Dissertations / Theses on the topic 'Paint formulation'

Interior flat, white latex paint is a common coating applied to walls around the world. Development of a coating with one coat hide capability is a pinnacle achievement for paint formulators as it has the potential to save consumers both time and money. One coat paints already exist on the market, but they are limited in color, coverage, and often have many disclaimers. Work done was part of a project initiated by ChemoursTM Titanium Technologies. The goal of the project presented in this article was to create an interior flat, white latex paint that yields a spread rate of greater than 400 ft2/gal., which is advertised by many below critical pigment volume concentration (CPVC) commercial paints. In order to achieve this goal, an above CPVC paint with a high TiO2 content was created and continuously improved. Improvement of the formulation involved numerous experimental variations including adjustments to the hydroxyethylcellulose (HEC) molecular weight, dispersant chemistry, latex chemistry, TiO2 concentration, extender package, and rheology modifier type. The sheen value, relative light scattering, and spread rate were the main measurements conducted in order to judge formulation improvement. Complications with the spread rate procedure forced its adaptation in order to collect less variable data with the high density, shear thinning formulations. It was found that shorter opacity charts yielded more precise spread rate data than the longer opacity charts. An attempt at correlating rheology with sheen development resulted in the conclusion that the pigment and extender particle package is the greatest driving factor behind sheen reduction. The rheology modifier type and dispersant chemistry did not affect the flatness of the paint nearly as much. A Keyence VR-3000 series One-Shot 3D Measuring Macroscope was used to show that surface roughness does not directly correlate to the sheen value when a number of flat paints with different sheens were analyzed. This project is an ongoing effort and the information contained in this document will substantially help future development.

Uma forma de reduzir a difusão de agentes agressivos para o interior do concreto é através da aplicação de sistemas de pintura, que funcionam como uma barreira ao ingresso destes agentes. A difusão dos agentes através de películas de pintura está relacionada com a sua porosidade, que, por sua vez, depende principalmente do teor e estrutura química da resina e do teor e morfologia dos pigmentos. Esta tese teve por objetivo principal demonstrar que, com uma formulação adequada, as tintas à base de resina acrílica podem ser utilizadas como barreira de proteção eficiente contra a penetração de água e vapor de água, anidrido carbônico (C\'O IND.2\') e íons cloreto, em estruturas de concreto ou em outros tipos de substratos. As formulações das tintas foram definidas em função do tipo de acabamento final e obtidas pela variação da relação pigmento/resina. Foram realizados ensaios de caracterização nas tintas líquidas e nas resinas utilizadas na preparação das tintas estudadas, bem como ensaios de desempenho nas películas livres e em concretos pintados, que apresentavam resistência à compressão de 20 e 40 Mpa. Para a medida da resistência à penetração dos agentes agressivos no concreto, foram desenvolvidos ensaios acelerados, com base em metodologias de avaliação de argamassas e concretos, adaptados a substratos pintados. A microestrutura das películas de tinta foi correlacionada com as propriedades físicas das películas e dos concretos pintados. Os resultados obtidos mostram a importância da formulação das tintas nos fenômenos de transporte e, além disso, mostram que tintas acrílicas e as estirenoacrílicas com diferentes temperaturas vítreas (Tg) apresentam comportamento físico distinto. Tintas de acabamento semi-brilho conferem boa proteção contra a penetração de agentes agressivos no concreto, enquanto que as de acabamento fosco apresentam função mais decorativa do que de proteção.
The diffusion of aggressive agents into concrete can be reduced by the application of painting systems which work as barriers to these agents. The capacity of these agents to pass through the paint is related to its porosity, which in turn is mainly dependent on the structure and content of the resin and on the morphology and content of the pigments. The main objective of this thesis is to demonstrate that with adequate formulation, paints based on acrylic resin polymers can be used as efficient barriers against the penetration of water and water vapour, carbon dioxide and chloride in concrete structures or any other porous substrate. Paint formulations were defined based on the final appearance (gloss) and obtained by varying the pigmentbinder ratio. Characterization tests on the liquid paints and polymers prepared for this study were done, as were performance tests on free dry films and painted concrete substrates, with compressive strength of 20 MPa and 40 MPa. In order to determine the effectiveness of paint in inhibiting the diffusion of aggressive agents into concrete, accelerated tests based on methodologies for the evaluation of mortars and concrete were developed. The films microstructures were correlated with their physical properties and with painted concrete. The results showed that the formulation of the paints has a important effect on the transport mechanism and also that acrylic and styrene-acrylic paints with different transition temperatures (Tg) do not present the same physical behavior. Glossy paints presented a high level of protection against the penetration of aggressive agents whereas matte finishes offered a more aesthetic function rather than protection.

Water-borne latex coatings represent a safer, more user-friendly, and environmentally responsible alternative to solvent-borne coatings, and are growing in popularity each year. However, these coatings often exhibit unfavorable performance when exposed to water for extended periods of time. This prolonged exposure often results in water uptake, which may give rise to other detrimental effects such as a decrease in modulus, blushing or water-whitening, reduced serviceable life, and softening of the film. In this study, various polymer composition latex design spaces are studied to develop an understanding of how water uptake can be modulated and minimized using common synthetic approaches. Factors including monomer selection, particle size, polymer molecular weight, crosslinking density, surfactant choice and particle stabilization, processing variables and Tg are considered. In addition, some formulation modifications including PVC, film thickness, and choice of coalescent package are explored to gain a more comprehensive understanding of final product performance. In quantifying the total water uptake of the films, gravimetric analysis tends to be the preferred method employed in the coatings industry. However, other analytical approaches can be used to better understand the effect that water has on the properties of the film. These methods may include differential scanning calorimetry, electrochemical impedance spectroscopy, immersion testing using dynamic mechanical analysis, and others. In the work, it has been shown that interparticle crosslinking, surfactant, and monomer selection can have an extreme influence on the water uptake of free films. Film samples exhibit a range of water uptake values from nearly 200% to less than 5% over a one-week soak in deionized water. It is thought that the surfactant may provide hydrophilic channels that allow water to v penetrate the film and form heterogeneous domains within the coating. These domains then grow and scatter light, leading to water-whitening and an increase in mass when compared to the dry film. Utilizing monomers with differing relative solubilities in water, such as methyl methacrylate and styrene, further allow control of this effect. Interparticle crosslinking via keto-hydrazide crosslinking, which is achieved during the film formation process, can also prevent the formation and growth of these large water domains, thus resulting in better performing films.

Les peintures sont omniprésentes dans nos civilisations modernes et décorent presque tous les supports et ce dans des domaines très variés. L'utilisation massive des peintures pose cependant des problèmes environnementaux et de santé publique, de par la présence de solvants qui, lors du séchage, s'évaporent et émettent des composés organiques volatiles (COV) néfastes pour l'environnement et l'homme. Une démarche européenne et mondiale de réduction d'émission des COV est donc en cours depuis quelques années. De plus, l'engouement croissant pour le développement durable pousse à la transition de produits pétrosourcés vers des produits biosourcés, à coûts et performances similaires. Les résines alkydes en émulsions, développées au début du XXème siècle, constituent une alternative de choix car émettant une quantité limitée de COV et obtenues par polycondensation de matières premières renouvelables. Après un état de l'art sur le contexte des peintures actuelles et la composition d'une peinture alkyde en émulsion, leurs propriétés physiques et chimiques ont été étudiées. Après ce travail de formulation, deux additifs ont été synthétisés afin d'augmenter le taux de biosourcé des peintures alkydes en émulsion : un épaississant et un agent dispersant. De par la présence de surfactants, les formules de peintures alkydes en émulsion sont pour l'heure moins compétitives que les peintures alkydes en phase solvant. En conséquence, la première émulsion alkyde sans tensioactif a été développée et ses performances évaluées en peinture
Paints and coatings occupy a prominent place in the cultural history of mankind. People have always been fascinated by colors and used paints to decorate and beautify themselves and their environment. Nevertheless, these products bring a lot of problems. For instance, some paints still contain organic solvents, which have negative impacts on the environment and human health. Due to environmental legislations and the need to reduce VOCs emission (volatile organic compounds), water-based paints have attracted a lot of interest. Moreover, the raising sustainability awareness is a driving force for the transition from petrobased to biobased products with equivalent costs and performances. In this context, alkyd resin emulsion, introduced in the 1990s, still continue to be the most widely used binder, because they have low VOCs level and are synthesized by polycondensation reactions of renewable raw materials. After reviewing the current state of the art regarding the alkyd paint emulsion, their physical and chemical properties were studied. Two additives, respectively a rheology modifier and a dispersing agent, were also synthesized, in order to increase the biobased content of alkyd paint emulsion Due to the presence of wetting agent, alkyd emulsion paints are still less competitive than solvent-borne alkyd paints. The first surfactant free alkyd emulsion was consequently developed and its film properties characterized in paint formulation

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O presente trabalho trata da obtenção de tinta utilizando dois pigmentos em dois vernizes diferentes (Epóxi–Ep e Poliuretana–PU) e dos testes de eficiência dessas tintas para prevenção da corrosão em aços. Um pigmento a base de Polianilina (Pani) na presença do ácido dodecilbenzeno sulfônico (ADBS) e o outro a base do compósito Pani-Fe3O4. A Pani sintetizada quimicamente foi secada a vácuo e caracterizada pelas técnicas de espectroscopia de Infravermelho e de UV/Vis. As placas de aço carbono SAE 1006 com e sem revestimentos foram submetidas a ensaio cíclico de corrosão em uma câmara de névoa salina (CNS). O monitoramento da corrosão foi feito por análises de fotografia e microscopia óptica. A interação camada-substrato foi investigada por meio da espectroscopia de impedância eletroquímica (EIE) e a superfície dos revestimentos por Espectroscopia Raman. No geral, os resultados indicaram que a Pani-ADBS teve maior desempenho no verniz Ep do que no verniz PU, enquanto o pigmento Pani-Fe3O4 apresentou maior desempenho no verniz PU. Existe evidência de que a Pani-ADBS adicionada ao Ep, na concentração de 0,1%, resulta em melhor proteção do aço ao final do ensaio de 30 dias. O indicativo pode ser visto pela maior resistência (3,95 x 109 ·cm2) e menor capacitância (7,14 x 10-11 F·cm-2). Discussão similar também pode ser feita com o revestimento PU, uma vez que ele apresentou maior resistência da camada (9,81 x 108 ·cm2) e menor capacitância (8,06 x 10-11 F·cm-2). Essa evidência também foi observada pelos resultados de potencial de circuito aberto (Eca). O espalhamento Raman detectou indícios de degradação química dos revestimentos Ep e PU. Baseado nos resultados obtidos neste trabalho é razoável a utilização do modelo ácido-base para explicar o mecanismo de proteção do aço pelos pigmentos Pani-ADBS e Pani-Fe3O4. O mecanismo de proteção do aço ainda carece de mais estudos, entretanto os resultados de potencial de circuito aberto e impedância eletroquímica sugerem que o mecanismo de proteção pode ser explicado por barreira física e em termos de compatibilidade entre o pigmento e a matriz polimérica.
This work describes the production of paints using two pigments in two different polymer matrices (epoxy-Ep and polyurethane-PU) and tests efficiency of these formulations in the prevention of corrosion in steel. A Polyaniline (Pani) based pigment in the presence of a functionalized protonic acid, known as dodecylbenzene sulfonic acid (DBSA) and the other based on Pani-Fe3O4 composite. The chemically synthesized Pani powder was vacuum-dried and characterized by infrared spectroscopy and UV/Vis. The paints were applied to metallic carbon steel SAE 1006 plates. The plates were subjected to cyclic corrosion essay to test the performance of the coatings against corrosion. The film-substrate interaction was investigated by electrochemical impedance spectroscopy (EIS). Raman spectroscopy was used for chemical analysis of surface coatings. It was observed that the Pani-DBSA had its most pronounced effect on the epoxy varnish than in the polyurethane varnish. While the pigment Pani-Fe3O4 showed better performance in the polyurethane varnish. There is evidence that PANI-DBSA added to the Ep at a concentration of 0.1% results in better protection of steel at the end of the 30 day test. This indication can be seen by the increased resistance (3.95 x 109 ·cm2) and a lower capacitance (7.14 x 10-11 F·cm-2). Similar discussion can also be done with the PU coating, as it showed the highest resistance (9.81 x 108 ·cm2) and a lower capacitance (8.06 x 10-11 F·cm-2). These results were confirmed by open circuit the potential (Eoc). The Raman scattering detected chemical evidence of Ep and PU coatings degradation. According to the results obtained in this study, it is reasonable to use the acid-base model to explain the steel protective mechanism by Pani-DBSA and Pani-Fe3O4 pigments. The steel protection mechanism still needs more studies; however, the results of open circuit potential and electrochemical impedance suggest that the protection mechanism can be explained by a physical barrier and in terms of polarity between pigment and matrix.

Le seul traitement de la maladie coeliaque est de suivre un régime sans gluten. La fabrication de pain sans gluten relève du défi technologique, car le gluten joue un rôle prépondérant en panification. Les pains sans gluten actuellement proposés sont de qualité éloignée de celle d’un pain avec gluten et évoluent très vite après la cuisson vers un état rassi. L’introduction d’une étape de congélation dans le procédé de fabrication pourrait palier le problème de conservation du pain sans gluten, en permettant d’améliorer la mise à disposition d’un produit frais pour le consommateur. Néanmoins, il a été établi, pour le pain avec gluten, que la congélation a un impact non négligeable sur la qualité du produit. Après la mise au point, en procédé conventionnel, d’une formule de pain sans gluten, l’effet de la congélation de la pâte sans gluten non fermentée a été étudié et les caractéristiques des pâtes et des pains évaluées. Une diminution du volume spécifique des pains, une augmentation de la dureté de la mie et une distribution plus homogène des alvéoles sont observés pour les pains issus d’une pâte ayant été congelée par rapport aux pains obtenus en procédé conventionnel. Certaines propriétés rhéologiques de la pâte sont affectées par l’étape de congélation, pouvant expliquer les caractéristiques des pains. Enfin, l’impact de la congélation n’étant pas négligeable sur le produit fini, une optimisation de la formule a été entreprise, par un ajustement de la quantité d’eau et l’introduction d’hydroxy-propyl-methyl-cellulose, dans le but d’obtenir des pains, issus de pâtes congelées, avec des caractéristiques proches de celles obtenues en procédé conventionnel
A strict gluten-free diet for life is, to date, the only treatment for coeliac disease patients. Development of such products is a technological challenge, because of the unique properties of gluten in breadmaking. In consequence, gluten-free breads currently proposed on the market have very different characteristics from gluten bread, and stale quickly after baking step. The introduction of a freezing step into the breadmaking process could allow the gluten-free bread preservation, by improving the availability for the consumer of fresh bread. Nevertheless, it has been established that the freezing process has a negative impact on gluten bread. Firstly, a gluten-free formulation was developed in conventional breadmaking process in order to provide bread with similar characteristics to French-bread. Then, the effect of freezing on the non fermented gluten-free dough was evaluated on the bread and dough characteristics. A quality loss was observed particularly on specific volume, crumb hardness and gas cell distribution. Some dough viscoelastic properties were modified that could explain the lower gas retention capacity. Finally, as the freezing step is not without consequences on the final product, optimization of formulation was carried out in order to provide, by the non fermented process, bread with similar characteristics of those obtained by conventional breadmaking process. Three levels of water and hydroxylpropyl-methyl-cellulose were tested. Dough rheological properties and bread characteristics were measured for all formulations. Correlations between specific volume and several rheological data were identified allowing to link dough properties and bread quality

The intention and purpose of the present thesis is to prepare a series of protective coatings using some conducting polymers (CPs) as corrosion inhibitors. The use of organic paints is the most common method for corrosion prevention. Anticorrosive coatings form a class of high-performance systems with a very wide range of applications and being classified in two broad groups: heavy-duty coatings, for high performance, and light-duty coatings, for medium performance. The first class being required for highly aggressive medium, like oil platforms, bridges, chemical industry plants, containers, shipping, and others; the late being employed mainly for outside industrial environments, urban environments, houses, offices, and others. This thesis consists of an overview and a compendium of the following work stages and results: 1. Preparation of nanostructured CPs for corrosion inhibition: Study of the ability of poly(N-methylpyrrole) to form nanostructures and the performance of such nanostructures when act as anticorrosive additive of organic coatings. 2. Partial replacement of metallic zinc dust usually employed in heavy duty protective coatings, by a small concentration of CPs: Study of the use of a small amount of polyaniline emeraldine salt as a partial substitute of metallic zinc dust in marine epoxy primers in order to maintain corrosion inhibition. 3. Evaluation of an environmentally friendly anticorrosive pigment for alkyd priming: Study of the substitution of a high concentration of zinc phosphate, commonly employed in light-duty coatings, by a very low concentration of polyaniline emeraldine base (undoped form), polyaniline emeraldine salt (doped form) and an eco-friendly polythiophene derivative (partially oxidized) in an alkyd coatings and the study of their protective performance using accelerated corrosion assays. 4. Preparation of a novel epoxy coating, based on DMSO as green solvent and free of zinc anticorrosive pigment, and its application on carbon steel protection: Formulation and evaluation of a novel anticorrosive epoxy coating based on DMSO solvent and free of zinc, using polyaniline emeraldine base and poly[2,2’-(3-methylacetate)thiophene] as anticorrosive pigments. All the results derived from the present thesis have been accepted or have been sent for publication in international journals and also reported in some international congresses, as we point below: 1. M. Martí, G. Fabregat, F. Estrany, C. Alemán, E. Armelin, “Nanostructured conducting polymer for dopamine detection”, J.Mater. Chem., 2010, 20, 10652-10660. 2. E. Armelin, M. Martí, F. Liesa, J.I. Iribarren, C. Alemán, “Partial replacement of metallic zinc dust in heavy duty protective coatings by conducting polymer”, Prog. Org. Coat., 2010, 69, 26-30. 3. M. Martí, G. Fabregat, D.S. Azambuja, C. Alemán, E. Armelin, “Evaluation of an environmentally friendly anticorrosive pigment for alkyd primer”, Prog. Org. Coat., 2012, 73, 321–329. 4. M. Martí, L. Molina, C. Alemán, E. Armelin, “Replacement of toxic solvents and anticorrosive pigments used in solvent-borne epoxy coatings by safer functional organic compounds”, submitted for publication in Journal of Hazardous Materials, 2013. 5. M. Martí, E. Armelin, J. Iribarren, C. Alemán. Soluble polythiophenes as anticorrosive additives for marine epoxy paints”, submitted for publication in Materials and Corrosion, 2013. 6. G. Fabregat, M. Martí, F. Estrany, C. Alemán, E. Armelin, “Nanostructured Poly(N-Methylpyrrole) and Its Application in Dopamine Detection”, E-MRS 2010 Spring Meeting. 2010, Strasbourg, France. 7. E. Armelin, M. Martí, F. Estrany, C. Alemán, “Environmentally friendly anticorrosive additive to replace zinc and its compounds in alkyd and epoxy primers”, 12th Mediterranean Congress of Chemical Engineering: shaping the future of chemical engineering. 2011, Barcelona, Spain
El propósito de la presente tesis es preparar una serie de recubrimientos protectores empleando polímeros conductores (CPs) como inhibidores de la corrosión. El uso de pinturas orgánicas es el método más empleado para la prevención de la corrosión. Los recubrimientos anticorrosivos forman una clase de sistemas de alto rendimiento con una amplia variedad de aplicaciones y pueden ser clasificados en dos grandes grupos: recubrimientos de altas prestaciones y recubrimientos de suaves prestaciones. El primero de ellos es el que se emplea en estructuras expuestas a ambientes muy agresivos, tales como: plataformas petrolíferas, puentes, plantas industriales químicas, contenedores, barcos, entre otros; y el último es el que se suele emplear en el exterior de ambientes industriales, ambientes urbanos, casas, oficinas, entre otros. La presente tesis consiste en un compendio de las siguientes etapas del trabajo y resultados: 1. Preparación de CPs nanoestructurados para inhibición de la corrosión: Estudio de la habilidad del Poli(N-metilpirrol) para formar estructuras nanoestructuradas y la actuación de éstas como aditivo anticorrosivo en recubrimientos orgánicos. 2. Sustitución parcial del zinc metálico en polvo habitualmente empleado en pinturas de altas prestaciones, por una pequeña cantidad de CP: Estudio del uso de pequeñas concentraciones de polianilina sal emeraldina (PAni-EB), como sustituto parcial del zinc metálico en polvo, en pinturas de imprimación epoxi marinas, con el objetivo de mantener la inhibición a la corrosión. 3. Evaluación de pigmentos anticorrosivos amigables con el medio ambiente para pinturas de imprimación alquídicas: Estudio de la sustitución de una elevada concentración de fosfato de zinc, generalmente empleado en recubrimientos de suaves prestaciones, por una concentración muy baja de PAni-EB (forma no-dopada), PAni-ES (forma dopada) y un derivado del politiofeno (parcialmente dopado) en un recubrimiento alquídico, y el estudio de sus capacidades protectoras empleando ensayos de corrosión acelerados. 4. Preparación de una nueva pintura epoxi, basada en DMSO como disolvente ecológico y libre de pigmento anticorrosivo de zinc, y su aplicación para la protección de acero al carbono: Formulación y evaluación de una nueva pintura epoxi basada en DMSO como solvente y empleando PAni-EB y poli[2, 2’-(3-metilacetato)tiofeno] como nuevos pigmentos anticorrosivos. Todos los resultados obtenidos en la presente tesis han sido aceptados o han sido enviados para publicación en revistas internacionales; además, algunos resultados han sido divulgados recientemente en congresos internacionales, tal y como se describe abajo: 1. M. Martí, G. Fabregat, F. Estrany, C. Alemán, E. Armelin, “Nanostructured conducting polymer for dopamine detection”, J. Mater. Chem., 2010, 20, 10652-10660. 2. E. Armelin, M. Martí, F. Liesa, J.I. Iribarren, C. Alemán, “Partial replacement of metallic zinc dust in heavy duty protective coatings by conducting polymer”, Prog. Org. Coat., 2010, 69, 26-30. 3. M. Martí, G. Fabregat, D.S. Azambuja, C. Alemán, E. Armelin, “Evaluation of an environmentally friendly anticorrosive pigment for alkyd primer”, Prog. Org. Coat., 2012, 73, 321–329. 4. M. Martí, L. Molina, C. Alemán, E. Armelin, “Replacement of toxic solvents and anticorrosive pigments used in solvent-borne epoxy coatings by safer functional organic compounds”, enviado para publicación en Journal of Hazardous Materials, 2013. 5. M. Martí, E. Armelin, J. Iribarren, C. Alemán. Soluble polythiophenes as anticorrosive additives for marine epoxy paints”, enviado para publicación en Materials and Corrosion, 2013. 6. G. Fabregat, M. Martí, F. Estrany, C. Alemán, E. Armelin, E-MRS 2010 Spring Meeting. 2010, Strasbourg, France. 7. E. Armelin, M. Martí, F. Estrany, C. Alemán, 12th Mediterranean Congress of Chemical Engineering: shaping the future of chemical engineering. 2011, Barcelona, Spain.

Ces travaux de thèse avaient pour but de formuler, de caractériser et de valider un pain élaboré à partir de farines sélectionnées pour améliorer son pouvoir satiétogène. Fort est de constater que depuis plusieurs décennies, la prévalence du surpoids et de l'obésité est croissante. Les risques liés à l'obésité ont un impact sur l'espérance de vie qui stagne dans certains pays développés. Pour lutter contre cette pandémie, la consommation de fibres alimentaires semblerait avoir un effet positif sur la diminution de la sensation de faim, sur la diminution des prises caloriques ainsi que sur la diminution du poids chez des personnes obèses. Ainsi, ce travail de thèse a d'abord consisté à formuler deux pains expérimentaux enrichis en fibres : un pain typé " pain complet " (PF1) et un pain typé " pain aux céréales ". (PF2) Afin de valider les effets de ces pains sur l'organisme, deux types d'études ont été menés : des études à court terme et des études à long terme. Deux études ont été réalisées à court terme. La première étude a montré que le pain le plus enrichi en fibres était considéré comme plus rassasiant qu'un pain de mie blanc, et les participants diminuaient les quantités consommées pour ce type de pain. La deuxième étude a montré que la réapparition de la faim était plus lente pour le pain le plus riche en fibres. Enfin, une étude à long terme menée auprès de participants normopondéraux consistait à proposer une quantité fixe et importante des pains PF1 et PF2 au petit-déjeuner. Au bout de 15 jours d'exposition, les participants déclaraient avoir moins faim suite à la consommation de ces pains enrichis en fibres. De plus, pour le pain PF1, les participants diminuaient leur prise calorique comparativement à une situation contrôle. Au final, l'ensemble de ces études a permis de cibler un pain expérimental et un paradigme à suivre pour une étude menée auprès de participants en surpoids et obèses dans le cadre d'un régime amaigrissant, pour améliorer le bien-être lié au vécu de ce régime.

Aujourd’hui, le marché de la peinture automobile est gouverné par une demande pour des couleurs profondes et vives avec effets. Dans le domaine de la peinture automobile, l’exigence est très haute car la couleur est associée à un signe de qualité. Dans une collision classique, différentes parties du véhicule peuvent être endommagées avec généralement une partie de la carrosserie qui est touchée. La partie endommagée doit être réparée, poncée et préparée avant d’être repeinte. Pour réduire les coûts, le carrossier doit préparer une peinture avec un bon contretypage de teinte, et ce aussi vite que possible. Il s’agit donc pour la formulation de la peinture de réparation de reproduire les effets, aussi bien colorés que texturés, à partir de pigments absorbants ou à effets (particules d’aluminium, de nacre …). Il est relativement simple de qualifier les effets colorés à partir des courbes de réflectance puis des coordonnées CIELab. Cependant, la définition de la texture engendrée par les particules à effets est assez complexe et n’est encore qu’à ses prémices, avec des paramètres qui souvent ne correspondant pas aux phénomènes réellement perçus par l’œil humain. Dans le cadre de ce travail de thèse, la mobilisation de connaissances expertes à travers différentes sessions de tri libre et de brainstorming a permis la mise en évidence de descripteurs de texture réellement perceptifs. De plus, la mise en place de métriques de texture conçues à partir de préconisations réellement perceptives, a rendu possible l’obtention de valeurs correspondant à un observateur moyen pour chacun de ces paramètres descripteurs. Ces paramètres ayant été élaborés à partir des observations d‘évaluateurs expérimentés. La transposition de ces vérités terrain en descripteurs physiques de texture a permis l’obtention d’une corrélation entre le perceptible et le mesurable. Dans la procédure développée, l’œil humain a été remplacé par un appareil photo numérique agissant en qualité d’intégrateur tristimulaire d’informations radiométriques. En essayant de reproduire les conditions d’observation lors de la phase d’acquisition d’images, il a été ainsi possible de caractériser les phénomènes de texture par analyse d’image et de les corréler aux valeurs de l’observateur moyen préalablement défini
Nowadays, the automotive coating market is governed by a demand for deep and vibrant colors with effects. In this field, the requirement is very high because the color is associated with a sign of quality. In a typical collision, different parts of the vehicle may be damaged. The damaged part must be repaired, sanded and prepared before being painted. To reduce costs, the body shop must then prepare a paint with a good color matching, and thus as fast as possible. It is therefore necessary for the formulation of the repair coating to reproduce the effects, both colored and textured, from absorbent or effect pigments (aluminum particles, pearlescent materials …) from a characterization of the concerned vehicle coating. It is relatively simple to qualify the colored effects from the reflectance curves and then the CIELab coordinates. However, the description of the texturing effect generated by the distribution of effect particles at the microstructure scale is quite complex. The metrological approach of the perceptive properties is still at its beginnings. The parameters used do not necessarily correspond directly to the phenomena actually perceived by the human eye. As part of this thesis work, the mobilization of expert knowledge through various sessions of free sorting and brainstorming on coated samples made it possible to highlight really perceptive texture descriptors. These descriptors have been the subject of "objective" evaluations by experienced observers. They thus made it possible to associate a quantitative evaluation scale with each descriptor. This stage of the present thesis work allowed the establishment of ground truth data materialized by a set of reference samples representing different ordered levels of a descriptor. These ground truth data were then used to design a set of measurable physical texture descriptors that were directly correlated to perceptual scales constructed in the previous step. In the procedure developed, the human eye has been replaced by a digital camera acting as a tristimulus integrator of radiometric information. The image acquisition phase was a decisive step in the process: it was necessary to reproduce the conditions of evaluation of the properties perceived, recognized and retained during the various stages using expert human observers. It was then possible to characterize the texture phenomena by image analysis and to correlate them with the values of the previously defined mean observer

La terre est le premier matériau de construction par les hommes, disponible et peu consommateur d’énergie. Aujourd’hui encore, environ 30 % des habitants de la planète vit dans des habitats en terre, et pour les pays en développement, ce pourcentage s’élève à 50 % de la population rurale. De plus, les matériaux à base de terre permettent un meilleur équilibre et contrôle du climat thermique et acoustique intérieur par rapport aux matériaux usuels de construction. Cependant, la majorité des constructions en terre ne répondent pas aux exigences actuelles en termes de contraintes mécaniques, thermiques ou architecturales. Afin de répondre à ces exigences, un travail tant au niveau scientifique qu’au niveau des praticiens est à accomplir dans ce domaine.L’objectif de cette étude est de déterminer l’influence des propriétés des matériaux utilisés sur le comportement mécanique et hygrothermique de composites terre-fibres végétales. Pour cela, différents types de sols et de fibre végétales (paille de lin, paille de blé) ont été utilisés. Ensuite, les performances mécaniques (compression, flexion) et hygrothermiques (sorption/désorption, perméabilité à la vapeur d’eau, conductivité thermique) ont été déterminées pour différents composites terre-fibres végétales. Les résultats montrent que l’utilisation de paille de lin permet d’obtenir des performances mécaniques supérieures à celles obtenues pour la paille de blé. Cependant, il est à noter que l’introduction de fibres aux sols diminue les performances mécaniques due à la diminution de la densité du matériau. Aucune influence claire de la longueur des fibres sur les performances mécanique n’a été constatée. L’étude du comportement hygrothermique a permis de montrer que le comportement à la sorption/désorption du matériau terre-fibres végétales peut être approximer à partir des résultats obtenus pour les matériaux de base. De plus, il a été démontré que l’évolution de la conductivité thermique du matériau terre-fibres végétales au cours du séchage est reliée au comportement au retrait
Soil is the first construction material used by man, widely available and low energy consuming. Indeed, about 30% of the current world population lives in earthen structures and, in developing countries, this rate rise to 50%, mostly rural. Moreover, earth-based materials allow an improved balance and control of thermal and acoustic indoor climate compared to industrial construction materials. However, most of earthen structures do not reach current requirements in terms of mechanical, thermal or architectural. To respond to these requirements, a work at scientific and craftsman levels is necessary.The objective of this study is to determine the influence of materials’ properties on the mechanical and hygrothermal behaviour of earth-fiber composites. In order to do this, different types of soil and plant fiber (flax straw, wheat straw) were used. Then, mechanical (compression, bending) and hygrothermal performances (sorption / desorption, water vapor permeability, thermal conductivity) were determined for different soil-fiber composites. Results show that the use of flax straw provides better mechanical performances than use of wheat straw. However, it should be noted that fibers addition to soil decreases mechanical performance due to the decrease of material density. No clear influence of fiber length on mechanical performance was found. The study of hygrothermal behaviour has shown that the sorption / desorption behaviour of earth-fiber material can be approximated from the results obtained from basic materials. In addition, it has been shown that the thermal conductivity evolution of earth-fiber material during drying is related to the shrinkage behaviour

La structure alvéolaire et la fermeté de la mie des produits céréaliers de cuisson sont deux facteurs de qualité que la profession cherche à maîtriser. Dans ce contexte, des outils d'aide à la décision proposant, notamment, l'apport des paramètres de composition et du procédé intervenant dans la construction de la structure alvéolaire seraient utiles. Une série de « pains de mie enrichis », contenant les composants de base du pain (farine, eau, sel, levure) plus du saccharose et de l'huile de colza, a été fabriquée. Les gammes de concentration en eau, huile et saccharose, respectivement 50-60%, 2-20% et 0-15% (p/p base farine) ont été choisies de manière à fabriquer des produits de masse volumique réaliste par rapport aux produits du commerce (0,25-0,36 g/cm3) et de structures alvéolaires variées : mies fines ou grossières, homogènes ou hétérogènes. Les produits ont été caractérisés à toutes les étapes de leur fabrication en utilisant différentes techniques permettant l'observation de la structure et l'étude des propriétés rhéologiques et thermiques du produit. Ces techniques ont été choisies en fonction de l'échelle souhaitée et des propriétés à caractériser. Parmi elles, la microscopie, la rhéologie, l'analyse calorimétrique différentielle, l'analyse d'images, l'analyse sensorielle. En sélectionnant, à chaque étape de fabrication les paramètres pertinents et indépendants, et en analysant, ensuite, les corrélations toutes étapes confondues, il apparaît, notamment, que, pour la gamme de compositions étudiées dans ce travail, la masse volumique du produit alvéolaire dépend essentiellement de la viscosité et du caractère rhéofluidifiant de la pâte. La finesse de la mie est corrélée à la valeur de tan δ mesurée à l'issue du gonflement des grains d'amidon, et une fois que le réseau de gluten a thermocoagulé. L'hétérogénéité de la mie semble liée au niveau du caractère rhéodurcissant de la pâte en fin de fermentation. L'étude systématique de l'effet composition (farine, huile et saccharose) permet également de proposer des pistes de choix de compositions permettant l'obtention de structures alvéolaires souhaitées.

Ces travaux ont pour objectif de décrire l’impact de la congélation et de la précuisson, ainsi que l’impact d’ingrédients à bénéfice santé sur le développement de l’arôme du pain. Les propriétés physiques et la flaveur globale des produits ont été analysées sensoriellement et instrumentalement. Ce travail a nécessité l’optimisation d’une technique d’extraction des composés volatils permettant d’obtenir des extraits représentatifs de l’odeur du pain. Deux techniques d’extraction en conditions dynamiques ont ensuite été développées : un prototype de bouche artificielle qui reproduit les conditions de mastication en bouche humaine et qui extrait les composés volatils responsables de l’arôme du pain, ainsi qu’un système assurant le piégéage des composés volatils libérés au cours de la cuisson des pains. Il a été demontré que les étapes de précuisson et de congélation n’avaient pas d’influence sur la qualité organoleptique des produits pour un même niveau de cuisson. L’analyse de différentes formules avec des qualités nutritionnelles améliorées (pain sans gluten, pain enrichi en fibres (inuline), pain complet enrichi en phytase) a mis en évidence l’impact de ces formulations sur le profil aromatique du pain. Il a alors été démontré que l’ajout d’inuline accélère la cuisson des pains. De plus, pour un même niveau de cuisson, l’inuline modifie peu la perception des pains, ce qui en fait une perspective intéressante pour améliorer leur qualité nutritionnelle sans modifier leur appréciation par les consommateurs. Par ailleurs, l’étude de la cinétique de cuisson de ces pains a permis d’identifier des indicateurs physiques de l’évolution de la réaction de Maillard
This work aims to describe the impact of freezing and partbaking, as well as the impact of functional ingredients on the development of the aroma of bread. The physical properties and the overall flavor of the products were analyzed sensory and instrumentally. This work required the optimization of an extraction technique of volatile compounds to obtain extracts representative of the smell of bread. Two extraction techniques in dynamic conditions were then developed: an artificial mouth device that mimics the conditions of human mastication and which was able to extract the volatile compounds responsible for the aroma of bread, and a system which permits the trapping of volatile compounds released during the baking of bread. Results demonstrated that the freezing and partbaking stages did not affect the organoleptic quality of products. The analysis of different formulations with improved nutritional qualities (gluten-free bread, bread enriched with fiber (inulin), bread enriched with phytase) highlighted the impact of these formulations on the flavor profile of the bread. It was shown that adding inulin accelerates bread baking. In addition, for the same level of baking, inulin modifies a little the perception of breads, which makes it an attractive prospect to improve their nutritional quality without affecting their appreciation by consumers. Furthermore, the study of the kinetics of the bread baking permitted to identify physical indicators of the evolution of the Maillard reaction

Le pétrissage et la fermentation des pâtes constituent deux étapes clé de la panification. Lors du pétrissage, l'oxygène incorporé à la pâte alimente en substrat oxydant les réactions d'oxydation, pour la plupart enzymatiques, conduisant au développement des réseaux de gluten et d'arabinoxylanes donnant à la pâte ses propriétés viscoélastiques et son aptitude à la rétention gazeuse. Lors de la fermentation, la production de dioxyde de carbone par la levure conditionne la levée du pâton. Un pétrin-fermenteur étanche, le sitoxygraphe, a été utilisé pour quantifier, à tout instant au cours du pétrissage et de la fermentation, la consommation d'oxygène et la production de dioxyde de carbone en distinguant la part de CO2 qui est retenue par la pâte de celle qui apparaît dans la phase gazeuse. Une modification de la formulation de la pâte de farine de blé – par l'ajout, seul ou en mélange, de levure, d'oses oxydases, de farine de fève ou de soja, de lipases – augmente sa consommation d'oxygène, et affecte sa teneur en acides gras polyinsaturés, son état d'agrégation des protéines et ses propriétés rhéologiques. Il existe, par exemple, une compétition pour l'utilisation de l'oxygène entre la levure, qui respire durant le pétrissage, et les oxydoréductases endogènes ou exogènes. Elle se traduit par une diminution des effets biochimiques et rhéologiques des oxydoréductases exogènes. L'utilisation d'atmosphères enrichies en oxygène en début de pétrissage devrait permettre de limiter ces compétitions et donc d'amplifier l'activité des oxydoréductases exogènes
Kneading and fermentation of dough are two key steps in bread making. During kneading, incorporated oxygen into dough supplies in oxidizing substrate oxidation reactions, most of them are enzymatic, leading to the development of gluten and arabinoxylans networks giving dough viscoelastic properties and its ability to gas retention. During fermentation, the production of carbon dioxide by yeast determines the volume increase of the dough. An airtight knerder-fermenter, the sitoxygraphe, has been used to quantify, at any moment during of kneading and fermentation, oxygen consumption and carbon dioxide production by distinguishing the part of CO2 that is retained by dough from that which appears in the gas phase. A modification of dough formulation prepared with wheat flour - by adding one or a mix of, yeast, oses oxidases, horse bean or soybean flour, lipases - increases oxygen consumption and affects its content of polyunsaturated fatty acids, its protein aggregation and its rheological properties. For example, there is a competition for the use of oxygen between the yeast, which breathes during kneading and endogenous or exogenous oxidoreductases. It results in a decrease of rheological and biochemical effects of exogenous oxidoreductases. The use of atmospheres enriched with oxygen at the beginning of kneading should allow limiting these competitions and amplifying exogenous oxidoreductases activity

Endometrios är en vanlig gynekologisk problematik som ofta är smärtsam. Trots att flera studier påpekar hög prevalens av psykiatrisk komorbiditet bland kvinnor med endometrios och att psykoterapeutiska och psykologiska insatser förordas så finns mycket lite forskning kring psykologisk behandling vid endometrios. Den här studien var explorativ och undersökte kvantitativa effekter och kvalitativa detaljer från tre fallstudier av kognitiv beteendeterapi vid smärtsam endometrios. Behandlingen innehöll fyra behandlingsmoment; psyko-edukation, fallformulering, beteendeförändring/exponering samt mindfulness och gavs i komprimerad form vid fem behandlingssessioner. Behandlingarna föll väl ut och fick positiva utvärderingar av samtliga patienter. Resultaten var blandade men vissa förbättringar kunde ses. En patient hade i slutet av studien ökad livskvalitet, sänkt nedstämdhet, minskad katastrofiering, ökad aktivitet och sänkt funktionsnedsättning. Den andra patienten beskrev behandlingen positivt men fick få utslag i mätningar utöver tendens till minskad katastrofiering. I slutet av studien färgades hennes mätningar av förändrat hälsotillstånd, som antagligen överskuggade eventuella positiva effekter av behandlingen. Den tredje patienten hade svårigheter med att följa behandlingsplanen och hade en varierande funktionsnivå. Problem uppstod kring hennes mätresultat men de visade tendens till ökad livskvalitet, minskad katastrofiering och minskad funktionsnedsättning. Resultaten ses som lovande och ytterligare utveckling av kognitiv beteendeterapeutisk behandling vid smärtsam endometrios föreslås.
Endometriosis is a common gynecological disorder which is often painful. Dispite several studies remarking on the high prevelence of psychiatric comorbidity among women with endometriosis, and that psychological treatments are recommended, there is very little research of psychological treatment of endometriosis. This study was explorative and investigated quantitative effects and qualitative details from three case studies of cognitive behavioural therapy for painful endometriosis. The treatment contained four components: psychoeducation, case formulation, behavioural change/exposure, and mindfulness. The treatment was given in a short form of five sessions. The treatments went well and reseaved positive evalutations from all patients. The results were mixed, but some improvements were noticed. One patient had at the end of the study elevated life quality, reduced depression, reduced catastrophizing, increased activity and reduced disability. The second patient described the treatment positively, but showed few changes apart from tendency to reduced catastrophizing. At the end of the study her results were affected by changes in her physical condition, which probably overshadowed any positive results from the treatment. The third patient had difficulties with following the treatment plan, and had a variable level of functioning. Problems arose with her measures, but the measures showed tendency to improved life quality, reduced catastophizing and reduced disability. The results of the study are promising and further development of cognitive behavioural therapy for painful endometriosis are suggested.

碩士
國立臺灣大學
森林學研究所
87
The objectives of this study are to explore the effective formulation of intumescent fire retardant paints for wood-based material. They were prepared by varying chemical kinds and their mixing ratio, and evaluated according to CNS 13552 and CNS 6532 for combustibility, CNS 10757 for durability. The experimental results are summerized as follows: 1. Char-forming agent is important to the formation of fire- retardant paint. The ratio of char-forming agent and main binder in the paint( using pentaerythritol for char-forming agent and polyvinyl acetate emulsion resin for binder in this experiment) must be higher than 3/2 to meet the requirement of Grade 3 incombustibility test as specified in CNS 6532.And the ratio of dehydrating agent and blowing agent between 1/1 and 3/2 (ammonium polyphosphate/melamine in this study) in the formation of fire-retardant paint will have the best synergism .So, we can understand that the best formation of fire-retardant paint is PVAc15%, PER35%, Melamine25% and APP25% (paint B3) or Melamine20% and APP30% (paint B4) in 60% solid content. 2.The more weight percentage of nitrogen in blowing agent , it shows the better fire-resisting proformance. 3.We can evaluate the smoke evolution、weight loss and the thickness of blowing layer with the results of CNS 6532 by measuring the blowing-layer thickness with the “burn through” method.

碩士
國立臺灣大學
森林學研究所
92
The main purpose of wood treated with fire retardants is to improve safety in case of fire. The objective of this study is to discuss the effective fire-retardant property and coating performance of intumescent fire retardant paint in using different binding resin. The research methods are using different mixing ratios of different binding resins with acid precursor, carbon source and blowing agent to manufacture intumescent fire retardant paints. In order to know coating property of fire retardant, pyrolysis and heat of combustion, the intumescent fire retardant paint was evaluated by surface testing machine, thermalgravimetric analyzer and oxygen bomb calorimeter. The experimental results are summarized as follows: 1. In fire-retardant test, the best combination ratio of binding resin and carbon source is 15/35. The worst performance of four binding resins is the styrene monomer contained resin. The best two are EVA and VAC resin. 2. The best fire-retardant performance of four binding resins is the Vinyl acetate contained resin. 3. In terms of tdθ and tdθ1 values of CNS 6532, utilizing binding resin only is not enough to form the layer of char to be fire-retardant; therefore, the said resin must add extra carbon sources to form the said layer. 4. To reduce or change the heat of combustion in polymer materials will make protect material being uneasy to burn after firing.

博士
國立成功大學
化學系碩博士班
94
ABSTRACT Buprenorphine, an opioid analgesic, is used not only for the treatment of pain but also for the treatment of physical dependence to opioids. Because, in clinical practice, a long-acting drug is inspired, extending the duration of buprenorphine would make it more valuable for clinical use.The aim of this dissertation was to design and develop a series of novel long-acting formulations of buprenorphine and its derivatives for the treatment of pain and opioid dependence. The major works included in this study were: 1. design and development of novel formulations of buprenorphine and its prodrugs, 2. evaluation of the analgesic effect of these formulations, 3. study the mechanism of their actions, 4. evaluation of the effect of these formulations on physical dependence to morphine. The results of the dissertation included: 1. the long-acting formulations of buprenorphine and its prodrugs were developed, 2. the analgesic effects of long-acting formulations of buprenorphine and its prodrugs were confirmed. Among these formulations, buprenorphine decanoate demonstrated the longest duration of action, 3. in in vivo study, buprenorphine prodrugs were completely converted to buprenorphine and the mechanism of their long-acting effect was due to the slow release of prodrugs from the injection site, and 4. the long-acting formulations of buprenorphine and its prodrugs were effective in the management of physical dependence to morphine. Buprenorphine propionate demonstrated a rapid onset and long-duration of action of 171 hours.