It was investigated characteristics of surfaces of offset printing plates. A method of measurement of wetting angle was improved and there were investigated the wetting characteristics of hydrophilic surfaces of offset printing plates and their dependence on dampening solution and on printed run. Experimentally investigated 16 offset printing plates. Wetting angle increases with the run. Surface roughness was investigated using profilograph. Changes of surface roughness during printing were determined and it was found that during printing quantity of bigger over 1 µm irregularities increases.

Isocyanates, aromatic-, aliphatic- and alkanolamines are commonly used in the industry today. Millions of workers in Europe are exposed. The most frequent health symptoms are respiratory and dermal disorder. Due to the health risk most of the compounds in this thesis are regulated by authorities and have occupational exposure limits (OELs). Consequently, reliable and robust air sampling methods are urgently needed. In this thesis dry samplers for isocyanates, aliphatic- and alkanolamines have been developed and evaluated. The isocyanate sampler is now a commercial product (ASSET EZ4-NCP Dry Sampler, Supelco). The samplers were based on a denuder with a filter in series. The denuder and filter were impregnated with di-n-butylamine for the isocyanate sampler and with sulphuric acid for the aliphatic- and alkanolamine sampler. The robustness of the dry samplers was extensively evaluated. This was performed in a climate chamber containing a controlled atmosphere of the studied compounds. New methods based on hydrophilic interaction liquid chromatography (HILIC) coupled with tandem mass spectrometry (MSMS) were developed for determination of aromatic-, aliphatic- and alkanolamines in aqueous solutions. Isocyanates were determined by reversed-phase liquid chromatography MSMS. HILIC in combination with MS is a most powerful system, and highly sensitive determinations, several orders of magnitude below the OELs, of polar compounds present in the work environment can be accomplished. The selected samplers enable sampling during short sampling times and for whole work shifts. The samplers can be stored for months before and after sampling. The performance of the samplers was unaffected by variation in temperature, humidity, flow-rate and pre- and post-sampling of ambient air. Sampling for the compounds studied is now greatly simplified, and assessment of the work environment is facilitated. / <p>At the time of the doctoral defence the following papers were unpublished and had a status as follows: Paper 1: Epub ahead of print; Papers 3-5: Manuscripts</p>

Le collage direct consiste en la mise en contact de deux surfaces suffisamment lisses et propres pour qu'une adhésion puisse se créer sans ajout de matière à l'interface. Ce procédé réalisable à l'échelle industrielle trouve son intérêt dans l'empilement de structures ou de matériaux pour la microélectronique ou les microtechnologies. Il s'avère alors important de maîtriser ce procédé et cela passe notamment par la compréhension des mécanismes physico-chimique se produisant lors du collage. Le but de ce travail de thèse est donc l'étude des mécanismes mis en jeu dans le collage hydrophobe de silicium et le collage hydrophile d'oxydes de silicium déposés.Dans cette étude, des procédés de collage direct hydrophobe de plaques de silicium (100) reconstruit ont été développés, ainsi que des collages de surfaces hydrophiles d'oxyde de silicium déposés préparées par des activations plasma azote ou oxygène ou par un procédé de polissage mécano-chimique. Le comportement de toutes ces structures a été étudié à plusieurs stades du procédé, en particulier lors des traitements thermiques de consolidation de l'interface de collage. Pour ce faire, différentes techniques de caractérisation ont été mises en oeuvre comme la mesure d'énergie de collage, l'observation de la défectivité par microscopie acoustique, la spectroscopie infrarouge et la réflectivité des rayons X. Cela a ainsi permis de suivre la fermeture de l'interface de collage en température d'un point de vue chimique et mécanique et des mécanismes de collage ont alors pu être proposés pour toutes les structures étudiées. Des recommandations ont également pu être faites pour l'obtention de collages d'oxydes de silicium déposés efficaces et de qualité. / Direct wafer bonding refers to a process by which two mirror-polished wafers are put into contact and held together at room temperature by adhesive force, without any additional material. This technology feasible at an industrial scale generates wide interest for the realization of stacked structures for microelectronics or microtechnologies. In this context, a precise understanding of bonding mechanisms is necessary. Consequently, the aim of this work is to study the bonding mechanisms for hydrophobic silicon reconstructed surfaces and hydrophilic deposited silicon oxides surfacesIn this study, bonding of hydrophobic silicon reconstructed surfaces and bonding of hydrophilic deposited silicon oxides prepared either by plasma activation or chemical-mechanical polishing were analyzed, as a function of post-bonding annealing temperature. For this, several characterization techniques have been used: bonding energy measurement, acoustic microscopy in order to observe defectivity, infrared spectroscopy and X-Ray reflectivity. Thus the bonding interface closure has been analyzed from a chemical and mechanical point of view and bonding mechanisms have been proposed for the studied bonded structures. Finally the study of deposited silicon oxide bonding prepared either by plasma activation or by chemical-mechanical polishing has lead to some recommendations for efficient and high quality deposited silicon oxides bonding.

L'objectif de cette thèse est le développement de nouveaux échangeurs d'anions à base d’ionosilices. Différents matériaux contenant des entités ammoniums ont été synthétisés par la procédure d'hydrolyse-polycondensation à partir de précurseurs silylés d'ammonium. Ces solides, présentant différentes textures, différentes architectures ou des morphologies ont été obtenus en faisant varier des paramètres de réaction, comme par exemple la nature du tensioactif utilisé. Outre les caractérisations structurales et texturales (adsorption-désorption d’azote, DRX, MET / MEB), nous nous sommes concentrés sur les analyses plus détaillée des propriétés physico-chimiques de ces ionosilices. En particulier, elles présentent une contribution hydrophile élevée par rapport aux silices mésoporeuses classiques ou les organosilices du type PMO (Periodic Mesoporous Organosilica). En outre, ces propriétés interfaciales d’hydrophilie peuvent être modulées soit par l'utilisation de différents précurseurs d'ammonium, soit par l'incorporation par échange d'anions hydrophobes. Enfin, nous avons utilisé ces nouveaux matériaux pour la rétention d’espèces anioniques en milieu aqueux. Nos études montrent que ces ionosilices sont des échangeurs d'anions très efficaces présentant une capacité d'adsorption de Cr (VI) élevée (jusqu’à 2.5 mmol g-1). Ces matériaux possèdent également une capacité d’adsorption d’iodure élevée combinée à une bonne stabilité radiolytique pour des applications de rétention de radionucléides. Des résultats similaires ont été obtenus pour des polluants organiques anioniques tels que les principes actifs (le diclofénac, le sulindac et le p-aminosalicylate) ou des colorants (méthyl orange). Outre le grand potentiel d’application de ces matériaux dans les procédés de séparation, cette étude donne un aperçu intéressant de la morphologie des matériaux grâce à l'accessibilité presque complète des sites cationiques. Toutes ces caractéristiques font de ces matériaux des systèmes de choix pour les applications dans le traitement de l’eau polluée, le stockage à long terme des déchets radioactifs et en tant que support de catalyseur. / The objective of this thesis is the development of new anion exchangers based on ionosilica materials. Various materials containing ammonium groups were synthesized by template directed hydrolysis-polycondensation reactions starting from silylated ammonium precursors. Solids displaying different textures, architectures and morphologies were obtained via the modifications of reaction parameters, such as the nature of the used surfactant. Besides the standard structural and textural characterizations (N2 adsorption, XRD, TEM / SEM), we focused on a more detailed physico-chemical analysis of these original and innovative materials. Ionosilicas show an unusually high hydrophilicity compared to classical mesoporous silica or organosilicas of the PMO-type (Periodic Mesoporous Organosilica). Furthermore, the hydrophilicity of ionosilicas can be finely tuned either by the use of various ammonium precursors or the incorporation via exchange of hydrophobic anions. Finally, we used these new anion exchangers for the removal of various anionic species in aqueous media. Our studies show that ionosilicas are highly efficient anion exchanger displaying high capacity for the adsorption of Cr (VI) (up to 2.5 mmol g-1). These materials exhibit also high capacity of iodide combined with high radiolytic stability for radionuclides uptake. Similar results were obtained for organic anionic pollutants, e.g. drugs (diclofénac, sulindac and p-aminosalicylate) and dyes (methyl orange). Besides the high potential of these materials in separation processes, this study gives interesting insights in the materials morphology through the nearly complete accessibility of the cationic sites. All these features make ionosilicas materials of choice for solid-liquid separation processes in water treatment, depollution of industrial wastewater, the nuclear fuel cycle or catalytic support.

Made available in DSpace on 2016-12-12T20:15:50Z (GMT). No. of bitstreams: 1 Jorge Batista - resumo.pdf: 37444 bytes, checksum: 8f8f7a4b6f5f96a5fc6085e5128c66c2 (MD5) Previous issue date: 2013-03-22 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The control of surface wettability is an issue of great scientific interest because of the large number of applications both as hydrophobic to hydrophilic surfaces, such as medical instruments, fluidic microdevices, coating for microdevices, manipulation of nanoparticles, microscale motors, lubricants, waterproofing surfaces and even instruments for domestic use. The objectives of this work are to compare the values obtained in experiments with surfaces of well-defined topography with available theoretical models and characterize the transition between hydrophobic and superhydrophobic surfaces with the proposition of configurations and criteria that lead to a better understanding of the wettability and superhydrophobic surfaces production, in the light of the energy minimization. / O controle da molhabilidade de superfícies é um tema de grande interesse científico em função da grande quantidade de aplicações, tanto para superfícies hidrofílicas quanto hidrofóbicas, como é o caso de instrumentos médicos, microdispositivos fluídicos, recobrimento para microdispositivos, manipulação de nanopartículas, motores em microescala, lubrificantes, impermeabilização de superfícies e mesmo em instrumentos de uso doméstico. Os objetivos deste trabalho são comparar os valores obtidos em experimentos com superfícies de topografia bem definida com os modelos teóricos disponíveis e caracterizar a transição entre superfícies hidrofóbicas e superhidrofóbicas, com a proposição de configurações e critérios que levem a um melhor entendimento da molhabilidade e da produção de superfícies superhidrofóbicas, sob a luz da minimização de energia.

Made available in DSpace on 2014-12-17T14:16:25Z (GMT). No. of bitstreams: 1 IuryEGF_DISSERT_partes_autorizadas.pdf: 116631 bytes, checksum: 3dcaa9a01c6b9b2ba123ac09b7c86c26 (MD5) Previous issue date: 2009-09-28 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The fat acid esters and tocopherolic derivatives are of great economic interest in many industries. The sunflower oil, which had its rich constitution in these composites, is a very interesting raw material source for the job in some sectors as bio-carburants, bio-lubrificants, bio-surfactants, dispersing agents, food industries, medicines and cosmetics. A system emulsified steady from this oil can wide be used in the therapeutical one, therefore it is of easy acceptance for the patient, for being pharmaceutical forms that allow a better medicine administration. The chemical composition characteristics, rich in unsaturad fat acid and tocopherolic derivatives, the sunflower oil, make of the emulsified systems contend this oil a proposal promising for formularizations of pharmaceutical and cosmetic use with antirust and photoprotection. The general objective of this work was to apply the HLB beddings to determine the sunflower oil critical HLB and, from this, to be able to evaluate the ideal mixture of the constituent of this system through the study of the ternary diagrams for the determination of the ratio of constituent that will generate the emulsion most steady / Os ?steres de ?cidos graxos e os derivados tocofer?licos s?o de grande interesse econ?mico em muitas ind?strias. O ?leo do girassol, devido a sua constitui??o rica nesses compostos ? uma fonte muito interessante de mat?ria-prima para o emprego em v?rios setores como biocombust?veis, lubrificantes, biosurfactantes, dispersantes, ind?strias de alimentos, medicamentos e cosm?ticos. Um sistema emulsionado est?vel a partir deste ?leo pode ser largamente empregado na terap?utica, pois ? de f?cil aceita??o pelo paciente, por serem formas farmac?uticas que permitem melhor administra??o de um medicamento. As caracter?sticas da composi??o qu?mica, rica em ?cidos graxos insaturados e derivados tocofer?licos, do ?leo de girassol, fazem dos sistemas emulsionados contendo este ?leo uma proposta promissora para formula??es de uso farmac?utico e cosm?tico com a??es antioxidante e fotoprotetora. O objetivo geral deste trabalho foi aplicar os fundamentos de HLB para determinar o HLB cr?tico do ?leo de girassol e, a partir disso, poder avaliar a mistura ideal dos constituintes desse sistema atrav?s do estudo dos diagramas tern?rios para a determina??o da propor??o de constituintes que gerar? a emuls?o mais est?vel

Aujourd’hui, l’impact des conservateurs sur l’homme est remis en question. Il a été entrepris de mieux comprendre les agents antimicrobiens d’un point de vue physico-chimique pour fournir des règles de formulation, qui pourront être utilisées pour proposer à nos laboratoires de formulation des alternatives aux antimicrobiens classiquement utilisés. Ce travail a consisté en la compréhension des caractéristiques structurelles de molécules ayant, entre autre, des propriétés antimicrobiennes ; l’analyse des mécanismes physico-chimiques qui relient ces caractéristiques structurelles à leurs propriétés ; l’optimisation, à la lumière de ces informations, de la formulation de ces molécules. L’étude des familles chimiques, complétée par une étude plus large reliant la modélisation QSAR aux propriétés antimicrobiennes, a permis de conclure que certaines familles d’alcools et dérivés sont des alternatives de choix aux antimicrobiens usuels. Les caractéristiques permettant les meilleures performances étant : une structure asymétrique marquée ; une tête polaire comportant deux groupements hydrophiles, type diol ou mono glycéride ; une longueur de chaîne apolaire comprenant entre 6 et 12 carbones, avec un optimum entre 7 et 10 carbones ; le calcul du HLB résultant de ces caractéristiques donne un HLB compris entre 7 et 11. Les dérivés acides ou la famille des décanols ont permis de préciser l’intérêt d’une insaturation ou la présence d’un β-hydroxy. L’impact de la formulation d’une molécule modèle, le caprate/caprylate de glycérol a montré que dans une émulsion directe, les tensioactifs hydrophiles piègent dans leurs micelles l’actif, ce qui induit une diminution de l’activité antimicrobienne. L’épaisseur hydrophile des têtes polaires empêchent le passage de l’actif en dehors de la micelle vers le micro-organisme. Il est donc recommandé d’utiliser la quantité de tensioactif utile pour tapisser sans excès la surface des gouttes d’huiles. L’épaisseur des têtes polaires hydrophile peut être réduite en sélectionnant les tensioactifs, par exemple des ioniques phosphatés. D’autres paramètres ont été démontrés comme influant, dans une moindre mesure : il est recommandé de privilégier les gélifiants aux tensioactifs lors de l’élaboration d’une texture, d’optimiser le taux d’actif antimicrobien sur taux d’huile et d’utiliser de préférence des huiles peu solvantes de l’actif. / Nowadays, preservatives in personal care are obviously a current issue. The aim of this study was to find out rules for molecular design and formulation conception dealing with a physico-chemistry point of view, in order to avoid classic preservatives. We have studied on structural features for antimicrobial activity and their behaviors in direct emulsions. After studies of various structural families, and a wide QSAR analysis, the result was that molecule with one or two alcohol groups are among the better antimicrobial agents. Especially, we focus on some characteristics, which improve considerably the antimicrobial activity : an asymmetric structure ; a two-hydroxylated polar head like diols or monoglycerids ; the main hydrocarbon tail should contain between 6 and 12 carbons with an optimum between 7 and 10 ; with these characteristics, the HLB value must be located between 7 and 11. An unsaturated bond in a linear chain or a β-hydroxylated group leads to an increase of decontamination. The impact of the formulation in direct emulsions of a model molecule, glycerol octanoate/decanoate, seemed to show that hydrophilic surfactants trap in their micelles the active product, which induces a decrease of the antimicrobial activity. The hydrophilic thickness of polar heads prevents the passage of the active product beyond the micelle to the micro-organism. It is therefore recommended that the quantity of surfactant used to create and stabilize the drops of oil be reduce to a minimum. The hydrophilic thickness of polar heads may be reduced by selecting the surfactants, for example an ionic phosphate. Other parameters have been demonstrated as affecting, to a lesser extent: it is recommended polymers and micro gels are used rather than surfactants in the preparation of a texture to customize the ration antimicrobial on oil and to use preferably non-polar oil.

Abstract Volatile Organic Compounds (VOCs) in wastewaters from the chemical industry are of major concern because of their environmental and health impacts. The reclamation of VOCs from wastewaters would not only reduce the hazard to the environment but also contribute to an efficient use of resources. The thesis explores the reclamation of n-butanol and dichloromethane from sodium chloride containing mixtures by pervaporation. Another aim was to gain understanding of mass transport phenomena during the pervaporation of multicomponent systems, and the effect of sodium chloride on the pervaporation performance. In this work, the reclamation of n-butanol and dichloromethane was conducted as a sequence of pervaporation stages which utilised first hydrophobic and then hydrophilic membranes. The objective was to segregate the mixture of n-butanol/dichloromethane/sodium chloride/water into three different streams: a re-use quality concentrate of VOCs, brine, and discharge quality purified water. The effect of the experimental variables, VOCs feed concentration, feed temperature and sodium chloride content on the performance of the pervaporation stages was studied. A statistical design, response surface methodology, was used to further resource efficiency. The results indicate the potential of pervaporation for the reclamation of n-butanol and dichloromethane from aqueous mixtures. A single step of pervaporation of n-butanol/dichloromethane/sodium chloride/water systems using the CMX-GF-010-D (Celfa) and PERTHESE® 500-1 (P 500-1) membranes does not sufficiently concentrate the VOCs for direct re-use. It is also demonstrated that the electrolyte does not permeate through the membranes and does not affect their separation effectiveness significantly. The pervaporation of the water/dichloromethane/n-butanol system using the hydrophilic poly(vinyl alcohol)-titanium dioxide/polyacrylonitrile/polyphenylene sulfide (PVA-TiO2/PAN/PPS) membrane is effective for dewatering purposes. The membrane shows impermeable features towards dichloromethane in the studied conditions. The analysis of the mass transport phenomena demonstrates that, under the experimental conditions studied, the resistance towards the mass transport of the compounds through the membrane is mainly exhibited by the membrane itself. This study also shows the advantage of analysing the effect of temperature on membrane permeation by the permeation activation energy instead of by the apparent activation energy.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21963号 / 工博第4618号 / 新制||工||1720(附属図書館) / 京都大学大学院工学研究科高分子化学専攻 / (主査)教授 山子 茂, 教授 辻井 敬亘, 教授 大内 誠 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

The thesis deals with the use of hydrophilic mineral wool in green roof structures. In the first part of the thesis, based on current legislation, there are summarized relevant technical properties of the hydrophilic wool. Specific demands on the green roof parts were classified and the work was consequently updated by the research of available products from the national market. A large part of the thesis consists of the extended documentation of technical properties of new products and also the changes that are associated with ageing after the material incorporation into the structure. Not only the laboratory properties of the material itself, but also properties of the material embedded in green roof structure were measured, for example an acoustic capabilities. Water accumulation properties of the mineral wool were documented on the real roof models too. Various impacts were observed by using mineral wool in comparison with substrate assemblies. Additional experiments were applied on using different types of mineral wool for an assessment of specific green roof vegetation adaptation. The environmental product declarations for each mineral wool product were calculated with the specific software using LCA methodology. In this way, the environmental impacts of mineral wool could be compared with other materials, such as artificial substrates, foils, etc. As a conclusion of the research results were summarized and reported demands for the hydrophilic mineral wool use in the green roof structures.