Improved fabrication of poly(vinylindenefluoride)-hexafluoropropylene (PVDF-HFP) thin films is of particular interest due to the high electric coercivity found in the beta-phase structure of the thin film. We show that it is possible to obtain high-quality, beta-phase dominant PVDF-HFP thin films using a direct approach to Langmuir-Blodgett deposition without the use of annealing or additives. To improve sample quality, an automated Langmuir-Blodgett thin film deposition system was developed; a custom dipping trough was fabricated, a sample dipping mechanism was designed and constructed, and the system was automated using custom LabVIEW software. Samples were fabricated in the form of ferroelectric capacitors on substrates of glass and silicon, and implement a unique step design with a bottom electrode of copper with an aluminum wetting layer and a top electrode of gold with an aluminum wetting layer. Samples were then characterized using a custom ferroelectric measurement program implemented in LabVIEW with a Keithley picoammeter/voltage supply to confirm electric coercivity properties. Further characterization using scanning electron microscopy and atomic force microscopy confirmed the improvement in thin film fabrication over previous methods.

Indiana University-Purdue University Indianapolis (IUPUI) / Improved fabrication of poly(vinylindenefluoride)-hexafluoropropylene (PVDF-HFP) thin films is of particular interest due to the high electric coercivity found in the beta-phase structure of the thin film. We show that it is possible to obtain high-quality, beta-phase dominant PVDF-HFP thin films using a direct approach to Langmuir-Blodgett deposition without the use of annealing or additives. To improve sample quality, an automated Langmuir-Blodgett thin film deposition system was developed; a custom dipping trough was fabricated, a sample dipping mechanism was designed and constructed, and the system was automated using custom LabVIEW software. Samples were fabricated in the form of ferroelectric capacitors on substrates of glass and silicon, and implement a unique step design with a bottom electrode of copper with an aluminum wetting layer and a top electrode of gold with an aluminum wetting layer. Samples were then characterized using a custom ferroelectric measurement program implemented in LabVIEW with a Keithley picoammeter/voltage supply to confirm electric coercivity properties. Further characterization using scanning electron microscopy and atomic force microscopy confirmed the improvement in thin film fabrication over previous methods.

This work presents a systematic study of the mechanochemical processes leading to chemical reactions occurring due to effects of high-strain-rate deformation associated with uniaxial strain and uniaxial stress impact loading in highly heterogeneous metal powder-based reactive materials, specifically compacted mixtures of Ti/Al/B powders. This system was selected because of the large exothermic heat of reaction in the Ti+2B reaction, which can support the subsequent Al-combustion reaction. The unique deformation state achievable by such high-pressure loading methods can drive chemical reactions, mediated by microstructure-dependent meso-scale phenomena. Design of the next generation of multifunctional energetic structural materials (MESMs) consisting of metal-metal mixtures requires an understanding of the mechanochemical processes leading to chemical reactions under dynamic loading to properly engineer the materials. The highly heterogeneous and hierarchical microstructures inherent in compacted powder mixtures further complicate understanding of the mechanochemical origins of shock-induced reaction events due to the disparate length and time scales involved. A two-pronged approach is taken where impact experiments in both the uniaxial stress (rod-on-anvil Taylor impact experiments) and uniaxial strain (instrumented parallel-plate gas-gun experiments) load configurations are performed in conjunction with highly-resolved microstructure-based simulations replicating the experimental setup. The simulations capture the bulk response of the powder to the loading, and provide a look at the meso-scale deformation features observed under conditions of uniaxial stress or strain. Experiments under uniaxial stress loading reveal an optimal stoichiometry for Ti+2B mixtures containing up to 50% Al by volume, based on a reduced impact velocity threshold required for impact-induced reaction initiation as evidenced by observation of light emission. Uniaxial strain experiments on the Ti+2B binary mixture show possible expanded states in the powder at pressures greater than 6 GPa, consistent with the Ballotechnic hypothesis for shock-induced chemical reactions. Rise-time dispersive signatures are consistently observed under uniaxial strain loading, indicating complex compaction phenomena, which are reproducible by the meso-scale simulations. The simulations show the prevalence of shear banding and particle agglomeration in the uniaxial stress case, providing a possible rationale for the lower observed reaction threshold. Bulk shock response is captured by the uniaxial strain meso-scale simulations and is compared with PVDF stress gauge and VISAR traces to validate the simulation scheme. The simulations also reveal the meso-mechanical origins of the wave dispersion experimentally recorded by PVDF stress gauges.

Les recherches que nous présentons dans ce mémoire s'inscrivent dans le cadre du développement de nouvelles structures et de l'étude de matériaux accordables en vue d'une intégration industrielle comme radôme actif.Plus particulièrement, ils consistent en la réalisation d'un dispositif micro-onde permettant à la fois un filtrage et une agilité fréquentiels en espace libre. Des structures basées sur des surfaces sélectives en fréquences, pour l'aspect filtrage, et sur des matériaux de type ferroélectrique, pour l'aspect accordabilité, sont développées. Des modélisations et des simulations électromagnétiques montrent que le changement de permittivité du matériau, obtenu par application d'un champ électrique externe, permet le pilotage fréquentiel de la transmission de la structure. Une mise en oeuvre expérimentale complète ces travaux, au cours de laquelle des prototypes ont été fabriqués par des techniques de photolithographie, puis caractérisés en espace libre grâce à un banc ABmm. Les mesures micro-ondes valident ainsi les résultats de simulations menées en amont et montrent les possibilités de contrôler la fréquence de transmission du radôme. / The research we present in this memory registers within the framework to develop new structures and to study tunable materials for an industrial integration as an active radome. Specifically, they consist of achieving a free space microwave device for both a filtering behaviour and a frequency agility behaviour. Structures based on frequency selective surfaces, for the filtering aspect, and on ferroelectric materials for the tuning aspect, are developed. Modeling and simulations show that the change of the material permittivity, obtained by applying an external electric field, enable piloting the transmission frequency of the structure. An experimental implementation complete this work and prototypes have been fabricated by photolithography techniques and then characterized in free space with a bench ABmm. Thus, microwave measurements validate the results of simulations and show the possibility to control the frequency transmission of the radome.

Filmes de poli(fluoreto de vinilideno-co-trifluoretileno), P(VDF-IrFE), com uma razão molar 70/30 de VDF e IrFE, respectivamente, foram expostos à radiação-X sob vácuo em uma ampla faixa de doses de irradiação. Este é um copolímero estatístico e semi-cristalino que possui a especial característica de cristalizar espontaneamente numa estrutura ferroelétrica. Ele também possui uma transição de fase ferro-paraelétrica detectável, definida como a temperatura de Curie (Tc). Devido a estas características tem despertado considerável interesse, em especial na área da eletrônica como elemento transdutor. As modificações induzidas foram investigadas por espectroscopia fotoacústica no infravermelho (FT-IR/PAS), assim como FI-IR por transmitância, calorimetria exploratória diferencial (DSC), termogravimetria (IG), difração de raios-X, UV/Visível e espectroscopia Raman. As técnicas espectroscópicas vibracionais (fotoacústica no IR, Raman e absorção no IR) foram utilizadas na identificação de bandas relacionadas às regiões cristalinas e amorfas, formação e rompimento de ligações e presença de novos grupos funcionais. Nos espectros IR e Raman são observadas duas bandas que estão relacionadas às regiões cristalinas e sofrem mudanças nas suas intensidades relativas de acordo com a dose de radiação. Essas mudanças podem ser interpretadas como aumento ou diminuição do grau de cristalinidade, e também em termos de modificações de arranjos cristalinos. A difração de raio-X mostrou o aparecimento de um pico, próximo àquele da fase ferroelétrica, sob aumento da dose de radiação, devido a um processo de modificação do arranjo cristalino acima da dose de 480 kGy. Foi observado um aumento de intensidade no referido pico de difração, correspondendo a um aumento do grau de cristalinidade da amostra. As curvas de DSC mostraram picos endotérmicos correspondentes a fusão e transições de fases que, através de suas variações, possibilitam avaliar os efeitos da irradiação com raios-X. Os espectros UV/Visível mostraram absorções dos cromóforos cujas intensidades de banda aumentam com a dose de radiação e diminuem durante o envelhecimento da amostra. Os dados indicam que a radiação-X induz uma modificação no arranjo cristalino do P(VDF-TrFE). Tal modificação, é provavelmente uma mudança de estrutura ferroelétrica para outra, paraelétrica. / Poly(vinylidene fluoride-co-trifluoroethylene) films, P(VDF-TrFE), with a molar ratio 70/30 of VDF and TrFE units, respectively, were exposed to X-ray radiation under vacuum in a wide range of irradiation doses. This is a statistic semi-crystalline copolymer and displays the unique feature of a spontaneous crystallization into a ferroelectric structure. It also possesses a detectable ferro-paraelectric transition, the Curie temperature (Tc). Due to these characteristics considerable interest in such copolymer has been generated, specially in electronics as a transducer element. The induced modifications were investigated by Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS) as well as transmittance FT-IR, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction, UV/Visible and Raman spectroscopies. The spectroscopic vibrational techniques (FT-IR/PAS, FT-IR and Raman) were used to identify bands related to crystalline and amorphous regions, bond formation, bond scission and presence of new functional groups. In both IR and Raman spectra were observed a couple of bands related to the crystalline regions that undergo changes of relative intensities with the radiation dose. These changes may be interpreted as an increase or decrease of the crystallinity degree, and also modifications of crystal structure. X-ray diffraction showed a new peak, close to that of the ferroelectric phase, under increasing radiation doses, due to a modification of crystal structure process above 480 kGy dose. An increase in the intensity of the former diffraction peak was observed, corresponding to an increase in the crystallinity degree. The DSC curves showed the endothermic peaks corresponding to the melting and the phase transitions, whose variations allow an evaluation of the effects of X-ray radiation. UV/Visible spectra showed chromophores absorptions whose band intensities increase by radiation dose and decrease during sample\'s aging. The data indicate that P(VDF-TrFE) under X-ray radiation exposition undergoes a crystal structure modification, probably a change of a ferroelectric structure to another one, paraelectric.

Filmes de poli(fluoreto de vinilideno-co-trifluoretileno), P(VDF-IrFE), com uma razão molar 70/30 de VDF e IrFE, respectivamente, foram expostos à radiação-X sob vácuo em uma ampla faixa de doses de irradiação. Este é um copolímero estatístico e semi-cristalino que possui a especial característica de cristalizar espontaneamente numa estrutura ferroelétrica. Ele também possui uma transição de fase ferro-paraelétrica detectável, definida como a temperatura de Curie (Tc). Devido a estas características tem despertado considerável interesse, em especial na área da eletrônica como elemento transdutor. As modificações induzidas foram investigadas por espectroscopia fotoacústica no infravermelho (FT-IR/PAS), assim como FI-IR por transmitância, calorimetria exploratória diferencial (DSC), termogravimetria (IG), difração de raios-X, UV/Visível e espectroscopia Raman. As técnicas espectroscópicas vibracionais (fotoacústica no IR, Raman e absorção no IR) foram utilizadas na identificação de bandas relacionadas às regiões cristalinas e amorfas, formação e rompimento de ligações e presença de novos grupos funcionais. Nos espectros IR e Raman são observadas duas bandas que estão relacionadas às regiões cristalinas e sofrem mudanças nas suas intensidades relativas de acordo com a dose de radiação. Essas mudanças podem ser interpretadas como aumento ou diminuição do grau de cristalinidade, e também em termos de modificações de arranjos cristalinos. A difração de raio-X mostrou o aparecimento de um pico, próximo àquele da fase ferroelétrica, sob aumento da dose de radiação, devido a um processo de modificação do arranjo cristalino acima da dose de 480 kGy. Foi observado um aumento de intensidade no referido pico de difração, correspondendo a um aumento do grau de cristalinidade da amostra. As curvas de DSC mostraram picos endotérmicos correspondentes a fusão e transições de fases que, através de suas variações, possibilitam avaliar os efeitos da irradiação com raios-X. Os espectros UV/Visível mostraram absorções dos cromóforos cujas intensidades de banda aumentam com a dose de radiação e diminuem durante o envelhecimento da amostra. Os dados indicam que a radiação-X induz uma modificação no arranjo cristalino do P(VDF-TrFE). Tal modificação, é provavelmente uma mudança de estrutura ferroelétrica para outra, paraelétrica. / Poly(vinylidene fluoride-co-trifluoroethylene) films, P(VDF-TrFE), with a molar ratio 70/30 of VDF and TrFE units, respectively, were exposed to X-ray radiation under vacuum in a wide range of irradiation doses. This is a statistic semi-crystalline copolymer and displays the unique feature of a spontaneous crystallization into a ferroelectric structure. It also possesses a detectable ferro-paraelectric transition, the Curie temperature (Tc). Due to these characteristics considerable interest in such copolymer has been generated, specially in electronics as a transducer element. The induced modifications were investigated by Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS) as well as transmittance FT-IR, differential scanning calorimetry (DSC), thermogravimetry (TG), X-ray diffraction, UV/Visible and Raman spectroscopies. The spectroscopic vibrational techniques (FT-IR/PAS, FT-IR and Raman) were used to identify bands related to crystalline and amorphous regions, bond formation, bond scission and presence of new functional groups. In both IR and Raman spectra were observed a couple of bands related to the crystalline regions that undergo changes of relative intensities with the radiation dose. These changes may be interpreted as an increase or decrease of the crystallinity degree, and also modifications of crystal structure. X-ray diffraction showed a new peak, close to that of the ferroelectric phase, under increasing radiation doses, due to a modification of crystal structure process above 480 kGy dose. An increase in the intensity of the former diffraction peak was observed, corresponding to an increase in the crystallinity degree. The DSC curves showed the endothermic peaks corresponding to the melting and the phase transitions, whose variations allow an evaluation of the effects of X-ray radiation. UV/Visible spectra showed chromophores absorptions whose band intensities increase by radiation dose and decrease during sample\'s aging. The data indicate that P(VDF-TrFE) under X-ray radiation exposition undergoes a crystal structure modification, probably a change of a ferroelectric structure to another one, paraelectric.

The presented thesis investigates the transfer of drug molecules across interfaces that mimic biological membrane barriers. The permeability of drug molecules across biological membrane mimics has been investigated in a novel artificial membrane permeation assay configuration using an in situ time-dependent approach and reproducible rotation of the membrane. A method to determine the membrane permeability from the knowledge of measured permeability and the applied stirring rate is presented. The initial transient of the permeation response, previously not observed in situ, is investigated and its importance in data evaluation is discussed. The permeability coefficients of 31 drugs are optimised for the conditions found in vivo and a correlation with the fraction absorbed in humans is presented. The evidence for ionic and/or ion-pair flux across the artificial membrane obtained from measurement of permeability at different pH is supported by the investigation of the permeation assay with external membrane polarisation. The permeability coefficient of the solute's anionic form is determined. Liquid/liquid electrochemistry has been used to study the transfer of ionized species across the interface between water and 1,2-dichloroethane. An alternative method to study the transfer of partially ionised drug molecules employing a rotating liquid/liquid interface is presented. In addition, a bipolar electrochemical cell with a rotating-disc electrode is developed and its properties investigated in order to verify the hydrodynamics of the rotating artificial membrane configuration. Finally, in support of the electrochemical techniques used is this thesis, a detailed preparation and evaluation of the silver/silver sulphate reference electrode is presented.

This work studies the influence of field effect on large area 2 dimensional ribbons of fluids. A fluid of choice is confined in the channel of a metal-insulator-channel-insulator-metal architecture and is subjected to constant (d.c) or alternating (a.c) fields (de-pending on the application) along with a pressure drive flow. A general fluid would be composed of molecules having certain polarizability and be a dispersion of non-ionic and ionic particulates. The field effect response under pressure driven flow for this fluid would result in electrophoresis, electro osmosis, dielectrophoresis, dipole-dipole interaction and inverse electro osmosis phenomena. Using some of these phenomena we study applications related to desalination and energy harvesting with saline water as the ex-ample fluid for the former case, and solution processed poly vinyldene fluoride (PVDF) for the latter case. The geometrical features of \large area" and the \ribbon shape" can be taken advantage of to influence the design and performance for both applications. With regards to desalination, it is shown via experiments and theoretical models that the presence of alternating electric fields aid in ion separation along the flow when the saline water is subjected to laminar flow. Moreover, the power consumption is low due to the presence of the insulator. An average of 30% ion removal efficiency and 15% throughput is observed in the systems fabricated. Both performance parameters are discussion can be improved upon with larger channel lengths. The \2-D ribbon" and alternating field effect aid in achieving this by patterning the randomly distributed ions in the bulk into a smooth sheet charge and then repelling this sheet charge back into the bulk. The electric field exhibited by this sheet charge helps trap more ion sheets near the interface, thereby converting a surface ion trapping phenomena (when d.c is used) to a bulk phenomena and thereby improving efficiency. With regards to energy harvesting, a solution of PVDF in methyl ethyl ketone and 1-methyl-2-pyrollidone is confined to the \2-D ribbon" geometry and subject to high d.c fields. This aids in combining the fabrication, patterning and poling process for PVDF into one setup. Since the shape of the ribbon is defined by the shape of the channel, the ribbons (straight or serrated) can be used to sense forces of various magnitudes. More importantly experiments and theoretical models are studied for energy harvesting. Since the ribbon geometry defines the resonant frequency, large PVDF ribbon can be used to harvest energy from low frequency vibrations. Experiments show that up to 60 microwatt power can be harvested at 200 Hz and is sufficient to supplement the power for ICs.

Mechanical vibrations in large structures such as buildings, bridges, dams and critical frequencies in large machinery generally have low frequencies (100Hz-1000Hz). To monitor large areas of such structures we need huge network of low cost, easily manufacturable, self-powered and stand-alone vibration spectrum sensors. The sensors should also consume very little power during their overall operation cycle and have moderately high frequency resoultion. The thesis provides mathematical analysis, design and development of stand-alone, low frequency vibration spectrum analyzer .A mechanically stretched polymer piezoelectric membrane, which has a fixed length and tension, can act as a single frequency detector due to its unique resonant frequency. Stretching multiple ribbons of diffferent lengths and tensions, a vibration spectrum analyzer, which gives the Fourier frequency components present in an arbitrary mechanical input vibration, can be designed. The thesis presents a detailed description of experiments to evaluate a low frequency vibration spectrum analyzer system that accepts an incoming input vibration and directly provides the spectrum as output. Polymer piezoelectric materials being easily manufacturable these sensors can be deployed in wide area sensor networks that monitor large structures. The thesis also shows design of a vibration energy harvesting system based on the concept of harvesting energy at low frequencies. The need for developing such an energy harvesting system arises from the necessity of making the vibration sensor, self-powered. Multiple experimental tests were performed before developing a prototype vibration energy harvesting circuit.

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.