No / A comprehensive study has been undertaken into a 13th century Coptic-Byzantine icon from the St. Mercurius Church, St. Mercurius monastery, Old Cairo, Egypt. The layered structure, pigment composition and varnish identification were revealed by means of optical and Raman microscopy and gas chromatography¿mass spectrometry (GC¿MS). The structure of the icon comprised six layers; wooden panel, canvas, white ground, two bole layers and a single paint layer. Azurite (2CuCO3·Cu(OH)2), cinnabar (mercuric (II) sulfide ¿-HgS), yellow ochre (Fe2O3·H2O), hydromagnesite Mg5(CO3)4(OH)2·4H2O and lamp black (carbon, C) are the pigments identified in the icon. The green paint area is of interest as it is applied neither with a green pigment nor with a mixture of a blue and yellow pigment. Instead, a yellow layer of dammar resin was applied on top of blue azurite to obtain the green colour. Pinaceae sp. resin mixed with drying oil was used as a protective varnish.

This thesis describes how life history characteristics of the varnish clam (Nuttallia obscurata), and interactions with the physical environment and other species, have contributed to its successful invasion in coastal British Columbia. Lab and field experiments were conducted to investigate varnish clam larval ecology (i.e. larval rearing experiments), adult population dynamics (i.e. annual population surveys, mark-recapture and length-frequency analysis, growth modeling) and ecological interactions with native species (i.e. predator/prey preference feeding trials). Using these results, a matrix demographic model was developed to determine which life history stage contributes the most to varnish clam population growth. Larval rearing experiments indicated that temperature and salinity tolerances of varnish clam larvae are comparable to native species, however the planktonic phase is slightly longer (3-8 weeks). Based on local oceanographic circulation, varnish clam larvae have the potential to disperse throughout their entire geographic range in just one reproductive season. Varnish clam population surveys revealed spatiotemporal variation in density and size. No relationships were evident between varnish clam density and the number or density of co-occurring bivalve species. Length-frequency analysis suggested that recruitment varies among sites, with high post-settlement mortality coinciding with high recruitment. The presence of similar recruitment pulses at geographically separate sites indicates regional scale processes may influence recruitment. Individual growth rates iii varied among sites, with higher growth corresponding to lower population densities and water temperature. Monthly survival rates ranged from 0.81 – 0.99 and were lower for clams 10-30 mm. Predator/prey preference feeding trials showed that crabs prefer varnish clams to local species when clam burial depth is limited. Crabs therefore have the potential to influence varnish clam distributions, particularly on beaches where the varnish clam is unable to bury deeply. Based on matrix demographic analysis, adult survival (e.g. clams ≥ 40 mm) is the most crucial factor for varnish clam population growth, and drives the observed population growth differences between sites. This study of the varnish clam invasion demonstrates that its success lies in both species (e.g. lengthy planktonic phase, high survival) and regional (e.g. favourable ocean circulation patterns for rapid dispersal) characteristics. Measures to reduce introductions should be targeted in areas where introductions are likely to have the furthest reaching impacts.

CAPES; CNPq; Fundação Araucária / Esta tese de doutorado apresenta um sistema de monitoração heterogêneo para a caracterização do processo de secagem e cura de filmes poliméricos e resina odontológica. Essa caracterização é de suma importância para aperfeiçoar o processo de fabricação e a escolha das matérias-primas dos mesmos, uma vez que parâmetros como a variação da espessura e a deformação mecânica no material estão diretamente ligadas à sua qualidade e durabilidade. O sensor heterogêneo emprega técnicas complementares para a quantificação de múltiplos parâmetros físicos, visando a compreensão das etapas que acontecem durante o processo de secagem e cura. Os ensaios se deram em períodos de 24 horas analisando amostras de tinta e verniz acrílicos e resina dentária. Foram quantificadas deformações longitudinais, variação de massa, espessura e índice de refração médio. Nas amostras de tinta e verniz acrílicos, obteve-se redução entre 60% e 70% no valor inicial da espessura, enquanto o comportamento do índice de refração do verniz foi associado às diferentes etapas do processo de secagem. As amostras de resina odontológica apresentaram redução da espessura menor que 5% em todos os ensaios realizados, percentual semelhante à variação do índice de refração. Todavia, as redes de Bragg identificaram um aumento de temperatura da resina odontológica de aproximadamente 20°C durante a fotoativação. A flexibilidade do sistema sensor heterogêneo demonstrado permite a análise do processo de secagem ou cura de uma ampla gama de filmes poliméricos e resinas, sem a necessidade de adaptações significativas no arranjo experimental. Com uma caracterização correta das etapas envolvidas na secagem ou cura, todo o processo que vai desde a formulação do produto à aplicação final pode ser otimizado, levando à melhoria da relação custo-benefício para cada aplicação pretendida. / This thesis presents a heterogeneous system to characterize the drying and curing process of polymer films and dental resin. This characterization is important to improve the manufacturing process and the choice of the raw materials, since parameters such as thickness variation and the mechanical deformation in the material are directly related to their quality and durability. The sensor employs heterogeneous complementary techniques for the quantification of multiple physical parameters, aimed to understand the steps that occur during drying and curing. The tests took place in periods of 24 hours analyzing samples of both acrylic paint and varnish, as well as dental resin. Longitudinal deformation, mass variation, thickness and mean refractive index were quantified. In samples of acrylic paint and varnish, a reduction between 60% and 70% in the initial value of the thickness was obtained, while the behavior of the refractive index of the varnish was associated with the different stages of the drying process. Samples of dental resin presented thickness decreasing less than 5% in all tests, percentage similar to the variation of the refractive index. However, fiber Bragg gratings have identified a temperature increase of the dental resin about 20 ° C during the polymerization. The flexibility of the heterogeneous sensor system demonstrated allows the analysis of drying or cure processes of a great variety of polymer films and resins, without the need for important changes in the experimental setup. With the correct characterization of the stages involved in the drying or cure, the whole process from the product formulation to the final application may result in an optimized and cost effective product for any intended application.

This work deals with properties of electro insulating varnishes and composite materials. The general aim is to study the influence of nanoparticles on dielectric properties of electro insulating varnishes.

Indiana University-Purdue University Indianapolis (IUPUI) / The majority of currently marketed fluoride varnishes (FV) have not been evaluated for their effectiveness in preventing dental caries. Fundamental research on FVs and how different formulations affect adherence to teeth, fluoride release into saliva and uptake by teeth is virtually non-existent. The objective of this work was to investigate the anti-caries potential, measured as fluoride release into saliva, change in surface microhardness of early enamel caries lesions, and enamel fluoride uptake, of multiple commercially available FVs. We have found that FVs differed in their release characteristics, rehardening capability, and ability to deliver fluoride to demineralized lesions. In addition to our in vitro work, we have conducted a clinical study that aimed to compare saliva and plaque fluid fluoride concentrations following the application of three commercially available FV treatments at predetermined post application time points. We also investigated the change in fluoride concentration in saliva and plaque fluid fluoride from baseline to each post application predetermined time point. We found that FVs varied in their release of fluoride into saliva and plaque fluid but shared common trends in release characteristics. The outcomes of our in vitro and in vivo investigations demonstrate a great variation in anti-caries potential of FVs. This may be attributed to different compositions and physical properties of the tested FVs.

Un modèle pharmacocinétique à base physiologique (PBPK) d’exposition par inhalation à l’éthanol a antérieurement été développé en se basant sur des données provenant d’une étude chez des volontaires exposés par inhalation à plus de 5000 ppm. Cependant, une incertitude persiste sur la capacité du modèle PBPK à prédire les niveaux d’éthanolémie pour des expositions à de faibles concentrations. Ces niveaux sont fréquemment rencontrés par une large partie de la population et des travailleurs suite à l’utilisation de produits tels que les vernis et les solutions hydroalcooliques (SHA). Il est ainsi nécessaire de vérifier la validité du modèle existant et de déterminer l’exposition interne à l’éthanol dans de telles conditions. Les objectifs du mémoire sont donc 1) de documenter les niveaux d’éthanolémie résultant de l’exposition par inhalation à de faibles concentrations d’éthanol (i.e., ≤ 1000 ppm) et de valider/raffiner le modèle PBPK existant pour ces concentrations ; et 2) de déterminer les concentrations d’éthanol atmosphérique provenant d’utilisation de SHA et de vernis et de prédire les niveaux d’éthanolémie découlant de leur utilisation. Les données toxicocinétiques récoltées chez des volontaires nous suggèrent qu’il est insuffisant de limiter au foie la clairance métabolique de l’éthanol lors d’exposition à de faibles niveaux d’éthanol, contrairement aux expositions à de plus forts niveaux. De plus, il a clairement été démontré qu’un effort physique léger (50 W) influençait à la hausse (2-3 fois) l’éthanolémie des volontaires exposés à 750 ppm. L’ajout au modèle PBPK d’une clairance métabolique de haute affinité et de faible capacité associée aux tissus richement perfusés a permis de simuler plus adéquatement la cinétique de l’éthanolémie pour des expositions à des concentrations inférieures à 1000 ppm. Des mesures de concentrations d’éthanol dans l’air inhalé générées lors d’utilisation de SHA et de vernis ont permis de simuler des expositions lors de l’utilisation de ces produits. Pour l’utilisation de 1,5 g et 3 g de SHA dans un local peu ventilé, des concentrations sanguines maximales (Cmax) de 0.383 et 0.366 mg.L-1 ont été respectivement simulées. Dans un local bien ventilé, les Cmax simulées étaient de 0.264 et 0.414 mg.L-1. Selon les simulations, une application de vernis résulterait en une Cmax respectivement de 0.719 mg.L-1 et de 0.729 mg.L-1, chez les hommes et femmes. Les Cmax sanguines d’éthanol estimées suites aux différentes simulations sont inférieures à la concentration toxique pour les humains (100 mg.L-1). Ainsi, de telles expositions ne semblent pas être un danger pour la santé. Les résultats de cette étude ont permis de mieux décrire et comprendre les processus d’élimination de l’éthanol à faibles doses et permettront de raffiner l’évaluation du risque associé à l’inhalation chronique de faibles niveaux d’éthanol pour la population, particulièrement chez les travailleurs. / A physiologically based pharmacokinetic model (PBPK) on inhalation exposure to ethanol has previously been developed based on data from an inhalation study in volunteers exposed to more than 5000 ppm. However, there remains uncertainty about the ability of the PBPK model to predict the blood levels of ethanol (BLE) for exposure to low concentrations. These levels are frequently encountered by a large part of the population and workers by using products such as varnishes and alcoholic solutions (HAS). It is therefore necessary to verify the validity of the existing model and determine the internal exposure to ethanol in such conditions. The objectives of this master’s thesis are 1) to document the BLE resulting from inhalation exposure to low concentrations of ethanol (i.e., ≤ 1000 ppm) and validate/refine the existing PBPK model for these concentrations, and 2) to determine the atmospheric concentrations of ethanol following the use of alcoholic solutions (HAS) and varnish as well as to predict the BLE resulting from their use. Toxicokinetic data collected from volunteers suggest that it is insufficient to limit metabolic clearance of ethanol to the liver during exposures to low levels of ethanol, unlike exposures to stronger levels. In addition, it was clearly demonstrated that light exercise (50W) increased (2-3 fold) the BLE in volunteers exposed to 750 ppm. An addition to the PBPK model of a metabolic clearance of high affinity and low capacity associated with richly perfused tissue was performed to simulate more accurately the toxicokinetic data from low and high ethanol exposure levels. Measurements of ethanol concentrations in inhaled air generated during the use of HAS and varnishes were used to simulate the exposure during the use of these products. The simulation for HAS, for 1.5 g and 3 g, gave a maximum blood concentration (Cmax) of 0.383 and 0.366 mg.L-1 respectively in a poorly ventilated room. In a well-ventilated room, the simulated Cmax for 1.5 g and 3 g of HAS were 0.264 and 0.414 mg.L-1, respectively. The simulation results from the use of ethanol-based varnish yielded a Cmax for men and women of 0.719 and 0.729 mg.L-1 respectively. The blood Cmax of ethanol previously listed for the various simulations are well below the toxic dose for humans (50 mg.L-1). Thus, such exposures do not seem to be a health hazard. The results of this study helped to better describe and understand the elimination of ethanol at low doses and refine the evaluation process associated with chronic inhalation of low levels of ethanol to the population risk, particularly in workers.

Un modèle pharmacocinétique à base physiologique (PBPK) d’exposition par inhalation à l’éthanol a antérieurement été développé en se basant sur des données provenant d’une étude chez des volontaires exposés par inhalation à plus de 5000 ppm. Cependant, une incertitude persiste sur la capacité du modèle PBPK à prédire les niveaux d’éthanolémie pour des expositions à de faibles concentrations. Ces niveaux sont fréquemment rencontrés par une large partie de la population et des travailleurs suite à l’utilisation de produits tels que les vernis et les solutions hydroalcooliques (SHA). Il est ainsi nécessaire de vérifier la validité du modèle existant et de déterminer l’exposition interne à l’éthanol dans de telles conditions. Les objectifs du mémoire sont donc 1) de documenter les niveaux d’éthanolémie résultant de l’exposition par inhalation à de faibles concentrations d’éthanol (i.e., ≤ 1000 ppm) et de valider/raffiner le modèle PBPK existant pour ces concentrations ; et 2) de déterminer les concentrations d’éthanol atmosphérique provenant d’utilisation de SHA et de vernis et de prédire les niveaux d’éthanolémie découlant de leur utilisation. Les données toxicocinétiques récoltées chez des volontaires nous suggèrent qu’il est insuffisant de limiter au foie la clairance métabolique de l’éthanol lors d’exposition à de faibles niveaux d’éthanol, contrairement aux expositions à de plus forts niveaux. De plus, il a clairement été démontré qu’un effort physique léger (50 W) influençait à la hausse (2-3 fois) l’éthanolémie des volontaires exposés à 750 ppm. L’ajout au modèle PBPK d’une clairance métabolique de haute affinité et de faible capacité associée aux tissus richement perfusés a permis de simuler plus adéquatement la cinétique de l’éthanolémie pour des expositions à des concentrations inférieures à 1000 ppm. Des mesures de concentrations d’éthanol dans l’air inhalé générées lors d’utilisation de SHA et de vernis ont permis de simuler des expositions lors de l’utilisation de ces produits. Pour l’utilisation de 1,5 g et 3 g de SHA dans un local peu ventilé, des concentrations sanguines maximales (Cmax) de 0.383 et 0.366 mg.L-1 ont été respectivement simulées. Dans un local bien ventilé, les Cmax simulées étaient de 0.264 et 0.414 mg.L-1. Selon les simulations, une application de vernis résulterait en une Cmax respectivement de 0.719 mg.L-1 et de 0.729 mg.L-1, chez les hommes et femmes. Les Cmax sanguines d’éthanol estimées suites aux différentes simulations sont inférieures à la concentration toxique pour les humains (100 mg.L-1). Ainsi, de telles expositions ne semblent pas être un danger pour la santé. Les résultats de cette étude ont permis de mieux décrire et comprendre les processus d’élimination de l’éthanol à faibles doses et permettront de raffiner l’évaluation du risque associé à l’inhalation chronique de faibles niveaux d’éthanol pour la population, particulièrement chez les travailleurs. / A physiologically based pharmacokinetic model (PBPK) on inhalation exposure to ethanol has previously been developed based on data from an inhalation study in volunteers exposed to more than 5000 ppm. However, there remains uncertainty about the ability of the PBPK model to predict the blood levels of ethanol (BLE) for exposure to low concentrations. These levels are frequently encountered by a large part of the population and workers by using products such as varnishes and alcoholic solutions (HAS). It is therefore necessary to verify the validity of the existing model and determine the internal exposure to ethanol in such conditions. The objectives of this master’s thesis are 1) to document the BLE resulting from inhalation exposure to low concentrations of ethanol (i.e., ≤ 1000 ppm) and validate/refine the existing PBPK model for these concentrations, and 2) to determine the atmospheric concentrations of ethanol following the use of alcoholic solutions (HAS) and varnish as well as to predict the BLE resulting from their use. Toxicokinetic data collected from volunteers suggest that it is insufficient to limit metabolic clearance of ethanol to the liver during exposures to low levels of ethanol, unlike exposures to stronger levels. In addition, it was clearly demonstrated that light exercise (50W) increased (2-3 fold) the BLE in volunteers exposed to 750 ppm. An addition to the PBPK model of a metabolic clearance of high affinity and low capacity associated with richly perfused tissue was performed to simulate more accurately the toxicokinetic data from low and high ethanol exposure levels. Measurements of ethanol concentrations in inhaled air generated during the use of HAS and varnishes were used to simulate the exposure during the use of these products. The simulation for HAS, for 1.5 g and 3 g, gave a maximum blood concentration (Cmax) of 0.383 and 0.366 mg.L-1 respectively in a poorly ventilated room. In a well-ventilated room, the simulated Cmax for 1.5 g and 3 g of HAS were 0.264 and 0.414 mg.L-1, respectively. The simulation results from the use of ethanol-based varnish yielded a Cmax for men and women of 0.719 and 0.729 mg.L-1 respectively. The blood Cmax of ethanol previously listed for the various simulations are well below the toxic dose for humans (50 mg.L-1). Thus, such exposures do not seem to be a health hazard. The results of this study helped to better describe and understand the elimination of ethanol at low doses and refine the evaluation process associated with chronic inhalation of low levels of ethanol to the population risk, particularly in workers.

L’objectif de ces travaux a été de développer des vernis acrylate photo-polymérisables à 100% d’extrait sec, destinés à protéger des pièces thermoplastiques en polycarbonate contre les endommagements mécaniques, en particulier contre la rayure. Les relations entre la composition, la structure et les propriétés de ces revêtements ont été explorées. Pour ce faire ont été étudiées la morphologie, les propriétés thermomécaniques ainsi que la résistance à la rayure des matériaux. Cette dernière a été évaluée par des tests de micro-scratch. La cinétique de formation des réseaux polymères a elle aussi été étudiée, par photo-DSC. Tous les matériaux étudiés présentent, en analyse thermomécanique dynamique, un module élevé à l’état caoutchoutique ainsi qu’une large relaxation mécanique. Un vernis pétro-sourcé à 100% d’extrait sec, qualifié de standard, a servi de point de départ à ces travaux. Il a tout d’abord été comparé à un vernis commercial solvanté photo-polymérisable, spécialement conçu pour la protection de pièces thermoplastiques. Celui-ci s’est avéré être plus efficace en termes de résistance à la rayure. Dans un deuxième temps, a été étudiée l’influence sur les propriétés du vernis standard pétro-sourcé d’un monomère multicyclique entrant dans sa composition. La modification de son pourcentage n’a permis d’apporter aucun bénéfice en termes de résistance à la rayure. Des nanoparticules de silice, d’alumine ou de zircone, disponibles sous forme de dispersion dans un monomère acrylate, ont ensuite été incorporées dans le vernis standard pétro-sourcé. Une organisation particulière de la nano-silice et de la nano-alumine au sein des matériaux étudiés a pu être observée par microscopie électronique en transmission. Il a été constaté que le taux de charge doit être élevé pour observer une augmentation du module élastique et une amélioration de la résistance à la rayure du vernis (≥15% massique dans le cas de la nano-silice). Par ailleurs, l’ajout de 5% massique de nano-silice dans le vernis n’a conduit à aucune modification de sa cinétique de photo-polymérisation. Enfin, une partie des composés acrylate pétro-sourcés du vernis standard a été substituée par des acrylates bio-sourcés disponibles industriellement. La cinétique de photo-polymérisation des deux types de vernis est similaire. Les conclusions de la comparaison entre les vernis bio-sourcés et le vernis standard pétro-sourcé en termes de résistance à la rayure dépendent de l’épaisseur des revêtements étudiés. L’ajout d’un composé monoacrylate bio-sourcé à la formulation des vernis tend à améliorer la recouvrance élastique des revêtements de faible épaisseur. L’acrylate d’isobornyle est en particulier intéressant, car il a aussi tendance à retarder l’apparition des craquelures au cours de la rayure. / The aim of this work was to develop 100% solids photo-polymerizable acrylate coatings, intended to protect thermoplastic pieces made of polycarbonate against mechanical damage, in particular scratches. The relationships between the composition, the structure and the properties of these coatings were examined. For this purpose the morphology, the thermomechanical properties and the scratch resistance of the materials, assessed by micro-scratch tests, were studied. The kinetics of the polymer network formation was also studied by photo-DSC experiments. All the materials feature a high elastic modulus and a broad mechanical relaxation in dynamic thermomechanical analysis. A 100% solids petro-based coating (standard) constituted the starting point of this work. First it was compared to a commercial photo-polymerizable coating containing solvents, specially designed to protect thermoplastic pieces. This commercial coating turned out to be more efficient against scratches. In a second time was studied the influence of the percentage of a multicyclic monomer, taking part in the composition of the standard petro-based coating, on the properties of the latter. The modification of its proportion does not bring any advantage concerning the scratch resistance. Silica, alumina and zirconia nanoparticles, dispersed in an acrylate monomer, were then incorporated in the standard petro-based coating. A particular organization of the silica or alumina nanoparticles in the materials could be observed by transmission electron microscopy. A high filler content is required to observe an increase in the elastic modulus and an enhancement of the scratch resistance of the coating (≥15% by weight for the nano-silica). Moreover, no change of the photo-polymerization kinetics was noticed through the addition of 5% by weight of nano-silica in the coating. Finally, some of the petro-based acrylate compounds of the standard coating were substituted by commercially available bio-based acrylate monomers. Both types of coatings feature similar polymerization kinetics. The conclusions concerning the comparison of the scratch resistance of the bio-based and standard petro-based coatings depend on their thickness. The incorporation of a bio-based monoacrylate compound in low thickness coatings tends to improve the elastic recovery. Isobornyl acrylate is particularly interesting since it also tends to delay the apparition of cracks along the scratch.

Le travail présenté porte sur l’étude de la résistance à la rayure d’un vernis acrylate liquide à 100% d’extrait sec et photo-réticulable, en fonction des conditions de réticulation et d’application. Ce vernis est destiné à être appliqué sur des substrats thermoplastiques. Une première étude réalisée sur support polycarbonate a permis de mettre en évidence l’interaction entre le supporte et les monomères du vernis. La photo-polymérisation nécessite une source de rayonnement UV afin de former le réseau 3D. L’évolution de l’énergie (dose UV) et de la puissance (pic d’irradiance UV) a été décrite en fonction des différents paramètres de réglages (vitesse de défilement et position de l’échantillon sous la lampe, distance entre ces deux derniers, focalisation du rayonnement,). La résistance à la rayure des revêtements a été caractérisée par le test de microscratch qui permet de mettre en évidence la transition ductile/fragile, ainsi que le comportement élastique du système feuil/substrat et donne une information sur le travail d’adhésion, selon le mode de rupture. Ces analyses ont été complétées par la mesure du taux de conversion. Le réglage du rayonnement UV permet de modifier les propriétés finales du revêtement. Il existe également un lien entre l’angle d’incidence du rayonnement, l’épaisseur de vernis, et un préchauffage des matériaux avant l’application ou la réticulation, sur le taux de conversion et la résistance mécanique du film. La rhéologie du vernis, en vue d’une application au bol rotatif avec effet électrostatique, a été étudiée. Nous avons montré l’influence du chauffage du vernis sur la viscosité. Les essais en conditions semi-industrielles ont permis de mettre en évidence les paramètres procédés impactant l’aspect et le tendu de la pièce. / This research aimed to study the impact of the application and the curing process conditions on the UV-cured coating properties. The UV formulation is a high solid content clear-coat, containing acrylates oligomer and monomers, and developed for thermoplastics substrate, to protect them against scratches. The characterization of the coating and the polycarbonate substrate showed the interaction between the two polymers. UV irradiation is the key to create the polymer network. Several parameters can affect the evolution of its energy and intensity: the conveyor speed, the position of the sample under the bulb, the distance between the last two, and the focalisation of the UV rays. The coating is then analysed in terms of scratch resistance, by the microscratch test. This test gives information about the ductile/brittle transition, the elastic behaviour and the adhesion work. It is completed by the reticulation rate measure. These properties can be modified by the UV radiation setting and the process conditions, like the angle of the support, the coating thickness, and the thermic pre-treatment of the materials before the application or the curing. The clear coat is aimed to be sprayed by electrostatic rotary deposition. The study of the rheological behaviour of the liquid coating showed an impact of the heating on its viscosity. Semi-industrials tests allowed highlighting the process parameters in order to improve the coating levelling and appearance.

Die Kasseler Gemäldegalerie Alte Meister hat ihren Schwerpunkt in der niederländischen, flämischen und deutschen Malerei des 17. und 18. Jahrhunderts. Dazu zählt eine der größten und bedeutendsten Sammlungen von Rembrandt. Die wichtigsten und umfangreichsten Erwerbungen fanden bis zur Mitte des 18. Jahrhunderts unter den Landgrafen von Hessen-Kassel statt. Die Firnisse zahlreicher Gemälde, darunter Hauptwerke der Galerie, sind dick, stark gegilbt und verschiedentlich borkenartig craqueliert. Diese Firnisse sind vielschichtig. Mehrheitlich stammen ihre Firnisschichten von historischen Restaurierungen. Vielfach erscheint eine Firnisabnahme als wünschenswert, in einigen Fällen erweist sie sich aber als riskant und außergewöhnlich schwierig oder aus konservatorischen Gründen als unmöglich. Die Arbeit ist in drei Hauptteile gegliedert. Im ersten Teil wird die Restaurierungsgeschichte der Kasseler Galerie von den 1750er bis zu den 1960er Jahren anhand von schriftlichen Quellen dargestellt. Bedeutende historische Persönlichkeiten der Restaurierung, Maltechnik und Kunsttechnologie waren in Kassel praktisch (Alois Hauser d. Ä. und d. J.) oder als Gutachter (Kurt Wehlte und Max Doerner) tätig. Die restauratorischen Maßnahmen und verwendeten Materialien waren vielfältig. Es fanden ganzflächige und partielle Abnahmen, Dünnungen und Trennungen von Firnissen statt. Firnisse wurden in verschiedener Weise regeneriert, Gemälde wurden neu gefirnisst oder aber überfirnisst. Vielfach kommt ein sensibler Umgang mit den Kunstwerken und ihren Erhaltungszuständen zum Ausdruck. Im zweiten Teil werden die Grundlagen und Methoden der Objektuntersuchung vorgestellt. Deformationen, Rissbildungen und Schichtenstörungen an Gemälden werden auf der Grundlage ausgewählter Literatur der Lack- und Anstrichwissenschaften, der Materialwissenschaften und Bruchmechanik neu betrachtet. Wesentliche Aspekte sind die innere Spannung von Schichten, der Einfluss von Löse- und Quellungsprozessen auf ihre mechanischen Eigenschaften sowie mehrschichtige Systeme und die Interaktion der einzelnen Schichten. Für die lichtmikroskopische Untersuchung der Gemäldeoberflächen und Querschliffe werden verschiedene Grundlagen geschaffen. Eine für diese Arbeit konzipierte grafische Strukturanalyse ermöglicht die Darstellung und Auswertung der Schichtenkonstellationen sowie der Rissbildungen und Deformationen der Bildoberflächen. Es wird ein Löseversuch am Querschliff entwickelt, mit dem sich Tendenzen des heutigen Löseverhaltens mehrschichtiger Firnisse darstellen und von Lösemitteln beeinflusste Schadensprozesse rekonstruieren lassen. Die koaxiale oder Hellfeld-Beleuchtung wird als ein wesentlicher Bestandteil der lichtmikroskopischen Untersuchung von Gemäldeoberflächen und Querschliffen etabliert. Zudem werden die Möglichkeiten einer Bestimmung von originalen Firnisschichten durch eine mikroskopische Untersuchung aufgezeigt. Die erstmalige Bestandaufnahme der Sammlung, die heute ca. 1600 Werke zählt, ergibt, dass 74 Gemälde eine erhebliche Firnisgilbung und gleichzeitig auffällige Firnisdeformationen aufweisen. Der dritte und umfangreichste Teil stellt die Untersuchung von vier Gemälden als Fallstudien dar. Die ausgewählten Werke sind Bartholomeus Frans Douven, Susanna und die beiden Alten, 1722, Rembrandt, Die Heilige Familie mit dem Vorhang, 1646, Jacob Jordaens (1593-1678), Das Bohnenfest (Der König trinkt) und Melchior de Hondecoeter (1636-1695), Die weiße Henne mit Küchlein. Auf der Grundlage des maltechnischen Aufbaus und der individuellen Restaurierungsgeschichte der Gemälde werden die Schichten und Schichtenfolgen sowie die Schäden und Veränderungen der Firnisse dargestellt. Zudem wird die Wirkung von Lösemitteln bei früheren Restaurierungen rekonstruiert. Die Fallstudien geben Einblick in die Möglichkeiten, Risiken und Grenzen einer Abnahme, Dünnung oder Trennung von Firnissen mit Lösemitteln. In einer Fallstudie wird zudem eine mechanische Firnisdünnung untersucht. In drei Fallstudien werden partielle Zwischenfirnisse festgestellt, in einem Fall kann ein originaler Firnis bestimmt werden. Die mehrschichtigen Firnisse weisen vielfältige Schichtenstörungen auf, die Folge von historischen Restaurierungen sind. Auffällige borkenartige Deformationen stehen in Zusammenhang mit Vertiefungen entlang ehemaliger Firnisrisse. Im Querschliff und insbesondere im Bereich des Craquelés erkennt man das partielle Anlösen und Auflösen der Schichtgrenzen sowie die Migration von Firnis und Farbe. Die zum Teil gravierende Lösemittelempfindlichkeit der Malschicht resultiert vor allem aus den partiellen Zwischenfirnissen. Ein zusätzliches Schadensrisiko stellt das ungleiche Löseverhalten des Firnisses dar. Der Firnis wird vorrangig entlang des aktuellen und ehemaligen Craquelés ausgeschwemmt, so dass das Lösemittel dort länger direkt auf die Malschicht einwirkt. Die Ursachen dafür liegen wiederum in den Deformationen und Schichtenstörungen des Firnisses. Die mechanische Dünnung durch Abschleifen mit Firnispulver bietet eine aus konservatorischer Sicht unbedenkliche Alternative. Es werden die Möglichkeiten, aber auch die engen Grenzen ihrer Anwendung aufgezeigt. Die vorliegende Arbeit leistet einen Beitrag zur Kunsttechnologie, zur Restaurierungsgeschichte, zu Methoden und Techniken der Untersuchung und Dokumentation und schließlich zur Konzeption von praktischen Restaurierungen. / The main focus of the Old Masters Picture Gallery Kassel is on Dutch, Flemish and German paintings of the 17th and 18th centuries, including one of the largest and most significant Rembrandt collections. The most important and extensive acquisitions were made under the Landgraves of Hesse-Kassel until the mid-18th century. The varnishes of numerous paintings, among them the key works of the gallery, are thick, strongly yellowed and occasionally feature bark-like craquelures. These varnishes are multi-layered, with most layers stemming from historical conservation treatments. Quite often, varnish removal appears desirable, but in some cases it proves to be risky and extraordinarily difficult, or even impossible for conservation reasons. The paper is structured in three main sections. The first section describes the conservation history of the Old Masters Picture Gallery Kassel from the 1750s to the 1960s based on written sources. Prominent historical personalities dedicated to conservation, painting techniques and art technology were practitioners in Kassel (Alois Hauser the Elder and the Younger) or functioned as experts (Kurt Wehlte and Max Doerner). A wide variety of conservation measures and materials were applied. Complete and partial removals, thinnings and separations of varnish were conducted. Varnishes were regenerated in different ways, paintings were re-varnished or over-varnished. In many instances one can find a sensitive treatment of the artworks and their visibly aged conditions. The second section elaborates the basics and methods of object examination. Deformations, cracking and layer disruptions on paintings are reappraised based on selected literature dealing with organic coating sciences, material sciences and fracture mechanics. Crucial aspects include the internal stress of layers, the impact of dissolution and swelling processes on their mechanical qualities, as well as multi-layered systems and the interaction between individual layers. Different foundations are created for the light-microscopic examination of painting surfaces and cross-sections. A graphical structure analysis conceived for this work allows depicting and evaluating constellations of layers as well as cracking and deformations on the painting surfaces. A solubility test on the cross-section is developed, presenting tendencies of today’s solvent behaviour of multi-layered varnishes and reconstructing damage processes influenced by solvents. The coaxial or bright field illumination is established as a crucial component of the light-microscopic examination of painting surfaces and cross-sections. Furthermore, the possibilities of determining original varnish layers through light-microscopic examination are demonstrated. The first stocktaking of the collection that today comprises ca. 1.600 works comes to the result that 74 paintings reveal considerable varnish yellowing along with conspicuous varnish deformations. The third and longest section presents the examination of four paintings as case studies. The selected works are Bartholomeus Frans Douven, Susanna and the Elders, 1722, Rembrandt, The Holy Family with a Curtain, 1646, Jacob Jordaens (1593-1678), The Bean Festival (The King Drinks), and Melchior de Hondecoeter (1636-1695), The White Hen with Chicken. Based on the structure of the paintings and their individual conservation histories, the layers and layer sequences as well as damage and changes to the varnishes are described. Furthermore, the effect of solvents during earlier conservation treatments is reconstructed. The case studies give an insight into the possibilities, risks and limitations of removing, thinning and separating varnishes with solvents. In one case study, mechanical varnish thinning is also examined. In the case studies, partial intermediate varnishes are ascertained, and in one, an original varnish layer can be determined. The multi-layered varnishes reveal a range of layer defects resulting from historical conservation treatments. Conspicuous bark-like deformations are linked to depressions along former varnish cracks. In the cross-section and especially in the area of the craquelures, the partial solvating and dissolution of layer boundaries as well as the migration of varnish and paint are established. The extreme solvent sensitivity of the paint layer detected in some cases mainly results from the partial intermediate varnishes. The varying solubility of the varnish poses a further damage risk. The varnish is predominantly washed out along the current and former craquelures, so that the solvent directly affects the paint layer for a longer period of time. The reasons for this, in turn, lie in the deformations and layer defects of the varnish. Mechanical thinning by means of sanding with varnish powder offers a harmless alternative from a conservation point of view. The potentials but also strong limitations of its application are shown. This paper makes a contribution to art technology, to the history of conservation, to methods and techniques of examining and documenting, and finally to the conception of practical conservation treatments.