O presente trabalho teve por objetivo compreender o papel de íons metálicos na degradação de gordura vegetal e animal, assim como na geração de formiatos. Nesse contexto foram investigados: 1) o papel de formaldeído na corrosão de peças de chumbo e a possibilidade de CO2 ser reduzido a ácido fórmico (ou formiato) por íons metálicos presentes em vidro; 2) o papel de íons metálicos na degradação de gordura animal e vegetal, desde que um grande número de pigmentos são minerais e tais gorduras foram frequentemente utilizadas em pinturas. Espectroscopia Raman foi a principal técnica empregada nas investigações, nas quais também foram usadas FTIR, difratometria de raios X, microscopia eletrônica de varredura, refletância no visível e análise elementar (C e H). Os resultados obtidos indicaram que formaldeído é agressivo a Pb mesmo na ausência de oxidantes como H2O2 e formiatos foram detectados como produto de corrosão para concentrações de aldeído tão baixa quanto 100 ppb (100% de umidade relativa). As concentrações investigadas de H2CO foram 100 ppb, 500 ppb, 1,2 ppm, 44 ppm e 1,6x102 ppm e para todas essas foram observadas bandas de carbonato e de formiato, embora em muitos casos os espectros não foram simplesmente a soma das contribuições das bandas de Pb(HCO2)2 e PbCO3, revelando um complexo equilíbrio envolvendo as concentrações de H2CO, CO2 e H2O. O efeito de umidade relativa (54%, 75% e 100%) foi estudado e formiato foi detectado mesmo em umidade relativa de 54%. Os mesmos produtos de corrosão foram observados quando cupons de Pb e PbO foram expostos a formaldeído, evidenciando o papel da camada de óxido na oxidação de formaldeído a formiato. Quando o efeito de Fe(III) foi considerado, câmaras climáticas foram usadas e o efeito de íons metálicos foi investigado na presença e ausência de luz. Linoleato de metila, gordura vegetal e animal foram mantidos por 8 dias sob condições controladas e as mudanças na composição foram acompanhadas por espectroscopia Raman e FTIR. As amostras mostraram ser sensíveis tanto a luz quanto a Fe(III), no entanto, problemas com as duplicatas não permitiram que conclusões pudessem ser obtidas dos experimentos. Como uma etapa preliminar no intuito de estender os estudos de degradação de gorduras à química forense, um desenho de suposta autoria de Tarsila do Amaral que teria sido feito na década de 1920, foi analisado por microscopia Raman. Ftalocianina azul (ftalocianina de cobre) foi encontrada como componente dos traços verdes e desde que esse pigmento começou a ser comercializado em 1937, pelo menos a data assinalada ao desenho não é correta. / The present work aimed at the understanding of the role played by metal ions on the degradation of vegetal and animal fats and on formates formation. The following issues were addressed: 1) the effect of formaldehyde on the corrosion of Pb objects and the possibility of CO2 reduction to formic acid (or formate) by the metal ions present in glass framework; 2) the effect of metal ions on the degradation of vegetal and animal fats, since a large number of pigments are minerals and such fats were often used as paint binders in the past. Raman microscopy was the main technique employed in the investigations which also used FTIR, XRD, SEM, UV-VIS absorption and elemental analysis (C and H). The obtained results indicated that formaldehyde is harmful towards Pb even in the absence of oxidants such as H2O2 and formates were detected among the corrosion products for aldehyde concentrations as low as 100 ppb (100% relative humidity). The investigated H2CO concentrations were 100 ppb, 500 ppb, 1,2 ppm, 44 ppm and 1,6x102 ppm for all of them bands assigned to carbonates and formate were observed, although in most cases the spectra were not simply the sum of Pb(HCO2)2 and PbCO3 contributions revealing a quite complex equilibria involving H2CO, CO2 and H2O concentrations. The effect of relative humidity (54%, 75% and 100%) was studied and formate was detected even at 54% RH. The same corrosion products were observed when both Pb cupons and PbO were exposed to formaldehyde thus making clear the role played by the oxide layer in the formaldehyde to formate oxidation. When the effect of Fe(III) was considered, a home made environmental chamber was used and the effect of the metal ions was investigated in the presence and absence of light. Methyl linoleato, vegetal and animal fats were kept by 8 days under controlled conditions and the changes on composition were followed by Raman and FTIR spectroscopies. The samples proved to be sensitive to both light and Fe(III), however, problems with the replicates so far don\'t allow any conclusion to be driven from the experiments. As a preliminary step in the attempt to extend the fat degradation study to forensic, a draw supposedly authored by Tarsila do Amaral in the 1920 decade was investigated by Raman microscopy. Phthalocyanine Blue (copper phthalocyanine) was found as a component of the green traces and since phthalocynines trade started in 1937, at least the date assigned to the draw is not correct

Depuis 2001 et la création d'un observatoire de la qualité de l'air intérieur (OQAI), la qualité de l'air intérieur est devenue un enjeu majeur de santé publique et fait l'objet d'un cadre réglementaire qui continue d'évoluer au cours des dernières années. Deux décrets récents, en France, prévoient la mise en œuvre de l'étiquetage des matériaux de construction en fonction de leurs émissions de composés organiques volatils (COV) (décret n° 2011-321, 23/03/2011) et le contrôle de la concentration des polluants (benzène et formaldéhyde) avec un guide des valeurs pour les bâtiments ouverts au public (n ° 2011-1728, 12/02/2012). De nos jours, la méthode analytique utilisée pour mesurer la concentration en formaldéhyde dans l'air consiste en un prélèvement sur cartouche de 2,4-dinitrophénylhydrazine (DNPH), qui est analysée par chromatographie en phase liquide après extraction. Cette méthode nécessite un équipement lourd et une étape en laboratoire est nécessaire. La société Ethera développe et commercialise des capteurs spécifiques pour la détection et la mesure du formaldéhyde avec des échantillonneurs passifs ou actifs. Ce capteur est basé sur des matrices nanoporeuses contenant du Fluoral-P (4-amino-3-pentène-2-one), qui réagit sélectivement avec le formaldéhyde pour produire un composé coloré de la 3,5-diacétyl-1,4-dihydrolutidine (DDL). La DDL est détectée à 420nm par lecture optique et la différence de densité optique mesurée avant et après l'exposition du capteur est directement proportionnelle à la concentration en formaldéhyde dans l'air intérieur. Le but de cette thèse est d'améliorer les performances des échantillonneurs passifs. Les différentes phases du développement des échantillonneurs passifs sont étudiées (conception, évaluation en chambre d’exposition) avec différentes approches et méthodologies. Deux axes d'étude sont considérés: une approche théorique et des essais en laboratoire. Une approche théorique a été mise en œuvre pour optimiser un échantillonneur passif ou dimensionner un nouveau préleveur. Les tests de laboratoire ont permis d'évaluer les paramètres métrologiques des échantillonneurs passifs (limite de détection, sensibilité, répétabilité, linéarité ...) et les effets des facteurs d'exposition (température, humidité relative, concentration). / Since 2001 and the creation of a French Indoor Air Quality Observatory (OQAI), indoor air quality has become a major public health issue. It is the subject of a regulatory framework that continues to evolve in recent years. Two recent decrees, in France, foresee the implementation of the labeling of building materials according to their emissions of volatile organic compounds (VOCs) (decree n°2011-321, 23/03/2011) and the survey of air concentration of two pollutants (benzene and formaldehyde) with guide values in public buildings (n°2011-1728, 2/12/2012). Today, the analytical method used to measure formaldehyde concentration in air consists in a 2,4-dinitrophenylhydrazine (DNPH) sampling cartridge which is analyzed by liquid chromatography after solvent extraction. This method is time consuming, expensive and complicated to perform. The company Ethera develops and markets specific, sensitive sensors for detection and measurement of formaldehyde with passive or active samplers. This sensor is based on a nanoporous matrix containing Fluoral-P (4-amino-3-penten-2-one), which selectively reacts with formaldehyde to produce a colored compound the 3,5-diacetyl-1,4-dihydrolutidine (DDL). DDL is detected at 420nm by optical reading and the difference of the optical density measured before and after exposition of the sensor is directly proportional to the concentration of formaldehyde in air. The purpose of this thesis is to improve the performance of passive samplers. The different phases of the development of passive samplers are studied (design, evaluation in environmental chamber) with different approaches and methodologies. In fact, two axis of study are considered: a theoretical approach and laboratory tests. Theoretical approach will be implemented to optimize a passive sampler or for sizing a new one based on the study of theoretical sampling rates. Laboratory tests will allow to assess metrological parameters of passive samplers (detection limit, sensitivity, repeatability, linearity…) and to estimate effects of exposure factors (temperature, relative humidity, concentration levels …).

Submitted by Fernanda Aparecida Alonge Minutti (fer.alonge@gmail.com) on 2018-05-30T16:01:45Z No. of bitstreams: 1 Fernanda A A Minutti_Dissertação completa_FINAL.pdf: 6994835 bytes, checksum: ab3793efb49bc877a92e10fe9d2d04cd (MD5) / Approved for entry into archive by Lucilene Cordeiro da Silva Messias null (lubiblio@bauru.unesp.br) on 2018-05-30T17:03:36Z (GMT) No. of bitstreams: 1 minutti_faa_me_bauru.pdf: 6888158 bytes, checksum: 03946ea4b9fd3ef6aec72596a601b833 (MD5) / Made available in DSpace on 2018-05-30T17:03:36Z (GMT). No. of bitstreams: 1 minutti_faa_me_bauru.pdf: 6888158 bytes, checksum: 03946ea4b9fd3ef6aec72596a601b833 (MD5) Previous issue date: 2018-01-24 / O presente trabalho apresenta uma alternativa para a minimização do descarte atual, crescente e inadequado do resíduo agronômico pena de galinha (Chicken Feather). Assim, foram estabelecidos parâmetros para gerar um novo produto, painéis de compósitos, com adição de resina ureia-formaldeído, visando verificar as propriedades e possibilidades de aplicação deste produto na construção civil. Ao longo do levantamento bibliográfico, notou-se que a pena de galinha é um tema ainda pouco explorado em pesquisas, traduzindo-se em uma lacuna a ser preenchida. Foi escolhida a resina ureia-formaldeído por ser um componente chave muito utilizado na indústria de chapas particuladas de madeira, o que facilitaria na avaliação comparativa de desempenho do novo compósito. Durante a realização da etapa experimental, constatando-se uma grande dificuldade na trituração das penas, optouse por usá-las inteiras. Ao final desta etapa, a qualidade física das chapas foi insuficiente para a produção dos corpos de prova necessários à realização dos ensaios de caracterização física e mecânica, sendo direcionado aos ensaios de desempenho térmico, para aplicação deste compósito como isolante térmico em edificações. Com a realização destes ensaios, constatou-se o potencial de adequação do material para esta aplicação. Comparados com materiais para isolamento térmico existentes no mercado, os painéis com pena de galinha apresentaram desempenho compatível, bloqueando cerca de 20ºC de temperatura entre uma face e outra. Desta forma, conclui-se que a pena de galinha é um resíduo agronômico com considerável potencial de aproveitamento na produção de painéis, para uso como material isolante térmico em componentes para construção civil. / The present work presents an alternative for the minimization of current, increasing and inadequate disposal of agronomic chicken feather residue. Thus, parameters were established to generate a new product, composite panels, with addition of ureaformaldehyde resin, in order to verify the properties and possibilities of application of this product in civil construction. Throughout the bibliographical survey, it was noticed that the feather of chicken is a subject still little explored in researches, translating into a lacuna to be filled. The urea-formaldehyde resin was chosen as a key component widely used in the wood particleboard industry, which would facilitate the comparative evaluation of the new composite performance. During the realization of the experimental stage, it was verified a great difficulty in the crushing of the feathers, it was chosen to use them whole. At the end of this stage, the physical quality of the panels was insufficient for the production of the test specimens necessary for the physical and mechanical characterization tests, being directed to the thermal performance tests, for the application of this composite as thermal insulation in buildings. With the accomplishment of these tests, it was verified the potential of suitability of the material for this application. Compared with existing insulation materials on the market, the panels with chicken feather showed compatible performance, blocking about 20ºC of temperature between one face and another. Thus, it is concluded that the chicken feather is an agronomic residue with considerable potential for use in the production of panels, for use as thermal insulation material in components for civil construction.

Considerando a grande quantidade de resíduos sólidos, como a palha e o bagaço de cana, gerados devido às atividades agrícolas, procurou-se desenvolver um projeto que utilize esses resíduos para obtenção de produtos com maior valor agregado, visando atender às expectativas em termos econômicos e ambientais. O bagaço da cana é um resíduo gerado em grandes proporções no Brasil. O Estado de São Paulo instituiu uma lei que proíbe a prática da queimada, para fins de colheita, pelo fato de causar sérios problemas ambientais e danos à saúde da população das cidades produtoras de cana, tornando a palha mais um resíduo em abundância. O bagaço e agora a palha da cana são queimados em caldeiras para a geração de energia nas próprias usinas de açúcar e álcool. Os excedentes deste processo podem ser utilizados para a obtenção de produtos de maior valor agregado, desde polpas celulósicas bem como a produção de ligninas que podem ser utilizadas em resinas para fabricação de aglomerados. Para o uso integral da biomassa lignocelulósica é necessário fazer a separação de seus constituintes majoritários: celulose, hemicelulose e lignina. Neste trabalho, os processos de separação utilizados foram a polpação etanol-água e a técnica de explosão a vapor tendo a palha e o bagaço da cana como materiais de partida. As ligninas obtidas pelo processo etanol-água foram oxidadas em meio ácido sob condições diferentes para determinar as cinéticas da oxidação e as energias de ativação destas ligninas. Ligninas oxidadas apresentam fortes propriedades quelantes e podem ser aplicadas no tratamento de efluentes para remoção de metais pesados. A oxidação foi realizada em meio ácido acético utilizando o sitema catalítico Co/Mn/Br à 50, 80 e 115°C por 5 h. A energia de ativação calculada para as ligninas de bagaço e de palha apresentaram um valor de 23,4 kJ/mol e 34,2 kJ/mol, respectivamente, indicando que a lignina de palha é mais reticulada. O estudo cinético da oxidação foi avaliado por UV-Visível. Espectros de infravermelho de várias amostras de ligninas oxidadas foram submetidas à Analise por Componentes Principais (PCA). Os resultados mostraram suaves modificações na estrutura da lignina após a reação de oxidação. A lignina obtida pela técnica de explosão a vapor foi testada em resinas para fabricação de aglomerados, juntamente com resinas à base de farinha de soja e de tanino. Foram ainda fabricadas resinas utilizando o glioxal em substituição do formaldeído, que é um material tóxico. Lignina glioxilada foi adicionada à resina de farinha de soja glioxilada em substituição das resinas PF ou de isocianato (pMDI), visando uma maior utilização de material natural na resina. As formulações que continham 70 ou 80% de material natural apresentaram resultados dentro dos padrões exigidos. As resinas com 70% de material natural podem ser utilizadas em menor porporção na madeira e também podem ser utilizados tempos de prensagem menores, que são industrialmente significativos. A melhor formulação encontrada foi utilizando farinha de soja pré-cozida glioxilada (SG) com a adição de tanino e pMDI, onde as proporções de material foram SG/T/pMDI 54/16/30 (m/m) . / Considering the large amount of agricultural residues, such as straw and sugarcane bagasse, generated due to agricultural activities, we sought to develop a project that proposes the use of these residues to obtain products with higher value, to acchieve expectations in terms of cost and environment. Bagasse from sugarcane is a by-product generated in large proportions in Brazil. São Paulo State introduced a law which prohibits the practice of burning for harvesting because of causing serious environmental problems and damage to the health of the population of cities close to cane producers, making straw an other abundant residue. Sugarcane bagasse and straw are burned in boilers for generation of energy in sugar and alcohol industries. However, excess of those by-products could be used to obtain products with higher value, as cellulosic pulps with applications in cardboard packing and the application in resins for the manufacture of particleboard. For the integral use of the vegetable biomass it is necessary separate the major components: cellulose, hemicellulose and lignin, and for this purpose ethanol-water pulping and steam explosion process were used, with the sugarcane bagasse and straw. Lignins obtained by ethanol-water pulping were oxidized in acidic medium under different conditions to study kinetics of the oxidation and calculate the activation energies of these lignins. Oxidized lignins presents very strong chelating properties and could be applied in effluents treatments for heavy metals removal. The oxidation of lignins were performed using acetic acid and Co/Mn/Br catalytical system at 50, 80 and 115°C for 5 h. Activation energy (Ea) was calculated for lignins from sugarcane bagasse and straw and presented Ea of 34.4 kJ.mol-1 and 23.3 kJ.mol-1, respectively, indicating higher crosslinked formation for straw. A kinetic study of the oxidation was evaluated by UV/Visible. FTIR spectra of various samples of oxidized lignins were submitted to Principal Component Analysis (PCA). The results showed slight structure modifications in lignins after oxidation reaction. Lignin obtained by the steam explosion process was tested in resins for the manufacture of particleboards, together with resin-based soy flour and tannin. Resins were manufactured to substitute formaldehyde (a toxic material) with glyoxal. Glyoxalated lignins were added to glyoxalated soy flour in place of PF resins or the isocyanate (pMDI), aiming greater use of natural materials in resins. Adhesive resin formulations in which the total content of natural material is either 70 or 80% of the total resin solids content gave good results. The resins comprising 70% by weight of natural material can be used in a much lower proportion on wood chips and can afford pressing times fast enough to be significant under industrial panel pressing conditions. The best formulation of all the ones tried was the one based on glyoxalated precooked soy flour (SG), to which a condensed tannin was added in water solution and pMDI, where the proportions of the components SG/T/pMDI was 54/16/30 by weight.

Propriedades benéficas são associadas ao consumo moderado de vinho devido à presença dos compostos fenólicos. Uma dose diária de vinho de até 200 ou 300 mL é sugerida para mulheres e homens, respectivamente. Entretanto, dentre os compostos presentes nos vinhos, podem ser encontrados compostos carbonílicos tóxicos, como o formaldeído, acroleína, acetaldeído, furfural e carbamato de etila, os quais tem sido associados a efeitos adversos à saúde humana, incluindo o câncer. O objetivo deste trabalho foi desenvolver e validar um método para a quantificação simultânea destes compostos tóxicos através da microextração em fase sólida no modo headspace associada à cromatografia gasosa acoplada à espectrometria de massas quadrupolar no modo de monitoramento de íons selecionados (HS-SPME- GC/qMS-SIM) e caracterizar o risco relacionado à exposição a estes compostos. Quatro etapas da vinificação (uva, mosto, após a fermentação alcoólica e vinho) e vinhos comercialmente disponíveis foram analisados com o uso da GC/qMS-SIM após verificar as coeluições através da cromatografia gasosa bidimensional abrangente acoplada ao detector de espectrometria de massas por tempo de voo (GC×GC- TOFMS). O acetaldeído e a acroleína derivatizados coeluíram na primeira dimensão cromatográfica com o limoneno e o hexanoato de metila, respectivamente. Em função disso, foram escolhidos como íons quantificadores na análise por GC/qMS, íons que não foram encontrados no espectro de massas dos compostos coeluídos. Os parâmetros de validação (LOD, LOQ, recuperação, repetibilidade e reprodutibilidade) mostraram que a HS-SPME-GC/qMS-SIM é adequada para quantificar simultaneamente os cinco compostos tóxicos. A acroleína foi encontrada em concentrações similares na uva e mosto, e não foi detectada após a fermentação alcoólica e no vinho. O acetaldeído foi detectado em menores concentrações no mosto e em maiores níveis após a fermentação alcoólica. A concentração de furfural foi maior nas uvas do que nas demais etapas. O carbamato de etila não foi detectado nas etapas da vinificação e nos vinhos comerciais. Os níveis de formaldeído ficaram entre os valores de LOD e LOQ em todas as etapas da vinificação e nos vinhos comerciais. Além disso, nos vinhos comercialmente disponíveis, a acroleína foi encontrada em 50% das amostras, o acetaldeído e o furfural estavam presentes em todas as amostras. O único composto cuja ingestão pode representar risco a saúde é a acroleína. Dessa forma, este estudo contribuiu para identificar os pontos críticos de controle relacionados à presença de compostos tóxicos durante a vinificação, incluindo a produção do acetaldeído durante a fermentação alcoólica e a contaminação das uvas com acroleína e furfural através do ar atmosférico. Além disso, os resultados da ocorrência destes compostos tóxicos em vinhos comercialmente disponíveis poderão contribuir para a criação de uma legislação nacional que estabeleça limites dos mesmos nesta bebida. / Beneficial properties are associated with moderate consumption of wine due to the presence of phenolic compounds. A daily intake of wine of up to 200 or 300 mL is suggested for women and men, respectively. However, toxic carbonyl compounds such as formaldehyde, acetaldehyde, acrolein, furfural and ethyl carbamate can be found among the compounds present in wines, which have been associated with adverse effects on human health, including cancer. The objective of this work was to develop and validate a method for simultaneous quantification of these toxic compounds through headspace solid phase microextraction associated with gas chromatography with quadrupole mass spectrometric detection in selected-ion monitoring mode (HS-SPME-GC/qMS-SIM) and characterize the risk related to exposure to these compounds. Four vinification steps (grape, must, after alcoholic fermentation and wine) and commercially available wine were analyzed using GC/qMS-SIM after checking the coelutions by comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (GC×GC-TOFMS). The derivatized acetaldehyde and acrolein coeluted in the first chromatographic dimension with limonene and methyl hexanoate, respectively. Based on this, were chosen as quantifiers ions in GC/qMS analysis, ions that were not found in the mass spectra of the coeluted compounds. The validation parameters (LOD, LOQ, recovery, repeatability and reproducibility) showed that HS-SPME-GC/qMS-SIM is adequate to simultaneously quantify the five toxic compounds. Acrolein was found at similar concentrations in grape and must, and was not detected after alcoholic fermentation and in wine. Acetaldehyde was detected at lower concentrations in the must and at higher levels after alcoholic fermentation. The concentration of furfural was higher in the grapes than in the other stages. Ethyl carbamate was not detected in the vinification steps and in commercially wine. Formaldehyde levels were between the LOD and LOQ values at all stages of winemaking and commercial wines. In addition, in commercially available wines, acrolein was found in 50% of samples, acetaldehyde and furfural were present in all samples. The only compound whose intake may pose a health risk is acrolein. Thus, this study contributed to identify critical control point related to the presence of toxic compounds during winemaking, including the production of acetaldehyde during alcoholic fermentation and the contamination of grapes with acrolein and furfural through atmospheric air. In addition, the results of the occurrence of these toxic compounds in commercially available wines may contribute to the creation of national legislation that establishes limits of the same in this drink.

A corrosão é um processo eletroquímico espontâneo e, sabendo que diversos metais estão sujeitos a este fenômeno, a sua deterioração é inevitável, o que impõe à comunidade científica desafios para retardar tal efeito. A literatura sobre o tema aponta como uma das ações mais recorrentes para alcançar esse retardo a aplicação superficial de películas poliméricas, dentre as quais destaca-se o desenvolvimento de revestimentos inteligentes. A incorporação na tinta de formadores de filmes encapsulados confere ao revestimento a característica de autorreparação, e a escolha de silanos como agentes reticulantes se destaca positivamente, uma vez que o filme gerado pela molécula apresenta caráter hidrofóbico. Nesse contexto, o objetivo deste estudo é verificar, primeiro, a melhor condição de reticulação do silano na presença de radiação ultravioleta e, segundo, se a adição de microcápsulas de poli(ureia-formaldeído-melamina) contendo metacriloxissilano em uma tinta epóxi base solvente confere a este revestimento proteção contra a corrosão, pelo efeito de autorreparação. Para isso, estudou-se a cinética de polimerização do formador de filme e o seu encapsulamento em microcápsulas de poli(ureia-formaldeído-melamina). Determinada a melhor condição de encapsulamento, corpos de prova de aço carbono foram pintados com a tinta contendo as microcápsulas produzidas. O efeito de autorreparação - desencadeado pela ruptura das microcápsulas ao se provocar um defeito mecânico no revestimento - foi comprovado pelas técnicas de espectroscopia de impedância eletroquímica (EIE), técnica de varredura por eletrodo vibratório (SVET) e por ensaio acelerado de corrosão em câmara de névoa salina. / Corrosion is a spontaneous electrochemical process and, knowing that several metals are subjected to this phenomenon, its deterioration is inevitable, which imposes challenges for scientific community to delay this effect. The literature on this subject points out, as one of the most recurrent actions to achieve this delay, the superficial application of polymer films, which stands out the development of smart coatings with self-healing properties. The incorporation of encapsulated film formers gives to coatings the self-healing ability, and the choice of silanes as film-forming agent stands out positively since the film has a hydrophobic character. In this context, the aims of this study are, firstly, verify the best crosslinking condition of silane induced by UV light and, secondly, investigate whether the addition of poly(urea-formaldehyde-melamine) microcapsules containing methacryloxysilane into the solvent-based epoxy coating brings protection to this coating against corrosion by self-healing effect. For this purpose, the polymerization kinetics of the film former by ultraviolet radiation and their encapsulation in poly(urea-formaldehyde-melamine) microcapsules were studied. Given the best encapsulation condition, carbon steel panels were coated with the self-healing paint. The self-healing effect - triggered by the rupture of the microcapsules caused by an induced mechanical defect in the coating - was demonstrated by techniques as electrochemical impedance spectroscopy (EIS), scanning vibrating electrode technique (SVET) and by accelerated corrosion tests in salt spray chamber.

Un des enjeux pour améliorer la qualité de l’air intérieur des bâtiments est d’adopter de bonnes pratiques, notamment en matière de sélection des matériaux lors des phases de conception. Pour cela, des outils d’aide à la décision/conception sont indispensables en support à ces bonnes pratiques pour atteindre une maîtrise globale de la qualité de l’air intérieur. Dans le domaine du bâtiment, il n’existe pas à ce jour d’outil opérationnel permettant d’estimer, en amont d’une construction, la qualité de l’air intérieur. Des travaux sont engagés sur ce thème mais ils se heurtent à un manque d’informations sur le comportement des matériaux lorsque ceux-ci sont associés et soumis à des conditions normales d’usage. Ces travaux de thèse avaient donc pour objectif d’évaluer le comportement de matériaux (source ou puits) vis-à-vis de la contamination aux composés organiques volatils (COV) et au formaldéhyde lorsqu’ils sont évalués seuls dans des conditions normalisées retenues pour l’étiquetage sanitaire, mais aussi lorsqu’ils sont mis en œuvre dans des projets de construction (impact du changement d’échelle et effet d'assemblage). La méthodologie développée a donc associé des essais à l’échelle du matériau et à l’échelle d’une pièce dans le but d’acquérir des données d’entrée à un modèle pour la prédiction des concentrations et l’évaluation des contributions respectives des différents processus (émissions primaires, échanges aux interfaces air/surfaces intérieures,…) à la contamination intérieure par les COV. Une première partie de ce travail a consisté à évaluer en laboratoire les échanges de COV et de formaldéhyde à l'interface matériau-air pour une sélection de matériaux de construction et de décoration. Les émissions primaires ont été déterminées selon la méthode normalisée ISO 16000-9 et par une méthode d’échantillonnage passif basée sur un couplage cellule d'émission/micro-extraction sur phase solide (SPME) (dispositif DOSEC-SPME) et l’effet de l’assemblage de matériaux et de composants sur la qualité de l’air intérieur a été étudié. Les constantes d’adsorption/désorption du formaldéhyde sur les matériaux sélectionnés ont ensuite été déterminées par une méthodologie innovante. Ces constantes, ainsi que les données d’émission, ont été rassemblées dans une base données pour servir de critères (ou indicateurs) pour la sélection de matériaux respectueux de la qualité de l’air intérieur (QAI). Dans une deuxième partie, les résultats obtenus en conditions de laboratoire ont été confrontés à ceux obtenus en conditions réelles à l’échelle d’une pièce dans le cadre d’une étude de plusieurs mois dans le but de mettre en évidence l’impact du changement d’échelle. La dernière partie de cette thèse a consisté à développer un modèle de prévision de la QAI intégrant les données d'adsorption/désorption préalablement déterminées. A terme, la base de données et le modèle ont vocation à constituer des outils de gestion pour orienter les choix en matière de matériaux, de configuration et d'usage d’un bâtiment dans l’optique d’une réduction à la source des émissions de COV dans l’air intérieur. / One of the challenges for improving the indoor air quality of buildings is to adopt good practices, especially in the selection of materials during design phases. To this end, decision-making / design tools are essential in support of these good practices to achieve global control of indoor air quality.In the building sector, there is currently no operational tool to estimate the indoor air quality in building. Work is underway on this theme, but they encounter a lack of information on the behavior of materials when they are associated and subject to normal conditions of use.The purpose of this thesis was therefore to evaluate the behavior of materials (source or sink) with respect to contamination with volatile organic compounds (VOCs) and formaldehyde when they are evaluated alone under standardized conditions selected for health labeling, but also when they are implemented in construction projects (impact of the change of scale and the effect of assembly). The developed methodology has therefore combined material-scale and room-scale testing to acquire input data to a model for concentration prediction and assessment of the respective contributions of different processes (primary emissions, exchanges at air / interior surfaces interfaces, ...) to internal contamination by VOCs.A first part of this work consisted of laboratory evaluation of VOC and formaldehyde exchanges at the material-air interface for a selection of construction and decoration materials. The primary emissions were determined according to the ISO 16000-9 standard method and a passive sampling method based on solid-phase emission / micro-extraction (SPME) (DOSEC-SPME device) and the effect of the assembly of materials and components on indoor air quality has been studied. The adsorption / desorption constants of formaldehyde on the selected materials were then determined by an innovative methodology. These constants, as well as emission data, have been collated into a database to serve as criteria (or indicators) for the selection of IAQ-compliant materials.In a second part, the results obtained under laboratory conditions were compared with those obtained under real-world conditions on a scale of a part in a study of several months in order to highlight the impact of the change of scale.The last part of this thesis consisted in developing an IAQ prediction model integrating previously determined adsorption / desorption data. Ultimately, the database and the model are intended to constitute management tools to guide the choice of materials, configuration and use of a building with a view to reducing emissions at the source VOC in the indoor air.

<p>This thesis studied environmental factors in relation to asthma and respiratory symptoms among schoolchildren in two countries. In Sweden, 1014 pupils (5-14 year) in 8 schools participated. Wheeze was reported by 7.8%, current asthma by 5.9%, doctor-diagnosed asthma by 7.7%, cat allergy by 6.8% and dog allergy by 4.8%. Current asthma was less common among those consuming more fresh milk and fish. Doctor-diagnosed asthma was less common among those consuming olive oil. Cat, dog and horse allergens were common in settled dust and related to respiratory symptoms. Pupils consuming butter and fresh milk had less respiratory symptoms in relation to allergen exposure. In schools with increased levels of microbial volatile organic compounds and selected plasticizers (Texanol and TXIB) asthma and respiratory symptoms were more common.</p><p>In Korea, 2365 pupils (9-11 year) in 12 schools participated (96%). In total, wheeze was reported by 8.0%, current asthma by 5.7%, doctor-diagnosed asthma by 5.4%, cat allergy by 2.6% and dog allergy by 4.9%. Contamination of dog and mite (<i>Dermatophagoides farinae</i>) allergen was common while cat allergen was uncommon. Remodelling, changing floor and building dampness at home were positively associated with asthma and respiratory symptoms. The strongest associations were found for floor dampness. Indoor/outdoor concentration of NO₂, formaldehyde and ultrafine particles (UFP) at schools were positively associated with asthma and respiratory symptoms. </p><p>When comparing Sweden and Korea, Korean pupils had more breathlessness and asthma but reported less cat and pollen allergy. Swedish schools had CO₂-levels below 1000 ppm, while most Korean schools exceeded this standard. Since both home and school environment may affect pupil’s asthma and respiratory symptoms, air quality should be an important health issue. Moreover, changes in dietary habits may be beneficial to decrease asthma and allergies. Furthermore, interaction between diet and environment needs to be further investigated.</p>

This thesis studied environmental factors in relation to asthma and respiratory symptoms among schoolchildren in two countries. In Sweden, 1014 pupils (5-14 year) in 8 schools participated. Wheeze was reported by 7.8%, current asthma by 5.9%, doctor-diagnosed asthma by 7.7%, cat allergy by 6.8% and dog allergy by 4.8%. Current asthma was less common among those consuming more fresh milk and fish. Doctor-diagnosed asthma was less common among those consuming olive oil. Cat, dog and horse allergens were common in settled dust and related to respiratory symptoms. Pupils consuming butter and fresh milk had less respiratory symptoms in relation to allergen exposure. In schools with increased levels of microbial volatile organic compounds and selected plasticizers (Texanol and TXIB) asthma and respiratory symptoms were more common. In Korea, 2365 pupils (9-11 year) in 12 schools participated (96%). In total, wheeze was reported by 8.0%, current asthma by 5.7%, doctor-diagnosed asthma by 5.4%, cat allergy by 2.6% and dog allergy by 4.9%. Contamination of dog and mite (Dermatophagoides farinae) allergen was common while cat allergen was uncommon. Remodelling, changing floor and building dampness at home were positively associated with asthma and respiratory symptoms. The strongest associations were found for floor dampness. Indoor/outdoor concentration of NO2, formaldehyde and ultrafine particles (UFP) at schools were positively associated with asthma and respiratory symptoms. When comparing Sweden and Korea, Korean pupils had more breathlessness and asthma but reported less cat and pollen allergy. Swedish schools had CO2-levels below 1000 ppm, while most Korean schools exceeded this standard. Since both home and school environment may affect pupil’s asthma and respiratory symptoms, air quality should be an important health issue. Moreover, changes in dietary habits may be beneficial to decrease asthma and allergies. Furthermore, interaction between diet and environment needs to be further investigated.

En funktionsbeläggning består av ett polymert material som beläggs till en textil yta. Denna typ av beläggning används för funktionsplagg och det belagda materialet har som uppgift att skydda användaren från vatten samtidigt som den har god ånggenomsläpplighet. För att tvärbinda funktionsbeläggningen och öka dess hållfasthet appliceras ett översta skikt av polymer som kallas topcoat. En topcoat innehåller tvärbindande ämnen som till exempel isocyanater eller formaldehyd. Dessa ämnen är mycket miljö- och hälsoskadliga. Denna studie har genomförts i syfte att undersöka möjligheten till en reducering av mängden topcoat och därmed minskning av skadliga kemikalier, i en funktionsbeläggning. En mikroporös polyuretanbeläggning applicerades på en polyesterväv med valsrakling. Därefter belades två vattenbaserade topcoats innehållande olika tvärbindare: en med formaldehyd och en med isocyanater, genom luftrakling. Genom att späda den ena topcoaten med olika mängd vatten, variera lutningen av beläggningskniven och ändra knivens tryck mot väven vid beläggning utvecklades sex olika material. Väven med beläggning och olika variation av topcoat testades sedan med avseende på kvalitet. Tester av materialens vattentäthet, ånggenomsläpplighet och nöthållfasthet utfördes. Mängden applicerad topcoat undersöktes genom areaviktoch tjockleksmätning. De belagda ytorna granskades i mikroskop för att analysera eventuella variationer mellan materialen. De belagda materialen var inte vattentäta (&lt;100 cm vattenpelare). Studien visar dock att materialet belagt med en formaldehydbaserad topcoat som spätts med 68 % vatten visar statistiskt säkerställt högre medelvärde i vattentäthetstestet, jämfört med det material som belagts på samma vis men med den ospädda varianten av samma topcoat. Resultaten från areavikts- samt tjockleksmätningen visade inte med säkerhet om vinkeln på knivens lutning eller dess tryck mot väven hade någon påverkan på mängden topcoat som belades. Alla material med de spädda varianterna av topcoat visade god ånggenomsläpplighet, vilken också förbättrades avsevärt efter tvätt samtidigt som materialens vattentäthet inte försämrades i samma skala. Detta resultat är mycket intressant då bibehållen vattentäthet i kombination med god ånggenomsläpplighet efter tvätt är en viktig egenskap för funktionsbeläggningar. Slutledningsvis visar resultaten på möjligheter i att späda topcoaten innan applicering och därigenom uppnå intressanta materialegenskaper i kombination med minskad kemikalieanvändning. Vidare undersökningar krävs dock för att säkerställa eftersträvad vattentät funktion.