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La mise au point d'une cellule de SOFC haute performance de configuration anode support pour un fonctionnement sous méthane pur nécessite l'élaboration d'un film mince d'électrolyte et le développement d'une architecture innovante permettant le reformage d'hydrocarbures. La première partie du travail a consisté en l'élaboration de films minces d'électrolyte de zircone stabilisée à l'oxyde d'yttrium par atomisation électrostatique sur un substrat composite poreux NiO-8YSZ. Cette technique originale a permis l'obtention de films minces, denses et étanches à partir d'une suspension, présentant des propriétés électriques comparables à celles d'un échantillon massif de même composition. La seconde partie du travail a porté sur la mise au point d'une cellule de SOFC optimisée dont l'architecture innovante intégrant une membrane anodique catalytique est basée sur le concept associant le reformage interne progressif et le découplage électro-catalytique. Une séquence d'élaboration établie spécifiquement conditionne l'assemblage des éléments optimisés de la cellule. L'adaptation de la cellule dans un banc de mesures a permis la réalisation de tests électrochimiques sous hydrogène et méthane à haute température. Le fonctionnement stable du dispositif pendant plus de 1000 h sous méthane pur avec un taux d'utilisation optimisé, sans apport extérieur d'eau et sans dépôt de carbone a validé le concept étudié. / The design of a high performance anode supported SOFC operating under pure methane requires the elaboration of a thin film of electrolyte and the development of an original architecture adapted to the reforming of hydrocarbons. The first part of this work was dedicated to the elaboration of yttria stabilized zirconia thin films of electrolyte by ESD onto a NiO-8YSZ porous substrate. This original technique has allowed the fabrication of thin, dense and gas-tight films starting from a suspension, with good electrical properties comparable to that of a bulk sample of the same nature. The second part of this work concerned the design of an optimized SOFC cell with an original architecture integrating an anodic catalytic membrane based on a concept gathering the gradual internal reforming and the electro-catalytic dissociation. The assembly of the optimized components is conditioned by an elaboration sequence specifically established. The adjustment of the cell in a test bench led to the achievement of electrochemical tests in hydrogen and methane at 800°C. The stable operating of the cell fueled by pure and dry methane with optimized faradaic efficiency for more than 1000 h without carbon deposition proved the viability of the studied concept.

Recent development in portable electronics and electric vehicles have increased the demand for high performance lithium ion batteries. However, it is still challenging to produce high energy and high power lithium ion batteries. The major objective of this research is to fabricate advanced electrode materials with enhanced power density and energy density. Porous Li4Ti5O12 (LTO) and its nanocomposites (with Si and reduced graphene oxide (rGO)) synthesized by electrostatic spray deposition (ESD) technique were mainly studied and promising electrochemical performance was achieved. In chapter 3, porous LTO thin film electrode was synthesized by ESD to solve the low energy density and low power density issues by providing good ionic and electronic conductivities. Electrochemical test results showed that it had a large specific capacity of 357 mAh g-1 at 0.15 A g-1, which was even higher than its theoretical capacity. It also exhibited very high rate capability of 98 mAh g-1 at 6 A g-1. The improved electrochemical performance was due to the advantage of ESD generated porous structures. In order to further enhance the power density of LTO, ESD derived LTO/rGO composite electrodes were studied in chapter 4. In chapter 5, high energy density component Si was introduced viii into LTO composite. The synergistic effect between commercial LTO and Si powder was studied. Then, ESD derived LTO/Si/rGO composite was prepared and evaluated. At 0.15 A g-1, a stable capacity of 624 mAh g-1 was observed, which was much higher than the capacities of LTO and LTO/rGO electrodes. In addition, effect of activation process on electrochemical performance of carbon nanofibers (ACNFs) and feasibility of ion intercalation into 2D MMT montmorillonite clay (MMT) were studied and discussed in chapter 6. In summary, we have successfully synthesized various LTO based electrodes by ESD. Both high energy and high power density were achieved as compared to commercial LTO electrode. Through electrochemical characterization and charge storage distribution analysis, origins of the high rate capability were proposed. This work demonstrates ESD as a powerful tool for fabricating high performance porous structures and nanocomposite electrode materials.

<div><p></p><p><i>Key Question: How to develop technologies to understand and solve a multi-scale global crisis resulting from rapid transmission of contagious respiratory viruses in pandemic phases?</i></p> <p>A two-pronged approach to optimize the existing solutions and combat the DIRECT and INDIRECT transmission of respiratory pathogens.</p> <p>• I. Optimization of multiple layers in a filter/ mask with physical – biochemical properties</p> <p>• II. Characterization of surfaces based on best parameters for disinfection using electrostatic deposition </p> <p> </p><br><p></p></div>

<p>Electrostatic spray is a spray that is induced by an interaction between the surface charge on the liquid meniscus and the externally applied electrical field that forms a conical shape known as the Taylor Cone. Electrostatic spray can be seen in a variety of different fields in modern times, such as, agriculture, combustion, space propulsion, and medical applications. The experimental setup for any electrostatic spray consists of the following components: a syringe pump filled with an ionic fluid, a high voltage power supply, and a ground source. The orientation of the nozzle, set to a horizontal or vertical orientation, and the interface that is examined, liquid/air or liquid/liquid interface are two parameters that can vary from one setup to another while still using the same components to form the electrostatic spray. In this experimental study, the characteristic of the electrostatic spray of two immiscible fluids, liquid/liquid interface, with a horizontal nozzle orientation, was analyzed. The two immiscible fluids that were chosen for this experiment were olive oil, the ambient fluid, and pure ethanol, the working fluid. A set range of 0 – 5 kV with an increment of 0.5 kV was applied to the working fluid with a flowrate of 0.1 mL/min. The distance between the nozzle and the copper disk was also altered for three different distances, 22.09, 14.6 and 10.33 mm. Different patterns and trajectories were captured and analyzed using both a high-speed camera and a long exposure camera. Formation of vortices was recorded in the induced flow. The general trend was found was an increase in the droplets’ velocity with the increase of the applied voltage. Additionally, there was an increase in the droplets’ velocity was recorded as the copper disk was moved closer to the nozzle. A dimensional number, Jowaiser’s number Jo, has been proposed where it relates the electric forces to the inertial forces. It can be used to predicts the phase that the flow experiences. The four phases that a flow can experience are the droplet phase, transition phase, spray phase, and the shorting phase.  </p>

Ba(Zr0.1Ce0.7Y0.2)O3-£_ (BZCY) shows high proton conductivity as well as high chemical stability over a wide range of solid oxide fuel cell (SOFC) operating conditions. Sm0.5Sr0.5CoO3-£_ (SSC) cathode deposited by electrostatic spray deposition (ESD) on SOFC half cell obtained via tape-casting shows porous and reticular microstructure, and the SOFC single cell consists of substrate/ BZCY+NiO/ BZCY/ SSC. The electrolyte thickness decrease from 22 £gm, 20 £gm, 17.6 £gm to 15.1 £gm after sintering as the content of carbon pore former in the corresponding anode functional layer increased from 0.0 wt.%, 5.0 wt.%, 10.0 wt.% to 15.0 wt.%, and the maximum power density of corresponding cells at 700¢J varies from 476.89 mW/cm2, 713.34 mW/cm2, 862.50 mW/cm2 to 706.89 mW/cm2, respectively.

Made available in DSpace on 2015-03-26T13:23:24Z (GMT). No. of bitstreams: 1 texto completo.pdf: 1133650 bytes, checksum: 37109fbba216bce41090549d526583e0 (MD5) Previous issue date: 2008-02-25 / The technology of application of agricultural defensives in tree like plants and orchard plants in general way, still little is researched in Brazil. Ahead of requirements of the international market, the application technology must take care of some parameters that will give the credibility of the Brazilian products in the exterior market, as for the certification and traceability. With the globalization of good agricultural practices, Global Good Agricultural Practices (GLOBALGAP), demand it more criterion of the producers, of the social and sustainable points of view. The certification guarantees to the final consumer that the production was in accordance with sustainable norms, that is, use of pesticide, in accordance with preset norms, aiming to a lesser level of residues in the end items, mainly in the ones of consumption in natura. Already the traceability allows the consumer to know all the description and practical of production of the agriculturist, allowing, thus, to know how many sprayings had been carried through, the type of defensive and the dosage and volume of spray mixture used. The sprayings in fruitful plants are characterized by high volume of spray mixture for hectare, having increased the cost of production, the contamination of the workers and the ambient contamination. It is a process where the efficiency of the spraying and the effectiveness of control of the plagues and illnesses are on directly relation with the kind of spray used, being this the responsible one for the deposition of the drops, begin it a responsible for the asset in the interior of the canopy of plants. In this type of spraying, the majority of the drops does not penetrate in the canopy of the plants, had as impediment the external leaves. This work had as objective to develop an electrostatic spray and a device capable to increase the penetration of electrically loaded drops in the interior of the canopy of the plants. In the development of the electrostatic spray, it used as high-voltage source, A bobbin of an automobile ignition system to an electronic circuit fed by a 12 volts battery. With the highvoltage source installed in the spray, it was possible to get eight chains, with tensions varying of 4,2 and 12,8 kV, what allowed to reach values of relation load/mass of 0,3 mC kg-1 to 4,1 mc kg-1, in different outflows. For the development of the electronic device of attraction of drops, they had been distributed conducting metallic in the interior of the canopy of the plants, with the intention to attract the drops with electric loads. Water sensitive cards in the thirds superior, average and inferior, in three different depths of the canopy of the plant and carried through sprayings with and without load, and with the presence and absence of the device had been distributed. The efficiency of the electrostatic spraying and the device was based on the density of drops (drops cm-2) and on the covering (%). In all the studied conditions, the biggest density of drops and the biggest covering had been gotten in the external part of the canopy. / A tecnologia de aplicação de defensivos agrícolas em plantas arbóreas, frutíferas de modo geral, ainda é pouco pesquisada no Brasil. Diante das exigências do mercado internacional, a tecnologia de aplicação deve atender a alguns parâmetros que darão a credibilidade dos produtos brasileiros no mercado exterior, no que se refere à certificação e rastreabilidade. Com a globalização das boas práticas agrícolas, a Global Good Agricultural Practices (GLOBALGAP) passou a exigir mais critério dos produtores, dos pontos de vista social e sustentável. A certificação garante ao consumidor final que a produção foi de acordo com normas sustentáveis, ou seja, uso de insumos conforme as normas preestabelecidas, visando a um menor nível de resíduos nos produtos finais, principalmente nos de consumo in natura. Já a rastreabilidade permite ao consumidor conhecer todo o histórico e práticas de produção agrícola, permitindo, assim, saber quantas pulverizações foram realizadas, o tipo de defensivo e a dosagem e volume de calda usados. As pulverizações em plantas frutíferas são caracterizadas por alto volume de calda por hectare, aumentando o custo de produção, a contaminação dos trabalhadores e a contaminação ambiental. É um processo em que a eficiência da pulverização e a eficácia de controle das pragas e doenças estão ligadas diretamente ao tipo de pulverizador utilizado, sendo este o responsável pela deposição das gotas com princípio ativo no interior do dossel das plantas. Nesse tipo de pulverização, a maioria das gotas não penetra no dossel das plantas, devido ao impedimento das folhas externas. Este trabalho teve como objetivo desenvolver um pulverizador eletrostático e um dispositivo capaz de aumentar a penetração de gotas carregadas eletricamente no interior do dossel das plantas. No desenvolvimento do pulverizador eletrostático, foi usada como fonte de alta tensão uma bobina de ignição automotiva, ligada a um circuito eletrônico, alimentado por 12 volts. Com a fonte de alta tensão instalada no pulverizador, foi possível obter nove correntes, com tensões variando de 4,2 a 12,8 kV, o que permitiu atingir valores de relação carga/massa de 0,3 mC kg-1 a 4,1 mC kg-1, em diferentes vazões. Para o desenvolvimento do dispositivo eletrônico de atração de gotas, foram distribuídos condutores metálicos no interior do dossel das plantas, com o propósito de atrair as gotas com cargas elétricas. Foram distribuídos cartões hidrossensíveis nos terços superiores, médios e inferiores, em três profundidades do dossel da planta e realizadas pulverizações com e sem carga e com a presença e ausência do dispositivo. A eficiência da pulverização eletrostática e do dispositivo foi baseada na densidade de gotas (gotas cm-2) e na cobertura (%). Em todas as condições estudadas, a maior densidade de gotas e a maior cobertura foram obtidas na parte externa do dossel.

With the ever-advancing technology, there is an incessant need for reliable electrochemical energy storage (EES) components that can provide desired energy and power. At the forefront of EES systems are electrochemical capacitors (ECs), also known as supercapacitors that typically have higher power and superior cycle longevity but lower energy densities than their battery counterparts. One of the routes to achieve higher energy density for ECs is using the hybrid EC configuration, which typically utilizes a redox electrode coupled with a counter double-layer type electrode. In this dissertation, both scale-up (coin-cell type) as well as scale-down (on-chip miniaturized) hybrid ECs were designed, constructed and evaluated. The first part of the dissertation comprised material identification, syntheses, and electrochemical analyses. Lithium titanate-anatase titanium oxide (Li4Ti5O12-TiO2) composites were synthesized via electrostatic spray deposition (ESD) and characterized in both half-cell and full-cell assembly against lithium and nanostructured carbon based counter electrodes, respectively. The second redox type material studied for hybrid electrochemical capacitors was ESD derived manganese oxide (MnOx). The MnOx electrodes exhibited a high gravimetric capacitance of 225F g-1 in aqueous media. Further improvement in the rate handling of the MnOx electrodes was achieved by using CNT additives. The MnOx-CNT composites were tested in full-cell assembly against activated carbon counter electrodes and tested for different anode and cathode mass ratios in order to achieve the best energy-power tradeoff, which was the second major goal of the dissertation. The optimized hybrid capacitor was able to deliver a high specific energy density of 30.3 Wh kg-1 and a maximal power density of 4kW kg-1. The last part of the dissertation focused on a scale-down miniaturized hybrid microsupercapacitor; an interdigitated electrode design was adopted in order to shorten the ion-transport pathway, and MnOx and reduced graphene oxide (rGO) were chosen as the redox and double layer components, respectively. The hybrid microsupercapacitor was able to deliver a high stack energy density of 1.02 mWh cm-3 and a maximal stack power density of 3.44 W cm-3, both of which are comparable with thin-film batteries and commercial supercapacitor in terms of volumetric energy and power densities.

<p>  </p> <p>With the recent growth in demand for biologics across the globe, it remains critical to manufacture these biologics in solid-state to improve stability as well as to increase the ease of transportation across the world. To meet these increased demands, it is of paramount importance to use various processing methods that have shorter processing times. It is also important to understand the impact of the processing methods and various formulation components on the stability of the proteins.  In Chapter 1, a review of the various processing methods that are used in the industry along with additional processing methods that are being investigated will be discussed. The common drying methods such as lyophilization and spray drying along with the novel techniques as well as specific examples of processing parameters to improve the processing conditions that better suit the protein formulations will be mentioned. </p> <p>The studies in Chapter 2 examined the effects of processing methods (freeze drying and spray freeze drying) and the excipients on the protein structure and physical stability. Protein solids containing one of two model proteins (lysozyme or myoglobin) were produced with or without excipients (sucrose or mannitol) using freeze drying or spray freeze drying (SFD). The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), differential scanning calorimetry (DSC), circular dichroism spectrometry (CD), size exclusion chromatography (SEC), BET surface area measurements, and solid-state hydrogen-deuterium exchange with mass spectrometry (ssHDX-MS). ssFTIR and CD could identify little to no difference in the structure of the proteins in the formulation. ssHDX-MS was able to identify the population heterogeneity, which was undetectable by conventional characterization techniques of ssFTIR and CD. ssHDX-MS metrics such as Dmax and peak area showed a good correlation with the protein physical instability (loss of the monomeric peak area by size exclusion chromatography) in 90-day stability studies conducted at 40oC for lysozyme.  The higher specific surface area was associated with greater loss in monomer content for myoglobin-mannitol formulations as compared to myoglobin-only formulations. Spray freeze drying seems a viable manufacturing technique for protein solids with appropriate optimization of formulations. The differences observed within the formulations and between the processes using ssHDX-MS, BET surface area measurements, and SEC in this study provide an insight into the influence of drying methods and excipients on protein physical stability.</p> <p>Based on this work, it was identified that spray freeze drying can be a viable alternative to produce solid-state protein formulations with similar stability as the freeze drying process. However, due to the long processing times and scale-up issues involved in the spray freeze drying process, there is a necessity to explore additional drying processes. Chapter 3 focuses on using another novel technique known as electrostatic spray drying (ESD) to produce solid-state protein formulations at lower drying temperatures than conventional spray drying and its effect on protein stability. A mAb formulation was dried by either conventional spray drying or electrostatic spray drying with charge (ESD). The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), differential scanning calorimetry (DSC), size exclusion chromatography (SEC), and solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS). Particle characterizations such as BET surface area, particle size distribution, and particle morphology were also performed. Conventional spray drying of the mAb formulation at the inlet temperature of 70oC failed to generate dry powders due to poor drying efficiency; electrostatic spray drying at the same temperature at 5kV enabled the formation of powder formulation with satisfactory moisture contents. Deconvoluted peak areas of deuterated samples from the ssHDX-MS study showed a good correlation with the loss of the monomeric peak area measured by size exclusion chromatography in the 90-day accelerated stability study conducted at 40oC. Low-temperature (70oC inlet temperature) drying with an electrostatic charge (5kV) led to better protein physical stability as compared with the samples spray-dried at the high temperature (130oC inlet temperature) without charge.</p> <p>This study shows that electrostatic spray drying can produce solid monoclonal antibody formulation at a lower inlet temperature than traditional spray drying with better physical stability. While ESD can be a viable option for thermal-sensitive formulations, it is important to understand the impact of various formulation components on the stability of the proteins while using spray drying. Based on our previous studies, a good understanding of the effect of different sugars and the presence of surfactants on the spray-dried proteins has been established. However, the impact of the selection of buffer on protein stability has not been studied. In Chapter 4, the effect of buffer salts on the physical stability of spray dried and lyophilized formulations of a model protein, bovine serum albumin (BSA) were examined. BSA formulations with various buffers were dried by either lyophilization or spray drying. The protein powders were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), powder X-ray diffraction (PXRD), size exclusion chromatography (SEC), solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS), and solid-state nuclear magnetic resonance spectroscopy (ssNMR). Particle characterizations such as BET surface area, particle size distribution, and particle morphology were also performed. Results from conventional techniques such as ssFTIR did not exhibit correlations with the physical stability of studied formulations. Deconvoluted peak areas of deuterated samples from the ssHDX-MS study showed a satisfactory correlation with the loss of the monomeric peak area measured by SEC (R2 of 0.8722 for spray-dried formulations and 0.8428 for lyophilized formulations) in the 90-day accelerated stability study conducted at 40oC. PXRD was unable to measure phase separation in the samples right after drying. In contrast, ssNMR successfully detected the occurrence of phase separation between the succinic buffer component and protein in the lyophilized formulation, which results in a distribution of microenvironmental acidity and the subsequent loss of long-term stability. In summary, this study demonstrated that buffer salts have less impact on physical stability for the spray-dried formulations than the lyophilized solids.</p> <p>The study in Chapter 5 looked at examining the physical stability of spray freeze dried (SFD) bovine serum albumin (BSA) solids produced using the radio frequency (RF)-assisted drying technique. BSA formulations were prepared with varying concentrations of trehalose and mannitol, with an excipient-free formulation as control. These formulations were produced using traditional spray freeze drying (SFD) or RF-assisted spray freeze drying (RFSFD). The dried formulations were then characterized using solid-state Fourier transform infrared spectroscopy (ssFTIR), Karl Fischer moisture content measurement, powder X-ray diffraction (PXRD), size exclusion chromatography (SEC), solid-state hydrogen/deuterium exchange with mass spectrometry (ssHDX-MS). Traditional characterization tools such as ssFTIR and moisture content did not have a good correlation with the physical stability of the formulations measured by SEC. ssHDX-MS metrics such as the maximum deuterium uptake (Dmax) (R2 = 0.791) and deconvoluted peak areas of the deuterated samples (R2 = 0.914) showed a satisfactory correlation with the SEC stability data. RFSFD improved the stability of formulations with 20 mg/ml of trehalose and no mannitol and had similar stability with all other formulations as compared to SFD. This study demonstrated that the RFSFD technique can significantly reduce the duration of primary drying cycle from 48 h to 27.5 h while maintaining or improving protein physical stability as compared to traditional lyophilization.</p> <p>Lastly, Chapter 6 consists of a summary of the conclusions formed from the work presented in this thesis. Furthermore, suggestions for future work are provided based on observations of results, less-explored areas of formulation and processing conditions as well as characterization tools to understand effects on protein physical stability.</p> <p><br></p>

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