O presente trabalho investiga o fenômeno termodifusivo em dispersões coloidais de nanopartículas magnéticas de óxidos de ferro em água (ferrofluidos), com a formação de dupla camada elétrica em torno das partículas. A estabilidade da partícula em solução é controlada pela concentração de íons. Ao estabelecer uma diferença de temperatura através da amostra líquida, ocorre o efeito de termodifusão (efeito Soret) das partículas e de íons em solução. Este efeito é o movimento das partículas para o lado frio ou quente do gradiente de temperatura. O acúmulo para um dos lados do gradiente de temperatura depende das características da solução. O efeito Soret de ferrofluidos em soluções ácidas e básicas é descrito a partir da determinação experimental das grandezas físicas envolvidas na difusão das partículas. O coeficiente Soret ST e o coeficiente de difusão são determinados em experimentos ópticos de lente de matéria, utilizando o aparato experimental de Varredura-Z, e de espalhamento Rayleigh forçado para termodifusão. Para investigar a resposta dos íons ao gradiente de temperatura, são realizadas medidas do potencial termoelétrico em uma célula termoelétrica, gerado a partir da difusão das cargas dispersas no líquido. O potencial superficial das partículas também é investigado experimentalmente, para descrever a interação das partículas com o campo termoelétrico. Os experimentos são realizados em função da temperatura da amostra e usados para descrever os resultados ST(T) das partículas, a partir de equações dos principais modelos teóricos. Os resultados mostram as diferenças e semelhanças do efeito Soret das nanopartículas em soluções ácidas e básicas, e que em ambos os casos a termodifusão de nanopartículas reflete o comportamento termodifusivo dos íons dispersos em solução. / This work investigates the thermal diffusion phenomena in colloidal dispersions of iron oxide magnetic nanoparticles dispersed in water (ferrofluid). The particles are stable in water due to electrical double layer around the particles, controlled by the ionic concentration. A temperature gradient throughout the ferrofluid sample causes the thermodiffusion (Soret effect) of dispersed particles and ions. This effect is the movement of particles to the cold or hot side of the temperature gradient. The particles migration for a given side depends on the characteristics of the sample. The Soret effect of ferrofluids in acidic and basic solutions is described by the experimental measurements of the physical parameters associated to particles diffusion. The Soret coefficient ST and the mass diffusion coefficient are measured in the matter lens experiment in the Z-scan experimental setup, and by the use of Thermal Diffusion Forced Rayleigh Scattering experiments. Concerning the ionic response to the temperature gradient the thermoelectric field generated by charges diffusion is measured in a thermoelectric cell. The surface potential of the particles is also measured to describe its interactions with the thermoelectric field. These experiments are made as function of the temperature of the sample and the results are applied to describe the ST(T) of particles by the use of equations from the main theoretical models. The results show differences and resemblances of the Soret effect in acidic and basic nanoparticles solutions. In both kind of solutions the thermodiffusion of nanoparticles is mainly ruled by the thermodiffusion of ions dispersed in solution.

Nanoparticle assemblies are of current interest as they are used in a wide variety of industrial and biomedical applications. This work presents two studies aimed at understanding the magnetization dynamics and interparticle interactions in nanoparticle assemblies and various types of ferrofluids. First, we studied the influence of varying strengths of dipolar interaction on the static and dynamic magnetic properties of surfactant-coated monodispersed manganese-zinc ferrite nanoparticles using reversible transverse susceptibility. We tracked the evolution of the anisotropy peaks with varying magnetic field, temperature, and interaction strength. The anisotropy peaks of weakly interacting particles appears as non-symmetric peaks and at lower fields in a unipolar transverse susceptibility scan. On the other hand, a strongly interacting particle system exhibits symmetric anisotropy peaks situated at higher field values. In the second study, we successfully synthesized stable ferrofluids out of high quality Fe 3O4 and CoFe2O4 nanoparticles. Such ferrofluids are excellent systems for the investigation of physics of relaxation phenomena in magnetic nanoparticles. Motivated by the need to understand their peculiar magnetic response, a comparative study on Fe 3O4 - and CoFe 2O4 -based ferrofluids was performed. We investigated cases in which particle blocking and carrier fluid freezing temperatures were close and far apart from each other. Our experimental results reveal the true origin of the glass-like relaxation peaks that have been widely observed in ferrofluids by many groups but remained largely unexplained. Contrary to the speculation of previous literature, we argue that the formation of the magnetic anomaly is due not only to the particle blocking but also to its correlation with the the carrier fluid freezing effects. It is also shown that the nature of these peaks is strongly affected by varying particle size and carrier fluid medium. Quantitative fits of the frequency dependent AC susceptibility to the Vogel-Fulcher scaling law clearly indicate that the blocking of magnetic nanoparticles in the frozen state significantly affects the interparticle dipole-dipole interaction, causing characteristic spin-glass-like dynamics. A clear correlation between the blocking and freezing temperatures emerges from our studies for the first time.

O presente trabalho investiga o fenômeno termodifusivo em dispersões coloidais de nanopartículas magnéticas de óxidos de ferro em água (ferrofluidos), com a formação de dupla camada elétrica em torno das partículas. A estabilidade da partícula em solução é controlada pela concentração de íons. Ao estabelecer uma diferença de temperatura através da amostra líquida, ocorre o efeito de termodifusão (efeito Soret) das partículas e de íons em solução. Este efeito é o movimento das partículas para o lado frio ou quente do gradiente de temperatura. O acúmulo para um dos lados do gradiente de temperatura depende das características da solução. O efeito Soret de ferrofluidos em soluções ácidas e básicas é descrito a partir da determinação experimental das grandezas físicas envolvidas na difusão das partículas. O coeficiente Soret ST e o coeficiente de difusão são determinados em experimentos ópticos de lente de matéria, utilizando o aparato experimental de Varredura-Z, e de espalhamento Rayleigh forçado para termodifusão. Para investigar a resposta dos íons ao gradiente de temperatura, são realizadas medidas do potencial termoelétrico em uma célula termoelétrica, gerado a partir da difusão das cargas dispersas no líquido. O potencial superficial das partículas também é investigado experimentalmente, para descrever a interação das partículas com o campo termoelétrico. Os experimentos são realizados em função da temperatura da amostra e usados para descrever os resultados ST(T) das partículas, a partir de equações dos principais modelos teóricos. Os resultados mostram as diferenças e semelhanças do efeito Soret das nanopartículas em soluções ácidas e básicas, e que em ambos os casos a termodifusão de nanopartículas reflete o comportamento termodifusivo dos íons dispersos em solução. / This work investigates the thermal diffusion phenomena in colloidal dispersions of iron oxide magnetic nanoparticles dispersed in water (ferrofluid). The particles are stable in water due to electrical double layer around the particles, controlled by the ionic concentration. A temperature gradient throughout the ferrofluid sample causes the thermodiffusion (Soret effect) of dispersed particles and ions. This effect is the movement of particles to the cold or hot side of the temperature gradient. The particles migration for a given side depends on the characteristics of the sample. The Soret effect of ferrofluids in acidic and basic solutions is described by the experimental measurements of the physical parameters associated to particles diffusion. The Soret coefficient ST and the mass diffusion coefficient are measured in the matter lens experiment in the Z-scan experimental setup, and by the use of Thermal Diffusion Forced Rayleigh Scattering experiments. Concerning the ionic response to the temperature gradient the thermoelectric field generated by charges diffusion is measured in a thermoelectric cell. The surface potential of the particles is also measured to describe its interactions with the thermoelectric field. These experiments are made as function of the temperature of the sample and the results are applied to describe the ST(T) of particles by the use of equations from the main theoretical models. The results show differences and resemblances of the Soret effect in acidic and basic nanoparticles solutions. In both kind of solutions the thermodiffusion of nanoparticles is mainly ruled by the thermodiffusion of ions dispersed in solution.

Particle dispersions provide a promising tool for the engineering of functional materials that exploit self-assembly of complex structures. Dispersion made from magnetic colloidal particles is a great choice; they are biocompatible and remotely controllable among many other advantages. However, their dominating dipolar interaction typically limits structural complexity to linear arrangements. This paper shows how a magnetostatic equilibrium state with noncollinear arrangement of the magnetic moments, as reported for ferromagnetic Janus particles, enables the controlled self-organization of diverse structures in two dimensions via constant and low-frequency external magnetic fields. Branched clusters of staggered chains, compact clusters, linear chains, and dispersed single particles can be formed and interconverted reversibly in a controlled way. The structural diversity is a consequence of both the inhomogeneity and the spatial extension of the magnetization distribution inside the particles. We draw this conclusion from calculations based on a model of spheres with multiple shifted dipoles. The results demonstrate that fundamentally new possibilities for responsive magnetic materials can arise from interactions between particles with a spatially extended, anisotropic magnetization distribution.

Systems of interacting colloidal particles are ideal tools for studies of pattern formation and collective non-equilibrium dynamics on the mesoscopic scale. These processes are governed by the interaction between the particles, which can be tuned by sophisticated fabrication. In this thesis, self-assembly of artificially designed magnetic spheres dispersed in water has been studied via video microscopy. The particles are based on silica microspheres with hemispherical ferromagnetic coating of [Co/Pd] multilayers with perpendicular magnetic anisotropy. These particles are exceptional in that they exhibit an off-centered net magnetic moment and yet obey rotational and mirror symmetry. It has been demonstrated how these magnetic properties provide innovative flexibility in pattern formation and collective dynamics based on magnetostatic interactions on the mesoscopic scale. The results are supported by analytical and numerical calculations of interacting spheres with radially shifted point dipoles (sd-particles). In two dimensions, the particles spontaneously self-assemble into branched structures as a result of a bistable assembly behavior where neighboring particles exhibit a non-collinear magnetic orientation. It has been shown that these features, which are atypical for homogeneous systems of magnetic particles, can be reproduced by simulation. It employs a theoretical model of a sphere that contains a distribution of three radially shifted point dipoles in analogy to the magnetization distribution in the coated particles. The stability of the assembly has been examined further by external manipulation using optical tweezers and homogeneous magnetic fields. A rich variety of stable structures with diverse spatial and magnetic ordering has been found. Particularly, the collective alignment of the specially designed particles in external fields opens completely new possibilities for the remote control over reversible pattern formation on the micrometer scale. In time-dependent fields, the collective dynamics of the anisotropic particles has revealed a novel approach for magnetically actuated translation. The variety of stable structures particularly enables control over this motion. / Kolloidale Suspensionen sind geeignete Systeme zur Untersuchung von Strukturbildung und kollektiver Nichtgleichgewichtsdynamik in mesoskopischen Größenskalen. Diese Vorgänge werden durch die Wechselwirkung zwischen den Teilchen bestimmt, welche durch geeignete Partikelherstellung angepasst werden kann. In der vorliegenden Arbeit wird ein System von künstlich hergestellten magnetischen Partikelsuspensionen mittels Videomikroskopie untersucht. Quarzglas-Mikrokugeln wurden halbseitig mit einer ferromagnetischen Dünnschicht aus [Co/Pd] Multilagen mit senkrechter Anisotropie beschichtet. Solche Partikel sind ausgezeichnet durch ein resultierendes magnetisches Moment mit Rotations- und Spiegelsymmterie, welches zusätzlich vom Mittelpunkt der Kugel verschoben ist. Die vorliegende Arbeit zeigt, dass diese Besonderheit zu einer bisher unbekannten Flexibilität bei der mesoskopischen Strukturbildung und der kollektiven Dynamik auf der Basis magnetostatischer Wechselwirkung führt. Die vorgestellten Ergebnisse werden durch analytische und numerische Berechnungen unterstützt, denen ein Modell einer idealen Kugel mit verschobenem Dipol zugrunde liegt. Die zweidimensionale Selbstanordnung der Partikel zeigt experimentell zwei stabile Formen der Verknüpfung, welche zu verzweigten Strukturen mit unterschiedlich magnetischer Ausrichtung benachbarter Partikel führen. Diese für ein homogenenes System magnetischer Partikel außergewöhnlichen Eigenschaften konnten in Simulationen durch ein Modellsystem aus Kugeln mit drei verschobenen Punktdipolen reproduziert werden. Darüber hinaus wurde die spontante Anordnung unter externer Manipulation mittels optischer Pinzette und magnetischen Feldern untersucht. Es konnte eine Vielfalt an stabilen Strukturen mit verschiedenen magnetischen und strukturellen Anordnungen gefunden werden. Insbesondere die kollektive Ausrichtung dieser Partikel in externen Feldern eröffnet neuartige Möglichkeiten, kontrolliert und reversibel Mikrostrukturen zu erzeugen. In zeitabhängigen Feldern zeigen die anisotropen Partikel zusätzlich eine kollektive Dynamik welche eine neue Möglichkeit zum magnetischen Antrieb von Partikelagglomeraten eröffnet. Die Vielfalt der möglichen stabilen Strukturen erlaubt es in besonderer Weise diese Bewegung zu steuern.

Systems of interacting colloidal particles are ideal tools for studies of pattern formation and collective non-equilibrium dynamics on the mesoscopic scale. These processes are governed by the interaction between the particles, which can be tuned by sophisticated fabrication. In this thesis, self-assembly of artificially designed magnetic spheres dispersed in water has been studied via video microscopy. The particles are based on silica microspheres with hemispherical ferromagnetic coating of [Co/Pd] multilayers with perpendicular magnetic anisotropy. These particles are exceptional in that they exhibit an off-centered net magnetic moment and yet obey rotational and mirror symmetry. It has been demonstrated how these magnetic properties provide innovative flexibility in pattern formation and collective dynamics based on magnetostatic interactions on the mesoscopic scale. The results are supported by analytical and numerical calculations of interacting spheres with radially shifted point dipoles (sd-particles). In two dimensions, the particles spontaneously self-assemble into branched structures as a result of a bistable assembly behavior where neighboring particles exhibit a non-collinear magnetic orientation. It has been shown that these features, which are atypical for homogeneous systems of magnetic particles, can be reproduced by simulation. It employs a theoretical model of a sphere that contains a distribution of three radially shifted point dipoles in analogy to the magnetization distribution in the coated particles. The stability of the assembly has been examined further by external manipulation using optical tweezers and homogeneous magnetic fields. A rich variety of stable structures with diverse spatial and magnetic ordering has been found. Particularly, the collective alignment of the specially designed particles in external fields opens completely new possibilities for the remote control over reversible pattern formation on the micrometer scale. In time-dependent fields, the collective dynamics of the anisotropic particles has revealed a novel approach for magnetically actuated translation. The variety of stable structures particularly enables control over this motion. / Kolloidale Suspensionen sind geeignete Systeme zur Untersuchung von Strukturbildung und kollektiver Nichtgleichgewichtsdynamik in mesoskopischen Größenskalen. Diese Vorgänge werden durch die Wechselwirkung zwischen den Teilchen bestimmt, welche durch geeignete Partikelherstellung angepasst werden kann. In der vorliegenden Arbeit wird ein System von künstlich hergestellten magnetischen Partikelsuspensionen mittels Videomikroskopie untersucht. Quarzglas-Mikrokugeln wurden halbseitig mit einer ferromagnetischen Dünnschicht aus [Co/Pd] Multilagen mit senkrechter Anisotropie beschichtet. Solche Partikel sind ausgezeichnet durch ein resultierendes magnetisches Moment mit Rotations- und Spiegelsymmterie, welches zusätzlich vom Mittelpunkt der Kugel verschoben ist. Die vorliegende Arbeit zeigt, dass diese Besonderheit zu einer bisher unbekannten Flexibilität bei der mesoskopischen Strukturbildung und der kollektiven Dynamik auf der Basis magnetostatischer Wechselwirkung führt. Die vorgestellten Ergebnisse werden durch analytische und numerische Berechnungen unterstützt, denen ein Modell einer idealen Kugel mit verschobenem Dipol zugrunde liegt. Die zweidimensionale Selbstanordnung der Partikel zeigt experimentell zwei stabile Formen der Verknüpfung, welche zu verzweigten Strukturen mit unterschiedlich magnetischer Ausrichtung benachbarter Partikel führen. Diese für ein homogenenes System magnetischer Partikel außergewöhnlichen Eigenschaften konnten in Simulationen durch ein Modellsystem aus Kugeln mit drei verschobenen Punktdipolen reproduziert werden. Darüber hinaus wurde die spontante Anordnung unter externer Manipulation mittels optischer Pinzette und magnetischen Feldern untersucht. Es konnte eine Vielfalt an stabilen Strukturen mit verschiedenen magnetischen und strukturellen Anordnungen gefunden werden. Insbesondere die kollektive Ausrichtung dieser Partikel in externen Feldern eröffnet neuartige Möglichkeiten, kontrolliert und reversibel Mikrostrukturen zu erzeugen. In zeitabhängigen Feldern zeigen die anisotropen Partikel zusätzlich eine kollektive Dynamik welche eine neue Möglichkeit zum magnetischen Antrieb von Partikelagglomeraten eröffnet. Die Vielfalt der möglichen stabilen Strukturen erlaubt es in besonderer Weise diese Bewegung zu steuern.