Made available in DSpace on 2014-12-17T15:14:57Z (GMT). No. of bitstreams: 1 TiberioMLA_DISSERT.pdf: 5996955 bytes, checksum: 689080ca5f207d43776c16e5aab237d7 (MD5) Previous issue date: 2012-07-27 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Today, one of the topics that attracts interest of the scientific community is the understanding of magnetic properties of magnetic systems with reduced dimensions, in particular, ferromagnetic thin films. In this case, the comprehension and control of these properties, as well as the development of routes to obtain them, are crucial issues in many aspects of current and future technologies for storage and transmission of information in the electro-electronic industry. There are several materials that exhibit soft magnetic properties, and we highlight the amorphous alloys and that ones obtained by partial crystallization, so-called nanocrystalline materials. The production of these alloys as magnetic ribbons is very common in scientific and technological area, but there are just a few works related to the production of these alloys as thin films. In this work, we studied the quasi-static magnetic properties of ferromagnetic thin films based on FeCuNbSiB in a wide range of thicknesses, from 20 to 500 nm, produced by sputtering. In particular, after the structural characterization performed via X-ray diffraction, the magnetic properties of the sets of samples were investigated using experimental magnetization curve, obtained using a vibrating sample magnetometer, as well as through theoretical curves obtained by theoretical modeling and numerical computation. The modeling process is based on the Stoner Wohlfarth model applied to three dimensions, and adds some energy terms, using as reference experimental results of magnetization. In this case, from the comparison between theoretical and experimental results and the analysis of the constant anisotropy behavior as a function of film thickness, we aim to obtain further information on the magnetization process of the samples, to identify routes for the production of thin films and develop a theoretical to films to use it, in the future, in the obtainment of the theoretical curves of some magnetic measurements, such as magnetoimpedance and magnetoresistance / Dentre os temas que despertam interesse da comunidade cient?fica atualmente est? o entendimento das propriedades magn?ticas de sistemas magn?ticos com dimens?es reduzidas, em particular, filmes finos ferromagn?ticos. Neste caso, a compreens?o e o controle destas propriedades, bem como o desenvolvimento de rotas para sua obten??o, s?o temas cruciais em muitos aspectos das tecnologias atuais e futuras de armazenagem e transmiss?o da informa??o na ind?stria eletro-eletr?nica. Dos materiais que exibem propriedades magn?ticas macias, destacam-se as ligas amorfas e as ligas obtidas por cristaliza??o parcial das mesmas, os chamados materiais nanocristalinos. A produ??o destas ligas na forma de fitas magn?ticas tem sido muito comum no meio tecnol?gico e cient?fico, por?m s?o escassas as produ??es de filmes finos desta liga. Neste trabalho, realizamos um estudo das propriedades magn?ticas quase-est?ticas de filmes ferromagn?ticos ? base de FeCuNbSiB, em uma vasta faixa de espessuras, de 20 a 500 nm, produzidos pela t?cnica de sputtering. Em particular, ap?s caracteriza??o estrutural, realizada via difratometria de raios-X, as propriedades magn?ticas dos conjuntos de amostras foram investigadas atrav?s de curvas de magnetiza??o experimentais, obtidas utilizando-se um magnet?metro de amostra vibrante, bem como atrav?s de curvas te?ricas obtidas atrav?s de modelagem e computa??o num?rica. O processo de modelagem toma como base o modelo Stoner-Wohlfarth aplicado para tr?s dimens?es, e acrescenta os alguns outros termos de energia, tomando como refer?ncia os resultados experimentais para magnetiza??o. Neste caso, a partir da compara??o dos resultados te?ricos e experimentais e da an?lise do comportamento das constantes de anisotropia em fun??o da espessura dos filmes, busca-se obter informa??es sobre o processo de magnetiza??o das amostras, identificar rotas para a produ??o de filmes finos e desenvolver uma abordagem te?rica para filmes com o intuito de, no futuro, utiliz?-la para a obten??o de curvas te?ricas de outras medidas magn?ticas, tais como magnetoimped?ncia e magnetoresist?ncia

[pt] Nanopartículas são importantes ferramentas utilizadas em medicina, tanto para diagnóstico como para tratamento de diversas doenças. Seus tamanhos podem ser controlados, variando de dezenas até centenas de nanômetros, tornando-as menores ou comparáveis às dimensões de células, bactérias e vírus. As nanopartículas magnéticas possuem um núcleo de material magnético recoberto por camadas de diferentes materiais, incluindo sílica ou um polímero. Esta cobertura é responsável pela funcionalização, de forma que elas realizem tarefas específicas, seja para funcionar como um marcador com fins diagnósticos e/ou como um transportador de fármacos. É muito importante no processo de fabricação e utilização das nanopartículas o conhecimento de suas propriedades magnéticas. Com este objetivo, construímos um magnetômetro baseado em um criorefrigerador com capacidade para medir propriedades magnéticas em função da temperatura desde ambiente até 6 K. Como sensor magnético utilizamos um elemento Hall de GaAs de baixo custo. O magnetômetro construído tem uma configuração diferente dos magnetômetros Hall tradicionais, já que neste caso a amostra se movimenta na região do sensor. De forma a aumentar a exatidão do momento magnético obtido, foi desenvolvido um modelo que leva em consideração a geometria da amostra. A resolução está limitada pelo sensor utilizado em 10-7 Am2. O magnetômetro foi calibrado de forma independente e seu desempenho foi comparado a magnetômetros de amostra vibrante (VSM) comerciais, apresentando erros menores que 2 porcento na magnetização obtida de diversas amostras. Todos os equipamentos envolvidos na operação do magnetômetro a baixas temperaturas são controlados utilizando a linguagem LabVIEW. Na versão atual do programa, curvas M x H e ZFC-FC podem ser obtidas. Como exemplo de aplicação, fabricamos nanopartículas magnéticas com núcleo de oxido de ferro pelo processo de coprecipitação em meio alcalino e recobrimos com surfactantes e SiO2. As propriedades magnéticas das nanopartículas foram obtidas utilizando o magnetômetro construído. As nanopartículas apresentaram comportamento superparamagnético e grande potencial para liberação controlada de drogas. / [en] Nanoparticles are important tools used in medicine, for diagnosis as well as for treatment of various diseases. Their sizes can be controlled, ranging from tens to hundreds of nanometers, enabling them to interact with cells, bacteria, and viruses. Magnetic nanoparticles have a core of magnetic material coated with layers of different materials, including silica or a polymer. This coating is responsible for their functionalization, so they can carry out specific tasks serving as a marker for diagnostic purposes and / or as a carrier for drugs. The knowledge of the magnetic properties of nanoparticles is very important in the manufacturing process and their use. With this aim, we built a magnetometer based on a cryorefrigerator capable of measuring their magnetic properties as a function of temperature from room temperature to 6 K. We used a low cost GaAs Hall element as its magnetic sensor. The magnetometer built has a different configuration from the traditional Hall magnetometers, since in this case the sample moves in the region of the sensor. A model which takes into consideration the geometry of the sample was developed in order to increase the accuracy of the magnetic moment obtained. The magnetometer resolution is limited by the Hall sensor used in 10-7 Am2. The magnetometer was calibrated independently and its performance was compared to commercial vibrating sample magnetometers (VSM) showing errors smaller than 2 percent in the magnetization obtained from various samples. All the equipment involved in the operation of magnetometers at low temperatures is controlled by using the LabVIEW language. The M x H e ZFC-FC curves can be obtained in the current version. We manufactured the core with magnetic nanoparticles of iron oxide by coprecipitation process in an alkaline medium, coated with surfactants and SiO2. The magnetic properties of the nanoparticles were obtained using the magnetometer built. The nanoparticles showed superparamagnetic behavior and great potential for controlled drug release.

The presented thesis includes investigations to fully characterize the electronic structure and magnetic properties ofselected manganese containing high-spin molecules by means of various X-ray spectroscopic, magnetic and theoretical methods. The investigations on the Mn4 star-shaped molecule havelead to a number of interesting results. Magneto-chemical studies exhibit very weak exchange coupling constantsbetween the four Mn(II) ions, leading to complicated low lying states in which the ground state is not well separated, resulting from a dominant weak ferromagnetic coupling and a giant moment of up to 20 µB/f.u. XMCD measurements revealed that almost the completemagnetic moment is located around the Mn(II) ions.This is in agreement with only a few charge transfer states foundwithin the detailed X-ray absorption spectroscopic study. The electronic structure and detailed magnetic properties of the star-shaped heteronuclear CrIIIMnII3 complex have been precisely investigated.With XPS the homovalency of Mn and Cr have been verified. The XA-spectra of the manganese and chromium L edges were measured and compared to earlier investigated Mn4 spectra.The combination high-magnetic field magnetic measurements and element selective XMCD of Mn and Cr L edges and quantum model calculations lead to a complete analysis of the magnetic structure of the CrMn3 magnetic core. The III valence state of the manganese ions in MnIII6O2Salox has been verified. From X-ray diffraction, typical Jahn-Teller distorted oxygen octahedra have been found for Mn(III) ions. Comparisons of XPS and XAS spectra of the complex to corresponding spectraof maganite and tetranuclear manganese(II) cluster it was definitely possible to identify MnIII6O2Salox as a pure Mn(III) compound.

Ziel der vorliegenden Arbeit ist es, das Preisach-Modell bezüglich stochastischer äußerer Felder und temperaturbezogener Aspekte zu untersuchen. Das phänomenologische Preisach-Modell wird oft erfolgreich angewendet, um Systeme mit Hysterese zu beschreiben. Im ersten Teil der Arbeit wird die Antwort des Preisach-Modells auf stochastische äußere Felder untersucht. Hier liegt das Augenmerk hauptsächlich auf der Autokorrelation; sie dient dazu den Einfluss des hysteretischen Gedächtnisses zu quantifizieren. Mit analytischen Methoden wird gezeigt, dass sich ein Langzeitgedächtnis, sichtbar in der Autokorrelation der Systemantwort, entwickeln kann, selbst wenn das treibende Feld unkorreliert ist. Im Anschluss werden diese Resultate, m.H. von Simulationen, auf äußere Felder ausgeweitet, die selbst Korrelationen aufweisen können. Der zweite Teil der Arbeit befasst sich mit dem Einfluss einer endlichen Temperatur auf das Preisach-Modell. Es werden unterschiedliche Methoden besprochen, wie das Nichtgleichgewichtsmodell in seiner mikromagnetischen Interpretation mit Temperatur als Gleichgewichtseigenschaft verknüpft werden kann. Eine Formulierung wird genutzt, um die Magnetisierung von Nickelnanopartikeln in einer Fullerenmatrix zu simulieren und mit Experimenten zu vergleichen. Des Weiteren wird die Relaxationsdynamik des Gedächtnisses des Preisach-Modells bei endlichen Temperaturen untersucht. / The aim of this thesis is to investigate the Preisach model in regard to stochastically driving and temperature-related aspects. The Preisach model is a phenomenological model for systems with hysteresis which is often successfully applied. Hysteresis is a widespread phenomenon which is observed in nature and the key feature of certain technological applications. Further, it contributes to phenomena of interest in social science and economics as well. Prominent examples are the magnetization of ferromagnetic materials in an external magnetic field or the adsorption-desorption hysteresis observed in porous media. Hysteresis involves the development of a hysteresis memory, and multistability in the interrelations between external driving fields and system response. In the first part, we mainly investigate the response of Preisach hysteresis models driven by stochastic input processes with regard to autocorrelation functions to quantify the influence of the system’s memory. Using rigorous methods, it is shown that the development of a hysteresis memory is reflected in the possibility of long-time tails in the autocorrelation functions, even for uncorrelated driving fields. In the case of uncorrelated driving, these long-time tails in the autocorrelations of the system’s response are determined only by the tails of the involved densities. They will be observed if there are broad Preisach densities assigning a high weight to elementary loops of large width and narrow input densities such that rare extreme events of the input time series contribute significantly to the output for a long period of time. Afterwards, these results are extended by simulations to driving fields which themselves show correlations. It is shown that the autocorrelation of the output does not decay faster than the autocorrelation of the input process. Further, there is a possibility that long-term memory in the hysteretic response is more pronounced in the case of uncorrelated driving than in the case of correlated driving. The behavior of the output probability distribution at the saturation values is quite universal. It is not affected by the presence of correlations and allows conclusions whether the input density is much more narrow than the Preisach density or not. Moreover, the existence of effective Preisach densities is shown which define equivalence classes of systems of input and Preisach densities which lead to realizations of the same output variable. The asymptotic behavior of an effective Preisach density determines the asymptotic correlation decay of the system’s response in the case of uncorrelated driving. In the second part, temperature-related effects are considered. It is reviewed how the non-equilibrium Preisach model in its micromagnetic picture can be related to temperature within the framework of extended irreversible thermodynamics. The irreversible response of a ferromagnetic material, namely, Nickel nanoparticles in a fullerene matrix, is simulated. The model includes superparamagnetism where ferromagnetism breaks down at temperatures lower than the Curie temperature and the results are compared to experimental data. Furthermore, we adapt known results for the thermal relaxation of the system’s memory in the form of a front propagation in the Preisach plane derived basically from solving a master equation and by the use of a contradictory assumption. A closer look is taken at short time scales which dissolves the contradiction and shows that the known results apply, taking into account the fact that the dividing line propagation starts with an additional delay time depending on the front coordinates in the Preisach plane. Additionally, it is outlined how thermal relaxation behavior in the Preisach model of hysteresis can be studied using a Fokker-Planck equation. The latter is solved analytically in the non-hysteretic limit using eigenfunction methods. The results indicate a change in the relaxation behavior, especially on short time scales.

Ziel der vorliegenden Arbeit ist es, das Preisach-Modell bezüglich stochastischer äußerer Felder und temperaturbezogener Aspekte zu untersuchen. Das phänomenologische Preisach-Modell wird oft erfolgreich angewendet, um Systeme mit Hysterese zu beschreiben. Im ersten Teil der Arbeit wird die Antwort des Preisach-Modells auf stochastische äußere Felder untersucht. Hier liegt das Augenmerk hauptsächlich auf der Autokorrelation; sie dient dazu den Einfluss des hysteretischen Gedächtnisses zu quantifizieren. Mit analytischen Methoden wird gezeigt, dass sich ein Langzeitgedächtnis, sichtbar in der Autokorrelation der Systemantwort, entwickeln kann, selbst wenn das treibende Feld unkorreliert ist. Im Anschluss werden diese Resultate, m.H. von Simulationen, auf äußere Felder ausgeweitet, die selbst Korrelationen aufweisen können. Der zweite Teil der Arbeit befasst sich mit dem Einfluss einer endlichen Temperatur auf das Preisach-Modell. Es werden unterschiedliche Methoden besprochen, wie das Nichtgleichgewichtsmodell in seiner mikromagnetischen Interpretation mit Temperatur als Gleichgewichtseigenschaft verknüpft werden kann. Eine Formulierung wird genutzt, um die Magnetisierung von Nickelnanopartikeln in einer Fullerenmatrix zu simulieren und mit Experimenten zu vergleichen. Des Weiteren wird die Relaxationsdynamik des Gedächtnisses des Preisach-Modells bei endlichen Temperaturen untersucht. / The aim of this thesis is to investigate the Preisach model in regard to stochastically driving and temperature-related aspects. The Preisach model is a phenomenological model for systems with hysteresis which is often successfully applied. Hysteresis is a widespread phenomenon which is observed in nature and the key feature of certain technological applications. Further, it contributes to phenomena of interest in social science and economics as well. Prominent examples are the magnetization of ferromagnetic materials in an external magnetic field or the adsorption-desorption hysteresis observed in porous media. Hysteresis involves the development of a hysteresis memory, and multistability in the interrelations between external driving fields and system response. In the first part, we mainly investigate the response of Preisach hysteresis models driven by stochastic input processes with regard to autocorrelation functions to quantify the influence of the system’s memory. Using rigorous methods, it is shown that the development of a hysteresis memory is reflected in the possibility of long-time tails in the autocorrelation functions, even for uncorrelated driving fields. In the case of uncorrelated driving, these long-time tails in the autocorrelations of the system’s response are determined only by the tails of the involved densities. They will be observed if there are broad Preisach densities assigning a high weight to elementary loops of large width and narrow input densities such that rare extreme events of the input time series contribute significantly to the output for a long period of time. Afterwards, these results are extended by simulations to driving fields which themselves show correlations. It is shown that the autocorrelation of the output does not decay faster than the autocorrelation of the input process. Further, there is a possibility that long-term memory in the hysteretic response is more pronounced in the case of uncorrelated driving than in the case of correlated driving. The behavior of the output probability distribution at the saturation values is quite universal. It is not affected by the presence of correlations and allows conclusions whether the input density is much more narrow than the Preisach density or not. Moreover, the existence of effective Preisach densities is shown which define equivalence classes of systems of input and Preisach densities which lead to realizations of the same output variable. The asymptotic behavior of an effective Preisach density determines the asymptotic correlation decay of the system’s response in the case of uncorrelated driving. In the second part, temperature-related effects are considered. It is reviewed how the non-equilibrium Preisach model in its micromagnetic picture can be related to temperature within the framework of extended irreversible thermodynamics. The irreversible response of a ferromagnetic material, namely, Nickel nanoparticles in a fullerene matrix, is simulated. The model includes superparamagnetism where ferromagnetism breaks down at temperatures lower than the Curie temperature and the results are compared to experimental data. Furthermore, we adapt known results for the thermal relaxation of the system’s memory in the form of a front propagation in the Preisach plane derived basically from solving a master equation and by the use of a contradictory assumption. A closer look is taken at short time scales which dissolves the contradiction and shows that the known results apply, taking into account the fact that the dividing line propagation starts with an additional delay time depending on the front coordinates in the Preisach plane. Additionally, it is outlined how thermal relaxation behavior in the Preisach model of hysteresis can be studied using a Fokker-Planck equation. The latter is solved analytically in the non-hysteretic limit using eigenfunction methods. The results indicate a change in the relaxation behavior, especially on short time scales.