Medidas de corrente termoestimuladas e de carga a temperatura constante, sob campo elétrico constante externo, foram realizadas no intuito de identificar além de cargas espaciais existentes em amostras comerciais de PVDF, também estudar o pico anômolo de corrente que se apresentou nas medidas isotérmicas. Este pico desaparecia em medidas subseqüentes, mas sua recuperação, apesar de lenta, foi registrada, principalmente se a amostra era conservada em ambiente úmido. Uma série de medidas feitas em diferentes umidades relativas do ar, cuidadosamente controladas, evidenciou que este fenômeno estava diretamente ligado à água absorvida pela amostra do ambiente externo. O efeito mostrou também ser fortemente dependente do campo aplicado. Um modelo baseado em dissociação iônica da água, provavelmente fracamente ligada a estrutura do polímero, foi desenvolvido, levando em consideração que o coeficiente de dissociação depende do campo elétrico, bem como do tempo de extração dos portadores dissociados da amostra. Nesta cinética controladora da corrente, é considerada também recombinação bi-iônica. / Thermally stimulated current and depolarization measurements were carried on commercially available samples of PVDF. The measurements were conducted under constant temperature and constant applied field in order to investigate an anomolous peak which appears in isothermal measurements, and also identify the presence of space charge. This peak is observed only in the first measurements, but it can recover if the sample is stored in a humid environment. Series of measurements was carried out with carefully controlled relative humidity from which one can conclude that the peak is directly linked to water absorved by the sample. This effect is shown to depend strongly on the applied electric field. A theoretical model based on ionic dissociation of water molecules - probably weakly attached to the polymer structure is developed to explain the experimental results. In the model, the dissociation coefficient and the time of escape of dissociated carriers are assumed to depend on the electric field. Bi-ionic recombination is also assumed to play an important role in the control of the kinetics of the process.

This thesis research focuses on the characterization of thinfilms made of poly(vinylidene fluoride) (PVDF) using an atomic force microscope. Thinfilms of PVDF were fabricated by a spin coating method with different conditions and characterized using the Atomic Force Microscopy (AFM) for morphological changes. Phase and conformational changes of PVDF were investigated using both wide angle X-ray diffraction (WAXD) and Fourier Transform Infrared Spectroscopy (FTIR). From this analysis, in-situ corona poling with annealing of spin-cast PVDF enabled a phase change from α to the mixture of β and γ phases. This process can decrease the complexity of the conventional method which requires mechanical stretching before poling PVDF in addition to thermal annealing for β phase transformation. This thesis describes some materials and surface properties of solution-cast PVDF thinfilms with various conditions such as topography and phase image, adhesion force, friction force, and roughness. Through the AFM topography and phase images, polymeric behavior and spherulites are discussed in the later part of the thesis.

Piezoelectric materials have been widely used in applications such as transducers, acoustic components, as well as motion and pressure sensors. Because of the material’s biocompatibility and flexibility, its applications in biomedical and biological systems have been of great scientific and engineering interest. In order to develop piezoelectric sensors that are small and functional, understanding of the material behavior is crucial. The major objective of this research is to develop a test system to evaluate the performance of a sensor made from polyvinylidene fluoride and its uses for studying insect locomotion and behaviors. A linear stage laboratory setup was designed and built to study the piezoelectric properties of a sensor during buckling deformation. The resulting signal was compared with the data obtained from sensors attached a cockroach, Blaberus discoidalis. Comparisons show that the buckling generated in laboratory settings can be used to mimic sensor deformations when attached to an insect. An analytical model was also developed to further analyze the test results. Initial analysis shows its potential usefulness in predicting the sensor charge output. Additional material surface characterization studies revealed relationships between microstructure properties and the piezoelectric response. This project shows feasibility of studying insects with the use of polyvinylidene fluoride sensors. The application of engineering materials to insect studies opens the door to innovative approaches to integrating biological, mechanical and electrical systems.

Hydrophobic microporous membranes have been widely used in water and wastewater treatment by microfiltration, ultrafiltration and membrane distillation. Poly(vinylidene fluoride) (PVDF) materials are one of the most popular polymeric membrane materials because of their high mechanical strength, excellent thermal and chemical stabilities, and ease of fabrication into asymmetric hollow fiber membranes. In this work, specialty PVDF materials (Kynar 741, 761, 461, 2851, RC-10186 and RC10214) newly developed by Arkema Inc. were used to develop hollow fiber membranes via the dry/wet phase inversion. These materials were evaluated from thermodynamic and kinetic perspectives. The thermodynamic analysis was performed by measuring the cloud points of the PVDF solution systems. The experimental results showed that the thermodynamic stability of the PVDF solution system was affected by the type of polymer and the addition of additive (LiCl); and the effects of the additive (LiCl) depended on the type of polymer. The kinetic experiments were carried out by determining the solvent evaporation rate in the “dry” step and the small molecules (solvent, additive) diffusion rate in the “wet step”. Solvent evaporation in the early stage could be expressed quantitatively. In the “wet” step, the concentrations of solvent and additive had a linear relationship with respect to the square root of time (t1/2) at the early stage of polymer precipitation, indicating that the mass-transfer for solvent-nonsolvent exchange and additive LiCl leaching was diffusion controlled. The kinetic analysis also showed that the slope of this linear relationship could be used as an index to evaluate the polymer precipitation rate (solvent-nonsolvent exchange rate and LiCl leaching rate). The extrusion of hollow fiber membranes was explored, and the effects of various fabrication parameters (such as dope extrusion rate, internal coagulant flow velocity and take-up speed) on the structure and morphology of the hollow fiber membranes were also investigated. The properties of the hollow fiber membranes were characterized by gas permeation method and gas-liquid displacement method. The morphology of the hollow fibers was examined by scanning electron microscope (SEM). It was found that Kynar 741 and 2851 were the best among the PVDF polymers studied here for the fabrication of hollow fiber membranes. In order to reduce the problems associated with the hydrophobicity of PVDF on hollow fiber module assembly, such as tubesheet leaking through problem and fouling problem, amine treatment was used to modify PVDF membranes. Contact angle measurements and filtration experiments were performed. Fourier-transform infrared (FT-IR) spectroscopy and energy dispersive x-ray analysis (EDAX) were used to analyze the modified polymer. It was revealed that the hydrophilicity of the modified membrane was improved by amine treatment and conjugated C=C and C=O double bonds appeared along the polymer backbone of modified PVDF. Hollow fiber membranes fabricated from Kynar 741 were tested for water desalination by vacuum membrane distillation (VMD). An increase in temperature would increase the water productivity remarkably. Concentration polarization occurred in desalination, and its effect on VMD could be reduced by increasing the feed flowrate. The permeate pressure build-up was also investigated by experiments and parametric analysis, and the results will be important to the design of hollow fiber modules for VMD in water desalination.

Hydrophobic microporous membranes have been widely used in water and wastewater treatment by microfiltration, ultrafiltration and membrane distillation. Poly(vinylidene fluoride) (PVDF) materials are one of the most popular polymeric membrane materials because of their high mechanical strength, excellent thermal and chemical stabilities, and ease of fabrication into asymmetric hollow fiber membranes. In this work, specialty PVDF materials (Kynar 741, 761, 461, 2851, RC-10186 and RC10214) newly developed by Arkema Inc. were used to develop hollow fiber membranes via the dry/wet phase inversion. These materials were evaluated from thermodynamic and kinetic perspectives. The thermodynamic analysis was performed by measuring the cloud points of the PVDF solution systems. The experimental results showed that the thermodynamic stability of the PVDF solution system was affected by the type of polymer and the addition of additive (LiCl); and the effects of the additive (LiCl) depended on the type of polymer. The kinetic experiments were carried out by determining the solvent evaporation rate in the “dry” step and the small molecules (solvent, additive) diffusion rate in the “wet step”. Solvent evaporation in the early stage could be expressed quantitatively. In the “wet” step, the concentrations of solvent and additive had a linear relationship with respect to the square root of time (t1/2) at the early stage of polymer precipitation, indicating that the mass-transfer for solvent-nonsolvent exchange and additive LiCl leaching was diffusion controlled. The kinetic analysis also showed that the slope of this linear relationship could be used as an index to evaluate the polymer precipitation rate (solvent-nonsolvent exchange rate and LiCl leaching rate). The extrusion of hollow fiber membranes was explored, and the effects of various fabrication parameters (such as dope extrusion rate, internal coagulant flow velocity and take-up speed) on the structure and morphology of the hollow fiber membranes were also investigated. The properties of the hollow fiber membranes were characterized by gas permeation method and gas-liquid displacement method. The morphology of the hollow fibers was examined by scanning electron microscope (SEM). It was found that Kynar 741 and 2851 were the best among the PVDF polymers studied here for the fabrication of hollow fiber membranes. In order to reduce the problems associated with the hydrophobicity of PVDF on hollow fiber module assembly, such as tubesheet leaking through problem and fouling problem, amine treatment was used to modify PVDF membranes. Contact angle measurements and filtration experiments were performed. Fourier-transform infrared (FT-IR) spectroscopy and energy dispersive x-ray analysis (EDAX) were used to analyze the modified polymer. It was revealed that the hydrophilicity of the modified membrane was improved by amine treatment and conjugated C=C and C=O double bonds appeared along the polymer backbone of modified PVDF. Hollow fiber membranes fabricated from Kynar 741 were tested for water desalination by vacuum membrane distillation (VMD). An increase in temperature would increase the water productivity remarkably. Concentration polarization occurred in desalination, and its effect on VMD could be reduced by increasing the feed flowrate. The permeate pressure build-up was also investigated by experiments and parametric analysis, and the results will be important to the design of hollow fiber modules for VMD in water desalination.

Piezoelectric materials have been widely used in applications such as transducers, acoustic components, as well as motion and pressure sensors. Because of the material’s biocompatibility and flexibility, its applications in biomedical and biological systems have been of great scientific and engineering interest. In order to develop piezoelectric sensors that are small and functional, understanding of the material behavior is crucial. The major objective of this research is to develop a test system to evaluate the performance of a sensor made from polyvinylidene fluoride and its uses for studying insect locomotion and behaviors. A linear stage laboratory setup was designed and built to study the piezoelectric properties of a sensor during buckling deformation. The resulting signal was compared with the data obtained from sensors attached a cockroach, Blaberus discoidalis. Comparisons show that the buckling generated in laboratory settings can be used to mimic sensor deformations when attached to an insect. An analytical model was also developed to further analyze the test results. Initial analysis shows its potential usefulness in predicting the sensor charge output. Additional material surface characterization studies revealed relationships between microstructure properties and the piezoelectric response. This project shows feasibility of studying insects with the use of polyvinylidene fluoride sensors. The application of engineering materials to insect studies opens the door to innovative approaches to integrating biological, mechanical and electrical systems.

This thesis research focuses on the characterization of thinfilms made of poly(vinylidene fluoride) (PVDF) using an atomic force microscope. Thinfilms of PVDF were fabricated by a spin coating method with different conditions and characterized using the Atomic Force Microscopy (AFM) for morphological changes. Phase and conformational changes of PVDF were investigated using both wide angle X-ray diffraction (WAXD) and Fourier Transform Infrared Spectroscopy (FTIR). From this analysis, in-situ corona poling with annealing of spin-cast PVDF enabled a phase change from α to the mixture of β and γ phases. This process can decrease the complexity of the conventional method which requires mechanical stretching before poling PVDF in addition to thermal annealing for β phase transformation. This thesis describes some materials and surface properties of solution-cast PVDF thinfilms with various conditions such as topography and phase image, adhesion force, friction force, and roughness. Through the AFM topography and phase images, polymeric behavior and spherulites are discussed in the later part of the thesis.

Orientador: José Antonio Malmonge / Resumo: Micro e nanofibras poliméricas têm despertado grande interesse de pesquisadores devido as suas potencialidades em diversas aplicações, atribuídas principalmente à grande área superficial destes materiais em associação com as propriedades dos polímeros. Uma das técnicas utilizadas para produção de micro e nanofibras é a solution blow spinning (SBS), ou fiação por sopro em solução. Neste trabalho foram obtidas microfibras de blendas de Poli(fluoreto de Vinilideno) (PVDF) e Poli(o-metoxianilina) (POMA), com a POMA em seu estado dopado e não dopado, pela técnica SBS. Para a dopagem da POMA foi utilizado o ácido p-toluenosulfônico (TSA). Obteve-se mantas com concentrações de PVDF/POMA-TSA de até 85/15 (m/mtotal), e de até 90/10 (m/mtotal) para PVDF/POMA. Foi possível observar a partir das imagens de MEV que os diâmetros médios das fibras diminuíram com o aumento da concentração de POMA, chegando a 0,22 µm para a maior proporção. Essa variação no diâmetro das microfibras é atribuído a variação da viscosidade da solução que diminui com o conteúdo da POMA na blenda. Os difratogramas de raios X indicaram que tanto a fase α quanto a fase β do PVDF foram obtidas no processo de fiação tanto para o PVDF puro bem como para a blendas, mostrando que o conteúdo de POMA na blenda não altera a fase do PVDF. A condutividade elétrica das fibras aumentou significativamente com a porcentagem de POMA (dopada) na blenda, elevando os valores em até 8 ordens de grandeza e atingindo uma condutividade ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Micro and polymeric nanofiber have arisen great interest of researchers because of their potential in various applications, mainly attributed to the large surface area of these materials in association to the properties of polymers and polymer blends. One of the techniques used for producing micro and nanofibres is the solution blow spinning (SBS). In this study microfibers of poly (vinylidene fluoride) (PVDF) and poly (o-methoxyaniline) (POMA) blends were obtained, with POMA in its doped and undoped state, by SBS technique. For POMA doping it was used p-toluenesulfonic acid (TSA). Mats with PVDF / POMA-TSA concentrations of 85/15 (m /mtotal), and up to 90/10 (m /mtotal) to PVDF / POMA were obtained. It was possible to observe from SEM images that the average fiber diameters decreased with increasing concentration of POMA, reaching 0,22μm at the highest proportion. The X-ray diffractograms showed that both α phase and β phase of PVDF were obtained in the spinning process. Such phases didn’t have their formation affected by the variations on the bend concentration. The electrical conductivity of the fibers increased significantly with the percentage of POMA (doped) in the blend, increasing values up to 108 orders of magnitude and reaching a conductivity of about 10-4 S/cm for the mats of PVDF/POMA on the reason 85/15. Furthermore, the mats of the blend showed good thermal stability up to the temperature of 200 °C. / Mestre

Myoelectric prosthesis on the market today are mostly very expensive and rarely allow the amputee any feedback, leaving the users separated from their own robotic arm. Integrating sensory systems into an arm which needs to be replaced several times during a lifetime may also not be cost efficient. With a sensory system tted in a removable and re-sizeable glove, the sensory system will not require a replacement unless broken. Using a exible, durable, low-cost material, sensitive to both change in pressure and temperature, this may be achieved. Using the pyroelectric properties of thin-film Polyvinylidene Fluoride, a sensor able to detect the incipient of slippage and its initial direction is achieved.

This thesis examines the value of using dispersed conductive fillers as a stress/strain sensing material. The effect of the intrinsic conductivity of the filler on the ability to be effective and the influence of filler concentration on the conductivity are also examined. To meet these objectives, nanocomposites of polyvinylidene fluoride (PVDF) with carbon nanofibers (CNFs) and carbon nanotubes (CNTs) were prepared by melt-blending using a twin screw extruder. Since PVDF has a potential to be piezoresistive based on the type of crystalline phase, the effect of CNFs on PVDF crystallinity, crystalline phase, quasi static and dynamic mechanical property was studied concurrently with piezoresponse. Three time dependencies were examined for PVDF/CNTs nanocomposites: quasi-static, transient and cyclic fatigue. The transient response of the strain with time showed viscoelastic behavior and was modeled by the 4-element Burger model. Under quasi-static loading the resistance showed negative pressure coefficient below yield but changed to a positive pressure coefficient after yield. Under cyclic load, the stress-time and resistance-time were synchronous but the resistance peak value decreased with increasing cycles, which was attributed to charge storage in the nanocomposite. The outcomes of this thesis indicate that a new piezoresponsive system based on filled polymers is a viable technology for structural health monitoring.