Orientador: Pascoal José Giglio Pagliuso / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-09-02T11:57:27Z (GMT). No. of bitstreams: 1 Souza_JeanCarlo_M.pdf: 4438731 bytes, checksum: aaba7a375b2b45b638619e944111c41b (MD5) Previous issue date: 2017 / Resumo: A ideia de topologia na Física da Matéria da Condensada, apesar de ter surgido com o efeito Hall quântico inteiro, só voltou a ser explorada recentemente na busca de novas fases da matéria depois do surgimento dos Isolantes Topológicos (ITs) 2D. Após a previsão teórica, e a descoberta experimental, foi proposto que esta nova fase poderia ser generalizada para sistemas 3D, em que o volume do material seria isolante com estados metálicos de superfície que possuiriam canais de spin polarizados. Apesar de diversos experimentos e o surgimento de outras fases topológicas da matéria subsequentes, ainda há dúvidas sobre a natureza dos ITs 3D. Os efeitos topológicos mais claros ainda não foram observados de forma inequívoca e reprodutível experimentalmente e ainda seria de extrema valia encontrar técnicas experimentais que possam complementar os mais discutidos experimentos de ARPES. Nesta dissertação foram estudadas duas famílias distintas de materiais propostas como possíveis ITs 3D: os binários Bi2Se3 e Sb2Te3 e o half-Heusler YPdBi. Utilizando a técnica de auto-fluxo e a fusão estequiométrica, os sistemas foram sintetizados dopados com os terras-rara Gd3+, Nd3+ e Er3+ para realizar estudos de ressonância de spin eletrônico (RSE) e do papel dos efeitos de campo cristalino (CEF) - no caso do half-Heusler. Para o ternário YPdBi foram feitos dois estudos. Na família dos half-Heuslers, a ordem topológica surge da relação entre o acoplamento spin-órbita e a hibridização, que está ligada com a mudança do parâmetro de rede, então os efeitos de CEF poderiam estar refletindo a transição entre a trivialidade e a não-trivialidade. A partir das medidas de susceptibilidade magnética em função da temperatura das amostras dopadas com Nd3+ e Er3+ combinadas com os estudos de RSE, foi possível extrair os parâmetros de campo cristalino (CFP) de quarta e sexta ordem. Comparando esses dados com resultados anteriores para o material, supostamente, não-trivial YPtBi, observou-se uma mudança sistemática no sinal dos CFP. Resultados prévios para as amostras de YPtBi dopadas com Nd3+ mostram uma evolução não usual para uma forma de linha difusiva com a potência de micro-onda. Neste trabalho também foi realizado um estudo da forma de linha em função da potência. Apenas a ressonância do Nd3+ para os monocristais de 10% de Nd em YPdBi mostrou uma forma de linha difusiva que evolui com a potência da micro-onda. No caso dos binários Bi2Se3 e Sb2Te3, o objetivo era otimizar a rampa de tratamento térmico para obter monocristais melhores que poderiam permitir a observação de um espectro totalmente resolvido do Gd3+. Após mudanças no crescimento dos monocristais, o espectro totalmente resolvido foi obtido para as amostras de Bi2Se3. No caso do Sb2Te3 apenas uma linha central com a estrutura fina colapsada foi observada. Acompanhando o deslocamento g e a evolução da largura de linha dH da RSE do Gd3+ com a temperatura, o comportamento negativo do deslocamento g para toda a faixa de temperatura indica que elétrons do tipo p são os grandes responsáveis pela formação da superfície de Fermi residual destes sistemas. Um aumento no coeficiente angular de dH em função da temperatura, a taxa Korringa b, foi observado em baixas temperaturas, logo diferentes concentrações de Gd3+ foram utilizadas para estudar este comportamento. Novamente observou-se um comportamento anômalo em baixas temperaturas, o que poderia estar relacionado com a evolução dos CFP com a temperatura. Todos esses resultados foram discutidos levando-se em conta a possibilidade de existência de topologia não-trivial na estrutura eletrônica desses materiais, com foco particular na relação da interação spin-órbita e os efeitos de campo cristalino com a manifestação da topologia não trivial nesses sistemas / Abstract: The idea of topological systems in Condensed Matter Physics, although already explored in the Quantum Hall Effect, has recently become a topic of intense scientific investigation. In particular, great efforts have been dedicated to the search for new quantum phases since the proposal of the Topological Insulators (TIs) in 2D. After the theoretical prediction and the experimental discovery of the TIs in the 2D case, the existence of the Quantum Hall Spin Effect in 3D, 3D TIs, was proposed, where an insulator bulk and metallic surface states with spin polarized channels could be experimentally realized. Although many experiments have been performed, and some groups claimed the direct observation of such new topological phases, there is still a lot of controversy about the nature of the 3D TIs and about the actual microscopic origin of the metallic states on the surface of the studied materials. Other signatures of the topological phases have not been unambiguously and repeatedly measured yet and there is an obvious lack of a supplementary lab technique to be compared to the most used technique to probe these states, which is ARPES. In this work we have studied two different classes of 3D TIs: the binaries Bi2Se3 and Sb2Te3 and the half-Heusler YPdBi. We have been able to grow single crystals of these materials pure and rare-earth doped with Gd3+, Nd3+ and Er3+ using the self-flux technique and the stoichiometric melting. The aim was to use these crystals to study Electron Spin Resonance (ESR) as a potential probe to investigate the existence of the metallic surface states and to explore the possible of the crystalline electrical field (CEF) effects on the formation of the non-trivial electronic structure of these materials. Regarding the YPdBi, our ESR and magnetization studies have revealed that, in the half-Heusler family, the topological order emerges from the interplay between spin-orbit coupling and the hybridization, which is connected with the changes on the lattice parameter. Thus, the CEF effects could reflect the transition from trivial to nontrivial topology. From the magnetic susceptibility data as a function of temperature from the Nd3+ and Er3+ doped samples combined with the ESR studies, it was possible to extract the fourth and sixth order crystal field parameters (CFP). Comparing our data with the previous results from YPtBi, which is a putative non-trivial material, a systematic change in the sign of the CFP was observed. Previous results with the YPtBi Nd-doped samples show an unusual evolution of the Nd3+ ESR line to a diusive-like line shape as a function of the microwave power. In this work we have performed a similar study of the Nd3+ ESR line shape as a function of the microwave power. Only for the single crystal of 10% Nd in YPdBi resonance shows a diffusive-like line shape that evolves with the microwave power. In the case of the binaries Bi2Se3 e Sb2Te3, the aim of this work was to optimize the heat treatment used in previous works of our group to obtain better single crystals that could allow the observation of the full resolved spectra from Gd3+. After many changes in the single crystal growth method, we were able to observe fully resolved Gd3+ ESR spectra in the Bi2Se3 samples. Regarding the Sb2Te3 single crystals, only a single Gd3+ Dysonian ESR line was observed. Following the Gd3+ ESR dg and dH as a function of temperature, the observed negative behavior of dg, in the whole temperature range studied, indicates that p-type electrons are the main source for the formation of the small the Fermi surface of these materials. An increase of the angular coefficient of dH as a function of temperature, the Korringa rate b, at low temperatures was observed and different concentrations of Gd3+ were required to investigate this anomaly. Again this anomalous behavior at low temperatures was observed for the all Gd-doped samples, which could be related to an evolution of CFP with temperature. We discuss our results taking into account the existence of non-trivial topological states in our samples and the role of spin-orbit and CEF effects might have in the formation of such states / Mestrado / Física / Mestre em Física / 132653/2015-0 / CNPQ / CAPES / FAPESP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O efeito magnetocalórico, base da refrigeração magnética, é caracterizado por duas quantidades: a variação isotérmica da entropia (ΔST) e a variação adiabática da temperatura (ΔTad) as quais podem ser obtidas sob variações na intensidade de um campo magnético aplicado. Em sistemas que apresentam anisotropia magnética, pode‐se definir o efeito magnetocalórico anisotrópico, o qual, por definição, é calculado através da variação na direção de aplicação de um campo magnético cuja intensidade se mantém fixa. Nos materiais de nosso interesse, o efeito magnetocalórico é estudado teoricamente partindo de um hamiltoniano modelo que leva em conta a rede magnética (que pode ser composta por diversas sub-redes magnéticas acopladas), rede cristalina e a dinâmica dos elétrons de condução. No hamiltoniano magnético são consideradas as interações de troca, Zeeman e campo cristalino (esta ultima responsável pela anisotropia magnética). Recentemente, estudamos o efeito magnetocalórico convencional e o efeito magnetocalórico anisotrópico nos compostos mononitretos com terras-raras, a saber: Ho(y)Er(1-y)N para as concentrações y= 0,1,0.5 e 0.75. Comparações entre nossos resultados teóricos e os dados experimentais para o EMC foram bastante satisfatórias [3,9]. Além disso, diversas predições teóricas como a existência de uma fase ferrimagnética no sistema Ho(y)Er(1-y)N (para a concentração y=0.5) e reorientações de spin nas sub-redes do Ho e Er foram feitas [25]. / The magnetocaloric effect, magnetic refrigeration base, is characterized by two quantities: the isothermal entropy change (ΔST) and the adiabatic temperature change (ΔTad) which can be obtained through variations in the intensity of a magnetic field applied. In systems which present magnetic anisotropy, one can define anisotropic magnetocaloric effect, which, by definition, is calculated through the variation the direction of application of a magnetic field whose intensity remains fixed. In the materials of our interest, the magnetocaloric effect is studied theoretically starting from a model Hamiltonian which takes into account the magnetic lattice (that can be composed of several magnetic sublattices coupled), crystalline lattice and the dynamics of the conduction electrons. In the magnetic hamiltonian are considered the exchange interactions, Zeeman and crystalline electrical field (this latter responsible for the magnetic anisotropy). Recently, we studied the conventional magnetocaloric effect and anisotropic magnetocaloric effect in mononitrides compounds with rare earths, namely: o(Y)Er(1-Y)N for concentrations y= 0,1,0.5 e 0.75 . Comparisons between our theoretical results and experimental data for EMC were quite satisfactory [26].Furthermore, several theoretical predictions how to the existence of a phase ferrimagnetic in the system Ho(y)Er(1-y)N (for concentration ) and spin reorientations in the sublattices of Ho and Er were made [25].

Neste trabalho investigou-se a obtenção do composto TiFe a partir da moagem de alta energia de misturas de pós de TiH2 e Fe, seguida de aquecimento sob vácuo para a reação de síntese. No lugar do Ti, o TiH2 foi escolhido como precursor em razão de sua fragilidade, benéfica para a diminuição da aderência dos pós ao ferramental de moagem. Foram preparados dois lotes de misturas obedecendo-se a relação Ti:Fe de 50:50 e 56:44. Ambos foram processados em um moinho do tipo planetário por tempos que variaram de 5 até 40 horas, sob atmosfera de argônio de elevada pureza. Em todos os experimentos foram mantidos constantes a velocidade de rotação do prato do moinho, a quantidade de amostra, o diâmetro e o número de bolas. As amostras moídas foram caracterizadas por calorimetria exploratória diferencial (DSC), termogravimetria (TG), microscopia eletrônica de varredura (MEV), difração de raios X (DRX) e fluorescência de raios X por dispersão de energia (EDXRF). Apenas TiH2 e Fe foram observados nas amostras moídas, com um grau crescente de mistura em função do tempo de moagem. O composto TiFe nanoestruturado (12,5 a 21,4nm) foi obtido de forma majoritária em todas as amostras após a reação de síntese promovida pelo tratamento térmico a 600ºC (873K). As amostras reagidas foram caracterizadas por microscopia eletrônica de transmissão (MET) e DRX. Um equipamento do tipo Sievert, operando sob um fluxo constante (modo dinâmico), foi utilizado para levantar as curvas termodinâmicas de absorção e dessorção de hidrogênio. Todas as amostras absorveram hidrogênio à temperatura ambiente (~298K) sem a necessidade de ciclos térmicos de ativação. Os melhores resultados foram obtidos com as amostras moídas por 25 e 40 horas, de composição não estequiométrica 56:44. Tais amostras absorveram e dessorveram hidrogênio à temperatura ambiente, sob os platôs de aproximadamente 6,4 e 2,2bar (~0,6 e 0,2MPa), respectivamente. A capacidade máxima de armazenamento foi de 1,06% em massa de hidrogênio (H:M~0,546), sob pressão de até 11bar (1,1MPa), com reversão de até 1,085% em massa de hidrogênio (H:M~0,559), sob pressão de até 1bar (0,1MPa). Estas amostras também apresentaram maior cinética de absorção e dessorção de hidrogênio com fluxos de 1,23 (25h) e 2,86cm3/g.min. (40h). Tais resultados são atribuídos à variação composicional da fase TiFe e à maior quantidade de TiH2 livre. / In this work high-energy ball milling from TiH2 and Fe powder mixtures, followed by post-heating under vacuum, were performed for the reaction synthesis of TiFe compound. TiH2 was used instead of Ti due to its brittleness, preventing strong particles adhesion to the grinding balls and vial walls. Two mixtures batches were prepared following Ti:Fe ratios of 50:50 and 56:44. Both of them were dry-milled in a planetary mill for times ranging from 5 to 40 hours, under high purity argon atmosphere. The speed of main disk rotation, the amount of sample, number and diameter of the balls were kept constant in all experiments. As-milled samples were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TG), scanning electron microscopy (SEM), X-ray diffraction (XRD) and energy dispersive X-ray fluorescence (EDXRF). As-milled materials presented only Fe and TiH2 phases showing increased mixture degree with the milling time. After heat treatment at 600ºC (873K), nanostructured TiFe compound (12.5 to 21.4nm) was mostly formed in all samples. Reacted samples were characterized by transmission electron microscopy (TEM) and XRD. Hydrogen absorption and desorption thermodynamics curves were determined in a Sievert-type apparatus operating at constant flow (dynamic mode). All samples absorbed hydrogen at room temperature (~298K) requiring no thermal activation cycles. Best results were seen on samples milled at 25 and 40 hours, with non-stoichiometric composition 56:44. Those samples absorbed and desorbed hydrogen at plateaus of 6.4 and 2.2bar (~0.6 and 0.2MPa), respectively. Maximum hydrogen storage capacity was 1.06 wt% (H:M~0,546) at 11bar (1.1MPa), with reversion of 1.085 wt% (H:M~0,559) at 1bar (0.1MPa). Higher hydrogen absorption and desorption kinetics were observed in those samples, as well, with flows of 1.23 (25h) and 2.86cm3/g.min. (40h). Such results were assigned to the compositional variation of TiFe phase and to the largest amount of free TiH2.

O NbAl3 e algumas ligas intermetálicas do sistema Nb-Ni-AI foram sintetizadas por combustão a partir dos pós de seus elementos constituintes. O efeito de variáveis de processo, como o tamanho de partícula dos pós, a composição química, a pressão de compactação, o tratamento de desgaseificação e a taxa de aquecimento, foram investigados na síntese do NbAl3 na forma de pastilhas cilíndricas. A síntese de ligas do sistema Nb-Ni-AI foi realizada a partir de misturas com as composições Nb10Ni70AI, Nb20Ni65AI e Nb30Ni60AI. A microestrutura das amostras reagidas foi caracterizada por microscopia óptica, microscopia eletrônica de varredura, EDS e difração de raios-X (método de Rietveld). Foram obtidas pastilhas de NbAl3 com 98,5 % da densidade teórica, superior ao valor encontrado na literatura (95%), mediante o controle de variáveis de processo. Nas pastilhas contendo níquel, a combustão ocorreu nas pastilhas de todas as composições. Fases metaestáveis, presentes na microestrutura das pastilhas baitas de reação, foram transformadas após tratamento térmico, originando ligas trifásicas com diferentes concentrações de fases (NbAl3, NiAI e NbNiAI), conforme a composição inicial do compactado. Algumas propriedades mecânicas de amostras brutas de reação e tratadas termicamente foram determinadas pela técnica da impressão (microdureza e tenacidade). Os resultados obtidos são comparáveis aos da literatura, salvo algumas discrepâncias atribuídas a processos de fabricação distintos. As etapas de reação da síntese do NbAl3 e de ligas Nb-Ni-AI foram posteriormente investigadas mediante interrupção da reação durante sua propagação ao longo de barras paralelepipédicas compactadas. Verificou-se que a síntese do NbAl3 ocorre pela dissolução de nióbio no alumínio fundido, seguida da precipitação do NbAl3. Nas amostras contendo níquel, a síntese ocorre em dois estágios: no primeiro estágio formam-se o Ni2Al3 ou o NiAl3, em quantidades relativas dependentes da composição geral. As reações deste primeiro estágio podem disparar as reações do segundo estágio, referentes à síntese do NbAl3. / NbAl3 and Nb-Ni-AI intermetallic alloys have been obtained by pressureless combustion synthesis from elemental powders. The effects of process variables as powder particle size, composition, compaction pressure (green density), degassing treatment and heating rate on the combustion (thermal explosion mode) of NbAl3 cylindrical pellets were studied. Combustion synthesis of Nb-Ni-AI alloys was performed on powder mixtures with nominal compositions Nb10Ni70AI, Nb20Ni65AI and Nb30NI60AI. The microstructure of reacted samples was characterized by optical microscopy, scanning electron microscopy, EDS and X-ray diffraction (Rietveld method). It was shown that careful control of the processing conditions allowed near full (98,5%) dense pellets of NbAl3. In the nickel containing pellets, reaction occurred for all the compositions investigated. Metastable phases were seen to be present in the as reacted pellets, which were transformed after a heat treatment, producing a three phase alloy (NbAl3, NiAI and NbNiAI) with different phase concentrations, depending on the initial compact composition. Some mechanical properties, like microhardness and tenacity were measured by microidentation technique on the as reacted and heat-treated samples. The results are comparable with the literature, excepted for some discrepancies caused by different fabrication processes. The reaction sequence for both cases (NbAl3 and Nb-Ni-AI alloys) was further investigated by DSC analysis and also by interrupting the reaction during its propagation along compacted parallelopipedal bars. It was found that the NbAl3 synthesis occurs through niobium dissolution in molten aluminum and precipitation of NbAl3. In the nickel containing samples, synthesis occurs as two-stage reaction: Ni2Al3 or NiAl3 are formed in the first stage, with relative amounts depending on the general composition. This first stage reaction can trigger the second one, related to the formation of NbAl3.

No description available.

Detailed, accurate measurements of critical current density and resistivity to determine the upper critical field have been made on a technological NbsAl conductor in magnetic fields up to 15 T, temperatures from 4.2 K up to the critical temperature and in the strain range from -1.8% to 0.7%. The uncertainty in temperature above 4.2 K was equivalent to ± 100 mK with a stability during the measurements of < 5 mK up to a limiting current of 80 A and a typical noise level of 1 µ Vm(^-1).When B(_c2){T,ε) is defined at 5%pn, 50%pn or 95%/%pn, an empirical relation is found where and an approximate relation, holds. The Jε data were parameterised using F(_p) = J(_E)B = A(ε)[Bc(_2)](^n)b(^p)(1-b)(^9) where b = B/B(_c2)(T,ε). When B(_c2)(T,ε) is constrained to be the value at 50%pn or 95%pn, the scaling law for F(_p) breaks down such that p and q are strong functions of temperature and q is also a strong function of strain. However, when B(_c2)(T,ε) is defined at 5%pn, there is good scaling where p and q are constants independent of temperature and strain. F(_p) can also be approximated by a Kramer form where the Ginzburg-Landau constant is γ is the electronic density of states and is interpreted as the average B(_c2) for the bulk where percolative current flow occurs. The critical current density of Hot Isostatic Pressed (HIP'ed) and unHIP'ed Nb(_3)Sn Modified Jelly Roll wires has also been measured at 4.2 K. The critical current and upper critical field were decreased for the HIP'ed sample. The reduced upper critical field of the HIP'ed wire was found to be less sensitive to strain than the unHIP'ed wire. The exponent of B(_c2) in the flux pinning scaling law increased from 0.86 to 2.14 as a result of the HIP processing.

Mo-Si-B alloys are a leading candidate for the next generation of jet turbine engine blades and have the potential to raise operating temperatures by 300-400°C. The alloys of interest are a three-phase mixture of the molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si (A15) and Mo5SiB2 (T2). A novel powder metallurgical method was developed which uses the reaction of molybdenum, silicon nitride (Si3N4) and boron nitride (BN) powders to synthesize a fine dispersion of intermetallics in a Moss matrix. The covalent nitrides are stable in oxidizing environments up to 1000ºC, allowing for fine particle processing. The process developed uses standard powder processing techniques to create Mo-Si-B alloys in a less complex and expensive manner than previously demonstrated. This powder metallurgy approach yields a fine dispersion of intermetallics in the Moss matrix with average grain sizes of 2-4μm. Densities up to 95% of theoretical were attained from pressureless sintering at 1600°C and full theoretical density was achieved by hot-isostatic pressing (HIP). Sintering and HIPing at 1300°C reduced the grain sizes of all three phases by over a factor of two. Microstructure examination by electron back-scatter diffraction imaging was used to precisely define the location of the phases and to measure the volume fractions and grain size distributions. Microstructural quantification techniques including two-point correlation functions were used to quantify microstructural features and correlate the BN reactant powder size and morphology to the distribution of the intermetallic phases. High-temperature tensile tests were conducted and yield strengths of 580MPa at 1100°C and 480MPa at 1200°C were measured for the Mo-2Si-1Bwt.% alloy. The yield strength of the Mo-3Si-1Bwt.% alloy was 680MPa at 1100°C and 420MPa at 1300°C. A review of the pertinent literature reveals that these are among the highest yield strengths measured for these compositions. The oxidation resistance in air at 1000 and 1100°C was examined. The protective borosilicate surface layer formed quickly due to the close spacing of intermetallic particles and pre-oxidation treatment was developed to further limit the transient oxidation behavior. An oxidation model was developed which factors in the different stages of oxidation to predict compositions that minimize oxidation.

Thèse (D.Eng.) -- Université du Québec à Chicoutimi, 2003. / Bibliogr.: f. [325]-340. Document électronique également accessible en format PDF. CaQCU

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