Flame synthesis is recognized as a much cheaper and higher throughput process for carbon nanotube/nanofiber (CNT/CNF) production compared to conventional catalytic processes like chemical vapor deposition (CVD). Nanostructured carbon materials, such as carbon nanotubes and nanofibers, exhibit superhydrophobic behavior over a range of pH values, including for corrosive liquids. Part of this research reports the development of a rapid on-demand process for the synthesis of superhydrophobic surfaces on silicon (Si) discs using an ethylene-air nonpremixed flame. Such superhydrophobic behavior, combined with increase in effective surface area due to carbon nanostructure (CNS) deposition and corresponding desirable size (nanoscale roughness) attract the growth and attachment of microbial colonies to these CNS-enhanced substrates. This has potentially high-impact application in microbial fuel cells (MiFCs) whereby stainless steel (SS) meshes coated with flame-deposited CNS are used as anodes and the electrons produced by attaching biofilms can generate electricity in a fuel cell. However, despite such and many other applications and promise of carbon nanotubes (CNTs), their production is generally based on empirical principles. There are only a few CNT formation models that predict the dependence of CNT growth on various synthesis parameters. Typically, these do not incorporate a detailed mechanistic consideration of the various processes that are involved during CNT synthesis. Herein, this need is addressed and a model is presented for catalytic CNT growth that integrates various interdependent physical and chemical mechanisms involved in CNT production. It is validated by comparing its predictions with experimental measurements for CVD synthesis of CNTs and a concise parametric study is presented. The results are extrapolated for flame synthesis that is recognized as a desirable cost-effective process for the bulk synthesis of CNTs, as already mentioned. The last part of this dissertation discusses an extension of the CNT growth model to silicon nanowire/nanowhisker (SiNW) synthesis. SiNWs are synthesized by a number of methods — catalysis by a metal (involving vapor-liquid-solid or VLS growth mode), molecular beam epitaxy, thermal evaporation and laser ablation to name a few. Our model pertains to metal-catalyzed VLS growth mode. / Ph. D.

It is estimated that approximately 2 million fires which occur in United States each year result in 1.2 million burn victims. Fibroblasts are responsible for responding to this tissue damage by breaking down the damaged extracellular matrix (ECM) and secreting a new ECM which aids in wound repair and supports the migration of immune cells. Pseudomonas aeruginosa is an opportunistic pathogen commonly associated with health-care infections (HCAIs) due to its ability to take advantage of immunocompromised hosts. However, little research has investigated how wound invading P. aeruginosa interacts with wound repairing fibroblasts. To address this lack of understanding, this thesis focuses on quantifying changes in fibroblast morphology, migratory behavior, and force exertion to investigate this host cell's response to representative cytotoxic (PAO1) and invasive (PA14) strains of P. aeruginosa. These assays study host cell-pathogen interactions on highly aligned nanofibers of varied spacing and diameter, which mimic the fibroblast deposited ECM and dictate fibroblast morphology. We discovered that the cytotoxic strain of P. aeruginosa induced significantly shorter fibroblast death times. Furthermore, two modes of death, sharp and gradual, were identified and found to be dependent on both fiber configuration and strain of P. aeruginosa. In addition, fibroblasts exposed to PAO1 migrating on the parallel formation were found to be significantly slower and less persistent than those exposed to PA14, however, fibroblasts exposed to both strains of bacteria were shown to exert similar forces. Lastly, exposure to PA14 led to the greatest change in actin, evident by increased actin punctae and less prominent actin stress fiber formation. / Master of Science / It is estimated that approximately 2 million fires which occur in United States each year result in 1.2 million burn victims. Fibroblasts respond to burn wounds by breaking down the damaged tissue fibers, termed extracellular matrix (ECM), and secreting a new ECM. Unfortunately, severe thermal injuries place hospitalized burn victims at high risk of infection. Pseudomonas aeruginosa is an opportunistic pathogen commonly associated with health-care infections (HCAIs) due to its ability to take advantage of immunocompromised hosts. However, little research has investigated how wound invading P. aeruginosa interacts with wound healing fibroblasts. To address this knowledge gap, this thesis focuses on quantifying changes in fibroblast shape, migratory behavior, and force exertion to investigate this host cell's response to two strains of P. aeruginosa, which employ different mechanisms of invasion. These interactions are studied on a platform of suspended nanofibers with controlled spacing and diameter, to dictate fibroblast shape and mimic the fibroblast deposited ECM. We discovered that the two strain of P. aeruginosa induced significantly different fibroblast death times. During death, it was observed that fibroblasts either balled up quickly, termed sharp death, or remained spread out, termed gradual death, dependent upon fibroblast shape and strain of P. aeruginosa introduced. In addition, significant differences in migration speed and persistence were found between fibroblasts exposed to the two strains of bacteria, however, both groups were shown to exert similar forces. Lastly, the fibrous proteins which make up the cytoskeleton of the cell, actin stress fibers, were found to vary among the control and bacteria treated cells.

京都大学 / 新制・課程博士 / 博士(農学) / 甲第25327号 / 農博第2593号 / 京都大学大学院農学研究科森林科学専攻 / (主査)教授 矢野 浩之, 教授 梅村 研二, 教授 和田 昌久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Polymer nanofibers used for the construction of triboelectric nanogenerator (TENG) and piezoelectric nanogenerator (PENG) are new and promising technologies for energy recovery. Thanks to the generation of electrical energy based on mechanical movement (deformation), these fibers can find application in the field of self-powered electronic devices. In this work, three nanofibrous structures of materials were prepared by electrostatic spinning: pure polyvinylidene fluoride (PVDF), pure polyamide-6 (PA6) and their mixed combination PVDF / PA6. Non-destructive analyzes such as Raman spectroscopy, FTIR, XPS and electron microscopy were used to study the properties of nanofibers. Analyzes confirmed the positive effect of electrostatic spinning of polymers on the support of the formation of highly polar crystalline -phase in PVDF and , -phase in PA6. The structure arrangement of the nanofibrous material and their defects were observed by scanning electron microscopy (SEM). Furthermore, the contact angle of the wettability of the liquid on the surface was measured for the materials, and the permittivity was measured to monitor the dielectric properties. The described results make the mixed material PVDF / PA6 very promising for further research in the field of nanogenerators and functional textiles.

Indiana University-Purdue University Indianapolis (IUPUI) / Purpose: Dental sealant forms a physical barrier to prevent pit and fissure caries; therefore, the retention rate becomes a main factor of the sealant’s effectiveness. Electrospun nylon-6/N6 nanofibers have shown good mechanical properties, such as high tensile strength and fracture toughness. Chitosan/CH has received significant attention due to properties such as antibacterial activity. The purpose of this study was to synthesize and evaluate the effect of incorporating N6 and CH electrospun nanofibers on the physical-mechanical and antibacterial properties of an experimental resin-based sealant. Methods and Materials: Nanofiber synthesis: N6 pellets were dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol at a concentration of 10wt%. Practical-grade chitosan was dissolved in trifluoroacetic acid and dichloromethane (60:40 TFA/DCM) at 7 wt%. Electrospinning parameters were optimized in order to fabricate defect-free N6 and chitosan nanofiber mats. Morphological and chemical characterizations were performed by scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy, respectively after vacuum drying the mats for 48 h. The average fiber diameter was determined from SEM images by measuring the diameter of 120 fibers using ImageJ software. Experimental Sealant: N6 and CH electrospun mats (3×3cm2) were immersed into a resin mixture of BIS-GMA/TEGDMA. Once no bubbles were seen, the resin-modified N6 and CH mats were put on a glass plate, light-cured (“TRIAD 2000”) for 2 min and then submitted to a cryomilling process to obtain a fine micron-sized powder. Three different filler levels (1 wt%, 2.5 wt%, 5 wt%) were used to prepare the N6 and CH incorporated resin-based sealants. Additionally, a commercially available resin-based sealant and the experimental resin mixture (unfilled) were used as controls. Three-point flexural testing, Vickers microhardness testing, and agar diffusion testing were performed on the experimental sealants and the commercial sealant. Data were analyzed by one-way ANOVA and Fisher's Protected Least Significant Differences Pair-wise comparisons between groups (5%). Results: The average fiber diameter for N6 was found to be 503±304 nm and 595±411 nm for CH. No significant difference was found between fiber diameter (p = 0.0601). FTIR confirmed the characteristic peaks for N6 ((CO-NH and [-(CH2)5-].) and CH (N-H and C2F3O2-). CH-5% group had significantly higher (p = 0.0000) FS (115.3±4.5 MPa) than all other groups. CH-1% and CH-2.5% groups had significantly higher FS than the control (unfilled) (p = 0.0016 and p = 0.0033 respectively); Helioseal Clear (p = 0.0000), and nylon groups. N6-5% had significantly higher flexural strength than Helioseal Clear (p = 0.0013) and N6-2.5% (p = 0.0250). CH-1% had significantly higher hardness values than all other groups, and CH-5% (p = 0.0414) had significantly higher values than N6-2.5%. No antibacterial inhibition was seen in any of the tested groups. Conclusions: CH and N6 nanofibers were successfully prepared via electrospinning and used to modify the experimental resin-based dental sealants. The overall results indicated that CH-containing sealants presented the highest flexural strength and hardness; however, none of the CH groups displayed antimicrobial properties. Further investigation is needed to enhance the physico-mechanical properties of the experimental resin-based sealants using nylon-6 and CH.

No description available.

No description available.

Le matériau composite Cu/NFC (Nano Fibre de Carbone) peut être utilisé en tant que drain thermique par les industriels de l'électronique de puissance. En remplacement du cuivre, il doit combiner une conductivité thermique élevée et un coefficient de dilatation thermique adapté à celui de la céramique du circuit imprimé (alumine ou nitrure d’aluminium). Après avoir étudié les propriétés de la matrice cuivre et des NFC, plusieurs méthodes de synthèse du composite Cu/NFC ont été développées. Le composite a tout d’abord été élaboré par métallurgie des poudres. Puis, dans le but d’améliorer l’homogénéité, il a été envisagé de revêtir individuellement chaque NFC par du cuivre déposé par voie chimique electroless ainsi que par une méthode originale de décomposition d’un sel métallique. Des mesures de densité et de propriétés thermiques (conductivité et dilatation) ainsi que les caractérisations microstructurales de ces matériaux montrent la complexité de l’élaboration d’un tel composite. En effet, la dispersion des nanofibres, la nature des interfaces fibres/matrice et surtout les phénomènes thermiques à l’échelle nanométrique sont autant de paramètres à contrôler afin d’obtenir les propriétés recherchées. La simulation numérique et analytique, qui a été mise en oeuvre en parallèle a été corrélée aux résultats expérimentaux, afin de prédire les propriétés finales de nos matériaux. / Cu/CNF (Carbon Nano Fiber) composite materials can be used as heat sink in power electronic devices. They can substitute Copper by combining a high thermal conductivity and a coefficient of thermal expansion close to the printed circuit one (alumina or aluminum nitride). After studying the properties of Copper matrix and CNF, three methods were set up for the elaboration of the Cu/CNF composite materials. It was first synthesized by a simple powder metallurgy process. Second, in order to obtain a better homogeneity, CNF were individually coated with Cu by an electroless deposition method. Third, an original technique involving the decomposition of a metallic salt has been used. Measurements of the density, the thermal properties (conductivity and dilatation), and the characterization of the microstructure of the composite materials have been performed. It reveals the complexity of the realization of such a composite. Indeed, the dispersion of CNF and the chemical nature of the Cu/CNF interfaces have to be controlled in order to reach the desired thermal properties. Analytical and numerical simulations have been conducted and correlated with the experimental results to predict final properties of our materials.

La filature par voie électrostatique consiste à dissoudre un polymère dans un solvant, puis soumettre cette solution à un champ électrostatique intense. Différents paramètres influencent l'obtention, la production et la régularité des nanofilaments obtenus. Parmi ces paramètres, il y a des paramètres physiques inhérents à la cabine de filage, des paramètres électriques et des paramètres liés à la solution. Pour obtenir des nanofilaments, la première étape est de déterminer le ou les meilleurs couples polymère-solvant ainsi que les conditions expérimentales optimales pour obtenir à la fois des produits homogènes et reproductibles. L'obtention de nanofilaments de caractéristiques mécaniques et de structures données est complexe et dépend à la fois de paramètres de filage, mais aussi des propriétés de la solution. Une des propriétés les plus importantes de la solution est sa viscosité. Il a donc été nécessaire d'étudier, pour différents couples solvant-polymère (PA, PAN, PLA, PHEA) leur comportement rhéologique. Ces études rhéologiques ont permises d'expliquer les morphologies des matériaux obtenus par la conformation macromoléculaire de la solution. Les non-tissés de nanofibres obtenus ont été caractérisés par Microscopie à Forces Atomiques (AFM), Microscopie Electronique à Transmission (MET) et à Balayage (MEE) pour les aspects morphologiques. D'autres caractérisations, thermique (DSC), spectroscopique (FTIR) et mécaniques (traction et indentation) ont complété la caractérisation de ces matériaux. A l'issue de l'étude précédente, les nanofibres ont été employées dans deux applications. (1) L'incorporation et la compatibilisation de nanorenforts à l'intérieur d'une matrice polymère (Polyacrylonitrile). L'influence sur les propriétés géométriques des nanofibres de façon globale, et plus finement, la morphologie de surface, ont été observées par une analyse AFM de nano-rugosité. (2) La réalisation à partir d'un biopolymère d'un guide tubulaire permettant la croissance cellulaire et la reconnexion de nerfs sectionnés. Il a fallu pour cela remplir un cahier des charges rigoureux en termes de dimensionnement, de structure, et de propriétés mécaniques. / Electrospinning is a process to produce the fibers in nano scale by injecting the polymer solution through a metallic needle to a high voltage electrical field. Different parameters affect the process production and regularity of obtained nano-web. Among these parameters, there are physical parameters depending on the electrospinning booth, electrical parameters and polymer solution properties. For nanofibers production, the first step is to determine the most efficient polymer-solvent pairs and the optimal experimental conditions for both homogeneous and reproducible products. Obtaining mechanical and morphological properties of nanofibers nonwowen is complex and depends on the electrospinning parameters, but also the solution properties. One of the most important properties of the solution is its viscosity. It was therefore necessary to study for the selected pairs (PA, PAN, PLA, PHEA) their rheological behaviour. These rheological studios allow to explain the morphology of obtained nanofibers, which could be explained by the conformation of the macromolecules in the solution. Nonwoven nanofibers obtained were characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM) and scanning electron microscopy (SEM) for morphological aspects. Other characterizations, thermal (DSC), spectroscopie (FTIR) and mechanical (tensile and indentation) completed the characterization of these materials. After these previous studios, the nanofibers have been used in two applications. (1) The incorporation of nanofillers and compatibilization within a polymer matrix (Polyacrylonitrile). The influence on the geometric properties of nanofibers, and surface morphology were observed by AFM nano-roughness analysis. (2) The production by electrospinning of a guide tube for cell growth and reconnection of severed nerves: from a biopolymer. The produced material had to meet strict specifications in terms of size, structure, and mechauical properties.

A síntese de Fischer-Tropsch é um processo de conversão do gás de síntese (CO + H2) em hidrocarbonetos de cadeias longas. Os catalisadores clássicos para a hidrogenação do CO são, principalmente, o Fe e o Co suportados em diferentes óxidos. O desempenho catalítico do catalisador é influenciado pelo tamanho, dispersão e grau de redução das partículas metálicas. Estudos recentes mostram uma promissora aplicação de materiais à base de nanofibras de carbono na catálise heterogênea. Estes materiais apresentam algumas vantagens em relação aos suportes catalíticos tradicionais, tais como: uma baixa interação metal-suporte, elevada área superficial, ausência de poros fechados, alta condutividade térmica, elevada inércia química e hidrofobicidade. Neste trabalho foram fabricados suportes catalíticos macroscópicos à base de nanofibras de carbono, empregando o método de vapor deposição, a partir da decomposição do etano. Os catalisadores foram preparados pela impregnação incipiente do Co e de promotores na superfície do suporte. Foram empregados os metais nobres, Ir, Pt e Ru, como promotores catalíticos, com o objetivo de incrementar a redutibilidade e a atividade do catalisador. Todos os catalisadores foram caracterizados por Quimissorção de CO, Fisissorção de N2, Redução a Temperatura Programada (TPR), Espectroscopia Fotoeletrônica de Raios X (XPS) e Microscopia Eletrônica de Transmissão (MET). Os catalisadores foram, então, testados na síntese de Fischer-Tropsch, utilizando um reator de leito fixo e fluxo contínuo, com análise simultânea dos produtos gasosos e controle sistemático da temperatura, pressão e vazão dos reagentes. Finalmente, foram analisados os produtos líquidos obtidos na reação com objetivo de conhecer a influência dos promotores na seletividade dos hidrocarbonetos formados. / Fischer-Tropsch synthesis is a process of converting the syngas (CO + H2) to long-chain hydrocarbons. The traditional catalysts for the CO hydrogenation are Fe and Co supported on different oxides. Catalytic performance of the catalyst is influenced by size, dispersion and degree of reduction of metal particles. Recent studies show a promising application of materials based on carbon nanofibers in heterogeneous catalysis. These materials have some advantages compared to traditional catalyst supports, such as a low metal support interaction, high surface area, no closed pores, high thermal conductivity, high chemical resistance, and hydrophobicity. In this work, based on macroscopic carbon nanofiber catalyst supports have been manufactured by employing the method of chemical vapor deposition from ethane decomposition. Catalysts were prepared by incipient wetness impregnation of Co and promoters on the support surface. Noble metals, Ir, Pt and Ru were used as catalytic promoters, with the aim of increasing the reductibility and catalyst activity. All catalysts were characterized by CO Chemisorption, N2 Physisorption, Temperature Programmed Reduction (TPR), X-ray Photoelectron Spectroscopy (XPS), and Transmission Electron Microscopy (TEM). The catalysts were then tested in the Fischer-Tropsch synthesis using a fixed bed reactor, continuous flow, with simultaneous analysis of gaseous products and systematic temperature control, pressure, and flow rate of the reactants. Finally, the liquid products obtained in the reaction were analyzed in order to determine the influence of promoters on the selectivity of hydrocarbons formed.