Submitted by Biblioteca do Instituto de Física (bif@ndc.uff.br) on 2017-07-14T19:39:29Z No. of bitstreams: 1 DissertaçãoClebson.pdf: 4945486 bytes, checksum: 38749676f1117adb73bf8a84b5f8989b (MD5) / Made available in DSpace on 2017-07-14T19:39:29Z (GMT). No. of bitstreams: 1 DissertaçãoClebson.pdf: 4945486 bytes, checksum: 38749676f1117adb73bf8a84b5f8989b (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Fundação de Amparo à Pesquisa do Estado do Rio de Janeiro / Com o desenvolvimento de novas tecnologias e os avanços nas técnicas de preparação de materiais, uma grande variedade de novos compostos puderam então ser sintetizados, dentre estes compostos estão os Magnetos Moleculares. Neste texto, apresentamos alguns fundamentos do magnetismo molecular, destacando o processo de construção de modelos para a descrição do comportamento magnético destes materiais através do ajuste dos dados da susceptibilidade magnética em função da temperatura. Buscamos compreender a maneira com que os diferentes parâmetros químicos e estruturais e afetam os mecanismos físicos que governam estes sistemas através do estudo de três séries de magnetos moleculares: um polímero bidimesional de Mn(II) sintetizado a partir do ácido 2,6-diclorobenzóico (C7H4Cl2O2), cujos parâmetros otimizados obtidos através do modelo sugerem que este composto possui um caráter global antiferromagnético; uma série de quatro compostos polinucleares de Cu(II) sintetizados com adenina (C5H5N5), cluster hexagonal heptanuclear ferromagnético e três cadeias antiferromagnéticas 2D dinucleares; uma série de quatro estruturas Metal-Orgânicas (Metal organic Frameworks-MOF) de Cu(II)-piperazina, onde foi feito um mapa das possíveis interações magnéticas para cada amostra. Por fim, como perspectiva para este trabalho pretendemos dar continuidade ao estudo de sistemas de magnetos moleculares dando ênfase à aplicação em informação quântica. / From the development of new technologies and advances in materials preparation techniques a wide variety of new compounds could be synthesized, among these compounds are the Molecular Magnets. In this paper, we present some fundamentals of molecular magnetism, highlighting the model-building process for the description of the magnetic behavior of these materials by fitting of the magnetic susceptibility as a function of temperature. Our goal is to understand how different chemical and structural parameters can affect the physical mechanisms that govern these systems . To achieve our aim we study three series of molecular magnets: a two-dimensional polymer Mn(II) synthesized from 2,6-acid dichlorobenzoic (C7H4Cl2O2), the optimized parameters obtained from the model suggest that this compound has an antiferromagnetic global character; a series of four polynuclear compounds of Cu(II) synthesized with adenine (C5H5N5), a ferromagnetic hexagonal cluster and three antiferromagnetic 2 D chains; a series of four Metal-Organic Frameworks (MOF) of Cu(II) -piperazine, where a magnetic interaction map was done for each sample. Finally, the perspective we intend to emphasize the study of molecular magnets systems with applications in quantum information.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / AÃos maraging sÃo ligas Ni-Co-Mo-Ti de ultra-alta resistÃncia e vasta aplicaÃÃo que vai desde a indÃstria bÃlica e nuclear atà componentes aeronÃuticos, vasos de pressÃo e a indÃstria esportiva. Atualmente estes aÃos vÃm sendo estudados para utilizaÃÃo em rotores de alta velocidade de motores de histerese. Os aÃos maraging apresentam algumas vantagens em comparaÃÃo a outros tipos de aÃos e ligas, pois apresentam nÃveis de resistÃncia mecÃnica extremamente elevados, excelente conformabilidade no estado solubilizado e grande capacidade de endurecer por envelhecimento. A utilizaÃÃo destes aÃos em motores de histerese à o motivo pelo qual se estudam suas propriedades magnÃticas. Para este fim, o material deve apresentar, alÃm de elevada resistÃncia mecÃnica, caracterÃsticas tÃpicas de materiais magneticamente macios. As propriedades magnÃticas do material sÃo mostradas e discutidas com o objetivo de determinar os melhores tipos de tratamento para utilizaÃÃo do aÃo nas condiÃÃes requeridas. AnÃlises de textura foram realizadas e discutidas com o objetivo de determinar a textura existente no material, bem como sua direÃÃo de fÃcil magnetizaÃÃo. As quantificaÃÃes das fases para as diferentes condiÃÃes de tratamento termomecÃnico foram realizadas por difraÃÃo de raios-X, atravÃs do mÃtodo de comparaÃÃo direta com o objetivo de analisar a influÃncia da austenita na textura, resistÃncia mecÃnica e propriedades magnÃticas do material. Ensaios de dureza foram realizados com o objetivo de analisar as propriedades mecÃnicas do material. As anÃlises revelaram que praticamente todas as amostras possuem os mesmos componentes de textura e a direÃÃo de fÃcil magnetizaÃÃo <100> apresenta-se no plano da chapa rotacionada de 45 em relaÃÃo à direÃÃo de laminaÃÃo. As propriedades magnÃticas medidas mostram que todas as amostras possuem os requisitos mÃnimos para utilizaÃÃo em motores de histerese, sendo as amostras com solubilizaÃÃo intermediÃria as menos indicadas a as amostras resfriadas em nitrogÃnio as mais indicadas para este tipo de aplicaÃÃo. / AÃos maraging sÃo ligas Ni-Co-Mo-Ti de ultra-alta resistÃncia e vasta aplicaÃÃo que vai desde a indÃstria bÃlica e nuclear atà componentes aeronÃuticos, vasos de pressÃo e a indÃstria esportiva. Atualmente estes aÃos vÃm sendo estudados para utilizaÃÃo em rotores de alta velocidade de motores de histerese. Os aÃos maraging apresentam algumas vantagens em comparaÃÃo a outros tipos de aÃos e ligas, pois apresentam nÃveis de resistÃncia mecÃnica extremamente elevados, excelente conformabilidade no estado solubilizado e grande capacidade de endurecer por envelhecimento. A utilizaÃÃo destes aÃos em motores de histerese à o motivo pelo qual se estudam suas propriedades magnÃticas. Para este fim, o material deve apresentar, alÃm de elevada resistÃncia mecÃnica, caracterÃsticas tÃpicas de materiais magneticamente macios. As propriedades magnÃticas do material sÃo mostradas e discutidas com o objetivo de determinar os melhores tipos de tratamento para utilizaÃÃo do aÃo nas condiÃÃes requeridas. AnÃlises de textura foram realizadas e discutidas com o objetivo de determinar a textura existente no material, bem como sua direÃÃo de fÃcil magnetizaÃÃo. As quantificaÃÃes das fases para as diferentes condiÃÃes de tratamento termomecÃnico foram realizadas por difraÃÃo de raios-X, atravÃs do mÃtodo de comparaÃÃo direta com o objetivo de analisar a influÃncia da austenita na textura, resistÃncia mecÃnica e propriedades magnÃticas do material. Ensaios de dureza foram realizados com o objetivo de analisar as propriedades mecÃnicas do material. As anÃlises revelaram que praticamente todas as amostras possuem os mesmos componentes de textura e a direÃÃo de fÃcil magnetizaÃÃo <100> apresenta-se no plano da chapa rotacionada de 45 em relaÃÃo à direÃÃo de laminaÃÃo. As propriedades magnÃticas medidas mostram que todas as amostras possuem os requisitos mÃnimos para utilizaÃÃo em motores de histerese, sendo as amostras com solubilizaÃÃo intermediÃria as menos indicadas a as amostras resfriadas em nitrogÃnio as mais indicadas para este tipo de aplicaÃÃo. / Maraging steels are alloys of Ni-Co-Ti-Mo ultra-high resistance and wide application ranging from the defense industry and nuclear power to aircraft components, pressure vessels and the sports industry. Currently these steels have been studied for use in high speed rotors hysteresis motors. The maraging steel have some advantages compared to other types of steels and alloys, as have levels of extremely high mechanical strength, excellent conformability in the solubilized state and great ability to harden by aging. The use of these steels in hysteresis motors is why we study their magnetic properties. To this end, the material must have, and high mechanical strength characteristics typical of magnetically soft material. The magnetic properties of the material are shown and discussed in order to determine the best types of treatment for use in the steel requirements. Textural analyzes were performed and discussed in order to determine the existing texture in the material, as well as its direction of easy magnetization. The quantification of phases for different conditions of thermomechanical treatment was performed by X-ray diffraction, using the method of direct comparison with the objective of analyzing the influence of austenite texture, mechanical and magnetic properties of the material. Hardness tests were performed to analyze the mechanical properties of the material. The analysis revealed that virtually all samples have the same texture components and the direction of easy magnetization <100> is presented in the plane of the plate rotated 45  relative to the direction of lamination. The magnetic properties measurements show that all samples have the minimum requirements for use in motor hysteresis, and the samples with the least intermediate solubilization indicated the samples cooled in nitrogen the most suitable for this type of application. / Maraging steels are alloys of Ni-Co-Ti-Mo ultra-high resistance and wide application ranging from the defense industry and nuclear power to aircraft components, pressure vessels and the sports industry. Currently these steels have been studied for use in high speed rotors hysteresis motors. The maraging steel have some advantages compared to other types of steels and alloys, as have levels of extremely high mechanical strength, excellent conformability in the solubilized state and great ability to harden by aging. The use of these steels in hysteresis motors is why we study their magnetic properties. To this end, the material must have, and high mechanical strength characteristics typical of magnetically soft material. The magnetic properties of the material are shown and discussed in order to determine the best types of treatment for use in the steel requirements. Textural analyzes were performed and discussed in order to determine the existing texture in the material, as well as its direction of easy magnetization. The quantification of phases for different conditions of thermomechanical treatment was performed by X-ray diffraction, using the method of direct comparison with the objective of analyzing the influence of austenite texture, mechanical and magnetic properties of the material. Hardness tests were performed to analyze the mechanical properties of the material. The analysis revealed that virtually all samples have the same texture components and the direction of easy magnetization <100> is presented in the plane of the plate rotated 45  relative to the direction of lamination. The magnetic properties measurements show that all samples have the minimum requirements for use in motor hysteresis, and the samples with the least intermediate solubilization indicated the samples cooled in nitrogen the most suitable for this type of application.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T18:57:13Z No. of bitstreams: 1 Dissertacao-AndreCavaignac.pdf: 10851210 bytes, checksum: da7f6d04592241587693042b0ee75bd7 (MD5) / Made available in DSpace on 2017-05-05T18:57:13Z (GMT). No. of bitstreams: 1 Dissertacao-AndreCavaignac.pdf: 10851210 bytes, checksum: da7f6d04592241587693042b0ee75bd7 (MD5) Previous issue date: 2015-06-12 / Structural, magnetic and magnetocaloric properties of the RMn2Si2 compounds (R = Tm, Dy and Tb) were studied. X ray diffraction analysis and structure Rietveld refinement shows that the samples crystallize with the desired tetragonal I4/mmm structural phase. Magnetization measurements shows second order magnetic phase transition from paramagnetic (PM) to ferromagnetic (FM) state for TmMn2Si2 compound around T = 5.2 K. On the other hand, DyMn2Si2 and TbMn2Si2 compounds present multiple phase transitions below 100 K. DyMn2Si2 present four magnetic phase transitions while TbMn2Si2 present two magnetic phase transition. Both compounds present first order FM phase transitions originated from ordering of rare earth sub-lattice. In addition, DSC measurements indicated that DyMn2Si2 and TbMn2Si2 compounds present high temperature phase transition at T~ 425 K and 444 K associated to the AFM coupling in the Mn sub-lattice. Magnetic hysteresis loop was used to characterize exchange bias effect in the DyMn2Si2 observed for magnetic fields higher than 35 kOe in which was associated to interactions between AFM and FM magnetic domain present in this compound. The largest magnetocaloric effect (MCE) was observed for TmMn2Si2 compound, when compared with other studied compound. The maximum values of entropy variation change −∆𝑆𝑀 𝑚á𝑥 and the Relative Cooling Power (RCP) found for TmMn2Si2 were, respectively, 18.5 J/kg.K and 247.5 J/kg for a magnetic field change (H) of 50 kOe. Significant values of −∆𝑆𝑀 𝑚á𝑥 (~8.2 J/kg.K and ~9.7 J/kg.K@50 kOe, respectively) and RCP (124.6 J/kg and 233 J/kg@50 kOe, respectively) as well as successive magnetic phase transitions were observed for DyMn2Si2 and TbMn2Si2 compounds. Also these two compound exhibits a table like EMC presenting a wide working window for practical applications. The results obtained for compounds motivate the preparation of a composite sample with the following concentrations 10% de TmMn2Si2, 15% de HoCoSi, 35% de DyMn2Si2 e 40% de TbMn2Si2, aiming further increase in the temperature range of maximum EMC. The maximum entropy change variation obtained for the composite sample was ~4.6 J/kg.K over a temperature range of ~80𝐾. Our results show that the compounds RMn2Si2 present important characteristics for application in magnetic refrigeration for cryogenic temperatures. Besides, it is possible to get a larger working region, when these compounds are associated forming a composite material. / Neste trabalho foi realizado um estudo das propriedades estruturais, magnéticas e magnetocalóricas dos compostos da série RMn2Si2 (R = Tm, Dy e Tb). A análise estrutural por difração de raios X e refinamento dos difratogramas pelo método de Rietveld mostraram que as amostras cristalizam na fase tetragonal grupo espacial I4/mmm. Com a medida de magnetização foi possível observar a transição de fase magnética de segunda ordem do estado paramagnético (PM) para ferromagnético (FM) para o composto TmMn2Si2 em torno de 5,2 K. Enquanto que para os compostos DyMn2Si2 e TbMn2Si2 observou-se a presença de transições múltiplas abaixo de 100 K. O DyMn2Si2 apresentou quatro transições de fase magnética enquanto que TbMn2Si2 apresentou duas. Em ambos os compostos, as transições ferromagnéticas atribuídas ao ordenamento da sub-rede da terra rara são de primeira ordem. Medidas DSC indicaram que DyMn2Si2 e TbMn2Si2 apresentam uma transição de fase em T~ 425 K e 444 K, respectivamente, ambas relacionadas ao acoplamento antiferromagnético na sub-rede do Mn. Com as medidas do loop de histerese magnética foi possível caracterizar o efeito de Exchange Bias (EB) para o DyMn2Si2, em campos magnéticos superiores a 35 kOe, o qual foi atribuído a interações entre os domínios AFM e FM presentes no material. A caracterização das propriedades magnetocalóricas do composto TmMn2Si2 mostrou uma variação de entropia magnética (-∆SM) mais intensa quando comparada aos outros compostos deste estudo. Os valores máximos obtidos para a variação isotérmica da entropia (−∆𝑆𝑀 𝑚á𝑥 ) e para o poder de resfriamento relativo (RCP) foram, respectivamente 18,5 J/kg.K e 247,5 J/kg, para ∆𝐻 = 50 kOe. Já os compostos DyMn2Si2 e TbMn2Si2 mostraram valores significativos de −∆𝑆𝑀 𝑚á𝑥 (~8,2 J/kg.K e ~9,7 J/kg.K@50 kOe, respectivamente) e RCP (124,6 J/kg e 233,6 J/kg@50 kOe, respectivamente) além de duas transições de fase magnética sucessivas, o que resultou em um EMC com comportamento do tipo table-like, caracterizado por uma ampla janela de trabalho com máximo EMC. Estes resultados motivaram a preparação de um compósito com as seguintes concentrações 10% de TmMn2Si2, 15% de HoCoSi, 35% de DyMn2Si2 e 40% de TbMn2Si2, visando ampliar ainda mais o intervalo de máximo EMC. A variação máxima de entropia obtida para o compósito foi da ordem de 4,6 J/kg.K num intervalo de temperatura de ~80𝐾. Os resultados obtidos sugerem que os compostos desta série apresentam características importantes para aplicação na refrigeração magnética em temperaturas criogênicas. Além disso, quando estes estão associados na forma de um compósito é possível obter uma grande ampliação na região de trabalho.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-08T20:28:10Z No. of bitstreams: 1 DelcicleideReis.pdf: 3837410 bytes, checksum: d063417815b0c49287d6fdb8d46998bd (MD5) / Made available in DSpace on 2017-05-08T20:28:10Z (GMT). No. of bitstreams: 1 DelcicleideReis.pdf: 3837410 bytes, checksum: d063417815b0c49287d6fdb8d46998bd (MD5) Previous issue date: 2016-07-29 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPQ) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Structural, magnetic and magnetocaloric properties of the RMn2Si2 compounds (R = Tm, Dy and Tb) were studied. X ray diffraction analysis and structure Rietveld refinement shows that the samples crystallize with the desired tetragonal I4/mmm structural phase. Magnetization measurements shows second order magnetic phase transition from paramagnetic (PM) to ferromagnetic (FM) state for TmMn2Si2 compound around T = 5.2 K. On the other hand, DyMn2Si2 and TbMn2Si2 compounds present multiple phase transitions below 100 K. DyMn2Si2 present four magnetic phase transitions while TbMn2Si2 present two magnetic phase transition. Both compounds present first order FM phase transitions originated from ordering of rare earth sub-lattice. In addition, DSC measurements indicated that DyMn2Si2 and TbMn2Si2 compounds present high temperature phase transition at T~ 425 K and 444 K associated to the AFM coupling in the Mn sub-lattice. Magnetic hysteresis loop was used to characterize exchange bias effect in the DyMn2Si2 observed for magnetic fields higher than 35 kOe in which was associated to interactions between AFM and FM magnetic domain present in this compound. The largest magnetocaloric effect (MCE) was observed for TmMn2Si2 compound, when compared with other studied compound. The maximum values of entropy variation change −∆𝑆𝑀𝑚á𝑥 and the Relative Cooling Power (RCP) found for TmMn2Si2 were, respectively, 18.5 J/kg.K and 247.5 J/kg for a magnetic field change (H) of 50 kOe. Significant values of −∆𝑆𝑀𝑚á𝑥(~8.2 J/kg.K and ~9.7 J/kg.K@50 kOe, respectively) and RCP (124.6 J/kg and 233 J/kg@50 kOe, respectively) as well as successive magnetic phase transitions were observed for DyMn2Si2 and TbMn2Si2 compounds. Also these two compound exhibits a table like EMC presenting a wide working window for practical applications. The results obtained for compounds motivate the preparation of a composite sample with the following concentrations 10% de TmMn2Si2, 15% de HoCoSi, 35% de DyMn2Si2 e 40% of TbMn2Si2, aiming further increase in the temperature range of maximum EMC. The maximum entropy change variation obtained for the composite sample was ~4.6 J/kg.K over a temperature range of ~80𝐾. Our results show that the compounds RMn2Si2 present important characteristics for application in magnetic refrigeration for cryogenic temperatures. Besides, it is possible to get a larger working region, when these compounds are associated forming a composite material. / Neste trabalho foi realizado um estudo das propriedades estruturais, magnéticas e magnetocalóricas dos compostos da série RMn2Si2 (R = Tm, Dy e Tb). A análise estrutural por difração de raios X e refinamento dos difratogramas pelo método de Rietveld mostraram que as amostras cristalizam na fase tetragonal grupo espacial I4/mmm. Com a medida de magnetização foi possível observar a transição de fase magnética de segunda ordem do estado paramagnético (PM) para ferromagnético (FM) para o composto TmMn2Si2 em torno de 5,2 K. Enquanto que para os compostos DyMn2Si2 e TbMn2Si2 observou-se a presença de transições múltiplas abaixo de 100 K. O DyMn2Si2 apresentou quatro transições de fase magnética enquanto que TbMn2Si2 apresentou duas. Em ambos os compostos, as transições ferromagnéticas atribuídas ao ordenamento da sub-rede da terra rara são de primeira ordem. Medidas DSC indicaram que DyMn2Si2 e TbMn2Si2 apresentam uma transição de fase em T~425 K e 444 K, respectivamente, ambas relacionadas ao acoplamento antiferromagnético na sub-rede do Mn. Com as medidas do loop de histerese magnética foi possível caracterizar o efeito de Exchange Bias (EB) para o DyMn2Si2, em campos magnéticos superiores a 35 kOe, o qual foi atribuído a interações entre os domínios AFM e FM presentes no material. A caracterização das propriedades magnetocalóricas do composto TmMn2Si2 mostrou uma variação de entropia magnética (-∆SM) mais intensa quando comparada aos outros compostos deste estudo. Os valores máximos obtidos para a variação isotérmica da entropia (−∆𝑆𝑀𝑚á𝑥) e para o poder de resfriamento relativo (RCP) foram, respectivamente 18,5 J/kg.K e 247,5 J/kg, para ∆𝐻 = 50 kOe. Já os compostos DyMn2Si2 e TbMn2Si2 mostraram valores significativos de −∆𝑆𝑀𝑚á𝑥 (~8,2 J/kg.K e ~9,7 J/kg.K@50 kOe, respectivamente) e RCP (124,6 J/kg e 233,6 J/kg@50 kOe, respectivamente) além de duas transições de fase magnética sucessivas, o que resultou em um EMC com comportamento do tipo table-like, caracterizado por uma ampla janela de trabalho com máximo EMC. Estes resultados motivaram a preparação de um compósito com as seguintes concentrações 10% de TmMn2Si2, 15% de HoCoSi, 35% de DyMn2Si2 e 40% de TbMn2Si2, visando ampliar ainda mais o intervalo de máximo EMC. A variação máxima de entropia obtida para o compósito foi da ordem de 4,6 J/kg.K num intervalo de temperatura de ~80𝐾. Os resultados obtidos sugerem que os compostos desta série apresentam características importantes para aplicação na refrigeração magnética em temperaturas criogênicas. Além disso, quando estes estão associados na forma de um compósito é possível obter uma grande ampliação na região de trabalho.

Abstract not available

Delamination along thin film interfaces is a prevalent failure mechanism in microelectronic, photonic, MEMS, and other engineering applications. Current interfacial fracture test techniques specific to thin films are limited by either sophisticated mechanical fixturing, physical contact near the crack tip, non-representative test specimens, or complicated stress fields. Moreover, these techniques are generally not suitable for investigating fatigue crack propagation under cyclical loading. A fixtureless and noncontact experimental test technique is thus proposed and implemented to study interfacial fracture for thin film systems. The proposed test incorporates permanent magnets surface mounted onto micro-fabricated released thin film structures. An applied external magnetic field induces noncontact monotonic or fatigue loading to initiate delamination along the interface between the thin film and underlying substrate. Characterization of the film deflection, peel angle, and delamination propagation is accomplished through in situ optical techniques. Analytical and finite-element models are used to extract fracture parameters from the experimental data using thin-film peel mechanics. The developed interfacial fracture test has been demonstrated for Cu thin films on a SiO₂/Si substrate.

This work presents the development of a GaN-based dilute magnetic semiconductor (DMS) by metal organic chemical vapor deposition (MOCVD) that is ferromagnetic at room temperature (RT), electrically conductive, and possesses magnetic properties that can be tuned by n- and p-doping. The transition metal series (TM: Cr, Mn, and Fe) along with the rare earth (RE) element, Gd, was investigated in this work as the magnetic ion source for the DMS. Single- phase and strain-free GaTMN films were obtained. Optical measurements revealed that Mn is a deep acceptor in GaN, while Hall measurements showed that these GaTMN films were semi-insulating, making carrier mediated exchange unlikely. Hysteresis curves were obtained for all the GaTMN films, and by analyzing the effect of n- and p-dopants on the magnetic properties of these films it was determined that the magnetization is due to magnetic clusters. These findings are supported by the investigation of the effect of TM dopants in GaN nanostructures which reveal that TMs enhance nucleation resulting in superparamagnetic nanostructures. Additionally, this work presents the first report on the development of GaGdN by MOCVD providing an alternate route to developing a RT DMS. Room temperature magnetization results revealed that the magnetization strength increases with Gd concentration and can be enhanced by n- and p-doping, with holes being more efficient at stabilizing the ferromagnetic signal. The GaGdN films obtained in this work are single-phase, unstrained, and conductive making them suitable for the development of multifunctional devices that integrate electrical, optical, and magnetic properties.

Mixed valence manganites with the perovskite structure R1-xAxMnO3 (where R = La, Nd, Pr and A = Ba, Ca, Sr, Pb) have been a popular subject of contemporary research because of their interesting physical properties such as competing magnetic orders, metal-insulator transitions and colossal magnetoresistance. A complex interplay between structure, electronic and magnetic properties results in rich phase diagrams involving various metallic, insulating and magnetic phases. A review of the literature related to rare-earth managnites clearly reveals that the systems with Pb as a divalent dopant are relatively less explored. This may be due to the volatile nature of lead based compounds which are used as precursors for preparing these systems. This has motivated us to take up research on Pb doped rare earth manganites. This thesis is divided into eight chapters. The first introductory chapter gives a brief review of the work on manganites which have already been reported in the literature following which the motivation for carying out the present investigation is given. The second chapter deals with technical details of various instruments used in the present reasearch work. The third chapter is related to growth of single crystals, their preliminary characterization, magnetization and resistivity studies. Single crystals of Pr1-xPbxMnO3 are grown by flux technique for different compositions. Crystals are characterized by energy dispersive x-ray analysis (EDAX) and inductively coupled plasma atomic emission spectroscopy (ICPAES) for compositional analysis. Magnetization and resistivity studies are carried out on Pr1-xPbxMnO3 for three compositions viz. x = 0.2, 0.23 and 0.3. The magnetization vs. temperature plots show that all the three compositions undergo a transition from paramagnetic to ferromagnetic state. The magnetization in the low temperature ferromagnetic region obeys Bloch`s law. The susceptibility in the paramagnetic region is fitted to Curie Weiss law. Deviation of susceptibilty from Curie Weiss law, a feature observed in all the three crystals has been attributed to formation of ferromagnetic clusters at ~ 250 K. The cluster formation has its implications on all other properties in the temperature range from TC to 250 K where TC is the magnetic transition temperature. Resistivity measurements are carried out on the same three compositions. The x = 0.2 and 0.23 compositions undergo a transition from paramagnetic insulating to ferromagnetic insulating phases. The x = 0.3 composition shows a metal – insulator transition at nearly 35 K above TC. Chapter 4 describes the critical behaviour of Pr1-xPbxMnO3 for two compositions, viz. x = 0.23 and 0.3. For critical studies, magnetization vs. field measurements are carried out in the temperature range TC ± 10 K. Using modified Arrott plots and Kouvel-Fisher method the critical exponents and precise value of TC are obtained. The x = 0.23 composition shows results which indicate a conventional second order phase transition shown by a 3D Heisenberg ferromagnet. It also obeys the universal scaling behaviour. However, the x = 0.3 composition shows deviation from this behaviour. Hence to probe further into the nature of magnetic transition of this compound the effective critical exponents are calculated as a function of reduced temperature ε (=(T-TC)/TC). Based on the behaviour of effective exponents the nature of the transition in the x = 0.3 composition is described in detail. The unconventional ordering is attributed to presence of possible magnetic frustration in the system. In chapter 5 the resistivity and magnetoresistance behaviour of the x = 0.23 and 0.3 crystals are discussed. Initially the nature of plots of temperature and field variation of resistivity are described for both the cases. Detailed measurements are carried out at the magnetic transition region. The analysis is carried out in terms of critical scattering behaviour at the transition region. The zero field resistivity is analyzed in terms of theory of Fisher and Langer, while the magnetoresistance is fitted to scaling theory at the critical region developed by Balberg and Helman. It is seen that the x = 0.23 crystal shows a critical behaviour in resistivity for zero field as well as in magnetoresistance close to TC. However, the behaviour of the x = 0.3 composition is more complex. A simpler critical scattering theory alone cannot explain its large negative magnetoresistance. Chapter 6 contains the EPR studies on the x = 0.23 and 0.3 compositions. Analysis is carried out in the paramagnetic region. The EPR signals are fitted to a modified Dysonian equation. The intensity, linewidth, and asymmetry parameter are obtained as a function of temperature from fitting. The parameters are obtained till 210 K for both compositions. The intensity is fitted to a Curie Weiss law. The linewidth shows a “bottleneck” mechanism and is proportional to conductivity. Hence it is fitted to activated behaviour. In addition, a secondary signal develops at low fields from 240 K and is present till 200 K in both the compositions. This is explained by means of phase separation. In chapter 7 the specific heat of the x = 0.23 and 0.3 compositions are discussed. The measurements are carried out from 2 to 300 K in zero field and also in the presence of 3 Tesla magnetic field. The analysis is carried out in two separate sections. The first section deals with the low temperature analysis from 2 to 80 K where apart from the usual lattice, electron and magnetic terms, presence of Schottky anomaly is also discussed. The Schottky peak occurs at a relatively higher temperature of around 40 K. Due to presence of higher order lattice terms the Schottky effect is not easily discernible. It is extracted only from fitting. In the second section, the specific heat associated with ferromagnetic – paramagnetic transition is extracted. The lattice term in the entire temperature range from 10 to 300 K except at the transition region is fitted to Einstein function. The magnetic specific heat is obtained by subtracting the Einstein specific heat from the total specific heat. The change in entropy due to magnetic transition is also calculated for both compositions. In chapter 8 the general conclusions derived from the work presented in this thesis are summarized along with the scope for future work in this system.

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The research in low-dimensional (low-D) quantum spin systems has become an arduous challenge for the condensed matter physics community during the last years. In systems with low dimensional magnetic interactions the exchange coupling is restricted to dimensions lower than the full three-D exhibited by the bulk real material. The remarkable interest in this field is fueled by a continuous stream of striking discoveries like superconductivity, quantum liquid and spin gap states, chiral phases, etc, derived from the strong effect of quantum fluctuations on the macroscopic properties of the system and the competition between electronic and magnetic degrees of freedom. The main goal of the current studies is to reach a broad understanding of the mechanisms that participate in the formation of those novel ground states as well as the characteristic dependence with respect to relevant physical parameters. In this thesis we present the results of an Electron Spin Resonance (ESR)-based study on different quasi-1D spin systems, exemplifying the realization of 1D-magnetic spin-chains typically containing transition metal oxides such as Cu2+ or V4+. The local sensitivity of the ESR technique has been considered useful in exploring magnetic excitation energies, dominant mechanisms of exchange interactions, spin fluctuations and the dimensionality of the electron spin system, among others. Aside from ESR other experimental results, e.g., magnetization and nuclear magnetic resonance besides some theoretical approaches were especially helpful in achieving a proper understanding and modeling of those low-D spin systems. This thesis is organized into two parts: The first three chapters are devoted to the basic knowledge of the subject. The first chapter is about magnetic exchange interactions between spin moments and the effect of the crystal field potential and the external magnetic field. The second chapter is a short introduction on exchange interactions in a 1D-spin chain, and the third chapter is devoted to ESR basics and the elucidation of dynamic magnetic properties from the absorption spectrum parameters. The second part deals with the experimental results. In the fourth chapter we start with the magnetization results from the zero-dimensional endohedral fullerene Dy3N@C80. This system is seemingly ESR “silent” at the frequency of X-band experiments. The fifth chapter shows an unexpected temperature dependence of the anisotropy in the homometallic ferrimagnet Na2Cu5Si4O14 containing alternating dimer-trimer units in the zig-zag Cu-O chains. In the sixth chapter different magnetic species in the layer structure of vanadium oxide nanotubes (VOx-NT) have been identified, confirming earlier magnetization measurements. Moreover the superparamagnetic-like nature of the Li-doped VOx-NT samples was found to justify its ferromagnetic character at particular Li concentration on the room temperature scale. In the seventh chapter the Li2ZrCuO4 system is presented as a unique model to study the influence of additional interactions on frustrated magnetism. The eighth chapter highlights the magnetic properties of the pyrocompound Cu2As2O7. The results suggest significant spin fluctuations below TN. The thesis closes with the summary and the list of references.