This thesis is an investigation of surface morphology and electronic structure of self-assembled monolayers (SAMs) and solid water films deposited on these SAMs using metastable impact electron spectroscopy (MIES) and infrared reflection-absorption spectroscopy (IRRAS). MIES uses electronically excited slow helium atoms which interact exclusively with the outermost surface layer. The results suggested that in the SAMs containing an odd number of carbon atoms the molecular orbitals localized on the terminal methyl groups are more exposed at the surface compared to those with an even number of carbon atoms. It was also established that solid water films are more uniform on a SAM substrate containing an odd number of carbon atoms. Thermal transformation of amorphous solid water to polycrystalline ice was also observed. MIES suggested that the molecular orbital of water attributed to the lone pair on the oxygen atom became less accessible at the surface upon the transformation.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(農学) / 甲第18312号 / 農博第2037号 / 新制||農||1020(附属図書館) / 学位論文||H26||N4819(農学部図書室) / 31170 / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 天野 洋, 教授 田中 千尋, 教授 松浦 健二 / 学位規則第4条第1項該当

Neste trabalho otimizou-se uma metodologia para a deposição de filmes de polianilina, PAni, na qual o substrato de vidro é inserido na solução em que se realiza a polimerização. Este método de deposição \"in situ\", feito a temperatura de O &#176C, permite obter filmes com boa uniformidade e com controle de espessura. A espessura dos filmes, da ordem de centenas de nanômetros, pode ser controlada através da concentração da solução do meio reacional. A morfologia da superfície do filme foi estudada usando a técnica de microscopia de força atômica. Os resultados mostraram que a rugosidade aumenta com a diminuição da concentração e com o tempo de deposição da camada de PAni. Para demonstrar a aplicação dos filmes de PAni foi construído um dispositivo eletroluminescente tendo o poli(-fenileno vinileno)-dodecilbenzeno sulfonato de sódio, PPV-DBS, como polímero ativo e usando uma camada de PAni como eletrodo injetor de buracos e janela transparente para a saída da luz. Mostrou-se que o dispositivo opera com uma tensão aproximadamente 3 vezes menor em comparação com um dispositivo sem a camada de PAni. / A method for deposition of polyaniline, PAni, onto glass substrates was studied. Substrates were inserted in the solution in which the polymerization reaction occurs. This method performed \"in situ\", at the temperature of 0 &#176C, gives very uniform films and allows the control of the thickness. Thickness, of the order of hundred nm, can be controlled varying the concentration of the solution in which the polymerization occurs. The morphology of the PAni layer was studied using a force atomic microscope, AFM. The roughness increased on the time of deposition of the layer and with the decrease of the concentration of the solution. In order to demonstrate the use of the PAni layer an electro luminescent device was built using as active polymer poly(-fenylene vinylene) -dodecilbenzene sulphonate of sodium, PPV-DVS, and the PAni layer as injector of holes and was transparent window for the emitted light. The device showed that it could be operated with a voltage that is three times smaller than a corresponding device without the PAni layer.

This thesis looks at the comparison between grain micromorphology of moraines, debris flows and similar accumulations. Moraine samples were taken in the Černé jezero Lake area, Bohemian Forest, in the Velická dolina Valley, High Tatras, and in the Labský důl Valley, Krkonoše Mts. Samples of debris flows and unverified accumulations were taken in the Důl Bílého Labe Valley, Krkonoše Mts., and further samples of accumulations were obtained from the valley of Prudký potok Stream, Králický Sněžník Mts., the valley of Vražedný potok Stream and Velká Kotlina, Hrubý Jeseník Mts. Sediments were examined under electron microscope and their morphological characteristics and influence of the environment were identified and described. Calculated exoscopic moraine standard was used for comparison of examined forms of relief using distance coefficients, statistical analysis were carried out which identified diagnostic characters for distinguishing moraines and debris flows. There was also calculated exoscopic standard for different types of moraines (frontal, lateral, basal). This research highlighted the differences between moraines and debris flows, and between different types of moraines. The study also proved that typical glacial microtextures, that are generally accepted, occur at similar levels on grains...

No / This study aimed at examining the biophysical characteristics of human derived keratinocytes (HaCaT) cultured on cholesteryl ester liquid crystals (CELC). CELC was previously shown to improve sensitivity in sensing cell contractions. Characteristics of the cell integrin expressions and presence of extracellular matrix (ECM) proteins on the liquid crystals were interrogated using various immunocytochemical techniques. The investigation was followed by characterization of the chemical properties of the liquid crystals (LC) after immersion in cell culture media using Fourier transform infrared spectroscopy (FTIR). The surface morphology of cells adhered to the LC was studied using atomic force microscopy (AFM). Consistent with the expressions of the integrins α2, α3 and β1, extracellular matrix proteins (laminin, collagen type IV and fibronectin) were found secreted by the HaCaT onto CELC and these proteins were also secreted by cells cultured on the glass substrates. FTIR analysis of the LC revealed the existence of spectrum assigned to cholesterol and ester moieties that are essential compounds for the metabolizing activities of keratinocytes. The immunostainings indicated that cell adhesion on the LC is mediated by self-secreted ECM proteins. As revealed by the AFM imaging, the constraint in cell membrane spread on the LC leads to the increase in cell surface roughness and thickness of cell membrane. The biophysical expressions of cells on biocompatible CELC suggested that CELC could be a new class of biological relevant material.

Alterações visuais, histoquímicas e micromorfológicas podem ser observadas em superfícies dentais submetidas ao clareamento, desencadeando sensibilidade, menor resistência ao desgaste, maior manchamento e aderência bacteriana. Uma forma de verificar a ocorrência de danos superficiais e sub-superficiais é através da permeabilidade e da avaliação superficial por meio de microscopia eletrônica de varredura. Assim, este estudo in vitro teve por objetivo avaliar a eficácia de clareamento em dentes manchados, a permeabilidade e a morfologia superficial do esmalte dental após tratamento com diferentes técnicas de aplicação do peróxido de hidrogênio a 35% (FGM) seguido ou não da aplicação de flúor. Foram utilizados 260 incisivos bovinos, com superfícies de esmalte de 10x10 mm de área. Após, os espécimes foram casualmente distribuídos (n = 10) e submetidos ao manchamento com café, chá preto e vinho tinto por 72 horas. As medidas de cor eram realizadas com espectrofotômetro de reflexão nos tempos inicial, após o manchamento e logo após a fase de clareamento. Após o período de manchamento os fragmentos eram clareados com peróxido de hidrogênio a 35% (FGM) - convencional, ativado com LED ou laser de Er:YAG seguido ou não da aplicação de flúor (Desensibilize KF 2%, FGM). Os grupos controles eram expostos: a saliva artificial e a aplicação de flúor + saliva artificial. O tratamento clareador foi realizado de acordo com as recomendações do fabricante. No restante do período diário, os espécimes eram imersos em saliva artificial. A seguir, os fragmentos foram subdivididos em dois fragmentos de aproximadamente 5x5 mm de área, sendo um submetido à avaliação da permeabilidade e o outro a avaliação da superfície do esmalte através de microscopia eletrônica de varredura. O método de coloração histoquímica foi utilizado para evidenciar a extensão da permeabilidade no esmalte. Do esmalte eram obtidos três cortes avaliados em microscopia óptica, através de um software de digitalização de imagem (Axion Vision 3.1) verificando a penetração dos íons cobre em relação à espessura total do esmalte. As fotomicrografias eletrônicas de varredura das superfícies vestibulares do esmalte, com aumento de 2000X, foram digitalizadas e avaliadas. Para as análises estatísticas, foi considerado o valor de alteração de cor de cada fragmento nos diferentes tempos de observação e a média das três secções de um mesmo dente para a avaliação da permeabilidade. Em relação à MEV observou-se que em relação aos processos de clareamento, foi encontrado diferenças quando comparadas aos grupos controles. Os grupos controles apresentaram superfícies dentais lisas e regulares. Já os grupos tratados com PH35% e PH 35% + LED apresentaram superfícies dentais marcadas pela presença dos prismas de esmalte suavemente esboçados em meio a um esmalte interprísmático de textura lisa. A aplicação do Er:YAG promoveu a remoção da camada aprismática e exposição clara dos prismas de esmalte, depressões, tornando a superfície porosa e irregular. Nos grupos em que se aplicou o flúor, independente do tipo de clareamento realizado, observou-se superfícies relativamente cobertas por um precipitado fusiforme. Em relação à permeabilidade, os resultados demonstraram não haver diferença significativa. Já em relação à alteração de cor foi encontrada diferença estatística ente o agente aplicado ativado pelo Er:YAG, o método a alcançar as tonalidades de cor mais claras, quando comparado aos métodos convencional e ativado pelo LED. Concluímos que novos estudos são necessários para que se estabeleçam parâmetros adequados e seguros para a aplicação do laser. Isso fará com que se consiga não só melhor tonalidade de cor, mas menores efeitos deletérios na morfologia superficial do esmalte clareado. / Visual changes, micromorphological and histochemical can be observed in areas subjected to dental bleaching, triggering sensitivity, lower wear resistance, increased staining and bacterial adhesion. One way to check the damage to surface and subsurface is through the permeability and surface evaluation by scanning electron microscopy. Thus, this in vitro study was to evaluate the effectiveness of whitening stained teeth, permeability and morphology of enamel after treatment with different techniques of application of hydrogen peroxide 35% (FGM) whether or not the application of fluoride . We used 260 bovine incisors with enamel surfaces of 10x10 mm in size. After, the specimens were randomly distributed (n = 10) and subjected to staining with coffee, black tea and red wine for 72 hours. The color measurements were made at a reflection spectrophotometer in early times, after staining and after the bleaching stage. After the period of staining the fragments were bleached with hydrogen peroxide 35% (FGM) - conventional activated LED or laser Er:YAG whether or not the application of fluoride (KF Desensibilize 2%, FGM). Control groups were exposed: the artificial saliva and fluoride application + artificial saliva. The bleaching treatment was performed according to the manufacturer\'s recommendations. The rest of the daily period, the specimens were immersed in artificial saliva. Next, the fragments were divided into two fragments of approximately 5x5 mm in size, being submitted to an evaluation of the permeability and the other to evaluate the enamel surface by scanning electron microscopy. The histochemical staining method was used to show the extent of the permeability of enamel. Enamel were obtained from three sections evaluated with optical microscopy, using a software image scanning (Axion Vision 3.1) verifying the penetration of copper ions in relation to the total thickness of enamel. The images of scanning electron photomicrographs of the vestibular enamel, an increase of 2000X were scanned and evaluated. For statistical analysis, we considered the color change of each fragment in different observation times and the average of three sections of the same tooth for assessing permeability. Regarding the SEM showed that in relation to the bleaching procedure, we found differences when compared to control groups. The control groups showed tooth surfaces smooth and regular. Since the groups treated with PH35% and 35% PH + LED tooth surfaces showed marked by the presence of enamel rods gently outlined in the midst of an enamel interprismatic smooth texture. The application of Er:YAG promoted the removal of the layer aprismatic and clear statement of the enamel prisms, depressions, making the surface porous and irregular. In groups that applied fluoride, regardless of the type of bleaching done, it was observed on surfaces covered by a precipitate fusiform. In relation to permeability, the results showed no significant difference. In relation to the color change was statistical difference between individual agents used and the Er:YAG method to achieve the color shades lighter when compared to PH35 and PH35% + LED. We conclude that further studies are needed to find themselves safe and appropriate parameters for the laser application. This will make you not only get better color tone, but less deleterious effects on enamel surface morphology cleared.

Alterações visuais, histoquímicas e micromorfológicas podem ser observadas em superfícies dentais submetidas ao clareamento, desencadeando sensibilidade, menor resistência ao desgaste, maior manchamento e aderência bacteriana. Uma forma de verificar a ocorrência de danos superficiais e sub-superficiais é através da permeabilidade e da avaliação superficial por meio de microscopia eletrônica de varredura. Assim, este estudo in vitro teve por objetivo avaliar a eficácia de clareamento em dentes manchados, a permeabilidade e a morfologia superficial do esmalte dental após tratamento com diferentes técnicas de aplicação do peróxido de hidrogênio a 35% (FGM) seguido ou não da aplicação de flúor. Foram utilizados 260 incisivos bovinos, com superfícies de esmalte de 10x10 mm de área. Após, os espécimes foram casualmente distribuídos (n = 10) e submetidos ao manchamento com café, chá preto e vinho tinto por 72 horas. As medidas de cor eram realizadas com espectrofotômetro de reflexão nos tempos inicial, após o manchamento e logo após a fase de clareamento. Após o período de manchamento os fragmentos eram clareados com peróxido de hidrogênio a 35% (FGM) - convencional, ativado com LED ou laser de Er:YAG seguido ou não da aplicação de flúor (Desensibilize KF 2%, FGM). Os grupos controles eram expostos: a saliva artificial e a aplicação de flúor + saliva artificial. O tratamento clareador foi realizado de acordo com as recomendações do fabricante. No restante do período diário, os espécimes eram imersos em saliva artificial. A seguir, os fragmentos foram subdivididos em dois fragmentos de aproximadamente 5x5 mm de área, sendo um submetido à avaliação da permeabilidade e o outro a avaliação da superfície do esmalte através de microscopia eletrônica de varredura. O método de coloração histoquímica foi utilizado para evidenciar a extensão da permeabilidade no esmalte. Do esmalte eram obtidos três cortes avaliados em microscopia óptica, através de um software de digitalização de imagem (Axion Vision 3.1) verificando a penetração dos íons cobre em relação à espessura total do esmalte. As fotomicrografias eletrônicas de varredura das superfícies vestibulares do esmalte, com aumento de 2000X, foram digitalizadas e avaliadas. Para as análises estatísticas, foi considerado o valor de alteração de cor de cada fragmento nos diferentes tempos de observação e a média das três secções de um mesmo dente para a avaliação da permeabilidade. Em relação à MEV observou-se que em relação aos processos de clareamento, foi encontrado diferenças quando comparadas aos grupos controles. Os grupos controles apresentaram superfícies dentais lisas e regulares. Já os grupos tratados com PH35% e PH 35% + LED apresentaram superfícies dentais marcadas pela presença dos prismas de esmalte suavemente esboçados em meio a um esmalte interprísmático de textura lisa. A aplicação do Er:YAG promoveu a remoção da camada aprismática e exposição clara dos prismas de esmalte, depressões, tornando a superfície porosa e irregular. Nos grupos em que se aplicou o flúor, independente do tipo de clareamento realizado, observou-se superfícies relativamente cobertas por um precipitado fusiforme. Em relação à permeabilidade, os resultados demonstraram não haver diferença significativa. Já em relação à alteração de cor foi encontrada diferença estatística ente o agente aplicado ativado pelo Er:YAG, o método a alcançar as tonalidades de cor mais claras, quando comparado aos métodos convencional e ativado pelo LED. Concluímos que novos estudos são necessários para que se estabeleçam parâmetros adequados e seguros para a aplicação do laser. Isso fará com que se consiga não só melhor tonalidade de cor, mas menores efeitos deletérios na morfologia superficial do esmalte clareado. / Visual changes, micromorphological and histochemical can be observed in areas subjected to dental bleaching, triggering sensitivity, lower wear resistance, increased staining and bacterial adhesion. One way to check the damage to surface and subsurface is through the permeability and surface evaluation by scanning electron microscopy. Thus, this in vitro study was to evaluate the effectiveness of whitening stained teeth, permeability and morphology of enamel after treatment with different techniques of application of hydrogen peroxide 35% (FGM) whether or not the application of fluoride . We used 260 bovine incisors with enamel surfaces of 10x10 mm in size. After, the specimens were randomly distributed (n = 10) and subjected to staining with coffee, black tea and red wine for 72 hours. The color measurements were made at a reflection spectrophotometer in early times, after staining and after the bleaching stage. After the period of staining the fragments were bleached with hydrogen peroxide 35% (FGM) - conventional activated LED or laser Er:YAG whether or not the application of fluoride (KF Desensibilize 2%, FGM). Control groups were exposed: the artificial saliva and fluoride application + artificial saliva. The bleaching treatment was performed according to the manufacturer\'s recommendations. The rest of the daily period, the specimens were immersed in artificial saliva. Next, the fragments were divided into two fragments of approximately 5x5 mm in size, being submitted to an evaluation of the permeability and the other to evaluate the enamel surface by scanning electron microscopy. The histochemical staining method was used to show the extent of the permeability of enamel. Enamel were obtained from three sections evaluated with optical microscopy, using a software image scanning (Axion Vision 3.1) verifying the penetration of copper ions in relation to the total thickness of enamel. The images of scanning electron photomicrographs of the vestibular enamel, an increase of 2000X were scanned and evaluated. For statistical analysis, we considered the color change of each fragment in different observation times and the average of three sections of the same tooth for assessing permeability. Regarding the SEM showed that in relation to the bleaching procedure, we found differences when compared to control groups. The control groups showed tooth surfaces smooth and regular. Since the groups treated with PH35% and 35% PH + LED tooth surfaces showed marked by the presence of enamel rods gently outlined in the midst of an enamel interprismatic smooth texture. The application of Er:YAG promoted the removal of the layer aprismatic and clear statement of the enamel prisms, depressions, making the surface porous and irregular. In groups that applied fluoride, regardless of the type of bleaching done, it was observed on surfaces covered by a precipitate fusiform. In relation to permeability, the results showed no significant difference. In relation to the color change was statistical difference between individual agents used and the Er:YAG method to achieve the color shades lighter when compared to PH35 and PH35% + LED. We conclude that further studies are needed to find themselves safe and appropriate parameters for the laser application. This will make you not only get better color tone, but less deleterious effects on enamel surface morphology cleared.

Actuellement, la restauration des oeuvres d’art, notamment des statues fracturées, repose sur des techniqueséprouvées, mais empiriques. Les statues endommagées comportent souvent des parties brisées. Leur restaurationconsiste la plupart du temps à les rassembler. Ainsi apparait la nécessité de prendre en compte lespropriétés mécaniques des interfaces entre les différentes parties brisées, ce qui permet de limiter l’ampleur desréparations et ainsi, de mieux conserver l’intégrité de l’oeuvre. Par ailleurs, les techniques numériques d’acquisition3D font leur entrée au service de la conservation du patrimoine. Cette thèse propose une méthodologiecapable d’utiliser des données issues d’une acquisition 3D pour simuler les opérations de restauration et leurseffets sur la structure de l’oeuvre. Les processus de restauration peuvent ainsi être testés et optimisés.Un scanner laser est utilisé pour l’acquisition de la géométrie des oeuvres, ce qui nous permet de reconstruireun modèle 3D pour la simulation numérique. Les calculs sont menés dans le cadre de la mécanique des milieuxcontinus déformables avec FLAC3D. Pour vérifier tous les points clés garantissant la stabilité mécanique, lecomportement des éléments de renforts et celui des interfaces entre les blocs ont été considérés. À partirdes résultats de ces études, une critique des stratégies de restauration mises en oeuvre ou envisageables estproposée.De plus, plusieurs méthodes de caractérisation visant à retrouver la provenance du matériau et/ou estimerles propriétés mécaniques de l’oeuvre sont proposées : caractérisations physico-chimiques et minéralogiques,essais non destructifs et destructifs. Une campagne expérimentale visant à caractériser le comportement desfractures en contact frottant avec acquisition de l’état de surface a été réalisée. Une analyse des corrélationsentre les propriétés mécaniques et morphologique des interfaces est ensuite élaborée. Enfin nous proposonsdes modèles prédictifs construits par régressions linéaires multiples et multivariées. Cette étude permet desimuler le comportement d’une oeuvre fracturée. / Currently, the artworks restoration, including broken statues, are based on proven but empirical techniques. Damaged statues often have broken parts. Restoration mainly consists in joining these parts. Thus appears the necessity of taking into account the interfaces mechanical properties between the different broken parts, reducing thereby the extent of repairs and thus better maintain the integrity of the work. Beside this, digital 3D acquisition techniques become more and more popular among the cultural heritage community. This thesis proposes a methodology able to use 3D acquisition datas to simulate the restoration operations and their effects on the structure. The restoration strategy can thus be tested and optimized. A laser scanner is used to acquire the statue geometry, allowing to reconstruct a 3D model for numerical simulation. Computations are carried out within the framework of deformable continuum mechanics using the FLAC3D software. In order to check all the key points ensuring mechanical stability, the behavior of reinforcing elements and those of the interfaces between blocks were considered. From the results of the present studies, a critical analysis of implemented or possible restoration strategy is proposed. In addition, several characterization methods to find the material origin and/or estimate the mechanical properties of the work are proposed : physico-chemical and mineralogical characterizations, non-destructive and destructive tests. An experimental campaign to characterize the behavior of fractures in contact with surface acquisition was performed. An analysis of correlations between mechanical and morphological interfaces properties is then developed. Finally, we propose a predictive modelling based on multiple linear and multivariate regressions. This study allow the simulation of fractured artworks behaviour.

No description available.

Ultrathin film nanocomposites are becoming increasingly important for specialized performance of commercial coatings. Critical challenges for ultrathin film nanocomposites include their synthesis and characterization as well as their performance properties, including surface roughness, optical properties (haze, refractive index as examples), and mechanical properties. The objective of this work is to control the surface roughness of ultrathin film nanocomposites by changing the average particle size and the particle volume fraction (loading) of monomodal particle size distributions. This work evaluated one-layer and two-layer films for their surface properties. Monodispersed colloidal silica nanoparticles were incorporated into an acrylate-based monomer system as the model system. Ultrathin nanocomposites were prepared with three different size colloidal silica (13, 45, and 120 nm nominal diameters) at three different particle loadings (20, 40, and 50 vol. % inorganic solids). Silica particles were characterized using DLS and TEM. AFM was used to measure the root mean square roughness (Rq), ΔZ, and location-to-location uniformity of one-layer and two-layer nanocomposite coatings. Developing an understanding about the properties affected by the type and amount of particles used in a nanocomposite can be used as a tool with nanocharacterization techniques to quickly modify and synthesize desired ultrathin film coatings.