Title: Preparation of Nanocomposites of Metal Oxides in Plasma Polymer and Study of Their Properties Author: Oleksandr Polonskyi Department: Department of Macromolecular Physics, MFF UK Supervisor of the doctoral thesis: Prof. RNDr. Hynek Biederman, DrSc. Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles University in Prague Abstract: This thesis is devoted to a study of nanocomposite films Al (Al oxide)/plasma polymer prepared by various techniques using magnetron sputtering, plasma polymerization and cluster beam deposition. The formation and deposition of metal/metal oxide nanoclusters using a gas aggregation cluster source (GAS) was also considered. The role of low concentration of oxygen in the aggregation gas on the process of Al and Ti cluster deposition was studied. Properties of the nanoclusters and nanocomposite films were characterized by various techniques. Morphology of the nanocomposites was examined by AFM, TEM or HRTEM and SEM. Elemental analysis and chemical composition of the films were studied by XPS and FTIR. Optical characterization of the prepared films was done by UV-Vis spectroscopy and spectroscopic ellipsometry. It has been shown that using GAS nanocomposite Al(AlxOy)/C:H may be prepared. Keywords: nanocomposite thin film, plasma polymer, metal...

Title: Plasma polymers in the nanostructured and nanocomposite coatings Author: Artem Shelemin Department / Institute: Department of the Macromolecular Physics Supervisor of the doctoral thesis: Prof. RNDr. Hynek Biederman, DrSc. Abstract: The thesis represents the main results of my research work aimed to study nanostructured and nanocomposite films of plasma polymer. A few alternative experimental approaches were developed and investigated which ranged from low pressure (gas aggregation cluster sources and glancing angle deposition) to atmospheric pressure (dielectric barrier discharge and plasma jet) plasma processing. The metal/metal oxide Ti/TiOx, AlOx and plasma polymer SiOx(CH), Nylon 6,6 nanoparticles were prepared. The analysis of morphology of deposited plasma polymer coatings was performed by AFM and SEM. The chemical composition of films was studied by XPS and FTIR. Keywords: plasma polymer, nanoparticle, thin film, nanostructures

Title: Plasma treatment of porous structures Author: Mykhailo Vaidulych Department / Institute: Department of Macromolecular Physics Supervisor of the doctoral thesis: Prof. Assist. Jan Hanuš, Ph.D., Department of Macromolecular Physics Abstract: The thesis is focused on the implementation of low-temperature plasma for the modification of porous materials. Two main strategies are involved: functionalization through the deposition of functional nanocomposite coatings and low-pressure plasma etching. In the first case, a gas-phase step-by-step deposition process based on the combination of deposition of nanoparticles and thin films was developed to obtain super-wettable nanocomposite coatings on filtration membranes. It was shown that the deposition parameters of thin films and particles of plasma polymer can tune the wetting characteristic of the membranes whereas embedding copper nanoparticles endows them with antibacterial properties. As a result, highly efficient superhydrophobic/superoleophilic and smart superamphiphilic membranes were successfully fabricated for oil/water separation. Plasma processing in the atmosphere of argon, oxygen or nitrogen was utilized to modify hard metal/polymer nanocomposites (Ag/a-C:H) with potential to be used as functional coatings for bone implants. An anisotropic etching...

Title: Preparation of nanostructured and nanocomposite thin films with plasma polymer matrix Author: Pavel Solař Department: Department of Macromolecular Physics, MFF, UK Supervisor of the doctoral thesis Prof. RNDr. Hynek Biederman, DrSc., Department of Macromolecular Physics, Faculty of Mathematics and Physics, Charles University in Prague Abstract: This thesis is devoted to study of nanostructured thin films implementing metal and plasma polymer particles and columns. Process of formation of particles from various materials has been studied. The particles size, shape and chemical composition has been characterized relative to the deposition conditions. Transport of metal and plasma polymer particles inside the particle source and from the particle source to substrate has been investigated. The particles were used in composite films especially to produce films with controlled roughness e.g. for investigation of influence of roughness on adhesion of cells. Preparation of columnar films by Glancing Angle Deposition has been studied and the particles have been used as seeds for the columnar growth. Keywords: Nanoparticles, Glancing Angle Deposition, plasma polymer, composite thin film

Title: Structuring of plasma polymers: new methods for fabrication of nano-architectured thin films Author: Daniil Nikitin Department / Institute: Department of Macromolecular Physics/Charles University Supervisor of the doctoral thesis: Doc. Ing. Andrey Shukurov, PhD, Department of Macromolecular Physics/Charles University Abstract: The PhD thesis aims at the investigation of nanostructures based on plasma polymers. The main attention is paid to the combination of a gas aggregation cluster source with plasma-assisted vapor phase deposition for the fabrication of metal-polymer nanocomposites with bactericidal potential. Copper nanoparticles were incorporated into a biocompatible matrix of plasma polymerized poly(ethylene oxide) (ppPEO). The efficiency of such nanocomposite against multi-drug resistant bacteria was demonstrated. It was found that the segmental dynamics of the plasma polymer significantly changed in the presence of nanoparticles as revealed by the measurements of the dynamic glass transition temperature. The nanoscale confinement crucially influences the non-fouling properties of poly(ethylene oxide). A separate chapter is dedicated to the examination of the nanoparticle formation, growth and transport inside the source. Copper and silver nanoparticles were detected in situ in the gas phase...

Title: Structuring of plasma polymers: new methods for fabrication of nano-architectured thin films Author: Daniil Nikitin Department / Institute: Department of Macromolecular Physics/Charles University Supervisor of the doctoral thesis: Doc. Ing. Andrey Shukurov, PhD, Department of Macromolecular Physics/Charles University Abstract: The PhD thesis aims at the investigation of nanostructures based on plasma polymers. The main attention is paid to the combination of a gas aggregation cluster source with plasma-assisted vapor phase deposition for the fabrication of metal-polymer nanocomposites with bactericidal potential. Copper nanoparticles were incorporated into a biocompatible matrix of plasma polymerized poly(ethylene oxide) (ppPEO). The efficiency of such nanocomposite against multi-drug resistant bacteria was demonstrated. It was found that the segmental dynamics of the plasma polymer significantly changed in the presence of nanoparticles as revealed by the measurements of the dynamic glass transition temperature. The nanoscale confinement crucially influences the non-fouling properties of poly(ethylene oxide). A separate chapter is dedicated to the examination of the nanoparticle formation, growth and transport inside the source. Copper and silver nanoparticles were detected in situ in the gas phase...

Les travaux présentés dans ce mémoire concernent la caractérisation par infrarouge à transformée de Fourier (FTIR) et par spectroscopie d’émission optique (SEO) des réactions chimiques entre post-décharges et précurseurs organosiliciés, avec comme exemple le cas du 3-aminopropyltriéthoxysilane (APTES). Le but est d’obtenir la rétention la plus élevée possible de fonctions amine -NH2 dans les revêtements ou dans les nanoparticules synthétisées. Tout d’abord, un état de l’art des post-décharges Ar-N2 et Ar-O2 et leurs applications est présenté ainsi que la cinétique d’interaction de l’APTES dans ces post-décharges, mettant en évidence le rôle des mélanges plasmagènes sur la décomposition du précurseur et sur la nature des films déposés. Ensuite l’étude de la décomposition de l’APTES dans une post-décharge Ar-N2 est réalisée. Les analyses par SEO et par FTIR in situ montrent le rôle des atomes d’azote N dans la formation des différents sous-produits, à savoir HCN, CO et C=O. Les nanoparticules synthétisées contiennent peu d’amine primaire, et présentent une concentration non négligeable d’azote sous forme d’amide secondaire. Dans le cas de l’étude de la décomposition de l’APTES dans la post-décharge Ar-O2 en mode pulsé, une tendance se dessine : les nanoparticules synthétisées en phase gazeuse lorsque les rapports cycliques augmentent ont une composition qui s’appauvrit en azote et en carbone mais s’enrichit en oxygène. Les groupements NH2 initiaux sont fortement convertis en groupement amide. Les nanoparticules synthétisées avec des rapports cycliques élevés ont des compositions différentes de celles des films minces déposés sur les parois, plus proches de la silice et ce en raison de la gravure par l’oxygène atomique qui les affecte davantage. Le comportement spécifique des atomes d’oxygène et d’azote en post-décharge rend difficile la rétention des amines dans les polymères plasmas. Enfin nous avons terminé par une étude de l’hydrodynamique dans le cas de l’interaction entre l’acétylène et une post-décharge Ar-O2 et établi l’importance de l’écoulement sur toute approche visant à faire des mesures FTIR résolues temporellement / The present work deals with the characterization by Fourier transform infrared spectroscopy (FTIR) and by optical emission spectroscopy of chemical reactions between a post-discharge and an organosilicon precursor: the 3-aminopropyltriethoxysilane (APTES). The aim is to keep the highest retention of amine functions -NH2 in coatings or in the synthesized nanoparticles. First, a state of the art of Ar-N2 and Ar-O2 post-discharges and their applications is presented as well as the kinetics of the interaction of APTES in these post-discharges, highlighting the role plasma gases on the decomposition of the precursor and the nature of the deposited films. Then, the study of the decomposition of APTES in an Ar-N2 post-discharge is carried out. Analysis by optical emission spectroscopy (OES) and in situ FTIR show the role of the nitrogen atoms N in the formation of various main by-products, namely HCN, CO and C=O. The synthesized nanoparticles contain few primary amines, and have a significant concentration of nitrogen in the form of secondary amide. In the case of interaction APTES with pulsed Ar-O2 afterglow, there is one main trend: the nanoparticles synthesized in the gas phase when the duty cycle increases have a composition that decreases in nitrogen and carbon but increases in oxygen. The -NH2 groups are efficiently converted into amide groups. The nanoparticles synthesized with high duty cycle exhibit compositions that are different from those of thin films deposited on the walls, the latter being close to silica because of the etching by atomic oxygen, which affects them more. The specific behavior of oxygen and nitrogen atoms in post-discharge makes difficult the retention of a high level of amines in plasma polymers. Finally, we finished with a study of the hydrodynamics in the case of the interaction of acetylene with an Ar-O2 post-discharge and proved the key role of the flow for any approach aiming at getting time-resolved FTIR measurements

Title: Modification of polymeric substrates by means of non-equilibrium plasma Author: Anna Kuzminova Department: Department of Macromolecular Physics Supervisor of the doctoral thesis: doc. RNDr. Ondřej Kylián, Ph.D. Abstract: Processing of polymeric materials by means of non-equilibrium plasma is a topic that reaches increasing attention, which is due to the wide range of possible applications. As an example can be mentioned processing of polymeric foils used for food packaging, where plasma treatment enables to improve their functional properties (e.g. increase their printability or enhance their barrier properties). In the frame of this PhD. thesis two different strategies suitable for the modification of polymeric materials were followed. The first one was based on treatment of polymers by atmospheric plasma. The main attention was devoted to the investigation of influence of atmospheric pressure plasma on surface properties of 8 commonly used polymers, namely on their chemical composition, morphology and wettability. In addition, it was observed that plasma treatment causes also alteration of their mechanical properties, may lead to their substantial etching and in some cases improves their biocompatibility. The second studied strategy was based on coating of polymers with thin functional...

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Contrairement aux méthodes de polymérisation par voie humide, la « plasma-polymérisation » de précurseurs siliconés (typiquement l'hexaméthyldisiloxane) fournit des couches minces peu solubles, considérées comme riches en chaines courtes et ramifiées, structures cycliques et réticulées, à mi-chemin entre un poly(diméthylsiloxane) (PDMS) et une silice. Ces caractéristiques confèrent des propriétés barrières, électriques ou mécaniques uniques aux substrats traités mais sont autant de difficultés pour leur analyse par spectrométrie de masse. La caractérisation fine d'un plasma polymère serait pourtant d'autant plus utile qu'elle permettrait – indirectement – de proposer ou de valider des mécanismes d'activation et d'oligomérisation du précurseur en phases plasma et solide, connaissance essentielle s'il en est pour la maîtrise des caractéristiques d'un dépôt. Cependant, l'interprétation de données MS/MS en vue de relier un comportement dissociatif à des caractéristiques structurales nécessite l'établissement préalable de règles de fragmentation à partir de modèles pertinents. En l'absence d'étalons plasma-polymère de structure contrôlée, il s'agit donc d'explorer différents modèles potentiels afin d'établir des relations structure/fragmentation pour comprendre les données MS/MS obtenues pour des échantillons réels. Ces études contribueront d'ailleurs à enrichir la littérature sur la fragmentation de polymères siliconés, très réduite en comparaison de polymères à chaine carbonée.A partir des données obtenues depuis les parties solubles de plasma-polymères, les comportements MS/MS d'un ensemble de polymères de référence dument choisis ont été explorés et explicités. / This thesis work aimed at describing the molecular and structural composition of silicon-based plasma-polymers (ppHMDSO) by mass spectrometry. Deposited under a micro-discharge regime at atmospheric pressure, these plasma-polymers exhibit a very low solubility in common solvents, assigned to their highly cross-linked structures, and are hence not easily amenable to ionization. Moreover, structural information cannot be readily deduced from fragmentation data obtained from species extractable from the studied thin films due to the lack of appropriate rules to understand dissociation of the observed gas-phase ions. This research work has thus consisted of developing an analytical strategy to address both of these challenging issues.Owing to the very limited number of articles dealing with tandem mass spectrometry of silicon-containing oligomers, mechanistic investigations were performed on the collision-induced decomposition of selected polymer standards holding different end-groups, expected to be relevant to characterize oligomers suspected to be present in the soluble part of the ppHMDSO samples. Focusing on ammonium adducts, fragmentation routes have first been established for symmetric poly(dimethylsiloxane) (PDMS) polymers holding trimethylsilyl, hydride, or methoxy terminations. POSS molecules were also investigated to understand the influence of cross-linked structures on PDMS adduct dissociation. Some discrepancies between MS/MS spectra of the standards and of the analytes were evidenced, assigned to random branching which could not be modeled by any commercially available compounds.