Aerosol electrostatics is an important property of pharmaceutical aerosols. The electrostatic properties of pMDI aerosols have been shown to be a function of both formulation and packaging components. The modified ELPI enables measurement of aerosol charge as a function of particle size, and the simultaneous determination of the mass distribution using chemical analysis. However, in order to fully assess the cause and effects of aerosol electrostatics in terms of its biological and regulatory implications, it is necessary to understand the basic charging mechanisms inside the pMDI formulation. Electrical resistivity and zeta potential measurements confirmed the presence of charged species within HFA based solutions and suspensions although the nature of these species remains unknown. These measurements were influenced by the cosolvent concentration and to a lesser extent by the presence of soluble drug and surfactant. The mean electrical resistivity of a 7% ethanol / 93% HFA 134a blend (0.83 ± 0.02 MΩ.cm) was significantly lower than that reported for HFA 134a (180 MΩ.cm). Albuterol sulfate demonstrated a positive zeta potential (75.9 ± 26.2 mV) in HFA 134a. Pilot molecular modeling studies, in conjunction with the analysis of particle interactions using HINT, provided an improved understanding of the possible interactions within albuterol sulfate HFA suspension pMDIs. The predominantly negative (-7597 ± 2063) HINT score signified unfavorable interactions between albuterol sulfate and HFA 134a molecules. Systematic investigations of the electrical properties of HFA solution and suspension pMDIs using the modified ELPI demonstrated that the electrical properties were a function of the formulation type (solution/suspension), formulation components and particle size. Experimental BDP solution pMDIs produced predominantly electropositive aerosols (net charge: 160 ± 30 pC) while albuterol sulfate pMDIs produced bipolar charged aerosol clouds (net charge: -162 ± 277 pC). Finally, the modified ELPI was recalibrated using commercially available polydisperse pMDIs as calibration aerosols with a reference Andersen cascade impactor. The mean cut-off diameters for stages 4-12 obtained following recalibration of the modified ELPI were 0.44, 0.56, 0.70, 1.01, 1.40, 2.12, 3.03, 4.75, 6.37 μm, respectively in comparison to those reported by the manufacturer (0.16, 0.27, 0.39, 0.62, 0.96, 1.62, 2.42, 4.05, 6.67 μm, respectively).

<p>The Earth's bow shock is a boundary where the solar wind becomes decelerated from supersonic to subsonic speed before being deflected around the Earth. This thesis presents measurements by the Cluster spacecraft upstream and at the Earth's quasi-parallel bow shock where the angle between the upstream magnetic field and the bow shock normal is less than 45 degrees. An intrinsic feature of quasi-parallel shocks is the ability of ions, that are reflected off the shock in a specular manner, to propagate far upstream and to interact with the incident solar wind. This leads to the generation of a variety of plasma waves, e.g., Ultra-Low Frequency (ULF) waves, which in their turn interact with the different ion populations. Some of the ULF waves are thought to steepen into so-called Short Large-Amplitude Magnetic Structures (SLAMS). </p><p>This thesis studies the impact of SLAMS on the incident solar wind. SLAMS are thought to play an important role in terms of 1) returning shock-reflected ions back to the shock where they can eventually contribute to downstream thermalisation and 2) local pre-dissipation of the solar wind. </p><p>The first electric field measurements of SLAMS showed a strong electric field rotation over SLAMS in association with the rotation of the magnetic field. This often leads to a local change from quasi-parallel to quasi-perpendicular conditions. In addition, short-scale electric field features were observed, e.g., spiky electric field structures associated with the leading edge of SLAMS and solitary electric field structures on Debye length scales, which are suggested to represent ion phase space holes. </p><p>Using the abilitiy of the four Cluster satellites to obtain propagation vectors of SLAMS and the high-resolution electric field measurements, the electric potential over SLAMS was studied. These structures are associated with a significant potential on the order of a few hundred to thousand Volt. Comparing these findings with data from the ion spectrometer, it was found that the bulk flow is locally significantly decelerated and moderately deflected and heated. In addition, SLAMS reflect incident ions on both the leading and trailing edge. The flux of so-called gyrating ions show a clear maximum in association with SLAMS. This indicates that SLAMS indeed play an important role for pre-dissipation of the solar wind upstream of the shock.</p>

The Earth's bow shock is a boundary where the solar wind becomes decelerated from supersonic to subsonic speed before being deflected around the Earth. This thesis presents measurements by the Cluster spacecraft upstream and at the Earth's quasi-parallel bow shock where the angle between the upstream magnetic field and the bow shock normal is less than 45 degrees. An intrinsic feature of quasi-parallel shocks is the ability of ions, that are reflected off the shock in a specular manner, to propagate far upstream and to interact with the incident solar wind. This leads to the generation of a variety of plasma waves, e.g., Ultra-Low Frequency (ULF) waves, which in their turn interact with the different ion populations. Some of the ULF waves are thought to steepen into so-called Short Large-Amplitude Magnetic Structures (SLAMS). This thesis studies the impact of SLAMS on the incident solar wind. SLAMS are thought to play an important role in terms of 1) returning shock-reflected ions back to the shock where they can eventually contribute to downstream thermalisation and 2) local pre-dissipation of the solar wind. The first electric field measurements of SLAMS showed a strong electric field rotation over SLAMS in association with the rotation of the magnetic field. This often leads to a local change from quasi-parallel to quasi-perpendicular conditions. In addition, short-scale electric field features were observed, e.g., spiky electric field structures associated with the leading edge of SLAMS and solitary electric field structures on Debye length scales, which are suggested to represent ion phase space holes. Using the abilitiy of the four Cluster satellites to obtain propagation vectors of SLAMS and the high-resolution electric field measurements, the electric potential over SLAMS was studied. These structures are associated with a significant potential on the order of a few hundred to thousand Volt. Comparing these findings with data from the ion spectrometer, it was found that the bulk flow is locally significantly decelerated and moderately deflected and heated. In addition, SLAMS reflect incident ions on both the leading and trailing edge. The flux of so-called gyrating ions show a clear maximum in association with SLAMS. This indicates that SLAMS indeed play an important role for pre-dissipation of the solar wind upstream of the shock.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21071号 / 工博第4435号 / 新制||工||1689(附属図書館) / 京都大学大学院工学研究科電気工学専攻 / (主査)教授 大村 善治, 教授 松尾 哲司, 准教授 小嶋 浩嗣 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Ultrafine particles are relevant to many practical applications, including froth flotation, emulsion and foam formation, printing, and drug delivery. Such particles have tremendous effect on the interfacial and hydrodynamic properties of the multiphase systems both in static and dynamic conditions. Combining experimental and theoretical approaches, this research scrutinizes a multidisciplinary subject focusing on hydrodynamic and physicochemical characteristics of the ultrafine particles at fluidic interfaces. In particular, the effect of ultrafine particles on the (i) surface activity of the surfactants of different charges, (ii) mobility of the interfaces, and (iii) kinetics of particles attachment are investigated. In the first part of this thesis the effect of negatively charged silica nanoparticles, as model particles for ultrafine particles, on the interfacial behavior of the cationic surfactant (CTAB) is investigated using Profile Analysis Tensiometry (PAT). The results indicate that neither surfactant concentration nor NPs alone can determine the surface tension of the system, and that the ratio of surfactants to nanoparticles is the decisive factor. Below a critical ratio, the surface tension values remain relatively constant as the free surfactant molecules are completely depleted from the solution due to the formation of nanoparticle-surfactant complexes. Above this critical ratio, the number of free surfactant molecules increases as the surfactant concentration increases, causing the surface tension to decrease. In this regime, free surfactant molecules and nanoparticle-surfactant complexes coexist and can co-adsorb at the interface. This is demonstrated by combining high amplitude compression and dynamic surface tension measurements. Furthermore, the effect of negatively charged nanoparticles on the surface activity of anionic surfactant (SDBS) in an aqueous phase is studied. Although recent studies indicate that nanoparticles increase the surface activity of surfactants through electrostatic repulsive forces, it is observed that the surface activity of surfactants is mainly affected by the change in ionic strength of the system due to the presence of nanoparticles. Several characteristic parameters including the equivalent concentration of the surfactant and the critical micelle concentration (CMC) are theoretically calculated and further employed to validate experimental observations. Based on the obtained results, a criterion to estimate the possible influence of the electrostatic repulsive forces for nanoparticles of different sizes and mass fractions is introduced. In the next step, the effect of ultrafine particles on the mobility of interfaces is investigated. The shear stress of the axisymmetric flow field triggers a nonuniform distribution of the surfactants at the surface of a rising bubble, known as stagnant cap, which gives rise to Marangoni stress that can reduce the mobility of the interface. The conditions in technological processes; however, usually deviate from the linear rise of a single bubble in a quiescent unbounded liquid. Asymmetric shear can act on the bubble surface due to the vorticity in the surrounding flow, or due to the bubble-bubble interactions, which can significantly change the surfactant distribution at the interface. To better understand this effect, Particle Image Velocimetry (PIV) is applied in an experimental setup that is specifically designed to study the hydrodynamics of bubbles and droplets and their interfacial mobility under asymmetric shear flow. Series of PIV experiments are performed with a buoyant bubble/pendant drop at the tip of a capillary placed in a defined shear flow in the presence of surfactants and nanoparticles. A direct experimental observation of the circulating flow at the interface under asymmetric shear, which prevents the formation of the typical stagnant cap is observed. The results show that the interface remains mobile under these conditions regardless of the surfactant concentration. The response of the interface to the surrounding asymmetric flow under successive reduction of the surface area revealed that in the presence of nanoparticles, a contiguous network of particles forms at the interface through densification of surface structures that can drastically change the interfacial mobility of the bubbles and drops. The immobilization is characterized by a dimensionless number, defined as the ratio of the interfacial elasticity to bulk shear forces, which provides an estimate of the interfacial forces required to impose interfacial immobility at a defined flow field. In the last part of this thesis, the kinetics of particles attachment to a buoyant bubble is investigated. The results showed that the technique can be used to investigate the floatability of different particles as a function of various parameters such as hydrophobicity, particle size, and number density. Furthermore, a specific setup was developed to collect the attached particles and measure their mass and size distribution after collection. For a monomodal particle system, the results indicated almost identical size distribution before and after collection with a slight shift to smaller sizes after collection. For a bimodal particle system, on the other hand, results showed that the majority of the collected particles belong to smaller fractions. Next, the effects of ultrafine particles on the kinetics of particle attachment and the distribution and mobility of particles on the bubble surface is studied. It is shown that the ultrafine particles can increase the attachment rate of fine particles and at the same time decrease their packing density. The presence of ultrafine particles at the interface strongly influenced the distribution of the fine particles on bubble surface. The effect is more pronounced for pre-compressed bubbles, where the dense layer of ultrafine particles on the bubble surface completely prevents the attachment of the fine particles. It is also observed that the mobility of the fine particles at the interface changes significantly when ultrafine particles are adsorbed on the bubble surface.

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:21:31Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:21:31Z (GMT). No. of bitstreams: 0 / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2016-06-22T11:21:31Z No. of bitstreams: 0 / Made available in DSpace on 2016-06-22T11:21:31Z (GMT). No. of bitstreams: 0 / O tratamento de câncer possui diversas modalidades. Uma delas é a utilização de fontes de radiação como principal protagonista do tratamento. A radioterapia e a medicina nuclear são exemplos desse tipo de tratamento. Por utilizarem a radiação ionizante como principal ferramenta para a terapia, há a necessidade de se efetuar diversas simulações do tratamento a fim de maximizar a dose nos tecidos tumorais sem ultrapassar os limites de dose nos tecidos sadios circunvizinhos. Os sistemas utilizados na simulação desses tipos de terapia recebem o nome de Sistemas de Planejamento Dosimétrico. A medicina nuclear e a radioterapia possuem seus próprios sistemas de planejamento dosimétricos devido a grande diversidade das informações necessárias às suas simulações. Os sistemas de planejamento em radioterapia são mais consolidados do que os de medicina nuclear e por tal motivo um sistema que aborde tanto os casos de radioterapia como de medicina nuclear contribuiria para significativos avanços na área de medicina nuclear. Dessa forma, o objetivo do trabalho foi modelar um Sistema de Planejamento Dosimétrico com o uso do código de Monte Carlo MCNP6 Monte Carlo N-Particle Transport Code que permitisse incorporar os casos de radioterapia e medicina nuclear e que fosse extensível a novos tipos de tratamentos. A modelagem desse sistema resultou na construção de um Framework, orientado a objetos, nomeado IBMC o qual auxilia no desenvolvimento de sistemas de planejamento que necessitam interpretar grandes quantidades de informações com o objetivo de escrever o arquivo base do MCNP6. O IBMC permitiu desenvolver de maneira rápida e prática sistemas de planejamento para radioterapia e medicina nuclear e os resultados foram validados com sistemas já consolidados. Ele também mostrou alto potencial para desenvolver sistemas de planejamento de novos tipos de tratamentos que utilizam a radiação ionizante. / Tese (Doutorado em Tecnologia Nuclear) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Nous avons étudié l'effet des rayons cosmiques dans les détecteurs en utilisant un bolomètre de germanium composite NTD à basse température, et une source de particules alpha comme source générique d'impulsions. Nous avons caractérisé ce bolomètre en constatant que la forme de son impulsion était due à la combinaison de sa réponse impulsionnelle (la somme de deux exponentielles doubles), et des effets liés à la position découlant de la thermalisation des phonons balistiques en phonons thermiques dans son absorbeur. Nous avons établi un schéma décrivant la forme de l'impulsion dans ce bolomètre en comparant une impulsion mathématique générique à une seconde description basée sur la physique thermique. Nous constatons que la thermalisation des phonons balistiques, suivie de la diffusion thermique, jouent un rôle important dans la forme de l'impulsion, en parallèle avec le couplage électrothermique et les effets électriques dépendant de la température. Nous avons modélisé les impulsions en observant que leur comportement peut être reproduit en tenant compte de la réflexion de phonons balistiques sur le bord de l’absorbeur, avec un couplage thermique fort au capteur central du bolomètre. Compte tenu de ces résultats, nous étudions également les effets des rayons cosmiques sur l’instrument Athena X-Ray Integral Field Unit (X-IFU), en produisant des timelines simulées et en testant la hausse de la valeur moyenne de la température (RMS) sur la plaquette du détecteur. Nous montrons que le flux thermique attendu des rayons cosmiques est au même ordre de grandeur que le maximum autorisé ΔTRMS ce qui constitue une menace sur le budget de la résolution énergétique de l'instrument. / We have studied the effect of cosmic rays in detectors using a composite NTD germanium bolometer at low temperatures and an alpha particle source as a generic source of pulses. We have characterised this bolometer, finding that its pulse shape is due to a combination of its impulse response function (the sum of two double exponentials), and position-dependent effects arising from thermalisation of ballistic phonons into thermal phonons in its absorber. We have derived a scheme for describing the pulse shape in this bolometer, comparing a generic mathematical pulse shape with a second description based on thermal physics. We find that ballistic phonon thermalisation, followed by thermal diffusion, play a significant role in the pulse shape, along with electro-thermal coupling and temperature-dependent electrical effects. We have modelled the pulses, finding that their behaviour can be reproduced accounting for ballistic phonon reflection off the absorber border, with a strong thermal coupling to the bolometer’s central sensor. With these findings, we also investigate the effects of cosmic rays on the Athena X-Ray Integral Field Unit (X-IFU), producing simulated timelines and testing the average RMS temperature increase on the detector wafer, showing that the expected cosmic ray thermal flux is within the same order of magnitudeas the maximum allowed ΔTRMS, posing a threat to the instrument’s energy resolution budget.

The goal of this Master thesis is to demonstrate Witteńs mechanism in selected extensions of the Standard model based on the Pati-Salam gauge group. The purpose of this mechanism is to obtain an extremely large Majorana mass term for right-handed neutrinos at the two-loop level and consequently light physical masses of neutrinos using the type I see-saw mechanism. The existence of corresponding Feynman diagrams without any interactions of vector bosons is presented. While it is impossible to construct this type of corrections in minimal SO(10) or SU(5)xU(1) model in Pati-Salam model they may be even dominant. Subsequently, implications of possible partial gauge coupling unification or even embedding of the Pati-Salam group into a gauge group of "Great Unified Theory" are considered. At the end the possibility of unacceptably fast proton decay is inspected. The discussed models are concluded to be potentially realistic but only at the cost of predictivity, since completely unknown Yukawa couplings appear in numerous key relations. 1

With the aim of developing a deeper understanding of particle behaviour within nano-hybrid materials, this thesis investigates the particle-particle and particle-polymer interactions that influence and control cellulose nanocrystal dispersion in aqueous and non-aqueous environments. / Cellulose nanocrystals (CNCs) are rigid rod-shaped nanoparticles derived from bio-based resources and are considered an emerging nanomaterial based on their commercial availability and favourable properties. CNCs have great potential as reinforcing agents in hybrid materials and composite applications if they are well-dispersed. Whereas colloidal stability is effectively described by established theories, dispersing nanoparticles from an aggregated state, and their interaction with polymers can be difficult to predict and control. Herein, the particle-particle and particle-polymer interactions that govern CNC dispersibility in aqueous and non-aqueous environments are examined. The surface chemistry, morphology and colloidal/thermal stability of CNCs from North American industrial producers were extensively characterized such that particle interactions could be reproducibly measured from a known starting material. Industrially produced CNCs compared well to those produced at the bench-scale, implying that laboratory results should be translatable to the development of new CNC-based products. To examine particle-particle interactions within dry CNC aggregates, a surface plasmon resonance-based platform was developed to monitor CNC film swelling in a range of solvents and salt solutions. Water was observed to interrupt particle-particle hydrogen bonding most effectively, however film stability, and ultimately particle aggregation, was maintained by strong van der Waals interactions. Moreover, particle spacing and overall film thickness was found to be independent of the CNC surface chemistries and surface charge densities examined, yet the rate of film swelling scaled with the ionic strength of the surrounding media. Polyethylene glycol (PEG) was used as a model, non-ionic, water-soluble polymer to investigate polymer adsorption to CNC surfaces in water. PEG did not adsorb to CNCs despite the abundance of hydroxyl groups, which is in direct contrast to silica particles that are well known to hydrogen bond with PEG. Combining the knowledge of both particle-particle and particle-polymer interactions, PEG nanocomposites reinforced with CNCs and silica were compared and particle dispersibility was related to composite performance. Although PEG does not adsorb to CNCs in aqueous environments, polymer adsorption does occur in dry polymer nanocomposites leading to good dispersibility and improved mechanical properties. Overall, the work presented here yields new insight into the forces that govern CNC dispersion and provides a foundation from which a variety of new CNC-based products can be developed. / Thesis / Doctor of Philosophy (PhD) / Using particles derived from renewable resources to reinforce plastics and other materials has the potential to make products lighter, stronger and more environmentally friendly. However, to make these products we need to understand how to control and distribute particles uniformly throughout hybrid/composite materials. This work uses particles extracted from trees and cotton, known as cellulose nanocrystals, to reveal which factors govern particle dispersion in reinforced composite materials. To do so, first the properties and performance of commercially available cellulose nanocrystals were extensively analyzed and compared to form the basis from which interactions can be understood. Next, particle films were measured in water, organic solvents and salt solutions to better understand how aggregated cellulose nanocrystals can be separated within composite materials. The interactions between water-soluble polymers and cellulose nanocrystals were then investigated to reveal how polymer adsorption impacts particle dispersibility. Finally reinforced polymer composites were prepared with uniformly distributed cellulose nanocrystals and the crystallization and mechanical properties were investigated. By developing a deeper understanding of the factors that control cellulose nanocrystal dispersion we can learn how to make a variety of new and improved environmentally conscious products.