In der magnetischen Formgedächtnislegierung Ni-Co-Mn-In kann eine reversible Umwandlung von einer niedrigsymmetrischen, para- oder antiferromagnetischen Phase (Martensit) in eine hochsymmetrische ferromagnetische Phase (Austenit) sowohl durch eine Temperaturerhöhung als auch durch das Anlegen eines Magnetfelds induziert werden. Da dünne Schichten sich als interessantes Modellsystem für magnetische Formgedächtnislegierungen erwiesen haben, wird diese Umwandlung und der mit ihr verbundene inverse magnetokalorische Effekt an epitaktischen Ni-Co-Mn-In-Schichten untersucht. Die Temperatur des Substrats während der Herstellung wird als entscheidender Parameter für die Zusammensetzung und chemische Ordnung der Schicht identifiziert. Untersuchungen der Struktur mittels Röntgenbeugung zeigten, in Übereinstimmung mit dem Konzept des adaptiven Martensits, die Koexistenz von Austenit, moduliertem und nichtmoduliertem Martensit bei Raumtemperatur. Dieses Ergebnis wird durch Gefügeabbildungen untermauert. Die Transformation wird sowohl durch temperaturabhängige Röntgenbeugung als auch durch temperatur- und feldabhängige Magnetisierungsmessungen untersucht. Die berechnete Änderung der magnetischen Entropie ist etwa halb so groß wie in massivem Ni-Co-Mn-In. Schließlich wird bei tiefen Temperaturen eine unidirektionale Austauschkopplung zwischen Restaustenit und Martensit nachgewiesen, die auf einen antiferromagnetischen Martensit schließen lässt. / The magnetic shape memory alloy (MSMA) Ni-Co-Mn-In shows a reversible transformation from a para- or antiferromagnetic low symmetry phase (martensite) into a ferromagnetic phase of high symmetry (austenite). This transformation can either be induced by raising the temperature or applying a magnetic field. Since thin films have be shown to be an interesting model system for MSMAs, this transformation and the associated inverse magnetcaloric effect are investigated in epitaxial Ni-Co-Mn-In films. The temperature of the substrate during deposition is identified as the essential parameter controlling both composition and chemical order. By studying structure using x-ray diffraction (XRD) the coexistence of austenite and modulated (14M) as well as nonmodulated martensite (NM) is shown. Coexistence of NM and 14M is also visible in micrographs of the films surface. This confirms results obtained for epitaxial Ni-Mn-Ga and validates the concept of adaptive martensite in this alloy. The transformation is investigated by temperature-dependent XRD and temperature- and field-dependent magnetometry. A positive change in entropy is calculated which is about half compared to bulk. Finally, an exchange bias between residual austenite and martensite is observed, which suggests an antiferromagnetic order in the martensitic state.

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.

The crystalline iron-based nanowires encapsulated by multiwalled carbon nanotubes have been the subject of numerous studies owing to the range of potential applications. The presence of a-Fe (bcc)/y -Fe(fcc) junctions o ers the possibility of exploitation of the exchange bias effect, an interfacial magnetic phenomenon that plays a major role in magnetocaloric cooling, spintronic and high-density magnetic storage devices. This work is concerned with the synthesis and microstructural characterization of Fe-based and NiFe nanowires encapsulated by multiwall carbon nanotube radial structures. The known attributes of these structures are well matched to the magnetocaloric application. The primary aim of this work was to determine the unknown microstructural details of the encapsulated nanowire that are of relevance to the magnetocaloric application (junction types, location and orientation relative to the nanotube axis). The secondary aim was to explore the modi cation of the synthesis route to promote desirable attributes. This is the first report of a-Fe/y -Fe sequential junctions and a-Fe/Fe3C concentric junctions in encapsulated Fe-based nanowires. The presence of a-Fe/y -Fe junctions was inferred from the observation of a-Fe nanowires terminated by a ~100 nm length y-Fe crystallites of larger diameter. The a-Fe/Fe3C junctions exhibit the Bagaryatski orientation relationship: [110 ]bcck[100 ]orth. The degree of substrate roughness was found to be a means of tailoring details of the structure and composition of the encapsulated nanowires. NiFe encapsulated nanowires were found to contain crystallites of a-NiFe, y-NiFe and Ni3Fe and the sequential junctions -NiFe/Ni3Fe and a-NiFe/y-NiFe junctions.

Orientador: Antonio Manoel Mansanares / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Física Gleb Wataghin / Made available in DSpace on 2018-09-26T17:20:21Z (GMT). No. of bitstreams: 1 Soffner_MaxErik_D.pdf: 4836506 bytes, checksum: af3488da1f4fb5e63235f4be7bcfa8bd (MD5) Previous issue date: 2010 / Resumo: O efeito magnetocalórico (EMC) tem sido amplamente estudado devido à sua possível aplicação em refrigeração magnética. A busca por materiais adequados se intensificou na última década, havendo demanda não só pela preparação de novos materiais como por sua completa caracterização. O objetivo deste trabalho é a aplicação das técnicas fototérmicas na caracterização de materiais que apresentam o efeito magnetocalórico. Primeiramente, versaremos sobre a Magnetoacústica. Trata-se de uma adaptação da técnica Fotoacústica e que se revelou promissora na área devido à sua alta sensibilidade e por deixar de lado questões sobre a validade da teoria envolvida nos métodos tradicionais. Recentemente, a detecção acústica do EMC foi explorada em outro trabalho do grupo, sendo proposto um modelo simples para determinar a variação adiabática de temperatura (? Tad). Aqui, exploramos a técnica em uma abordagem diferente, tendo como principal objetivo a determinação da variação isotérmica de entropia (? ST) para diferentes variações de campos magnéticos. A utilização de técnicas fototérmicas para a determinação do ? ST é a novidade deste trabalho. Os materiais analisados foram o gadolínio, que apresenta transição de fase magnética de 2a ordem e um composto da família Gd5 (Ge1-x Si x) 4, que apresenta transição de fase magnética-cristalográfica de 1a ordem. Os resultados positivos mostraram uma maneira alternativa na caracterização do EMC, trazendo vantagens sobre os métodos tradicionais em várias situações. Em paralelo, a técnica de ressonância ferromagnética fototermicamente modulada (PM-FMR) foi utilizada no estudo de filmes finos de gadolínio. O crescente interesse em filmes finos nos dias de hoje requer novos estudos sendo propícia a caracterização dos mesmos por diferentes técnicas. Através da PM-FMR, foi possível observar as transições de fase magnéticas para filmes com diferentes espessuras e tratamentos térmicos, depositados sobre substratos de quartzo e silício. Os resultados foram comparados com medidas tradicionais de ressonância ferromagnética e de magnetização. Apesar dos resultados serem, de modo geral, conhecidos o maior interesse está na evolução da técnica. Por possuir resolução espacial na escala de micrometros, permite obter imagens magnéticas, as quais não são possiveis pelos métodos tradicionais / Abstract: The magnetocaloric effect (MCE) has been widely studied because of its possible application in magnetic refrigeration. The search for suitable materials has intensified over the last decade, with a demand not only for the preparation of new materials but also for their complete characterization. The aim of this work is to apply the photothermal techniques to the characterization of materials with magnetocaloric effects. First, we will discuss the Magnetoacoustic technique. This is an adaptation of the Photoacoustic techinique, and it has proved to be promising in the magnetocaloric field due to its high sensitivity. Moreover, this technique is not limited by the validity of the theories involved in traditional methods. Recently, the acoustic detection of MCE was explored in another work of this research group and a simple model for determining the adiabatic temperature variation (? Tad) was proposed. Here, we used a different approach to determine the isothermal entropy change ( ? ST ) the ? ST is the novelty of this work. The analyzed materials were gadolinium, which shows a second order magnetic phase transition, and a Gd5 (Ge1-x Six) 4 family compound, which has a first order magnetic-crystallographic phase transition. The positive results showed an alternative way to characterize the MCE, proving to have advantages over traditional methods in many cases. In parallel, the photothermally modulated ferromagnetic resonance technique (PMFMR) was used in the study of thin films of gadolinium. Currently, there is a growing interest in thin films, and this has encouraged researches to use different characteriza tion techniques. Using PM-FMR, we observed the magnetic phase transitions for the films with different thicknesses and thermal treatments, deposited on quartz and silicon substrates. Our findings were compared with traditional results of ferromagnetic resonance and magnetization. Although the overall results are known, the main interest is in the evolution of the technique. The spatial resolution in the micrometer scale allows for magnetic images, which are not possible using traditional methods / Doutorado / Física da Matéria Condensada / Doutor em Ciências

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.

The overall goals of the present PhD research are to explore the giant magnetoimpedance (GMI) and giant magnetocaloric (GMC) effects in functional magnetic materials and provide guidance on the optimization of the material properties for use in advanced magnetic sensor and refrigeration applications. GMI has attracted growing interest due to its promising applications in high-performance magnetic sensors. Research in this field is focused on the development of new materials with properties appropriate for practical GMI sensor applications. In this project, we have successfully set up a new magneto-impedance measurement system in the Functional Materials Laboratory at USF. We have established, for the first time, the correlation between sample surface, magnetic softness, critical length, and GMI in Co-based amorphous ribbon materials, which provide a good handle on selecting the suitable operating frequency range of magnetic materials for GMI-based field sensor applications. The impact of field-induced magnetic anisotropy on the GMI effect in Co-based nanocrystalline ribbon materials has also been investigated, providing an important understanding of the correlation between the microstructure, magnetic anisotropy, and GMI in these materials. We have shown that coating a thin layer of magnetic metal on the surface of a magnetic ribbon can reduce stray fields due to surface irregularities and enhance the magnetic flux paths closure of the bilayer structure, both of which, in effect, increase the GMI and its field sensitivity. This finding provides a new way for tailoring GMI in surface-modified soft ferromagnetic ribbons for use in highly sensitive magnetic sensors. We have also introduced the new concepts of incorporating GMI technology with superparamagnetic nanopthesiss for biosensing applications and with carbon nanotubes for gas and chemical sensing applications. GMC forms the basis for developing advanced magnetic refrigeration technology and research in this field is of topical interest. In this project, we have systematically studied the ferromagnetism and magnetocaloric effect in Eu8Ga16Ge30 clathrate materials, which are better known for their thermoelectric applications. We have discovered the GMC effect in the type-VIII clathrate and enhanced refrigerant capacity in the type-I clathrate. We have successfully used the clathrates as excellent host matrices to produce novel Eu8Ga16Ge30-EuO composite materials with desirable properties for active magnetic refrigeration technologies. A large refrigerant capacity of 794 J/kg for a field change of 5 T over a temperature interval of 70 K has been achieved in the Eu8Ga16Ge30-EuO composite with a 40%-60% weight ratio. This is the largest value ever achieved among existing magnetocaloric materials for magnetic refrigeration in the temperature range 10 K - 100 K. The excellent magnetocaloric properties of the Eu8Ga16Ge30-EuO composites make them attractive for active magnetic refrigeration in the liquid nitrogen temperature range.