Tissue engineering and regenerative medicine aim to develop materials that mimic some of the characteristics of the tissue they are replacing and control the growth and proliferation of cells. Despite exceptional advances in the range and quality of materials used, much remains to discover about the processes regulating interfaces between cells and their surroundings, or at cell-material interfaces. In order to study and control such interactions, scientists have produced engineered matrices aiming to mimic some of the feature of natural extra-cellular matrix (biochemistry, geometry/topography and mechanical properties). In order to pattern 2D-nanofibers on relatively large areas and throughput, allowing comprehensive biological studies, we developed a nano-fabrication technique based on the deposition of sparse mats of electrospun fibres with different diameters. These mats are used as masks to grow cell resistant polymer brushes from exposed areas. After removal of the fibres, the remaining brushes define a quasi-2D fibrous pattern onto which ECM molecules such as fibronectin can be adsorbed. Chapter 2 includes details of the techniques used to produce and characterize the fibrous nanopattern. Chapter 3 is focused on cell phenotype observed on the different nanofibres sizes. Adhesion assays showed that cell spreading, shape and polarity are regulated by the size of fibres but also the density of the nanofibres, similarly to previous observations made on circular nanopatterns. We then focused on the study of focal adhesion formation and maturations on these nanofibres and the role of key proteins involved in the regulation of the adhesion plaque: integrins and vinculin. Cells expressing different integrins were found to sense the nanoscale geometry differently. Vinculin sensing is the topic of Chapter 4. Although vinculin recruitment dynamics was affected by the nanofibrous patterns and focal adhesions arrange differently on the nanofibres, this protein does not seem to mediate nanoscale sensing. In Chapter 5, we finally focused on the role of the actin cytoskeleton as a direct sensor of nanoscale geometry. A gradual decrease in stress fibre formation was observed as the nanofibres dimensions decrease. Live imaging also demonstrated that the geometry of the extracellular environment strongly affects cytoskeleton rearrangement, stress fibres formation and disassembly. We identify the role of cytoskeleton contractility as an important sensor of the nanoscale geometry. Our study provides a deeper insight in understanding cell adhesion to the extracellular environment and the role of the matrix geometry and topography on such phenomena, but also raises questions regarding the more detailed molecular sensory elements enabling the direct sensing of nanoscale geometry through the actin cytoskeleton.

Fracture mechanics plays an important role in understanding the performance of all types of materials including Functionally Graded Materials (FGMs). Recently, FGMs have attracted the attention of various scholars and engineers around the world since its specific material properties can smoothly vary along the geometries. In this thesis, the Finite Block Method (FBM), based on a 1D differential matrix derived from the Lagrangian Interpolation Method, has been presented for the evaluation of the mechanical properties of FGMs on both static and dynamic analysis. Additionally, the coefficient differential matrix can be determined by a normalized local domain, such as a square for 2D, a cubic for 3D. By introducing the mapping technique, a complex real domain can be divided into several blocks, and each block is possible to transform from Cartesian coordinate (xyz) to normalized coordinate (ξησ) with 8 seeds for two dimensions and 20 seeds for three dimensions. With the aid of coefficient differential matrix, the differential equation is possible to convert to a series of algebraic functions. The accuracy and convergence have been approved by comparison with other numerical methods or analytical results. Besides, the stress intensity factor and T-stresses are introduced to assess the fracture characteristics of FGMs. The Crack Opening displacement is applied for the calculation of the stress intensity factor with the FBM. In addition, a singular core is adopted to combine with the blocks for the simulation of T stresses. Numerical examples are introduced to verify the accuracy of the FBM, by comparing with Finite Element Methods or analytical results. Finally, the FBM is applied for wave propagation problems in two- and three-dimensional porous mediums considering their poroelasticities. To demonstrate the accuracy of the present method, a one-dimensional analytical solution has been derived for comparison.

La conversion d’énergie par effet thermoélectrique (TE), qui peut être utilisée pour convertir de la chaleur perdue en électricité, a reçu une attention soutenue ces dernières décennies. L’efficacité d’un système TE est caractérisé par le facteur de mérite adimensionnel, ZT=(S²σ/κ)T, où S, σ, κ, et T sont respectivement le coefficient Seebeck, la conductivité électrique, la conductivité thermique et la température absolue. Récemment, les matériaux à base de chalcogénures de cuivre ont attiré un intérêt au sein de la communauté de la thermoélectricité du fait de leur conductivité thermique faible, qui conduit à des propriétés thermoélectriques prometteuses. BiCuSeO et BaCu2Se2 sont deux de ces matériaux. Ils possèdent une conductivité thermique intrinsèquement très faible et un coefficient Seebeck élevé. Mais leur conductivité électrique est faible, ce qui limite l’amélioration de leurs propriétés thermoélectriques.Dans cette thèse, la conductivité électrique de BiCuSeO est améliorée par dopage par Ba et par texturation. Se est substitué à S dans BiCuSeO pour réduire les coûts et diminuer la conductivité thermique. Un dopage par Na est effectué dans BaCu2Se2 pour augmenter sa concentration de porteurs et améliorer sa conductivité électrique. / The thermoelectric (TE) energy conversion technology, which can be used to convert wasted heat into electricity, has received much attention in the past decade. The efficiency of TE devices is characterized by the dimensionless figure of merit ZT=(S²σ/κ)T, where S, σ, κ, and T are the Seebeck coefficient, the electrical conductivity, the thermal conductivity, and the absolute temperature, respectively.Recently, copper chalcogenides based materials have attracted extensive interest in the thermoelectric community due to low thermal conductivities, which lead to the promising excellent thermoelectric properties. BiCuSeO and BaCu2Se2 are two of them. They exhibit intrinsically very low thermal conductivity and large Seebeck coefficient. But their electrical conductivity is low, limiting the enhancement of their thermoelectric properties.In this thesis, Ba doping and texture are taken out in BiCuSeO to improve its electrical conductivity. Se is substituted by S in BiCuSeO to decrease its price and decrease its thermal conductivity. Na doping is taken out in BaCu2Se2 to increase its carrier concentration and improve its electrical conductivity.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / A teoria dinÃmica da difraÃÃo de raios X Ã uma teoria que ao contrÃrio da teoria cinemÃtica tem sua origem nas equaÃÃes de Maxwell e na lei de Bragg e com um tratamento fÃsico mais completo e adequado levando em consideraÃÃo todas as interaÃÃes entre os campos de onda eletromagnÃticos dentro do cristal e logo, leva em conta tambÃm, as propriedades fÃsicas do meio cristalino. Estas interaÃÃes trazem consigo efeitos que sÃo desprezados na teoria cinemÃtica, teoria mais tradicional e mais comumente utilizada quando se trata de difraÃÃo de cristais pouco espessos. Este trabalho visa calcular os perfis de difraÃÃo pela teoria dinÃmica com o intuito de confirmar e analisar a presenÃa dos efeitos dinÃmicos que, por sua vez, se acentuam com o aumento da espessura da amostra. Esses efeitos sÃo a absorÃÃo anÃmala e os efeitos de extinÃÃo. Os cÃlculos foram feitos com o uso da linguagem de programaÃÃo Fortran 90 aplicados em monocristais de silÃcio, germÃnio, arseneto de gÃlio e fosfeto de Ãndio, com o objetivo de estudar a influÃncia da espessura do cristal e da razÃo entre as partes imaginÃria e real do fator de estrutura, nos perfis de difraÃÃo. Por fim, tendo-se a largura a meia altura, determinados pelos grÃficos dos perfis, em funÃÃo da espessura pÃde-se concluir que a equaÃÃo de Scherrer se aplica bem em cristais pouco espessos, regiÃo de espessura onde os efeitos dinÃmicos sÃo desprezÃveis.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第19096号 / エネ博第320号 / 新制||エネ||65 / 32047 / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 松田 一成, 教授 岸本 泰明, 教授 大垣 英明 / 学位規則第4条第1項該当

Organic-based electronic devices have received considerable attention because of their presumable advantages over traditional inorganic-based electronics, such as low cost, flexibility, and applicability for large area production. Because of the possible commercialization of electronic products based on organic conducting materials, it is important to develop a variety of organic semiconductors (OSCs) that are categorized as hole transporting (p-type), electron-transporting (n-type) or ambipolar transporting (both hole and electron). P-type OSCs have been the most thoroughly studied. N-type semiconductors are much less common and the charge carrier mobilities have lagged considerably behind their p-type counterparts. Fullerene-based materials are currently the most widely used n-type semiconductors in OPVs. The cage-like structure associated with buckminsterfullerene is made of fused six- and five-member rings. Acenaphthylene is a basic fragment of C60 and has shown potential as a valuable building block for n-type OSCs. To utilize this promising structure, the acenaphthylene unit has been incorporated into a variety of molecular structures to produce both small molecule and polymeric materials. We started with the study of fully unsaturated tetraquinane derivatives, which contain four linearly fused five-membered rings. The desired diacenaphthylpentalenes were synthesized via a palladium-catalyzed dimerization of 1-iodo-2-arylethynyl-acenaphthylenes. The compounds are benchtop and solution stable and behave as hole-transporting or ambipolar semiconductors in organic field effect transistors. The X-ray crystal structure demonstrates the importance the fused naphthalene units as they stabilize the pentalene core with an extended π-framework. The tetraquinane derivatives possess high optical gap materials owing to a forbidden HOMO to LUMO transition, yet have narrow electrochemical gaps and are reduced at small negative potentials giving lowest unoccupied molecular energy levels of -3.57 to -3.74 eV. In addition to the unsaturated tetraquinane derivatives, this thesis also includes work on the creation of macrocycles containing acenaphthylene or cyclopenta[cd]perylene units. The stabilized annulenes, with rigid and π-conjugated structures, have potential application as discotic liquid crystals and porous organic solid. 1H NMR and low resolution mass spectra gave solid proof that a target macrocycle was synthesized; however, the tedious work up and limited purification techniques did not enable large scale synthesis. The investigation of new donor-acceptor copolymers incorporating acenaphthylene or cyclopenta[cd]perylene units was also explored. Since the molecular scaffolds of the desired polymers have structural resemblance and electron affinities compared to bis-imide rylene dyes (NDI and PDI), the resulting materials have relavence for a varety of OSC based devicse. UV-Vis spectroscopy and cyclic voltammetry were utilized to probe the photoelectronic properties of these materials.

In this thesis,zirconium carbide (ZrC) layers were deposited on graphite substrates using a CVD reactor at temperatures ranging from 1250 °C to 1450 °C in steps of 50 °C. The deposited layers were characterised by XRD, Raman Spectroscopy and SEM.ZrCsamples were also prepared by spark plasma sintering (SPS), at 1700, 1900 and 2100 °C at 50 MPa for 10 minutes. The phase and microstructure after the sintering process were investigated by XRD and SEM. Iridium (Ir) thin films were deposited on these ZrCsamples and annealed in vacuum at temperatures of 600 and 800 °C for 2h. The phase composition, solid-state reactions and surface morphology were investigated by GIXRD and SEM. XRD was used to identify the phases present in the as-deposited and annealed samples. It showed that Ir2Zr was the initial phase formed at 600 °C. At temperature 800 °C IrZr formed. / Thesis (PhD (Physics))--University of Pretoria, 2019. / University of Pretoria / Physics / PhD (Physics) / Unrestricted

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Metallurgy and Material Science, 1974. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. Bibliography: leaves 56-59. / by Thomas Maurice Devine, Jr. / Ph.D.

Indiana University-Purdue University Indianapolis (IUPUI) / Electrospinning has gained immense interests in recent years due to its potential application in various fields, including energy storage application. The V2O5/GO as a layered crystal structure has been demonstrated to fabricate nanofibers with diameters within a range of ~300nm through electrospinning technique. The porous, hollow, and interconnected nanostructures were produced by electrospinning formed by polymers such as Polyvinylpyrrolidone (PVP) and Polyvinyl alcohol (PVA), separately, as solvent polymers with electrospinning technique. In this study, we investigated the synthesis of a graphene-modified nanostructured V2O5 through modified sol-gel method and electrospinning of V2O5/GO hybrid. Electrochemical characterization was performed by utilizing Arbin Battery cycler, Field Emission Scanning Electron Microscopy (FESEM), X-ray powder diffraction (XRD), Thermogravimetric analysis (TGA), Mercury Porosimetry, and BET surface area measurement. As compared to the other conventional fabrication methods, our optimized sol-gel method, followed by the electrospinning of the cathode material achieved a high initial capacity of 342 mAh/g at a high current density of 0.5C (171 mA/g) and the capacity retention of 80% after 20 cycles. Also, the prepared sol-gel method outperforms the pure V2O5 cathode material, by obtaining the capacity almost two times higher. The results of this study showed that post-synthesis treatment of cathode material plays a prominent role in electrochemical performance of the nanostructured vanadium oxides. By controlling the annealing and drying steps, and time, a small amount of pyrolysis carbon can be retained, which improves the conductivity of the V2O5 nanorods. Also, controlled post-synthesis helped us to prevent aggregation of electro-spun twisted nanostructured fibers which deteriorates the lithium diffusion process during charge/discharge of batteries.

京都大学 / 0048 / 新制・課程博士 / 博士(エネルギー科学) / 甲第19096号 / エネ博第320号 / 新制||エネ||65(附属図書館) / 32047 / 京都大学大学院エネルギー科学研究科エネルギー応用科学専攻 / (主査)教授 松田 一成, 教授 岸本 泰明, 教授 大垣 英明 / 学位規則第4条第1項該当 / Doctor of Energy Science / Kyoto University / DFAM