Chemical sensors based on arrays of polymer-coated surface acoustic wave (SAW) devices are required for defense applications that provide a combination of sensitivity, selectivity, portability and response time. The primary challenge in the development of these polymer-based microsensors is the need to reproducibly deposit high quality, defect-free polymer coatings onto microelectrodes. Coating methods such as air brushing and solvent casting have proven unreliable and I have investigated the possibility of depositing polymer films on microelectrodes using electrostatic processing methods. In this work AC electrospraying was used to deposit nanoscale polymer films onto the surface of microelectrodes. The alternating polarity of the electric field eliminates surface charge accumulation and the polymers were deposited uniformly across both electrically insulating and conducting surface regions. In a different work, DC electrospraying was used to deposit patterned organic coatings onto the surface of microelectrodes. The surface of the microelectrode array consisted of an alternating pattern of insulating, grounded-metallic and ungrounded metallic regions, each with a width of 15µm. The charged particles were deposited only onto the grounded-metallic surface regions where there is an electrical path for charge dissipation. No polymer deposition was observed on the insulating or ungrounded-metallic regions due to the effects of surface charge accumulation. Also, I, DC electrodeposited organic molecules within the pores of ceramic film. Due to electrospraying, this film has a strong built-in electric field that induces Stark effect in the organic molecules, providing a unique new technology for bio and chemical sensing. Electrospinning has been used to produce polymer nanofibers with diameters ranging from a few microns to less than 100 nanometers. Due to mechanical oscillations of the electrically charged fibers during electrospinning, they are usually collected in the form of a non-woven mat without any significant fiber orientation. I have developed a new method for making highly aligned arrays of polymer nanofibers by using an AC coupled DC field to drive the electrospinning process. This new "biased AC electrospinning" method can be used to deposit aligned arrays of polymer nanofibers onto virtually any substrate. Potential applications of well-ordered nanofiber materials include tissue engineering, filtration, drug delivery and microelectronics.

After a major flooding disaster, construction materials will be scarce during early recovery stages and any material of reasonable quality would be useful. Instead of importing higher quality material from sites a considerable distance away, on-site material may be useable. This thesis explores usage of specialty portland cements, and in some cases polymer fibers, as stabilization additives to fine grained soils with elevated moisture contents. The primary objective of this thesis is to develop strength, modulus, and ductility trends for a variety of soil types, cementitious materials, cementitious material contents, and moisture contents, and to use the data to compare specialty grind portland cements to commercially available portland cement from the same production facility. The secondary objective is to evaluate the effect of polymer fibers combined with portland cement for the same mixtures. Over 1300 Unconfined Compression (UC) tests were conducted to complete these two objectives.

<p>To fully optimize devices for solar energy conversion, a comprehensive understanding of how excitons migrate in materials for solar cell devices is crucial. Understanding the mechanisms behind exciton diffusion and energy transfer will enable the fabrication of highly efficient devices. However to thoroughly study exciton properties, techniques implementing high spatial (nm sizes) and temporal (fs time scales) resolution is required. Herein, we utilize transient absorption microscopy (TAM) with 50 nm spatial resolution and 200 fs temporal resolution to elucidate exciton diffusion in polymeric materials for solar energy conversion.</p> <p>While organic devices are inexpensive and require simpler fabrication procedures than inorganic materials, their device efficiencies often suffer due to their semi-crystalline nature, lending to short diffusion lengths which lead to trap sites and inevitably recombination. It has been demonstrated that achieving long-range exciton diffusion lengths is possible through coherence effects. Coherence can be found in an intermediate electronic coupling region where delocalization and localization compete.</p> <p>To exploit coherence effects, we study polymeric systems in which polymer chains are highly aligned via simple and scalable procedures; semiconducting fibers and solution coated films. In studying the fiber, we first implement polarized photoluminesce (PL) to determine optical ansitropy. From the polarized PL and PL images, it is observed that emission intensities are largest when probing along the transition dipole moment of the polymer. This suggests a type of Förester Resonance Energy Transfer mechanism in which excitons hop from one polymer chain to another.</p> <p>Solution coated polymer films are also studied to understand exciton diffusion as a function of deposition methods. By varying the solution concentration as well as coating rate, we are able to tune the morphology of the film. We observe a strong dependence between diffusion constant and deposition parameters, with diffusion constants of <i>ca.</i> 9, 13 and 33 cm²/s for three different films. The results obtained in this thesis are preliminary steps in an effort to elucidate energy transfer mechanisms and rates.</p><br>

At the ballistic limit velocity of a soft armor target pack, the impact response has been shown to be decoupled in the thickness direction, with the initial few plies behaving in an inelastic fashion via off-axis failure modes such as transverse shear or diametral compression. Past the initial few layers, the remaining plies dissipate energy via membrane-like responses, which only involve in-plane tensile failure modes of the constituent fibers. Since these initial plies only contribute to energy absorption via inelastic kinetic energy transfer, previous studies have shown that these plies may be replaced with another material with other desirable properties, such as lower manufacturing costs or stab-resistance.<div>However, the methodology of determining these parameters is still largely empirical. Armor panels are typically impacted and the shot outcomes subsequently evaluated in order to achieve a quantitative ballistic performance for the panel. Additionally, the ballistic performance is usually determined with respect to a particular projectile. Several models have been proposed to provide an efficient method of predicting ballistic limit determination, but results are sometimes difficult to translate across different projectile-target pairs.<br></div><div>The main research direction in the first volume looking at soft armor impact failure modes and design optimization is obviously of immediate relevance to this dissertation. We start off with an examination of the different types of failure modes that impact on fibrous armors may yield. Subsequently, building on these concepts, we take a deeper look into how different impact parameters cause different failure modes,and we end with a discussion of how the armor panel may be designed around these different failure modes. Although some rudimentary analytical and modeling efforts have been put forth, the current work places more emphasis heavily on experimental techniques and observations, as is the nature of the work typically produced by our research group.<br></div><div><br></div>

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No description available.

L’électrofilage est un procédé permettant de préparer des fibres possédant un diamètre de l’ordre du micromètre ou de quelques centaines de nanomètres. Son utilisation est toutefois limitée par le manque de contrôle sur la structure et les propriétés des fibres ainsi produites. Dans ce travail, des fibres électrofilées à partir de mélanges de polystyrène (PS) et de poly(vinyl méthyl éther) (PVME) ont été caractérisées. La calorimétrie différentielle à balayage (DSC) a montré que les fibres du mélange PS/PVME sont miscibles (une seule transition vitreuse) lorsque préparées dans le benzène, alors qu'une séparation de phases a lieu lorsque le chloroforme est utilisé. Les fibres immiscibles sont néanmoins malléables, contrairement à un film préparé par évaporation du chloroforme qui a des propriétés mécaniques médiocres. Des clichés en microscopies optique et électronique à balayage (MEB) ont permis d’étudier l'effet de la composition et du solvant sur le diamètre et la morphologie des fibres. Des mesures d’angles de contact ont permis d’évaluer l’hydrophobicité des fibres, qui diminue avec l’ajout de PVME (hydrophile); les valeurs sont de 60° supérieures à celles des films de composition équivalente. Un retrait sélectif du PVME a été réalisé par l’immersion des fibres dans l’eau. La spectroscopie infrarouge a montré que la composition passe de 70 à 95% de PS pour une fibre immiscible mais seulement à 75% pour une fibre miscible. Ces résultats indiquent que la phase riche en PVME se situe presque uniquement à la surface des fibres immiscibles, ce qui a été confirmé par microscopie à force atomique (AFM) et MEB. Finalement, l’effet du mélange des deux solvants, lors de l’électrofilage du mélange PS/PVME, a été étudié. La présence du chloroforme, même en quantité réduite, provoque une séparation de phases similaire à celle observée avec ce solvant pur. / Electrospinning is a simple method for the preparation of polymer fibers with diameters of hundreds of nanometers to a few micrometers. Although it is a versatile method, some issues remain in the control of the structure and properties of electrospun fibers. In this study, fibers electrospun from polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends were characterized. Differential scanning calorimetry (DSC) revealed that fibers electrospun from benzene are miscible while a phase separation occurs when the fibers are electrospun from chloroform. While films cast from chloroform show poor mechanical properties, immiscible fibers are ductile. The effects of the blend composition and the solvent on the fiber diameter and morphology were observed by scanning electron microscopy (SEM) and optical microscopy. Afterwards, contact angle measurements were made to evaluate the hydrophobicity of the fibers which decreases as hydrophilic PVME is added to the blend; the values for the fibers were found to be 60° higher than their equivalent in films. PVME was selectively removed from the immiscible fibers by complete immersion into water. Infrared spectroscopy revealed that this process increases the PS content from 70 to 95% for immiscible fibers but only to 75% for miscible fibers. These results show that the PVME-rich phase is almost completely distributed on the fiber surface, which was confirmed by atomic force microscopy (AFM) and SEM. Finally, the electrospinning of PS/PVME blends from chloroform/benzene solutions was studied. The presence of chloroform, even as a residual amount, causes a phase separation just as it does in fibers electrospun from pure chloroform.

L’électrofilage est un procédé permettant de préparer des fibres possédant un diamètre de l’ordre du micromètre ou de quelques centaines de nanomètres. Son utilisation est toutefois limitée par le manque de contrôle sur la structure et les propriétés des fibres ainsi produites. Dans ce travail, des fibres électrofilées à partir de mélanges de polystyrène (PS) et de poly(vinyl méthyl éther) (PVME) ont été caractérisées. La calorimétrie différentielle à balayage (DSC) a montré que les fibres du mélange PS/PVME sont miscibles (une seule transition vitreuse) lorsque préparées dans le benzène, alors qu'une séparation de phases a lieu lorsque le chloroforme est utilisé. Les fibres immiscibles sont néanmoins malléables, contrairement à un film préparé par évaporation du chloroforme qui a des propriétés mécaniques médiocres. Des clichés en microscopies optique et électronique à balayage (MEB) ont permis d’étudier l'effet de la composition et du solvant sur le diamètre et la morphologie des fibres. Des mesures d’angles de contact ont permis d’évaluer l’hydrophobicité des fibres, qui diminue avec l’ajout de PVME (hydrophile); les valeurs sont de 60° supérieures à celles des films de composition équivalente. Un retrait sélectif du PVME a été réalisé par l’immersion des fibres dans l’eau. La spectroscopie infrarouge a montré que la composition passe de 70 à 95% de PS pour une fibre immiscible mais seulement à 75% pour une fibre miscible. Ces résultats indiquent que la phase riche en PVME se situe presque uniquement à la surface des fibres immiscibles, ce qui a été confirmé par microscopie à force atomique (AFM) et MEB. Finalement, l’effet du mélange des deux solvants, lors de l’électrofilage du mélange PS/PVME, a été étudié. La présence du chloroforme, même en quantité réduite, provoque une séparation de phases similaire à celle observée avec ce solvant pur. / Electrospinning is a simple method for the preparation of polymer fibers with diameters of hundreds of nanometers to a few micrometers. Although it is a versatile method, some issues remain in the control of the structure and properties of electrospun fibers. In this study, fibers electrospun from polystyrene (PS)/poly(vinyl methyl ether) (PVME) blends were characterized. Differential scanning calorimetry (DSC) revealed that fibers electrospun from benzene are miscible while a phase separation occurs when the fibers are electrospun from chloroform. While films cast from chloroform show poor mechanical properties, immiscible fibers are ductile. The effects of the blend composition and the solvent on the fiber diameter and morphology were observed by scanning electron microscopy (SEM) and optical microscopy. Afterwards, contact angle measurements were made to evaluate the hydrophobicity of the fibers which decreases as hydrophilic PVME is added to the blend; the values for the fibers were found to be 60° higher than their equivalent in films. PVME was selectively removed from the immiscible fibers by complete immersion into water. Infrared spectroscopy revealed that this process increases the PS content from 70 to 95% for immiscible fibers but only to 75% for miscible fibers. These results show that the PVME-rich phase is almost completely distributed on the fiber surface, which was confirmed by atomic force microscopy (AFM) and SEM. Finally, the electrospinning of PS/PVME blends from chloroform/benzene solutions was studied. The presence of chloroform, even as a residual amount, causes a phase separation just as it does in fibers electrospun from pure chloroform.

A new paradigm of electronic devices with bio-inspired features is aiming to mimic the brain’s fundamental mechanisms to achieve recognition of very complex patterns and more efficient computational tasks. Networks of electropolymerized dendritic fibers are attracting much interest because of their ability to achieve advanced learning capabilities, form neural networks, and emulate synaptic and plastic processes typical of human neurons. Despite their potential for braininspired computation, the roles of the single parameters associated with the growth of the fiber are still unclear, and the intrinsic randomness governing the growth of the dendrites prevents the development of devices with stable and reproducible properties. In this manuscript, we provide a systematic study on the physical parameters influencing the growth, defining cause-effect relationships for direction, symmetry, thickness, and branching of the fibers. We build an electrochemical model of the phenomenon and we validate it in silico using Montecarlo simulations. This work shows the possibility of designing dendritic polymer fibers with controllable physical properties, providing a tool to engineer polymeric networks with desired neuromorphic features.

The diploma thesis deals with self-healing of concrete composite. In the theoretical part, it represents the effect of polymer microfibers on reducing the development of cracks and on improving self-healing properties. It also describes the most commonly used types of bacteria used to enhance the self-healing process and their effect both alone and in interaction with fibers, calcium sources and absorbent additives. It also represents auxiliary additives in the form of superabsorbent polymers. In the practical part, it verifies the influence of the above elements and describes how much the self-healing of concrete has been enhanced by the use of combinations of fibers, absorbent polymers and a source of calcium in the form of calcium lactate. It also indicates whether the self-healing properties used were not improved at the expense of deteriorating the mechanical properties of the composite.