Neste trabalho estudamos os aspectos teóricos dos efeitos magnetocalórico e barocalórico em sistemas físicos simples com dois e quatro níveis de energia. Para esta finalidade utilizamos um hamiltoniano que considera um sistema de momentos localizados interagindo entre si e com um campo magnético externo. No hamiltoniano também são incluídos a interação magnetoelástica, e um termo extra para simular anisotropia. O efeito de pressão externa é levado em consideração através da renormalização do parâmetro deinteração de troca. Fizemos um estudo sistemático das propriedades magnetocalóricas e barocalóricas para vários conjuntos de parâmetros do modelo. Os resultados obtidos mostram diversos tipos de comportamento dos potenciais magnetocalóricos, como o efeito mesa, o efeito inverso, o efeito gigante e uma estrutura com dois picos. / In this work we study the theoretical aspects of the magnetocaloric and barocaloric effect in simple physical systems with two and four energy levels. In order to do that, we used a Hamiltonian that consider local magnetic moments interacting among them and with an external magnetic field.We include in the Hamiltonian the magnetoelastic interaction, and an extra term to simulate anisotropy. We consider the external pressure effect using a renormalization of the interaction exchange parameter. We performed systematical study about the magnetocaloric and barocaloric properties for a lot of sets of model parameters. The results show different types of behavior of the magnetocaloric potentials, such as the table-like effect, the inverse effect, the giant effect and a structure with two peaks.

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].

Orientador: Flávio César Guimarães Gandra / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-08-30T17:33:36Z (GMT). No. of bitstreams: 1 Monteiro_JoseCarlosBotelho_D.pdf: 10216375 bytes, checksum: 06d25402d8c5828939f2e7fa0710efbe (MD5) Previous issue date: 2016 / Resumo: Esta tese tem como principal objetivo desenvolver, apresentar e justificar a utilização de uma metodologia experimental que permita avaliar o efeito magnetocalórico (EMC), em qualquer tipo de material, de modo que as medidas reflitam a resposta real que a amostra fornece ao ser submetida a ciclos de magnetização similares àqueles que ocorrem em sistemas de refrigeração magnética. Para tal, construímos sistemas de medidas que utilizam dispositivos Peltier como sensores de fluxo de calor, capazes de realizar medidas diretas da quantidade de calor que a amostra absorve ou libera em situações aonde há variação de temperatura, campo magnético ou do ângulo entre direção do cristal e o campo aplicado. Na primeira parte do trabalho, foram realizadas medidas no sistema com dispositivos Peltier desenvolvido para uso no equipamento comercial PPMS - Physical Property Measurement System (Sistema de medidas de propriedades físicas) da Quantum Design. Utilizamos os métodos indiretos de medida do EMC mais comuns na literatura (medidas via curvas de magnetização e calor específico) para comparação com as medidas diretas de fluxo de calor através de varredura de campo obtidas pelo nosso sistema. Esta análise foi feita inicialmente em duas amostras com transições magnéticas de primeira e segunda ordem, consideradas como amostras padrão na área do EMC: Gadolínio e a liga Gd5Ge2Si2. Discutimos as diferenças encontradas e definimos aquele que acreditamos ser o protocolo de medidas mais correto para a avaliação do EMC para fins práticos. A partir desta conclusão, analisamos três outras amostras que apresentam comportamentos não usuais e alto potencial magnetocalórico e discutimos as diferenças. Perdas do EMC por histerese foram obtidas experimentalmente. Na segunda parte, com o auxílio de um calorímetro com o elemento Peltier capaz de realizar um giro de até 80° sob campo constante de até 1,9 T, realizamos o estudo do efeito magnetocalórico anisotrópico (EMC-ani) em amostras monocristalinas da família RAl2, obtidas pelo processo de Czochralski. Primeiramente medidas de calor específico e do EMC convencional foram realizadas nos monocristais, através do protocolo definido como ideal na primeira parte do trabalho, utilizando o sistema Peltier do PPMS. A partir desses dados, fomos capazes de obter o EMC-ani, de modo indireto, pela subtração das curvas obtidas. Por fim utilizamos o sistema Peltier de giro para realizar medidas diretas do EMC-ani em monocristais de DyAl2. Os resultados das medidas indiretas e diretas foram comparados com cálculos obtidos através de um modelo autoconsistente / Abstract: This thesis aimed to develop, present and justify the use of a methodology that allows one to evaluate the magnetocaloric effect (MCE), for any kind of material, such that the results reflects the real behavior of the sample submitted to magnetization cycles similar to those of magnetic refrigeration systems. To do so, we built measurement systems that uses Peltier devices as heat flux sensors to determine the heat absorbed or released by the sample in situations where the temperature, magnetic field, or angle between a given crystal direction and field changes. In the first part of the work, we report measurements using a Peltier device system developed for use with the Quantum Design PPMS (Physical Property Measurement System). We evaluated the indirect MCE measurements by using the most common techniques found in literature (through magnetization or specific heat curves) and compared to the direct heat flux measurements obtained through field sweep scans with our system. This analysis was initially made with two samples that present a first and a second order magnetic transition, considered as standard samples at MCE research area: Gadolinium and the Gd5Ge2Si2 alloy. We discussed the differences found and defined the measurement protocol that we believe to be correct to the practical evaluation of the MCE. From this conclusion, we analyzed three other samples that present uncommon behavior and high magnetocaloric potential and discussed their differences. MCE hysteresis losses were experimentally obtained. In the second part, with the aid of a calorimeter built with Peltier devices capable of perform an 80° rotation under constant magnetic field up to 1,9 T, we made the study of the Anisotropic Magnetocaloric Effect (MCE-ani) in monocrystalline samples of the RAl2 family grown by the Czochralski method. First, we made specific heat and conventional MCE measurements with the ideal protocol that was defined in the first part of the work, using the PPMS Peltier system. From these data, we were able to calculate indirectly the MCE-ani by subtracting the acquired curves. Finally, we used the Peltier rotation system to perform direct measurements of the MCE-ani in DyAl2 single crystals. The results of the indirect and direct measurements were compared with calculations achieved using a self-consistent process / Doutorado / Física / Doutor em Ciências / 1060137/2011 / CAPES

Fin des années 1980, la découverte de l'effet magnétorésistif géant, qui se caractérise par une variation importante de la résistance électrique d'un matériau lorsqu'on le soumet à un champ magnétique, a eu un impact très important tant au niveau des études fondamentales qu'en vue d'applications industrielles telles que la réduction de la taille des disques durs des ordinateurs (Prix Nobel d'A. Fert en 2007). L'engouement ainsi suscité a permis de mettre en évidence cet effet, au début des années 1990, dans les couches minces d'oxyde de type pérovskite ABO3 et plus particulièrement dans les manganites de terres rares (Ln1-xAx)MnO3. Le but de ce travail s'inscrit dans ce cadre et concerne l'élaboration et l'étude des propriétés physiques (structurales, magnétiques, de transport et magnétocaloriques) de nouveaux manganites qui pourraient avoir des applications dans un domaine connexe qui est la réfrigération magnétique. En effet, cette dernière décennie, a vu les découvertes de nouveaux composés présentant des effets magnétocaloriques géants qui ont conduit aux premiers essais de laboratoire de la réfrigération magnétique. Celle-ci semble être l'une des alternatives très sérieuses pour le remplacement des systèmes de réfrigération classique basés sur la compression-détente des gaz. Cette nouvelle technique, comparée aux techniques traditionnelles, présente plusieurs avantages, elle est plus efficace sur le plan énergétique, plus compacte et surtout moins nuisible à l'environnement. La première partie de ce travail porte sur l'élaboration et la caractérisation des composés de formule La1-xCexMnO3. Nous avons étudié l'effet du recuit sur les propriétés morphologique, structurale, magnétique et magnétocalorique de ces composés. L'application du modèle de Landau, en bon accord avec les résultats expérimentaux de la mesure l'entropie magnétique SM, a montré que la nature de transition de phase dépend aussi de la température de recuit. La composition x=0.4 de ce composé présente la valeur la plus élevée du facteur de mérite RCP, ce qui en fait un bon candidat pour les applications à la réfrigération magnétique. Dans une deuxième partie une étude des propriétés morphologique, structurale, magnétique et magnétocalorique des manganites de formule La0,7Ca0,15Sr0,15Mn1-xFexO3 a été réalisée. Le fer n'influe pas sur les propriétés structurales mais entraîne une diminution de la température de Curie TC. Afin d'approfondir ces études, nous avons proposé un matériau composite basé sur deux composés La0,7Ca0,15Sr0,15Mn1-xFexO3 (x = 0,025 et 0,75). La variation d'entropie du composite reste approximativement constante entre 260 et 300 K. En conséquence, ce matériau composite peut être un très bon candidat pour la réfrigération magnétique au voisinage de l'ambiante. Dans une dernière partie, nous avons étudié l'effet du double échange, de la méthode de préparation, le rayons du site A et la nature magnétique du dopant au site B sur les propriétés magnétocaloriques en caractérisant la famille des composés La0,6A0,4Mn1-xFexO3 (A= Ca, Sr et 0≤x≤0,2) par diffraction des rayons X et par mesures magnétiques. D'une part, l'entropie magnétique maximale augmente avec le rayon du site A et est peu affecté par le rayon du site B et d'autre part, la méthode de préparation solide-solide est à privilégier puisqu'elle permet d'obtenir les plus grandes valeurs d'entropie magnétique maximale. / Since the discovery of the giant magnetoresistance effect (end of 1980s), which is characterized by a large change in the electrical resistance of a material under the effect of a magnetic field, a major impact has been motivated both on fundamental and practical aspects (Nobel Prize of A. Fert in 2007). The intensive research activities in this field have leaded in the end of 1990 to point out the giant magnetoresitance in thin films of perovskite family, in particular the manganites (Ln1-xAx)MnO3. The aim of this work concern the study of the structural, magnetic, electrical and magnetocaloric properties of new manganites based materials in view of their application in the magnetic cooling. It is worth noting that in recent years, a giant magnetocaloric effect has been reported in several materials leading to the implementation of new efficient magnetic cooling systems. This technology is considered actually as the most alternative to replace the classical systems based on the compression-relaxation process. Compared with conventional refrigeration, magnetic cooling presents relevant advantages such as a decrease of energy consumption (high efficiency) and reduction of the acoustic and environmental pollution (elimination of the standard coolants: CFC, HCFC). The first part of this work concerns the elaboration as well as the characterization of the compound with La1-xCexMnO3 formula. We have studied the role of the annealing on the morphological, structural, magnetic and magnetocaloric properties of these materials. Using the Landau theory, we have calculated the magnetic entropy change ΔSM, which is found in good agreement with the measurements, and we have shown that the nature of the magnetic transition depends also on the annealing temperature. The compound with the composition x = 0.4, presents a large value of the figure of merit RCP, which make this material a good candidate for magnetic cooling application. In the second part, a detailed study of the morphological, structural, magnetic and magnetocaloric properties of the compounds with La0,7Ca0,15Sr0,15Mn1-xFexO3 formula has been performed. The iron Fe don't affect the structural properties, but induces a decrease of the Curie temperature. Based on the La0,7Ca0,15Sr0,15Mn1-xFexO3 (x = 0, 025 et 0,075) compositions, a composite material was proposed. The entropy change of the composite remains approximately constant in the temperature range between 260 and 300 K. Consequently, the proposed composite can be a good refrigerant for room temperature applications, in particular the magnetic cooling systems that use AMR or Ericsson thermodynamic cycles. In the last part, we have investigated the effect of the double exchange, preparation method and, ionic radius in A site and the magnetic nature on the doping in B site on the physical properties of La0,6A0,4Mn1-xFexO3 (A= Ca, Sr et 0≤x≤0,2) by using X-rays diffraction and magnetic measurements. The results demonstrate that the maximum entropy change increases with the ray of A site while it is slightly affected by the B site ray. On the other hand, it seems that the solid-solid preparation technique allows to obtain compounds with high magnetocaloric performances.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Em geral, o efeito magnetocalórico (EMC) é caracterizado pela variação adiabática da temperatura (ΔTad) e a variação isotérmica da entropia (ΔST) sob variações do campo magnético. Devido as aplicações tecnológicas do EMC na refrigeração magnética, que não apresentam efeitos perigosos para o meio ambiente e tem o potencial para reduzir o consumo de energia, os estudos sobre o EMC tem crescido ao longo dos anos . Neste trabalho, estudamos as propriedades magnéticas e magnetocalóricos da série Gd (1-Y) Pr (Y) Ni2 com Y = 0; 0,25; 0,5; 0,75 e 1 A série dos compostos RNi2 compostos cristalizam na fase de Laves cúbico C15, o que torna o Campo Elétrico Cristalino cúbico um quadro adequado para descrever a anisotropia magnética sobre estes compostos . Além do modelo hamiltoniano inclui contribuições do efeito Zeeman e as interações de troca indireta entre Gd-Gd, Gd-Pr e íons Pr-Pr. Vale a pena notar que o GdNi2 apresenta um arranjo ferromagnético com temperatura de transição de cerca de 78 K e o composto PrNi2 é paramagnético. Os potenciais magnetocalóricos foram calculados e comparados com os dados experimentais. Além disso, investigamos a influência da direção do campo magnético sobre as quantidades magnéticas e no EMC investigada. / In general, the magnetocaloric effect (MCE) is characterized by the adiabatic temperature change, (ΔTad) , and the isothermal entropy change, (ΔST) , under changes of the magnetic field intensity. Due to technological applications of the MCE on magnetic refrigeration, which do not present hazardous effects to the environmental and has the potential to lower energy consumption, the interest on the MCE had grown over the years . In this work, we have studied the magnetic and magnetocaloric properties in the series Gd(1-Y)Pr(Y)Ni2 with Y = 0, 0.25, 0.5, 0.75 and 1. The RNi2 (R = Rare-earth) compounds crystallize in the cubic laves phase, which makes the cubic CEF an appropriate framework to describe the magnetism on these compounds . Besides CEF, the model Hamiltonian includes contributions of the Zeeman effect, and the indirect exchange interactions among Gd-Gd, Gd-Pr and Pr-Pr ions. It is worth noticing that the GdNi2 presents a ferromagnetic arrangement with transition temperature around 78 K and the PrNi2 compound is paramagnetic. The temperature dependences of the magnetocaloric potentials were simulated and compared with the experimental data. Furthermore, the influence of the magnetic field direction on the magnetocaloric quantities was theoretically investigated.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T20:42:39Z No. of bitstreams: 1 MayanneSilva.pdf: 14921508 bytes, checksum: f23bae019911ebcb5c64e47d629239c8 (MD5) / Made available in DSpace on 2017-05-05T20:42:39Z (GMT). No. of bitstreams: 1 MayanneSilva.pdf: 14921508 bytes, checksum: f23bae019911ebcb5c64e47d629239c8 (MD5) Previous issue date: 2016-11-28 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) / Here we report the structural, magnetic and magnetocaloric properties of DyMX (M = Cu and Pt; X = Si and Ge) and R2CuSi3 (R = Eu, Nd and Dy) intermetallic compounds. Polycrystalline samples were synthesized by arc melting under argon atmosphere. X-ray diffraction (XRD) analysis by Rietveld method confirm the desired crystallographic phase for all studied samples. Magnetization data show antiferromagnetic ordering around 12.8 K, 4.36 K, 8.7 K and 8.8 K for DyCuSi, DyCuGe, DyPtSi and DyPtGe, respectively. External applied magnetic field induces metamagnetic phase transitions in these compounds. However, the values of magnetic moment in T = 2 K and H = 5T () were lower than the respective values of the R ion effective magnetic moment, indicating that not all magnetic moments are oriented to the external applied field, in H = 5T. Eu2CuSi3 compound presented two ferromagnetic transitions at ܶ = 39.5 K and ܶ = 30 K for H ≤ 0.2 T. On the other hand, Nd2CuSi3 end Dy2CuSi3 magnetization data present characteristic of spin glass behavior in low temperatures (T ≤ 5.6 K for R = Nd e T ≤ 9.5 K for R = Dy) and low magnetic field (H < 0.2 T). When the external magnetic field increase, the magnetization increase faster and show saturation tendency in H = 5 T which indicate ferromagnetic interaction. Our results show a significant magnetocaloric effect (MCE) for all studied samples, which was characterized by a broad peak in the entropy variation change curves ሺȂ οܵ௠ሻ associated with the magnetic transition. The maximum MCE was obtained for DyCuSi compound ( = 23.7 J/kg.K and ܴܥ = ܲ421.5 J/kg), which indicate that this compound belongs to the class of magnetic materials with giant magnetocaloric effect. Large MCE was obtained for DyCuGe, Nd2CuSi3 e Dy2CuSi3 ( values ranging from 11.4 to 14.8 J/kg K). While conventional MCE was observed for DyPtGe, DyPtGe and Eu2CuSi3 compound values ranging from 8.1 to 11.2 J/kg.K). The obtained results, indicate that the DyMX and R2CuSi3 studied compound present interesting characteristics for application as refrigerant material in cryogenic temperatures. / Nesse trabalho estudou-se as propriedades estruturais, magnéticas e magnetocalóricas de compostos intermetálicos das famílias DyMX (M = Cu e Pt; X = Si e Ge) e R2CuSi3 (R = Eu, Nd e Dy) visando avaliar a potencialidade destes para aplicação na refrigeração magnética. As amostras foram sintetizadas por fusão em forno à arco voltaico, sob atmosfera de argônio. Medidas de difração de raios-X e a análise dos difratogramas com o método Rietveld mostraram que as amostras sintetizadas apresentaram a fase cristalográfica desejada. As medidas de magnetização mostraram que os compostos da série DyMX apresentam ordenamento antiferromagnético em torno de 12,8 K, 4,36 K, 8,7 K e 8,8 K para DyCuSi, DyCuGe, DyPtSi e DyPtGe, respectivamente. A aplicação de campo magnético externo induz transições metamagnéticas nesses materiais abaixo de . Porém, os valores do momento magnético em T= 2 K e H= 5 T foram menores que os respectivos valores do momento efetivo do íon magnético trivalente na matriz metálica, indicando que nem todos os spins estão orientados com o campo aplicado. Já dentre os compostos R2CuSi3, o Eu2CuSi3 apresentou duas transições ferromagnéticas = 39,5 K e = 30 K. Enquanto que Nd2CuSi3 e Dy2CuSi3 apresentaram comportamento típico de spin-glass, em baixas temperaturas (T≤ 5,6 K para R= Nd e T= 9,5 K para R= Dy) e baixos campos magnéticos (H< 0,1 T). Com o aumento do campo externo aplicado a magnetização aumenta rapidamente e mostra tendência de saturação em H= 5 T, indicando interação ferromagnética. Os resultados mostram que o efeito magnetocalórico (EMC) dos compostos estudados apresenta valores expressivos, tendo sido caracterizado por um pico alargado nas curvas de variação isotérmica da entropia associado com a transição magnética dos respectivos compostos. O máximo EMC obtido foi o do DyCuSi ( = 23,7 J/kgK e = 421,5 J/kg), o que sugere que este composto pertence à classe dos materiais magnéticos com EMC gigante. Os compostos DyCuGe, Nd2CuSi3 e Dy2CuSi3 apresentaram EMC grande ( entre 11,4 e 14,8 J/kg.K) e os demais pertencem a classe de materiais com EMC convencional ( entre 8,1 e 11,2 J/kg.K). Os resultados obtidos para as duas séries de compostos intermetálicos estudados nesse trabalho indicam que estes apresentam características interessantes para a aplicação como material refrigerante em temperaturas criogênicas.

Submitted by Maria Aparecida (cidazen@gmail.com) on 2017-05-17T12:56:09Z No. of bitstreams: 1 Emanoel Laurertan.pdf: 6139159 bytes, checksum: fd73d36355b7767418dd1da09e0e7b80 (MD5) / Made available in DSpace on 2017-05-17T12:56:09Z (GMT). No. of bitstreams: 1 Emanoel Laurertan.pdf: 6139159 bytes, checksum: fd73d36355b7767418dd1da09e0e7b80 (MD5) Previous issue date: 2015-07-10 / CAPES, FAPEMA,CNPQ / Magnetic and magnetocaloric properties of RPtGa (R = Dy, Ho e Er) and HoTSi (T = Mn, Co e Cu) compound have been studied. The samples crystallographic phase was confirmed by X-ray diffraction and Rietveld refinement analysis. Magnetization analysis show that RPtGa compounds exhibit antiferromagnetic ordering, with Néel temperature (TN) around 15 K, 6,3 K and 4 K for R = Dy, Ho and Er, respectively. HoMnSi and HoCuSi compounds present antiferromagnetic ordering at TN = 15 K and 7 K, respectively, while HoCoSi shows ferromagnetic ordering around 15 K. The external magnetic field application induces metamagnetic transitions in these materials (except for HoCuSi) below TN. However, the magnetic moment at T = 2 K and H = 50 kOe is smaller than the respective effective magnetic moment values in the metallic matrix (μeff), indicating that not all spins are aligned with external applied field. A large peak in the isothermal entropy change (- SM) curves, associated with the magnetic transition, is observed for all studied compounds. Negative magnetocaloric effect (MCE) was observed for RPtGa and HoMnSi samples due to antiferromagnetic ordering. Significant values of -ΔSM and adiabatic temperature change (ΔTad) were obtained in a relatively large temperature range (~15 K) for HoPtGa compound, evidencing a table like behavior. The maximum values of -ΔSM and the relative cooling power (RCP) obtained were 20.4 J/kgK and 475.14 J/kg for HoCoSi, and 31.2 J/kgK and 592.18 J/kg for HoCuSi, respectively, at H = 50 kOe, which suggest that these compounds belongs to a magnetic materials class with giant MCE. The RPtGa maximum values of Tad obtained in this work were comparable or even bigger than the respective values reported in literature for others RTX compounds, in the same temperature range. Furthermore, the observed magnetocaloric properties such as table like behavior and giant MCE without hysteresis losses, indicate that the compounds studies in this works present interesting magnetocaloric properties for application as refrigerant material in cryogenic temperatures (T < 20 K). / Neste trabalho, apresentamos um estudo das propriedades magnéticas e magnetocalóricas dos compostos das séries RPtGa (R = Dy, Ho e Er) e HoTSi (T = Mn, Co e Cu). Medidas de difração de raios X e o refinamento Rietveld dos difratogramas comprovaram que as amostras apresentam a fase cristalográfica. Medidas de magnetização mostram que os compostos da série RPtGa apresentam ordenamento antiferromagnético com temperatura de Néel (TN) em torno de 15 K, 6,3 K e 4 K para R = Dy, Ho e Er, respectivamente. Os compostos HoMnSi e HoCuSi apresentam ordenamento antiferromagnético em TN = 15 K e 7 K, respectivamente, enquanto HoCoSi ordena-se ferromagneticamente em 15 K. A aplicação de campo magnético externo induz transições metamagnéticas nesses materiais (exceto no HoCuSi) abaixo de TN. Porém, os valores do momento magnético em T = 2 K e H = 50 kOe é menor que os respectivos valores do momento efetivo do íon magnético na matriz metálica (μeff), indicando que nem todos os spins estão orientados com o campo. Em todos os compostos estudados, observou-se um pico alargado nas curvas de variação isotérmica da entropia (- SM) associado com a transição magnética. Efeito magnetocalórico (EMC) negativo, foi observado para as amostras RPtGa e HoMnSi, devido ao ordenamento antiferromagnético. Valores significativos de -ΔSM e da variação adiabática da temperatura (ΔTad) foram obtidos em uma região relativamente ampla de temperatura (~15K), evidenciando características de um comportamento tipo “table-like” no composto HoPtGa. Os valores máximos de -ΔSM e o poder de resfriamento relativo (RCP) obtidos para HoCoSi ( = 20,4 e RCP = ) e HoCuSi ( = 31,2 J/kgK e RCP = ) em ΔH = 50 kOe, sugerem que estes compostos pertencem a classe dos materiais magnéticos com EMC gigante. Os valores máximos de ΔTad obtidos para os compostos RPtGa são comparáveis ou até maiores que os obtidos para outros compostos da família RTX reportados na literatura, no mesmo intervalo de temperatura. Além disso, as propriedades magnetocalóricas observadas, tais como EMC tipo “table-like” e EMC gigante, sem perdas por histerese, indicam que os compostos estudados neste trabalho possuem propriedades magnetocalóricas interessantes para a aplicação como material refrigerante em temperaturas criogênicas (T < 20K).

Ni-Co-Mn-In system is a new type of magnetic shape memory alloys (MSMAs) where the first order structural and magnetic phase transitions overlap. These materials can generate large reversible shape changes due to magnetic-field-induced martensitic transformation, and exhibit magneto-caloric effect and magnetoresistance. Ni-Co-Mn-Sn alloys are inexpensive alternatives of the Ni-Co-Mn-In alloys. In both materials, austenite has higher magnetization levels than martensite. Fe-Mn-Ga is another MSMA system, however, whose magnetization trend is opposite to those of the Ni-Co-Mn-X (In-Sn) systems upon phase transformation. The MSMAs have attracted great interest in recent years, and their magnetic and thermo-mechanical properties need to be further investigated. In the present study, the effects of indium concentration, cooling, and annealing on martensitic transformation and magnetic response of single crystalline Ni-Co-Mn-In alloys were investigated. Increasing indium content reduced the martensitic transformation start (Ms) temperature, while increasing temperature hysteresis and saturation magnetization. Increasing annealing temperature led to an increase in the Ms temperature whereas annealing at 400 degrees C and 500 degrees C led to the kinetic arrest of austenite. Cooling after solution heat treatment also notably affected the transformation temperatures and magnetization response. While the transformation temperatures increased in the oil quenched samples compared to those in the water quenched samples, these temperatures decreased in furnace cooled samples due to the kinetic arrest. The possible reasons for the kinetic arrest are: atomic order changes, or precipitate formation. Shape memory and superelastic response, and magnetic field-induced shape recovery behavior of sintered Ni43Co7Mn39Sn11 polycrystalline alloys were also examined. The microstructural analysis showed the existence of small pores, which seem to increase the damage tolerance of the sintered polycrystalline samples. The recoverable transformation strain, irrecoverable strain and transformation temperature hysteresis increased with stress upon cooling under stress. Moreover, magnetic-field-induced strain due to the field-induced phase transformation was confirmed to be 0.6% at 319K. Almost perfect superelastic response was obtained at 343K. A magnetic entropy change of 22 J kg-1 K-1 were determined at 219K from magneto-caloric effect measurements which were conducted on annealed Ni43Co7Mn39Sn11 ribbons. Magnetic characteristics and martensitic transformation behavior of polycrystalline Fe-Mn-Ga alloys were also examined. Cast alloys at various compositions were undergone homogenization heat treatments. It was verified by magnetization measurements that the alloys heat treated at 1050 degrees C shows martensitic transformation. The heat treatment time was determined to be 1 day or 1 week depending on the compositions.

The aim of the study, which was carried out in two main parts, was to investigate the atomic and magnetic ordering in various full Heusler alloy systems.In the theoretical part of the thesis, investigations based on the statiscothermodynamical theory of ordering by means of Bragg-Williams-Gorsky (BWG) method combined with electronic theory in the pseudopotential approximation have been conducted to model order-order (L21&amp / #8596 / B2) and order-disorder (B2&amp / #8596 / A2) phase transformations in Ni-Mn-C (C=Ga, In, Sb) and A2BGa (A=Fe, Ni, Co / B=Ni, Mn, Co, Fe) Heusler alloys. The partial ordering energies, calculated according to the electronic theory of alloys in pseudopotential approximation for the first two coordination spheres were utilized as input data for the theoretical superlattice formation models based on BWG approximation. Furthermore, the trends of L21&amp / #8596 / B2 transition temperatures with electron concentration at A, B and C atomic sites were determined. In the experimental part of the thesis, structural and magnetic properties of Ni-Mn-Ga and Ni-Mn-Al Heusler alloys were investigated. For the Ni-Mn-Ga Heusler alloy system, it was found that the martensitic (TM) and Curie temperatures (TC) merge for Ni54Mn20Ga26 and Ni56Mn18Ga26 alloys by compositional tuning. For the Ni-Mn-Al Heusler alloy system, it was found that ferromagnetism was introduced into these alloys by low temperature aging, as a result of the stabilization of the L21 phase. In addition to that, magnetocaloric effect (MCE) was determined in the vicinity of the first order magneto-structural transition for Ni-rich Ni-Mn-Ga alloys and near the second order magnetic transition for the Ni2MnAl alloy.

Made available in DSpace on 2016-12-12T20:15:53Z (GMT). No. of bitstreams: 1 Dissertacao Mariana.pdf: 1116675 bytes, checksum: 738c76deac0f2328b64e8c58a2cbbd57 (MD5) Previous issue date: 2009-06-26 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The double exchange model is used to describe different magnetocaloric materials containing localized magnetic moments and itinerant electrons. The model includes the Hund ruleexchange J betweenthelocalized spinsand theconductionelectrons. By using the equation of motion method, we apply a higher-order decoupling for the conduction electron Green s functions. The magnetism of the localized moments is described in terms of an effective Heisenberg model. We obtain a simple description of the magnetization curves and the isothermal entropy change &#916;S. The results exhibit an additional low-temperature bump in the &#916;S curves at low concentrations n separated from the usual maximum at the critical temperature. The method can also be addressed to the Kondo lattice compounds, in the case of a negative couping J. / O modelo da dupla troca é utilizado para descrever diferentes materiais magnetocalóricos contendo momentos magnéticos localizados e elétrons itinerantes. O modelo inclui a regra de Hund para a troca J entre os spins localizados e elétrons de condução. Utilizando o método de equações de movimento, aplicamos um desacoplamento de ordem superior para as funções de Green dos elétrons de condução. O magnetismo dos momentos magnéticos localizados é descrito em termos do modelo de Heisenberg efetivo. Obtemos uma descrição simples das curvas de magnetização e variação isotérmica da entropia &#916;S. Os resultados exibem uma elevação nas curvas &#916;S em baixa concentração de n separada do Maximo usual na temperatura cr&#305;tica. O método pode também se aplicado aos compostos da rede Kondo, no caso de acoplamento negativo J.