A technology with the potential to create efficient and compact refrigeration devices is an active magnetic regenerative refrigerator (AMRR). AMRRs exploit the magnetocaloric effect displayed by magnetic materials whereby a reversible temperature change is induced when the material is exposed to a change in applied magnetic field. By using the magnetic materials in a regenerator as the heat storage medium and as the means of work input, one creates an active magnetic regenerator (AMR). Although several laboratory devices have been developed, no design has yet demonstrated the performance, reliability, and cost needed to compete with traditional vapor compression refrigerators. There are many reasons for this and questions remain as to the actual potential of the technology. The objective of the work described in this thesis is to quantify the actual and potential performance of a permanent magnet AMR system. A specific device configuration known as a dual-nested-Halbach system is studied in detail. A laboratory scale device is created and characterized over a wide range of operating parameters. A numerical model of the device is created and validated against experimental data. The resulting model is used to create a cost-minimization tool to analyze the conditions needed to achieve specified cost and efficiency targets. Experimental results include cooling power, temperature span, pumping power and work input. Although the magnetocaloric effect of gadolinium is small, temperature spans up to 30 K are obtained. Analysis of power input shows that the inherent magnetic work is a small fraction of the total work input confirming the assumption that potential cycle efficiencies can be large. Optimization of the device generates a number of areas for improvement and specific results depend upon targeted temperature spans and cooling powers. A competitive cost of cooling from a dual-nested-Halbach configuration is challenging and will depend on the ability to create regenerator matrices with near-ideal adiabatic temperature change scaling as a function of temperature. / Graduate / 0548 / 0791 / 0607 / atura@uvic.ca

An alternative cycle proposed for refrigeration and gas liquefaction is active magnetic regenerator (AMR) refrigeration. This technology relies on solid materials exhibiting the magnetocaloric effect, a nearly reversible temperature change induced by a magnetic field change. AMR refrigeration devices have the potential to be more efficient than those using conventional refrigeration techniques but, for this to be realized, optimum materials, regenerator design, and cycle parameters must be determined. This work focuses on the development and validation of a transient one-dimensional finite element model of an AMR test apparatus. The results of the model are validated by comparison to room temperature experiments for varying hot heat sink temperature, system pressure, and applied heat load. To demonstrate its applicability, the model is then used to predict the performance of AMRs in situations that are either time-consuming to test experimentally or not physically possible with the current test apparatus.

The impact of B substitution in Ni50Mn35In15-xBx Heusler alloys with x = (0, 0.5, 0.75, 1, 1.1 1.5, and 2) on the structural, magnetic, transport, and parameters of magnetocaloric effect has been studied by means of room temperature XRD-diffraction, differential scanning calorimetry (DSC), and thermomagnetic measurements (in a magnetic field up to 5 T and temperature interval 5-400 K). Direct adiabatic temperature (ΔTAD) measurements have been carried out for an applied magnetic field change (ΔH) of 1.8 T. The partial substitution of In by B in Ni50Mn35In15-xBx Heusler alloys induced a non-linear temperature shift of the magnetostructural transition while Curie temperature (TC) was found to be nearly constant (TC ~ 320 K) for all compounds. The transition temperatures (T-x) phase diagram has been constructed for H = 0.005 T. The MCE parameters were found to be larger or comparable to parameters observed in other MCE materials, such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X=In, Al, and Ge) Heusler alloys. It has been demonstrated that the martensitic transformation temperature and the corresponding ∆SM can be tuned through a slight variation in composition of B in NiMnInB alloys. A magnetoresistance associated with martensitic transformation was found to be -60% for x = 0.75 at T = 240 K for a magnetic field change of 5 T. The maximum absolute value of ΔTAD = 2.5 K was observed at the magnetostructural transition for Ni50Mn35In14.5B0.5. The roles of the magnetic and structural changes on the transition temperatures are discussed.

The magnetocaloric and thermomagnetic properties of the Ni1-xCrxMnGe1.05 (for x = 0, 0.035, 0.070, 0.105, 0.110, 0.115, and 0.120) system have been studied by X-ray diffraction, differential scanning calorimetry (DSC), resistivity and magnetization measurements. A change in crystal structure from orthorhombic to hexagonal was observed in the XRD data with an increase in chromium concentrations. The values of the cell parameters and volume of the unit cell for hexagonal phase were determined. It was found that the partial substitution of Cr for Ni in Ni1-xCrxMnGe1.05 results in a first order magnetostructural transition from antiferromagnetic to ferromagnetic (FM) at TM of about132 K, 100 K, and 110 K for x= 0.105, 0.115, and 0.120, respectively. A FM to paramagnetic second order transition has been observed at TC around 200K. A magnetic entropy change of = 4.5 J/kg K, 5.6 J/Kg K, and 5.06 J/Kg K was observed in the vicinity of TC for x = 0.105, 0.115, and 0.120 respectively at ΔH = 5T. The values of the latent heat and corresponding total entropy changes have been determined from Differential Scanning Calorimetry (DSC) measurements. Magnetoresistance values of about -5% were measured near TC for x =0.105. The maximum value of refrigeration capacity (RC) and relative cooling power (RCP) was found to be 155 J/Kg and 175 J/Kg respectively for x = 0.120. A concentration-dependent (T-x) phase diagram of transition temperatures has been constructed using the magnetic and DSC data. The structural, magnetic and magnetocaloric properties of GdNi2Mnx system (for x = 0.5, 0.6, 0.8, 1.0, 1.2, 1.4, 1.5) have been studied by x-ray diffraction and magnetization measurements. A mixture of the Laves phase C15 and a phase with rhombohedral structure PuNi3- type (space group R m) was observed in the XRD data. A second order magnetic phase transition from ferromagnetic (FM) to paramagnetic (PM) was found, characterized by a long-range exchange interaction as predicted by mean field theory. The maximum value of magnetic entropy changes, -∆SM, near TC for ∆H = 5T, was found to be 3.1 J/KgK, 2.8 J/KgK, 2.9 J/KgK, and 2.5 J/Kg K for x = 0.8, 1.2, 1.4, and 1.5 respectively. In spite of the low values of ΔSM, the RC and RCP value was found to be 176 J/Kg and 220 J/Kg for the GdNi2Mn0.8 compound, respectively.

Orientadores: Sergio Gama, Nilson Antunes de Oliveira / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-08T01:08:08Z (GMT). No. of bitstreams: 1 Campos_Arianade_D.pdf: 9214751 bytes, checksum: 227e7e0b1cc697ea73f810066346ff6d (MD5) Previous issue date: 2006 / Resumo: Neste trabalho descreveremos a obtenção dos compostos da família MnA s1-xAx (A= Te,P, Sb) e Mn1-xFe xAs para várias concentrações. Dividimos este trabalho em duas etapas, a primeira via obtenção em forno de alta pressão e a segunda via obtenção em forno tubular em tubos de quartzos. A primeira etapa, ainda se dividiu em obtenção indireta e direta dos materiais. Na obtenção indireta dos materiais, focamos nosso trabalho nos compostos de MnAs e MnSb para a produção da série MnAs1-xSbx. Na obtenção direta, partimos dos elementos para sintetizar os materiais, utilizando o mesmo método adotado na obtenção indireta. Na segunda etapa do trabalho, obtemos os compostos diretamente em tubos de quartzo. As amostras produzidas foram caracterizadas por difração de raios-X, microscopia óptica, microscopia eletrônica de varredura utilizando a técnica de WDS e, finalmente, análises magnéticas para a obtenção do efeito magnetocalórico de cada material, e assim a avaliação destes materiais como possíveis candidatos a materiais refrigerantes. Após o cálculo do efeito magnetocalórico, utilizamos um modelo fenomenológico que considera a dependência da temperatura crítica da fase magnética na mudança de volume, o modelo utilizado parte das descrições propostas por Bean e Rodbell que correlaciona fortes interações magnetoelásticos com a transição de fase de primeira ordem / Abstract: In this work we describe the obtaining processes of the MnAs1-x Ax (A= Te, P, Sb) and Mn1-xFexAs series for several concentrations. We divided this work in two stages: in the first one the samples were obtained using a high pressure furnace and in the second one using a resistive furnaces with the samples sealed in quartz tubes. The first stage, can be split in direct and indirect obtaining of the materials. In the indirect obtaining of the materials, our work was focused on the MnAs and MnSb compounds for the production of the series MnAs1-xSbx. In the direct obtaining, we synthesized the materials directly from the elements, using the same method adopted in the indirect obtaining. In the second stage of the work, we obtained the samples directly from the elements in quartz tubes. The produced samples were characterized by ray-X diffraction, optical microscopy, electron microscopy using the WDS technique and finally magnetic analysis for the calculation of the magnetocaloric effect of each material and, in this way evaluate these materials as possible candidates to refrigerant materials. After the calculation of the magnetocaloric effect, we used a phenomenological model that considers the dependence of the critical temperature of the magnetic phase in the volume change, the model used part of the descriptions proposed by Bean and Rodbell [1] that correlates strong magnetoelastic interaction with the first order phase transition / Doutorado / Física da Matéria Condensada / Doutor em Ciências

The structural, electronic, magnetic, magnetocaloric, and transport properties of doped Ni-Mn-(In, Sn) based Heusler alloys were studied using neutron diffraction, x-ray diffraction (XRD), differential scanning calorimetry (DSC), high field magnetization, specific heat, x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism (XMCD), and hydrostatic pressure measurements. The adiabatic temperature change (∆Tad) by a direct method and through thermomagnetic measurements in magnetic fields up to 14 T has been performed for these alloys. Also the mixed effect of pressure and magnetic field on the transition temperature of these alloys are discussed. In order to develop new magnetocaloric and multifunctional materials, the synthesis and characterization of Heusler alloys in reduced dimensions, i.e., ribbons and thin films has been performed. In addition, the structural, magnetic, and magnetocaloric properties of Ni-based binary alloys were investigated, including saturation magnetization and Curie temperature (TC) for the possible applications in self controlled magnetic hyperthermia applications.

O efeito magnetocalórico, i.e., o aquecimento e/ou resfriamento de um material magnético sob variação do campo magnético aplicado é a base da refrigeração magnética.O efeito magnetocalórico é caracterizado pela variação da entropia em um processo isotérmico (O efeito magnetocalórico, i.e., o aquecimento e/ou resfriamento de um material magnético sob variação do campo magnético aplicado é a base da refrigeração magnética. O efeito magnetocalórico é caracterizado pela variação da entropia em um processo isotérmico (ΔSiso) e pela variação da temperatura em um processo adiabático ΔTad.Apesar dos inúmeros trabalhos experimentais e teóricos publicados nessa área, muitos aspectos desse efeito ainda não são bem compreendidos.Nesse trabalho discutimos os efeitos da anisotropia sobre as propriedades magnetocalóricas de um sistema de momentos magnéticos localizados. Para essa finalidade, utilizamos um modelo de spins interagentes com um termo de anisotropia uniaxial do tipo DS2 z , onde D é um parâmetro. Nesse modelo, em que o eixo z é a direção de fácil magnetização, a magnitude do parâmetro de anisotropia e a direção do campo magnético aplicado têm um papel fundamental no comportamento das grandezas magnetocalóricas ΔSiso e ΔTad. Realizamos um estudo sistemático para um sistema com J = 1 aplicando o campo magnético em diferentes direções. Os resultados mostram que, quando o campo magnético é aplicado ao longo da direção z, as grandezas magnetocalóricas apresentam o comportamento normal (valores positivos de ΔTad e valores negativos de ΔSiso para ΔB > 0). Quando o campo magnético é aplicado em uma direção diferente do eixo z, as grandezas magnetocalóricas podem apresentar o comportamento inverso (valores negativos de ΔTad e valores positivos de ΔSiso para ΔB > 0) ou o comportamento anômalo (troca de sinal nas curvas de ΔTad e ΔSiso). Resultados equivalentes também foram obtidos para um sistema com J = 7=2. / The magnetocaloric effect, i.e., heating and/or cooling of a magnetic material subjected to magnetic field variation is the basis of magnetic refrigeration. The magnetocaloric effect is caracterized by the entropy change in an isothermic process (ΔSiso) and by the temperature change in an adiabatic process (ΔTad). Despite the large number of experimental and theoretical works published in this area, there are many aspects of the magnetoccaloric effect which are not yet completely understood.In this work we discuss the effects of anisotropy on the magnetocaloric properties of a system of localized magnetic moments. In order to do that, we used a model of interacting spins with a uniaxial anisotropy term DS2 z , where D is a parameter. In this model, where the z axis is the easy magnetization direction, the magnitude of the anisotropy parameter and the direction of the applied magnetic field have an important role in the behavior of the magnetocaloric quantities ΔSiso and ΔTad. We perform a systematic study for a system with J = 1 by applying the magnetic field in different directions. The results show that, when the magnetic field is applied in the z direction, the magnetocaloric quantities have the normal behavior (positive values of ΔTad and negative values of ΔSiso with ΔB > 0). When the magnetic field is applied in a direction different from the z axis, the magnetocaloric quantities can show the inverse behavior (negative values of ΔTad and positive values of ΔSiso with ΔB > 0) or the anomalous behavior (change of sign in the curves of ΔTad and ΔSiso). Similar results have also been obtained for a system with J = 7=2.

O efeito magnetocalórico, i.e., o aquecimento e/ou resfriamento de um material magnético sob variação do campo magnético aplicado é a base da refrigeração magnética.O efeito magnetocalórico é caracterizado pela variação da entropia em um processo isotérmico (O efeito magnetocalórico, i.e., o aquecimento e/ou resfriamento de um material magnético sob variação do campo magnético aplicado é a base da refrigeração magnética. O efeito magnetocalórico é caracterizado pela variação da entropia em um processo isotérmico (ΔSiso) e pela variação da temperatura em um processo adiabático ΔTad.Apesar dos inúmeros trabalhos experimentais e teóricos publicados nessa área, muitos aspectos desse efeito ainda não são bem compreendidos.Nesse trabalho discutimos os efeitos da anisotropia sobre as propriedades magnetocalóricas de um sistema de momentos magnéticos localizados. Para essa finalidade, utilizamos um modelo de spins interagentes com um termo de anisotropia uniaxial do tipo DS2 z , onde D é um parâmetro. Nesse modelo, em que o eixo z é a direção de fácil magnetização, a magnitude do parâmetro de anisotropia e a direção do campo magnético aplicado têm um papel fundamental no comportamento das grandezas magnetocalóricas ΔSiso e ΔTad. Realizamos um estudo sistemático para um sistema com J = 1 aplicando o campo magnético em diferentes direções. Os resultados mostram que, quando o campo magnético é aplicado ao longo da direção z, as grandezas magnetocalóricas apresentam o comportamento normal (valores positivos de ΔTad e valores negativos de ΔSiso para ΔB > 0). Quando o campo magnético é aplicado em uma direção diferente do eixo z, as grandezas magnetocalóricas podem apresentar o comportamento inverso (valores negativos de ΔTad e valores positivos de ΔSiso para ΔB > 0) ou o comportamento anômalo (troca de sinal nas curvas de ΔTad e ΔSiso). Resultados equivalentes também foram obtidos para um sistema com J = 7=2. / The magnetocaloric effect, i.e., heating and/or cooling of a magnetic material subjected to magnetic field variation is the basis of magnetic refrigeration. The magnetocaloric effect is caracterized by the entropy change in an isothermic process (ΔSiso) and by the temperature change in an adiabatic process (ΔTad). Despite the large number of experimental and theoretical works published in this area, there are many aspects of the magnetoccaloric effect which are not yet completely understood.In this work we discuss the effects of anisotropy on the magnetocaloric properties of a system of localized magnetic moments. In order to do that, we used a model of interacting spins with a uniaxial anisotropy term DS2 z , where D is a parameter. In this model, where the z axis is the easy magnetization direction, the magnitude of the anisotropy parameter and the direction of the applied magnetic field have an important role in the behavior of the magnetocaloric quantities ΔSiso and ΔTad. We perform a systematic study for a system with J = 1 by applying the magnetic field in different directions. The results show that, when the magnetic field is applied in the z direction, the magnetocaloric quantities have the normal behavior (positive values of ΔTad and negative values of ΔSiso with ΔB > 0). When the magnetic field is applied in a direction different from the z axis, the magnetocaloric quantities can show the inverse behavior (negative values of ΔTad and positive values of ΔSiso with ΔB > 0) or the anomalous behavior (change of sign in the curves of ΔTad and ΔSiso). Similar results have also been obtained for a system with J = 7=2.

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

Neste trabalho 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.