 (T), causou uma busca frenética por materiais leves com estruturas cristalinas semelhantes e constituídos por elementos simples, e com potencial para substituir os já estabelecidos Nb-Ti e Nb3Sn na fabricação de fios e fitas supercondutoras. Entretanto, apesar de apresentar alta Tc os valores de Hc2, para o MgB2, decaem rapidamente quando submetidos a um campo magnético externo, principalmente devido ao fraco aprisionamento das linhas de fluxo magnético no material. Além disso, o processo de deformação plástica do conjunto que contém o pó granular, constituído pelos metais utilizados como barreira de difusão e como estabilizador térmico e elétrico, é desafiador, pois há dificuldades devido ao endurecimento dos metais por trabalho a frio e à acomodação do pó supercondutor. O objetivo deste trabalho é desenvolver um processo para a fabricação de fios multifilamentares de MgB2, dopado com carbono sob a forma de grafite e com a adição de diboretos com estrutura cristalina semelhante à do MgB2, além da otimização dos processos de deformação mecânica, dos tratamentos térmicos intermediários e a caracterização das propriedades cristalográficas, microestruturais e supercondutoras do fio. A metodologia utilizada para a produção do fio é a Powder-In-Tube (PIT) ex-situ com: moagem do pó realizado em moinho de alta energia, dopagem química com grafite, adição de diboreto de vanádio (VB2), inclusão de magnésio em excesso e uso de ácido esteárico (C18H36O2) como agente controlador do processo. A deformação mecânica foi feita por meio de forjamento rotativo (Rotary Swage - RS). Os resultados finais sugerem que a rota utilizada para o processo de fabricação do fio multifilamentar de MgB2 dopado com grafite e com introdução de VB2, deve ser alterada para utilizar MgB2 produzido em laboratório a partir do magnésio e de boro puros, com certificado de pureza, com o uso da metodologia in-situ, em glove-box com atmosfera controlada e com teor de oxigênio e de umidade monitorados. O processo descrito neste trabalho aperfeiçoa metodologias apresentadas na literatura e garante a integridade do fio durante todo o processo de fabricação. Além disto, sugere-se a utilização de um material de reforço externo, tais como: ferro, Glidcop (Cu-Al 15) ou aço ixox (SUS 316L) para que o fio tenha maior resistência mecânica à tração e menor custo. / The discovery of superconductivity in magnesium diboride (MgB2) in 2001 with critical temperatute (Tc) of 39 K and upper critical magnetic field (Hc2) (H?c 2 (0)) _ 40 (T), caused a frenetic search for lightweight materials with similar crystalline structures and constituded by simple elements, and with potential to replace the already traditional Nb-Ti and Nb3Sn in the manufacturing of superconducting wires and tapes. However, despite the MgB2 has high Tc, the Hc2 values decay rapidly when an external magnetic field is applied, mainly due to the poor pinning of the magnetic flux lines in the material. Furthermore, the plastic deformation process of the set containing the granular powder, constituded of metals used as diffusion barrier termal and electric stabilizer, is a challenge, because the hardening of the metals by cold working and the accommodation of the superconducting powder. The objective of this work is to develop a process for the manufacture of multifilamentary MgB2 wires, doped with carbon in the form of graphite and addition of diborides with crystalline structure similar to MgB2, as well as the optimization of the mechanical deformation processes, of the intermediate heat treatments and the characterization of the crystallographic, microstructural and superconducting properties of the wire. The methodology used for the production of the wire was the Powder-In-Tube (PIT) ex-situ with: milling of the powder in a high energy ball mill, chemical doping with graphite, addition of vanadium diboride (VB2), magnesium in excess and use of stearic acid (C18H36O2) as a process controlling agent. The mechanical deformation was done by means of rotary swaging. The final results suggest that the route used for the fabrication process of the graphite-doped MgB2 multifilamentary wire with introduction of VB2, should be changed to use MgB2 produced in laboratory from pure magnesium and boron, with a certificate of purity, using the in-situ methodology in a glove-box with controlled and monitored atmosphere with respect to the oxygen and humidity contents. The process described in this work improves methodologies shown in literature and guarantees the integrity of the wire during the entire fabrication process. In addition, it is suggested the use of an external reinforcing material, such as: iron, Glidcop (Cu-Al 15) or stainless steel (SUS 316L), so that the wire has a higher mechanical tensile strength and a lower cost.

Au Yeung Yue Fung. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2002. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Au Yeung Yue Fung. / Abstract --- p.i / 論文摘要 --- p.ii / Acknowledgements --- p.iii / Table of Contents --- p.iv / List of Figures --- p.vi / List of Tables --- p.viii / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Genesis --- p.1-1 / Chapter 1.2 --- Aims and Objectives --- p.1-2 / Chapter 1.3 --- Layout of thesis --- p.1-3 / References --- p.1-4 / Chapter Chapter 2 --- Literature review / Chapter 2.1 --- Introduction to superconductor --- p.2-1 / Chapter 2.2 --- MgB2 --- p.2-3 / Chapter 2.2.1 --- Significance of MgB2 --- p.2-3 / Chapter 2.2.2 --- Structure and properties of MgB2 --- p.2-4 / Chapter 2.2.3 --- Superconducting mechanism of MgB2 --- p.2-5 / Chapter 2.2.4 --- Physical properties of boron and boride --- p.2-7 / Chapter 2.2.5 --- Physical properties of magnesium --- p.2-7 / Chapter 2.2.6 --- Formation of MgB2 --- p.2-8 / Chapter 2.2.7 --- MgB2 thin films --- p.2-9 / Chapter 2.2.7.1 --- Substrate --- p.2-11 / Chapter 2.2.7.2 --- Substrate temperature --- p.2-12 / Chapter 2.3 --- Contradictions as revealed by existing literatures --- p.2-13 / References --- p.2-14 / Chapter Chapter 3 --- Preparation and characterization of bulk MgB2 / Chapter 3.1 --- Bulk MgB2 fabrication / Chapter 3.2 --- Measurement and analysis techniques of bulk MgB2 --- p.3-4 / Chapter 3.2.1 --- XRD --- p.3-4 / Chapter 3.2.2 --- Meissner effect measurement --- p.3-5 / Chapter 3.3 --- Sintering time of MgB2 --- p.3-6 / Chapter 3.4 --- Concentration of Mg in sintering MgB2 --- p.3-8 / Chapter 3.5 --- Sintering temperature of MgB2 --- p.3-11 / Chapter 3.6 --- Thermal stability of MgB2 --- p.3-13 / Chapter 3.7 --- MgB2 in water --- p.3-17 / References --- p.3-19 / Chapter Chapter 4 --- Preparation and characterization of MgB2thin films / Chapter 4.1 --- Thin film deposition --- p.4-1 / Chapter 4.1.1 --- Facing-target sputtering (FTS) --- p.4-2 / Chapter 4.1.2 --- Vacuum system --- p.4-4 / Chapter 4.1.3 --- Asymmetric bipolar pulsed DC power source --- p.4-6 / Chapter 4.2 --- Fabrication of MgB2 targets --- p.4-10 / Chapter 4.3 --- Substrates --- p.4-11 / Chapter 4.4 --- Deposition procedure --- p.4-12 / Chapter 4.5 --- Deposition condition --- p.4-13 / Chapter 4.5.1 --- Deposition power --- p.4-15 / Chapter 4.5.2 --- Deposition pressure --- p.4-13 / Chapter 4.5.3 --- Annealing temperature --- p.4-18 / Chapter 4.5.4 --- Substrate temperature --- p.4-21 / Chapter 4.5.5 --- Conclusion --- p.4-26 / References --- p.4-29 / Chapter Chapter 5 --- Failed attempts of MgB2 films fabrication by in situ method / Chapter 5.1 --- In-situ method --- p.5-1 / Chapter 5.2 --- Additional FTS guns with Mg target --- p.5-2 / Chapter 5.3 --- Diode sputtering --- p.5-4 / Chapter 5.4 --- Co-evaporating fabrication --- p.5-6 / Chapter Chapter 6 --- Conclusion --- p.6-1

A descoberta da supercondutividade no diboreto de magnésio (MgB2) em 2001 com temperatura crítica (Tc) de 39 K e campo magnético crítico superior (Hc2) (H?c2 (0)) _ 40 (T), causou uma busca frenética por materiais leves com estruturas cristalinas semelhantes e constituídos por elementos simples, e com potencial para substituir os já estabelecidos Nb-Ti e Nb3Sn na fabricação de fios e fitas supercondutoras. Entretanto, apesar de apresentar alta Tc os valores de Hc2, para o MgB2, decaem rapidamente quando submetidos a um campo magnético externo, principalmente devido ao fraco aprisionamento das linhas de fluxo magnético no material. Além disso, o processo de deformação plástica do conjunto que contém o pó granular, constituído pelos metais utilizados como barreira de difusão e como estabilizador térmico e elétrico, é desafiador, pois há dificuldades devido ao endurecimento dos metais por trabalho a frio e à acomodação do pó supercondutor. O objetivo deste trabalho é desenvolver um processo para a fabricação de fios multifilamentares de MgB2, dopado com carbono sob a forma de grafite e com a adição de diboretos com estrutura cristalina semelhante à do MgB2, além da otimização dos processos de deformação mecânica, dos tratamentos térmicos intermediários e a caracterização das propriedades cristalográficas, microestruturais e supercondutoras do fio. A metodologia utilizada para a produção do fio é a Powder-In-Tube (PIT) ex-situ com: moagem do pó realizado em moinho de alta energia, dopagem química com grafite, adição de diboreto de vanádio (VB2), inclusão de magnésio em excesso e uso de ácido esteárico (C18H36O2) como agente controlador do processo. A deformação mecânica foi feita por meio de forjamento rotativo (Rotary Swage - RS). Os resultados finais sugerem que a rota utilizada para o processo de fabricação do fio multifilamentar de MgB2 dopado com grafite e com introdução de VB2, deve ser alterada para utilizar MgB2 produzido em laboratório a partir do magnésio e de boro puros, com certificado de pureza, com o uso da metodologia in-situ, em glove-box com atmosfera controlada e com teor de oxigênio e de umidade monitorados. O processo descrito neste trabalho aperfeiçoa metodologias apresentadas na literatura e garante a integridade do fio durante todo o processo de fabricação. Além disto, sugere-se a utilização de um material de reforço externo, tais como: ferro, Glidcop (Cu-Al 15) ou aço ixox (SUS 316L) para que o fio tenha maior resistência mecânica à tração e menor custo. / The discovery of superconductivity in magnesium diboride (MgB2) in 2001 with critical temperatute (Tc) of 39 K and upper critical magnetic field (Hc2) (H?c 2 (0)) _ 40 (T), caused a frenetic search for lightweight materials with similar crystalline structures and constituded by simple elements, and with potential to replace the already traditional Nb-Ti and Nb3Sn in the manufacturing of superconducting wires and tapes. However, despite the MgB2 has high Tc, the Hc2 values decay rapidly when an external magnetic field is applied, mainly due to the poor pinning of the magnetic flux lines in the material. Furthermore, the plastic deformation process of the set containing the granular powder, constituded of metals used as diffusion barrier termal and electric stabilizer, is a challenge, because the hardening of the metals by cold working and the accommodation of the superconducting powder. The objective of this work is to develop a process for the manufacture of multifilamentary MgB2 wires, doped with carbon in the form of graphite and addition of diborides with crystalline structure similar to MgB2, as well as the optimization of the mechanical deformation processes, of the intermediate heat treatments and the characterization of the crystallographic, microstructural and superconducting properties of the wire. The methodology used for the production of the wire was the Powder-In-Tube (PIT) ex-situ with: milling of the powder in a high energy ball mill, chemical doping with graphite, addition of vanadium diboride (VB2), magnesium in excess and use of stearic acid (C18H36O2) as a process controlling agent. The mechanical deformation was done by means of rotary swaging. The final results suggest that the route used for the fabrication process of the graphite-doped MgB2 multifilamentary wire with introduction of VB2, should be changed to use MgB2 produced in laboratory from pure magnesium and boron, with a certificate of purity, using the in-situ methodology in a glove-box with controlled and monitored atmosphere with respect to the oxygen and humidity contents. The process described in this work improves methodologies shown in literature and guarantees the integrity of the wire during the entire fabrication process. In addition, it is suggested the use of an external reinforcing material, such as: iron, Glidcop (Cu-Al 15) or stainless steel (SUS 316L), so that the wire has a higher mechanical tensile strength and a lower cost.