Masters of Science / Rare-earth (RE) compounds have been an attractive subject, based on the unique electronic structures of the rare-earth elements. In particular, the RETX (RE = rare-earth, T = 3d/4d/5d, transition metals, and X = p – block elements) series is a large family of intermetallic compounds which crystallizes in different crystal structure depending on the constituents. Most of these compounds crystalize in the hexagonal, orthorhombic, and tetragonal crystal structure. On the other hand, the family of compounds RET2X2 adopted the tetragonal crystal structure of the ThCr2Si2 or the CaBe2Be2 with different space groups. Owing to the different crystal structure, these compounds show versatile magnetic and electrical properties such as Kondo effect, complex magnetic behaviour, valence fluctuation, unconventional and conventional superconductivity, heavy fermion behaviour, Fermi and non – Fermi liquid behaviour, metamagnetism, spin – glass, memory effect, crystal electric field (CEF), magnetoresistance and magnetocaloric effect. The history of magnetism reveals that it is closely related to practical applications and magnetic materials from the most vital components in many applications. These are memory devices, permanent magnets, transformer cores, magneto-mechanical devices and magneto-electronic devices. Recent additions to this list include magnetic refrigeration through the studies of magnetocaloric effect as well as spintronics. Magnetic refrigeration (MR) is an emerging technology and shows real potential to enter conventional markets and the principles of MR obeys the magnetocaloric effect (MCE), which is based on the effect caused by a magnetic field on the materials that accept the property of varying the magnetic entropy, as well as its temperature when varying the magnetic field. In this thesis, we report giant magnetocaloric effect and magnetic properties of NdPd2Al2 and RECuGa (RE = Nd, Dy, and Ho) compounds. These investigations were done through measurements of X – ray diffraction (XRD), magnetic susceptibility, ((T)), magnetization, (M(H)), isothermal magnetization, (M(H, T)), heat capacity, (Cp(T)) and electrical resistivity, ((T)). MCE has been studied from the isothermal magnetization and heat capacity measurements.The first chapter of the thesis describes the theoretical background from which the experimental results have been analyzed and interpreted. This is followed by the chapter which presents experimental details and methodology carried out in this thesis. Chapter three presents the results and discussion of the transport, magnetic and magnetocaloric properties of NdPd2Al2 compounds. XRD studies confirm the tetragonal CaBe2Ge2 – type structure with space group P4/nmm (No. 129). The results of (T), (T) and Cp(T) indicate a putative antiferromagnetic (AFM) phase transition at low temperature at, TN = 3 K. On the other hand, (T) data at high temperatures follow the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent Nd3+ ion. The magnetization results indicate metamagnetic – like transition at a low field that bears a first-order character which corroborates with the Below – Arrott plots. Giant MCE was obtained for the NdPd2Al2 compound similar to those reported for potential magnetic refrigerant materials. Chapter four discusses the magnetic and thermodynamic properties of the series of compounds RECuGa where RE = Nd, Dy, and Ho. XRD studies indicate the orthorhombic CeCu2 – type crystal structure with space group Imma (No. 74) for all three compounds. Magnetic measurements indicate a putative AFM phase transition below 𝑇𝑁 = 7.1, 8.5, and 3.7 K for Nd, Dy, and Ho compounds, respectively. The high-temperature (T) data for all three compounds follow the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent rare-earth ion. Again, large MCE were obtained for all three compounds similar to those reported for materials that can be used as magnetic refrigerant materials.

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The metamagnetic transition from an antiferromagnetic (AF) to the ferromagnetic (FM) state in FeRh alloys and the accompanying magnetocaloric effect (MCE) have been investigated with a particular attention to the sample preparation routes. Direct measurements of the adiabatic temperature change show that the MCE in FeRh remains partly reversible despite the hysteresis and exceeds the effect in the benchmark material Gd by 15 %. The AF−FM transition is strongly affected by the microstructure that is formed depending on the heat treatment parameters. This can explain the discrepancy in the reported data over 80 years of research. The effect on the magnetic properties is found to originate from the interaction of the major α'-phase with the secondary γ-phase that has been typically ignored for its negligible magnetic contribution. The nominal composition of the magnetic α'-phase is found to differ from the actual one for binary and substituted FeRh alloys. The elements can be redistributed within the two phases in such a way, that the actual amount of the doping element in the α'-phase that experiences the AF−FM transition is greatly reduced. This demonstrates the significance of microstructural studies, especially when comparing experimental results with theoretical calculations and developing routes to tune and optimize the magnetocaloric properties of materials.

The magnetic properties of NiMnGe1−xAlx, Ni50Mn35(In1−xBx)15, Ni50Mn35In14.5B0.5 (Bulk, As-Solidified and Annealed melt-spun ribbon) and RE-Infuse Carbon Nanotubes, have been studied by x-ray diffraction, differential scanning calorimetry (DSC), and magnetization measurements. Partial substitution of Al for Ge in NiMnGe1−xAlx results in a first-order magnetostructural transition (MST) from a hexagonal ferromagnetic to an orthorhombic antiferromagnetic phase at 186 K (for x = 0.09). A large magnetic entropy change of ∆SM = -17.6 J/kg K for ∆H = 5 T was observed in the vicinity of TM = 186 K for x = 0.09. This value is comparable to those of well-known giant magnetocaloric materials, such as Gd5Si2Ge2, MnFeP0.45As0.55, and Ni50Mn37Sn13. The values of the latent heat (L = 6.6 J/g) and corresponding total entropy changes (∆ST = 35 J/kg K) have been evaluated for the MST using DSC measurements. Large negative values of ∆SM of -5.8 and -4.8 J/kg K for ∆H = 5 T and up to 9T in the vicinity of TC were observed for x = 0.09 and 0.085, respectively. The impact of B substitution in Ni50Mn35In15-xBx Heusler alloys on the structural, magnetic, transport, and parameters of the magnetocaloric effect (MCE) has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (H) up to 5 T, and in the temperature interval 5-400 K ). Direct adiabatic temperature change (ΔTAD) measurements have been carried out for an applied magnetic field change of 1.8 T. The transition temperatures (T-x) phase diagram has been constructed for H = 0.005 T. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X=In, Al, and Ge) Heusler alloys. The maximum absolute value of ΔTAD = 2.5 K was observed at the magnetostructural transition for Ni50Mn35In14.5B0.5. The structural phase transition temperatures, phase structure, and parameters of the magnetocaloric effect (MCE) of Ni50Mn35In14.5B0.5 as Bulk, As-Solidified and Annealed melt-spun ribbon has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (oH) up to 5 T, and in the temperature interval 5–400 K). Magnetic and structural transitions in Ni50Mn35In14.5B0.5 as ribbons were found to coincide in Ni50Mn35In14.5B0.5 bulk sample, leading to a large magnetocaloric effects associated with the first-order magnetostructural phase transition. In comparison to the bulk Ni50Mn35In14.5B0.5 alloys, both the martensitic transition temperature (TM) and Curie temperature (TC) shifted to lower temperatures. Magnetic measurements revealed that the ribbons undergo a structure transformation similar to the bulk material at the martensitic transformation. The temperature of the transformation depends strongly on lattice parameters of the ribbons. MST shows a weak broad magnetic transition at TCM∼ 160 K, while the Curie temperature of AST TCA is ∼ 297 K. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X = In, Al, and Ge) Heusler alloys. These results suggest the possibility to control the martensitic transition in Ni50Mn35In14.5B0.5 through rapid solidification process. A comparison of magnetic properties and magnetocaloric effects in Ni50Mn35In14.5B0.5 alloys as Bulk, As-Solidified and Annealed ribbons is discussed. Carbon nanotube (CNT)/metal-cluster-based composites are envisioned as new materials that possess unique electronic properties which may be utilized in a variety of future applications. Super paramagnetic behavior was reported for CNTs with Gd ions introduced into the CNT openings by internal loading with an aqueous GdCl3 chemical process. In the current work, the magnetic properties of the CNT/Gd composites were obtained by the joining and annealing of Gd metal and CNTs at 850 °C for 48 h. Energy dispersive X-ray analysis shows the presence of Gd intermingled with the CNT walls with maximum and average Gd concentrations of about 20% and 4% (by weight), respectively. The Gd clusters have a non-uniform distribution and are mostly concentrated at the ends of the CNTs. A ferromagnetic-type transition at TC ∼ 320 K, accompanied by jump like change in magnetization and temperature hysteresis typical for the temperature induced first order phase transitions has been observed by magnetization measurements. It was found that Gd infused into the CNTs by the annealing results in a first order paramagnetic-ferromagnetic transition at TC = 320 K.

This project presents an attempt to construct a setup and implement a reliable technique for measuring the magnetocaloric effect (MCE) on various materials via a direct method for the acquisition of the data. The main objective of the latter is to produce a ∆Tadiabatic vs T graph over a reasonable temperature span (-100◦C up to 220◦C) by thermal monitoring of a magnetic material exposed to an oscillating magnetic field with a maximum strength of 1.2T. The setup consists of a vacuum-insulated glass tube containing the sample placed between two electromagnets of a vibrating-sample magnetometer (VSM) and increasingly heated by a resistance wire, while the temperature is recorded directly by a thermocouple. The first experiments are performed on Gadolinium (Gd) samples as a reference material in order to verify the overall reliability of the system. The obtained results on Gadolinium show that meaningful data can be acquired with this direct method, although the initially-extracted ∆Tadiabatic near room temperature stands at the accuracy limit (25%) generally accepted with this method. Unexpected interference signals from the thermocouple are encountered for high temperatures and are shown to be due to magnetic dependence from one of its constituents. Data from high temperatures can however be reliably corrected with respect to a baseline signal from a neutral nonmagnetic material. As such magnetocaloric properties of two Manganese-rich high entropy alloys are investigated with one exhibiting at most ∆Tadiabatic = 0.2◦C at its Curie temperature TC = 60◦C. Suggestions regarding the possibility of operating the setup at sub-zero temperatures are put forward and promising results from a new spot- welded thermocouple show a significantenhancement of the initial setup accuracy. / Detta projekt presenterar ett försök att konstruera en installation och implementera en pålitlig teknik för att mäta den magnetokolorisk effekten (MCE) på olika material via en direkt metod för insamling av data. Det sistnämnda syftet är att producera en ∆Tadiabatisk vs T över ett rimligt temperaturintervall (-100◦C up to 220◦C). Detta genom en termisk övervakning av ett magnetiskt material utsatt för ett oscillerande magnetfält med en maximal magnitud på 1.2 T. Utrustningen utgörs av ett vakuumisolerade glasrör som innehåller provet, vilket är placerat mellan två elektromagneter från en vibrating-sample magnetometer (VSM) och som stegvis värms upp av en resistanstråd, medan temperaturen registreras direkt av ett termoelement. De inledande experimenten utförs på prover av Gadolinium (Gd) som referensmaterial för att verifiera systemets totala tillförlitlighet. De erhållna resultaten från Gadolinium proverna visar att meningsfulla data kan produceras med denna direkta metod. Även om de extraherade ∆Tadiabatisk vid rumstemperatur befinner sig inom precisions gränsen (25%), vilken är allmänt accepterad med avseende på den direkta metoden. Oväntade missvisande signaler från termoelementet uppträder vid höga temperaturer och visar sig bero på magnetiskt beroende från instumentet. Data från höga temperaturer kan emellertid pålitligt korrigeras med en baslinjesignal från ett neutralt icke-magnetiskt material. Därmed undersöks de magnetokoloriska egenskaper hos två Mangan-rika hög entropi legeringar, där en uppvisar som högst ∆Tadiabatisk = 0.2◦C vid dess Curie-temperatur TC = 60◦C. Förslag beträffande möjligheten att använda installationen vid temperaturer under noll läggs fram. Lovande resultat från ett nytt punktsvetsat termoelement visar en betydande förbättringav den inledande installationens noggrannhet.

The alloys FeMnSi and Fe2MnCrSi were obtained in arc furnace in a helium atmosphere at the water-cooled copper ingot mold with the double remelting. Homogenizing annealing of the samples was carried out in a vacuum furnace at 950°C. X-ray analysis was carried out for structure investigation of the alloys. The diffraction patterns were obtained on the X-ray diffractometer Bruker D8 Advance, measurement results were processed using software FullProf v.2.05. Measurement of magnetization isotherms and dependences of the magnetization of alloys on magnetic field were carried out with vibration magnetometer7407 VSM (Lake Shore Cryotronics) in magnetic fields up to 1.7 T at temperature 80 – 400 K. Changes in magnetic part of entropy in various magnetic fields from 0.01 to 1.7 T calculated from isotherms. For sample Fe1.75Mn1.25Si it is shown that at the Curie temperature dependence of the changes of entropy on the magnetic field is almost linear. Obtained dependence of the magnetization on the field at temperatures Tc - 50 K (Tc – the Curie temperature) for all investigated compounds showed that the magnetization of samples decreases with increasing concentration of manganese and chromium. The Curie temperature for alloys Fe3-xMnxSi decreases with increasing of manganese concentration. For alloys Fe2Mn1-xCrxSi the Curie temperature increase with with increasing of chromium concentration. ∆T-effect for all compounds was measured by direct method on an automated installation for measurement of the specific heat and magnetocaloric effect MagEq MMS SV3 (AMT&C) in magnetic field 1.7 T at temperature 85-370 К. The magnitude of the magnetocaloric effect of the investigated compounds kept constant in the investigated manganese and chromium concentration range including at room temperature. / В дуговой печи были получены сплавы FeMnSi и Fe2MnCrSi в атмосфере гелия на водоохлаждаемой медной изложнице с двухкратной переплавкой. Гомогенизирующий отжиг образцов проводился в вакуумной печи при температуре 950°С. Для исследования структуры всех сплавов был проведен рентгеноструктурный анализ. Дифрактограммы были получены на рентгеновском дифрактометре Bruker D8 Advance, результаты измерения были обработаны с использованием программного обеспечения FullProf v.2.05. На вибрационном магнитометре 7407 VSM (Lake Shore Cryotronics) в магнитных полях до 1.7 Тл в температурном интервале от 80 до 400 K проведены измерения изотерм намагниченности и измерена зависимость намагниченности сплавов от магнитного поля. Рассчитано по изотермам изменение магнитной части энтропии в различных полях от 0.01 до 1.7 Тл. Для образца Fe1.75Mn1.25Si показано, что при температуре Кюри зависимость изменения энтропии от величины поля почти линейна. Полученные зависимости намагниченности от поля при температурах Tc – 50 К (Tc – температура Кюри) для всех исследуемых соединений показали, что намагниченность образцов уменьшается при увеличении концентрации марганца и хрома. Температура Кюри сплавов Fe3-xMnxSi уменьшается с ростом концентрации марганца. При увеличении концентрации хрома в соединении Fe2Mn1-xCrxSi температура Кюри растет. На автоматизированной установке для измерения магнитокалорического эффекта и теплоемкости MagEq MMS SV3 (AMT&C) измерен прямым методом ∆T-эффект всех соединений в магнитном поле 1.7 Тл в диапазоне температур 85-370 К. Величина магнитокалорического эффекта изученных соединений сохраняется неизменной в исследованном диапазоне концентраций марганца и хрома в том числе и при комнатной температуре.

No description available.

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 (ΔTS); que são 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 sob variações na direção de aplicação de um campo magnético cuja intensidade mantém‐se fixa, e é caracterizado por duas quantidades: a variação anisotrópico‐isotérmica da entropia (ΔSan) e a variação anisotrópico‐adiabática da temperatura (ΔTan). O efeito magnetocalórico e o efeito magnetocalórico anisotrópico foram estudados nos compostos intermetálicos formados por terras e outros materiais não magnéticos: RNi2, RNi5, RZn e Gd1‐nPrnAl2. Os cálculos foram feitos partindo de hamiltonianos modelo que incluem as interações de troca, Zeeman, de campo cristalino e quadrupolar. / The magnetic refrigeration is based on the magnetocaloric effect. The magnetocaloric potential is characterized by the two thermodynamics quantities: the isothermal entropy change (ΔSiso) and the adiabatic temperature change (ΔTad), which are calculated upon a change in the intensity of the applied magnetic field. In anisotropic magnetic systems it is observed a change in the magnetocaloric effect, since this potential becomes strongly dependent on the direction in which the external magnetic field is applied. The anisotropy in such magnetic systems can lead to an inverse magnetocaloric effect, as well as to the definition of an anisotropic magnetocaloric effect, that by definition is calculated upon a magnetic field which intensity is kept fixed and which orientation is changed from a hard direction of magnetization to the easy direction of magnetization. This anisotropic magnetocaloric effect was performed for the RAl2 intermetallic compounds considering a microscopic model Hamiltonian that includes the Zeeman interaction, the exchange interaction (taken in the mean field approximation) and the crystalline electrical field, that is responsible for the anisotropy in the RAl2 compounds. The anisotropic magnetocaloric was fully investigated for the serie RAl2 and compared with the usual magnetocaloric effect and several curves of (ΔSiso) and (ΔTad) were obtained.

La réfrigération magnétique attire beaucoup d’attention ces dernières années parce qu’elle est considérée comme une technologie respectueuse de l’environnement et énergétiquement économique. Aujourd’hui, cette technologie avancée est encore en phase de recherche que des dispositifs de réfrigérations magnétiques soient déjà opérationnels. Ce travail de thèse consiste à étudier la potentialité de résistance à la corrosion de différents types de matériaux magnétocaloriques (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga et Pr0.66Sr0.34MnO3) en contact avec un fluide caloporteur. Afin de comprendre les propriétés magnétocaloriques des matériaux, nos recherches se sont aussi focalisées sur les relations entre la transition magnéto-structurales d’alliages Heusler Ni2Mn0.75Cu0.25Ga et (i) la distribution cationique au sein de la structure cristalline et/ou (ii) la microstructure. Finalement, le diagramme de phase magnétique et nucléaire en lien avec les effets magnétocalorique obtenu grâce à la diffraction de neutrons et de pérovskite Pr1-xSrxMnO3 (0.25≤x≤0.45) est également présenté. / Magnetic refrigeration has gained lot of importance and attention as they are highlighted to be environmental friendly, energy efficient. Presently, though at research stage, the magnetic refrigerators are pushed towards realization in domestic application with extensive work on materials and with few working models. One critical issue, the potential resistance to corrosion in case of different class of magnetocaloric materials (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga and Pr0.66Sr0.34MnO3) against the heat transport fluid is addressed. To better understand and improve the observed magnetocaloric properties in Heulser alloys Ni2Mn0.75Cu0.25Ga and to elaborate the same with the magneto-structural relation, studies on (i) cation distribution with in crystal structure and/or (ii) microstructural dependence are presented. Nuclear and magnetic phase diagram based on detailed neutron diffraction and magnetism studies for magnetocaloric perovskite oxide Pr1-xSrxMnO3 (0.25≤x≤0.45) is also presented

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / SOUSA, Vinícius da Silva Ramos de. O efeito magnetocalórico anisotrópico nos compostos RAl2 (R = Dy, Er, Ho, Nd e Tb). 2008. 99f. Dissertação (Mestrado em Física) - Instituto de Física Armando Dias Tavares, Universidade do Estado do Rio de Janeiro, Rio de Janeiro, 2008. O efeito magnetocalórico é a base da refrigeração magnética. O potencial magnetocalórico é caracterizado por duas quantidades termodinâmicas: a variação isotérmica da entropia (ΔSiso) e a variação adiabática da temperatura (ΔTad), as quais são calculadas sob uma variação na intensidade do campo magnético aplicado ao sistema. Em sistemas magnéticos que apresentam uma anisotropia magnética é observada uma mudança no efeito magnetocalórico, isto porque este potencial torna-se fortemente dependente da direção de aplicação do campo magnético. A anisotropia em sistemas magnéticos pode levar a um efeito magnetocalórico inverso, assim como à definição de um efeito magnetocalórico anisotrópico, o qual por definição é calculado para um campo cuja intensidade é mantida constante e cuja orientação variamos de uma direção difícil de magnetização para a direção fácil de magnetização. O efeito magnetocalórico anisotrópico foi estudado para os compostos intermetálicos de terras raras do tipo RAl2 considerando-se um modelo microscópico que leva em conta as interações de troca (na aproximação de campo médio), de Zeeman e a interação de campo elétrico cristalino, que é a responsável pela anisotropia nos compostos RAl2. O efeito magnetocalórico anisotrópico foi investigado para a série RAl2 e comparado com o efeito magnetocalórico usual. / The magnetic refrigeration is based on the magnetocaloric effect. The magnetocaloric potential is characterized by the two thermodynamics quantities: the isothermal entropy change (ΔSiso) and the adiabatic temperature change (ΔTad), which are calculated upon a change in the intensity of the applied magnetic field. In anisotropic magnetic systems it is observed a change in the magnetocaloric effect, since this potential becomes strongly dependent on the direction in which the external magnetic field is applied. The anisotropy in such magnetic systems can lead to an inverse magnetocaloric effect, as well as to the definition of an anisotropic magnetocaloric effect, that by definition is calculated upon a magnetic field which intensity is kept fixed and which orientation is changed from a hard direction of magnetization to the easy direction of magnetization. This anisotropic magnetocaloric effect was performed for the RAl2 intermetallic compounds considering a microscopic model Hamiltonian that includes the Zeeman interaction, the exchange interaction (taken in the mean field approximation) and the crystalline electrical field, that is responsible for the anisotropy in the RAl2 compounds. The anisotropic magnetocaloric was fully investigated for the serie RAl2 and compared with the usual magnetocaloric effect and several curves of (ΔSiso) and (ΔTad) were obtained.