Polyoxazolines are class of polymers which are suitable for medical applications because they have many interesting properties. These polymers are characterized by antibacterial properties so they can stop bacterial colonization of medical devices and significantly reduce the risk of infection. Furthermore, polyoxazolines are interesting for good biocompatibility. Basic topic of this diploma work is preparation of oxazoline-based thin films by plasma polymerization. Thin films were prepared by plasma polymerization from 2-methyl-2-oxazoline vapors in a nitrogen atmosphere in a dielectric barrier discharge. During the deposition was increased the substrate temperature. Polyoxazoline films were analyzed by several diagnostic methods. Physical and chemical properties of thin films were studied by SEM, AFM, FTIR by measuring contact angles and nanoindentation method. The films were found to be homogeneous, hydrophilic and have a higher nitrogen content. Furthermore, films showed viscoelastic properties. Polyoxazoline films were subjected to antibacterial and biocompatibility tests and the result showed, that films have antibacterial properties and support of viability cells viability.

The theoretical part of the thesis is focused on surface treatments, their evaluation from the point of view visual properties, plasma-enhanced chemical vapor deposition and analysis of thin layers prepared by plasma polymerization. The experimental part of the thesis deals with surface treatment of stainless steel AISI 304. Thin layers of pp-HMDSO (plasma-polymer) and of DLC are deposited on the steel´s surface for the purpose of preparing transparent layer, which protect steel´s surface against of making finger prints visible. As an objective method is chosen an immersion test in artificial sweat solution according to standard ČSN EN ISO 105-E04. Evaluation of the test is measured by a gloss-meter and by a colorimeter. Prepared layers are identificated by FTIR method.

Usage of complexes in homogeneous catalysis for synthesis functional materials with defined properties is one of the most significant areas of research organometallic compounds of lanthanides in the last decade. One of the way became polymers with defined properties is for example ring opening polymerization. Aliphatic polyesters, which are biodegradable and biocompatible (useful for biomedicine), can be prepared by this method. Theoretical part of this work includes preparation of lanthanidocenes, their characterization and possibilities of their use for polymer synthesis. The aim of experimental part was performance and optimizing synthesis of series lanthanocen chlorides complex (Sm, Nd a Pr) and new monopentamethylcyklopentadienyl complexes. Introduced structural types were chosen for their possibility of polymerization activity or their activation by adding alkyl reagents. The complexes were spectral characterized by 1H NMR, and IR spectroscopy. Structure was defined by roentgen structural analysis. Catalytic activities for polymerization of ?-caprolacton in toluen (laboratory temperature) were performed for selected complexes. Polycaprolactone was characterized by gel permeation chromatography and NMR.

Syntéza polylaktidu (PLA) polymerací za otevření kruhu cyklického monomeru (ROP) může být uskutečněna různými způsoby. Literatura uvádí více než 100 katalytických systémů, jejichž pomocí lze polylaktid a jiné biodegradabilní alifatické polyestery získat. Například organokovové katalyzátory na bázi Sn, Zn, Al atd. se po splnění své polymerační funkce stávají kontaminanty a pro humánní implantáty je použití takového materiálu diskutabilní. V současné době jsou v centru výzkumné pozornosti nové N-heterocyklické karbenové katalyzátory. Tyto „metal-free“ katalytické struktury jsou schopné reprodukovatelně řídit syntézu polymerů předem definované molekulové hmotnosti s definovanými koncovými skupinami a nízkou polydisperzitou, která je charakteristická pro živý průběh polymerace. Nabízí se možnost syntézy blokových kopolymerů a různorodých makromolekulárních architektur. Předložená diplomová práce se zabývá studiem polymerace cyklického monomeru D,L-laktidu katalyzované N-heterocyklickým karbenem. Polymerace byly vedeny v přítomnosti benzylalkoholu jako iniciátoru v roztoku THF. Byl sledován vliv složení reakčního systému monomer – iniciátor – katalyzátor. Dále byly připraveny polymery opticky čistého L-laktidu s makroiniciátory PEG s Mn = 1000 a 2000 g/mol. Střední číselná molekulová hmotnost (Mn) a polydisperzita (PDI) byly stanoveny pomocí GPC. Definovatelnost koncových skupin vybraných polymerů byla prokázána pomocí 1H NMR.

The degree of polymerization (DP) is the main factor which plays a role in cellulose aging. The adverse consequence of cellulose fibers aging is the deterioration of mechanical and optical properties. Viscometry is a technique which is frequently used for determination of degree of polymerization of cellulose fibers. The aim of the work was to determine the degree of polymerization of cotton fabrics and to investigate the dependence of DP on number of washing and dying. Next task was to investigate if there exists a corellation between DP and results from thermal and thermo-oxidative degradation studied by methods of thermal analysis. First, the traditional viscometry was employed to determine DP of cellulose fibers. It has been demonstrated that number of washing and dying decreases the DP. In the second part the differential scanning calorimetry (DSC) and thermogravimetry (TG) were used. DSC provided values of combustion heat and TG allowed the detail evaluation of degradation steps; obtained results were further used for correlation with DP. Methods of thermal analysis revealed differences between cotton wool and treated fabrics. Combustion heat did not show any correlation with DP. In contrast, results from TG suggested some promising correlations which could be used for the prediction of cotton fabrics DP using thermal analysis in the future.

Title: In-flight modification of nanoparticles by chemically active plasma Author: Hana Libenská Department: Department of Macromolecular Physics Supervisor: Mgr. Jan Hanuš Ph.D., Department of Macromolecular Physics Abstract: This diploma thesis is focused on a fabrication of the iron nanoparticles using the gas aggregation source with a planar magnetron and their in flight modification by chemically active plasma. The modification of the nanoparticles is based on a radiofrequency glow discharge, that takes place right after the nanoparticles flew out of the gas aggregation source. Nanoparticles are prepared in an argon atmosphere in which a small amount of the n-hexane has been admixed. This n-hexane impurity caused an increase in a deposition rate and higher time stability. The modification takes place in a glow discharge containing a pure argon, or in the mixtures of argon with n-hexane, ethylendiamine, hydrogen or nitrogen. Prepared nanoparticles were characterized using the X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, X-ray diffraction and other techniques. The main aim of this work was to study the influence of the additional discharge on the iron nanoparticles. The chemical composition of the nanoparticles was measured immediatelly after their deposition without...

Bearing in mind environmental concerns and global trends in ecology, biodegradable polyesters have gained enormous attention as alternative to non-biodegradable, commercial polymers used mainly in packaging industry contributing to the worldwide environment pollution. However, substitution of conventional polymers with biodegradable polyesters is limited due to their inferior mechanical and barrier properties, which can be improved by the introduction of relatively small content of non-toxic nanofillers. Nevertheless, environmental pollution is not only affected by material itself, but also manufacturing and processing sector in terms of energy sustainability. In case of the latter, low energetic processes are nowadays preferential. Thus, using microwave irradiation as the more efficient energy source, which can lead to shortening of process time, has become currently investigated subject. In this thesis, microwave-assisted in-situ synthesis of biodegradable nanocomposites based on polycaprolactone and non-toxic clay nanoparticles (layered double hydroxides) was studied and described in detail in four subsections (4.1-4.4). The first subsection (4.1) describes one-pot synthesis of Mg2+ /Al3+ layered double hydroxides functionalized with highly microwave-absorbing ionic liquids. In order to improve...

Thesis in theoretical part is focused on the principle of spectroscopic ellipsometry and formation of thin films by plasma-enhanced chemical vapor deposition (PECVD). In the experimental part we describe the deposition system, ellipsometer and mathematical evaluation of ellipsometric data, materials used for film formation and processing of the samples. Single-layer and multilayer structures of polymeric materials were prepared. We revealed that the optical properties of thin films are independent of film thickness. We also described the effect of the effective power and deposition gas mixture on optical properties of thin films.

The work focuses on new processes for the preparation of lactic acid derivatives. The main objective was to verify the feasibility of preparing high molecular weight polylactide using ethyl lactate as a precursor of lactide synthesis. Part of the work is devoted to the new ethyl lactate synthesis method. The experimental part of the thesis is divided into partial key steps on the way from the lactic acid to the high molecular polylactide. The preparation of anhydrous ethyl ester of lactic acid (EtLA) was solved in an innovative way using alcoholysis of the oligomeric lactic acid. A kinetic model for isothermal alcoholysis and equimolar reactants ratio was derived from this method. The ethyl lactate was oligomerized by transesterification into the low and high molecular weight oligomer with the help of newly found catalysts suitable for the reaction medium. Stannous lactate was used as catalyst for oligomerization of the low molecular weight polymer suitable for the preparation of lactide (Mn 1000 g.mol-1). Experimental polymerization of ethyl lactate into high molecular weight product in tens of kDa has been investigated with newly synthesized tetraethyllactoyl titanate, Ti(EtLA)4. The laboratory method was derived for the depolymerization of the oligomer into lactide. Optimal conditions found for lactidation are as follow: temperature 225 ° C, pressure 2 kPa, catalysis 0,05 mol% of stannous lactate (with respect to oligomer lactate units). The prepared lactide was refined to polymer grade purity by distillation and subsequent recrystallization from ethyl acetate and toluene. The method for the preparation of high molecular weight PLA through ROP polymerization of lactide has been optimized. By optimization, suitable catalyst concentration was found in combination with the polymerization temperature and the polymerization length. An equimolar mixture of Tin 2-ethylhexanoate and 1-decanol was used as the catalytic system. The optimal ROP conditions for achieving the maximum molecular weight and suppressed polymer coloration (yellowing) are: catalyst concentration 0,01 mol%, temperature 160 °C, and polymerization length 4 hours. PLA with molecular weight Mw= 447 ± 7,8 kg.mol-1 was prepared at these conditions and good repeatability of the result was achieved. The effect of naturally occurring lactide contaminants and their influence on the course and ROP result was experimentally verified on the optimized polymerization system. The purpose was to explore the effect of lactide contamination with water and ethanol as natural lactide contaminants. The results clearly confirm the orderly lower sensitivity of the polymerization system for the presence of ethanol as compared to water contamination. In the case of the presence of water, the course and the result of the polymerization in terms of both the conversion and achieved molecular weights are negatively affected, even when the water content is in the order of 0,001%. Conversely, the presence of ethanol has a positive effect on lactide conversion and polymer polydispersity. Lactides with an alcohol content of about one-tenth of a percent are suitable to reach molecular weights of PLA similar to commercially available products. This difference shoves a significant advantage in the proposed technology of preparing PLA from ethyl lactate, especially for easier purification of crude lactide into polymer grade purity.

Tato dizertační práce se zabývá studiem morfogeneze dimethakrylátových sítí. V práci byly využity zjednodušené systémy založené na monomerech, které bývají typicky využívány jako složky matric pryskyřičných kompozitních materiálů využívaných v oblasti záchovné stomatologie. Kinetika a mechanismy formování polymerních sítí byly studovány především s ohledem na strukturu jednotlivých monomerů, jejich vzájemný molární poměr a koncentraci iniciačního systému využitého pro radikálovou polymeraci. Vypočtené profily konverze funkčních skupin a reakčních rychlostí byly využity jako základ pro pochopení a interpretaci mechanismů morfogeneze sítí a porovnání se známými modely. Dále byla studována kinetika termické degradace, která je s morfologií vytvrzených sítí přímo spjata. V rámci takto charakterizovaných systémů byla stanovena teplotní závislost dynamického modulu a byl popsán vztah mezi supra-molekulární strukturou dimethakrylátových sítí a jejich viskoelastickou odezvou v daném teplotním rozmezí. Kinetika polymerace byla studována pomocí diferenční kompenzační foto-kalorimetrie (DPC) a infračervené spektroskopie (FTIR). Proces termické degradace byl analyzován pomocí termo-gravimetrické analýzy (TGA). Viskoelastické parametry byly charakterizovány pomocí dynamicko-mechanické analýzy (DMA). Reaktivita jednotlivých systémů je přímo odvozena od molekulární struktury monomerů, která ovlivňuje mobilitu reagujících složek v průběhu polymerace. Kinetika polymerace je řízena především difúzí, přičemž její rychlost je dána tuhostí monomerní páteře, koncentrací funkčních skupin a vlivem fyzikálních interakcí. Omezená mobilita rostoucích řetězců, postranních funkčních skupin i samotných monomerů vede k monomolekulární terminaci makro-radikálů a omezení stupně konverze funkčních skupin. Vzhledem k tomu, že k zásadnímu omezení mobility dochází již v počáteční fázi polymerace, tj. v bodu gelace, je případná termodynamická nestabilita vedoucí k fázové separaci polymerujícího systému potlačena a proces kopolymerace je ve své podstatě náhodný. To bylo prokázáno i prostřednictvím identifikace jedné teploty skelného přechodu u charakterizovaných kopolymerů. Heterogenní charakter morfogeneze je spjat s rozdílnou reaktivitou postranních funkčních skupin. V počátečních fázích polymerace dochází k propagaci reakcí postranní funkční skupiny s radikálem na stejném rostoucím řetězci, což vede ke vzniku tzv. primárního cyklu. Pravděpodobnost cyklizace souvisí především s flexibilitou monomerní páteře. Heterogenita polymerace je charakterizována vznikem vnitřně zesítěných struktur, tzv. mikrogelů, a jejich následným spojováním. Tuhost monomeru naopak přispívá k vyšší efektivitě zesítění a více homogenní morfologii vytvrzené sítě. Heterogenita dimethakrylátových sítí se odráží v mechanismu termické degradace, přičemž přítomnost strukturně odlišných domén vede k rozkladu ve dvou krocích. Průběh soufázového modulu a teplota skelného přechodu korelují s tuhostí polymerních sítí, efektivitou zesítění a přítomností fyzikálních interakcí, které vyztužují strukturu sítě nad rámec kovalentního zesítění. Heterogenní morfologie sítí se projevuje rozšiřováním spektra relaxačních časů. Experimentální data jsou v kvalitativní shodě s existujícími numerickými modely popisujícími kinetiku radikálové polymerace multifunkčních monomerů.