Les matériaux nanostructurés multifonctionnels à base de terre rare (R) et métal de transition (T) présentent un intérêt croissant dans la recherche scientifique. Le développement de cet axe est basé sur la maitrise de la structure fondamentale et le comportement de la matière à l’échelle nanométrique. Dans ce travail, nous nous sommes intéressés aux alliages Pr5Co19, leurs dérivés carburés et hydrurés. Ce système cristallise dans la structure rhomboédrique de type Ce5Co19 de groupe d’espace R-3m. Le composé Pr5Co19 présente une transition magnétique de l’état ferromagnétique à l’état paramagnétique à 690 K. Une anisotropie uniaxiale avec un champ coercitif de l’ordre de 1.5 T ont été enregistrés à la température ambiante.Par ailleurs, Nous avons observé que l’insertion d’un élément léger tel que le carbone ou l’hydrogène est un moyen efficace permettant d’augmenter la température de Curie par rapport au composé parent. Les nanomatériaux, de formule générale Pr5Co19Hx, présentent des cycles d’absorption et désorption réversibles, avec une capacité d’absorption de l’hydrogène égale à 12H/f.u, soit 0.5 hydrogène par maille (H/M) au total.Parallèlement, nous nous sommes intéressés à l’étude de l’effet magnétocalorique des intermétalliques de type Pr-Co. Le composé Pr5Co19 présente un effet magnétocalorique géant de l’ordre de 5.2 J/kg.K pour un faible champ appliqué.Les nanomatériaux intermétalliques de type Pr5Co19 peuvent être ainsi considérés comme des composés multifonctionnels. Grâce à leurs propriétés structurales, magnétiques et magnétocaloriques, ils s’avèrent être de bons candidats dans le domaine des aimants permanents, mais aussi pour la réfrigération magnétique à haute température et pour le stockage de l’hydrogène, vu le besoin croissant en énergie alternative moins polluante / Multifunctional nanomaterials based on rare-earth (R) and transition metal (T) present a major interest in scientific research. We are interrested in the Pr5Co19 alloy. This system crystallizes in the rhombohedral Ce5Co19-type structure with space group R-3m. The Curie temperature Tc is about 690 K. We determined the value of the magnetization at saturation MS = 83 Am2 / kg using the approach law to saturation. A uniaxial anisotropy with a coercive field equal to 1.5 T at room temperature were obtained.Moreover, we have observed that the insertion of a light element such as carbon or hydrogen, allows to increase the Curie temperature of the system. The Pr5Co19Hx hydrides present a reversible cycle of absorption/desorption, with a hydrogen absorption capacity equal to 12H / f.u, or 0.5H / M in total.We are also interested in the study of the magnetocaloric effect of the intermetallics Pr-Co type. We have shown that Pr5Co19 compound has a giant magnetocaloric effect, of about 5.2 J / kg.K at low field.The intermetallic nanomaterials Pr5Co19 could be used as a multifunctional compound. These results indicate that it is an attractive alloy due to its structural, magnetic and magnetocaloric properties. It could be good candidates for permanent magnets, but also for magnetic refrigeration at high temperature and for hydrogen storage

The goals of this work are the optimization of the magnetocaloric effect in Gadolinium thin film structures. We approach this issue from two directions, that of process optimization and of interface effects. Past results showed Gd2O3 in our Gadolinium thin films, and the presence of such oxide seemed to grow with the temperature at which the film was grown or annealed. Comparison of samples grown without chamber gettering to those that were gettered show differences in their structural and magnetic properties, and we conclude that gettering is an effective step in enhancing the quality of Gd thin film samples. Early work with Gd/W heterostructures showed a diminished magnetization of the interfacial gadolinium, which reduces the magnetocaloric response as magnetic entropy is proportional to m2/3. It is known that Fe interfaces can boost the Gd moments per atom to above that seen in bulk. As such, we fabricated a series of Fe/Gd heterostructures to study the effects on the structural and magnetic properties of Gd thin films. The use of Fe as a base layer shows increased high frequency oscillations in X-ray reflectivity measurements, indicating sharp interfaces between Gd and Fe. The magnetocaloric measurements produce a magnetic entropy curve with a novel tail extending leftward, making this an improved material over Gd for applications around 240K. All the same, vector magnetometry is needed to ensure that such tail is not due to rotations within the plane and is a direction for further study.

This thesis documents the work and research effort on the design, fabrication and testing of a magnetocaloric MEMS microcooler, focusing on the testing of the microcooler at low magnetic fields. The phenomenon of magnetocaloric effect (MCE), or adiabatic temperature change, which is obtained by heating or cooling magnetic materials due to a varying magnetic field, can be exploited in the area of magnetic refrigeration as a reliable, energy-efficient cooling system. In particular, its applications are being explored primarily in cryogenic technologies as a viable process for the liquefaction of hydrogen. The challenge for magnetic refrigeration is that the necessary MCE is most easily achieved with high magnetic fields (5-6 Tesla) provided by superconducting magnets. However, a significant magnetocaloric effect can be exhibited at lower magnetic fields (1-2 Tesla) by carefully controlling initial temperature conditions as well as by selecting, preparing and synthesizing the optimal fabrication process of Silicon (Si) wafers. A microcooler was integrated based on previous works of others and tested. Finally, testing of the magnetocaloric effect was conducted and results analyzed. Experimental results in these domains demonstrate that magnetic refrigeration can be part of the best current cooling technology, without having to use volatile, environmentally hazardous fluids. The MEMS magnetocaloric refrigerator demonstrated a ~ -12°C change in the temperature of cooling fluid at a magnetic field of 1.2 T.

In this project we studied the effect of different parameters on heat transfer in two-dimensional microchannels, microtubes and also tube-in-block heat exchangers for various engineering applications. These included the use of flow restrictions to enhance local heat or mass transfer rate, enhancement of conjugate heat transfer with discrete heating and magnetic coolers (or heaters) associated with magnetic refrigeration system. The results of this research will help in designing the heating or cooling systems and selection of their appropriate geometrical dimensions and materials for specific applications. Types of problems studied in this project are: steady state analysis of forced convection around a restricted flow passage in a micro channel, effect of protrusions in a microtube or microchannel for conjugate heat transfer with uniform or discrete heating and transient analysis of heat transfer in trapezoidal microchannels under time varying heat source. For each of these problems a numerical simulation model was developed. The mass, momentum, and energy conservation equations were solved in the fluid region and energy conservation in the sold region to arrive at the velocity and the temperature distributions. Detailed parametric study was carried out for each problem. The parameters were shape and size of the restriction/protrusion, number of restrictions/protrusions, wall thickness, Reynolds number, solid materials and working fluids. The results showed that in microtubes the local value of Nusselt number increases at the restriction/protrusion and the global value for the whole tube is somewhat lower. For a two-dimensional microchannel, both the local Nusselt number at the restriction/protrusion as well as the global Nusselt number for the entire channel is higher. In the trapezoidal channels the results showed that with the increase in Reynolds number, the outlet temperature decreased and the average heat transfer coefficient increased. With an increase in magnetic field there was an increase in the solid fluid interface temperature and in turn the average heat transfer coefficient increased. With a decrease in the channel height and width there was an increase in the average Nusselt number in the channel.

The objective of this work is to assess the potential of Mn-Fe-Si-P for magnetic heat pump applications. Mn-Fe-Si-P is a first order transition magnetocaloric material made from safe and abundantly available constituents. A significant magnetocaloric effect occurs at the transition temperature of the material. The transition temperature can be tuned by changing the atom ratios to a region near room temperature. Mn-Fe-Si-P in magnetic heat pumps is investigated by determining the material's properties, 1D system modeling and experiments in a magnetic heat pump prototype. We characterize six samples of Mn-Fe-Si-P, based on their heat capacity and magnetization. The reversible component of the adiabatic temperature change is found from the entropy diagram and compared to cyclic adiabatic temperature change measurements. Five of the six samples are selected to be formed into epoxy xed crushed particulate beds, which can be installed into a magnetic heat pump prototype. A system model is constructed to understand the losses of the magnetic heat pump prototype. Several experiments are performed with Gd with rejection temperatures around room temperature. Including dead volume and casing losses improves the modeling outcomes to match the experimental results closer. Experiments with Mn-Fe-Si-P are performed. Five materials are formed into modular beds that can be combined into two layer configurations. Six experimental configurations are tested, one single layer regenerator test with a passive lead second layer, and five experiments using two layers with varying transition temperature spacing between the materials. The best performance of the beds was found at close spacing at suitable rejection temperatures. It was found that at far spacing, the performance of stronger materials would produce a lower temperature span than that of weaker materials at close spacing. The experiments provide results that are used to validate the system modeling approach using the material data obtained of the Mn-Fe-Si-P samples. We integrate material properties into a system model. A framework is proposed to take into account the hysteresis. This framework shows an improvement of the predicted trend for a single layer case. The proximity of simulation and experimental multi-layering results are dependent on the rejection temperature. At the higher end of the rejection temperature the modeling results over-predict the temperature span around the active region. At lower rejection temperatures the simulation under-predicts the experimental temperature span. The inclusion of experimental pressure drop improved the trends found at higher rejection temperatures. A further improvement was found varying the interstitial heat transfer term. Modeling future research should focus on characterizing the thermo-hydraulic closure relationships for crushed particulate epoxy xed beds, and improvements to the heat loss model. Mn-Fe-Si-P is able to produce a temperature span, when a suitable set of Mn-Fe- Si-P materials are selected based on minimal hysteresis, making it a viable material for magnetic heat pump applications. The performance of Mn-Fe-Si-P is further improved by layering materials with a closely spaced transition temperature. Future research should focus on increasing the production of Mn-Fe-Si-P materials with low hysteresis, and improving the regenerator matrix geometry and stability. / Graduate

Orientadores: Sergio Gama, Ekkes Bruck / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-10T04:26:45Z (GMT). No. of bitstreams: 1 Caron_Luana_D.pdf: 3120809 bytes, checksum: 0f270249e6bc452525873f2d4479ba9d (MD5) Previous issue date: 2008 / Resumo: Nesta tese de doutoramento são apresentados os resultados do estudo das propriedades magnéticas, magnetocalóricas e estruturais de algumas séries de compostos que são de interesse para aplicação em refrigeração magnética baseada no efeito magnetocalórico. Os métodos de preparação da série MnFe P1-xAsx são estudados de forma a otimizar o tempo de preparação e as propriedades magnétocalóricas. Uma nova série de compostos baseada na anterior, a MnFeGe1-xSix foi descoberta, apresentando transições de fase magnética de segunda ordem e uma variação linear dos parâmetros de rede em função da concentração de Si no intervalo 0 £ x £ 0,7. Também foi descoberto, associado à uma transição magnética de segunda ordem, o efeito magnetocalórico no composto MnFeSn cujo TC situa-se em torno da temperatura ambiente. Foi feito o estudo do efeito magnetocalórico dos compostos baseados no Mn2Sb com o Mn parcialmente substituído por Cr, V, Co e Cu e o Sb substituído por Ge. Nestes compostos uma transição do tipo Exchange Inversion é induzida pelas substituições, transformando o estado ferrimagnético em antiferromagnético em baixa temperatura, dando origem ao chamado efeito magnetocalórico inverso. Ainda foi desenvolvido um modelo fenomenológico para descrever tal transição e o efeito magnetocalórico associado. Por fim é reportado o efeito magnetocalórico colossal nos compostos M n1-xCux As, devido ao qual os métodos de medida magnéticos do efeito magnetocalórico são revistos. A partir dos resultados em diferentes procedimentos de medida, é proposta uma forma de medir o efeito em materiais altamente histeréticos que não leva a resultados espúrios / Abstract: On this PhD thesis some results on the magnetic, magnetocaloric and structural properties of some series of compounds suitable for applications on magnetocaloric effect-based refrigeration are presented. The FeMnP1-xAsx series preparation methods are studied in order to optimize their magnetocaloric properties as well as to shorten its preparation time. A new series of compounds based on the previous one was studied, the MnFeGe1-xSix. These compounds present a second-order magnetic phase transition and a linear change in lattice parameters with Si content on the 0 £ x £ 0.7 range. Also associated with a second-order phase transition, the magnetocaloric effect on FeMnSn was discovered around room-temperature. A careful study of Mn2Sb-based compounds with Mn partially substituted by Cr, V, Co and Cu and Sb by Ge was performed. On these compounds an Exchange Inversion transition is induced by substitutions taking the material from the ferrimagnetic to the antiferromagnetic state with decreasing temperature, giving rise to the so-called inverse magnetocaloric effect. A phenomenological theoretical model was also developed to describe such transitions and their associated magnetocaloric effect. Finally we report on the colossal magnetocaloric effect on Cu-substituted MnAs compounds. Due to this compound¿s unusual behavior, the magnetic measurements of the magnetocaloric effect are reviewed. Based on the results of different measurement procedures a new method of measurement for highly hysteretic compounds is proposed which leads to non spurious results / Doutorado / Materiais Magneticos e Propriedades Magneticas / Doutor em Ciências

L’objectif de ce travail est de développer un modèle multi-physique et multi-échelle de Régénérateur Magnétique Actif en vue d’optimiser le fonctionnement d’un système de réfrigération magnétique. Le modèle numérique développé lors de cette thèse est un modèle multi-physique et multi-échelle qui prend en compte trois phénomènes distincts (le magnétisme, la fluidique et le transfert de chaleur), chacun à une échelle différente (micro-échelle, mini-échelle et macro-échelle). Une étude expérimentale a été menée afin de déterminer les propriétés thermophysiques des matériaux magnétocaloriques et d’intégrer les résultats de ces mesures dans le modèle numérique. Le modèle a été validé par une comparaison avec des données expérimentales et les résultats obtenus ont montré une bonne corrélation entre les résultats du modèle et les mesures. Enfin, le modèle a été exploité par une analyse de sensibilité des paramètres en vue d’étudier le fonctionnement ainsi que les performances du système. Ce modèle permettra d’identifier une stratégie de conception optimale d’un Régénérateur Magnétique Actif afin de concevoir des systèmes de réfrigération magnétique performants. / The objective of this work is the developing of a multi-physics and multi-scale numerical model of an Active Magnetic Regenerator in order to optimize the operation of a magnetic refrigeration system. The numerical model developed in this thesis is a multi-physics and multi-scale model that takes into account simultaneously three distinct phenomena (magnetism, fluid flow and heat transfer), each on a different scale (micro-scale, mini-scale scale and macro-scale). An experimental study was conducted to determine the thermophysical properties of magnetocaloric materials and integrate the results of these measurements in the numerical model. The model has been validated by comparison with experimental data and the results showed a good correlation between the model results and measurements. Finally, the model was exploited by an analysis of parameter sensitivity allowing studying the operation and performance of the system. This model will identify an optimal design strategy of an Active Magnetic Regenerator in order to design high-performance magnetic refrigeration systems.

The effect of doping on the crystal structure, magnetic, magnetocaloric and transport properties of MnM′Ge (M′ = Ni, Co) intermetallic compounds and NiMnX (X = Sn, In) Heusler alloys have been studied by room temperature X-ray diffraction (XRD), differential scanning calorimetry (DSC), and magnetization measurements. The studied magnetic systems include Ni1-xCrxMnGe1.05 (0 ≤ x ≤ 0.120), Mn1-xAlxCoGe (0 ≤ x ≤ 0.05), MnCo1-xZrxGe (0.01 ≤ x ≤ 0.04), Mn1-xAgxCoGe (0.01 ≤ x ≤ 0.10), Ni50-xRxMn35Sn15 (x = 0, 1 and R = La, Pr, Sm), Ni43-xRxMn46Sn11 (x = 0, 1 and R = Pr, Gd, Ho, Er), and Ni50Mn35In15-xBix (0 ≤ x ≤ 1.5).A temperature induced first-order structural transition characterized by a change in crystal structure from high temperature austenite phase (AP) with Ni2In-type Hexagonal structure to low temperature martensite phase (MP) with TiNiSi-type orthorhombic structure was observed at T = TM (martensitic transition temperature) in some of the MnM′Ge-based compounds. The partial substitution of doping elements such as Cr, Al, Zr, and Ag resulted in a decrease in TM and at certain concentration, TM was found to decrease below / coincide with the ferromagnetic transition temperature (TC) of AP. Therefore, such system show a first-order magnetostructural transition (MST).In Ni1-xCrxMnGe1.05, a MST from antiferromagnetic (AFM) orthorhombic to ferromagnetic (FM) hexagonal phase was observed for 0.105 ≤ x ≤ 0.120. Both direct and inverse MCE were observed in this compound. The peak values of the magnetic entropy change (ΔSMpeak ) in the vicinity of TC for ΔH = 5T were found to be 4.5 J/kg K, 5.6 J/Kg K, and 5.1 J/Kg K for x = 0.105, 0.115, and 0.120 respectively. A magnetic field-induced transition from an AFM to a FM state in the martensite structure was observed in annealed Ni0.895Cr0.105MnGe1.05 melt-spun ribbons, which led to a coupled MST from a FM martensite to a PM austenite phase with a large change in magnetization. As a result of the field-induced MST, a large ΔSMpeak value of 16.1 J kg-1 K-1 (which is about a four times larger than the bulk) and Refrigeration capacity (RC-1) =144 J kg-1 at μ0∆H = 5 T was found. It was also found that the ribbon samples showed excellent magnetic reversibility that is important for application. MCE parameters, adiabatic temperature change (∆Tad) and |〖∆S〗_M |, with maximum value of ~ 2.6 K (µoH = 10 T) and 4.4 J kg-1 K-1(µo∆H = 5 T), respectively, were observed in the vicinity of TC. The ∆Tad (T) curves obtained for µoΔH = 10 T and magnetization isotherms were found to be completely reversible, which indicates the reversibility of the MCE in this system. A large temperature span (of about 61 K) and a non-saturating behavior of ∆Tad were observed at magnetic fields up to 10 T. The adiabatic temperature change was found to be a linear function of (µoH)2/3 near TC in accordance with Landau’s theory of phase transitions.In MnCoGe compounds doped with Al, Zr, and Ag, a tunable MST from the paramagnetic hexagonal to ferromagnetic orthorhombic phase was observed. The maximum ΔSM values of about 18, 7.2, and 22 J kg-1 K-1for ∆H = 5T at TM was observed for Al, Zr, and Ag doped compounds, respectively. The corresponding maximum value of RC was found to be (303, 266, and 308) JKg-1.The new compounds containing low concentration of rare earth (R) metals: Ni50-xRxMn35Sn15, Ni43-xRxMn46Sn11, with R = La, Pr, Sm, Gd, Ho, Er and Ni50Mn35In15-xBix were synthesized. The compounds crystallized in the cubic L21 austenite phase (AP) or a mixture of AP and low temperature martensitic phase (MP) at room temperature. For Ni50-xRxMn35Sn15 and Ni43-xRxMn46Sn11 alloys, TM shifted towards higher temperature with rare-earth doping, thus stabilizing the MP at higher temperature. A maximum shift in TM by ~ 60-62 K relative to the parent compound (TM = 190-195 K) was observed for the Ni49LaMn35Sn15 and Ni42PrMn46Sn11. TM shifted towards lower temperature if Bi is placed in In position in Ni50Mn35In15-xBix. A maximum shift of ~ 36 K was detected for x = 1.5. Abnormal shifts in TC and TM to higher temperatures were observed at high field for Bi concentration ≥ 0.5.The ground state magnetization decreased with the rare-earth doping and increasing Bi content. The compounds exhibit both inverse and normal magnetocaloric effects. Large values of ∆SM = 12 (Ni49PrMn35Sn15), 32 Jkg-1K-1(Ni42PrMn46Sn11), 28 Jkg-1K-1 (Ni42GdMn46Sn11), 25 Jkg-1K-1 (Ni42HoMn46Sn11), 40 J/kg K (Ni50Mn35In15) and 34 J/kg K (Ni50Mn35In15-xBix, x = 0.25) were found at TM for ∆H = 5T that can be tuned in a wide temperature range. RC values ranging from 267-336 Jkg-1 at TC, 182 -250 Jkg-1 at TM and 144-165 Jkg-1 at TC were found with ∆H = 5T for Ni50-xRxMn35Sn15, Ni43-xRxMn46Sn11, and Ni50Mn35In15-xBix, respectively. Significant magnetoresistance (MR) values of -30%, -20 % and -30% were observed in Ni49LaMn35Sn15, Ni42GdMn46Sn11, and Ni50Mn35In14.5Bi0.5 compounds, respectively, at TM and ∆H = 5T. A large exchange bias effect with HEB ~ 1.1 kOe at 10 K was observed for the Ni42PrMn46Sn11 compound in its MP. Thus, the pronounced multifunctional properties such as shape memory effects, MCE, EB, and MR make these new systems promising for the ongoing development of magnetocaloric and multifunctional technologies.

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