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Dissertations / Theses on the topic 'Hybridní materiál'
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Neboha, Oksana. "Příprava struktur duplexního typu cestou mechanického legování a SPS." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2020. http://www.nusl.cz/ntk/nusl-416614.
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This master´s thesis focuses on duplex microstructures preparation by powder metallurgy. A hybrid material can be created by combining two or more existing materials in different geometries, and thus the newly formed composite can provide a superposition of the properties of the starting materials (powders). This means that it will have an improved combination of the required properties. The theoretical part describes in detail the hybrid materials and the architectured materials that contain highly controlled structures. Structure control allows to change the variety of possible geometries and opens up a number of other useful properties. Therefore, this thesis also deals with the mechanical alloying and SPS. The experimental part describes procedures of preparation of four samples of composites with a duplex structure from a powder of a significantly tough alloy (austenitic steel 316L) in combination with a powder of a significantly strong alloy (titanium carbonitride). A crucial part of this thesis is characterization of these four samples by electron microscopy methods (SEM, TEM, EDS) and supported by hardness measuring.
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Jetela, Václav. "Hybridní lepené spoje kovových a kompozitních materiálů." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2016. http://www.nusl.cz/ntk/nusl-241199.
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The first part of the diploma thesis with name „Hybrid adhesive bonded joints of metals and composite materials“ comprise surface pretreatment review. There is also mentioned current review of adhesives for composite and aluminium adherends. The second part of the thesis is dedicated to lap hybrid joint shear strength tests. The effects of adherend thickness, overlap lenght and surface pretreatment on shear strength were investigated. Measured parameters of hybrid joints are proved with a FE analysis with enough accuracy. Conclusions could be used for optimum design of hybrid joint with aluminium and composite adherends.
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Mechref, Elias. "Synthèse, caractérisation et mise en œuvre d’un matériau hybride organique-inorganique photosensible de type résine positive : application à la fabrication de dispositifs de microfuidique par écriture Laser." Thesis, Montpellier, 2015. http://www.theses.fr/2015MONTS071.
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Depuis quelques décennies, les matériaux composites organique/inorganique font l’objet de nombreux travaux de recherches. En raison de leurs propriétés uniques et intermédiaires entre les deux mondes minérales et organiques, ces matériaux sont d’un grand intérêt pour des nombreuses applications tel que le domaine, d’optique, la microfluidique, la microélectronique…, La synthèse de ce type des matériaux est réalisée à moindre coût en deux étapes : La synthèse du réseau inorganique est effectué par procédé sol-gel , tant qu’à la partie organique des compositions de type résines négatives et positives possède la particularité d’être photo-réticulables sous irradiation (UV et visible). Parallèlement, est apparue la lithographie par écriture laser (spot de quelques microns). Elle s’avère très pertinente pour la mise au point d’un procédé pour lequel des objets de petites dimensions (quelques Microns) et de petites surfaces sont à réaliser car elle permet de s’affranchir de la fabrication de masques. Cette technique associée aux résines négatives, n’est pas idéale pour la fabrication d’objets de grandes surfaces en raison de temps de fabrication induits trop long. Il est, par exemple, extrêmement compliqué et couteux d’utiliser l’écriture Laser pour la réalisation de dispositifs microfluidiques. En effet, la création de canaux de taille micronique nécessite une très grande surface à insoler. Il est donc bien plus pertinent de travailler sur l’association de l’écriture laser avec une résine de type positive. L’objectif principal de ce travail est la synthèse, l’optimisation et mise en œuvre d’un matériau hybride photosensible de type résine positive : Application à la fabrication des capteurs microfluidiques. Notre choix s’est porté sur le poly(amic acid) PAA de masse molaire 2340 g/mol comme partie organique, connu pour ces bonnes propriétés mécaniques et sa grande stabilité thermique. Le travail est centré d’une part, sur la synthèse d’une résine positive photosensible à la longueur d’onde utilisée (365 nm) à base du polymère PAA. En général, les PAA sont très solubles dans une solution alcaline aqueuse, dû à la présence d’acide carboxylique. Afin d’améliorer le contraste entre la partie insolée et non insolée après le développement, un inhibiteur de dissolution 1,3,5-tris[(2-vinyloxy)ethoxy]benzène (TVEB) est greffé au PAA via la fonction vinyl éther. Ce dernier permet la réduction de la teneur en acide carboxylique dans le motif répétitif du polymère et comme conséquence diminuer la dissolution de la partie non insolée. D’autre part, la synthèse du matériau hybride à base de la résine photosensible optimisée, est réalisée par greffage d’un précurseur ORMOSIL le 4-vinyléther-phenyltriéthoxysilane (VEPTES) pré-hydrolysé par procédé sol-gel comme partie inorganique à notre polymère. Afin d'optimiser le matériau, une étude structurale a été réalisée depuis la synthèse du solution jusqu'à l'obtention des dépôts et enfin la création des canaux microfluidiques. Une amélioration significative au niveau des propriétés mécaniques et thermiques est notée au niveau du polymère par ajout d’une partie minéraleIn recent decades, the organic / inorganic composite materials are the subject of many research works. Because of their unique properties and intermediate between inorganic and organic worlds, these materials are of great interest for many applications such as the area, optical, microfluidics, microelectronics ... The synthesis of this type of materials is carried out at a lower cost in two stages: The synthesis of inorganic network is made by sol-gel process, as well as the organic part of the negative and positive resin type compositions has the particularity of being photo-crosslinked under irradiation ( UV and visible).Meanwhile, the lithography by laser writing has appeared (spot a few microns). It is particularly appropriate for the development of a method for which small objects (a few microns) and small surfaces are to achieve because it eliminates the production of masks. This technique associated with negative resins, is not ideal for manufacturing large objects surfaces due to induced production time too long. It is, for example, be extremely complicated and expensive to use writing laser for producing microfluidic devices. Indeed, the creation of micron-sized channels requires a very large surface area to be exposed. It is therefore more appropriate to work on the combination of laser writing with a resin positive type. The main objective of this work is the synthesis, optimization and implementation of a photosensitive hybrid material resin positive type: Application to the fabrication of microfluidic sensors. Our choice fell on the poly(amic acid) PAA with molar mass of 2340 g/mol as an organic part, known for its good mechanical properties and high thermal stability.The work focuses on a part, on the synthesis of a positive photosensitive resin at the wavelength used (365 nm) based on the PAA polymer. In general, PAA are very soluble in an aqueous alkaline solution, due to the presence of carboxylic acid. In order to improve the contrast between the irradiated and unirradiated part after the development, an dissolution inhibitor 1,3,5-tris [(2-vinyloxy) ethoxy] benzene (TVEB) is grafted to the PAA via the vinyl ether function. This allows the reduction of the carboxylic acid content in the repeating unit of the polymer and as a consequence reduces the dissolution of the non-exposed part.On the other part, the synthesis of the hybrid material based on the optimized photosensitive resin is formed by grafting a precursor ORMOSIL 4-vinylether-phenyltriethoxysilane (VEPTES) pre-hydrolyzed by sol-gel method as the inorganic part to our polymer. In order to optimize the material, a structural study was conducted for the synthesis of the solution until the deposits and the creation of microfluidic channels. A significant improvement in mechanical and thermal properties is recorded at the polymer by adding an inorganic portion
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Schlierf, Andrea. "Graphene organic hybrid materials." Thesis, Strasbourg, 2014. http://www.theses.fr/2014STRAF050/document.
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En 2004, le carbone, la base de toute vie connue sur Terre, a marqué les esprits une fois de plus: Les scientifiques de l’Université de Manchester au Royaume Uni ont pu extraire une matière carbonée complètement nouvelle, le graphène à partir d’un morceau de graphite comme celui qui compose les crayons. À l’aide d’un ruban adhésif, ils ont obtenu une paillette de carbone de l’épaisseur d’un atome seulement, à une époque où beaucoup pensaient qu’un matériaux cristallin aussi fin ne pouvait pas être stable. Le graphène parfait est une couche monoatomique composée d’atomes de carbone hybridés sp2, arrangés en structure alvéolaire; sa structure chimique particulière lui donne des propriétés physiques et chimique remarquable. Le graphène est devenu rapidement la matière carbonée la plus intensivement étudiée parmi celles «possiblement révolutionnaires», avec ses applications potentielles s’étendant de la microélectronique aux composites, des énergies renouvelables à la médecine. En 2010, Geim et Novoselov ont été récompensés par le prix Nobel de physique pour leurs «expériences révolutionnaires sur les matériaux bi-dimensionnels en graphène» qui a ouvert une nouvelle ère dans la science des matières carbonées.La chimie non-covalente du graphène est exploitée et étudiée dans cette thèse dans le but de concevoir, produire, transformer et caractériser les nouveaux matériaux hybrides graphène-organique. L’étendue de ce travail couvre les aspects mécanistiques de l’exfoliation en phase liquide du graphène avec des colorants, les aspects fondamentaux des interactions entre le graphène et le chromophore, en phase liquide et solide, ainsi que l’élaboration de suspensions hybrides de graphène dans le but d‘applications en électronique organique et dans les matériaux composites polymères fonctionnelsIn 2004, carbon, the basis of all known life on earth, has surprised once again: Researchers from University of Manchester, UK, extracted a completely new carbon material, graphene, from a piece of graphite such as is found in pencils. Using adhesive tape, they obtained a flake of carbon with a thickness of just one single atom, at a time when many believed it impossible for such thin crystalline materials to be stable. Pristine graphene is a mono-atomic sheet of, sp2 hybridized carbon atoms arranged in a honeycomb network; this particular chemical structure gives rise to its outstanding physical and chemical properties. Graphene rapidly became the most intensively studied among the ‘possibly revolutionary’carbon materials, with its potential applications reaching from microelectronics to composites, from renewable energy to medicine. In 2010, Geim and Novoselov were honored with the Nobel Prize in Physics for their “ground breaking experiments regarding the two-dimensional material graphene” that started a new era in the science of carbon materials.In this thesis we exploit and study the non-covalent chemistry of graphene to design, produce, process and characterize novel graphene organic hybrid materials. The scope of this work covers mechanistic aspects of graphene liquid phase exfoliation with dyes, fundamental aspects of graphene chromophore interactions in liquid and solid phase and the formulation of graphene hybrid suspensions towards application in organic electronics and functional polymer composite materials
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Kročová, Blanka. "Částicové kompozity vyztužené krátkými vlákny." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2012. http://www.nusl.cz/ntk/nusl-216855.
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This diploma thesis examines the effect of short fiber reinforcement in particle composite with a polymer matrix and the effect of its structure on the mechanical properties. It studies the refraction toughness depending on the addition of short polyvinylalcohol fibers (PVAL), nanosilica and pulverized polymethylacrylate (PMMA) to a dimethylacrylate matrix. Matrix strengthening was characterised with the help of differential compensation photocalorimetry. The inner structure of the composite and the morphology of fracture were studied using a scanning electron microscope. For the tested samples, the modules of elasticity and toughness were measured, the critical values of stress intensity factor and the energy release rate were determined. The findings suggest that the limit value of short fibers content is 4 vol. %. This content of fibers significantly increases the tenacity of the material but at the same time the uniform distribution of fibers and the ease of preparation of the material decrease. Within the possible applications, the manipulation of this material worsens as well. The fibers content of 2 ± 0.5 vol. % is an acceptable compromise between good treatability, uniform distribution of fibers and the required mechanical properties. During the study of the fracture surfaces of the material, different types of fibers disruption were witnessed (extraction from the matrix, plastic deformation, fibrillation on the surface of the fibers, fracture) depending on the type of used matrix and filling.
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Wehbi, Mohammad. "Fluoropolymers functionalized by phosphorous and silicon groups : syntheses, characterization and applications." Thesis, Montpellier, 2018. http://www.theses.fr/2018MONTS134/document.
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Les polymères fluorés sont des macromolécules intéressantes qui, en raison de leurs propriétés uniques, sont souvent utilisées dans des applications spéciales dans les industries du bâtiment, de l'aérospatiale, du génie chimique, du traitement des textiles, optiques et de la microélectronique. Cette thèse se concentre sur le développement de polymères fluorés fonctionnels à base de phosphore et de silane par la co/terpolymérisation radicalaire conventionnelle de monomères fonctionnels avec le fluorure de vinylidène (VDF). Ces monomères fonctionnels ont été préparés à partir de la modification de l'acide 2- (trifluorométhyl) acrylique (MAF) pour préparer des MAF-ester avec le groupement fonctionnel souhaité. Tout d'abord, une étude fondamentale concernant la cinétique de polymérisation du VDF avec MAF-TBE a montré que ces paires de monomères ont une tendance à se propager de manière croisée, ce qui donne des copolymères alternés. On a ensuite préparé du MAF avec une fonction phosphonate (MAF-DMP) et sa copolymérisation avec du VDF a permis d'obtenir du PVDF à fonctionnalité phosphonate qui, après l'hydrolyse consécutive du groupe phosphonate en acide phosphonique, avait des propriétés anticorrosion sur l'acier. De façon similaire, un monomère de MAF porteur une fonction carbonate cyclique (MAF-cyCB) a également été copolymérisé avec du VDF. Les groupes carbonate cycliques dans le copolymère de PVDF obtenu ont ensuite été ouverts par 1'aminopropyltriéthoxysilane pour introduire un groupe silane, qui, par son hydrolyse, a permis au copolymère d'adhérer fortement sur les substrats. Enfin, un terpolymère à base de PVDF fonctionnel porteur à la fois un groupe phosphonate et un groupe triéthoxysilane a été préparé. Le groupe silane a ensuite été hydrolyse et réticulé pour obtenir un réseau 3D de polymères. Enfin, l'hydrolyse du groupe phosphonate en acide phosphonique a conduit à une matière pouvant être utilisée dans l'extraction des ions Eu (III) de l'eauFluorinated polymers are intresting macromolecules which due to their unique properties are often used in special applications in building industries, aerospace, chemical engineering, optics, textile treatment and microelectronics. This thesis focusses on the development of phosphorous and silane functional fluorinated polymers through the conventional radical co/terpolymerization of functional monomers with vinylidene difluoride (VDF). These functional monomers were prepared from the modification of 2-(Trifluoromethyl)acrylic acid (MAF) to prepare MAF-esters with the desired functional group. First a fundamental study regarding the kinetics of polymerization of VDF with MAF-TBE revealed that these monomer pair tends to cross propagate resulting in an alternating copolymer. Phosphonate functional MAF (MAF-DMP) was then prepared and its copolymerization with VDF led to phophonate functional PVDF, that after the consequent hydrolysis of the phosphonate group into phosphonic acid showed anticorrosion properties to steel. Following the same concept, a cyclic carbonate functional MAF monomer (MAF-cyCB) was also copolymerized with VDF. The cyclic carbonate groups in the obtained PVDF copolymer was then opened by aminopropyltriethoxysilane to introduce a silane group, that by its hydrolysis allowed the copolymer to adhere strongly onto substrates. Finally, a terpolymer based on PVDF functional with both a phosphonate and a triethoxysilane group is prepared. The silane group was then hydrolyzed and crosslinked to obtain a 3D network of polymers. Finally, the hydrolysis of the phosphonate group into phosphonic acid led to material that can be employed in Eu(III) ion extraction from water
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Smrčková, Markéta. "Hybridní kompozity kombinující krátká houževnatá vlákna a částicové plnivo v polymerní matrici." Master's thesis, Vysoké učení technické v Brně. Fakulta chemická, 2011. http://www.nusl.cz/ntk/nusl-216678.
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In this work, the effect of adding short deformable polyvinylalcohol fibers into dimethacrylate resins on mechanical properties of composite materials was investigated. Furthermore, micro- or nano-fillers were added into the matrix. The effect of filler/short fibers combination on mechanical properties of so-called hybrid composites was studied. Composites were characterized by differential compensation photocalorimetry (DPC), termogravimetric (TGA) and dynamic mechanical (DMA) analysis. The fracture surfaces were examined using scanning electron (SEM) and confocal laser (CLSM) microscopy. Elastic modulus and strength, the critical value of stress intensity factor and strain energy release rate and the viscoelastic properties of composite materials were measured. The mechanical properties of composite materials are affected not only by the type of filler/reinforcement, but also by properties of the matrix. These properties also depend on the way of network formation during photo-initiated polymerization. For this reason, heat of polymerization, degree of conversion and the maximum polymerization rate of mixture of dimethacrylate monomers were determined.
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Roleček, Jakub. "Příprava hybridních keramických materiálů metodou ice-templating." Doctoral thesis, Vysoké učení technické v Brně. CEITEC VUT, 2019. http://www.nusl.cz/ntk/nusl-408061.
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Ice-templating, známý také jako freeze-casting, je relativně jednoduchou, levnou a velmi univerzální technikou pro výrobu porézních keramických struktur s řízenou mikrostrukturou. Takto připravené keramické struktury jsou použity pro výrobu hybridních keramických kompozitů, nebo jako biokeramické scaffoldy. Hybridní keramické kompozitní materiály jsou založeny na napodobování přírodních/ biologických materiálů. Hlavním cílem je napodobit v přírodě se vyskytující zhouževnaťující mechanismy tím, že porézní keramické struktury jsou po slinutí napuštěny polymerními materiály. Hlavním problémem při výrobě porézních keramických vzorků s velkými rozměry, pomocí metody ice-templating, je dosažení řízeného růstu ledových krystalů v celém objemu vzorku. Aby tedy bylo možné získat velké keramické vzorky s dobře definovanou lamelární strukturou je třeba proces ice-templatingu velmi přesně kontrolovat. Biologická aktivita biokeramických materiálů závisí na kombinaci fyzikálních a chemických charakteristik, které silně souvisejí s jejich mikrostrukturou. Porozita scaffoldů musí být vzájemně propojená a velikostí pórů dostatečně velká pro úspěšný růst kostní tkáně v celém objemu implantátu. Prezentovaná disertační práce je zaměřena na problematiku zvětšování rozměrů keramických vzorků připravených pomocí metody ice-templating, vytvoření víceúrovňové porozity uvnitř vzorků a výrobu hybridních keramických kompozitů pro balistickou ochranu. Keramické suspenze pro ice-templating byly úspěšně připraveny z různých prášků (zejména hydroxyapatitu a oxidu hlinitého s různým plněním keramického prášku od 7,5 obj.% do 45 obj.%. Byl také studován vliv aditiv na utváření lamelární drsnosti a mezilamelárních přemostění. V současnosti je zkoumán dopad těchto strukturních prvků na výsledné mechanické vlastnosti. Hybridní kompozity oxid hlinitý/polymer byly úspěšně navrženy a připraveny z destiček z oxidu hlinitého připravených metodou ice-templating s délkou lamel až 70 mm a různých polymerních pryskyřic. Byla testovány mechanické vlastnosti hybridních kompozitů oxid hlinitý/polymer a výsledky ukázaly, že ice-templating je robustní metodou pro výrobu hybridních kompozitů keramika-polymer s dobrým poměrem pevnost/hustota. Avšak balistické testy hybridních kompozitů oxid hlinitý/polymer odhalily, že většina kompozitů vytvořených v rámci této práce nebyla schopna účinně zastavit střely s průbojným jádrem. Ukázalo se, že kombinace procesu ice-templating a nepřímého 3D tisku umožňuje výrobu biokeramických scaffoldů pro kostní náhrady z hydroxyapatitu s víceúrovňovou porozitou, což by se mohlo ukázat jako prospěšné pro vývoj bioaktivních vysoce porézních scaffoldů se zvýšenou biologickou aktivitou. Ice-templating také významně ovlivnil změnu fázového složení během slinování hydroxyapatitových vzorků.
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Burglova, Kristyna. "Design of easily accessible organosilanes for functional sol-gel hybrid materials." Thesis, Montpellier, Ecole nationale supérieure de chimie, 2012. http://www.theses.fr/2012ENCM0021.
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Les organosilices sont des matériaux en plein essor, qui combinent les propriétés des fragments organiques et ceux de la matrice siliciée. Ces matériaux hybrides ont trouvé des applications dans les domaines de la catalyse, de l'optique, de l'électronique etc. Ils peuvent être préparés par le procédé sol-gel à partir d'organosilanes contenant des fragments organiques à propriétés désirées. Pour former ces matériaux, il est essentiel de simplifier la préparation des organosilanes fonctionnels en réduisant le nombre d'étapes réactionnelles. Aussi, l'un des buts de cette thèse est de développer une méthode de préparation sélective, universelle et à spectre large pour les organo(trialcoxy)silanes. Dans ce but, la réaction Click de CuAAC, connue comme une approche simple de couplage, a été adaptée pour les composés sensibles à l'eau. En utilisant des azotures ou des alcynes contenant la fonction triéthoxysilane avec des partenaires organiques, nous avons réussi à préparer des séries de précurseurs silylés par réaction Click. La réaction est rapide, quantitative et sélective, et tolère une gamme étendue de substrats. De plus, de nouveaux alcynes et azotures comportant deux fonctions triéthoxysilyle ont été préparés, afin d'être clickés sur différentes molécules organiques. Ces précurseurs bissilylés sont des organo(triéthoxy)silanes clickables, précurseurs de silsesquioxanes pontés. En utilisant des molécules fonctionnelles comportant un seul site de dérivatisation, des organosilanes pontés peuvent être obtenus, présentant un fragment organique pendant. De plus, un précurseur contenant une fonction alcyne protégée a été obtenu, ce qui permettra la formation de matériaux multifonctionnels. Certains des précurseurs sol-gel obtenus ont été transformés en matériaux hybrides par le procédé sol-gel. Ceux contenant des fragments organiques connus comme des ligands chiraux actifs ont été choisis pour des tests en catalyse asymétrique. Par ce biais, des ligands chiraux supportés ont été formés, et testés pour quelques réactions bien connues. De plus, cette thèse s'est intéressée à la nano-structuration de matériaux. Des molécules contenant des systèmes aromatiques et des fonctions urée, capables de s'auto-assembler grâce à des interactions non covalentes, ont été conçues et préparées. Dans certains cas, en particulier les systèmes à base de Binol avec des fonctions urée, des nanostructures régulières ont été observées sur des surfaces localisées. En conclusion, les travaux présentés dans cette thèse ont apporté de nouvelles possibilités pour la synthèse d'organo(triéthoxy)silanes, ainsi que des matériaux hybrides à propriétés et applications cibléesOrganosilicates are attracting considerable attention, owing to the combined properties of the organic fragment and inorganic silica matrix. These hybrid materials have found application in catalysis, optics, electronics, etc. They can be prepared by the sol-gel hydrolysis of functional organosilanes with the desired properties. To apply these materials in industry, it is essential to make the preparation of these silylated precursors easier and more efficient by reducing the number of reaction steps. Therefore one of the aims of this thesis is to develop a universal, wide scope and selective method of preparation for trialkoxyorganosilanes. For this purposes the “CuAAC reaction”, known for its simple approach, has been adapted for water-sensitive substrates. Using a silylated azide or silylated alkyne with an organic counterpart, we were able to prepare a series of clicked sol-gel precursors. The reaction is quantitative, fast, and selective and tolerates a wide range of substrates. Moreover, new bissilylated alkynes and azides which can be clicked to various organic molecules were prepared. They represent new families of bridged organotrialkoxysilanes to which a desired organic molecule, bearing only one bonding site, can be incorporated as a pending group with a targeted functionality. Furthermore, a bissilylated precursor bearing a protected alkyne function was prepared, allowing the synthesis of bifunctional materials. Some of the prepared precursors were transformed into hybrid silicas by the sol-gel process. Those containing organic molecules known as active chiral ligands for enantioselective reactions were chosen. By this way, supported chiral ligands were formed and we tested their activity according to known reactions. Additionally, in this thesis the structuring of the materials was also attempted. Molecules bearing aromatic systems and urea functions, which are capable of self-organization thanks to the weak non-covalent bonding interactions, were designed and prepared. In some cases, especially Binol systems with urea function, regular nanostructures on localized areas have been observed. Overall, this thesis brings new possibilities in the synthesis of both trialkoxyorganosilanes precursors and hybrid materials with desired properties and applications
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Bratton, G. J. "Silicate/silicon hybrid materials." Thesis, University of Greenwich, 1986. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234283.
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Žák, Tomáš. "Využití hybridní technologie Laser-TIG pro svařování rozdílných materiálů používáných v energetice." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2019. http://www.nusl.cz/ntk/nusl-400985.
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Thesis is focused on analyzing the influence of preheating process parameters using electric arc from TIG torch during laser welding on weld properties of stainless steel and carbon steel with higher strength. In this thesis experiment was done in which metal sheets 3 mm thick from X12Cr13 and S355 steels were welded. Welding was done first with using only laser, then laser with TIG preheating and lastly laser with preheated material by induction heater. When TIG preheating was used than set welding current was changed on the power source. The welds were subsequently evaluated based on macrostructure, microstructure and Vickers hardness test.
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Lin, Qiqiao. "Luminescent hybrid materials for LED lighting." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLX036.
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Cette thèse visait à concevoir et à synthétiser des matériaux hybrides organiques-inorganiques à luminescence contrôlée et à les étudier en tant que luminophores pour l'éclairage à LED. L'objectif final était d'obtenir une source de lumière blanche. En effet, les LED blanches commerciales sont constituées d'un dispositif émetteur bleu recouvert d'un luminophore jaune. La combinaison de ces deux couleurs produit une lumière blanche. Cependant, cette lumière n'est pas de bonne qualité car il lui manque une composante rouge. Cela entraîne un mauvais rendu des couleurs des objets éclairés par ces sources de lumière. Dans notre travail, des polymères conjugués de différentes couleurs d'émission ont été obtenus avec succès. En particulier, plusieurs émetteurs de blanc ont pu être isolés.Dans cette thèse, non seulement les procédures de synthèse et les caractérisations chimiques sont présentées en détail, mais également les études des propriétés photophysiques des polymères, en solution et à l'état solide. Des études à l'état solide ont été effectuées sur les polymères et sur les polymères dispersés dans une matrice polymère. Ces études ont permis d'identifier les facteurs limitants quant aux utilisations pratiques de ces matériaux. Des solutions ont été proposées pour améliorer les performances d’émission et de stabilité des matériaux. De plus, ces travaux ont permis d'introduire la 2,2’-bipyrimidine comme nouvelle unité constitutrice pour le développement de polymères conjuguésThis thesis aimed at designing and synthesizing organic-inorganic hybrid materials with controlled luminescence and at investigating them as phosphors for LED lighting. The final goal was to obtain a white source of light. Indeed, commercial white LEDs are made up of a blue emitting device covered with a yellow phosphor. Combining these two colors yields white light. However, this light is not of good quality as it lacks some red component. This results in a bad rendering of the colors of objects illuminated by these sources of light. In our work, conjugated polymers with different emission colors have successfully been obtained. In particular, several single white emitters have been isolated.In this PhD thesis, not only the synthetic procedures and chemical characterizations are presented in detail, but also the studies of the photophysical properties of the polymers, either in solution or in the solid state. Solid state studies were performed on the bulk polymers and on the polymers dispersed into a polymeric matrix. These studies have lead to identify the limiting factors that could hamper the use of the materials. Solutions have been proposed to improve the materials performance and stability. Furthermore, 2,2’-bipyrimidine has been introduced as a new synthon for designing and developing conjugated polymers
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Romanenko, Iuliia. "Preparation of well-defined Ir(I)-NHC based catalytic material for the hydrogenation of functional olefins." Thesis, Lyon 1, 2015. http://www.theses.fr/2015LYO10262/document.
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La réaction d'hydrogénation des alcènes est une réaction clé dans de nombreux procédés industriels permettant la production de produits de commodité et de spécialité. D’importants efforts de recherche ont donc été réalisés pour développer des systèmes catalytiques de plus en plus productifs et sélectifs. Parmi les nombreux catalyseurs homogènes et hétérogènes développés à ce jour, les complexes organométalliques d’Iridium(I), très prometteurs, ont été préparés depuis la découverte du catalyseur de Crabtree, [Ir(COD)(py)(PCy3)]BF4, pour répondre à des problèmes de sélectivité dans l'hydrogénation asymétrique ou celle d’oléfines tétrasubstituées fortement encombrées en conditions homogènes. Cependant, l'utilisation industrielle de ce complexe organométallique d’Ir (I) est limité par sa décomposition rapide en solution, qui conduit à la formation de complexes polynucléaires (hydrures pontés d'Iridium) très stables et inactifs en catalyse. Le but de ce travail de thèse a été de développer des matériaux catalytiques contenant des complexes Ir(NHC) isolés à la surface d’une silice contenant des fonctionnalités imidazolium parfaitement distribuées le long de ses canaux poreux. L'isolement des unités Ir(I) sur le support de silice devrait permettre d’empêcher les processus bimoléculaires de désactivation et faciliter la récupération du catalyseur. La préparation des matériaux catalytiques cible se fait grâce a la transformation des unités imidazolium contenues dans le matériau de départ en carbenes d’argent N-hétérocycliques, qui sont ensuite transmétallés en carbènes d’iridium avec le complexe [Ir(COD)Cl]2. Les matériaux obtenus ont été caractérisés par diverses techniques, notamment une technique de RMN très avancée : la RMN de l’état solide utilisant la polarisation nucléaire dynamique. Ceci a permis de mieux comprendre la structure moléculaire des sites de surface iridiés. Les performances catalytiques des complexes Ir-NHC supportés ont été testées dans réaction d’hydrogénation des alcènes et comparées à celles de leurs homologues homogènes. Divers substrats oléfiniques et différentes conditions de réaction ont été testées. Les résultats montrent que le catalyseur supporté est beaucoup plus stable et 50 fois plus actif en terme de vitesse et de productivité. Cette approche a été étendue au développement de catalyseurs d’iridium supportés sur polymère. Le support choisi a été un polyéthylene téléchélique contenant des fonctionnalités iodées terminales. Le solide obtenu après incorporation de l’iridium a été caractérisé par RMN et spectrométrie de masse (MALDITOF). Les performances catalytique de ce nouveau système ont été elles aussi comparées a celles de complexes homologues en solutionAlkene hydrogenation is a key in many bulk and fine chemicals production processes. Major efforts were therefore directed towards the preparation of ever more productive and selective catalysts. Among the large number of homogeneous and heterogeneous catalysts, promising Iridium (I) organometallic complexes were prepared since the discovery of the well-known Crabtree’s catalyst, [Ir(COD)(py)(PCy3)]BF4, to address selectivity issues in homogeneous asymmetric hydrogenation or hydrogenation of highly hindered tetrasubstituted olefins. However, the industrial use of Ir organometallic complexes as catalysts is limited by their fast decomposition leading to the formation of highly stable and inactive polynuclear iridium hydridebridged complexes. The goal of this PhD project was to elaborate supported Ir(I)-NHC catalytic material to prevent such bimolecular deactivation processes. The targeted supported Ir complexes were based on hybrid organic-inorganic material containing regularly distributed imidazolium units along the pore-channels of the silica framework. Beside the Ir-site isolation on the silica support, this catalytic system was also expected to ease catalyst recovery at the end of the hydrogenation. The preparation of the final systems relies on the preparation of supported silver carbenes first, and further transmetallation with an Ir-precursor, namely [Ir(COD)Cl]2. The materials were characterized by several techniques as for example advanced solid state NMR using Dynamic Nuclear Polarization to gain insight into the molecular structure of the Ir surface sites. Catalytic performances of the supported Ir-NHC complexes were tested in alkene hydrogenation and compared to those of homogeneous homologues. Several different substrates and reaction conditions were tested. The results showed that the supported catalyst was much more stable and 50 times more active in term of rate and productivity. A polymer supported Ir-complex was also elaborated using a telechelic polyethylene iodide as support. The polymeric materials were fully characterized by NMR and MALDI-TOF experiments and their catalytic performances were compared to those of molecular analogues and those of silica supported systems
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Hrubý, Jakub. "Příprava a charakterizace hybridních materiálů na grafenové bázi." Master's thesis, Vysoké učení technické v Brně. Fakulta strojního inženýrství, 2017. http://www.nusl.cz/ntk/nusl-318708.
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Grafen v kombinaci s komplexy kovů by mohl poskytnout nové přísutpy v hybridních materiálech založených na grafenové bázi a v oblasti molekulárního magnetismu. Obě témata jsou velmi diskutovaná jako taková, nicméně, výzkumu vedoucího k možnosti jejich míchání není mnoho. Vzorky byly připraveny sonikací grafitu v kapalné fázi, což vedlo k exfoliaci grafenu. Následně byly nadeponovány pomocí modiikované Lagmuirovy– Schaeferovy depoziční metody různé komplexy kovů na substrát pokrytý grafenem. Klíčovým krokem bylo určení vlastností takto připraveného materiálu. Proto byly následně vlastnosti takového hybridního materiálu charakterizovány pomocí vysokofrekvenční elektronové paramagnetické rezonance (angl. HFEPR), rastrovacího elektronového mikroskopu, (angl. SEM), Ramanovou spektroskopií a čtyř bodovou metodou měření odporu. V této práci jsme potvrdili naši presumpci, že je možné vytvořit hybridní materiál smícháním exfoliovaného grafenu s molekulárními magnety pro získání nových magnetických a elektronických vlastností, které by mohly být využity v další generaci detektorů a elektroniky.
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Ben, Sghaier Asma. "Hybrides polymer materials organic/inorganic nanoparticule." Thesis, Paris Est, 2018. http://www.theses.fr/2018PESC1163.
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La chimie d'interface du diazonium a progressé au cours des dernières années et s'est pratiquement impliquée dans tous les domaines de la science et technologie des matériaux. L’utilisation des sels de diazonium est justifiée par le fait qu’ils adhèrent aux surfaces avec de fortes énergies de liaison, en particulier sur le carbone sp², ce qui en fait d’excellents agents de couplage pour les polymères aux surfaces. Dans ce contexte, nous avons travaillé sur deux types de nanohybrides de nanotubes de carbone (NTC) : NTC-polytriazole (NTC-PTAz) et NTC-colorant. Le nanohybride NTC-PTAz a été synthétisé par polymérisation « click » en surface. Pour ce faire, les NTCs ont été greffés de groupes 4-azidophényle à partir du sel de diazonium correspondant. Le NTC modifié (NTC-N3) a servi de support pour une polymérisation confinée en surface de type polyaddition générant ainsi le nanohybride NTC-PTAz. Ce matériau a été caractérisé par ATG, XPS, IR et Raman. Ses applications potentielles sont dans le développent d’adsorbants de métaux lourds, l’immobilisation de nanocatalyseurs ou pour le stockage des gaz. La seconde partie de la thèse est plus étoffée et porte sur les nanotubes de carbone greffés de colorants diazotés Rouge Neutre (NR), Azure A (AA) et Rouge Congo (CR). L’analyse fine de ces matériaux a révélé une très forte adhésion des colorants aux NTCs et les couches superficielles ont des épaisseurs de 2 à 6 nm, sont homogènes et continues. Les NTC-colorant ont été incorporés dans des matrices élastomères de type EVA pour la réalisation d’actionneurs opto-thermiques implantés dans des pads pour non-voyant. Dans les matrices EVA, les NTCs greffés de colorants servent à capter la lumière et induire un changement de forme dans le pad qui soit palpable par le non voyant (250 µm). Les matrices EVA renforcées de nos nanotubes greffés de colorants ont été réalisées et testées par analyse mécanique dynamique. Les composites NTC/colorant-EVA sont flexibles et prometteurs pour le développement de nouveaux types des pads tactiles pour les non-voyants. Les nanohybrides NTC-NR ont servi comme capteurs chémo-résistifs pour la reconnaissance moléculaire de l’acétone.Dans une dernière application, le nanohybride CNT-CR a été étudié en tant qu’électrocatalyseur pour l’oxydation directe du méthanol. Des résultats intéressants ont été obtenus avec ces nanohybrides mais des améliorations significatives (rapport 3) des propriétés électrocatalytiques ont été obtenues avec des CNT-CR décorés avec des nanoparticules d'or. Le système électrocatalytique nouvellement conçu pourrait être considéré pour différentes applications prometteuses, notamment les capteurs, les biocapteurs, les catalyseurs hétérogènes pour les piles à combustible. Pour résumer, les nanohybrides à base de CNT nouvellement conçus présentent des performances uniques attribuées à la polyvalence de la chimie d'interface du diazonium pour la fixation efficace de couches moléculaires et macromoléculaires fonctionnelles. Les nanohybrides novateurs servent de blocs de construction pour la conception de matériaux nanocomposites à hautes performances potentiellement utiles dans les nouveaux défis socio-économiques tels que l’environnement, la biomédecine et l’énergieDiazonium interface chemistry has progressed over the last few years and practically involved in all areas of materials science and engineering. The rationale for employing diazonium salts is that they attach to surfaces with remarkable bond energies, particularly on sp² carbon materials, making them an ideal coupling agent for polymers to surfaces In this context, novel CNT-polytriazole (CNT-PTAz) and CNT-dye nanohybrids were designed and thoroughly characterized. First, CNT-PTAz nanohybrid was prepared by click polymerization: multiwalled carbon nanotubes (CNTs) were modified with azidophenyl groups (CNT-N3) from 4-azidobenzenediazonium precursor and served as nanoscale platform for the surface confined polyaddition. The CNT-PTAz nanohybrid was characterized by TGA, XPS, IR, and Raman. The robust CNT-PTAz is robust and has potential in developing heavy metal adsorbents, nanosupport for catalysts or for gas storage. In the second major part, we grafted CNT with diazotized Neutral red (NR), Azure A (AA) and Congo Red (CR) dyes by simple, spontaneous reaction of the diazonium salts and CNTs in water, at RT. A thorough investigation of the nanohybrids showed that the adhesion is strong (CNT-dye C-C bond energy higher than 150 kJ/mol), and the layer is uniform. These nanohybrids further served to reinforce ethylene-vinyl acetate (EVA) an elastomeric matrix. The reinforced matrix is flexible and serves as optothermal actuators where the grafted dye catches the light to induce mechanical changes in the matrix monitored by dynamic mechanical analysis. CNT/dye-reinforced EVA is a promising flexible composite for developing new types of visual-aid tablet for visually impaired people. The versatile CNT-dye nanohybrids are also unique chemiresistive gas sensors for the molecular recognition of acetone vapours. In a final application, CNT-CR nanohybrid was investigated as an electrocatalyst for the Direct Oxidation of Methanol. Interesting results were obtained with these nanohybrids but significant improvements (3-fold) of the electrocatalytic properties were achieved with CNT-CR decorated with gold nanoparticles. The newly designed electrocatalytic system could be regarded for different promising applications most likely as for sensors, biosensors, heterogeneous catalysts for fuel cells and for nanotechnology To summarize, newly designed CNT-based nanohybrids have unique performances ascribed to the versatility of the diazonium interface chemistry in efficiently attaching functional molecular and macromolecular layers. The novel nanohybrids serve as building blocks for designing high performance nanocomposite materials relevant to challenging timely social economic issues, namely environment, biomedicine and energy
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Evlyukhin, Egor. "Synthèse avancée de matériaux hybrides pHEMA-TiO₂ par méthode sol-gel et polymérisation induite par hautes pressions, analyse de leurs propriétés optiques." Thesis, Sorbonne Paris Cité, 2015. http://www.theses.fr/2015USPCD060.
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Les propriétés fonctionnelles spécifiques des matériaux hybrides organique-inorganique dépendent de leur structure à l’échelle microscopique ainsi que de la nature de l’interface entre leurs composantes organique et inorganique. L’une des voies principales pour synthétiser ces matériaux, consiste à incorporer des blocs inorganiques à l’intérieur d’un polymère. En pratique les applications des matériaux hybrides sont souvent limitées par leur comportement mécanique. En effet, l’augmentation de la concentration de la composante inorganique, à priori souhaitable pour améliorer les propriétés fonctionnelles du matériau, entraine généralement une dégradation des propriétés mécaniques en limitant l’étendue de la polymérisation de la phase organique. La fabrication de matériaux hybrides offrant une combinaison optimale des propriétés mécaniques et fonctionnelles est un problème important auquel nous apportons quelques éléments de réponses dans cette thèse. Pour cela nous démontrons et étudions une nouvelle approche pour la synthèse de matériaux hybrides photosensibles pHEMA-TiO₂ (pHEMA=poly-(2-hydroxyéthyl)méthacrylate) dans lesquels des nanoparticules inorganiques sont dispersées dans un polymère. Le procédé que nous proposons est basé sur l’utilisation de hautes pressions (HP)pour provoquer la polymérisation de la phase organique en l’absence de tout initiateur chimique. Nous avons d’abord observé la polymérisation spontanée du HEMA sous pression statique. La réaction se produit dans un domaine de pression limitée 0.1-1.6 GPa, en dessous du seuil de transition vitreuse, et est très peu efficace puisque le taux de conversion des monomères n’excède pas 28 % après 41 jours. La réaction peut cependant être considérablement accélérée lorsque l’échantillon sous pression est irradié dans le domaine UV. Nous avons montré que cela résultait de l’excitation à un photon de l’état triplet HEMA (T1) rendue possible par la modification de la structure électronique du HEMA sous HP. Cette méthode ne pouvant être utilisée pour la synthèse de matériaux photosensibles dans le domaine UV, nous avons développé une approche originale basée un cycle de compression-décompression. Lors de la phase de compression (> 6.5 GPa) des biradicaux (HEMA)₂ sont formés à partir de monomères excités HEMA (T1). À cette pression les contraintes stériques empêchent la formation de plus longs oligomères. La polymérisation ne se produit que dans une seconde étape lorsque l’échantillon, décompressé entre 0.1 et 2 GPa, est en phase liquide. Le taux de conversion des monomères dépasse alors 90 % en moins de 5 min. Les mesures de chromatographie d’exclusion stérique montrent la formation de longues chaines polymère (45000g/mol) et soulignent l’absence des dimères (HEMA)₂ ayant servis d’initiateurs de polymérisation. Cette seconde méthode de polymérisation s’est révélée extrêmement efficace pour synthétiser des hybrides pHEMA-TiO₂. Par rapport aux hybrides obtenus par voie classique à pression atmosphérique en utilisant des initiateurs de polymérisation thermique ou photonique, l’approche HP mise au point dans cette thèse permet de multiplier par un facteur trois la concentration de nanoparticules sans détériorer l’état de polymérisation de matériau. La sensibilité photonique des hybrides est ainsi augmentée sans dégradation des propriétés mécaniques. L’étude des propriétés photochromiques des hybrides montre que le rendement quantique de séparation des charges photo-induites et la capacité de stockage des électrons atteignent respectivement 15 % et 50%The specific functional properties of the organic-inorganic hybrid materials depend on their microstructure and the nature of the interface between their organic and inorganic components. The production of hybrid materials with an optimum combination of mechanical and functional properties is a major problem in hybrid materials science. In this thesis we adress this issue by studing and proposing a new approach for synthesizing of photosensitive pHEMA-TiO₂ hybrid materials in wich inorganic nanoparticles are dispersed in a polymer. The method that we propose is based on the high pressure (HP) induced polymerization of the organic phase in the absence of a chemical initiator. We first observed the spontaneous polymerization of HEMA under static pressure. The polimerization process takes place in pressure range below the glass transition point (0.1-1.6 GPa) and after 41 days monomer conversion yield (CY) does not exceed 28%. The reaction may be significantly accelerated when the pressurized sample is irradiated in the UV range. We then developed an original approach based on compression-decompression cycle. During the compression step (>6.5 GPa) the biradicals formed from the excited monomers HEMA (T1) lead to the formation of small oligomers. The polimerization occurs in the second step when the sample decompressed at pressures between 0.1 and 2 GPa. The CY of 90% in less than 5 min is achieved. The new HP approach allows multiply by a factor of 3 the contration of nanoparticles in hybrids without damaging of their polimerization state. These hybrids exhibit a quantum efficiency of photoinduced charge separation of 15% and an electron storage capacity of 50%
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Halttunen, Niki. "Nouvelle approche dans l'élaboration de cellules photovoltaïques : réseaux interpénétrés hybrides oxyde-polymère pour hétérojonctions p,n en volume." Thesis, Paris 6, 2015. http://www.theses.fr/2015PA066416/document.
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Les récents développements dans le domaine du photovoltaïque ont permis l'apparition de cellules utilisant des technologies nouvelles. Parmi elles on trouve les cellules photovoltaïques hybrides, cependant les méthodes de fabrication utilisées actuellement présentent des défauts. Cette thèse a pour but de proposer deux nouvelles approches pour la préparation de cellules photovoltaïques hybrides sous forme d'hétérojonctions en volume d'un oxopolymère de titane et d'un polythiophène. Dans un premier temps la formation de mésostructures vermiculaires dans des couches minces de TiO2 par autoassemblage par évaporation a été étudiée, l'oxopolymère amorphe obtenu a ensuite été cristallisé en conditions douces. Ces résultats ont ensuite été utilisés afin de préparer des matériaux hybrides à partir d'homopolymères de thiophène portant des substituants hexyl et acide, ainsi qu'à partir de copolymères. Des matériaux hybrides ne présentant pas de macroségrégation ont été obtenus pour un polymère portant des fonctions acides et pour les copolymères. Dans un second temps l'électrochimie du ferrocène et du cuivre ont été étudiés dans des films de TiO2 mésostructuré et mésoporeux, puis deux dérivés thiophène : le mot et l'edot ont été électropolymérisés dans ces structures. Des cellules photovoltaïques ont été préparées en utilisant ces matériaux hybrides et caractérisées par des mesures de la courbe I/E ainsi que par l'étude du rendement quantique externe, des facteurs de forme et des rendements ont été calculés. En conclusion, deux nouvelles approches de synthèse de matériaux hybrides ont été proposées et menées à bien les propriétés photovoltaïques et ces matériaux ont été mesuréesRecent advances in the field of photovoltaics have led to the emergence of new solar cell technologies. Among them can be found the hybrid solar cells, unfortunately the way such cells are built is still a source of problems. The aim of this phd is to develop two new approaches in the synthesis of hybrid materials as bulk heterojunctions. In first place the titanium dioxide component vas prepared by sol-gel process and its mesostructure was studied, low temperature crystallization was also investigated. Those results were used in order to prepare hybrid materials from preformed polymers. The behavior of polythiophènes with hexyl and carboxylic acid functions were used as well as copolymers bearing both functions. Hybrids without macrosegregations phenomena were obtained using acid bearing homopolymers as well as copolymers. The second approach was about investigating the electrochemical behavior of ferrocene and copper ions inside the mesoporosity, this first study was followed by a study of the electropolymerization of mot and edot inside the porosity in order to prepare hybrid materials. The obtained hybrids were studied in solar cells by measuring the I/V curve as well as the external quantum efficiency, fill factors and efficiencies were also obtained. To conclude, both approaches leaded to hybrid materials with measurable photovoltaic properties
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Forconi, Mattia. "Experimental analysis of a hybrid composite material." Master's thesis, Alma Mater Studiorum - Università di Bologna, 2017.
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The main aim of this thesis is to investigate the mechanical properties of a hybrid composite material under static loadings. The material is a composite laminate made by layers of carbon bars and a rubber layer. The thesis can be split into three main parts. In the first part a background about carbon bar composite is given and, subsequently, the research and main results on hybrid composites is introduced. The objective of this section is to provide a base on which built the main results of this work. In the second part it is explained how the test activities have been performed and the main results obtained. In particular, the effect of the introduction
of a rubber layer has been highlighted in each type of tests. In the last part, a finite element dynamical analysis is presented. A very simple transient analysis has been performed in order to foresee the dynamic behaviour of the hybrid. In conclusion, it has been demonstrated a relevant hybrid effect in the compressive and flexural properties. Those effects can be roughly reassumed in anincreasing specific stiffness for the compressive properties and in a large improvement of flexibility in the bending test. The numerical simulation shows that an increased damping effect is present, corresponding to an increase of rubber layer thickness.
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Hendon, Christopher Holman. "Hybrid semiconductors : design rules and material applications." Thesis, University of Bath, 2015. https://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.683540.
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Scott, Felicia Yi Xia. "Controlled Hybrid Material Synthesis using Synthetic Biology." Diss., Virginia Tech, 2017. http://hdl.handle.net/10919/86147.
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The concept of creating a hybrid material is motivated by the development of an improved product with acquired properties by amalgamation of components with specific desirable traits. These new attributes can range from improvements upon existing properties, such as strength and durability, to the acquisition of new abilities, such as magnetism and conductivity. Currently, the concept of an organic-inorganic hybrid material typically describes the integration of an inorganic polymer with organically derived proteins. By building on this idea and applying the advanced technologies available today, it is possible to combine living and nonliving components to synthesize functional materials possessing unique abilities of living cells such as self-healing, evolvability, and adaptability. Furthermore, artificial gene regulation, achievable through synthetic biology, allows for an additional dimension of the control of hybrid material function.
Here, I genetically engineer E. coli with a tightly controlled artificial protein construct, allowing for inducible expression of different amounts of the surface anchored protein by addition of varying concentrations of L-arabinose. The presence of the surface protein allows the cells to bind nonliving nanoparticle substrates, effectively turning the cells into living crosslinkers. By using the living crosslinker, I was able to successfully synthesize a robust, macroscale living-nonliving hybrid material with magnetic characteristics. Furthermore, by varying the particle size and inducer concentration, the resulting material exhibited alterations in structure and function. Finally, I was able to manipulate material kinetics within a PDMS channel by applying fluctuating magnetic fields and demonstrate material durability. These results demonstrate the ability to manipulate synthesis of living-nonliving hybrid materials, which demonstrate the potential for use in promising applications in areas such as environmental monitoring and micromachining. Additionally, this work serves as a foundational step toward the integration of synthetic biology with tissue engineering by exploiting the possibility of controlling material properties with genetic engineering.Ph. D.
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Pana, Cristina. "Development of new carbon hybrid materials for Li+ and Na+ ion batteries applications." Thesis, Mulhouse, 2018. http://www.theses.fr/2018MULH0541.
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Au cours des dernières années, de nombreuses recherches se sont concentrées sur les batteries afin de satisfaire leur demande croissante pour de nombreuses applications. Les matériaux hybrides métal/carbone ont fait l'objet d'une grande attention en tant qu'anodes pour les batteries ioniques Li et Na en raison de leur capacité plus élevée par rapport aux anodes graphite/carbone dur. Cependant, l'expansion de la taille des NPs métalliques et la forte capacité irréversible pendant le 1ercycle sont les principaux inconvénients à surmonter et représentent l'objectif principal de cette thèse. Trois types d'hybrides ont été étudiés (C@Sn et C@SiO2pour les LIBs, et C@Sb pour les NIBs) et des voies de synthèse originales ont été développées qui ont permis d'obtenir des matériaux avec des NPs petites et homogènes distribuées dans le réseau de carbone. Plusieurs paramètres expérimentaux ont été optimisés, conduisant à une vaste palette de matériaux avec des porosités, des structures et des granulométries différentes. La température et la charge de particules se sont avérées être les principaux paramètres affectant la porosité et la taille des particules ainsi que les performances électrochimiques. L'augmentation de la température et de la charge de NPs ont conduit à une porosité plus faible qui a permis de diminuer la capacité irréversible et d'améliorer la capacité réversible. En même temps, le cycle à long terme a été affecté négativement en raison de la formation de particules non confinées et agglomérées. Un compromis entre la charge de carbone/porosité/structure a été déterminé pour chaque système et les mécanismes électrochimiques traités sur la base d'analyses post-mortemDuring the last years a lot of research has been focused on batteries to satisfy their increasing demand for a broad application. Metal-based/carbon hybrid materials received great attention as anodes for Li and Na ion batteries due to their higher capacity compared to graphite/hard carbons anodes. However, the metal particle size expansion and the high irreversible capacity during cycling are the main inconvenients to be overcome and represent the main goal of this thesis. Three type of hybrids were studied(C@Sn and C@SiO2for LIBs, and C@Sb for NIBs) and original synthesis pathways were developed which allowed to obtain materials with small and homogeneous distributed particles in the carbon network. Several experimental parameters were tuned leading to a large pallet of materials exhibiting different porosities, structures and particle size/distribution. The temperature and the particle loading were found to be the main parameters affecting the porosity and the particle size and further the electrochemical performances. The increase of both temperature and particle loading lead to smaller porosity which successfully allowed to diminish the irreversible capacity and to improve the reversible capacity. In the same time, the long-term cycling was negatively affected due to the formation of un-confined and agglomerated particles. The extent of particle agglomeration and consequently of capacity fading was found to depend on the type of metal and synthesis route. A compromise between the carbon loading/porosity/structure was determined for each system and the electrochemical mechanisms addressed based on post-mortem analyses
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Pourcin, Florent. "Synthèse de nanoparticules de forme, taille et dispersion contrôlées pour l'élaboration de couches composites aux propriétés optiques modulables." Thesis, Aix-Marseille, 2018. http://www.theses.fr/2018AIXM0365/document.
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Les nanoparticules de métaux nobles possèdent des propriétés optiques étonnantes. Sous l’effet de la lumière, elles sont capables de résonner pour générer des plasmons de surface localisés. Ces plasmons absorbent ou diffusent la lumière aux longueurs d’ondes de ces résonnances et sont fortement dépendants de la forme, de la taille et de l’environnement des nanoparticules. Dans ce manuscrit, elles sont impliquées dans la conception de matériaux furtifs à des fins militaires.Des nanoparticules d’argent de formes contrôlées ont été associées à un polymère pour élaborer de nouveaux matériaux hybrides déposables par voie liquide sous la forme de couches minces.Un absorbeur quasi-parfait (98,8%) sur une gamme étroite de longueur d’onde a été obtenu en maintenant une très bonne dispersion des nanoparticules dans la couche, alors qu’un absorbeur large bande efficace (~90%) sur toute la gamme spectrale du visible a été réalisé en provoquant l’agrégation des nanoparticules. Une étude qualitative par microscopie et spectroscopie sur la densité et l’organisation des nanoparticules au sein de la couche mince a mis en évidence la présence de couplages plasmoniques de natures et d’intensités différentes en fonction de l’espacement entre les cubes. Il a été montré que les propriétés optiques mesurées étaient indépendantes de la nature du substrat utilisé, mais aussi indépendantes de l’angle de la lumière incidente sur une large gamme angulaire. Enfin, des systèmes multicouches déposés par voie liquide ont été explorés afin d’étendre l’absorption des couches jusqu’au proche infrarouge par l’ajout de matériaux tel que le l’oxyde de tungstèneNanoparticles of noble metals have unexpected optical properties. Under the effect of light, they are able to resonate, generating localized surface plasmon resonances that are used in many applications. These plasmons absorb and scatter the light at the wavelengths of these resonances and are highly dependent on the shape, the size and the environment of the nanoparticles. In this thesis, they are applied for the design of stealth materials for military purposes. For this, controlled shapes of silver nanoparticles were blended within a polymer to develop new hybrid materials that are solution-processed as thin layers. A quasi-perfect absorber (98,8%) in a precise range of wavelengths has been obtained by maintaining well-dispersed nanoparticles in the layer, while an effective broadband absorber (~90%) over the entire visible range has been achieved by triggering the aggregation of the nanoparticles. Microscopy and spectroscopy qualitative studies performed on the density and organization of the nanoparticles within the thin layers revealed the presence of plasmonic couplings of different natures and intensities as a function of the spacing between the cubes. It has been shown that the optical properties measured are independent of the nature of the substrates used and independent of the angle of the incident light on a wide angular range. Finally, solution-processing of multilayers systems was explored to extend the absorption of the layers to the near infrared by the addition of other materials such as tungsten oxide
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Johnson, Bret J. S. "Hybrid materials constructed from polyoxometalate /." Diss., ON-CAMPUS Access For University of Minnesota, Twin Cities Click on "Connect to Digital Dissertations", 2001. http://www.lib.umn.edu/articles/proquest.phtml.
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Holmstrom, Stewart. "Self-assembled bioinorganic hybrid materials." Thesis, University of Bristol, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.492556.
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The theme that is central to this thesis, connecting the three experimental chapters, is the synthesis and characterization of hybrid inorganic-organic nanocomposites, facilitated through inorganic and biological self-assembly.
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Burwood, Ryan Paul. "Towards semiconducting hybrid framework materials." Thesis, University of Cambridge, 2013. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.648156.
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Amarante, Tatiana Ribau. "New oxomolybdenum(VI) hybrid materials." Doctoral thesis, Universidade de Aveiro, 2013. http://hdl.handle.net/10773/12298.
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Doutoramento em QuímicaIn this thesis, 2,2’-bipyridine (bipy), di-tert-butyl-2,2’-bipyridine (di-t-Bubipy), 2,2’-bipyridine-5,5’-dicarboxylic acid (H2bpdc), 2-[3(5)-pyrazolyl]pyridine (pzpy) and 2-(1-pentyl-3-pyrazolyl)pyridine (pent-pp) ligands were used as the N,N-chelate ligands in the formation of discrete [MoO2Cl2L]-type complexes. These complexes were employed as precursors for the preparation in aqueous media of oxomolybdenum(VI) products with a wide range of structural diversity. Three distinct heating methods were studied: hydrothermal, reflux or microwave-assisted synthesis. An alternative reaction with the inorganic molybdenum(VI) trioxide (MoO3) and the ligands di-t-Bu-bipy, H2bpdc and pzpy was also investigated under hydrothermal conditions. The distinct nature of the N,N-chelate ligands and/or the heating method employed promoted the isolation of a series of new oxomolybdenum(VI) hybrid materials that clearly reflected the strong structure-directing influence of these ligands. Thus, this thesis describes the synthesis and characterization of the discrete mononuclear [MoO2Cl2(pent-pp)], the dinuclear [Mo2O6(di-t-Bu-bipy)2] and the octanuclear [Mo8O22(OH)4(di-t-Bu-bipy)4] complexes as well as the highly unique polymeric materials {[MoO3(bipy)][MoO3(H2O)]}n, (DMA)[MoO3(Hbpdc)]·nH2O, [Mo3O9(pzpy)]n and [Mo2O6(pent-pp)]n (fine structural details of compound [Mo2O6(pent-pp)]n are presently unknown; however, characterization data strongly pointed toward a polymeric oxide hybrid compound). The catalytic behaviour of the discrete complexes and the polymeric compounds was tested in olefin epoxidation reactions. Compounds [Mo3O9(pzpy)]n and [Mo2O6(pent-pp)]n acted as sources of soluble active species that where identified as the oxodiperoxido complexes [MoO(O2)2(pzpy)] and [MoO(O2)2(pent-pp)], respectively. The majority of the compounds here presented were fully characterized by using solid-state techniques, namely elemental analyses, thermogravimetry, FT-IR, solid-state NMR, electron microscopy and powder X-ray diffraction (both from laboratory and/or synchrotron sources).
Nesta tese as moléculas 2,2’-bipiridina (bipy), di-tert-butil-2,2’-bipiridina (di-t-Bu-bipy), ácido 2,2’-bipiridina-5,5’-dicarboxílico (H2bpdc), 2-[3(5)-pirazolil]piridina (pzpy) e 2-(1-pentil-3-pirazolil)piridina (pent-pp) foram utilizadas como ligandos bidentados de azoto para a formação de complexos do tipo [MoO2Cl2L], no intuito de investigar a diversidade estrutural de compostos pertencendo à família oxomolibdénio(VI). Foram estudados três métodos de aquecimento: o método hidrotérmico, de refluxo e por microondas. Foi também estudada sob condições hidrotérmicas a reacção alternativa envolvendo a utilização do composto inorgânico trióxido de molibdénio (MoO3) com os ligandos di-t-Bu-bipy, H2bpdc e pzpy. A natureza dos ligandos bidentados de azoto e/ou o método utilizado promoveram a formação de uma série de novos híbridos do tipo oxomolibdénio(VI) que claramente reflectiram a influência estruturante dos ligandos. Assim, esta tese descreve a síntese e caracterização do complexo mononuclear [MoO2Cl2(pent-pp)] , dinuclear [Mo2O6(di-t-Bu-bipy)2] e octanuclear [Mo8O22(OH)4(di-t-Bu-bipy)4] assim como dos materiais poliméricos {[MoO3(bipy)][MoO3(H2O)]}n, (DMA)[MoO3(Hbpdc)]·nH2O, [Mo3O9(pzpy)]n and [Mo2O6(pent-pp)]n (embora os detalhes estruturais deste polímero sejam ainda desconhecidos, os dados da sua caracterização remetem para um oxo-híbrido polimérico). O comportamento catalítico dos complexos e dos compostos poliméricos foi testado na reacção de epoxidação de olefinas. Os compostos [Mo3O9(pzpy)]n e [Mo2O6(pent-pp)]n deram origem a espécies activas solúveis respectivamente identificadas como os complexos oxodiperoxido [MoO(O2)2(pzpy)] e [MoO(O2)2(pent-pp)]. A maioria dos compostos aqui apresentados foram caracterizados através da utilização de técnicas de caracterização do estado sólido, nomeadamente análise elementar, análise termogravimétrica, FT-IV, RMN de estado sólido, microscopia electrónica e difracção de raio-X de pós (tanto de fontes do laboratório e/ou de sincrotrão).
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Almeida, José Carlos Martins de. "Hybrid materials for biomedical applications." Doctoral thesis, Universidade de Aveiro, 2016. http://hdl.handle.net/10773/15973.
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Doutoramento em Ciência e Engenharia de MateriaisThe increased longevity of humans and the demand for a better quality of life have led to a continuous search for new implant materials. Scientific development coupled with a growing multidisciplinarity between materials science and life sciences has given rise to new approaches such as regenerative medicine and tissue engineering. The search for a material with mechanical properties close to those of human bone produced a new family of hybrid materials that take advantage of the synergy between inorganic silica (SiO4) domains, based on sol-gel bioactive glass compositions, and organic polydimethylsiloxane, PDMS ((CH3)2.SiO2)n, domains. Several studies have shown that hybrid materials based on the system PDMS-SiO2 constitute a promising group of biomaterials with several potential applications from bone tissue regeneration to brain tissue recovery, passing by bioactive coatings and drug delivery systems. The objective of the present work was to prepare hybrid materials for biomedical applications based on the PDMS-SiO2 system and to achieve a better understanding of the relationship among the sol-gel processing conditions, the chemical structures, the microstructure and the macroscopic properties. For that, different characterization techniques were used: Fourier transform infrared spectrometry, liquid and solid state nuclear magnetic resonance techniques, X-ray diffraction, small-angle X-ray scattering, smallangle neutron scattering, surface area analysis by Brunauer–Emmett–Teller method, scanning electron microscopy and transmission electron microscopy. Surface roughness and wettability were analyzed by 3D optical profilometry and by contact angle measurements respectively. Bioactivity was evaluated in vitro by immersion of the materials in Kokubos’s simulated body fluid and posterior surface analysis by different techniques as well as supernatant liquid analysis by inductively coupled plasma spectroscopy. Biocompatibility was assessed using MG63 osteoblastic cells. PDMS-SiO2-CaO materials were first prepared using nitrate as a calcium source. To avoid the presence of nitrate residues in the final product due to its potential toxicity, a heat-treatment step (above 400 °C) is required. In order to enhance the thermal stability of the materials subjected to high temperatures titanium was added to the hybrid system, and a material containing calcium, with no traces of nitrate and the preservation of a significant amount of methyl groups was successfully obtained. The difficulty in eliminating all nitrates from bulk PDMS-SiO2-CaO samples obtained by sol-gel synthesis and subsequent heat-treatment created a new goal which was the search for alternative sources of calcium. New calcium sources were evaluated in order to substitute the nitrate and calcium acetate was chosen due to its good solubility in water. Preparation solgel protocols were tested and homogeneous monolithic samples were obtained. Besides their ability to improve the bioactivity, titanium and zirconium influence the structural and microstructural features of the SiO2-TiO2 and SiO2-ZrO2 binary systems, and also of the PDMS-TiO2 and PDMS-ZrO2 systems. Detailed studies with different sol-gel conditions allowed the understanding of the roles of titanium and zirconium as additives in the PDMS-SiO2 system. It was concluded that titanium and zirconium influence the kinetics of the sol-gel process due to their different alkoxide reactivity leading to hybrid xerogels with dissimilar characteristics and morphologies. Titanium isopropoxide, less reactive than zirconium propoxide, was chosen as source of titanium, used as an additive to the system PDMS-SiO2-CaO. Two different sol-gel preparation routes were followed, using the same base composition and calcium acetate as calcium source. Different microstructures with high hydrophobicit were obtained and both proved to be biocompatible after tested with MG63 osteoblastic cells. Finally, the role of strontium (typically known in bioglasses to promote bone formation and reduce bone resorption) was studied in the PDMS-SiO2-CaOTiO2 hybrid system. A biocompatible material, tested with MG63 osteoblastic cells, was obtained with the ability to release strontium within the values reported as suitable for bone tissue regeneration.
O aumento da longevidade dos seres humanos e a procura de uma melhor qualidade de vida têm conduzido a uma pesquisa contínua de novos materiais para implantes. O desenvolvimento científico, juntamente com uma crescente multidisciplinaridade entre as ciências dos materiais e as ciências da vida deram origem a novas abordagens, como a medicina regenerativa e a engenharia de tecidos. A busca de um material com propriedades mecânicas próximas das do osso humano produziu uma nova família de materiais híbridos que tiram partido da sinergia entre os domínios inorgânicos de sílica (SiO4), com base em composições de vidros bioativos obtidos por sol-gel, e os domínios orgânicos de polidimetilsiloxano, PDMS ((CH3)2.SiO2)n. Vários estudos têm demonstrado que os materiais híbridos baseados no sistema PDMS-SiO2 constituem um grupo de biomateriais promissores com várias aplicações potenciais tais como a regeneração de tecido ósseo e a recuperação do tecido cerebral, passando por revestimentos bioativos e sistemas de libertação controlada de fármacos. O objetivo do presente trabalho foi preparar materiais híbridos para aplicações biomédicas com base no sistema PDMS-SiO2 e contribuir para uma melhor compreensão das relações entre as condições de processamento sol-gel, as estruturas químicas, a microestrutura e as propriedades macroscópicas. Para alcançar tal objetivo, foram usadas diferentes técnicas de caracterização: espectroscopia de infravermelho por transformada de Fourier, ressonância magnética nuclear no estado sólido e no estado líquido, difração de raios-X, dispersão de raios-X de baixo ângulo, dispersão de neutrões de baixo ângulo, análise da área de superfície pelo método de Brunauer–Emmett–Teller, microscopia eletrónica de varrimento e microscopia eletrónica de transmissão. A rugosidade e a molhabilidade das superfícies foram analisadas por perfilometria óptica 3D e por medidas de ângulo de contacto, respectivamente. A bioatividade in vitro foi avaliada através de testes de imersão em plasma sintético e posterior observação da superfície dos materiais e análise do líquido sobrenadante por espectrometria de emissão atômica por plasma acoplado Indutivamente. A biocompatibilidade in vitro foi avaliada usando células osteoblásticas MG63. Materiais do sistema PDMS-SiO2-CaO foram inicialmente preparados usando o nitrato como fonte de cálcio. Para eliminar os resíduos de nitrato no produto final, devido à sua potencial toxicidade, é necessária uma etapa de tratamento térmico (acima dos 400° C). A fim de aumentar a estabilidade térmica dos materiais submetidos a altas temperaturas, foi adicionado titânio ao sistema híbrido. Obteve-se assim um material híbrido contendo cálcio, sem vestígios de nitrato, mantendo-se uma quantidade significativa de grupos metilo. A dificuldade de obter amostras monolíticas de híbridos PDMS-SiO2-CaO por síntese sol-gel e posterior tratamento térmico para eliminação de nitratos, criou um novo objetivo: a procura de fontes alternativas de cálcio. Novas fontes de cálcio foram avaliadas para substituir o nitrato tendo-se escolhido o acetato de cálcio devido à sua boa solubilidade em água. Estabeleceram-se protocolos de preparação por sol-gel a partir dos quais se obtiveram amostras monolíticas homogéneas. Além de melhorar a bioatividade, o titânio e o zircónio influenciam as características estruturais e microestruturais dos sistemas binários SiO2-TiO2 e SiO2-ZrO2, bem como dos sistemas PDMS-TiO2 e PDMS-ZrO2. Neste contexto, foram estudadas diferentes condições experimentais no processo sol-gel, de modo a compreender o papel destes aditivos no sistema SiO2-PDMS. Concluiu-se que o titânio e o zircónio influenciam a cinética do processo sol-gel devido à diferente reatividade dos despectivos alcóxidos, conduzindo à obtenção de xerogéis híbridos com diferentes características e morfologias. O isopropóxido de titânio, menos reativo do que o propóxido de zircónio, foi escolhido como fonte de titânio, usado como aditivo no sistema PDMS-SiO2CaO. Dois procedimentos diferentes de preparação por sol-gel foram seguidos, utilizando a mesma composição de base e o acetato de cálcio como fonte de cálcio. Foram obtidas diferentes microestruturas muito hidrofóbicas e ambas mostraram ser biocompatíveis após serem testadas com células osteoblásticas MG63. Finalmente, foi avaliado o papel do estrôncio (conhecido nos biovidros por favorecer a formação de tecido ósseo e reduzir a sua reabsorção) no sistema híbrido PDMS-CaO-SiO2-TiO2. O material produzido revelou-se biocompatível, através de testes com células osteoblásticas MG63, e com a capacidade de libertar estrôncio dentro dos limites considerados adequados para a reparação do tecido ósseo.
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Prévôt, Marianne. "Démonstrateurs des potentialités applicatives des clustomésogènes." Thesis, Rennes 1, 2014. http://www.theses.fr/2014REN1S164/document.
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Les clustomésogènes sont une nouvelle classe de cristaux liquides hybrides multifonctionnels découverts dans l'équipe CSM de l'Institut des Sciences Chimiques de Rennes en 2008. Ils sont constitués d'un cœur inorganique - des clusters de métaux de transition - auquel sont associés, de manière covalente ou électrostatique, des ligands organiques pro-mésogéniques. Ces matériaux hybrides associent les propriétés d'auto-assemblage des cristaux liquides aux propriétés intrinsèques des clusters métalliques. Le présent travail s'articule autour de clustomésogènes contenant des clusters octaédriques de molybdène, phosphorescents dans le rouge-proche infra-rouge, et aux rendements quantiques compris entre 10% et 50%. Ils sont synthétisés par approche ionique en vue de leur intégration dans des dispositifs optiques. La démarche consiste à rationaliser les relations structures-propriétés afin de contrôler l'arrangement des clustomésogènes à l'échelle nanométrique. Nous créons ainsi des états nématiques sur de larges gammes de température. Le transfert de ces systèmes dans des cellules électro-optiques est renforcé par leur miscibilité dans un certain nombre de cristaux liquides commerciaux. La nature et la concentration de ces derniers permet l'ajustement des températures de fonctionnement et le contrôle de la viscosité de l'état cristal-liquide. Nous montrons qu'il est possible de faire commuter l'intensité de photoluminescence des clustomésogènes de 50% par l'application d'un champ alternatif à la manière des systèmes d'affichage. L'intégration au sein de diodes électroluminescentes constitue le dernier volet de ce travail. La maîtrise de leur structure permet d'envisager leur potentiel dans des dispositifs d'éclairage. L'ensemble de ces études ouvre la voie aux clustomésogènes de molybdène comme alternative réaliste aux émetteurs inorganiques rouges actuelsClustomesogens are a new class of hybrid liquid crystals developed since 2008 in our laboratory. They are a combination of an inorganic core, namely transition metal clusters, linked with promesogenic organic ligands through covalent or electrostatic interactions. These hybrid materials associate liquid crystals self-assembling abilities to the metallic clusters intrinsic properties. This work present octahedral molybdenum cluster based clustomesogens, emitting, through phosphorence mechanisms, in the deep red area and exhibiting 10% to 50% quantum efficiency. These materials are produced via an ionic approach by replacing the alkali cations of the ternary solid state compounds with tailored promesogenic organic ones. The ambition of this work is to rationalize the structures-properties relationship to control, at the nanometric scale, the clustomesogens organization. This approach allows us to observe nematic liquid crystalline phases over a wide range of temperatures. As these compounds are miscible with commercial nematic liquid crystals, we could envision their use as emissive species in the design of electroswitchable luminescent liquid crystal cells. By changing the type and concentration of commercial liquid crystals, we could adjust the operating temperature range as well as the viscosity of the mixture. We also establish that it is possible to modulate the clustomesogens' photoluminescence by 50% by applying an alternative electric field, as in display devices. In the last part of this work, we study the integration of clustomesogens as the emissive species into electroluminescent diodes. Being able to control their structure should allow their use in lighting devices. These works pave the way for using Molybdenum clustomesogens as an alternative to inorganic compounds presently used as red light emitters
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Huo, Zhaohui. "Polyoxometalate - porphyrin hybrids systems : application for the photocurrent generation and the photocatalysis." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF032/document.
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Des films du type polyoxométallates-porphyrines ont été synthetisés et sont basés sur des interactions du types covalentes ou électrostatiques. Les films polyoxométallates–porphyrines sont obtenus par électro-oxydation de l’octaéthylporphyrine de zinc (ZnOEP) ou la 5,15-ditolylporphyrine (H2T2P) en présence de différents types of polyoxométallates (POMs) portant deux groupes pyridyles pendants (py-POM-py) Trois type de systèmes py-POM-py ont été utilises : i) un Lindqvist polyoxovanadate fonctionalisé via deux groupes tris-alkoxo , ii) un derive organosilyl fonctionalisé du type Keggin ou Dawson, et iii) des briques du type Dawson [P2W15V3O62]9− fonctionalisée avec des groupements organiques bis-pyridine de géométrie variée via un greffage diolamide). Tous ces films ont été testé pour la génération de photocourant et la photocatalyse de la réduction de métaux (Ag et Pt). Des films électrostatiques POM-porphyrin ont été également préparés par incorporation de polyanion du type Preyssler [NaP5W30O110]14- sur les films de porphyrine polycationic (poly-ZnOEP) électropolymérisés avec des espaceurs viologènes ou bis-viologènes. [NaP5W30O110]14- agit comme relais d’électron entre une porphyrine excitée ZnOEP* et le viologène (ou le bis-viologène) retardant la recombinaison de charge ce qui permet une augmentation du photocourant. Enfin, des nanoparticules POM@NPs (Pt, Au, Ag) ont été introduites en surface de copolymère polycationique à base de bis-porphyrine par métathèse afin d’augmenter l’efficacité de la génération de photocourant. La résonance de plasmon de surface localisée qui se produit à la surface des nanoparticules d'argent a sensiblement améliorée l'excitation électronique de porphyrinePolyoxometalates-porphyrin hybrid films were synthesized based on covalent or electrostatic interactions. Copolymeric polyoxometalate–porphyrin films were obtained by the electro-oxidation of zinc octaethylporphyrin (ZnOEP) or 5,15-ditolyl porphyrin (H2T2P) in the presence of a different type of polyoxometalates (POMs) bearing two pyridyl groups (py-POM-py). Three type of py-POM-py have been used: i) a tris-alkoxo functionalized Lindqvist polyoxovanadate, ii) an organosilyl functionalized Keggin-type [PW11Si2O40C26H16N2]3- and Dawson-type [P2W17Si2O62C26H16N2]6-, and iii) a bis-pyridine-substituted organo-polyoxometallic bricks using [P2W15V3O62]9− diolamide-grafting method with various geometries of the pendant group. All are applied for photocurrent generation and photocatalytical recovery of metals (Ag and Pt). Electrostatic POM-porphyrin films were also prepared by incorporated Preyssler type polyanion [NaP5W30O110]14- onto the electropolymerized polycationic porphyrin (poly-ZnOEP) with viologen or bis-viologen as spacers. [NaP5W30O110]14- as an efficient electron shuttle between the excited ZnOEP and viologen (or bis-viologen) which effectively retarded the fast charge pair recombination and enhanced the photocurrent magnitude. Later, we introduced nanoparticles POM@MNPs to a bis-porphyrin copolymer through metathesis reaction to further improve the efficiency of the photocurrent generation in which the localized surface plasmon resonance that occurs at the surface of silver nanoparticles has substantially enhanced the electronic excitation of surface-anchored porphyrin
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Dedecker, Kevin. "Multifunctional Hybrid materials for the capture and detection of volatile organic Compounds : Application to the preservation of cultural heritage objects." Thesis, Université Paris-Saclay (ComUE), 2019. http://www.theses.fr/2019SACLV003.
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Lors de leur stockage ou de leur exposition, les objets du patrimoine sont soumis à des processus physico-chimiques d’altération liés à leur environnement et en particulier à l’action de polluants primaires (e.g. dioxyde de soufre, oxydes d’azote), secondaires (ozone) ou de composés organiques volatils (COVs). Il a été démontré que ces gaz/vapeurs se comportent comme des agents d’hydrolyse et d’oxydation. L’acide acétique fait partie des COVs ayant un impact considérable et reconnu dans la conservation des objets du patrimoine en particulier des films photographiques. En vue de lutter contre ses effets délétères, ce projet de thèse s’est focalisé sur la conception de nouveaux matériaux poreux hybrides multifonctionnels appelés « Metal-Organic Frameworks » (MOFs) pour la capture sélective de l’acide acétique en présence d’humidité (40% humidité relative) et à température ambiante. Les remarquables propriétés d’adsorption (sensibilité, sélectivité et capacité) et la grande versatilité des MOFs (balance hydrophile/hydrophobe, taille/forme des pores,…) ont été utilisés pour préconcentrer de façon sélective l’acide acétique en milieu humide. Les matériaux les plus performants ont ensuite été préparés sous forme de nanoparticules pour l’élaboration de films minces de qualité optique afin d’en étudier les propriétés d’adsorption et de co-adsorption (acide acétique/eau) par ellipsométrie. L’incorporation de nanoparticules métalliques plasmoniques a ensuite été effectuée afin de concevoir un capteur colorimétrique. L’objectif final de ce travail est de concevoir un nouveau type d’adsorbant caractérisé par une capacité et une sélectivité d’adsorption élevée et dont on pourrait aisément déterminer le niveau de saturation en acide acétique afin d’anticiper son remplacement et ainsi assurer la préservation des objets stockés et exposés dans les muséesDuring their storage or their exhibition, the cultural heritage objects undergo physicochemical alteration processes related to their environment and in particular to the action of primary (e.g. sulfur dioxide, nitric oxides), secondary (ozone) pollutants or Volatile Organic Compounds (VOCs). It has been demonstrated that these gases/vapors are involved in hydrolysis and oxidation reactions. Among the most common VOCs encountered in museums, Acetic acid has a significant and recognized role in the deterioration of cultural heritage objects such as photographic films. In order to face this issue, this Ph.D. thesis focused on the design of new porous multifunctional hybrid materials denoted « Metal-Organic Frameworks » (MOFs) for the selective capture of acetic acid in the presence of moisture (40% relative humidity) and at room temperature. The remarkable adsorption properties (sensitivity, selectivity and capacity) and the great versatility of MOFs (hydrophicity/hydrophobicity balance, size/shape of pores,…) were used to preconcentrate selectively the acetic acid in humid conditions. The most performing materials were then prepared as nanoparticles and then used for the elaboration of high optical quality thin films in order to study the coadsorption (acetic acid/water) properties of MOFs by ellipsometry. The incorporation of plasmonic metal nanoparticles was then carried out in order to design a colorimetric sensor. The final objective is to devise a novel type of adsorbent that integrates a high VOC adsorption capacity and selectivity under humid conditions and an easy on-line monitoring of their saturation capacityin order to anticipate its replacement and therefore ensure the preservation of the stored and exhibited objects in museums
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Togonal, Alienor. "Silicon Nanowires for Photovoltaics : from the Material to the Device." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLX032/document.
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Les cellules solaires à base de nanofils de silicium offrent une alternative intéressante pour la réalisation de panneaux photovoltaïques à haut rendement et à faible coût. Elles bénéficient notamment des excellentes propriétés optiques des nanofils qui forment une surface à très faible réflectivité tout en piégeant efficacement la lumière. Dans cette thèse, nous utilisons et améliorons une méthode de gravure chimique peu coûteuse et industrialisable pour la fabrication de forêts de nanofils de silicium. En adaptant la mouillabilité du substrat et des nanofils, nous avons remédié au problème d'agglomération inhérent à cette méthode lorsqu’on veut obtenir des forêts denses et désordonnées de nanofils. En combinant cette méthode de gravure chimique à la lithographie assistée par nanosphères, nous avons pu fabriquer des réseaux ordonnés de nanofils avec un contrôle précis des propriétés géométriques (diametre des nanofils et distance entre eux). Les propriétés optiques de ces réseaux ont été étudiées théoriquement et expérimentalement afin d'identifier les configurations optimales. Nous avons ensuite fabriqué des cellules solaires à partir de ces différents types de nanofils et deux types de structures. Le premier type, des cellules solaires HIT (Hétérojonction avec couche mince Intrinsèque) à base de nanofils de silicium, a été fabriqué par RF-PECVD. L'optimisation des conditions de dépôt plasma nous a permis d'obtenir des cellules solaires hautement performantes: rendements de 12,9% et facteurs de forme au-delà de 80%. Le second type, des cellules solaires hybrides, est basé sur la combinaison d'une couche organique et des nanofils de silicium. La caractérisation des cellules fabriquées montre des rendements prometteurs. Enfin, nous présentons des résultats préliminaires pour transférer ces concepts à une technologie couches mincesSilicon Nanowire (SiNW) based solar cells offer an interesting choice towards low-cost and highly efficient solar cells. Indeed solar cells based on SiNWs benefit from their outstanding optical properties such as extreme light trapping and very low reflectance. In this research project, we have fabricated disordered SiNWs using a low-cost top-down approach named the Metal-Assisted-Chemical-Etching process (MACE). The MACE process was first optimized to reduce the strong agglomeration observed at the top-end of the SiNWs by tuning the wettability properties of both the initial substrate and the SiNWs surface. By combining the MACE process with the nanosphere lithography, we have also produced ordered SiNW arrays with an accurate control over the pitch, diameter and length. The optical properties of these SiNW arrays were then investigated both theoretically and experimentally in order to identify the geometrical configuration giving the best optical performance. Disordered and ordered SiNW arrays have been integrated into two types of solar cells: heterojunction with intrinsic thin layer (HIT) and hybrid devices. SiNW based HIT devices were fabricated by RF-PECVD and the optimization of the process conditions has allowed us to reach efficiency as high as 12.9% with excellent fill factor above 80%. Hybrid solar cells based on the combination of SiNWs with an organic layer have also been studied and characterized. The possible transfer of this concept to the thin film technology is finally explored
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Crivoi, Dana Georgiana. "Hybrid materials: discovering properties and mechanisms." Doctoral thesis, Universitat Rovira i Virgili, 2016. http://hdl.handle.net/10803/386445.
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Tot el que ens envolta és quiral, per tant, una de las propietats més importants que recau en la disposició i la acció de fàrmacs ve donada por la quiralitat de la substància activa. En conseqüència, la estereoquímica representa un camp actiu, canviant i desafiant que combina diferents disciplines de las ciències naturals que condueixen als resultats més espectaculars. En aquest context, la present tesis es centra en: i) el desenvolupament de nous sistemes catalítics per a la producció de substàncies quirals, ii) la comprensió dels mecanismes de reacció posteriors, i iii) el disseny de processos més ecològics i sostenibles. Bio-nanohíbrids amb una alta varietat de propietats van ser obtinguts mitjançant la immobilització de la L-leucina i la poli-L-leucina en l’espai entre capes de materials del tipus hidrotalcita. Aquests catalitzadors són ecològics, fàcils de sintetitzar i no requereixen pre-activació. Substàncies amb una aplicació potencial en la indústria química i farmacèutica van ser obtingudes utilitzant aquests nanohíbrids com a catalitzadors, emprant un únic reactor, en la reacció d’addició aldòlica i la reacció de condensació de Claisen-Schmidt /epoxidació Juliá-Colonna. La cooperació entre la ciència de superfícies i la catàlisis va permetre revelar el verdader mecanisme de Juliá-Colonna mitjançant l’anàlisi amb micro-balança de cristall de quarts amb dissipació (QCM-D). Per últim, però no menys important, els reactors híbrids de membrana catalítica es poden utilitzar en la transformació de reaccions complexes en altres més trivials, com la producció de peròxid d’hidrogen in-situ i la posterior epoxidació de la calcona.Todo lo que nos rodea es quiral, por lo tanto, una de las propiedades más importantes que subyace en la disposición y la acción de fármacos está dada por la quiralidad de la sustancia activa. En consecuencia, la estereoquímica representa un campo activo, cambiante y desafiante que combina diferentes disciplinas de las ciencias naturales que conducen a los resultados más espectaculares. En este contexto, la presente tesis se centra en: i) el desarrollo de nuevos sistemas catalíticos para la producción de sustancias quirales, ii) la comprensión de los mecanismos de reacción posteriores, y iii) el diseño de procesos más ecológicos sostenibles. Bio-nanohíbridos con una alta variedad de propiedades se obtuvieron mediante la inmovilización de L-leucina y poli-L-leucina en el espacio entre capas de materiales del tipo hidrotalcita. Estos catalizadores son ecológicos, fáciles de sintetizar y no requieren pre-activación. Sustancias con una aplicación potencial en la industria química y farmacéutica se obtuvieron utilizando estos nanohíbridos como catalizadores, empleando un único reactor, en la reacción de adición aldólica y la reacción de condensación de Claisen-Schmidt /epoxidación Juliá-Colonna. La cooperación entre la ciencia de superficies y la catálisis permitió revelar al verdadero mecanismo de Juliá-Colonna mediante el análisis con micro-balanza de cristal de cuarzo con disipación (QCM-D). Por último, pero no menos importante, los reactores híbridos de membrana catalítica se pueden emplear en la transformación de reacciones complejas en otras más triviales, como la producción de peróxido de hidrógeno in-situ y posterior epoxidación de la calcona.
Everything around us is chiral, thus, one of the most important properties which underlies the drug disposition and action is given by the chirality of the active substance. Consequently, stereochemistry represents an active, changing, and challenging field which combines different disciplines of natural sciences that lead to the most spectacular findings. In this context, the present thesis focuses on: i) the development of new catalytic systems for the production of chiral substances, ii) the understanding of the subsequent reaction mechanisms, and iii) the design of greener sustainable processes. Bio-nanohybrid materials with a high variety of properties were obtained by immobilizing L-leucine and poly-L-leucine in the interlayer space of hydrotalcite-type materials. These catalysts are eco-friendly, are facile to synthesize, and no pre-activation is required. Substances with potential application in pharmaceutical or fine chemical industries were obtained using these nanohybrids as catalysts in the aldol addition reaction and the one-pot Claisen-Schmidt condensation / Juliá-Colonna epoxidation reaction. Cooperation between surface science and catalysis revealed the real Juliá-Colonna mechanism by using quartz crystal microbalance with dissipation (QCM-D) analysis. Last but not the least, hybrid catalytic membrane reactors can be employed in transforming complex reactions into simpler ones, like the production of hydrogen peroxide in-situ and subsequent epoxidation of chalcone.
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Benge, Kathryn Ruth. "Hybrid Solid-State Hydrogen Storage Materials." The University of Waikato, 2008. http://hdl.handle.net/10289/2320.
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This thesis investigates the chemistry of ammonia borane (NH3BH3) relevant to the development of hydrogen storage systems for vehicular applications. Because of its high hydrogen content and low molecular weight ammonia borane has the potential to meet stringent gravimetric hydrogen storage targets of gt;9 wt%. Two of the three moles of H2 in ammonia borane can be released under relatively mild conditions, with the highest gravimetric yield obtained in the solid-state. However, ammonia borane does not deliver sufficient H2 at practical temperatures and the products formed upon H2 loss are not amenable to regeneration back to the parent compound. The literature synthesis of ammonia borane was modified to facilitate large scale synthesis, and the deuterated analogues ND3BH3 and NH3BD3 were prepared for the purpose of mechanistic studies. The effect of lithium amide on the kinetics of dehydrogenation of ammonia borane was assessed by means of solid-state reaction in a series of specific molar ratios. Upon mixing lithium amide and ammonia borane, an exothermic reaction ensued resulting in the formation of a weakly bound adduct with an H2N...BH3-NH3 environment. Thermal decomposition at or above temperatures of 50eg;C of this phase was shown to liberate gt;9 wt% H2. The mechanism of hydrogen evolution was investigated by means of reacting lithium amide and deuterated ammonia borane isotopologues, followed by analysis of the isotopic composition of evolved gaseous products by mass spectrometry. From these results, an intermolecular multi-step reaction mechanism was proposed, with the rates of the first stage strongly dependent on the concentration of lithium amide present. Compounds exhibiting a BN3 environment (identified by means of solid-state sup1;sup1;B NMR spectroscopy) were formed during the first stage, and subsequently cross link to form a non-volatile solid. Further heating of this non-volatile solid phase ultimately resulted in the formation of crystalline Li3BN2 - identified by means of powder X-ray diffractometry. This compound has been identified as a potential hydrogen storage material due to its lightweight and theoretically high hydrogen content. It may also be amenable to hydrogen re-absorption. The LiNH2/CH3NH2BH3 system was also investigated. Thermal decomposition occurred through the same mechanism described for the LiNH2/NH3BH3 system to theoretically evolve gt;8 wt% hydrogen. The gases evolved on thermal decomposition were predominantly H2 with traces of methane detected by mass spectrometry.
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Li, Zhi. "Electronic Structure Characterization of Hybrid Materials." Scholar Commons, 2014. https://scholarcommons.usf.edu/etd/5060.
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In this dissertation, the studies aim to characterize the electronic structure at the internal interface of hybrid materials. The characterization challenge is originating from the spectral superposition of hybrid constituents. A characterization protocol based on photoemission spectroscopy (PES) was developed and applied to investigate the orbital alignment at the internal interface of the oligothiophene-TiO2 and ArS-CdSe hybrid materials by characterizing the individual constituents and the assembly hybrids respectively. Electrospray deposition technique was used to deposit targeting materials which enabled preparation of thin films in vacuum minimizing ambient contaminations while transmission electron microscopy (TEM) was used to investigate the morphology and the particle size of the pure nanoparticles and the hybrids. Ultraviolet-visible (UV-vis) spectroscopy was also used in the estimation of the optical band gap of the pure nanoparticles and the HOMO-LUMO gap of the organic ligands.
One of the hybrid materials studied in this dissertation is oligothiophene-TiO2 nanoparticle hybrids in which the oligothiophene ligands are bonded to the surface of TiO2 nanoparticles covalently. This hybrid system was used to develop and demonstrate a measurement protocol to characterize the orbital alignment at the internal interface. Low intensity X-ray photoemission spectroscopy (LIXPS) was used to determine the work function of the oligothiophene ligands and the TiO2 nanoparticles. In combination with the highest occupied molecular orbital (HOMO) cutoff and the valence band maximum (VBM) measured by ultraviolet photoemission spectroscopy (UPS), the ionization energies (IE) of these two constituents were determined. X-ray photoemission spectroscopy (XPS) was used to characterize the core level emissions of the constituents and the hybrid assembly, which were used to determine the charge injection barriers at the internal interface.
The results showed that there was an interface dipole at the internal interface between organic and inorganic constituents of the hybrid. The dipole was determined to be 0.61 eV and the hole injection barrier at the internal interface amounted to 0.73 eV. The electron injection barrier was estimated by taking into account the gap between highest occupied and lowest unoccupied molecular orbitals (HOMO, LUMO). The procedure followed only suggested the presence of an insignificant barrier in the oligothiophene-TiO2 nanoparticle hybrids.
Arylthiol functionalized Cadmium Selenide (ArS-CdSe) is a novel hybrid material which can be used in hetero-junction solar cells. The ArSH ligands are bonded on the surface of the CdSe nanoparticles covalently through sulfur atoms serving as anchors. The internal interface in the ArS-CdSe hybrids between the organic constituent and the inorganic constituent was studied by the same characterization protocol developed in this dissertation. Furthermore, a physisorbed interface between the ArSH ligands and the CdSe nanoparticles was created through multi-step in-vacuum deposition procedure. The electrospray deposition technique enabled the formation of a well-defined physisorbed interface which was characterized by LIXPS, UPS and XPS for each deposition step. Accordingly, the orbital alignment at the physisorbed interface was determined.
Based on the results obtained, detailed orbital alignments at the ArSH/CdSe physisorbed interface and the internal interface in the ArS-CdSe hybrid materials were delineated and discussed. The hole injection and electron injection barrier at the physisorbed ArSH/CdSe interface are 0.7 eV and 1.0 eV respectively. An interface dipole of 0.4 eV was observed at the interface. In the ArS-CdSe hybrid materials, the electronic system of the ArSH component shifts down due to the charge transfer induced by the covalent hybridization. The hybridization also shifts the electronic system of the CdSe constituent to a lower energy level due to saturation of the unoccupied bonds of the Cd atoms on the surface. The hole injection barrier and electron injection barrier were determined to be 0.5 eV and 1.2 eV respectively. A small interface dipole (0.2 eV) was observed at the internal interface as a result of the presence of covalent bonds.
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Del, Rosso Maria Girolama. "Exploring supramolecular Interactions in hybrid materials." Thesis, Strasbourg, 2015. http://www.theses.fr/2015STRAF028/document.
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Ce travail visait à explorer les interactions supramoléculaires comme un outil dans les domaines de la chimie hôte-invité, les nanomatériaux et les nanotechnologies en général, afin de parvenir à des objectifs différents. D'abord, une interaction classique hôte-invité a été étudiée, au moyen d'une technique innovante telle que l'ITC, puis nous avons exploité les interactions supramoléculaires afin de maitriser la production de graphène exfolié en phase liquide, en mettant un accent particulier sur l'amélioration de la qualité et la quantité du matériau produit. Enfin, nous avons étendu l'utilisation de la chimie supramoléculaire à un dispositif réel par la fonctionnalisation des électrodes d'or avec des molécules photochromiques, ouvrant alors la voie à des dispositifs organiques multifonctionnels, pouvant être contrôlés par la lumièreThis work was aimed at exploring supramolecular interactions as a tool in the fields of host-guest chemistry, nanomaterials and in general nanotechnology, in order to achieve different goals. First, a classical host-guest interaction was studied by means of the ITC technique, then we exploited supramolecular interactions in order to harness the production of liquid-phase exfoliated graphene, with a particular focus on improving the quality and quantity of material produced. Finally, we extended the use of supramolecular chemistry to a real device by functionalization of gold electrodes with photochromic molecules, hence paving the way towards multifunctional organic devices and in prospective to graphene based light-controlled multifunctional devices
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Nicholls, Jennifer. "New inorganic and hybrid framework materials." Thesis, University of Liverpool, 2012. http://livrepository.liverpool.ac.uk/6233/.
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This thesis describes the formation of new inorganic and hybrid framework materials, from cationic layered structures through to three-dimensional frameworks, with potential applications in catalysis, gas storage and anion exchange. A study of the formation of a number of these materials is also discussed within this thesis. Chapter 1 presents a review of literature covering the area of hybrid and also cationic materials. This includes a discussion of hybrid materials such as coordination polymers and metal organic frameworks (MOFs), and also cationic materials such as layered double hydroxides (LDHs) and three recently reported cationic inorganic frameworks. Chapter 2 describes the hydrothermal synthesis of six new pillared layered lanthanide molybdate and tungstate phases. Five of these phases have a general composition of [Ln(H2O)MO4]2[A] (Ln= La- Nd, M = MoO4 or WO4, A = 1,5-NDS or 2,6-NDS) with the sixth phase, being pillared by fumarate, having the composition [Ce(H2O)MoO4]2[Fumarate]. Each phase consists of two-dimensional cationic inorganic layers comprising of a bilayer of polyhedra and are pillared by charge-balancing organic dianions. The catalytic and anion exchange capabilities of the NDS materials were tested. It was discovered that these materials are able to undergo successful anion exchange of the NDS anions, with dicarboxylates such as fumarate, terephthalate and 2,6-NDC. The tungstate containing phases were also tested for their catalytic properties and proved to be successful catalysts for the oxidative bromination of phenol red to bromophenol blue. Chapter 3 describes the hydrothermal synthesis of three new lanthanide phosphonoacetate coordination polymers, two having a general formula of [Ln(H2O)2][C2H2O5P] (where Ln = Er, Ho and Tb or Yb and Lu), which have infinite three-dimensional structures containing discrete LnO7 polyhedra connected together via O-P-O bridges, and the remaining phase having a composition of [YbC2H2O5P] consisting of one-dimensional chains of LnO7 polyhedra which are held together via pillaring phosphonoacetate anions to form a three-dimensional network. Porosity measurements confirmed each phase to be non-porous. Also hydrothermally synthesised are two organosulfonate coordination polymers with compositions of [Ln(H2O)5]2[2,6-AQDS]3•2H2O (Ln = La - Nd) and [Ln(H2O)5][C8H17SO3]3.2H2O (Ln = La and Nd). The former phase consists of layers of monomeric Nd polyhedra which are linked by 2,6-AQDS anions forming a three-dimensional network and the latter phase consists of two-dimensional layers of monomeric lanthanum cations which are bridged together by octanesulfonate anions to form a two-dimensional layered structure. Chapter 4 describes the study of the formation of pillared layered lanthanide molybdate and tungstate phases and also the dehydration of [Yb(H2O)2][C2H2O5P] to [YbC2H2O5P] using the in-situ energy dispersive X-ray diffraction technique. In-situ measurements of the formation of neodymium/molybdate/NDS phases allowed the observation and successful isolation of an intermediate phase which was detected during the formation of the required phase. Kinetic analysis, including calculation of the activation energy, was achieved for the formation of [La(H2O)WO4]2[1,5-NDS]. Also observed by in-situ measurements was the dehydration of [Yb(H2O)2][C2H2O5P] forming [YbC2H2O5P], which occurs via a dissolution/re-precipitation mechanism. Chapter 5 describes the boric acid flux preparation of lanthanide borate compounds with compositions [Ln(NO3)(H2O)2][B6O10(OH2)] (1) (Ln = La and Ce), [Ln(NO3)(H2O)2][B5O9(OH2)] (2) (Ln = Pr and Ce), and [Ln(B6O13H3)][BO3H2] (3) (Ln = Sm, Eu and Gd). 1 and 2 are found to have infinite three-dimensional structures consisting of either hexaborate clusters as found in 1 or pentaborate clusters as found in 2, with one dimensional channels being present in both structures. 3 differs to 1 and 2 as a two-dimensional layered structure is formed consisting of positively charged layers of gadolinium cations coordinated to unique hexaborate clusters, which are charge balanced by non-coordinating borate anions residing in the interlayer gallery. The anion exchange capabilities have been tested for 3 although this proved largely unsuccessful. Chapter 6 gives details of the syntheses of all the phases prepared during the course of this study and the analytical techniques used to characterise them.
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Guodong, Xu. "Fibre-cement hybrid composites." Thesis, University of Surrey, 1994. http://epubs.surrey.ac.uk/844012/.
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The theoretical stress-strain behaviour of individual fibre reinforced cement composites is reviewed. Based on the multiple cracking concept of the existing theory, analytical expressions are developed to describe the tensile stress-strain behaviour of a fibre-cement hybrid composite consisting of three components, i.e. two reinforcing fibres with different moduli, strengths and strains to failure and a common cement binder. The model predicts that the tensile stress-strain curve of the hybrid composites consists of five stages, instead of three stages of the existing models for individual fibre cements, and relates the tensile behaviour of each stage to the component properties of the components and the test system parameters. A description is given of the physical and mechanical properties of four types of reinforcing fibres used in the study. These were fibrillated polypropylene film, alkali-resistant glass, polyvinyl alcohol fibres and carbon fibres. A small number of direct tensile tests on continuous glass, carbon and polyvinyl alcohol were performed. The tensile stress-strain behaviour of four types of fibre-cement hybrid composites was studied with particular emphasis on that of the glass- polypropylene hybrids for which the flexural load-deflection behaviour was also examined. It is shown that the fibre-cement hybrid composites yield superior engineering properties over their parent composites and the improvements are sensitive to volume fractions of each of the two fibres. The measured tensile stress-strain curves of the hybrids were compared with the theoretical predictions and satisfactory agreement in general is obtained. Implications from the present work for the design of fibre-cement hybrid composites are assessed.
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Lopes, Leandro. "Étude et caractérisation de matrices hybrides polyether-siloxane utilisées pour la libération contrôlée de Diclofenac de Sodium et de complexes à base de Platine." Thesis, Paris 11, 2014. http://www.theses.fr/2014PA112146/document.
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La capacité à incorporer le diclofenac de sodium (DFS) ou des composés à base de platine comme le cisplatine (CisPt), le sel de Zeise ou le tétrachlorure de platine IV (PtCl₄) au sein des matrices hybrides basées sur les chaînes polyéther de caractère hydrophilique (PEO) ou hydrophobique (PPO) et utilisant comme points de réticulation des nodules de type siloxane a été étudiée. Ces composés d’intérêt académique possèdent des applications dans le traitement du cancer (cipslatine) ou en catalyse (sel de Zeise). Dans les matrices avec DFS la diminution de la température de fusion de l'hybride PEO1900 semi- cristallin et la réduction des valeurs de Tg associés aux mesures Raman confirment l'existence d'interactions entre le DFS et les chaînes PEO de la matrice hybride. La coexistence dans l’hybride de phase amorphe et cristalline a été clairement démontrée par la libération bimodale du médicament pour PEO1900 matrice.Les quantités optimales pour avoir une matrice homogène incorporant le CisPt sont 5.4 % m/m avec PEO1900 et 1.8% m/m avec PPO2000. Les mesures EXAFS et Raman convergent vers une préservation de la structure locale du CisPt dans les matrices. Les mesures de SAXS montrent que l’intensité du pic de corrélation entre nœuds de réticulation de type siloxane est affectée par l’incorporation du CisPt dans la matrice en diminuant d’intensité sans changer de position. Ce résultat est interprété par le remplissage de l’espace entre les nœuds par le CisPt. Les profils de libération des matrices PEO1900 montrent que la libération est indépendante de la concentration en CisPt et que le gonflement de la matrice est le mécanisme dominant permettant d’expliquer la cinétique de libération.Pour les hybrides incorporant PtCl₄, il a été montré la coexistence de deux entités de Pt, une espèce Pt(II) et une espèce Pt(IV). L’espèce Pt(II) est identifiée comme (PtCl₄)²⁻ alors que l’espèce Pt(IV) est PtCl₄ dissout dans la matrice. Le rapport entre espèces Pt(II) et Pt(IV) change avec la matrice : L’espèce Pt(II) est dominante pour les matrices à base de PEO alors que les proportions Pt(II) et Pt(IV) sont quasi équivalentes pour les matrices à base de PPO. Il est proposé que l’espèce (PtCl₄)²⁻ interagisse avec les groupements urée localisés en bout de chaînes ainsi qu’avec les chaînes polymériques par les groupements éther. Ces interactions sont favorisées par le caractère anionique de l’espèce Pt(II). L’espèce neutre PtCl₄ interagit avec la matrice de la même façon que le CisPt, ie en remplissant l’espace libre laissé par les chaînes polymériques. Lors des tests de libération, l’espèce neutre est facilement libérée en solution aqueuse, l’espèce anionique Pt(II) restant emprisonnée.Tout comme PtCl₄, le sel de Zeise se montre soluble dans les matrices hybrides et permet l'obtention d'échantillons homogènes et transparents. L’EXAFS et la spectroscopie Raman montrent que si les liaisons Pt-Cl des échantillons hybrides sont identiques à celles caractérisant le sel de Zeise, les vibrations Pt-C₂H₄ ne sont mises en évidence dans les échantillons qu’après une période de vieillissement. Pour la matrice hybride PEO1900 avec sel de Zeise, la formation de platine métallique au cours du processus de libération a été mise en évidence.L’analyse structurale des matrices incorporant différentes molécules de platine et la corrélation des résultats obtenus avec les tests de libération montrent que l’interaction faible avec la matrice des molécules neutres comme le CisPt est responsable d’une libération contrôlée par les propriétés de la matrice vis-à-vis du gonflement. L’incorporation d’espèces de Pt anioniques, comme (PtCl₄)²⁻ ou le sel de Zeise, conduit à des échantillons pour lesquelles les quantités d’espèces Pt libérées sont notablement plus faibles comparativement au CisPt. Les fortes interactions de la matrice avec les espèces anioniques sont responsables des difficultés rencontrées pour les libérer en solutionThe capacity of hydrophilic (POE) or hydrophobic (POP) siloxane-polyether hybrid matrixes to incorporate platinum based compounds like platinum (IV) tetrachloride (PtCl₄), cisplatin (CisPt), Zeise salt and sodium diclofenac (SDF) was studied. These compounds present academic interest and are applied in cancer disease treatment (CisPt) or catalysis (Zeise salt).The decrease in melting temperature of the semi-crystalline POE1900 hybrid and the decrease of the Tg values together with the Raman results confirm the interactions between SDF and the POE chains of the hybrid matrix. The coexistence of a crystalline and amorphous hybrid phase was clearly evinced by the bimodal drug release pattern achieved for the POE1900 matrix. Optimum amounts for the preparation of homogeneous matrix with CisPt are 5.4% m/m and with PEO1900 1.8% m/m with PPO2000. The local structure of CisPt inside the matrices is preserved. SAXS measurements show that the intensity of the correlation peak between siloxane crosslinks is affected by the CisPt incorporation in the matrix. The observed decrease in intensity without shift in position is interpreted as resulting from the filling of the space between the SiO2 nodes by CisPt. The release profiles of PEO1900 matrices show that the release is independent of the CisPt concentration and that the swelling of the matrix is the dominant process for explaining the release mechanism.For hybrids incorporating (PtCl₄), it has been shown the existence of two Pt entities, a Pt(II) species and a Pt (IV) ones. The Pt(II) species is identified as(PtCl₄)²⁻ whereas the Pt(IV) species is (PtCl₄) dissolved in the matrix. The ratio of Pt(II) and Pt(IV) species is dependent on the matrix nature: The Pt(II) species is dominant for the PEO-based matrices whereas Pt(II) and Pt(IV) proportions are almost equal for matrices based on PPO. It is proposed that the (PtCl₄)²⁻ species interact with the urea groups located at the ends of the polymeric chain and with the by ether groups of the polymer chains. These interactions are facilitated by the anionic nature of the species Pt(II). The neutral species PtCl₄ interact with the matrix in the same way that the CisPt, ie by filling the empty space between the polymer chains. During release essays, the neutral PtCl₄ species is easily released in aqueous solution, the anionic Pt (II) species remaining embedded inside the matrix. As PtCl₄, the Zeise salt is soluble in matrixes giving rise to homogeneous and transparent samples. Raman spectroscopy and EXAFS show that if the Pt-Cl bonds of the hybrid are identical to those found in the Zeise salt,Pt-C₂H₄ vibrations are only identified in the samples after a ageing period. For PEO1900 hybrid matrix loaded with Zeise salt, the formation of metallic platinum was observed during the release essays.The correlation of the structural results gained on the matrices incorporating different platinum molecules with the results of the release assays evidences that the weak interaction of neutral molecules with the matrix is responsible to the fact that the release of CisPt is mainly controlled by the swelling properties of the matrix. The incorporation of anionic Pt species, as (PtCl₄)²⁻ or Zeise salt, gives rise to samples for which the amount of released Pt species are significantly lower than the one obtained for hybrids loaded with CisPt. The strong interactions between the matrix and the anionic species are responsible for the fact that the anionic species is not easily released in solution
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Moussawi, Mhamad aly. "Assemblages à base de polyoxométallates : des interactions fondamentales aux matériaux hybrides supramoléculaires." Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLV078/document.
Full textAbstract:
Dans ce travail, nous présentons dans la première partie la substitution du molybdène par du tungstène dans les anions de type Keplerates, [{Mo6}12Mo30O312E60(AcO)30]42- (E = O or S). L'introduction du tungstène dans le milieu de synthèse a entraîné l'isolement d'une série de composés, [{WxMo6- x}12Mo30O312E60(AcO)30]42-, avec une teneur en métal variable dans leurs unités pentagonales {M6}. Une observation remarquable a révélé l'occupation sélective de la position centrale dans l'unité pentagonale par les atomes W. Cette observation a été étendue à d'autres structures telles que les roues du bleu du molybdène [Mo154O462H14(H2O)70]14- et l’anion Krebs [Mo36O112(H2O)16]8- qui ont également montré la même occupation préférentielle des atomes W pour le site héptavalent, au centre du pentagone. Dans la deuxième partie, nous nous concentrons sur l’élaboration d'un matériau hybride à trois composantes à base de polyoxométallates (POM), de clusters métalliques et de - cyclodextrine ( -CD). La conception de ce matériau suivant une approche synthétique basée sur la propagation à l’infini des interactions spécifiques entre la CD et les deux types d'unités inorganiques. Dans la dernière partie, nous étendons l’étude des interactions CD-POM aux structures POMs géantes telle que l’anneau du bleu du molybdène. Une complexation non conventionnelle résulte de l'encapsulation du macrocycle organique dans la cavité centrale du l’anneau inorganique anionique. Accroître la complexité du système en introduisant une troisième espèce, conduit à la formation d'un assemblage supramoleculaire hybride par agencement hiérarchique des molécules organiques et inorganiquesIn this work, we report in the first part the substitution of molybdenum by tungsten within Keplerate-type anions [{Mo6}12Mo30O312E60(AcO)30]42- (E = O or S). Introducing tungsten to the synthesis medium resulted in the isolation of a series of compounds, [{WxMo6- x}12Mo30O312E60(AcO)30]42, with variable metal content within their pentagonal units {M6}. An outstanding observation revealed the selective occupation of the central position in the pentagonal unit by the W atoms. This revelation was stretched to reach other historical structures as Mo-blue wheel [Mo154O462H14(H2O)70]14- and Krebs [Mo36O112(H2O)16]8- anions that also showed the same preferential occupation of W atoms for the heptacoordinated site. In the second part, we focus on the fabrication of a three-component hybrid material based on polyoxometalates (POMs), metallic clusters and -cyclodextrin ( -CD). Investigation of such material has been conducted using bottom-up approach by investigating the specific interactions between CD and both types ofinorganic units. Finally, the three componentsassociate together to give a well orderedpolymer-like hybrid chain that is derived ashydrogel and single crystals. In the last part, we extend the CD-POMinvestigation to reach giant POM structures asthe Mo-blue ring. A non-conventional complexation results from this interaction explained by the encapsulation of the organic macrocycle within the inorganic torus. Increasing the complexity of the system by introducing a third species provoked the formation of a hierarchical hybrid assembly
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Delchet, Carole. "Matériaux hybrides pour la décontamination et le confinement d'éléments mobiles : application au Césium." Thesis, Montpellier 2, 2013. http://www.theses.fr/2013MON20251/document.
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L'industrie nucléaire produit, de nos jours, une large gamme d'effluents radioactifs liquides contenant du césium. Les matériaux à base de cyanométallates présentent une très forte affinité pour l'incorporation de cet élément sur une grande plage de pH ainsi qu'une bonne résistance à l'irradiation ce qui les rend très intéressant pour la décontamination. Chaque année, à La Hague, plusieurs centaines de m3 d'effluents radioactifs sont traités par un précipité préformé de ferrocyanure de nickel massif (nommé PPFeNi, de formule générale K2xNi2-x[Fe(CN)6] avec 0,5>x>1,1). Cette technique présente de bons rendements de décontamination mais elle est lourde à mettre en œuvre et produit une boue qui se doit ensuite d'être traitée par les filières de déchets disponibles. L'objet de cette thèse est de trouver un matériau pour la décontamination du Cs à la fois efficace, sélectif, adapté au procédé de décontamination en continu (colonne) et compatible avec les déchets classiques (ciments ou verres). Pour atteindre ce but, nous avons plusieurs objectifs :i) L'étude de matériaux massif à base de cyanométallate afin d'améliorer les connaissances sur le mécanisme de fixation du césium sur ces composés en variant la nature du métal de transition et la présence ou non de potassium au sein de la structure cristalline,ii) La synthèse de nanocomposites contenant des nanoparticules de cyanométallates incorporées dans des matrices inorganiques de type silice mésostructurée et verre poreux. La silice est utilisée comme modèle, alors que le verre poreux mise en forme de bille sera utilisé en vue d'un procédé de décontamination. Les matériaux massifs à base de cyanométallate contenant du potassium dans la structure sont ceux qui possèdent la plus grande capacité de sorption vis-à-vis du Cs. Les matériaux hybrides contenant des nanoparticules de cyanométallates possèdent une capacité maximale absolue inférieure à celle des matériaux massifs respectifs, cependant rapporté à la quantité de particule sorbante, la capacité maximale de sorption des matériaux hybrides est supérieure à celle des massifs. En revanche, la sélectivité est comparable pour les matériaux hybrides et les matériaux massifs, avec un coefficient de distribution de l'ordre de 104 à 105 mL.g-1.Les performances des matériaux hybrides ont été évaluées sur des effluents réels. Ces matériaux semblent très prometteurs pour la décontamination d'effluents à partir d'un procédé de traitement en colonne puisqu'ils présentent d'une part une forte sélectivité vis-à-vis du césium et ce malgré une forte salinité de la solution à décontaminer et d'autre part une mise en forme (bille de verre) adaptée à ce type de procédéNuclear industry produced, nowadays, a wide range of liquid radioactive waste containing cesium. Materials based on cyanométallates exhibit a very high affinity for the inclusion of this element in a wide range of pH and a good resistance to ionising radiation which makes them very interesting for decontamination. Every year, at La Hague, several hundred m3 of radioactive waste are treated by a nickel ferrocyanide preformed precipitate in bulk form (PPFeNi, general formula K2xNi2-x [Fe (CN) 6] with 0,5> x> 1,1). This process shows a good decontamination but it's difficult to implement and it produces a sludge that must then be treated by waste channel available.The purpose of this thesis is to find a material for the decontamination of Cs which have a good capacity, selectivity, adapted for continuous decontamination process (column) and compatible with conventional waste (cement or glass). To achieve this goal, we have several objectives:i) The study of solid materials based on cyanometallate to improve knowledge on the mechanism of fixation of cesium on these compounds by varying the nature of transition metal and the presence or not of potassium in the crystal structure,ii) Synthesis of nanocomposites containing cyanometallate nanoparticles incorporated into inorganic matrices which are mesostructured silica and porous glass. Silica is used as a template, whereas the porous glass shaping ball will be used for a decontamination process.Bulk materials containing potassium in the structure present the greater sorption capacity toward Cs. Hybrid materials containing cyanometallate nanoparticles have a lesser absolute capacity than the respective bulk materials, however, based on the amount of sorbent particles, the maximum sorption capacity of hybrid materials is higher than bulk materials. However, the selectivity is comparable for hybrid and bulk materials with a distribution coefficient about 104 to 105 mL.g-1.The performance of the hybrid materials were evaluated on real effluents. These materials are very promising for the decontamination of effluents from a treatment process in column one hand they have a high selectivity towards cesium and despite high salinity of the solution to decontaminate and other formatting (glass beads) adapted to this type of process
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Bandiera, Nicholas Graham. "Hybrid inkjet and direct-write multi-material additive manufacturing." Thesis, Massachusetts Institute of Technology, 2010. http://hdl.handle.net/1721.1/111774.
Full textAbstract:
Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2017.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 77-79).
Recently there has been a trend towards combining multiple forms of additive manufacturing together for increased functionality, freedom and efficiency. In this work, two forms of multiple-material additive manufacturing technologies - inkjet and direct-ink writing - are combined in a hybrid system. Several advantages are realized due to the increased material library and geometric freedom as a result of new printing modalities. Initially, models of each process are reviewed and the processes are evaluated for compatibility. Then, the precision machine design of a passively-indexed, carousel-style, syringe tool holder is completed. An error budget employing Homogeneous Transformation Matrices was maintained to estimate the tooltip errors. In order to register these two non-contact printing processes, a unique approach to their registration to a common global origin was necessary. A single non-contact optical CCD micrometer is used to register the three spatial coordinates of the syringe tooltip. Measurements are performed to characterize the repeatability of the nozzle registration scheme and the constructed gantry and carousel system, which well exceeds the requirements and the predictions from the conservative error budget. This novel system can print with a wide array of inks, including those that solidify via polymerization or crosslinking, two part chemistries, solvent evaporation or sintering, as well as liquids, gels and pastes. These materials can have a wide range of mechanical properties and functionalities, for example electrical conductivity or force sensitive resistivity. Models for the extrudate flow rate are used alongside experimental determination of the extrudate cross-section to ensure accurate process congruence. Finally, printed results demonstrate the various printing techniques, highlight the expanded material library, and display novel assemblies not possible with conventional additive processes. One such example is a fully printed pressure sensor array.
by Nicholas Graham Bandiera.
S.M.
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Bandiera, Nicholas Graham. "Hybrid inkjet and direct-write multi-material additive manufacturing." Thesis, Massachusetts Institute of Technology, 2017. http://hdl.handle.net/1721.1/111774.
Full textAbstract:
Thesis: S.M., Massachusetts Institute of Technology, Department of Mechanical Engineering, 2017.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 77-79).
Recently there has been a trend towards combining multiple forms of additive manufacturing together for increased functionality, freedom and efficiency. In this work, two forms of multiple-material additive manufacturing technologies - inkjet and direct-ink writing - are combined in a hybrid system. Several advantages are realized due to the increased material library and geometric freedom as a result of new printing modalities. Initially, models of each process are reviewed and the processes are evaluated for compatibility. Then, the precision machine design of a passively-indexed, carousel-style, syringe tool holder is completed. An error budget employing Homogeneous Transformation Matrices was maintained to estimate the tooltip errors. In order to register these two non-contact printing processes, a unique approach to their registration to a common global origin was necessary. A single non-contact optical CCD micrometer is used to register the three spatial coordinates of the syringe tooltip. Measurements are performed to characterize the repeatability of the nozzle registration scheme and the constructed gantry and carousel system, which well exceeds the requirements and the predictions from the conservative error budget. This novel system can print with a wide array of inks, including those that solidify via polymerization or crosslinking, two part chemistries, solvent evaporation or sintering, as well as liquids, gels and pastes. These materials can have a wide range of mechanical properties and functionalities, for example electrical conductivity or force sensitive resistivity. Models for the extrudate flow rate are used alongside experimental determination of the extrudate cross-section to ensure accurate process congruence. Finally, printed results demonstrate the various printing techniques, highlight the expanded material library, and display novel assemblies not possible with conventional additive processes. One such example is a fully printed pressure sensor array.
by Nicholas Graham Bandiera.
S.M.
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Zhang, Weiwei. "Hybrid Integration of Er-doped Materials and CNTs on Silicon for Light Emission and Amplification." Thesis, Université Paris-Saclay (ComUE), 2017. http://www.theses.fr/2017SACLS001/document.
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Ce travail de thèse est une contribution à la thématique de l’intégration de matériaux actifs en photonique silicium pour la réalisation de fonctions actives. L’accent a été mis sur des matériaux préparés en couches minces pouvant être dépose sur substrats silicium pour la réalisation de sources de lumière intégrées. L’approche classique en photonique silicium dans le fenêtre télécom (1.55μm) repose sur l’utilisation de guides strip fabriqués à partir de substrats silicium sur isolant, SOI). Le choix qui été fait dans ce travail repose en revanche sur l’utilisation de guides à cœur creux (‘slot waveguides’) en raison de l’excellent recouvrement qu’ils permettent entre leur mode optique fondamental quasi-TE et les matériaux de couverture utilisés. Les contributions de cette thèse ont porté à la fois sur les étapes de conception/simulation et sur celles liées à l’optimisation des étapes de fabrication en salle blanche. Des guides slot Si/SiO2 et SiN/SiO2 et des résonateurs en anneaux basés sur ces guides ont conduit à : - des pertes de propagation typiquement comprises entre 1dB/cm et 7dB/cm. - des résonateurs à facteur de qualité de quelques dizaines de milliers pour des structures couvertes par des liquides d’indice. Dans un deuxième temps, les travaux poursuivis ont visé à l’intégration de matériaux actifs dopés à l’Erbium dans les guides à fentes présentés en première partie en vue de la démonstration de gain optique sur puce dans la fenêtre télécom (1.55μm). Une première collaboration nous a amené à la démonstration de gain optique sur puce à partir d’une géométrie de guide en arête inversée fabriqué en polymère actif. Un gain interne de l’ordre de 25dB sur puce a été obtenu par cette approche pour une puissance de pompe optique de l’ordre de 70 à 80mW. Une seconde collaboration s’est focalisée, quant à elle, sur l’intégration d’oxyde Al2O3 dans des guides à fentes SiN fabriqués à Orsay. Les problématiques d’intégration des matériaux ont été étudiées dans un premier temps. Le résultat le plus marquant a été obtenu pour un guide de longueur 400μm, pour lequel un gain relatif de 1.5dB a été obtenu pour une puissance de pompe de l’ordre de 50mW à longueur d'onde 1480nm. De manière complémentaire, nous avons exploré une seconde voie destinée à la démonstration de structures émettrices/amplificatrices sur puce, exploitant l’utilisation de nanotubes de carbone semi-conducteurs. Notre équipe du C2N, en forte collaboration avec le CEA-Saclay, a développé une méthode de préparation de solutions riches en nanotubes de carbone semi-conducteurs (séparation par centrifugation). Au final, les couches minces qui en ont résulté ont constitué un milieu actif qui a pu être intégré de manière planaire sur des échantillons de silicium pour le développement de fonctions optiques intégrées par intégration hybride. Par cette approche, nous avons démontré : - qu’un pompage vertical des structures photoniques pouvait donner lieu à une extraction de photoluminescence (PL) en sortie guidée par la tranche, dans des guides à fentes, - qu’un renforcement significatif de la PL était obtenu par effet de recyclage des photons dans des résonateurs diélectriques à base de guides à fente. Pour conclure, l’ensemble des travaux présentés dans cette thèse apporte une contribution au développement d’une photonique hybride sur silicium exploitant les propriétés de la plateforme de guidage optique sur SOI et celles de matériaux actifs (polymères dopés à l’Erbium ou aux nanotubes de carbone)This thesis is a contribution to the hybrid integration of active materials including Erbium-doped and carbon nanotubes rich layers on silicon for on-chip light emission.In a first step, we designed, fabricated, and characterized within the silicon-on-insulator and silicon nitride platforms a range of photonic structures including strip/slot waveguides, micro disks, strip/slot ring resonators, and micro cavities aiming at preparing a set of passive device building blocks needed for hybrid integration on Si. Silicon slot waveguides and slot ring add-drop resonators filled with index liquids with linear propagation losses 2-7 dB/cm and Q-factors up to 30,000, have been demonstrated around wavelength=1.55µm. Propagation loss of silicon nitride slot waveguides were minimized down to ~4dB/cm for compact spiral structures (2cm long, within ~500µm×500µm area). Air-band mode Nano beam cavities were also investigated, leading to Nano cavities with mode volumes V ~0.03(wavelength/n)^3 and Q-factors ~70,000 when filled with soft materials.In a second step, hybrid integration of Erbium doped materials and semiconducting single-wall carbon nanotubes (SWCNTs) was investigated for light emission under optical pumping.Integration of Erbium-doped materials was studied within the framework of two collaborations: Prof. Daming Zhang’s team, in State Key Laboratory on Integrated Optoelectronics, Jilin University, China, and Prof. Zhipei Sun, in Department of Micro- and Nanosciences, Aalto University, Finland. Erbium doped layers coming from Jilin were composed of Er3+ and Yb3+ co-doped core {shell} nanoparticles which were copolymerized with methyl methacrylate (MMA) to synthesize nanocomposite (PMMA-NPs: Er3+/Yb3+). We conducted the experimental characterization that led to the demonstration of an internal net gain up to 10-17dB/cm at wavelength=1.53µm in Erbium doped polymer rib waveguides fabricated in Jilin. The second Erbium doped material available during this thesis was based on Er2O3/Al2O3 atomic layers, grown in Aalto University. This collaboration was devoted to integrate high Erbium ion concentration (10E21/cm3) in oxide cladding layers on top of silicon nitride slot waveguides, which were fabricated in our group for the demonstration of on-chip optical net gain. The carried out experiments have conducted to the demonstration of 1.5-22.8dB/cm gain for sub millimeter length waveguides.In another direction, hybrid integration of SWCNTs emitting at wavelengths around 1.3 µm on ring resonators and Nano beam cavities has been investigated. First, we studied the coupling of SWCNTs photoluminescence (PL) in silicon micro-ring resonators and compared it with the PL intensity coupled into the bus waveguide . It has been shown that the pump beam polarization controls the light coupling into the straight bus waveguide. We demonstrated an enhancement of the PL intensity of 20dB at resonance. We also explored CNT hybrid integration with ultra-small mode volume Nano beam optical cavities, and hence with larger Purcell-like Q/V factors in comparison with the one obtained in micro-ring resonators. The results revealed that the PL resonance enhancement due to Nano beam cavity field confinement exhibited a nonlinear growth as a function of the pump power. It was also shown that the resonance of the PL peak intensity grows faster with the pump power than the PL background, which is accompanied by a line width narrowing of the resonance PL peak. This result is the first step to achieve an integrated laser based on carbon nanotubes
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Ayingone, Mezui Charyle. "Synthèses et caractérisations électrochimiques de matériaux hybrides à base de polyoxométallates." Thesis, Université Paris-Saclay (ComUE), 2016. http://www.theses.fr/2016SACLS513/document.
Full textAbstract:
Les polyoxométallates (POMs) peuvent être considérés comme des oxydes moléculaires de métaux de transition. Ils forment une famille de clusters moléculaires inorganiques dont les propriétés et les applications sont diverses et nombreuses. Ils sont notamment utilisés dans des domaines aussi divers que la catalyse, la biologie, ou encore la médecine. Les nanomatériaux de carbone sont une nouvelle classe de matériaux connus pour leur surface spécifique élevée et leur conductivité électrique accrue. Ce mémoire de thèse porte sur la synthèse et l’étude de différents systèmes moléculaires électro-catalytiques à base de POMs et de matériaux de carbone comprenant les nanotubes de carbone et le graphène, pour l’oxydation de l’eau ou la réduction des oxydes d’azote. La première partie de ce mémoire est consacrée à la synthèse, la caractérisation physico-chimique (spectroscopies infrarouge et UV-visible, analyse thermogravimétrique) et l’étude électrochimique (voltammétrie cyclique, coulométrie, microbalance couplé à l’électrochimie) d’un certain nombre de complexes poly-tungstiques prenant en sandwich des métaux de transition tels que le cobalt et/ou le manganèse. Deux d’entre eux, choisis pour l’étude de leurs propriétés électro-catalytiques, montrent une bonne activité électro-catalytique pour la réduction des oxydes d’azote et l’oxydation de l’eau. La seconde partie de ce mémoire est consacrée à l’optimisation des propriétés électrochimiques des POMs. Pour cela, les POMs sont immobilisés sur des matériaux de carbone structurés (graphène ou nanotubes de carbone simple paroi), et les matériaux hybrides obtenus sont caractérisés par différentes techniques analytiques : spectrométrie de photoélectrons X, spectroscopie infrarouge, voltammétrie cyclique et coulométriePolyoxometalates (POMs) may be considered as molecular oxides containing transition metals. They form a family of inorganic molecular clusters with a variety of properties and a myriad of applications. They are used in different fields such as catalysis, biology or medicine. Carbon nanomaterials are a new class of materials known for their high surface area and enhanced electrical conductivity. This thesis focuses on the synthesis and study of different electro-catalytic molecular systems based on polyoxometalates and carbon materials (such as carbon nanotubes and graphene) for water oxidation or nitrogen oxides reduction. The first part of this thesis is devoted to the synthesis, physicochemical characterisation (infrared and UV-Vis spectroscopies, TGA) and the electrochemical study (cyclic voltammetry, coulometry, electrochemistry coupled with microbalance) of several poly-tungstic complexes sandwiching transition metals such as cobalt and/or manganese. Two of them, selected for the study of their electro-catalytic properties, show good electro-catalytic activity for nitrogen oxides reduction and water oxidation. The second part of this thesis is devoted to the optimisation of the electrochemical properties of POMs. For this, POMs are immobilised on structured carbon materials (graphene or single wall carbon nanotubes), and the composite materials obtained are characterised by different analytical techniques: X-ray photoelectron spectroscopy, infrared spectroscopy, cyclic voltammetry and coulometry
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Stark, Sebastian. "Hybride Materialmodellierung für ferroelektroelastische Keramiken." Doctoral thesis, Saechsische Landesbibliothek- Staats- und Universitaetsbibliothek Dresden, 2017. http://nbn-resolving.de/urn:nbn:de:bsz:14-qucosa-217239.
Full textAbstract:
Ferroelektroelastische Keramiken besitzen aufgrund ihrer elektromechanischen Koppeleigenschaften Bedeutung in der Sensorik und Aktuatorik. Zur Vorhersage der Bauteileigenschaften und Beurteilung der Bauteilfestigkeit werden Materialmodelle benötigt. In der vorliegenden Arbeit wird ein mehrachsiges, ratenunabhängiges Materialmodell für ferroelektroelastische Keramiken einschließlich der zur effizienten Lösung notwendigen numerischen Methoden ausgearbeitet. Dabei erfolgt die Einbeziehung von Ansätzen aus der makroskopischen phänomenologischen und mikroelektromechanischen phänomenologischen Modellierung. Das resultierende Materialmodell stellt einen Versuch dar, die Vorteile beider Betrachtungsweisen zu vereinen und trägt deshalb die Bezeichnung "hybrid". In einem ersten Beispiel wird gezeigt, dass das hybride Materialmodell die für Barium-Titanat-Keramiken experimentell beobachtete Materialantwort reproduzieren kann. In einem zweiten Beispiel erfolgt die Anwendung auf morphotrope PZT-Keramiken. Dabei wird die in jüngerer Vergangenheit entdeckte monokline Phase zusammen mit der elektronenmikroskopisch beobachteten hierarchischen Struktur von Mikro- und Nanodomänen in vereinfachter Weise berücksichtigt. Auf Grundlage der getroffenen Modellannahmen gelingt es, die experimentell gemessene makroskopische Materialantwort der morphotropen PZT-Keramik PIC151 (PI Ceramic GmbH, Lederhose, Deutschland) für ausgewählte Lastfälle mit guter Genauigkeit vorherzusagenFerroelectroelastic ceramics are used in sensor and actuator applications due to their electromechanical coupling properties. In order to predict the behavior of components or to assess their strength, material models are required. In the present work, a multi-axial, rate-independent material model for ferroelectroelastic ceramics is elaborated. This includes the development of efficient numerical solution methods. By incorporating ideas from known macroscopic phenomenological and micro-electromechanical phenomenological models into the novel model, it is attempted to combine the advantages of both approaches. In a first example, it is shown that the hybrid model can reproduce the experimentally observed material response of barium titanate ceramics. In a second example, the model is applied to morphotropic PZT ceramics. In this context, the recently discovered monoclinic phase as well as the hierarchical structure of micro-domains and nano-domains observed by means of electron microscopy are taken into account in a simplified way. Based on the assumptions made, the experimentally measured material response of the morphotropic PZT ceramic PIC151 (PI Ceramic GmbH, Lederhose, Germany) is predicted with reasonable accuracy for selected load cases
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Patti, Alessandro. "Molecular Modeling of Self-Assembling Hybrid Materials." Doctoral thesis, Universitat Rovira i Virgili, 2007. http://hdl.handle.net/10803/8551.
Full textAbstract:
Los surfactantes son moléculas anfifílicas, con una cabeza solvofílica y una cola solvofóbica. Cuando la concentración de surfactante en solución es suficientemente alta, las moléculas se agregan entre ellas para proteger las partes solvofóbicas del contacto con el medio. Tales agregados pueden tener forma y tamaño muy diferentes, dependiendo del surfactante y de las condiciones del sistema. La auto-organización de los surfactantes (self-assembly), debida a un compromiso energético y entrópico de su estructura molecular, es la clave que permite observar cristales líquidos muy ordenados. En presencia de un precursor inorgánico y dependiendo de las interacciones que este precursor establece con el surfactante, se puede observar la formación del material híbrido. Los materiales híbridos constituyen un paso intermedio fundamental para la síntesis de los materiales mesoporosos ordenados, los cuales se obtienen eliminando la matriz orgánica (surfactante) del substrato inorgánico. El presente estudio tiene como principal objetivo estudiar bajo cuales condiciones los sistemas formados por un surfactante, un precursor inorgánico y un solvente, se auto-organizan para dar lugar a estructuras híbridas muy ordenadas. En particular nos proponemos individuar cuales son las características más importantes que los precursores inorgánicos deberían tener para poder observar la formación de materiales mesoporosos ordenados.
Simulaciones Monte Carlo en el colectivo canónico han sido utilizadas para analizar la agregación de los surfactantes en estructuras complejas, como micelas, cilindros organizados en forma hexagonal, o laminas, a partir de configuraciones totalmente desordenadas. Con particular interés hemos analizado el rango de condiciones que llevan a la formación de las estructuras cilíndricas, y estas mismas estructuras han sido comparadas en función de algunas importantes características morfológicas, como el tamaño de poro, el grosor de las paredes, la presencia y accesibilidad de los grupos funcionales en los poros. El modelo usado representa las moléculas de surfactante y de precursor inorgánico como cadenas de segmentos en una red tridimensional que discretiza el espacio en sitios de volumen unitario. Este modelo no entra en el detalle de las características físicas y químicas de las moléculas, pero permite reproducir su agregación en estructuras complejas en un tiempo de cálculo muy razonable. La separación de fase ha sido también evaluada recorriendo a una teoría de campo medio, la quasi-chemical theory, que, aunque no pueda predecir la formación de estructuras ordenadas, ha sido muy útil para confirmar los resultados de las simulaciones, sobretodo cuando no se observa formación de fases ordenadas.
El estudio de surfactantes distintos, uno modelado por una cadena lineal y otro con una cabeza ramificada, nos ha permitido evaluar algunas diferencias estructurales de los materiales obtenidos. La ramificación de la cabeza, que merecería un estudio más profundo del que hemos descrito en este trabajo, ha evidenciado unas interesantes consecuencias en el tamaño de los poros. Este mismo surfactante con cabeza ramificada ha sido elegido para la síntesis de agregados cilíndricos utilizados como templates en la formación, agregación, y condensación de una capa de sílica modelada a través de un modelo atomístico. En particular, hemos aislado uno de los cilindros presentes en los cristales líquidos de estructura hexagonal, y a su alrededor hemos simulado la formación de una capa de sílica utilizando un modelo atomístico. De esta forma, hemos obtenido un poro típico de una estructura mesoporosa más realista, sin necesidad de asumir una forma mas o menos cilíndrica del template, por ser este generado de la auto-agregación del surfactante.
Surfactants are amphiphilic molecules with a solvophilic head and a solvophobic tail. When the surfactant concentration in a given solution is high enough, the molecules aggregate between them to shield the solvophobic part from the contact with the solvent. Such aggregates can show very different sizes and shapes, according to the surfactant and the conditions of the system. The surfactants self-assembly, being due to an energetic and entropic compromise of their molecular structure, is fundamental to observe the formation of very ordered liquid crystals. In the presence of an inorganic precursor and depending on the interactions established between such a precursor and the surfactant, it is possible to synthesize a hybrid material. Hybrid materials are the key step for the formation of periodic ordered mesoporous materials, which can be obtained by eliminating the organic soft matter (the surfactants) from the inorganic framework. Periodic ordered mesoporous materials represent an important family of porous materials as they find a large number of applications in several industrial fields, such as separations, catalysis, sensors, etc. In the last decade, the range of potential applications has increased with the possibility of functionalizing the pore walls by incorporating organic groups during the synthesis, or with post-synthesis treatments.
In this work, we are interested in studying the formation of ordered materials when hybrid organic-inorganic precursors are used. Lattice Monte Carlo simulations in the NVT ensemble have been used to study the equilibrium phase behavior and the synthesis of self-assembling ordered mesoporous materials formed by an organic template with amphiphilic properties and an inorganic precursor in a model solvent. Three classes of inorganic precursors have been modeled: terminal (R-Si-(OEt)3) and bridging ((EtO)3-Si-R-Si-(OEt)3)) organosilica precursors (OSPs), along with pure silica precursors (Si-(OEt)4). Each class has been studied by analyzing its solubility in the solvent and the solvophobicity of the inorganic group.
At high surfactant concentrations, periodic ordered structures, such as hexagonally-ordered cylinders or lamellas, can be obtained depending on the OSPs used. In particular, ordered structures were obtained in a wider range of conditions when bridging hydrophilic OSPs have been used, because a higher surfactant concentration was reached in the phase where the material was formed. Terminal and bridging OSPs produced ordered structures only when the organic group is solvophilic. In this case, a partial solubility between the precursor and the solvent or a lower temperature favored the formation of ordered phases.
With particular interest, we have analyzed the range of conditions leaving to the formation of cylindrical structures, which have been evaluated according to the pore size distribution, the pore wall thickness, the distribution and the accessibility of the functional organic groups around the pores. The phase behavior has been also evaluated by applying the quasi-chemical theory, which cannot predict the formation of ordered structures, but was very useful to confirm the results of simulations, especially when no ordered structures were observed.
The study of the phase and aggregation behavior of two different surfactants, one modeled by a linear chain of head segments and the other modeled by a branched-head, permitted us to evaluate some structural differences of the materials obtained.
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Herigstad, Matthew Omon. "Hybrid Particle-Nonwoven Membrane Materials for Bioseparations." NCSU, 2009. http://www.lib.ncsu.edu/theses/available/etd-04042009-120426/.
Full textAbstract:
Adsorption separations performed in feed streams containing large particulates pose interesting problems, the solution of which would aid in many fields of bioseapartions. Production of biologically derived protein products is one of the most rapidly expanding sectors in the global economy. The capture and purification of these products has, of late, become the bottleneck of the industry and can account for approximately 50-80% of the production costs. The biopharmaceutical industry has begun to focus on improving overall economics by merging two or more separation schemes into one. The majority of the emphasis has been on combining the initial protein capture and host cell clearance steps; however, many of the currently available methods have shown little efficacy at large-scale. Additionally, interest in the clearance of pathogenic activity, most importantly infectious prions, from blood and blood derived products has grown over the past decade with the increased threat of blood-transfusion of variant Creutzfeldt-Jakob disease. This work characterizes the transport and binding properties of a novel hybrid particle-nonwoven membrane medium in which a polymeric chromatographic resin is entrapped between layers of a nonwoven polypropylene membrane (a particle-impregnated membrane or PIM). This membrane-supported resin construct offers the advantage of increased interstitial pore diameter to allow passage of cells and other debris in the feed, while providing sufficiently high surface area for product capture within the resin particles. Columns packed with stacked disks of PIM displayed excellent flow distribution, and had an interstitial porosity of εb = 0.48 ± 0.01, a 25-60% increase over those typically observed in a packed bed. These columns were able to pass over 95% of E. coli cells and human red blood cell concentrate (RBCC) in 30 column volumes, while maintaining a pressure drop significantly lower than that of a packed bed. The dynamic binding capacity of the chromatographic resin entrapped in the PIM packed column for bovine serum albumin (BSA) was essentially the same as that observed with the same volume of resin in a packed bed. Additionally, the binding of prion was characterized to PIM constructs containing an affinity ligand for PrPSc, in saline, RBCC, and human IgG solutions. The General Rate (GR) model of chromatography was used to analyze experiments indicating that the breakthrough and elution behaviors of the PIM column are predictable, and very similar to those of a normal packed bed. These results indicate that PIM constructs can be designed to process viscous mobile phases containing particulates while retaining the desirable binding characteristics of the embedded chromatographic resin. The PIM systems could find uses in adsorption separation processes from complex feed streams such as whole blood, cell culture, and food processing and could offer a process alternative to expanded beds.
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Han, Yung-Hoe. "Characterisation of organic-inorganic hybrid coating materials." Thesis, University of Cambridge, 2006. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.603637.
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Two types of coating materials were prepared by a sol-gel process and classified into two systems. In system I, four different types of the optically transparent organic-inorganic hybrid coating materials produced by The Welding Institute (TWI) using a patent method called Vitresyn, identical in terms of the precursors, but different in terms of their relative proportions, were examined. The precursors used for system I were tetraethoxysilane (TEOS), 3-(trimethoxysilyl)propyl methacrylate (MPTMA) and an aliphatic urethane acrylate. The coating materials were deposited on aluminium, brass and polycarbonate substrates by a flow coating method, and cured under a UV lamp for various times from 2 minutes to 40 minutes. In system II, MPTMA, Methyltrimethoxysilane (MTMS) and trimethoxysilypropyl acrylate (PATMS) were used as precursors. No urethane acrylate was used in this system. TEOS was used in system I as the primary inorganic precursor and urethane acrylate was used as the source of organic component. MPTMA was used as both a secondary inorganic source and a coupling agent between the organic and inorganic phases. To ascertain the interaction relationships between organic and inorganic phases in the hybrid materials, Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR) were used. It was found that a siloxane (SiO-Si) network is a backbone of the hybrid materials and that the network increases with increasing inorganic content in the hybrid materials. These organic-inorganic hybrid materials were mainly cross-linked by T3, Q3 and Q4 species. It was also found that UV curing leads to accelerated condensation reaction through the opening of C=C bonds in MPTMA and urethane acrylate. Microstructures in the coatings and interfaces between the coatings and the substrates were investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The coating thickness is dependent on the relative amount of organic resin added to the hybrid materials. The coating thickness increases as more organic resin (urethane acrylate) is used. Neither silica domains nor pores were observed in the coatings. It was concluded that the hybrid coating materials are a single featureless amorphous phase regardless of the organic/inorganic ratios. Scratch testing was used to study the scratch resistance of the hybrid materials and the interfacial strength between the coatings and the substrates. A micro-indentation adhesion test using focused ion beam (FIB) technologies was also used for investigating interfacial strength. The results showed that scratch resistance increases with an increase in the relative amount of organic resin added.
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Kim, Dae-Wook. "Machining and drilling of hybrid composite materials /." Thesis, Connect to this title online; UW restricted, 2002. http://hdl.handle.net/1773/7041.
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Occhi, Luca. "PEDOT:PSS-based hybrid materials for optoelectronics applications." Thesis, Imperial College London, 2017. http://hdl.handle.net/10044/1/61335.
Full textAbstract:
Organic electronics is a research area that, in recent year, has received increasing attention both from academia and industry. Performance of organic optoelectronic devices, such as organic light-emitting diodes (OLEDs) and organic photovoltaic devices (OPVs), relies on the electrical and optical characteristics of each component. However, the performance are frequently limited by the distribution of the internal electromagnetic field: an effective light management, involving either the incoupling of incident radiation (in case of photovoltaic cells and photo-detectors), or the outcoupling of emitted light (for light-emitting diodes), is crucial. The electric field distribution may be optimised by adjusting the device geometry or, alternatively, by modifying the optical properties (i.e. refractive index and absorption coefficient) of each component. Developing a material with tunable optical properties, whilst maintaining acceptable electrical characteristics, would offer a significant alternative in high-performance devices. Among the different compounds used in organic devices, the charge injection/extraction materials play a key role: the ubiquitous poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is an example of an organic compound often limited (in thickness) by the optical losses. In this work we introduce an innovative, solution-processable, inorganic/organic hybrid material based on PEDOT:PSS, which could be used as an efficient hole-transport layer, or as an electrode, in OLEDs and OPVs. The hybrid system exhibits high optical quality, a dramatic increase of refractive index (up to +12-13%), and a decrease in work function, whilst maintaining good electrical conductivity. We prove the effectiveness of our approach both by modeling the distribution of normalised modulus squared of the optical electric field in light-emitting structures. Furthermore, we fabricate and characterise optoelectronic devices (OLEDs and OPVs) with PEDOT:PSS hybrid hole-transport layers, demonstrating an increase of efficiency in the organic light-emitting diodes. Finally, we investigate the thermoelectric properties of hybrid material, thus opening interesting new applications for our hybrid compound.