Fiber pushout test models are developed for a fiber-matrix-composite with a nonhomogeneous interphase. Using design of experiments, the effects of geometry, loading and material parameters on critical parameters of the pushout test such as the load-displacement curve and maximum interfacial shear and normal stresses are studied. The sensitivity analysis shows that initial load displacement curve is dependent only on the indenter type and not on parameters such as fiber volume fraction, interphase type, thickness of interphase, and boundary conditions. In contrast, interfacial shear stresses are not sensitive to indenter type, while the interfacial radial stresses are mainly sensitive to fiber volume fraction and the boundary conditions.

La coextrusion est un process industriel de fabrication de films minces composés de plusieurs couches de polymères (PP/PP-g-Anhydride Maléique (PP-g-AM)/EVOH/PP-g-AM/PP) associant de propriétés intéressantes au matériau final. Lors de ce procédé, les films obtenus ne sont pas transparents mais présentent des granités. En effet, le liant ajouté contient des chaînes de PP-g-AM s’interpénètrent dans une couche du matériau et les têtes anhydride maléique réagissent avec l’autre couche créant in-situ des copolymères PP-g-AM-g-EVOH à l’interface.Mon premier travail était de mettre en évidence le rôle primordial des instabilités interfaciales sur la diminution de la transparence des films. Ceci a été rendu possible grâce à une observation des coupes transversales des films. Nous avons vu que plus la variation de l’épaisseur interne est grande, plus la qualité optique du film est mauvaise. Cette amplitude de variation est exacerbée dans le sens de la coextrusion. La cristallisation du PP observable au microscope optique par des sphérolites n’intervient qu’au second ordre.Il est connu que l’interface est stabilisée par la tension interfaciale, c’est pourquoi, dans un second temps, l’étude de l’interface a été menée La tension interfaciale a été mesurée par la méthode de relaxation de la goutte déformée. À une température supérieure à la température de fusion des deux polymères, l’EVOH est dispersé dans une matrice de liant PP-g-AM. Les gouttelettes d’EVOH sont soumises à un faible cisaillement. À l’arrêt de celui-ci, les gouttelettes relaxent pour retrouver leur forme d’équilibre, la forme sphérique. Le temps de relaxation est proportionnel à la tension interfaciale et au rapport des viscosités des polymères. Une des conséquences majeures de ces instabilités est la présence de défauts optiques rendant le film opaque, gênant pour les applications.Enfin, pour comprendre les résultats de tension interfaciale, il a fallu construire un protocole de dosage de copolymères à l’interface. Ce dosage absent de la littérature, a été le plus gros travail de ma thèse. Un protocole de dosage de copolymère à l’interface basé sur l’infrarouge est aujourd’hui validé et utilisé en recherche industrielle (ARKEMA, Serquigny). / Coextrusion is an industrial process which creates thin films of polymers (in this study : PP/PP-g-Anhydride Maleic (PP-g-AM)/EVOH/PP-g-AM/PP). These polymers give interesting properties to the final film. But some of these films have bad optical qualities with granity inside the film. Indeed, as the polymers are incompatibles, other polymers (PP-g-AM) which have adhesion role have to be added. These chains go into the interface to react with EVOH and create in situ way, copolymers PP-g-AM-EVOH.My first work was to identify the role of interfacial instabilities in the optical properties of the film. It was realised thanks to observations by optical microscope. Indeed, we have proove that there is a link between the variation of the intern thickness amplitude and the optical quality and this amplitude of variation grows in coextrusion direction. Spherulites in the bulk of each film influence less than the amplitude variation of intern thickness.This amplitude should depend on the interfacial tension, that is way, in the second part, we have measured the interfacial tension of different materials by drop deformed relaxtation method. At a temperature higher than the melted temperature of the polymers, a drop of EVOH is deformed in PP-g-AM matrix. A shear stress is applied to deformed the drop. When the shear stress is stopped, the drop from regular ellisoidal shape relaxes into its equilibrium shape, a spherical shape. The relaxation time is proportional to interfacial tension and viscosity ratio.This interfacial tension depends on the density of copolymers at the interface. So my final part was to caracterize copolymers. To titrate and study their reactivity, I had to set up a experiment which was not present in literature. This method was done by infrared and is now used in our industrial collaborator (ARKEMA, Serquigny).

Les mortiers colles se composent essentiellement de ciment, de sable, de charges minérales et d'une variété d'additifs (éthers de cellulose, entraînant d'air, latex) et sont utilisés pour coller des carreaux céramique (et d'autres pièces comme la pierre, le verre, etc.) aux substrats. Ils sont généralement appliqués dans une grande surface sur le substrat sous la forme de nervures sur lesquelles les carreaux sont mis. Afin d'obtenir une bonne performance, il est important que les propriétés rhéologiques du mortier permettent un bon contact entre les carrelages, même après plusieurs minutes (temps ouvert) d'exposition aux conditions ambiantes, soit à l'intérieur soit à l'extérieur des bâtiments. A cet effet, il est nécessaire d'éviter la formation d'une couche rigide et/ou sèche à l'interface mortier-air, qui peut être difficile à déformer ou à humidifier correctement la surface de la dalle. Comme le contact initial entre le mortier et le carrelage est la première étape pour le développement des propriétés adhésives entre les matériaux, une bonne compréhension de l'évolution des propriétés rhéologiques à l'interface air-mortier est d'une grande importance pour les producteurs de mortier et les utilisateurs. Dans ce contexte, cette thèse a d'abord développé des méthodes d'évaluation des propriétés interfaciales et une technique microscopique pour visualiser le contact. Ensuite, ces techniques combinées à des essais de tack test/ squeeze et à des procédés rhéologiques déjà existants peuvent être utilisé pour évaluer comment des additifs polymères tels que l'éther de cellulose influent sur les propriétés rhéologiques du mortier adhésif dans le volume et à l'interface pour mieux comprendre les propriétés adhésives. Et enfin, avec l'utilisation de la RMN, ces propriétés pourraient être corrélées avec l'évolution de la distribution de l'eau. / Adhesive mortars consist basically of cement, sand, mineral fillers and a variety of additives (cellulose ethers, air-entraining, latex) and are used to glue ceramic tiles (and other pieces like stone, glass etc) to substrates. They are usually applied in a large surface on the substrate in the form of ribs on which tiles are put. In order to obtain a good performance it is important that when the tile is installed, the mortar rheological properties allow for good contact between them, even after several minutes (open time) of exposure to ambient conditions either at internal or external building areas. For this purpose, it is necessary to avoid the formation of a rigid and/or dry layer at the mortar-air interface, which may be difficult to be deformed or wet the tile surface properly. As the initial contact between mortar and tile is the first step for the development of adhesive properties between the materials, a good comprehension of the rheological properties evolution at the air-mortar interface is of great importance for mortar producers and users. In this context, this thesis firstly developed methods to evaluate interfacial properties and a microscopical technique to visualize the contact. Then, those techniques combined with already existent squeeze flow/tack test and rheological methods can be used to evaluate how polymer additives such as cellulose ether influence the adhesive mortar rheological properties in the volume and at interface to further understand the adhesive properties. And finally, with the use of NMR, those properties could be correlated with water distribution evolution.

Silicon photovoltaic (PV) is a promising solution for energy shortage and environmental pollution. We are experiencing an era when PV is exponentially increasing. Global cumulative installation had reached 380 GW in 2017. Among which, silicon-based PV productions share more than 90% market. Performance of the first two-generation commercial popular silicon solar cells - Al-BSF and PERC - are limited by metal/Si contacts, where interface defects significantly reduce the open-circuit voltage. In this context, full-area passivation concepts are proposed for c-Si solar cells, with expectation to enhance the efficiency via reducing carrier recombination loss at the contact regions. In this thesis, poly silicon on oxide (POLO) passivating contact is developed for high efficiency c-Si solar cells. We unveiled the working mechanisms of POLO cells and then optimized the device performance based on our conclusion. We use boiling nitric acid to oxidize c-Si surface, which is of significance to determine the POLO working mechanisms. Phosphorus and boron doped silicon films are deposited by plasma enhanced vapor deposition (PECVD) or low-pressure vapor deposition (LPCVD) followed by high temperature (>800°C) annealing. SiOx structural evolution process under different annealing temperature was observed and the corresponding effects on passivation have been elucidated. The carrier transport mechanisms in the POLO contact annealed at high temperature, e.g. 800°C  900°C, were explored. We unveil that carrier transport in POLO structure is a combination of tunneling and pinhole transport, but dominant at varied temperature regions. Phosphorus-doped n-type POLO contact is optimized by several parameters, such as doping concentration, film thickness, annealing temperature, film deposition temperature, film relaxation time during annealing process, etc. We successfully obtained minority carrier lifetime over 10ms and contact resistivity lower than 30 mΩ·cm2. Boron-doped p-type POLO contact is also optimized by changing the doping concentration and annealing temperature. Finally, further hydrogen passivation is applied to enhance p-type POLO contact passivation, achieving an iVoc>690 mV, J0 <5 fA/cm2 and contact resistivity 1.3 mΩ·cm2. With the optimized n-type and p-type POLO contacts, an efficiency over 18% is achieved on n-type c-Si solar cells with a flat front surface.

京都大学 / 0048 / 新制・論文博士 / 博士(農学) / 乙第13247号 / 論農博第2872号 / 新制||農||1070(附属図書館) / 学位論文||H31||N5171(農学部図書室) / (主査)教授 松村 康生, 教授 丸山 伸之, 教授 谷 史人 / 学位規則第4条第2項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

Proper disposal of industrial brine has been a critical environmental challenge. Driven by the even-tightening environment protection regulations, the Zero-Liquid-Discharge (ZLD) has gradually become mandatory option for brine disposal, but its application is limited by the intensive energy consumption. The recent development of solar crystallizer provides a new strategy to achieve ZLD brine disposal. However, the research on solar crystallizer, employing photothermal material to convert solar energy to heat for interfacial brine evaporation and crystallization, is still at the early stage. This dissertation thoroughly investigated the solar crystallizer-based ZLD technology in a broad scientific and application context. The scaling formation while treating real brine, which has been the major barrier to the application of solar crystallizer, was confirmed first with a solar crystallizer device. With a rational designed anti-scaling mechanism, the scaling-free crystallization behavior and stable high water evaporation rate of 2.42 kg m-2 h-1 was achieved when treating real seawater brine. After verifying the feasibility of solar crystallizer towards real brine treatment, its performance was further improved by integrating convective airflow, which provided considerable environmental energy for water evaporation. Both experiment results and COMSOL simulation results confirmed that the maximum environmental energy harvesting can be achieved with the proper size of solar crystallizer. At last, this dissertation pioneered a novel concept of integrating adsorption process into solar crystallizer for simultaneously ZLD brine treatment and potassium extraction. Owing to the special ion concentration behavior of solar crystallizer, the adsorption capacity and selectivity coefficient of absorbent was enhanced by 19.5% and 48.8%, respectively, comparing with traditional bulk adsorption. This dissertation potentially unlocks a new generation of ZLD technology with low carbon footprint and source recovery. More research efforts will be inspired on its applications in real scenarios.

A new method for determining viscoelastic properties on the interfacial interface called interfacial rheology was intoduced and investigated. Measured data were compared with data from tanziometer for model system of surfactant. Three concentration renge of surfactant, namely SDS (anionic), TTAB (cationic) and Tween (nonionic), were measured. From the measured data the influence of structure, critical micellar concentration and charge on the viscoelastic properties of the interfacial interface was determined. Furthermore, this new method was used for biological systems and specifically for biofilms of two bacterial strains. First, the viscoelastic properties of biofilms on the agar were determined, and the viscoelastic properties dependence on temperature

Nach einer kurzen technischen Beschreibung der Mehrzweck-Thermohydraulikversuchsanlage TOPFLOW und der verwendeten Messtechnik werden die theoretischen Grundlagen zur Modellierung der Kondensation von Dampf in einer Wasserströmung erläutert. Dabei gehen die Autoren besonders auf die Auswahl geeigneter Modelle zur Beschreibung des Wärmeübergangs und der Zwischenphasengrenzfläche im Druckbereich zwischen 10 und 65 bar detailliert ein. Außerdem werden verschiedene Drift-Flux-Modelle auf ihre Tauglichkeit anhand von experimentellen Daten geprüft. Da Veränderungen thermodynamischer und strömungstechnischer Parameter hauptsächlich in axialer Richtung stattfinden, wurden diese Modelle in einen eindimensionalen Code eingebettet, mit dem der Strömungsverlauf entlang einer vertikalen Rohrleitung mit einer Länge von 8 m und einem Nenndurchmesser von 200 mm berechnet werden kann. Anschließend werden Aufbau und Funktion dieses Programms vorgestellt. Nachfolgend vergleichen die Autoren experimentelle und berechnete Strömungsverläufe bei der Kondensation von Dampf sowohl in einer unterkühlten Wasserströmung als auch nahe der Siedetemperatur. Dabei wird der Einfluss wichtiger Randbedingungen, wie z.B. Druck oder Primärblasengröße, auf die Kondensationsintensität analysiert. Eine Einschätzung der Fehlerbanden für die experimentellen Daten, die verwendeten Gittersensoren und die numerische Simulation schließen den Bericht ab.

Deux séries d'échantillon à base de PVDF ont été élaborées avec différentes fractions de dioxyde de titane TiO2 en utilisant deux modes d'élaboration : dispersion des nanoparticules de TiO2 par voie fondue habituelle et génération des charges de TiO2 basée sur des réactions d'hydrolyse-condensations d'un alkoxyde de titane (le n-tétrabutoxyde de titane). Dans cette étude, quatre techniques ont été utilisées pour étudier les processus de relaxation dans les polymères semi-cristallins. Le microscope électronique à balayage (MEB) pour étudier la dispersion des nanoparticules de TiO2 dans la matrice PVDF. La calorimétrie différentielle à balayage (DSC) a été utilisée dans cette étude pour caractériser thermiquement les échantillons polymériques semi-cristallins. L'analyse thermo-gravimétrique (ATG) a été utilisée pour voir l'effet de nanoparticules sur les propriétés thermiques du PVDF. De plus, la technique de spectroscopie diélectrique a été utilisée dans la thèse pour étudier l'influence du processus d'élaboration sur la mobilité moléculaire trouvée dans ces systèmes. On a montré que le comportement de ces nanocomposites est proche de celui de PVDF pur. Les changements principaux observés sont le ralentissement de la dynamique de la relaxation alpha (associée à la température de transition vitreuse) et la relaxation alpha c (associée à la phase cristalline) en fonction de l'augmentation de fraction volumique TiO2. L'existence des charges piégées aux interfaces qui met en cause la présence de la polarisation interfaciale (IP) dans les différents nanocomposites a aussi été analysée. Les additions de TiO2 diminuent la mobilité des chaînes polymériques ce qui rend difficile l'orientation des dipôles électriques et augmente l'énergie d'activation de la relaxation de polarisation interfaciale / Polyvinylidene fluoride (PVDF) films have been filled with different volume fraction of titanate dioxide TiO2 using two ways : dispersion in the melt or in-situ generation based on the hydrolysis-condensation reactions of titanium alkoxide inorganic precursor premixed with PVDF under molten conditions. In this study, four techniques were used to study the relaxation processes in the semi-crystalline polymers. The scanning electron microscope (SEM) was introduced in the field of polymer science to study the dispersion of TiO2 nanoparticules in the PVDF matrix. The differential scanning calorimetry (DSC) was used in this study to thermally characterize the semi-crystalline polymer samples. Thermal gravimetric analysis (TGA) was used to see the effect of nanoparticles on the thermal properties of PVDF. In addition, the dielectric spectroscopy technique was used in the thesis to study the influence of the process on the molecular mobility found in these systems. It was shown that the behavior of PVDF as a matrix in these nanocomposite is close to that of pure PVDF. The main changes observed is the slowing down of the dynamics of the alpha a (associated to the glass transition temperature) and the alpha c (associated to the crystalline phase) relaxations as a function of the TiO2 volume fraction increase. The existence of charge carriers trapping at the interfaces related to the interfacial polarization (IP) in the different nanocomposites has also been analyzed. The additions of TiO2 decrease the mobility of the polymer chains which makes difficult the orientation of electric dipole moment ending in an increase of the energy of activation of IP relaxation

Abstract: Understanding and controlling the ultrafast charge carrier and exciton dynamics at the interface of semiconductor nanocrystals (NCs) offer an excellent opportunity to improve the charge collection and the overall performance of many optoelectronic and energy-based devices. In this dissertation, we study how interfacial engineering of these materials can have a direct influence on controlling the charge transfer and the nonradiative losses in different donor-acceptor systems. The first introductory chapter provides an overview of all the fundamental photophysical processes controlling the interfacial phenomena. Then, the second chapter highlights all the chemicals and synthesis methods employed during this thesis. The subsequent two chapters discuss the detailed experimental studies and observations related to different materials and interfaces. First, it describes how we can dramatically tune the intersystem crossing (ISC) rate, the triplet state lifetime, turn on/off the electron injection at the CdTe-Prophyrin interface via tuning either the quantum dot size or the porphyrin molecular structure. Also, how the intermolecular distances, electronic coupling, and subsequently, the photoinduced charge transfer can be controlled by the interfacial electrostatic interactions at CdTe-Fullerene interfaces. Second, due to the promise that of perovskite NCs holds for improving many solar cell and optoelectronic applications, chapter 3 highlights the tremendous effect that the shape of perovskite nanocrystals has on the rate and the mechanism of charge transfer at the MAPbBr3- TCNE interface. Besides, it demonstrates how the confinement effect brought by changing the dimensionality influence the charge transfer dynamics at the MAPbBr3-BQ interface. Finally, it explains how the effective passivation of the surface defects and the subsequent suppression of the formation of surface nonradiative recombination centers in CsPbCl3 NCs controls the photoluminescence quantum yield and the photodetector performance.