Electron-lattice interactions are often considered not to play a major role in material's properties as they are assumed to be small, the second-order effects. However, this study shows the importance of taking these effects into account in the simulations. My results demonstrate the impact of the electron-lattice interaction on the physics of the material and our understanding from it. One way to study these effects is to add them as perturbations to the unperturbed Hamiltonians in numerical simulations. The main objective of this thesis is to study electron-lattice interactions in molecular and magnetic crystals. It is devoted to developing numerical techniques considering model Hamiltonians and first-principles calculations to include the effect of lattice vibrations in the simulations of the above mentioned classes of materials. In particular, I study the effect of adding the non-local electron-phonon coupling on top of the Holstein Hamiltonian to study the polaron stability and polaron dynamics in molecular crystals. The numerical calculations are based on the semi-empirical Holstein-Peierls model in which both intra (Holstein) and inter (Peierls) molecular electron-phonon interactions are taken into account. I study the effect of different parameters including intra and intermolecular electron-phonon coupling strengths and their vibrational frequencies, the transfer integral and the electric field on polaron stability. I found that in an ordered two dimensional molecular lattice the polaron is stable for only a limited range of parameter sets with the polaron formation energies lying in the range between 50 to 100 meV. Using the stable polaron solutions, I applied an electric field to the system and I observed that the polaron is dynamically stable and mobile for only a limited set of parameters. Adding disorder to the system will result in even more restricted parameter set space for which the polaron is stable and moves adiabatically with a constant velocity. In order to study the effect of temperature on polaron dynamics, I include a random force in Newtonian equations of motion in a one dimensional molecular lattice. I found that there is a critical temperature above which the polaron destabilizes and becomes delocalized. Moreover, I study the role of lattice vibrations coupled to magnetic degrees of freedom in finite temperature paramagnetic state of magnetic materials. Calculating the properties of paramagnetic materials at elevated temperatures is a cumbersome task. In this thesis, I present a new method which allows us to couple lattice vibrations and magnetic disorder above the magnetic transition temperature and treat them on the same footing. The method is based on the combination of disordered local moments model and ab initio molecular dynamics (DLM-MD). I employ the method to study different physical properties of some model systems such as CrN and NiO in which the interaction between the magnetic and lattice degrees of freedom is very strong making them very good candidates for such a study. I calculate the formation energies and study the effect of nitrogen defects on the electronic structure of paramagnetic CrN at high temperatures. Using this method I also study the temperature dependent elastic properties of paramagnetic CrN. The results highlight the importance of taking into account the magnetic excitations and lattice vibrations in the studies of magnetic materials at finite temperatures. A combination of DLM-MD with another numerical technique namely temperature dependent effective potential (TDEP) method is used to study the vibrational free energy and phase stability of CrN. We found that the combination of magnetic and vibrational contributions to the free energy shifts down the phase boundary between the cubic paramagnetic and orthorhombic antiferromagnetic phases of CrN towards the experimental value. I used the stress-strain relation to study the temperature-dependent elastic properties of paramagnetic materials within DLM-MD with CrN as my model system. The results from a combinimation of DLM-MD with another newly developed method, symmetry imposed force constants (SIFC) in conjunction with TDEP is also presented as comparison to DLM-MD results.I also apply DLM-MD method to study the electronic structure of NiO in its paramagnetic state at finite temperatures. I found that lattice vibrations have a prominent impact on the electronic structure of paramagnetic NiO at high temperatures and should be included for the proper description of the density of states. In summary, I believe that the proposed techniques give reliable results and allow us to include the effects from electron-lattice interaction in simulations of materials.

Particle accelerators produce beams of high-energy particles, which are used for both fundamental and applied scientific research and are critical to the development of accelerator driven sub-critical reactor systems. An effective magnetic shield is very important to achieve higher quality factor (Qo) of the cryomodule of a particle accelerator. The allowed value of field inside the cavity due to all external fields (particularly the Earth’s magnetic field) is ~15 mG or less. The goal of this PhD dissertation is to comprehensively study the magnetic properties of commonly used magnetic shielding materials at both cryogenic and room temperatures. This knowledge can be used for the enhanced design of magnetic shields of cryomodes (CM) in particle accelerators. To this end, we first studied the temperature dependent magnetization behavior (M-H curves) of Amumetal and A4K under different annealing and deformation conditions. This characterized the effect of stress or deformation induced during the manufacturing processes and subsequent restoration of high permeability with appropriate heat treatment. Next, an energy based stochastic model for temperature dependent anhysteretic magnetization behavior of ferromagnetic materials was proposed and benchmarked against experimental data. We show that this model is able to simulate and explain the magnetic behavior of as rolled, deformed and annealed amumetal and A4K over a large range of temperatures. The experimental results for permeability are then used in a finite element model (FEM) in COMSOL to evaluate the shielding effectiveness of multiple shield designs at room temperature as well as cryogenic temperature. This work could serve as a guideline for future design, development and fabrication of magnetic shields of CMs.

As ligas de FeRh apresentam um comportamento não usual quando encontradas próximas da composição equiatômica, sendo observada uma transição de fase magnetoestrutural de primeira ordem, na qual o sistema passa de um estado antiferromagnético para um estado ferromagnético com a temperatura crítica próxima da temperatura ambiente. A temperatura crítica de transição é fortemente dependente da composição da liga, das técnicas de produção e dimensionalidade da amostra, além de fatores externos como pressão e campo magnético. No presente trabalho foram depositados, via magnetron sputtering, filmes de FeRh (monocamadas) e FeRh/Fe (bicamadas) sobre substratos monocristalinos de MgO (001), sendo utilizado duas temperaturas de deposição diferentes: 798 K e 913 K. A estrutura cristalina dos filmes foi analisada através de técnicas de medidas de difração de raios X (varredura &theta - 2 &theta, varredura em &phi e rocking curves) e as composições e espessuras dos filmes foram analisadas por medidas de RBS. A principal diferença morfológica encontrada entre as amostras foi uma melhor uniformidade na distribuição de orientações dos grãos cristalinos nos filmes depositados na temperatura mais elevada. As propriedades magnéticas, medidas por meio de um VSM equipado com um criostato e um forno, evidenciaram diferenças entre as amostras depositadas nas diferentes temperaturas mencionadas, observando-se variações significativas nas temperaturas de transição de fase e diferentes larguras dos ciclos térmicos. Também foi observado, em todas as amostras, coexistência de fases antiferromagnética e ferromagnética na camada de FeRh, principalmente na região de baixas temperaturas. As amostras depositadas em 798 K foram mais favoráveis à formação da fase FeRh antiferromagnética e, no caso das bicamadas, também apresentaram um melhor acoplamento entre as camadas de FeRh e Fe que as amostras depositadas em 913 K, favorecendo um incremento do campo coercivo e da magnetização remanente relativa do sistema. / FeRh alloys, near the equiatomic composition, present an unusual magneto structural first-order phase transition in which the system changes from antiferromagnetic to ferromagnetic state at a critical temperature close to ambient temperature. The critical transition temperature is strongly dependent on the alloy composition, production techniques and dimensionality of the sample, as well as external factors such as pressure and magnetic field. In the present work, FeRh (monolayers) and FeRh/Fe (bilayers) films were deposited on monocrystalline MgO (001) substrates, via magnetron sputtering, at two different deposition temperatures: 798 K and 913 K. The crystalline structures of the films were analyzed by using different techniques of X-ray diffraction (&theta - 2 &theta scan, &phi scan and rocking curves). The compositions and thicknesses of the films were analyzed by RBS measurements. The main morphological difference between the samples was a better uniformity in the distribution of crystalline grain orientations in the films deposited at higher temperature. The magnetic properties, which were measured by a VSM equipped with a cryostat and an oven, revealed differences between the samples obtained at different temperatures. Significant variations in the critical phase transition temperatures and different widths of thermal cycles were observed. It was also observed, in all samples, coexistence of antiferromagnetic and ferromagnetic phases in the FeRh layer, mainly at low temperatures. The samples deposited at 798 K were more favorable to the formation of the antiferromagnetic FeRh phase. In addition, for the bilayers deposited at 798 K, it was observed a better coupling between the FeRh and Fe layers in comparison to samples deposited at 913 K, favoring an increase in the coercive field and the remanence magnetization.

Nanomateriais de fct-FePt, SmCo e Carbeto de Cobalto têm sido bastante estudados para a aplicação em gravação magnética e imãs de elevado desempenho, devido as suas energias magnetocristalinas e coercividades elevadas. Nanopartículas de FePt unidimensionais foram propostas na tentativa de obter melhora no alinhamento magnético das estruturas auto-organizadas. Neste trabalho, a formação de nanobastão e nanofios de FePt foi estudada através da presença de oleilamina e pequena quantidade de monóxido de carbono liberado pelo pentacarbonilferro(0). Estes dois parâmetros foram estudados a fim de analisar a influência no alongamento das nanopartículas e verificou-se que ambos atuam sinergicamente. Foram obtidos tanto nanofios de FePt ramificados de comprimento de 20-100 nm quanto nanobastões de FePt de 20-60 nm de comprimento, ambos com diâmetro de 2-3 nm. Todas as nanopartículas sintetizadas foram obtidas na fase cúbica de face centrada e o processo de tratamento térmico nas temperaturas de 450 oC e 560 oC levou a conversão para a fase tetragonal de face centrada, com custo da sinterização das nanopartículas. Os nanobastões, entretanto, apresentaram maior estabilidade térmica se comparado com o nanofio ramificado, obtendo propriedade ferromagnética na amostra. Alternativamente, têm sido obtidos satisfatoriamente nanobastões de platina para posterior recobrimento com ferro para a formação da liga FePt após o processo de recozimento. Na síntese de SmCo, foi estudada a formação da liga diretamente por via química através do uso de redutores comumente utilizandos em síntese de nanopartículas, porém foi possível observar apenas uma pequena quantidade da liga Sm2Co17 quando se utiliza o boroidreto de sódio. Isto se deve, principalmente, ao alto potencial de redução de Sm3+ e a sua instabilidade química. Entretanto, foram desenvolvidos métodos promissores para a obtenção de nanopartículas de CoO e SmCoO com tamanho e forma controlada. Além destes sistemas, tem sido obtidas diretamente através de síntese química nanopartículas de carbeto de cobalto com coercividade de até 2,3 kOe e magnetização de 45 emu/g, além de desenvolver um método geral de síntese de carbetos de outros metais. / SmCo, fct-FePt and CoC nanomaterials have been studied for application in magnetic recording and permanent magnets due to theirs high coercivity and magnetocrystalline anisotropy. One-dimensional FePt nanoparticles were proposed to improve the magnetic alignment of self-assembled system. In this work, the formation of FePt nanorods and nanowires was studied by using a small amount of carbon monoxide from the precursor pentacarbonyliron(0) and oleylamine. Both parameters of synthesis were studied and was verified that they influence the one-dimensional growth of FePt. In fact, branched FePt nanowires with 20 - 100 nm of length and nanorods with 20 - 60 nm were obtained, both with 2-3 nm of diameters. The FePt nanoparticles were obtained in face centered cubic phase and the transformation to face centered tetragonal phase was carry out in the temperatures of 450 oC and 560 oC, which led the formation of sintered nanoparticles. FePt nanorods have better thermal stability than nanowires according the results obtained. The platinum nanorods covered with iron oxide also were obtained to formation of FePt by thermal treatment. In concern of SmCo syntheses, the formation of SmCo phase directly by chemical synthesis was investigated by using some reduction agent, but was obtained a small amount of smco phase only if the sodium borohydrate was used in the synthesis. This could be occurred due to high reducing potential of Sm3+ and its chemical instability. However, some methods were obtained to obtain CoO and SmCoO nanoparticles with size and shape control. Furthermore, cobalt carbide nanoparticles were well obtained with coercivity of 2,3 kOe and magnetization of 45 emu/g, and a new general method to obtain metals carbides was developed.

O objetivo do presente trabalho foi desenvolver novos materiais magnéticos para ímãs de alta performance. Duas classes de materiais foram estudadas: materiais a base de (Nd,Sm)5(Fe,MT)17, onde MT é um metal de transição, e materiais nanocristalinos a base de (Nd,Pr)FeB com adições de TiC. As ligas (Nd,Sm)5(Fe,MT)17 foram preparadas por fusão em forno de arco e posteriormente foram tratadas termicamente por longos períodos (no mínimo 30 dias). Tentamos melhorar as propriedades magnéticas por meio de substituições químicas (Ti, Co, Mn, etc.) e/ou por introdução intersticial de deutério ou nitrogênio. As amostras foram caracterizadas via análise termomagnética (TMA), magnetometria de baixas temperaturas, difração de raios X e de nêutrons, e espectroscopia Mössbauer. Os principais resultados foram: a) aumento de Tc de até 70 º C; b) localização dos átomos de deutério na redecristalina. Ligas de (Nd,Pr) com adição de TiC foram preparadas por fusão de arco, sendo processadas via "melt spinning" e passando por tratamentos térmicos variados. Os promissores resultados na literatura para Nd2Fe14B+TiC foram obtidos também para Pr2Fe14B + TiC, mas não para os sistemas compostos pela fase φ e Fe3B com TiC. Porém, bons resultados foram obtidos em sistemas compostos pelas fases φ e α–Fe, com aumento de até 30% nos valores de campo coercivo Hc e aumentos de até 15% de (BH)max. / The aim of the present work was to develop new improved magnetic materials suitable for permanent magnets. Two kinds of materials were studied: (Nd,Sm)5(Fe,MT)17 based materials, were MT is a transition metal and, (Nd,Pr)FeB nanocrystalline materials (exchange spring magnets) with TiC additions. The 5:17 alloys were melted in an arc melting furnace followed by a long annealing (at least 30 days). We tried to improve the magnetic properties by means of chemical substitutions (Ti, Co, Mn, etc.) and/or by addition of interstitial atoms of deuterium or nitrogen. The samples were characterized by means of thermomagnetic analysis (TMA), low temperature magnetometry, X ray and neutron diffraction, and Mössbauer spectroscopy. The main results were: a) increase of Tc temperature (up to 70 ºC) and; b) determination of interstitial sites for deuterium. (Nd,Pr)FeB alloys with TiC additions were melted in an arc melting furnace, being processed in a melt spinner system. After the samples were heat treated at different temperatures. The promissing literature results for Nd2Fe14B+TiC were also obtained for Pr2Fe14B + TiC, but not for systems composed by Pr2Fe14B and Fe3B phases with TiC additions. However, good results were obtained in systems composed by Pr2Fe14B and α-Fe with TiC additions, with 30% increase on coercive field values Hc, and 15% increase on (BH)max.

Thermomagnetic motors can represent an alternative for the conversion of heat into mechanical energy, limited by the critical transition temperature (TC) of the used magnetic materials. Thus, by using materials with a TC close to room temperature, the energy available in the form of low-grade heat sources can be converted into useful mechanical work. This thesis proposes the development of a thermomagnetic motor to be operated with heat sources at temperatures in the range from 343 to 353 K, and a heat sink at room temperature, using water as the heat transfer fluid, presenting a novel approach to the construction of thermomagnetic devices. The design of this thermomagnetic motor was developed with the intent of producing a rotary movement, working similarly to an electric stepper motor, where instead of the electromagnetic coils being activated by an electric current, plates of a magnetic material change their magnetization state, due to a change in their temperature caused by the heat transfer with the heat transfer fluid. The analysis of the thermomagnetic motor proposed was done with the adoption of an integrated approach of numerical simulation and experimental validation. The evaluation of the motor is divided into the three main physical phenomena it encompasses: the magnetic field source, the heat transfer processes involved in the change of temperature of the magnetic material, and the system dynamics and power production. Each of these systems was modeled using computational tools. These models were then validated according to the data measured, obtained from a test stand of an idealized thermomagnetic motor, and for a rotary thermomagnetic motor. This methodology allowed a more comprehensive understanding of the critical working principles of the motor developed, and with that a fast advancement of the technology through a validated computational model. The computational models helped to identify the critical components to be improved in the development of these motors. These parameters can be guidelines for the design of thermomagnetic motors. One of the ways identified to produce a significant performance improvement, in the simulations, was the adoption of a control strategy that promotes the regeneration of heat in the plates of magnetic material, through which an improvement in the efficiency of 2.7 times could be achieved. / Motores termomagnéticos representam uma alternativa para a conversão de calor em energia mecânica, limitada apenas pela temperatura crítica da transição termomagnética (TC) dos materiais magnéticos. Ao usar materiais com TC próximo à temperatura ambiente, pode-se realizar a conversão da energia contida nas chamadas fontes pobres de calor, produzindo trabalho mecânico útil. Esta tese propõe o desenvolvimento de um motor termomagnético para operação com fontes de calor com temperaturas entre 343 e 353 K, e resfriamento à temperatura ambiente, utilizando a água como fluído de troca térmica, apresentando uma abordagem inovadora para dispositivos termomagnéticos. O motor foi projetado para produção de movimento rotativo de um eixo, per meio de um princípio similar ao de um motor de passo, no qual em vez de bobinas ativadas pela passagem de corrente elétrica, placas de material magnético sofrem uma mudança em seu estado de magnetização, devido à mudança de temperatura, causada pela troca de calor com a água. A análise do motor termomagnético proposto foi realizada com a adoção de uma abordagem integrada de simulações numéricas e validação experimental, dividindo a avaliação dos motores nos três principais fenômenos físicos envolvidos em seu funcionamento: a fonte de campo magnético, o processo de troca térmica envolvido na mudança de temperatura do material magnético, a dinâmica do sistema e produção de potência. Cada um destes sistemas foi modelado usando ferramentas computacionais. Os resultados obtidos foram então validados utilizando dados experimentais, obtidos a partir da construção e caracterização de uma bancada de testes para um motor termomagnético idealizado, e também para o motor termomagnético rotativo construído. Esta metodologia propiciou maior entendimento das funções críticas do motor desenvolvido, e possibilitou ainda sua otimização, através do estudo dos modelos computacionais validados. Os parâmetros obtidos ajudaram a identificar componentes críticos para melhoria no projeto do motor rotativo construído, e servem também como guias gerais para projetos de motores termomagnéticos. Um dos componentes com elevado potencial de melhoria foi a adoção de uma estratégia de controle para a regeneração do calor nas placas de material magnético, o que possibilitou, nas simulações, uma melhoria até 2,7 vezes na eficiência.

Dispositivos spintrônicos baseados no transporte de corrente polarizada em spin, torque de spins e em outros fenômenos representam grandes promessas no cenário da tecnologia de miniaturização dos dispositivos eletrônicos da atualidade. Materiais magnéticos de grande relevância tecnológica para diferentes áreas envolvem, apesar de exceções, filmes e estruturas multicamadas com alta complexidade. Avanços nesta área exigem o da estrutura das mesmas, em escala atômica, possibilitando o ajuste de suas propriedades físicas. O propósito deste trabalho é a preparação de estruturas multicamadas por sputtering, bem como o estudo de fenômenos magnéticos envolvidos nestas estruturas. O objetivo é produzir uma válvula de spin. Esta é uma estrutura multicamada composta por dois filmes ferromagnéticos separados por um espaçador não magnético. A magnetização de uma das camadas ferromagnéticas é livre para girar sob efeito de pequenos campos externos, enquanto a magnetização da outra camada ferromagnética permanece fixada por meio de acoplamento de troca com uma camada antiferromagnética. A estrutura é ajustada para permitir que pequenos campos magnéticos aplicados possam chavear a magnetização das camadas ferromagnéticas, de um estado antiparalelo à um estado paralelo, resultando na variação da resistividade elétrica da estrutura (efeito GMR). Otimização das condições de deposição foi necessária para obter estruturas com acoplamento por polarização de troca, e acoplamento antiferromagnético através do espaçador não magnético. A correlação entre as condições de deposição e as propriedades magnéticas dos filmes foi estudada. O trabalho apresentado nesta dissertação tem contribuído para a caracterização de filmes finos magnéticos, quais podem ser utilizados na produção de sensores magnéticos, e do novo sistema de sputtering montado no Laboratório de Física Aplicada do CDTN. / Spintronic devices based in the transport of spin polarized current, spins torque and other related phenomena represent big promises in the scenery of the technological miniaturization of current electronic devices. Magnetic materials of great technological relevance for different areas deal with, despite some exceptions, films and multilayered structures with high complexity. Advances on these fields require the control of those structures in atomic scale, in order to be able to tailor their physical properties. The purpose of this work is the preparation of multilayered structures by sputtering, as well the study of magnetic phenomena involved in this structures. The aim is to produce a spin valve. This is a multilayer structure composed of two ferromagnetic layers, separated by a non magnetic spacer. The magnetisation of one of the ferromagnetic layers is free to rotate under the effect of small external fields, whilst the magnetisation of the other ferromagnetic layer remains fixed by means exchange coupling to a antiferromagnetic layer. The structure is tailored to allow the small applied magnetic fields to switch the magnetisation of the ferromagnetic layers from antiparallel state to a parallel state resulting in the variation of the electrical resistivity of the structure (GMR effect). Optimization of deposition conditions was required to obtain structures with exchange bias coupling, and antiferromagnetic coupling through a non magnetic spacer. The correlation between the deposition conditions and the magnetic properties of the films was studied. The work presented in this dissertation has contributed to the characterisation of both magnetic thin films, which can be used on the production of magnetic sensors, and the new sputtering system assembled in the Applied Physics Laboratory of CDTN.

Imãs são corpos de materiais magnetizáveis utilizados para gerar um forte campo magnético em sua vizinhança. Essa característica faz com que sejam empregados em diversas aplicações na vida moderna, tais como motores para a indústria eletroeletrônica e automobilística, como elementos de fixação e em acoplamentos magnéticos na indústria mecânica. O mercado de ímãs permanentes movimenta atualmente cerca de US$ 5 bilhões por ano e está em plena expansão, sendo estimado um crescimento de 12% por ano até o final desta década de 90. Tal crescimento é atribuído aos \"novos materiais\" desenvolvidos a partir da década de 80 (ímãs de terras-raras) e aos novos mercados, que foram gerados pelos próprios \"novos materiais\" (Hart, 1996). Tratando-se de materiais tão ligados às facilidades da vida moderna, a pesquisa na área de imãs está intimamente ligada ao seu desenvolvimento tecnológico. Procura-se desenvolver imãs com as melhores propriedades magnéticas para as suas aplicações, investigando ao mesmo tempo os fenômenos que regem os mecanismos físicos de magnetização. / Permanent magnets composed of magnetic powders bonded with a polymer represent the fastest growing sector of the magnetic materials market since they are ideal for the fabrication of small motors. This work presents a magnetic and structural characterization of TIve eommereial bonded magnets, Reversible and irreversible components of the total magnetization as well as magnetic interactions in the five commereial magnets are also studied, the magnets are composed by ferrite and MQP-Q nanoerystelline powders and mixtures of these two powders with 80%, 60% and 40% ferrite. Magnelie interactions were analyzed by Henkel plots, gM plots and switching field distributions. In bonded magnets, since the magnetic particles are separated from each other by a binder, it is expected that interactions are mainly dipolar in Nature. There is a progressive change in the data as the fraction of MQP-Q powder is increased. The sample with 100% ferrite shows strong magnetizing interactions at low fields. Date for hybrid magnets present increasing demagnetizing interactions as the fermion of MQP-Q increases and for the 100% MQP-Q sample, the data indicate demagnetizing effects. Reversible and irreversible magnetization components were obtained by applying two methods commanly used in magnetic materials characterization, the DCD -IRM method and the reversible susceptibility method. For the 100% ferrite magnet, in which the reversible component is small, the methods lead lo similar results. The results for both methods diverge as the reversible component! Increases, which in this case occurs with the increase of the MQP-Q powder fraction. The divergence is attributed to the idealized conditions of non-inleracting particles assumed by the DCD-IRM method. Magnetic interactions and lotai magnetization components were also studied in a melt-spun nanocrystalline Nd9Fe85B5 sample. This composition is similar to that of the MQP-Q powder and the magnetic behavior of both the bonded magnetic and the nanocrystalline precursor could be compared. Micromagnetic simulations allowed the evaluation of exchange, anisotropy and magnetostatic interactions on the magnetization reversal of nanocryslalline romposlle systems. The Monte Carlo method was applied lo a linear array of 300 magnetic moments distributed in three grains, two magnetically hard with a soft grain between them.

With the discovery of appreciable room temperature magnetoresistance (MR) in high Curie temperature (Tc) ferrimagnetic double perovskites such as Sr2FeMoO6, research surrounding other materials of this type has expanded. Most ferrimagnetic double perovskites of the formula A2BB'O6 have non-magnetic A-site cations, such as Sr2+, Ca2+ or Ba2+. Replacing non-magnetic cations with magnetic variants offers further possibilities to tune magnetic effects. This thesis focuses on the substitution of non-magnetic A-site cations with relatively small magnetic Mn2+ cations. This substitution is made possible through the use of high-pressure/temperature (P/T) synthesis, and the characterisation of structural and magnetic properties of new phases discovered through these syntheses. The first of these new phases to be reported herein is Mn2FeReO6, which can be described as the Mn analogue of the well-known ferrimagnetic double perovskite Ca2FeReO6. These materials are well ordered with Fe3+/Re5+ on B-sites and crystallise in a P21/n structure. Mn2FeReO6 shows a high Tc of 520 K due to ferrimagnetic Fe/Re magnetic order above RT, and a large saturated magnetisation of 5.0 μB, which peaks at 75 K. Interestingly, the A-site Mn2+ (3d5) magnetic order has the effect of causing a spin reorientation of the Fe/Re sublattice observed by neutron powder diffraction (NPD) at temperatures below ~75 K. This causes the MR to exhibit the expected negative intergrain tunnelling behaviour above the transition and colossal positive behaviour below. Also reported are a series of perovskite related structures with formulae CaxMn2- xFeReO6 (x = 0.5, 1.0, 1.5). Of particular note among these is CaMnFeReO6, which exhibits 1:1 A-site ordering of Ca/Mn and adopts the P42/n space group. This material belongs to a family of newly discovered 'double double' perovskites, in which Ca/Mn order in columns pointing along the c-axis and Mn has alternating tetrahedral and square planar coordination environments. MR in this material remains negative down to 20 K, potentially due to the presence of Ca disrupting magnetic interactions between Mn2+ cations and suppressing the spin transition. Alternating coordination environments in the double double perovskite structure type were exploited in the synthesis of Ca(Mn0.5Cu0.5)FeReO6. This material also crystallises in the P42/n structure and is well ordered on B-sites, as evidenced by X-ray powder diffraction. Neutron diffraction yields, in addition to columnar order, a slight preference for Cu to occupy the square planar sites and for Mn to occupy tetrahedral sites. This doping of square planar sites with Cu has the effect of enhancing magnetic properties compared to CaMnFeReO6, increasing the saturated magnetisation, raising the ferrimagnetic ordering temperature of the B-sites from 500 to 560 K, and also having a profound effect on the observed MR effects, as a switch in the sign of the MR is observed in this material through a magnetic transition. Finally, B-site substitution has been experimented with in the synthesis of CaMnMnReO6. This also possesses the combined A and B-site orders observed in CaMnFeReO6 and an unusual magnetic structure, with perpendicular A and B-site magnetism due to frustration, deviating greatly from the magnetic structures of materials with B-site Fe/Re. In summary, this thesis compiles the synthesis and analysis of a series of new double perovskites, double double perovskites and a new 'triple double' five-fold cation ordered structure with a general formula of AA'0.5A''0.5BB'O6. These materials show that new types of structural ordering can be used to increase the number of degrees of freedom available for tuning the interplay between many different magnetic cations in different coordination environments.

Imãs são corpos de materiais magnetizáveis utilizados para gerar um forte campo magnético em sua vizinhança. Essa característica faz com que sejam empregados em diversas aplicações na vida moderna, tais como motores para a indústria eletroeletrônica e automobilística, como elementos de fixação e em acoplamentos magnéticos na indústria mecânica. O mercado de ímãs permanentes movimenta atualmente cerca de US$ 5 bilhões por ano e está em plena expansão, sendo estimado um crescimento de 12% por ano até o final desta década de 90. Tal crescimento é atribuído aos \"novos materiais\" desenvolvidos a partir da década de 80 (ímãs de terras-raras) e aos novos mercados, que foram gerados pelos próprios \"novos materiais\" (Hart, 1996). Tratando-se de materiais tão ligados às facilidades da vida moderna, a pesquisa na área de imãs está intimamente ligada ao seu desenvolvimento tecnológico. Procura-se desenvolver imãs com as melhores propriedades magnéticas para as suas aplicações, investigando ao mesmo tempo os fenômenos que regem os mecanismos físicos de magnetização. / Permanent magnets composed of magnetic powders bonded with a polymer represent the fastest growing sector of the magnetic materials market since they are ideal for the fabrication of small motors. This work presents a magnetic and structural characterization of TIve eommereial bonded magnets, Reversible and irreversible components of the total magnetization as well as magnetic interactions in the five commereial magnets are also studied, the magnets are composed by ferrite and MQP-Q nanoerystelline powders and mixtures of these two powders with 80%, 60% and 40% ferrite. Magnelie interactions were analyzed by Henkel plots, gM plots and switching field distributions. In bonded magnets, since the magnetic particles are separated from each other by a binder, it is expected that interactions are mainly dipolar in Nature. There is a progressive change in the data as the fraction of MQP-Q powder is increased. The sample with 100% ferrite shows strong magnetizing interactions at low fields. Date for hybrid magnets present increasing demagnetizing interactions as the fermion of MQP-Q increases and for the 100% MQP-Q sample, the data indicate demagnetizing effects. Reversible and irreversible magnetization components were obtained by applying two methods commanly used in magnetic materials characterization, the DCD -IRM method and the reversible susceptibility method. For the 100% ferrite magnet, in which the reversible component is small, the methods lead lo similar results. The results for both methods diverge as the reversible component! Increases, which in this case occurs with the increase of the MQP-Q powder fraction. The divergence is attributed to the idealized conditions of non-inleracting particles assumed by the DCD-IRM method. Magnetic interactions and lotai magnetization components were also studied in a melt-spun nanocrystalline Nd9Fe85B5 sample. This composition is similar to that of the MQP-Q powder and the magnetic behavior of both the bonded magnetic and the nanocrystalline precursor could be compared. Micromagnetic simulations allowed the evaluation of exchange, anisotropy and magnetostatic interactions on the magnetization reversal of nanocryslalline romposlle systems. The Monte Carlo method was applied lo a linear array of 300 magnetic moments distributed in three grains, two magnetically hard with a soft grain between them.