Orientador: Lauro Tatsuo Kubota / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T17:12:32Z (GMT). No. of bitstreams: 1 Giordano_GabrielaFurlan_M.pdf: 2251330 bytes, checksum: a6853decc37a3f82817a0457cc141778 (MD5) Previous issue date: 2015 / Resumo: Este trabalho teve como objetivo desenvolver um sistema eletroquímico capaz de detectar e quantificar etanol presente em amostras de vinho de cana-de-açúcar. Três métodos de modificação de eletrodo de níquel foram estudados visando à obtenção das espécies Ni(OH)2/NiOOH. Um dos métodos consistiu no condicionamento eletroquímico em NaOH, o outro, na oxidação química em persulfato de amônio e tratamento térmico e o terceiro, na deposição eletroquímica de Ni(OH)2 dopados com Co2+ e Cd2+, a partir de solução contendo os nitratos desses metais. Esse último apresentou resultados com maior repetibilidade de preparação e resposta. As técnicas SEM-FEG e XPS foram empregadas, a fim de caracterizar morfologicamente o Ni(OH)2 obtido e permitir determinações qualitativas e quantitativas sobre a composição química da superfície, respectivamente. Para a aplicação nas amostras empregou-se a técnica de extração por difusão gasosa através de uma membrana hidrofóbica. Assim, um módulo de extração foi construído no qual uma membrana de PTFE separou a solução de etanol - a ser analisada - de uma solução receptora de NaOH 100,0 mmol L-1, na qual o sistema eletroquímico foi acoplado. As condições aplicadas ao sistema foram otimizadas de modo a resultar em menores desvios das medidas analíticas. O vapor de etanol recolhido na solução de NaOH foi analisado utilizando o eletrodo de trabalho desenvolvido e foi possível monitorar soluções de etanol no intervalo 2,0 a 20,0% v/v. A concentração de etanol foi determinada em amostras de vinho de cana-de-açúcar por dois métodos diferentes: interpolação em curva analítica preparada em meio salino com condutividade similar às amostras e adição de padrão. Os resultados obtidos foram estatisticamente equivalentes em comparação com a técnica de FTIR, considerando nível de confiança de 95% / Abstract: This work describes the development of an electrochemical system to detect and quantify ethanol on fermentation broths. Three methods were studied to modify the electrode surface in order to obtain Ni(OH)2/NiOOH species: i) electrochemical cycling in NaOH solution; ii) chemical oxidation on ammonium persulfate and heat treatment; and, iii) electrochemical deposition of nickel, cobalt and cadmium from a solution containing the respective nitrates and application of cathodic current. The latter one showed good repeatability, therefore, an analytical curve was obtained by cyclic voltammetry technique and the analytical sensitivity was 1.2 ìA L mmol-1. Scanning electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the structures formed and allow qualitative and quantitative determination about the surface chemical composition. In order to provide selectivity to electrochemical determination of ethanol on complex samples, the electrochemical system was coupled to gas diffusion extraction through hydrophobic membrane. Thus, an extraction module was constructed in which a PTFE membrane separated the ethanol donor solution, standard or sample, from receptor solution, the electrolyte used on electrochemical analyses (100.0 mmol L-1 NaOH). The conditions applied to the system were optimized to yield repeatability on analytical measurements. In this platform, it was possible to monitor ethanol solutions in the range of 2.0 up to 20.0% v/v. Samples of fermentation broth were analyzed by two methods: direct interpolation on saline analytical curve with conductivity similar to samples and standard addition. The results were in agreement with respect to those obtained by FTIR method at 95% confidence level / Mestrado / Quimica Analitica / Mestra em Química

[ES] Un aumento de la generación de energía a partir de fuentes renovables (solar, eólica) requiere una alta flexibilidad de las redes eléctricas. En este sentido, las baterías de flujo redox de vanadio (BFRV) han demostrado una excelente capacidad para proporcionar dicha flexibilidad, mediante el almacenamiento eficiente de energía eléctrica en el rango de los kWh a los MWh. Sin embargo, sus elevados costes son en la actualidad unos de los mayores inconvenientes que dificultan una amplia penetración en el mercado. En la presente Tesis Doctoral se presenta el desarrollo y evaluación de una celda tubular especialmente diseñada con una membrana de 5.0mm. Las células tubulares así diseñadas deberían alcanzar una mayor densidad de potencia (kWm^(-3)). Del mismo modo, la sustitución de uno de los electrodos por un electrodo bifuncional de aire debería de incrementar la energía específica de dicha celda (Whkg^(-1)) y reducir, por tanto, los costes energéticos asociados (€/kWh). El diseño de la celda desarrollado en la presente Tesis Doctoral facilita la fabricación de los colectores y membranas actuales con el empleo de procesos de extrusión y marca un paso importante hacia la fabricación rentable de semiceldas y celdas completas en el futuro. Para evaluar el comportamiento de la nueva celda diseñada se han llevado a cabo estudios de polarización, de espectroscopia de impedancia, y medidas de ciclos de carga/descarga. Las celdas desarrolladas presentan una corriente de descarga máxima de 89.7mAcm^(-2) y una densidad de potencia de 179.2kW/m^3. Además, los bajos sobrepotenciales residuales obtenidos en los electrodos de la celda resultan prometedores. No obstante, la resistencia del área específica de celda de 3.2 ohm*cm² impone limitaciones significativas en la densidad de corriente. Eficiencias Coulomb del 95 % han sido obtenidas, comparables a los valores alcanzados en celdas planas de referencia. Sin embargo, las pérdidas óhmicas resultan elevadas, reduciendo la eficiencia energética del sistema al 56 %. Las celdas tubulares fabricadas con un electrodo de difusión de gas de una sola capa con Pt/IrO2 como catalizador permiten alcanzar densidades de corriente máximas de 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). Los elevados sobrepotenciales de activación y el reducido voltaje en circuito abierto (debido a potenciales mixtos) conducen a una densidad de potencia comparativamente baja de 15.4mW/ cm². El paso de iones de vanadio a través de la membrana se considera uno de los grandes inconvenientes en este tipo de celdas tubulares, lo que lleva a que la densidad de energía real de 23.2Wh l^(-1) caiga por debajo del valor nominal de 63.9Wh l^(-1). / [CAT] Un augment de la generació d'energia a partir de fonts renovables (solar, eòlica) requereix una alta flexibilitat de les xarxes elèctriques. En aquest sentit, les bateries de flux redox de vanadi (VRFB) han demostrat una excel·lent capacitat per a proporcionar aquesta flexibilitat, mitjançant l'emmagatzematge eficient d'energia elèctrica en el rang dels kWh als MWh. En la present Tesi Doctoral es presenta el desenvolupament i avaluació d'una cel·la tubular especialment dissenyada amb una membrana de 5.0mm. Les cèl·lules tubulars així dissenyades haurien assolir una major densitat de potència (kWm^(-3)). De la mateixa manera, la substitució d'un dels elèctrodes per un elèctrode bifuncional d'aire hauria d'incrementar l'energia específica d'aquesta cel·la (Whkg^(-1)) i reduir, per tant, els costos energètics associats (€/kWh). El disseny de la cel·la desenvolupat en la present tesi doctoral facilita la fabricació dels col·lectors i membranes actuals amb l'ocupació de processos d'extrusió i marca un pas important cap a la fabricació rendible de semiceldas i cel·les completes en el futur. Per avaluar el comportament de la nova cel·la dissenyada s'han dut a terme estudis de polarització, d'espectroscòpia d'impedància, i mesures de cicles de càrrega/ descàrrega. Les cel·les desenvolupades presenten un corrent de descàrrega màxima de 89.7mAcm^(-2) i una densitat de potència de 179.2kW/m^3. A més, els baixos sobrepotencials residuals obtinguts en els elèctrodes de la cel·la resulten prometedors. No obstant això, la resistència de l'àrea específica de cel·la de 3.2 ohm*cm² imposa limitacions significatives en la densitat de corrent. Eficiències Coulomb del 95 % han estat obtingudes, comparables als valors assolits en cel·les planes de referència. No obstant això, les pèrdues òhmiques resulten elevades, reduint l'eficiència energètica del sistema al 56 %. Les cel·les tubulars fabricades amb un elèctrode de difusió de gas d'una sola capa amb Pt/IrO2 com a catalitzador permeten assolir densitats de corrent màximes de 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). Els elevats sobrepotencials d'activació i el reduït voltatge en circuit obert (a causa de potencials mixtes) condueixen a una densitat de potència comparativament baixa de 15.4mW/ cm². El pas de ions de vanadi a través de la membrana es considera un dels grans inconvenients en aquest tipus de cel·les tubulars, el que porta al fet que la densitat d'energia real de23.2Wh l^(-1) caigui per sota del valor nominal de 63.9Wh l^(-1). / [EN] An increase of the power generation from volatile renewable sources (solar, wind) requires a high flexibility in power grids. All Vanadium Redox Flow Batteries (VRFBs) have demonstrated their ability to provide flexibility by storing electrical energy on a kWh to MWh scale. High power and energy specific costs do, however prevent a wide market penetration. In this dissertation a tubular cell design with a membrane diameter of 5.0mm is developed and evaluated. Tubular VRFB cells shall lead to an enhanced power den- sity (kWm^(-3)). Replacement of an electrode with a bifunctional air electrode (Vanadium/ Air Redox Flow Battery) shall allow to increase the specific energy (Whkg^(-1)) and reduce energy specific costs (€/kWh). The developed design facilitates a fabrication of the current collectors and membrane by an extrusion process and marks an important step towards the cost-efficient ex- trusion of entire half cells and cells in the future. To evaluate the cell performance and investigate loss mechanisms, polarization curve, electrochemical impedance spectroscopy and charge/discharge cycling measurements are conducted. Tubular VRFB cells with flow-by electrodes reveal a maximum dis- charge current and power density of 89.7mAcm^(-2) and 179.2kW/m^3, respectively. Low residual overpotentials at the cell's electrodes are encouraging, but the area spe- cific cell resistance of 3.2 ohm*cm² imposes limitations on the current density. Coulomb efficiencies of 95% are comparable to values of planar reference cells, but high ohmic losses reduce the system energy efficiency to 56 %. Tubular VARFB cells with a mono-layered gas diffusion electrode and a Pt/IrO2 catalyst allow for a maximum current density of 32mAcm^(-2) (Ecell =2.1 V/0.56V Ch/Dch). High activation overpotentials and a reduced open-circuit voltage (due to mixed potentials) lead to a comparably low power density of 15.4mW/ cm². Cross- over of vanadium ions through the membrane are considered as a major drawback for tubular VARFB cells and the actual energy density of 23.2Wh l^(-1) falls below the nominal value of Wh l^(-1). / Financial support of my research activities was provided by the BMBF through the common research project tubulAir±. / Ressel, SP. (2019). Tubular All Vanadium and Vanadium/Air Redox Flow Cells [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/131203 / TESIS

The aim of the presented Diploma Thesis was to develop a new method for the indirect determination of formaldehyde in wood-based products using gas-diffusion microextraction coupled with electrochemical detection on unmodified screen-printed electrodes (MLEM-SPCE). Formaldehyde released from the sample is derivatized using an acetylacetone reagent present in an acceptor solution. The product of derivatization of formaldehyde with acetylacetone is 3,5-diacetyl-1,4-dihydrolutidine (DDL) which forms a selective oxidation voltammetric peak at a potential of 0.4 V. Detection and quantification limits of 0.57 mg kg−1 and 1.89 mg kg−1 , respectively, were obtained, together with intra- and inter-day precision below 10% (as relative standard deviation, RSD). The developed methodology was applied to determine formaldehyde content in seven samples. Similar results were obtained from the European standard method EN 717-3 with a significant reduction of total analysis time. The developed method MLEM-SPCE, which combines the use of a new sample preparation procedure for volatile compounds with the firstly introduced determination of formaldehyde (as the derivative product DDL) on unmodified SPCEs, proves to be a promising alternative for the determination of formaldehyde in wood-based products and other samples.

Aufgrund des weltweit steigenden Energiebedarfs, dessen Deckung derzeit größtenteils auf fossilen Brennstoffen basiert, ist es nötig geworden, die Entwicklung alternativer Möglichkeiten zur Erzeugung von Elektroenergie als Primärenergie voranzutreiben. Eine dieser alternativen Möglichkeiten ist die Brennstoffezellentechnologie, welche sowohl in stationären als auch mobilen Anwendungen zum Einsatz kommen kann. Ihrer weitreichenden Verbreitung stehen bislang die aufgrund des großen Fertigungsaufwandes hohen Herstellungskosten der benötigten Komponenten im Wege. Hierzu zählen die Gasdiffusionslagen des weit verbreiteten Typs der wasserstoffbetriebenen Polymerelektrolytbrennstoffzelle. Es treten zwischen den einzelnen Fertigungsschritten im Herstellungsprozess dieser Gasdiffusionslagen Wechselwirkungen auf, die zu unerwünschten Materialveränderungen führen. Die Ursachen dieser Wechselwirkungen sind nicht vollends verstanden. Eine Vertiefung des Verständnisses der Herstellungsprozesse soll die Grundlage für eine Optimierung der Prozessführung bilden. Es sollen eine Kostenreduktion sowie eine Leistungssteigerung der Gasdiffusionslagen ermöglicht werden.:1 Einleitung 1 2 Stand der Technik 5 2.1 Brennstoffzellen 5 2.2 Gasdiffusionslagen 11 3 Problemstellung und Zielsetzung 17 4 Analyse und Klassifizierung von GDL-Fehlern 20 4.1 Fehlerklassifizierung 22 4.2 Fehleridentifizierung 26 4.3 Auswahl zu analysierender Fehlerbilder 27 4.4 Charakteristika der ausgewählten Fehlerbilder 42 4.4.1 Bahndeformationen 42 4.4.2 Umlaufende Verdickungen von Wickeln in Umfangsrichtung 44 4.4.3 Längs- und Queraufrauhungen sowie Rauhspuren 45 5 Theoretische Grundlagen 49 5.1 Physikalische und mechanische Grundlagen 49 5.1.1 Zug-, Biege- und Druckspannungen in Warenbahnen 49 5.1.2 Elastizitäts- und Kompressionsmoduli 52 5.1.3 Elastizität und Plastizität 53 5.1.4 Umformmechanismen im GDL-Basisvliesstoff und Versagensarten von Fasern 54 5.2 Statistik 55 5.2.1 Korrelationsanalyse 55 5.2.2 Regressionsanalyse 56 5.2.3 Zweistichproben-t-Tests und Konfidenzintervalle 56 5.2.4 Stichprobenumfang 57 5.3 Qualitätsregelkreise 58 6 Eingesetzte Untersuchungsmethoden 60 6.1 Mechanische Eigenschaften 64 6.1.1 Höchstzugkraft und Höchstzugkraftdehnung 64 6.1.2 Elastizitätsmodul und Kompressibilität 66 6.1.3 Elastische und plastische Deformation bei Zugbelastungen 67 6.1.4 Flächenmasse 70 6.1.5 Biegesteifigkeit 72 6.1.6 Dickenmessung 74 6.2 Thermische Eigenschaften 75 6.2.1 Wärmeleitfähigkeit 75 6.3 Bildgebende Verfahren 78 6.3.1 Schliffbildmikroskopie 78 6.3.2 Rasterelektronenmikroskopie 78 6.3.3 µ-Computertomographie 79 7 Herstellungsverfahren der untersuchten Gasdiffusionslagen im Überblick 81 8 Basisvliesstoffherstellung 84 8.1 Prozess der Vliesbildung und Verfestigung 84 8.2 Charakterisierung des GDL-Basisvliesstoffes 90 8.3 Fehlerbilder des GDL-Basisvliesstoffes 103 9 Dickenkalibrierung 113 9.1 Prozess der Dickenkalibrierung des GDL-Basisvliesstoffes 113 9.2 Charakterisierung des dickenkalibrierten GDL-Basisvliesstoffes 120 9.3 Fehlerbilder des dickenkalibrierten GDL-Basisvliesstoffes 130 9.3.1 Prozessbeobachtung 130 9.3.2 Hypothesenbildung und Verifikation 135 9.3.3 Maßnahmen zur Fehlervermeidung 146 10 Carbonisierung 156 10.1 Prozess der Carbonisierung 156 10.2 Charakterisierung carbonisierten GDL-Substrates 157 10.3 Fehlerbilder im Carbonisierprozess 163 11 Data Mining für die GDL-Herstellung 167 11.1 Datenerhebung 167 11.2 Auszuwertende Parameter 172 11.3 Ergebnisse der Parameteranalysen 173 12 Qualitätsregelkreise zum GDL-Produktionsprozess 178 12.1 Wulstbildung und Längsaufrauhung 178 12.2 Queraufrauhung 181 13 Zusammenfassung und Ausblick 184 14 Literaturverzeichnis 186 15 Abbildungsverzeichnis 192 16 Abkürzungsverzeichnis 201 17 Formelverzeichnis 203 18 Anlagenverzeichnis 204 / Due to worldwide increasing energy consumption, which is mainly covered by fossile fuels nowadays, it has become a necessity to further develop alternative possibilities to create electricity as primary energy. One alternative technology to accomplish this is fuel cell technology which can be used in stationary as well as in mobile applications. One aspect hindering its widespread use is the high manufacturing cost of the needed components due to the complicated production processes. Among these are gad diffusion layers of the commonly used hydrogen-driven polymer electrolyte fuel cells. There are interactions occurring between the several production steps leading to unwanted changes in material properties. The causes of these interactions are not completely understood. A deeper understanding of these shall be the basis for optimizations in process design and therefore cost reductions and improvements in performance of gas diffusion layers can be achieved.:1 Einleitung 1 2 Stand der Technik 5 2.1 Brennstoffzellen 5 2.2 Gasdiffusionslagen 11 3 Problemstellung und Zielsetzung 17 4 Analyse und Klassifizierung von GDL-Fehlern 20 4.1 Fehlerklassifizierung 22 4.2 Fehleridentifizierung 26 4.3 Auswahl zu analysierender Fehlerbilder 27 4.4 Charakteristika der ausgewählten Fehlerbilder 42 4.4.1 Bahndeformationen 42 4.4.2 Umlaufende Verdickungen von Wickeln in Umfangsrichtung 44 4.4.3 Längs- und Queraufrauhungen sowie Rauhspuren 45 5 Theoretische Grundlagen 49 5.1 Physikalische und mechanische Grundlagen 49 5.1.1 Zug-, Biege- und Druckspannungen in Warenbahnen 49 5.1.2 Elastizitäts- und Kompressionsmoduli 52 5.1.3 Elastizität und Plastizität 53 5.1.4 Umformmechanismen im GDL-Basisvliesstoff und Versagensarten von Fasern 54 5.2 Statistik 55 5.2.1 Korrelationsanalyse 55 5.2.2 Regressionsanalyse 56 5.2.3 Zweistichproben-t-Tests und Konfidenzintervalle 56 5.2.4 Stichprobenumfang 57 5.3 Qualitätsregelkreise 58 6 Eingesetzte Untersuchungsmethoden 60 6.1 Mechanische Eigenschaften 64 6.1.1 Höchstzugkraft und Höchstzugkraftdehnung 64 6.1.2 Elastizitätsmodul und Kompressibilität 66 6.1.3 Elastische und plastische Deformation bei Zugbelastungen 67 6.1.4 Flächenmasse 70 6.1.5 Biegesteifigkeit 72 6.1.6 Dickenmessung 74 6.2 Thermische Eigenschaften 75 6.2.1 Wärmeleitfähigkeit 75 6.3 Bildgebende Verfahren 78 6.3.1 Schliffbildmikroskopie 78 6.3.2 Rasterelektronenmikroskopie 78 6.3.3 µ-Computertomographie 79 7 Herstellungsverfahren der untersuchten Gasdiffusionslagen im Überblick 81 8 Basisvliesstoffherstellung 84 8.1 Prozess der Vliesbildung und Verfestigung 84 8.2 Charakterisierung des GDL-Basisvliesstoffes 90 8.3 Fehlerbilder des GDL-Basisvliesstoffes 103 9 Dickenkalibrierung 113 9.1 Prozess der Dickenkalibrierung des GDL-Basisvliesstoffes 113 9.2 Charakterisierung des dickenkalibrierten GDL-Basisvliesstoffes 120 9.3 Fehlerbilder des dickenkalibrierten GDL-Basisvliesstoffes 130 9.3.1 Prozessbeobachtung 130 9.3.2 Hypothesenbildung und Verifikation 135 9.3.3 Maßnahmen zur Fehlervermeidung 146 10 Carbonisierung 156 10.1 Prozess der Carbonisierung 156 10.2 Charakterisierung carbonisierten GDL-Substrates 157 10.3 Fehlerbilder im Carbonisierprozess 163 11 Data Mining für die GDL-Herstellung 167 11.1 Datenerhebung 167 11.2 Auszuwertende Parameter 172 11.3 Ergebnisse der Parameteranalysen 173 12 Qualitätsregelkreise zum GDL-Produktionsprozess 178 12.1 Wulstbildung und Längsaufrauhung 178 12.2 Queraufrauhung 181 13 Zusammenfassung und Ausblick 184 14 Literaturverzeichnis 186 15 Abbildungsverzeichnis 192 16 Abkürzungsverzeichnis 201 17 Formelverzeichnis 203 18 Anlagenverzeichnis 204

No description available.

Procedimentos analíticos espectrofotométricos foram desenvolvidos empregando etapas de separação e pré-concentração em sistemas de análises em fluxo com multi-impulsão ou lab-in-syringe, com aplicação a amostras de interesse agronômico (ferro em materiais vegetais e alimentos) e ambiental (cianeto dissociável em ácidos, ferro e antimônio em águas). A determinação de cianeto explorou a descoloração do complexo formado entre Cu(I) e ácido 2-2´-biquinolino-4,4´-dicarboxílico (BQA) pela presença de CN-, após a separação de HCN por difusão gasosa. Espectrofotometria com longo caminho óptico foi empregada para aumentar a sensibilidade, com resposta linear entre 5 e 200 g L-1, limite de detecção, coeficiente de variação (n = 10) e frequência de amostragem de 2,0 g L-1, 1,5% e 22 h-1, respectivamente. O procedimento consumiu apenas 48 ng de Cu(II), 5,0 g de ácido ascórbico e 0,9 g de BQA por determinação e gerou 2,6 mL de efluente. Tiocianato, nitrito e sulfito não afetaram a determinação de cianeto e peróxido de hidrogênio evitou a interferência de sulfeto até 200 g L-1. Os resultados para as amostras de águas naturais foram concordantes com o procedimento fluorimétrico em fluxo com 95% de confiança. Novas estratégias foram propostas para a extração em ponto nuvem (EPN) em fluxo: (i) a fase rica em surfactante foi retida diretamente na cela de fluxo, evitando a diluição; (ii) microbombas solenoide foram exploradas para melhorar a mistura e modular a vazão na retenção e remoção da fase rica, evitando a eluição com solvente orgânico e (iii) o calor liberado e os sais fornecidos por uma reação de neutralização em linha foram explorados para indução do ponto nuvem, sem dispositivo externo de aquecimento. Estas inovações foram demonstradas pela determinação espectrofotométrica de ferro baseada no complexo com 1-(2-tiazolilazo)-2-naftol (TAN). Resposta linear foi observada entre 10 e 200 g L-1, com limite de detecção, coeficiente de variação e frequência de amostragem de 5 g L-1, 2,3% (n = 7) e 26 h-1, respectivamente. O fator de enriquecimento foi de 8,9 com consumo apenas de 6 g de TAN e 390 g de Triton X-114 por determinação. Os resultados para amostras de águas foram concordantes com o procedimento de referência e os obtidos para digeridos de materiais de referência de alimentos concordaram com os valores certificados. A determinação espectrofotométrica de antimônio foi realizada explorando pela primeira vez a EPN em sistema lab-in-syringe. O complexo iodeto e antimônio forma um par iônico com H+, que pode ser extraído com Triton X-114. Planejamento fatorial demonstrou que as concentrações de ácido ascórbico, H2SO4 e Triton X-114, bem como as interações de segunda e de terceira ordem foram significativas (95% de confiança). Planejamento Box-Behnken foi aplicado para a identificação dos valores críticos. Robustez com 95% de confiança, resposta linear entre 5 e 50 g L-1, limite de detecção, coeficiente de variação (n = 5) e frequência de amostragem foram estimados em 1,8 g L-1, 1,6% e 16 h-1, respectivamente. Os resultados para amostras de águas naturais e medicamentos anti-leishmaniose foram concordantes com os obtidos por espectrometria de absorção atômica com geração de hidretos (HGFAAS) com 95% de confiança / Spectrophotometric analytical procedures were developed by exploiting separation and preconcentration steps in flow systems based on multi-pumping or lab-in-syringe approaches with application to agronomic (iron in plant materials and food) and environmental samples (acid dissociable cyanide, iron and antimony in waters). Cyanide determination exploited bleaching of the Cu(I)/2,2\'-biquinoline 4,4\'-dicarboxylic acid (BCA) complex by the analyte, after separation of HCN by gas diffusion. Long path length spectrophotometry was successfully exploited to increase sensitivity, thus achieving a linear response from 5 to 200 g L-1, with detection limit, coefficient of variation (n = 10) and sampling rate of 2 g L-1, 1.5% and 22 h-1, respectively. Each determination consumed 48 ng of Cu(II), 5 g of ascorbic acid and 0.9 g of BCA. As high as 100 mg L-1 thiocyanate, nitrite or sulfite did not affect cyanide determination and sample pretreatment with hydrogen peroxide avoided sulfide interference up to 200 g L-1. The procedure is environmentally friendly and presented one of the lowest detection limits associated to high sampling rate. The results for freshwater samples agreed with those obtained with the flow-based fluorimetric procedure at the 95% confidence level. Novel strategies were proposed for on-line cloud point extraction (CPE): (i) the surfactant-rich phase was retained directly into the flow cell to avoid dilution prior to detection; (ii) solenoid micro-pumps were explored to improve mixing and for flow modulation in the retention and removal of the surfactant-rich phase, thus avoiding the elution step with organic solvents and (iii) the heat released and the salts provided by an on-line neutralization reaction were exploited to induce cloud point without an external heating device. These approaches were demonstrated for the spectrophotometric determination of iron based on complex formation with 1-(2-thiazolylazo)-2-naphtol (TAN). A linear response was observed from 10 to 200 g L-1, with detection limit, coefficient of variation, and sampling rate of 5 g L-1, 2.3% (n = 7) and 26 h-1, respectively. The enrichment factor was 8.9 and the procedure consumed only 6 g of TAN and 390 g of Triton X-114 per determination. The results for freshwater samples agreed with the reference procedure and those obtained for certified reference materials of food agreed with the certified values. Spectrophotometric determination of antimony was performed for the first time exploiting CPE in the lab-in-syringe system. The antimony/iodide complex forms an ion-pair with H+, which can be extracted with Triton X-114. Factorial design showed that the concentrations of ascorbic acid, H2SO4 and Triton X-114, as well as the second and third order interactions were significant (95% confidence). The Box-Behnken design was applied to identify the critical values. The system is robust with 95% confidence and a linear response was observed from 5 to 50 g L-1, with detection limit, coefficient of variation (n = 5) and sampling rate of 1.8 g L-1, 1.6% and 16 h-1, respectively. The results for water samples and antileishmanial drugs agreed with those obtained by hydride generation atomic absorption spectrometry at the 95% confidence level

We are coming to realize that there is an urgent need to reduce energy usage in buildings and it has to be done in a sustainable way. This thesis focuses on the performance of the building envelope; more precisely thermal performance of walls and super insulation material in the form of vacuum insulation. However, the building envelope is just one part of the whole building system, and super insulators have one major flaw: they are easily adversely affected by other problems in the built environment.  Vacuum Insulation Panels are one fresh addition to the arsenal of insulation materials available to the building industry. They are composite material with a core and an enclosure which, as a composite, can reach thermal conductivities as low as 0.004 W/(mK). However, the exceptional performance relies on the barrier material preventing gas permeation, maintaining a near vacuum into the core and a minimized thermal bridge effect from the wrapping of barrier material round the edge of a panel. A serpentine edge is proposed to decrease the heat loss at the edge. Modeling and testing shows a reduction of 60% if a reasonable serpentine edge is used. A diffusion model of permeation through multilayered barrier films with metallization coatings was developed to predict ultimate service life. The model combines numerical calculations with analytical field theory allowing for more precise determination than current models. The results using the proposed model indicate that it is possible to manufacture panels with lifetimes exceeding 50 years with existing manufacturing. Switching from the component scale to the building scale; an approach of integrated testing and modeling is proposed. Four wall types have been tested in a large range of environments with the aim to assess the hygrothermal nature and significance of thermal bridges and air leakages. The test procedure was also examined as a means for a more representative performance indicator than R-value (in USA). The procedure incorporates specific steps exposing the wall to different climate conditions, ranging from cold and dry to hot and humid, with and without a pressure gradient. This study showed that air infiltration alone might decrease the thermal resistance of a residential wall by 15%, more for industrial walls. Results from the research underpin a discussion concerning the importance of a holistic approach to building design if we are to meet the challenge of energy savings and sustainability. Thermal insulation efficiency is a main concept used throughout, and since it measures utilization it is a partial measure of sustainability. It is therefore proposed as a necessary design parameter in addition to a performance indicator when designing building envelopes. The thermal insulation efficiency ranges from below 50% for a wood stud wall poorly designed with incorporated VIP, while an optimized design with VIP placed in an uninterrupted external layer shows an efficiency of 99%, almost perfect. Thermal insulation efficiency reflects the measured wall performance full scale test, thus indicating efficiency under varied environmental loads: heat, moisture and pressure. The building design must be as a system, integrating all the subsystems together to function in concert. New design methodologies must be created along with new, more reliable and comprehensive measuring, testing and integrating procedures. New super insulators are capable of reducing energy usage below zero energy in buildings. It would be a shame to waste them by not taking care of the rest of the system. This thesis details the steps that went into this study and shows how this can be done. / QC 20120228

Se han desarrollado métodos basados en análisis por inyección en flujo multijeringa (MSFIA) para determinar automáticamente sulfuro en muestras ambientales y aguas residuales, con detección espectrofotométrica previa transformación química del analito (acoplamiento oxidativo del sulfuro con N-N-dimetil-p-fenilendiamina en presencia de Fe(III) para formar azul de metileno).- Sistema MSFIA con difusión gaseosa para aislar el analito de matrices complejas sin ningún pretratamiento manual de la muestra.- Sistema MSFIA con pre-concentración en fase sólida (optrodo de reflectancia difusa sobre disco de membrana) para determinar niveles traza. - Método MSFIA que combina separación y pre-concentración en línea del sulfuro, para ofrecer elevadas selectividad y sensibilidad.- Sistema MSFIA inteligente totalmente automatizado para determinar sulfuro en un amplio rango de concentraciones, capaz de auto-ajustarse sin ninguna intervención del analista.- Estudio comparativo de metodologías en flujo para determinar sulfuro en matrices acuosas. Se discuten críticamente distintas técnicas y sistemas de detección empleados. / Multisyringe flow injection analysis (MSFIA) systems for automatic determination of sulfide in environmental and wastewater samples have been developed exploiting spectrophotometric detection prior derivatization of the analyte (oxidative coupling of sulfide with N-N-dimethyl-p-phenylenediamine in presence of Fe(III) to form methylene blue).- A MSFIA system was coupled to gas-diffusion separation to achieve the isolation from complex matrices without any pre-treatment batch sample.- An optrode using disk-based solid-phase extraction in a MSFIA set-up is proposed to determine trace levels.- A hyphenated method that combines the separation and pre-concentration is presented reaching high selectivity and sensitivity. - A fully automated smart MSFIA system for sulfide monitoring in a wide concentration range is proposed choosing by itself the best approach to quantify the analyte without the analyst intervention.- A review of flow-based methodologies for sulfide determination in aqueous matrices is presented. The characteristics of automated protocols using several detection systems are discussed.

Cette étude a pour but de documenter la relation qui existe entre les propriétés de transfert d’un matériau (répartition en taille de pores, porosité totale accessible à l’eau, saturation en eau), et son coefficient de diffusion. Pour cela, des matériaux ayant une porosité quasi-monomodale sont utilisés : verres Vycor® et géopolymères ; ainsi que des matériaux ayant une porosité complexe : pâtes de ciment CEM V. L’utilisation des verres Vycor® et des géopolymère permet de quantifier la diffusion gazeuse, en fonction de la saturation en eau, de matériaux ayant des pores de même dimension, ou du moins, de même ordre de grandeur. L’utilisation des pâtes de ciment permet quant à elle, de vérifier s’il est possible de décomposer le coefficient de diffusion d’un matériau dont la porosité est complexe, en un assemblage de coefficients de diffusion de matériaux dont la porosité est quasi-monomodale. Pour cela, on s’attachera à particulièrement à étudier l’impact de l’agencement du réseau poreux sur le coefficient de diffusion.Les travaux se décomposent en trois parties :• Etude des caractéristiques géométriques du réseau poreux des matériaux étudiés. Il sera utilisé la porosimétrie par intrusion de mercure, la porosimétrie à eau, des essais de sorption / désorption d’azote, et des essais de désorption d’eau.• Mesure expérimentale du coefficient de diffusion des matériaux, en fonction de leur humidité relative de stockage et de leur saturation en eau.• Modélisation du coefficient de diffusion des matériaux utilisés, et étude de l’impact de l’agencement de leur réseau poreux (tortuosité, connexion des pores entre eux) / This work documents the relationship that exists between the transfer properties of a material (pore size distribution, total porosity accessible to water, water saturation degree), and its diffusion coefficient. For this sake, materials having a quasi mono modal porosity are used: Vycor® glasses and geopolymers. We also use materials having a complex porosity: CEM V cement pastes. The use of Vycor® glasses and geopolymers allows quantifying the gas diffusion coefficient through materials having known pores size, as a function of their water saturation degree. The use of cement pastes allows checking if it is possible to decompose the diffusion coefficient of a complex porosity material, in an assembling of diffusion coefficients of quasi mono modal porosity materials. For this sake, the impact of pore network arrangement on the diffusion coefficient is studied in great details. This study is divided into three parts:• Measurement of the geometric characteristics of materials porous network by means of the mercury intrusion porosimetry, water porosimetry, isotherms of nitrogen sorption / desorption, and water desorption tests.• Measurement of the materials diffusion coefficient, as a function of their relative humidity storage, and their water saturation degree.• Modeling the diffusion coefficient of the materials, and study the impact of the pore network (tortuosity, pores connection)

Procedimentos analíticos espectrofotométricos foram desenvolvidos empregando etapas de separação e pré-concentração em sistemas de análises em fluxo com multi-impulsão ou lab-in-syringe, com aplicação a amostras de interesse agronômico (ferro em materiais vegetais e alimentos) e ambiental (cianeto dissociável em ácidos, ferro e antimônio em águas). A determinação de cianeto explorou a descoloração do complexo formado entre Cu(I) e ácido 2-2´-biquinolino-4,4´-dicarboxílico (BQA) pela presença de CN-, após a separação de HCN por difusão gasosa. Espectrofotometria com longo caminho óptico foi empregada para aumentar a sensibilidade, com resposta linear entre 5 e 200 g L-1, limite de detecção, coeficiente de variação (n = 10) e frequência de amostragem de 2,0 g L-1, 1,5% e 22 h-1, respectivamente. O procedimento consumiu apenas 48 ng de Cu(II), 5,0 g de ácido ascórbico e 0,9 g de BQA por determinação e gerou 2,6 mL de efluente. Tiocianato, nitrito e sulfito não afetaram a determinação de cianeto e peróxido de hidrogênio evitou a interferência de sulfeto até 200 g L-1. Os resultados para as amostras de águas naturais foram concordantes com o procedimento fluorimétrico em fluxo com 95% de confiança. Novas estratégias foram propostas para a extração em ponto nuvem (EPN) em fluxo: (i) a fase rica em surfactante foi retida diretamente na cela de fluxo, evitando a diluição; (ii) microbombas solenoide foram exploradas para melhorar a mistura e modular a vazão na retenção e remoção da fase rica, evitando a eluição com solvente orgânico e (iii) o calor liberado e os sais fornecidos por uma reação de neutralização em linha foram explorados para indução do ponto nuvem, sem dispositivo externo de aquecimento. Estas inovações foram demonstradas pela determinação espectrofotométrica de ferro baseada no complexo com 1-(2-tiazolilazo)-2-naftol (TAN). Resposta linear foi observada entre 10 e 200 g L-1, com limite de detecção, coeficiente de variação e frequência de amostragem de 5 g L-1, 2,3% (n = 7) e 26 h-1, respectivamente. O fator de enriquecimento foi de 8,9 com consumo apenas de 6 g de TAN e 390 g de Triton X-114 por determinação. Os resultados para amostras de águas foram concordantes com o procedimento de referência e os obtidos para digeridos de materiais de referência de alimentos concordaram com os valores certificados. A determinação espectrofotométrica de antimônio foi realizada explorando pela primeira vez a EPN em sistema lab-in-syringe. O complexo iodeto e antimônio forma um par iônico com H+, que pode ser extraído com Triton X-114. Planejamento fatorial demonstrou que as concentrações de ácido ascórbico, H2SO4 e Triton X-114, bem como as interações de segunda e de terceira ordem foram significativas (95% de confiança). Planejamento Box-Behnken foi aplicado para a identificação dos valores críticos. Robustez com 95% de confiança, resposta linear entre 5 e 50 g L-1, limite de detecção, coeficiente de variação (n = 5) e frequência de amostragem foram estimados em 1,8 g L-1, 1,6% e 16 h-1, respectivamente. Os resultados para amostras de águas naturais e medicamentos anti-leishmaniose foram concordantes com os obtidos por espectrometria de absorção atômica com geração de hidretos (HGFAAS) com 95% de confiança / Spectrophotometric analytical procedures were developed by exploiting separation and preconcentration steps in flow systems based on multi-pumping or lab-in-syringe approaches with application to agronomic (iron in plant materials and food) and environmental samples (acid dissociable cyanide, iron and antimony in waters). Cyanide determination exploited bleaching of the Cu(I)/2,2\'-biquinoline 4,4\'-dicarboxylic acid (BCA) complex by the analyte, after separation of HCN by gas diffusion. Long path length spectrophotometry was successfully exploited to increase sensitivity, thus achieving a linear response from 5 to 200 g L-1, with detection limit, coefficient of variation (n = 10) and sampling rate of 2 g L-1, 1.5% and 22 h-1, respectively. Each determination consumed 48 ng of Cu(II), 5 g of ascorbic acid and 0.9 g of BCA. As high as 100 mg L-1 thiocyanate, nitrite or sulfite did not affect cyanide determination and sample pretreatment with hydrogen peroxide avoided sulfide interference up to 200 g L-1. The procedure is environmentally friendly and presented one of the lowest detection limits associated to high sampling rate. The results for freshwater samples agreed with those obtained with the flow-based fluorimetric procedure at the 95% confidence level. Novel strategies were proposed for on-line cloud point extraction (CPE): (i) the surfactant-rich phase was retained directly into the flow cell to avoid dilution prior to detection; (ii) solenoid micro-pumps were explored to improve mixing and for flow modulation in the retention and removal of the surfactant-rich phase, thus avoiding the elution step with organic solvents and (iii) the heat released and the salts provided by an on-line neutralization reaction were exploited to induce cloud point without an external heating device. These approaches were demonstrated for the spectrophotometric determination of iron based on complex formation with 1-(2-thiazolylazo)-2-naphtol (TAN). A linear response was observed from 10 to 200 g L-1, with detection limit, coefficient of variation, and sampling rate of 5 g L-1, 2.3% (n = 7) and 26 h-1, respectively. The enrichment factor was 8.9 and the procedure consumed only 6 g of TAN and 390 g of Triton X-114 per determination. The results for freshwater samples agreed with the reference procedure and those obtained for certified reference materials of food agreed with the certified values. Spectrophotometric determination of antimony was performed for the first time exploiting CPE in the lab-in-syringe system. The antimony/iodide complex forms an ion-pair with H+, which can be extracted with Triton X-114. Factorial design showed that the concentrations of ascorbic acid, H2SO4 and Triton X-114, as well as the second and third order interactions were significant (95% confidence). The Box-Behnken design was applied to identify the critical values. The system is robust with 95% confidence and a linear response was observed from 5 to 50 g L-1, with detection limit, coefficient of variation (n = 5) and sampling rate of 1.8 g L-1, 1.6% and 16 h-1, respectively. The results for water samples and antileishmanial drugs agreed with those obtained by hydride generation atomic absorption spectrometry at the 95% confidence level