Electrospinning process is a simple and widely used method for producing polymeric nanofibres. However, despite its popularity, significant challenges remain in controlling the fibre deposition due to the complex nature of electrospinning process. The process is renowned for its chaotic motion of fibre deposition, also known as the whipping instability. This instability is caused by electrostatic and fluid dynamics interactions of the charged jet and it is partly responsible for the thinning of the fibres into nanoscale diameters. Due to the instability, an electrospinning process typically deposits random orientated fibres in a circular deposition area. Furthermore, there is no control over the location where the fibres land on the collector electrode except that the fibres always travel through the shortest trajectory between the source and the collector electrodes. In this study, an alternative controlled deposition technique was proposed based on electric field manipulation (EFM). The main hypothesis of this study is that a consistent and repeatable method of controlled deposition can be achieved by using EFM. EFM was achieved by introducing a pair of charged auxiliary electrodes positioned adjacent and perpendicular to the fibre deposition direction. The applied voltage of either direct current (dc) or time-varying (ac) voltage at the auxiliary electrodes act as control to influence the spatial location and size of the deposition area. Samples were produced on black paper substrates and scanned into greyscale images. An image analysis technique was developed to measure the shift and size of the deposition area. A computer simulation was used to calculate the electric field strength and to simulate the behaviour of fibre response based on the trajectory of a charged particle. An image analysis based on greyscale intensity measurement was also developed to examine the uniformity of the deposition area. Finally, fibre characterisation was carried out to examine the fibre morphology, diameter, and orientation based on scanning electron micrographs. The results from this study showed that EFM can provide a consistent and repeatable control of the deposition area. When the auxiliary electrodes were independently charged with two dc voltages, it was observed that the deposition area moved away from the most positive electrode. The magnitude of shift of the deposition area was found to increase linearly with voltage difference between the auxiliary electrodes. Furthermore, the aspect ratio of the deposition area (ratio of width over height) decreased linearly with base voltage i.e. lower of the two auxiliary electrode voltages. These two controls were found to act independently from each other and can be described as two separate controls i.e. voltage difference for spatial location and base voltage for aspect ratio of the deposition area. A similar response was observed in simulation i.e. the particle moved away from the most positive electrode. Simulation results also showed that the x-axis component of the electric field (Ex) was responsible for the shift in location and the reduction of aspect ratio of the deposition area. When the auxiliary electrodes were charged with two antiphase time-varying voltages, continuous scanning of the electrospinning jet was observed producing a wide electrospun fibre mat. It was first thought the smooth oscillation of a sine wave would produce a more uniform deposition pattern compared to a triangle wave, but the results showed otherwise. The inferior uniformity of the sine wave sample was found due to the variability of the jet scanning speed when compared to the constant speed achieved when using a triangle wave. It was also observed that the deposition pattern can be further improved by using two clipped triangle wave voltages. The results open up the possibility for further exploiting the control voltage to achieve the desired deposition pattern. Two case studies were presented to demonstrate the applicability of the technique in real electrospinning applications. In the first case study, it was demonstrated that the continuous scanning of electrospinning jet was capable of eliminating the stripe deposition pattern which is commonly associated to a multi-spinneret electrospinning system. In the second case study, it was found that the alignment and distribution of aligned fibres in a gap electrospinning system can be improved by using the EFM technique. A new technique was also introduced to produce a multi-layer orientated fibre construct. These application examples showed that the EFM technique is ready for the production of engineered electrospun fibre constructs. This would extend the use of electrospun fibres to applications which is currently limited by geometrical constraints of the fibre constructs.

Electrospinning produces submicron fibers from a wide range of polymer/solvent systems that enable a variety of different applications. In electrospinning process, a straight polymer/solvent charged jet is initially formed, followed by a circular moving jet in the shape of a cone, called the bending region. The process physics in the bending region are difficult to study since the jet diameter cannot be measured directly due to its rapid motion and small size (~microns and smaller), and due to complex coupling of multiple forces, mass transport, and changing jet geometry. Since the solutions studied are hydrophilic, they readily absorb ambient moisture. This thesis explores the role of the bending region in determining the resulting electrospun fiber diameter through a combined experimental and modeling analysis for a variety of hydrophilic polymer/solvent solutions. Electrospinning experiments were conducted over a broad range of operating conditions for 4 different polymer/solvent systems. Comparison of the final straight jet diameters to fiber diameters reveals that between 30% to 60% jet thinning occurs in the bending region. These experiments also reveal that relative humidity significantly affects the electrospinning process and final fiber diameter, even for non-aqueous solutions. A model is developed to obtain insight into the bending region process physics. Important ones include understanding the mass transport for non-aqueous hydrophilic jets (including solvent evaporation and water absorption on the jet surface, radial diffusion, and axial advection), and the coupling between the mass and force balances that determines the final fiber diameter. The absorption and evaporation physics is validated by evaporation experiments. The developed model predicts fiber diameter to within of 8%, even though the solution properties and operating conditions that determines net stretching forces and net evaporation rates vary over a large range. Model analysis reveals how the net evaporation rate affects the jet length and net stretching force, both of which ultimately determine the fiber diameter. It is also shown that the primary impact of RH on the process is through occupation of the surface states that limits solvent evaporation rate, rather than the amount of water absorbed. Correlation functions between process conditions, solution properties and the resulting fiber diameters are discussed.

Electrospinning is a technique to achieve nanometer scale fibers. Similar to the conventional spin methods of making fabric, the viscous polymer solution is ejected from a spinneret; stretched and solidified in the air, the solution forms the fibers. The different part of electrospinning among others is that the fibers are driven by the electrostatic force, which induces the repulsion inside the liquid and further reduces the diameter. The resultant product is a non-woven membrane, which is porous; and the pore size is around several nanometers to a micrometer wide. In this work, the relationship between the diameter of electrospun silica fibers, experimental parameters such as concentration and voltage, and between pore size of the fiber membrane and experimental time were studied. Materials used in the process are Polyvinylpyrrolidone (PVP), butanol and spin-on-glass coating solution, which act as polymer carrier, solvent, and silica-precursor, respectively. Polymer/silica precursor composite fibers were ejected from the needle of a plastic syringe when an electrical field, as high as several kV/cm, was applied. Then silica fibers were achieved by baking the composite ones at 773 oK for 12 h. Electrospun silica nanofibers were characterized as a function of polymer solution parameters. The calcined fibers were examined by using a field emission scanning electron microscope. The results showed that the fiber diameters decrease with decreasing proportion of polymer and silica precursor, and increase with a higher electric field. Pore sizes, defined as the grid areas enclosed by fibers on nearby layers, were also examined and showed no time-dependent tendency when the electrospin time was between 1-5 min. Fiber membranes were then used as the platform for protein detection. The results were compared with the control, which used glass slides as the platform. The results make it possible to make a more sensitive biosensing device.

Developing renewable materials to reduce the dependence on fossil fuel as a feedstock for a wide range of applications is becoming increasingly acknowledged as important in society. Chitin, the second most abundant biopolymer in nature, is an ideal candidate for diverse applications because of its remarkable properties, such as abundance, renewability, biodegradability, biocompatibility, antibacterial activity, chemical functionality, and high stiffness and strength. Despite these inherent advantages, chitin is currently still underutilized mainly due to its strong molecular interactions, which make it insoluble in common solvents. Currently, its major applications are limited to biomedical engineering, such as tissue engineering, wound dressing and sutures. This thesis aims to explore and enable the potential utilization of chitin in other fields where it may serve as a renewable functional advanced material. Here, a number of novel chitin-based materials were developed successfully without employing chitin dissolution. These include chitin nanofibers (CNFs), porous chitin with tunable structures, chitin-reinforced polymer composites and chitin-stabilized aqueous foams. Moreover, the properties of these materials including interfacial, optical, thermal, and mechanical characteristics were determined, and their potential utilizations were demonstrated. Briefly, in chapter 2, CNFs with diameters of ~20 nm were successfully extracted from crab α-chitin by a high pressure homogenization process. The produced CNFs were dispersed well in water without forming strong network structures due to their electrostatic repulsions. The obtained CNF film has a high residue amount (40%) when heated up to 1000 ˚C. Meanwhile, it exhibited high optical transparency as well as great gas barrier properties. In chapter 3, on the basis of the obtained CNFs in chapter 2, versatile porous structures including oriented sheets and three-dimensional aperiodic nanofiber networks were achieved by using a freeze drying technique. Since the formation of nanofibrous structures cannot be predicted by the widely-used particle encapsulation model, a modified structure formation mechanism was proposed. In chapter 4, the structure-property relationships of the CNF/poly(ethylene oxide)(PEO) nanocomposites were established. We demonstrated that the CNFs formed network structures in PEO matrix and had hydrogen bonding interaction with PEO. The CNFs can greatly enhance the mechanical properties of PEO, such as elastic modulus and tensile strength. In chapter 5, the aqueous foams stabilized by high-aspect-ratio CNFs were developed. The created foams exhibited strong hindrance on film drainage, coalescence and disproportionation. The fibrillated CNFs alone were not able to stabilize air bubbles, but the addition of small amounts of valeric acids in CNF dispersion can make chitin foamable. The results clearly showed that valeric acid modified CNFs reduced the surface tension of aqueous dispersion and were attached at the air-water interface. Overall, this research has provided many new insights for the fabrication, characterization, and utilization of chitin, and has built a solid foundation for further exploiting chitin for diverse applications.

Orientador: Edison Bittencourt / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T11:03:39Z (GMT). No. of bitstreams: 1 Millas_AnaLuizaGarcia_M.pdf: 27876166 bytes, checksum: ca1630199ae2b6bb6f1e2d15d0c50fa8 (MD5) Previous issue date: 2012 / Resumo: A ciência dos biomateriais e a nanotecnologia caminham juntas em busca de novas alternativas e da melhoria das propriedades físicas, químicas e mecânicas dos materiais, relacionadas à alta razão superfície/volume e às dimensões nanométricas que possibilitam obter ótimo desempenho com pouca quantidade de material. Esse trabalho objetivou a produção de nanofibras biodegradáveis e biocompatíveis a partir da solução de acetato de celulose a 10(%m/m) dissolvido em sistema de acetona e água (4:1). A pesquisa partiu da instalação de um equipamento de electrospinning e do estudo dos parâmetros que influenciam o processo e a formação de nanofibras através dessa tecnologia. Concentrações entre 1% e 15% dos óleos naturais das espécies Copaifera langsdorffii e Cymbopogon nardus com comprovadas propriedades cicatrizantes, analgésicas, antimicrobianas e de repelência a insetos foram misturadas a solução de acetato de celulose e estudou-se a influência desses compostos sobre o processo de eletrofiação e a estrutura das fibras confeccionadas. Com foco no óleo de copaíba verificou-se por cromatografia gasosa a sua presença nas nanofibras e foram feitos testes preliminares de viabilidade celular e biocompatibilidade in vitro. A intenção futura dessa pesquisa é a aplicação desse material na área da medicina regenerativa de tecidos, como curativos e scaffolds. O material foi caracterizado por Microscopia Óptica (MO), Microscopia Eletrônica de Varredura (MEV), Análise Termogravimétrica (TGA), Calorimetria Diferencial Exploratória (DSC), Condutividade das soluções e Cromatografia Gasosa (CG) / Abstract: The science of biomaterials and nanotechnology combine in the search of new alternatives to improve the physical, chemical, and mechanical properties of materials associated with the high surface area to volume ratio, and nanometer dimensions, that provide optimum performance with small amounts of the nano-material. This study aimed to produce biodegradable and biocompatible nanofibers from cellulose acetate at 10 (%w/w) dissolved in acetone and water system (4:1). The research started from the installation of electrospinning equipment and studying the parameters influencing the process and the formation of nanofibers through this technology. Concentrations between 1% and 15% of natural oils, such Copaifera langsdorffii and Cymbopogon nardus with proven wound healing, analgesics, antimicrobial and insect repellent properties were mixed with the solutions of cellulose acetate. The presence and the influence of these two oils on the electrospinning process and the structure of the fibers prepared were evaluated. The future intention of this work is to apply these nanofibers in the regenerative medicine field, as bandages and scaffolds. The material was characterized by Optical Microscopy, Scanning Electron Microscopy (SEM), Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), Conductivity and Gas Chromatography (GC). Preliminary tests of cell viability in vitro were performed / Mestrado / Ciencia e Tecnologia de Materiais / Mestra em Engenharia Química

Les travaux de recherche de ce manuscrit s’inscrivent dans le cadre d’une coopération scientifique avec la société STMicroelectronics de Tours concernant les interconnexions des prochaines générations de circuits intégrés. L’intégration de nanotubes de carbone comme connecteurs en microélectronique de puissance, limiterait sévèrement les effets d’échauffements dans les empilements de puces, permettant une meilleure dissipation de la chaleur. Ce travail de thèse avait pour objectif de déterminer un procédé de croissance reproductible de nanotubes de carbone d’au moins 20 dm de long, en tapis perpendiculaire au substrat, peu pollué par du carbone amorphe afin de réaliser un véhicule test permettant de mesurer les propriétés thermiques et électriques du tapis de nanotubes obtenu. Le dispositif expérimental présenté utilise l’ablation laser pour le dépôt de catalyseur (fer) la méthode de CVD assistée par plasma radiofréquence d’éthylène et d’hydrogène pour la croissance de nanotubes de carbone. Des conditions optimales d’obtention des tapis répondant aux critères de réalisation des démonstrateurs, ont été définies à la suite d’une étude paramétrée. Pour les mesures électriques, des plots d’or servant d’électrodes, sont déposés sur les tapis de nanotubes. Lors des tests électriques 4 pointes sur le démonstrateur réalisé, le comportement ohmique des tapis de nanotubes a été mis en évidence. Une puissance de 300 mW/mm2 est déposée sur les plots sans aucun dommage pour les nanotubes, et une résistivité de l’ordre de 10-3 L.m a été estimée. Pour les tests thermiques, une couche mince de titane absorbant l’énergie d’un faisceau laser UV pulsé représentant la source de chaleur, est déposée sur le tapis de nanotubes. Des valeurs de conductivité thermique apparente de 200 – 300 W/m/K et intrinsèque de 660W/m/K ont été déterminées par méthode de pyrométrie infrarouge résolue en temps. / This manuscript presents the research work done in the frame of scientific cooperation with the company STMicroelectronics in Tours concerning the interconnections for the next generation of integrated circuits. The integration of connectors based on carbon nanotubes in microelectronic would severely limits the effects of overheating in the stacks of chips, allowing a better heat dissipation. The aim of this PHD work was the determination of a reproducible carbon nanotubes carpet growth process at least 20 dm long, perpendicular to the substrate, slightly polluted by amorphous carbon in order to achieve a test vehicle for measuring thermal and electrical properties of carbon nanotubes carpet. The experimental device combines laser ablation process for the deposit of catalyst (iron) and RF plasma Enhanced CVD method with a mixture of ethylene and hydrogen gases for the growth of carbon nanotubes. Optimal conditions for obtaining carpet criteria for test vehicle realization have been defined from a parameterized study. For electrical measurements, gold layers as electrodes are deposited on nanotube carpets. Four probes electrical test is achieved and an ohmic behaviour of nanotube carpet is evidenced. A power of 300 mW/mm2 is deposited without any damage for the nanotubes and the carpet resistivity is estimated to be 2,99.10-3 L.m. For thermal testing, a titanium thin film is deposited on the carpet in order to absorb the UV pulsed laser beam representing the heating source. An apparent thermal conductivity value of 200 - 300 W/m/K and an intrinsic value of 660W/m/K were determined by time resolved infrared pyrometry method.

京都大学 / 0048 / 新制・課程博士 / 博士(農学) / 甲第22497号 / 農博第2401号 / 新制||農||1077(附属図書館) / 学位論文||R2||N5277(農学部図書室) / 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 和田 昌久, 教授 辻井 敬亘 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

The goal of this thesis was to summarize basic options of fiber spinning and manufacturing and their usability in industry. Methods of nanofiber spinning are described in the teoretical part, alongside the materials used in experimental part. The experimental part was focused on creating of workflow of defined nanofibers in laboratory enviroment, the possible modification of nanofibers with aditives. The release of aditives from different nanofibers into different enviroments was measured.

Nanofabrication techniques produce materials with enhanced physicochemical properties through a combination of nanoscale roughness and the use of chemically diverse polymers which enable advanced applications in separation science (air/water purification), tissue engineering, and biosensing. Since the late 1990’s, electrospinning has been extensively studied and utilized to produce nano- to microfiber meshes with 3D porosity on the gram scale. By combining a high surface area to volume ratio and tunable surface chemistry, electrospinning is a facile platform for generating non-woven polymeric fibers for many biomedical and industrial applications. This thesis describes three applications of electrospun nano- and microfiber meshes spun from both commercially available and novel polymer systems for: 1) oil and water separation after an accidental oil spill; 2) ultraviolet light controlled protein and cell patterning throughout 3-dimensional nanofiber meshes; and 3) novel diagnostic platform by combining electrospun nanofiber meshes with solid state nanopores for enhanced single molecule nucleic acid and protein detection. Each application embodies the philosophy that electrospun materials have the potential to solve a wide variety of problems by simply tuning the physicochemical properties and mesh morphologies towards the design requirements for a specific problem. For example, to solve the problem of recovering crude oil after an oil spill while generating a minimal waste burden, a hydrophobic and biodegradable microfiber mesh was designed to repeatedly separate oil and water and naturally biodegrade after use. In order to solve the problem of spatiotemporal placement of cells within a 3-dimensional tissue engineering construct, an ultraviolet light activated mesh was designed to transition from hydrophobic (water impermeable) to hydrophilic (water permeable) upon exposure to ultraviolet light facilitating protein and cell patterning. Finally to address two problems with single molecule solid state nanopore biosensors, namely rapid nucleic acid translocation rates and limited protein identification capabilities, a new biosensor platform was developed based on two novel polymeric systems which were synthesized and electrospun into high surface area nanofiber mesh coatings. / 2018-02-17T00:00:00Z

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