Title: Stability of plasma polymers under various conditions. Author: Jindřich Matoušek Department/Institute: Department of Macromolecular Physics/Charles University in Prague Supervisor of the doctoral thesis: prof. RNDr. Hynek Biederman, DrSc., Department of Macromolecular Physics Abstract: The depositions of plasma polymer thin films were carried out using plasma polymerization depostition. The working gas mixture consisted of argon and monomer vapours. The source monomers used were n-hexane and terthiophene. The depositions of nanocomposite thin films Sn/pp n-hexane by means of magnetron sputtering in a working gas mixture of argon and n-hexane were done. The resulting thin films were characterized by XPS, FTIR, AFM, SEM, TEM, optical microscope and elipsometry. The influence of deposition parameters on the resulting thin film propertires was studied. The ageing of the thin films in humidity and distilled water was studied. The current-voltage characteristics of selected thin films were measured. Keywords: plasma polymer, nanocomposite, ageing.

Nanostructured thin films deposited by magnetron sputtering and gas aggregation sources of nanoparticles are studied especially with regards to their use in biomedical applications. The possibility of using plasma polymers for the preparation of antibacterial coatings is tested first. It is presented that sputtered nylon 6,6 films may be impregnated by antibiotics. The subsequent release of antibiotics from such prepared reservoirs may be tuned by their thickness, chemical composition, or by an additional barrier layer. The second studied type of antibacterial coatings is based on metallic nanoparticles overcoated with sputtered PTFE. It is shown that by a proper choice of the number of nanoparticles and thickness of fluorocarbon overlayer, a significant antibacterial effect can be achieved while maintaining the biocompatibility of produced nanocomposite coatings. The possibility to enhance the antibacterial effect by impregnation of plasma polymer/nanoparticle nanocomposites by antibiotics is also verified. Nanoparticle sources are used to study two-component films with 2D gradient character, too. A simple analytical model is developed allowing description and design of such nanomaterials. Its suitability is experimentally verified on 2D gradients combining Ag and Cu nanoparticles. Finally, an original...

Title: XPS analysis of plasma polymers and nanocomposite films without breaking vacuum Author: Anna Artemenko Institute: Charles University in Prague, Department of Macromolecular Physics Supervisor of the doctoral thesis: Prof. RNDr. Hynek Biederman, DrSc., Charles University in Prague, Department of Macromolecular Physics. Abstract: Plasma polymers and metal/ plasma polymer nanocomposites have been widely used for various biomedical proposes. Naturally, surface properties of the coatings such as high wettability, stability on the open air and in aqueous media, resistance towards different sterilization processes and cells adhesion are required for bioapplications. This thesis is mainly dedicated to the investigation of chemical composition of deposited coatings using XPS analysis. Nylon-like plasma polymer, PEO-like coatings, fluorocarbon plasma polymer (PTFE) films and Au/PEO-like, Ag/C:H, Al/C:H nanocomposites were chosen as the subject material. In addition, results of XPS measurements were used for the computer simulation for calculation of filling factor of metal/ plasma polymer nanocomposites. These results were in a good agreement with experimental data. Keywords: plasma polymer, nanocomposite, XPS analysis, bioapplication, simulation.

Presented work is focused on the deposition and characterization of thin and ultrathin plasma polymer films, then also on the preparation of nanocomposites metal/plasma polymer. The characterization of plasma polymer films was partly done in-situ without exposing the samples to the atmosphere. The thickness of prepared films was measured by spectral ellipsometry, the chemical composition was measured by XPS. The morphology and optical properties of deposited films were measured ex-situ. It is shown that during the initial stages of growth the properties of plasma polymer films depend on their thickness and also on the material of the substrate. Many interesting applications were explored for prepared nanocomposites metal/plasma polymer. They can be used as superhydrophobic coatings, gradient coatings, substrates for Raman spectroscopy or as antibacterial coatings. Moreover, special optical properties of prepared nanocomposites were studied in detail. Presented work has an experimental character.

Organic-inorganic polymer hybrids containing butyl stannoxane dodecamer cages (Sn_POSS) as nano-building blocks were prepared and investigated. Sn_POSS was employed as a linear, crosslinking or non-bonding molecularly blended unit. For this purpose, it was synthesized with two acrylamido, primary- or secondary amino, or with two additional non- functional groups, which were attached via ionic-bonded sulfonate substituents. The nano- building block was then incorporated in matrices such as PS, PAOS, PETA, PEMA, PHEMA and PPO-based epoxies (the latter with different mesh sizes). Sn_POSS reinforces the studied matrixes by filler-filler interactions (self-assembly to nano-domains). Specific interactions of the ionic bonds of Sn_POSS with suitable pendant groups of the matrixes also can generate reinforcement and suppress filler aggregation. Moreover, the Sn_POSS can undergo several types of chemical reactions like heat-induced oligomerization, dissociation of the ionic substituents, acidolysis of the Sn-butyl bonds, as well as radical reactions of the latter. The influence of ionically bonded cages on the hybrids' morphology, as well as their ability of dissociation and short-distance migration in the polymer network at elevated temperature, was evaluated by TEM, IR and NMR analyses. The mechanical...

Tato dizertační práce je zaměřená na základní výzkum procesů samouspořádávání nanočástic v polymerních kapalinách a na vlastnosti připravených polymerních nanokompozitů s řízenou disperzí nanočástic. Navzdory současnému pokroku v porozumění polymerních nanokompozitech, stále chybí mnohé fundamentální znalosti relaxačních a mechanických vlastností polymerních nanostruktur, které by mohly poskytnout klíčové informace pro návrh hierarchických funkčních kompozitů zpracovatelných aditivními výrobními technikami. Hlavní důraz byl kladen na výzkum vlivu postupu přípravy nanokompozitu na finální stav disperze nanočástic, přípravu řízených nanostruktur – individuálně dispergované nanočástice, řetězci vázáné klastry a kontaktní agregáty - a určení jejich relaxačních a mechanických vlastností. Navíc byly nanočástice využity jako „sondy“ v polymerní matrici, které ovlivňují segmentální uspořádání a relaxační dynamiku polymerních řetězců a mohou poskytnout o těchto dějích zásadní informace. Tento přístup může pomoci nalezení vztahů mezi segmentální dynamikou na nano škále a mechanickými vlastnostmi polymerních skel na makro škále, což je náročný fundamentální problém s extrémní technologickou důležitostí. Neroubované keramické nanočástice a polymerní skla byly použity, aby se minimalizoval vliv silných interakcí mezi nanočásticemi a řetězci. Podrobný výzkum byl vykonán na modelovém systému PMMA/SiO2 a následně rozšířen na systémy s jinými matricemi (PC a PS) a jinými nanočásticemi (ZnO2 and Fe2O3) za účelem zobecnění obdržených výsledků. Byla určena závislost relaxačních a mechanických vlastností (teplota skelného přechodu, reptační čas, modul kaučukovitého plata, počet zapletenin, napětí na mezi kluzu, pokles napětí po mezi kluzu, elastický modul, modul deformačního zpevnění a odezvy při toku za studeny) na nanostruktuře, objemovém zlomku a složení. Získané výsledky byly interpretovány za použití současných modelů. Stanovené relaxační a mechanické vlastnosti byly propojeny, aby poskytli informace o molekulárních deformačních procesech řídících mechanickou odezvu makroskopických kompozitních těles.

This diploma thesis deals with the study of isothermal crystallization of nanocomposite materials based on isotactic polypropylene (iPP) and nanosilica, depending on the volume fraction (0, 2, 4 and 6 %) and type of silica and the crystallization temperature. Fumed silica and four types of silica with different surface treatment were used as filler. The crystallization performed at temperatures 136, 138, 140 and 142 °C has been studied in-situ using polarized optical microscope and the crystallization rate was evaluated from the growing radius of spherulites. It can be stated that particles of silica have been inbuilt into the spherulites due to the linear growth of spherulites of all composite materials. The most significant increase of the crystallization rate of iPP was caused by fumed silica, the most significant decrease was caused by silica TS-720 at volume fraction 4 %. The crystallization rate (G) has been slightly increased with the increasing volume fraction of filler at 136 °C, the G slightly decreased at 138 °C and there was no trend of G for two higher temperatures. Also, it was not possible to exactly evaluate the influence of the surface treatments. The reason is the most probably uneven (non-homogenous) distribution of nanosilica as revealed thermogravimetric analysis. The crystallization kinetics was evaluated according to the Lauritzen-Hoffmann theory. The morphological part of the study showed that iPP was in ? and ß-structure and spherulites of ? phase were of the type I, II and mixed.

The presented work deals with preparation of test samples filled microparticles of mica and nanoparticles of silicon dioxide (SiO2). Monitors the impact of climatic conditions and filler on electrical properties of composite materials. Electrical properties of composite materials are measured by dielectric relaxation spectroscopy. Test samples influence of epoxide resin TSA 220S and polyester resin DOLPHON XL 2102. Varnishes are modified with different weight percentage of nanoparticles of silicon dioxide, or micronized mica. The results of this project are frequency dependencies of parts of complex permittivity and their evaluation.

Polymerní biomateriály jsou jedním ze současných populárních témat vzhledem k možnosti potenciální aplikace v tkáňovém inženýrství a řízeného dávkování léčiv v organismech. Kolagen je jako jeden z nejčastěji se vyskytujících proteinů zvláště zajímavý díky svým rozmanitým vlastnostem bez imunoreakce organismu příjemce. Tato práce je zaměřena na samouspořádávací procesy, kinetiku, obecné zákonitosti řídící proces samouspořádání a mechanické vlastnosti kolagenních roztoků. Dále je zkoumán efekt hydroxyapatitových nanočástic na samouspořádávání kolagenu a mechanické vlastnosti výsledných nanokompozitních hydrogelů. Jsou objasněny možné mechanismy interakcí mezi kolagenem I a hydroxyapatitem spolu s popisem vývoje struktury a vlastností na různých úrovních struktury. Byly měřeny a molekulárně interpretovány závislosti viskoelastických veličin na smykové rychlosti spolu s viskoelastickým chováním. Dále byla studována struktura kolagenních scaffoldů a určen vliv HAP a síťování. Závěrem byly diskutovány výsledky v souvislosti s jejich aplikovatelností v tkáňovém inženýrství chrupavek tvrdých tkání a v regenerativní medicíně.

The work deals mainly with preparation protocol of nanocomposites. The task of this work is to study structural and procedural parameteres that control the dispersion of nanoparticles in polymer solution to be able to prepare desired spatial organization of nanoparticles. The work resolves the effect of various components such as polymer matrices, nanoparticles and solvent, in which matrices and nanoparticles are blended. Used components control final dispersion state of nanoparticles and it influences also properties of investigated materials such as glass transition temperature, stiffness and rheological properties.