L’objectif de cette étude est de synthétiser et de caractériser des polyesters entre le diméthylcétène et des composés carbonylés choisis (acétone, méthyléthylcétone et acéthaldéhyde) par deux voies distinctes : une copolymérisation directe, et une voie passant d’abord par la synthèse de la beta-lactone puis sa polymérisation par ouverture de cycle. La caractérisation a mis en évidence la structure parfaitement alternée du polyester entre le diméthylcétène et l’acétone, et des structures plus complexes avec la méthyléthylcétone et l’acétaldéhyde. Les analyses ont également montré le caractère polymorphe complexe de ces copolymères. Les trois beta-lactones correspondantes ont également été synthétisées. Seule la polymérisation de la beta-lactone avec l’acétaldéhyde a été menée à bien, du fait de son faible encombrement stérique. Enfin, une étude cinétique par infrarouge a également été effectuée et a permis de mieux connaître les cinétiques de polymérisation par ouverture de cycle. / The aim of this study is to synthesise and to characterise polyesters between dimethylketene and chosen carbonyled compounds (acetone, methylethylketone and acetaldehyde) by two distinct pathways: a direct copolymerisation, and another path proceeding in the synthesis of the beta-lactone then its ring opening polymerisation. The characterisation has highlighted the perfectly alternated structure of the polyester between dimethylketene and acetone, and more complex structures with dimethylketone and acetaldehyde. The analyses have also shown the complex polymorphism of these copolymers. The three corresponding beta-lactones have been synthesised. Only the polymerisation of the acetaldehyde beta-lactone has been accomplished because of its weak steric hindrance. At last, an infrared kinetic study has also been carried out and has permitted a better comprehension of the kinetic of the ring opening polymerisation.

Les polyesters insaturés sont des résines thermodurcissables particulièrement appréciées pour leur facilité de mise en œuvre et leur coût modéré. Cependant, comme tous les polymères organiques ils ont une réaction au feu médiocre, ce qui est critique dans un certains nombres de d'applications. L'objectif de cette thèse était d'élaborer de nouvelles formulations de résines ayant un comportement au feu amélioré. La première stratégie développée a été le greffage de monomères phosponés dans la matrice polyester. Des monomères méthacryliques et styrénique ont été synthétisés et utilisés pour remplacer une partie du styrène dans la résine. La stabilité thermique des résines modifiées est diminuée, mais leur comportement au feu est globalement meilleur. Des effets du phosphore en phase gazeuse et en phase condensée ont pu être mis en évidence.Dans une seconde partie, une sélection de particules se distinguant par leur nature, leur taille et leur facteur de forme a été testée. Si l'impact des ces charges est assez limité lorsqu'elles sont utilisées individuellement, des tests calorimétriques ont révélé que certaines combinaisons de particules pouvaient améliorer significativement la réaction au feu des résines. Enfin, des associations d'additifs phosphorés et de particules submicroniques ont été investiguées. Le polyphosphate d'ammonium se distingue des autres additifs par un impact très important sur le comportement au feu et particulièrement par le charbonnement important qu'il engendre, cependant sa combinaison avec des charges inorganiques ne s'est pas révélée probante. / Unsaturated polyesters are thermoset resins particularly appreciated for their low cost and easy processing. Nevertheless one of their main drawbacks is their poor fire resistance. The aim of this PhD thesis was to prepare new resin formulations with an improved fire behaviour. The first part of this work was dedicated to the grafting of phosphorous monomers in the polyester matrix. Methacrylic and styrenic monomers were synthesized and used to replace of part of the styrene in the resin. Resin thermal stability was decreased, but on the whole their fire behaviour was improved. Condensed phase and gas phase effects of phosphorus were highlighted.In a second part, a screening of various kinds of particles with different sizes was performed. Calorimetric tests revealed that, while the effect of these particles used alone is limited, a decrease of resin flammability could be achieved with specific combinations. Finally, commercial phosphorous additives were associated with submicronic fillers. From all the additives tested, ammonium polyphosphate stands out, with a powerful impact on the resin fire reaction and especially a much increased charring. However, its combination with inorganic particles was not conclusive.

No description available.

The diploma thesis deals with the design and stress-strain analysis of a flexible coupling composed of individual rubber-textile segments. This concept allows the manufacturer to simplify and unify the production thanks to the ability to use a single segment design for multiple coupling configurations and thus leads to a reduction in costs on the part of the manufacturer. From the consumer side this allows only mechanically or chemically damaged segments to be replaced instead of the entire coupling and saves costs for the potential user. The coupling assembly is primarily designed according to the parameters of intercity electric units and locomotives, however, the individual flexible segments are not limited by this use. When designing a coupling assembly, it is necessary to place requirements primarily on the high safety of all components. The operating mode, in which the relative displacement of the input and output shafts can occur, indicates a relatively wide range of transmitted loads which, if any assembly part is improperly designed, can cause problems leading to temporary putting the entire machine/vehicle out of order. The most critical areas of the assembly include the flexible segments, the bolt connections, the strength of the hubs and the spline joint for torque transfer. Last but not least, the requirements for the non-complex production of components must be taken into account, together with the assembly and maintenance without collision of the components and the necessary tools. In order to verify the above-mentioned requirements, stress-strain analyses are performed simulating the variation of operating load conditions. Due to the reduction of hardware requirements and computational time, together with the absence of experimentally measured data of rubber and PES codes, the flexible segments were modelled at a lower level with a reduced material model favouring the tensile properties of PES cords. However, this reduction provides a more conservative approach, as this use causes higher stresses on the steel components of the assembly. Subsequently, a stress analysis of the splined joint is performed. Due to the absence of specific shaft geometry models of commercial motors and gearboxes, a parallel splines were chosen for this purpose and designed according to the specified maximum torque. The last part of the thesis is focused on verifying the tensile properties of an individual flexible segment.

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.

The dissertation work focuses on the whole route of material development starting from the investigations of properties of the initial (raw) HBPs to their applications. Each research step is given in a separate chapter to enhance attention to various aspects of the aim of the work. Thus, every chapter is started with an introduction. After that, the methods applied and experimental procedure are described. Next part tries to give the comprehensive description of the results obtained. At the end of the chapter, the main points are summarized. The Chapter 1 gives the theoretical description of the main experimental techniques used in this work. In Chapter 2 the chemical (chemical composition, purity, typical structure elements) and physical (glass transition temperature, the temperature of the maximum decomposition, the thermal stability at the high temperatures, molar mass, polydispersity and possible aggregation in solution) properties examined by different techniques of polymer analysis are described. The Chapter 3 is divided into three separate parts: In Chapter 3.1 the description of the formation and modification of inter- and intramolecular hydrogen bonds of hydroxyl terminated HBP is presented to reveal the information of hydroxyl groups re- and/or association due to the high temperatures applied. In Chapter 3.2 the nature of the solid-liquid interface of HBP thin films have been studied by different surface sensitive techniques with respect to further protein adsorption investigations. In Chapter 3.3 the strategy for the fabrication of surface attached carboxyl terminated HBP using "grafting to" technique is developed. The Chapter 4 consists of two parts: The first (theoretic) part outlines the basic principles of protein chemistry, factors influencing on the protein molecule stability in aqueous medium, the mechanism of protein adsorption and forces involved in the adsorption process. In the second part the combination of different in situ techniques was applied to obtain a comprehensive description of complex adsorption processes of protein molecules on different polymer surfaces.

Die vorliegende Arbeit liefert einen Beitrag zum Verständnis der komplexen Struktur-/Eigenschaftsbeziehungen dünner Schichten hochverzweigter Polyester. Für die umfassende Charakterisierung wurde eine Vielzahl analytischer Methoden kombiniert. Des Weiteren wurde das Anwendungspotential dieser Schichten hinsichtlich möglicher Sensoranwendung anhand der Adsorption von Modellproteinen gewichtet. Dazu war es notwendig verschieden Methoden zur Stabilisierung dieser Schichten zu entwickeln.

<p>This dissertation focused on cured-in-place-pipe (CIPP) technology, which is being used to repair sewer pipes across the globe. The CIPP process involves the manufacture of a new fiber-reinforced composite plastic pipe inside an existing damaged pipe. By 2022, the global CIPP market will exceed $2.5 billion and constitute 40% of the U.S. pipe rehabilitation market. In recent years, concerns about the type, magnitude, and toxicity of chemical air emissions associated with CIPP installations have markedly increased. CIPP installations in Asia, Europe, Oceania, and North America have been associated with indoor and ambient air contamination incidents, afflicted schools, daycare centers, homes, and offices and prompted building evacuations. This research program was designed to better understand chemical release into the air during CIPP composite manufacture and the human health risks. Principles and techniques from the environmental engineering, air quality, material science, and risk analysis were applied. This dissertation contains three chapters and each chapter is a stand-alone manuscript, with the first chapter already having been published.</p><p>Chapter 1 involved the characterization of chemical emissions for steam-cured CIPP installations in Indiana (IN, sanitary sewer) and California (CA, storm sewer). It was discovered that a complex multiphase mixture of organic vapor, water vapor, and particulate (condensable vapor and partially cured resin) was emitted. Chemicals captured included a variety of hazardous air pollutants, carcinogens, endocrine disrupting compounds, and other chemicals with little toxicity data. The materials captured in California during 4 CIPP installations, when normalized against styrene concentration, exhibited different toxicity towards mouse cells. This toxicity indicated that non-styrene compounds were probably responsible for toxicity. Testing revealed significant and previously unreported worker and public safety chemical risks existed with CIPP installations.</p><p>Chapter 2 describes experiments conducted to determine which CIPP manufacturing conditions (i.e. curing pressure, temperature, time and ventilation) influenced chemical air emissions during and after composite manufacture. During thermal manufacture, approximately 8.87 wt% volatile organic compounds (VOC) was released into the air at standard pressure. For the CIPP styrene-based resin examined, chemical volatilization during manufacture was influenced by pressure, but temperature and heating time did not influence the composition of chemical residual inside the new composite. All cured composites, regardless of temperature or heating time, contained approximately 3 wt% VOC. No statistical difference was found for either: (1) VOC loading across cured composites or (2) styrene emission into the air across cured composites despite different curing temperature and heating times. Styrene was the most abundant compound detected in the composite and in air. High styrene air concentration signals inhibited the author’s ability to determine if other non-styrene compounds were emitted into the air. Short-term ventilation (2 hr) of the new composite reduced styrene air concentration to near zero in 10 min, but styrene levels rebounded when ventilation was halted. Due to the high styrene loading in the cured composite, it is expected that ventilation will only temporarily reduce VOC air levels in pipes, manholes, and other affected spaces.</p><p>Chapter 3 includes inhalation health risk assessment due to chemical emission from CIPPs during manufacture and use. Publicly available worksite data for ultraviolet (UV)-light and steam-CIPP installations were utilized and Monte Carlo simulation was applied. Data-gaps were also identified. Health risks associated with newly manufactured (post-cured) chemical emission from lab scale CIPPs were also evaluated. For CIPP resins and post-cured CIPPs 31 chemicals have been quantified among which many are unique volatile organic chemicals VOCs, but only 8 air testing studies were found. At a steam-CIPP worksite, VOCs were found in a condensed multiphase mixture discharged into air, 4 VOCs were detected in the vapor phase, while only styrene vapor phase results could be used for risk assessment. Worksite styrene levels (1,825 ppm_v, 1,070 ppm_v, 220-270 ppm_v, 140 ppm_v) have been reported indicating a health risk can exist. Monte Carlo simulation using literature data revealed that for the single UV-CIPP and single steam-CIPP study negligible styrene HQs were found, while unacceptable styrene LECRs% > 10⁻⁴ (i.e. 37-38%) were obtained. Monte Carlo simulation on laboratory data showed that post-cured emissions from the composite cured longer increased the unacceptable styrene LECR (from 17.86% to 21.12%) and HQ (0.95% to 8.04%). Whereas curing the composite at greater temperature reduced the styrene LECR and HQ to 0.89%. and 0, respectively. Ventilation also diminished the acceptable LECR% in all composites but did not reduce the carcinogenic health risk to an acceptable level. Health risk can exist as evidenced by limited air testing data. More studies are needed to examine inhalation health risks associated with the CIPP manufacturing process and newly manufactured plastics.</p>

No description available.

The use of synthetic materials for tissue and organ reconstruction, i. e. tissue engineering, has become a promising alternative to current surgical therapies and may overcome the shortcomings of the methods in use today. The challenge is in the design and reproducible fabrication of biocompatible and bioresorbable polymers, with suitable surface chemistry, desirable mechanical properties, and the wanted degradation profile. These material properties can be achieved in various manners, including the synthesis of homo- and copolymers along with linear and star-shaped architectures. In many applications the materials’ three-dimensional structure is almost as important as its composition and porous scaffolds with high porosity and interconnected pores that facilitate the in-growth of cells and transportation of nutrients and metabolic waste is desired. In this work linear and star-shaped polymers have been synthesized by ring-opening polymerization using a stannous-based catalyst and a spirocyclic tin initiator. A series of linear copolymers with various combinations of 1,5-dioxepane-2-one (DXO), Llactide (LLA) and ε-caprolactone (CL) have been polymerized using stannous octoate as catalyst. It is shown that the composition of the polymers can be chosen in such a manner that the materials’ mechanical and thermal properties can be predetermined. A solvent-casting and particulate leaching scaffold preparation technique has been developed and used to create three-dimensional structures with interconnected pores. The achieved physical properties of these materials’ should facilitate their use in both soft and hard tissue regeneration. Well defined star-shaped polyesters have been synthesized using a spirocyclic tin initiator where L-lactide was chosen as a model system for the investigation of the polymerization kinetics. Neither the temperature nor the solvent affects the molecular weight or the molecular weight distribution of the star-shaped polymers, which all show a molecular weight distribution below 1.19 and a molecular weight determined by the initial monomer-to-initiator concentration. / QC 20101217