Em tempos nos quais a sociedade se volta a reflexões sobre questões climáticas e energéticas, células a combustível surgem como uma alternativa promissora no âmbito das políticas que visam o desenvolvimento sustentável. Nesse sentido, há ainda desafios a serem superados nas esferas fundamental e aplicada. Entender o papel das espécies presentes no eletrólito de suporte é fundamental em tal descrição. Especificamente no caso de ânions dissolvidos no eletrólito, o papel mais comumente atribuído é o de inibir o processo eletrocatalítico de interesse, por meio do bloqueio de sítios superficiais. No entanto, atribui-se recentemente ao ânion BF4- um efeito diverso; o aumento dos valores de corrente de eletro-oxidação em baixos potenciais. Apresenta-se na presente dissertação, um estudo sistemático deste processo, empregando a técnica da nanobalança eletroquímica a cristal de quartzo (NECQ), em conjunto com técnicas eletroquímicas tradicionais. Tal estudo revelou a ocorrência de diferenças notáveis nos perfis voltamassométricos do sistema eletroquímico quando da adição de pequenas quantidades do reagente HBF4. Tais diferenças têm caráter bastante especial, uma vez que nos perfis voltamétricos não são observadas diferenças marcantes nos valores de corrente entre o sistema eletroquímico com a adição de pequenas quantidades do reagente HBF4 e o sistema eletroquímico sem a adição desse reagente. À partir dos métodos utilizados e das evidências experimentais observadas, é possível inferir que o comportamento peculiar até então atribuído ao HBF4 na verdade resulta de uma contaminação com o semimetal arsênio, apesar de o rótulo do fabricante não informar sobre a possibilidade da ocorrência de traços do semimetal. / In times where the society turns its reflections on climate and energy questions, fuel cells appear as a promising alternative for the policies aimed at sustainable development. In this sense, there are still challenges to overcome in fundamental and applied levels. Understand the role of species in the supporting electrolyte is crucial in such a description. Specifically in the case of anions dissolved in the electrolyte, the most commonly assigned role is to inhibit the electrocatalytic process of interest, through blockade of surface sites. However, to the anion BF4- is recently attributed a diverse effect, the increase of the current values of electro-oxidation at low potentials. It is presented in this dissertation, a systematic study of this process, using the technique of the electrochemical quartz crystal nanobalança (EQCN), combined with traditional electrochemical techniques. This study revealed the occurrence of remarkable differences in the voltamassometric profiles of the electrochemical system when adding small amounts of reagent HBF4. Such differences are special features, since in the voltammetric profiles marked differences are not observed in current values between the electrochemical system with or without the addition of small amounts of reagent HBF4. On the basis of methods utilized and the experimental evidence observed, it is possible to infer that the peculiar behavior previously attributed to HBF4 actually results from a semimetal contamination with arsenic, although the manufacturer\'s label gives no information about the occurrence of traces of the semimetal.

More commonly referred to as a quartz crystal microbalance (QCM), thickness-shear mode (TSM) quartz resonator devices utilize an acoustic wave to establish a bulk-detection mechanism prompting their utilization as gravimetric sensors with nanogram mass sensitivity and capability to measure various film property dynamics, due to variations in the system environment, of thin-films that are uniformly distributed across the resonator surface. The development of an absolute TSM-based nanobalance and an experimental technique using conventional TSM resonators for the real-time measurement of the change in the viscoelastic shear modulus and fractional free-hole volume of a poly(isobutylene) film due to the sorption of various organic vapors are presented in this thesis work. Development of an electrode-modified TSM quartz resonator that is responsive to nanogram mass loadings, while exhibiting a mass sensitivity profile that is independent of material placement on the sensor platform, is detailed in this thesis work. The resulting nanogram balance would greatly enhance the field of mass measurement and become useful in applications such as droplet gravimetry, the study of non-volatile residue (NVR) contamination in solvents. A ring electrode design predicted by an analytical theory for sensitivity distribution to achieve the desired uniform mass sensitivity distribution is presented in this work. Using a microvalve capable of depositing nanogram droplets of a polymer solution, and a linear stepping stage for radial positioning of these droplets across the sensor platform, measurements of the mass sensitivity distributions were conducted and are presented. The measurements agree well with theory. Further improvements are possible and are identified to achieve better uniformity and to reduce the instability in the resonant frequency of these devices. Additionally, droplet gravimetric results for NVR in methanol droplets using the modified TSM devices are presented, which compare well with determinations made by evaporation of larger volumes of the stock solutions. Storage modulus, G', loss modulus, G", and, consequently, the shear modulus, G (G=G'+jG"), of polymer and polymer/solvent systems were measured in this work using a TSM quartz resonator. The polymer poly(isobutylene) was spin-coated as a film of a few microns thickness on the surface of the TSM device and, upon inducing oscillation of the device at its resonance frequency (several mega-Hertz), the impedance characteristics were measured. In addition, the poly(isobutylene) film was exposed to known weight concentrations, up to 20%, of benzene, chloroform, n-hexane, and dichloromethane vapors diluted in nitrogen gas, and the impedance characteristics were measured. Data collected from the impedance analyzer were examined by modeling the polymer and polymer/solvent loaded TSM device with an electrical equivalent circuit and a mechanical perturbation model to reliably yield the shear modulus. Using a superposition theory and the shear modulus, the fractional free volume of the polymer/solvent systems were determined. These results correlate well with values found using the Vrentas-Duda free-volume (FV) theory. A novel experimental technique for measuring fractional free-hole volumes of polymer/solvent mixtures is established in this thesis work.

Em tempos nos quais a sociedade se volta a reflexões sobre questões climáticas e energéticas, células a combustível surgem como uma alternativa promissora no âmbito das políticas que visam o desenvolvimento sustentável. Nesse sentido, há ainda desafios a serem superados nas esferas fundamental e aplicada. Entender o papel das espécies presentes no eletrólito de suporte é fundamental em tal descrição. Especificamente no caso de ânions dissolvidos no eletrólito, o papel mais comumente atribuído é o de inibir o processo eletrocatalítico de interesse, por meio do bloqueio de sítios superficiais. No entanto, atribui-se recentemente ao ânion BF4- um efeito diverso; o aumento dos valores de corrente de eletro-oxidação em baixos potenciais. Apresenta-se na presente dissertação, um estudo sistemático deste processo, empregando a técnica da nanobalança eletroquímica a cristal de quartzo (NECQ), em conjunto com técnicas eletroquímicas tradicionais. Tal estudo revelou a ocorrência de diferenças notáveis nos perfis voltamassométricos do sistema eletroquímico quando da adição de pequenas quantidades do reagente HBF4. Tais diferenças têm caráter bastante especial, uma vez que nos perfis voltamétricos não são observadas diferenças marcantes nos valores de corrente entre o sistema eletroquímico com a adição de pequenas quantidades do reagente HBF4 e o sistema eletroquímico sem a adição desse reagente. À partir dos métodos utilizados e das evidências experimentais observadas, é possível inferir que o comportamento peculiar até então atribuído ao HBF4 na verdade resulta de uma contaminação com o semimetal arsênio, apesar de o rótulo do fabricante não informar sobre a possibilidade da ocorrência de traços do semimetal. / In times where the society turns its reflections on climate and energy questions, fuel cells appear as a promising alternative for the policies aimed at sustainable development. In this sense, there are still challenges to overcome in fundamental and applied levels. Understand the role of species in the supporting electrolyte is crucial in such a description. Specifically in the case of anions dissolved in the electrolyte, the most commonly assigned role is to inhibit the electrocatalytic process of interest, through blockade of surface sites. However, to the anion BF4- is recently attributed a diverse effect, the increase of the current values of electro-oxidation at low potentials. It is presented in this dissertation, a systematic study of this process, using the technique of the electrochemical quartz crystal nanobalança (EQCN), combined with traditional electrochemical techniques. This study revealed the occurrence of remarkable differences in the voltamassometric profiles of the electrochemical system when adding small amounts of reagent HBF4. Such differences are special features, since in the voltammetric profiles marked differences are not observed in current values between the electrochemical system with or without the addition of small amounts of reagent HBF4. On the basis of methods utilized and the experimental evidence observed, it is possible to infer that the peculiar behavior previously attributed to HBF4 actually results from a semimetal contamination with arsenic, although the manufacturer\'s label gives no information about the occurrence of traces of the semimetal.

Les spectroscopies de diffusion inélastique de la lumière (Raman/Brillouin) sont un outil versatile qui permet d'étudier les phonons thermiques de la matière à différentes échelles. Dans les milieux nano-granulaires, l'étude des phonons acoustiques dont la longueur d'onde est grande devant le diamètre D des grains (?/D >> 1) permet de caractériser l'élasticité macroscopique gouvernée par la loi du contact de Hertz. La validité de la loi de contact est étudiée pour des poudres d'oxyde constituées de nanoparticules sphériques d'une taille de quelques nanomètres. Lorsque la demi-longueur d'onde des phonons acoustiques devient égale à la dimension du confinement (diamètre D pour les sphères, épaisseur e pour une plaquette), la propagation n'est plus possible et un phénomène de résonance mécanique apparaît. La spectroscopie Raman basse fréquence a été utilisée pour caractériser les modes de vibration acoustique de nanoplaquettes semiconductrices habillées d'un « manteau » organique. Lorsque l'épaisseur est suffisamment faible (e ~1 nm) une forte déviation de la fréquence de résonance est observée par rapport au modèle de la plaquette libre, attribuée à la présence des molécules organiques et est interprétée par un effet nano-balance. Lorsque l'objet confinant est un nano-dimère métallique, une hybridation plasmonique et acoustique des nanoparticules ont lieu conjointement. L'excitation résonante du plasmon dimèrique permet d'observer à l'échelle d'un dimère unique la diffusion par les modes de vibration dipolaire hybridé l=1 ainsi que les modes non hybridés de moment angulaire l >2, interdits par les règles de sélection précédemment établies pour ce régime de taille / Inelastic light scattering spectroscopies (Raman/Brillouin) are a versatile tool to study thermal phonons at various scales. In nano-granular media, the study of acoustic phonons with a wavelength much greater than the grain diameter D (?/D >> 1) allows one to characterize the macroscopic elasticity governed by Hertz law of the contact. The validity of Hertz law is studied for powders made of oxide nanoparticles a few nanometers in diameter. When the phonon half-wavelength reaches the confinement dimension (diameter D for spheres, thickness e for plates) propagation is forbidden and mechanical resonances occur. Low frequency Raman spectroscopy has been used to characterize the acoustic resonances of semiconducting nanoplatelets “dressed” with an organic surfactant layer. When the thickness becomes thin enough (e ~ 1 nm), the resonance frequency is significantly downshifted compared to a free platelet, attributed to a mass load effect due to the organic molecules. When the confining object is a metallic nano-dimer, both plasmonic and acoustic hybridization occur at the same time. The resonant excitation of the dimeric plasmon allows one to observe down to single nano-object scale the inelastic scattering by dimer hybridized dipolar vibration modes l=1 as well as non-hybridized modes with higher angular momentum l >2, known to be Raman inactive in this size range according to previously established selection rules. Possibilities for a new plasmon-vibration coupling mechanism are discussed

De l'automobile à l'aéronautique en passant par le biomédical, tout domaine d'applications utilise des capteurs dont certains sont à sortie fréquentielle. L'arrivée de nouveaux matériaux piézoélectriques a ouvert une porte vers des applications inaccessibles jusqu'à lors et essentiellement à hautes températures. L'orthophosphate de gallium est l'un de ces nouveaux matériaux piézoélectriques ayant de plus un fort facteur de couplage. Ce mémoire porte sur l'étude et la réalisation de capteurs en orthophosphate de gallium fonctionnant en ondes de volumes. La première partie consiste à étudier la sensibilité et stabilité thermique en élaborant un modèle analytique de poutre vibrant en élongation, flexion et torsion. Au cours de cette partie est démontrée l'existence de coupes compensées en température pour ces différents modes. Cette étude théorique est ensuite complétée par une analyse utilisant la méthode des éléments finis (MEF). La réalisation de résonateurs dans diverses orientations cristallographique est effectuée, dont celles compensées en températures. Les mesures associées à ces structures sont confrontées aux résultats théoriques. Vient ensuite l'application d'un biocapteur fonctionnant en cisaillement d'épaisseur. Un modèle éléments finis est élaboré pour étudier l'influence de certains paramètres sur le comportement du capteur. Une comparaison entre le modèle établi et les mesures expérimentales est également présentée. Ces résultats positifs ouvrent des perspectives d'évolution décrites en conclusion.