Title: PFM and Raman spectroscopy of selected dielectric materials Author: Fedir Borodavka Institute: Department of Dielectrics, Institute of Physics of the Academy of Sciences, Na Slovance 2, 182 21, Prague 8, Czech Republic Supervisor: Ing. Ivan Gregora, CSc. Training institute: Department of Dielectrics, Institute of Physics of the Academy of Sciences, Na Slovance 2, 182 21, Prague 8, Czech Republic Consultants: RNDr. Stanislav Kamba, CSc. and RNDr. Vladimír Vorlíček, CSc. Abstract: The thesis is devoted to a detailed investigation of dielectric materials using Raman spectroscopy and PFM microscopy techniques. Phonon properties of a newly synthesized guanylurea(1+) hydrogen phosphite single crystals have been studied. A tentative assignment of the observed Raman peaks has been done and the sets of A′ MIX, A′ TO and A′′ TO mode frequencies have been determined. Phonon behaviour of BiMnO3 ceramics, obtained from Raman spectra, has been char- acterized. After comparing the factor group analysis with the Raman spectra it has been concluded that the material has a centrosymmetric C2/c structure and is not ferroelectric. Lattice modes of the complex La1/2Na1/2TiO3 single crystal have been investigated. We have numerically analysed the intensity behaviour of the sharp peak at 455 cm−1 on heating and...

La séparation magnétique est utilisée dans le domaine de la purification de l’eau. Des nanoparticules magnétiques fonctionnalisées ou nues sont en charge de capter un polluant ciblé puis sont enlevées de l’eau par l’application d’un champ magnétique. Nous avons montré que l’utilisation d’un ferrofluide aqueux classique constitué de nanoparticules d’oxyde de fer recouvertes par une double couche de surfactant d’acide oléique permet une adsorption efficace des cations métalliques (ion nickel Ni2+) puis leur enlèvement en utilisant des microparticules magnétiques. Nous avons montré que des interactions magnétiques suffisamment fortes entre les nanoparticules induisent une transition de phase colloïdale. Il existe trois régimes de captage qui dépendent de deux paramètres, le premier paramètre est lié à l’intensité du champ magnétique et le second est la concentration en nanoparticules. En présence de l’écoulement de la suspension des nanoparticules, le captage des nanoparticules est toujours régi par la concentration en nanoparticules et également par le nombre de Mason. Nous avons mené une expérience de captage des nanoparticules par un milieu poreux. L’efficacité de filtration est liée à la compétition entre les forces hydrodynamiques et magnétiques ainsi que de la séparation de phase au sein de la suspension. Les théories développées lors de ce travail sont en accord raisonnable avec les résultats expérimentaux et montrent l’augmentation de l’efficacité de captage des nanoparticules avec l’augmentation de l’intensité du champ magnétique et de la concentration en nanoparticules ainsi que la diminution de l’efficacité de captage avec l’augmentation du nombre de Mason. / Magnetic separation is used in the domain of water purification. In these systems, functionalized or bare magnetic nanoparticles are used to capture a target pollutant then they are extracted from water by an applied magnetic field. We have shown that a classical aqueous ferrofluid composed by iron oxide nanoparticles covered with an oleic acid double layer allows efficient adsorption of metallic cations (nickel ion Ni2+) followed by nanoparticle extraction with the help of magnetic microparticles. We have shown that strong enough magnetic interactions between nanoparticles can induce a colloidal phase transition. There exists three capture regimes which depend on two parameters, the first one is related to the magnetic field intensity and the second is the nanoparticle concentration. In the presence of the flow of nanoparticle suspension, the nanoparticle capture is always governed by the nanoparticle concentration and also by Mason number. We have carried out an experiment on nanoparticle capture in a porous medium. The filtration efficiency is related to the competition between the hydrodynamic and magnetic forces, as well as to the phase separation in the suspension bulk. The theories developed in the frames of this work show a reasonable agreement with the experimental results. They predict an increase of the capture efficiency with an increase of the magnetic field intensity and the nanoparticle concentration as well as a decrease of the capture efficiency with the growth of the Mason number.

Cette thèse traite les problèmes statistiques suivants : la sélection de variables dans le modèle de régression linéaire en grande dimension, le clustering dans le modèle de mélange Gaussien, quelques effets de l'adaptabilité sous l'hypothèse de parcimonie ainsi que la simulation des processus Gaussiens.Sous l'hypothèse de parcimonie, la sélection de variables correspond au recouvrement du "petit" ensemble de variables significatives. Nous étudions les propriétés non-asymptotiques de ce problème dans la régression linéaire en grande dimension. De plus, nous caractérisons les conditions optimales nécessaires et suffisantes pour la sélection de variables dans ce modèle. Nous étudions également certains effets de l'adaptation sous la même hypothèse. Dans le modèle à vecteur parcimonieux, nous analysons les changements dans les taux d'estimation de certains des paramètres du modèle lorsque le niveau de bruit ou sa loi nominale sont inconnus.Le clustering est une tâche d'apprentissage statistique non supervisée visant à regrouper des observations proches les unes des autres dans un certain sens. Nous étudions le problème de la détection de communautés dans le modèle de mélange Gaussien à deux composantes, et caractérisons précisément la séparation optimale entre les groupes afin de les recouvrir de façon exacte. Nous fournissons également une procédure en temps polynomial permettant un recouvrement optimal des communautés.Les processus Gaussiens sont extrêmement utiles dans la pratique, par exemple lorsqu'il s'agit de modéliser les fluctuations de prix. Néanmoins, leur simulation n'est pas facile en général. Nous proposons et étudions un nouveau développement en série à taux optimal pour simuler une grande classe de processus Gaussiens. / This PhD thesis deals with the following statistical problems: Variable selection in high-Dimensional Linear Regression, Clustering in the Gaussian Mixture Model, Some effects of adaptivity under sparsity and Simulation of Gaussian processes.Under the sparsity assumption, variable selection corresponds to recovering the "small" set of significant variables. We study non-asymptotic properties of this problem in the high-dimensional linear regression. Moreover, we recover optimal necessary and sufficient conditions for variable selection in this model. We also study some effects of adaptation under sparsity. Namely, in the sparse vector model, we investigate, the changes in the estimation rates of some of the model parameters when the noise level or its nominal law are unknown.Clustering is a non-supervised machine learning task aiming to group observations that are close to each other in some sense. We study the problem of community detection in the Gaussian Mixture Model with two components, and characterize precisely the sharp separation between clusters in order to recover exactly the clusters. We also provide a fast polynomial time procedure achieving optimal recovery.Gaussian processes are extremely useful in practice, when it comes to model price fluctuations for instance. Nevertheless, their simulation is not easy in general. We propose and study a new rate-optimal series expansion to simulate a large class of Gaussian processes.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18951号 / 工博第3993号 / 新制||工||1615(附属図書館) / 31902 / 京都大学大学院工学研究科合成・生物化学専攻 / (主査)教授 北川 進, 教授 松田 建児, 教授 安部 武志 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

権利表示を行うこと, 出典表示を行うこと, 出版社版へのリンクを表示すること / 京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19488号 / 理博第4148号 / 新制||理||1596(附属図書館) / 32524 / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 大西 明, 准教授 菅沼 秀夫, 教授 田中 貴浩 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20364号 / 工博第4301号 / 新制||工||1666(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 邑瀬 邦明, 教授 杉村 博之, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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The magnetic properties of NiMnGe1−xAlx, Ni50Mn35(In1−xBx)15, Ni50Mn35In14.5B0.5 (Bulk, As-Solidified and Annealed melt-spun ribbon) and RE-Infuse Carbon Nanotubes, have been studied by x-ray diffraction, differential scanning calorimetry (DSC), and magnetization measurements. Partial substitution of Al for Ge in NiMnGe1−xAlx results in a first-order magnetostructural transition (MST) from a hexagonal ferromagnetic to an orthorhombic antiferromagnetic phase at 186 K (for x = 0.09). A large magnetic entropy change of ∆SM = -17.6 J/kg K for ∆H = 5 T was observed in the vicinity of TM = 186 K for x = 0.09. This value is comparable to those of well-known giant magnetocaloric materials, such as Gd5Si2Ge2, MnFeP0.45As0.55, and Ni50Mn37Sn13. The values of the latent heat (L = 6.6 J/g) and corresponding total entropy changes (∆ST = 35 J/kg K) have been evaluated for the MST using DSC measurements. Large negative values of ∆SM of -5.8 and -4.8 J/kg K for ∆H = 5 T and up to 9T in the vicinity of TC were observed for x = 0.09 and 0.085, respectively. The impact of B substitution in Ni50Mn35In15-xBx Heusler alloys on the structural, magnetic, transport, and parameters of the magnetocaloric effect (MCE) has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (H) up to 5 T, and in the temperature interval 5-400 K ). Direct adiabatic temperature change (ΔTAD) measurements have been carried out for an applied magnetic field change of 1.8 T. The transition temperatures (T-x) phase diagram has been constructed for H = 0.005 T. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X=In, Al, and Ge) Heusler alloys. The maximum absolute value of ΔTAD = 2.5 K was observed at the magnetostructural transition for Ni50Mn35In14.5B0.5. The structural phase transition temperatures, phase structure, and parameters of the magnetocaloric effect (MCE) of Ni50Mn35In14.5B0.5 as Bulk, As-Solidified and Annealed melt-spun ribbon has been studied by means of room-temperature X-ray diffraction and thermomagnetic measurements (in magnetic fields (oH) up to 5 T, and in the temperature interval 5–400 K). Magnetic and structural transitions in Ni50Mn35In14.5B0.5 as ribbons were found to coincide in Ni50Mn35In14.5B0.5 bulk sample, leading to a large magnetocaloric effects associated with the first-order magnetostructural phase transition. In comparison to the bulk Ni50Mn35In14.5B0.5 alloys, both the martensitic transition temperature (TM) and Curie temperature (TC) shifted to lower temperatures. Magnetic measurements revealed that the ribbons undergo a structure transformation similar to the bulk material at the martensitic transformation. The temperature of the transformation depends strongly on lattice parameters of the ribbons. MST shows a weak broad magnetic transition at TCM∼ 160 K, while the Curie temperature of AST TCA is ∼ 297 K. The MCE parameters were found to be comparable to those observed in other MCE materials such as Ni50Mn34.8In14.2B and Ni50Mn35In14X (X = In, Al, and Ge) Heusler alloys. These results suggest the possibility to control the martensitic transition in Ni50Mn35In14.5B0.5 through rapid solidification process. A comparison of magnetic properties and magnetocaloric effects in Ni50Mn35In14.5B0.5 alloys as Bulk, As-Solidified and Annealed ribbons is discussed. Carbon nanotube (CNT)/metal-cluster-based composites are envisioned as new materials that possess unique electronic properties which may be utilized in a variety of future applications. Super paramagnetic behavior was reported for CNTs with Gd ions introduced into the CNT openings by internal loading with an aqueous GdCl3 chemical process. In the current work, the magnetic properties of the CNT/Gd composites were obtained by the joining and annealing of Gd metal and CNTs at 850 °C for 48 h. Energy dispersive X-ray analysis shows the presence of Gd intermingled with the CNT walls with maximum and average Gd concentrations of about 20% and 4% (by weight), respectively. The Gd clusters have a non-uniform distribution and are mostly concentrated at the ends of the CNTs. A ferromagnetic-type transition at TC ∼ 320 K, accompanied by jump like change in magnetization and temperature hysteresis typical for the temperature induced first order phase transitions has been observed by magnetization measurements. It was found that Gd infused into the CNTs by the annealing results in a first order paramagnetic-ferromagnetic transition at TC = 320 K.

Bacterial membranes act as protective barriers and help to regulate molecular interactions between a cell and its surrounding environment. External chemical and physical influences have the potential to alter the properties of bacterial membranes and therefore impact the viability of the cell. This can stem from natural or seasonal changes to the local environment (e.g., temperature, pH, and salinity), or even deliberate application of an antimicrobial agent. Regardless, understanding exactly how such external stimuli influence bacterial membrane properties is of fundamental importance, both in terms of basic microbiology as well as for designing pharmaceutical interventions. Experimentally, this is a non-trivial task as this requires selective isolation of a signal arising from the membrane, which is typically buried in the overwhelming background response of the surrounding bulk environment. In particular, our lab has previously developed the surface-sensitive nonlinear optical method, second harmonic light scattering (SHS), as a means of interrogating molecular interactions at the membrane surfaces of living cells, even for multimembrane systems (e.g., Gram-negative bacteria). In this dissertation, time-resolved SHS was employed to study a variety of membrane properties across two separate projects, including 1) chemical and physical induced changes in membrane permeability and 2) temperature-induced membrane permeability changes. Specifically, in the first project (Chapter 4), the influence of the signaling molecule, indole, on the permeability of the bacterial cytoplasmic membrane was quantified. It was revealed that the interaction of indole with the tryptophan specific transporting protein, Mtr permease, resulted in enhanced passive diffusion across the membrane. For the second project (Chapter 5), we examined the influence of temperature on the rate of passive diffusion across a membrane, both in model systems (liposomes) and in living cells (E. coli). For both bacterial and liposome systems, increasing temperatures resulted in a modest increase in passive diffusion rates across the membrane. However, when the temperature range included a phase transition, passive diffusion increased by an order of magnitude. Therefore, by monitoring transport rate in relation to temperature, membrane phase transitions can be quantitatively determined based on the characteristic discontinuities in the measured trend. / Chemistry

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