This thesis is part of an on going project within Autoliv Sweden AB to develop the process in changing the material in airbags. Most airbags are today constructed of fabric in polyamide 6.6 (PA6.6) and the thesis view the possibility of changing the material to one of three different polyesters (PET1, PET2, PET3). Both materials have different properties that have been looked into by two test methods, linear testing and dynamic testing with cold gas. The two testing methods were conducted on plain fabric and on fabric with seam to see differences in the materials when subjected to different stress caused by force or pressure. During testing the seam rupture was measured by filming the test sequences, and used for visual analysis. Tensile testing was conducted using a constant-rate-of-extension machine where the material is subjected to linear force until rupture. Dynamic testing was done with a cold nitrogen gas system using vessels to build up pressure that then releases towards the material putting it under stress. Tensile testing results for elongation do not have significant differences between testing in plain fabric or fabric with seam. PET2 have highest elongation in warp and weft. Visual analysis of specimens shows difference in how materials break, where the reference material in PA6.6 breaks more even than in PET materials. Dynamic testing show that the biggest seam opening do not occur at the highest pressure. In order to understand what is happening with the fabric during testing, three different times have been chosen in the pressure-time chart. Results in dynamic testing on fabric with seam show that PET3 have the smallest seam opening while reference material in PA6.6 has the largest opening. All PET materials have similar properties even if these are not always same as reference material in PA6.6. We can neither discard nor confirm our hypothesis of seam slippage and elongation relates equally in the same material independent of test method. From these results PET2 would not be recommended due to seam opens most at maximum force and the material has the biggest elongation. PET3 would be the recommended material, since seam opening is smallest at measured pressure. / Program: Textilingenjörsutbildningen

<p>Organic nitrogen compounds are important in environmental systems because they are prevalent in natural waters but are also components of polymers within membrane filters that are used for water treatment. In both of these cases, these compounds can be exposed to free chlorine during disinfection, which can trigger a set of reactions that can form a host of different halogenated by-products. When such by-products form during water treatment disinfection, these by-products, known as nitrogen-based disinfection by-products (N-DBPs), can be highly toxic and affect human and ecosystem health. Alternatively, when such reactions occur during membrane filtration, the organic nitrogen compounds, which are embedded within the upper layer polymer structure of the membrane filter, can degrade when free chlorine is applied. Therefore, this research was aimed at exploring the chemistry behind how specific types of organic nitrogen compounds which are found in these applications, such as tertiary amines and amides, react with free chlorine. It particularly focused on assessing the kinetics and by-product formation of these reactions under variable water quality conditions (e.g., pH, halide concentrations, and precursor doses).</p> <p> </p> <p>More specifically, in the first phase of this work, the roles of tertiary amines in enhancing disinfection by-product (DBP) formation, such as trihalomethanes (THMs) and haloacetic acids (HAAs), during chlorination of aromatic compounds were studied. The results indicated that in synthetic solutions, chloroform (CHCl₃) and trichloroacetic acid (TCAA) were enhanced by up to 20× with tertiary amines at low dose ([tertiary amine]₀ = 0.5×[aromatic compound]₀). The enhancement effect was also dependent on the aromatic compound type, tertiary amine type and dose, and water conditions such as pH and bromide concentrations. Thus, THMs and HAAs were predicted to be enhanced when the aromatic compound reacted with R₃N-X⁺ (X=Br or Cl) and was not outcompeted by aromatic compound or tertiary amine reaction with free chlorine or bromine alone. In the second phase of this work, the reaction kinetics, by-product formation, and overall mechanisms of a polyamide-based monomer with chlorine were evaluated under varying water conditions. The current known mechanism, Orton Rearrangement, was reevaluated, and new mechanisms were proposed, where it was found that N-halogenation and ring halogenation were two independent pathways. The ability to choose either pathway was highly dependent on the water quality condition of the aqueous solution. The roles of different chlorinating/brominating agents were also investigated where certain species-specific rate constants were obtained. For the N-halogenation pathway, only chlorination and no bromination occurred in which the reactivity of the chlorinating agents likely decreased such that ClO^->HOCl. However, for the ring halogenation pathway, both chlorination and bromination occurred in which the reactivity of the chlorinating and brominating agents decreased such that Cl₂ >HOCl, and BrCl > BrOCl > Br₂ > Br₂O > HOBr, respectively. Overall, this study suggests that a number of unique reactions can occur for various types of organic nitrogen compounds which: (i) allow them to affect water quality by enhancing DBP formation, (ii) but, when integrated into a polymer matrix used for water treatment, can induce reactions that lead to permanent structural damage of the polymer. In all cases, the extent of these reactions is strongly governed by the surrounding water matrix.</p>

Spent oil based drilling fluid and cutting wastes are global liabilities due to their hazardous hydrocarbon content which impacts negatively on flora, fauna, and global carbon footprint. The formulation of two demulsifiers to ensure chemically enhanced phase separation of this waste into oil, water and solid components was successfully carried out in addition to recycling the solid phase into PA6 nanocomposite materials. Initial characterisation of the untreated waste was carried out by Fourier Transform Infra Red (FTIR) for total petroleum hydrocarbon (TPH) analysis, Inductively coupled plasma optical emission spectrometry (ICPOES) for quantitative elemental analysis and Energy dispersive xray analysis (EDXA) for qualitative elemental composition amongst other characterisation methods. The analysis showed that the sample had a high hydrocarbon load of 662,500mg/kg and a high heavy metal load for Pb of 122mg/kg. No As, Cd, Hg were detected. The demulsifier formulations were composed of isopropanol, sodium dodecyl sulphate, poloxamer, sodium chloride, chitosan in 0.2M acetic acid and deionised water for demulsifier S4 and addition of phosphoric acid for demulsifier S3. Hydrocarbon reduction on the extracted solid phase nanofiller S3 and nanofiller S4 was 98.6% and 98.5% respectively after demulsification. The demulsified spent oil based drilling fluid solid extracts were below OSPAR regulation of < 1% oil on cutting by weight. However, recycling of the recovered solid was carried out in order to achieve environmentally sustainable management of the waste in Polyamide 6 (PA6) nanocomposite manufacture/fabrication. The formulation of different blends of PA6 nanocomposite materials from untreated, demulsifier treated and thermally treated drilling fluid and cuttings was successfully achieved. Nanocomposite leaching test showed Pb immobilisation. The flexural and compressive - modulus and strength of the PA6 were markedly improved in the presence of the nanofillers and glass fibre. This was attributed to the reinforcement, exfoliating, stiffening, rigidity effect of the nanofillers. S6 (untreated drilling fluid) nanofillers significantly improved the mechanical properties of PA6. This was attributed to the increased interfacial bonding between the fillers and the polymer matrix as a result of the petroleum hydrocarbon present in the sample. The Thermogravemetric analysis (TGA) results showed that nanocomposites PA6/S3 and PA6/S3/GF30 had improved the thermal stability of PA6 by 13.6% and 38.8% respectively compared to PA6/S2 and PA6/S2/GF30 (simulated commercial nanocomposite materials) that improved PA6 by 9.7% and 35.8% respectively.

Monitores de LCD (Liquid Crystal Display) para computador são equipamentos eletroeletrônicos que têm como destino de descarte os aterros sanitários ou a incineração. O vidro presente nas telas de LCD pode ser reaproveitado como carga em matrizes poliméricas para melhorar as propriedades mecânicas das mesmas ampliando o seu mercado de aplicação. A Poliamida-6 (PA-6) é um dos mais importantes plásticos de engenharia comercializados, devido as suas ótimas propriedades mecânicas e térmicas. Porém, a PA-6 é higroscópica e apresenta baixa estabilidade dimensional. A adição de cargas inorgânicas além de elevar o módulo de elasticidade do polímero, eleva a estabilidade dimensional devido à redução da absorção de água. Desse modo, compósitos de PA-6 reforçados com cargas particuladas provenientes de telas de LCD e microesferas de vidro, cargas usualmente empregadas pela indústria, foram processados em laboratório em extrusora dupla-rosca. Os corpos de prova foram obtidos por injeção e suas propriedades foram avaliadas por ensaio de resistência à tração, ensaio de resistência ao impacto Izod, com e sem entalhe, microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC), análise termogravimétrica (TG) e difração de raios X (DRX). Os resultados indicaram que todas as cargas estudadas provocaram redução na resistência à tração da matriz de PA-6 e em sua resistência ao impacto, embora em alguns casos não tenham causado perdas significativas nos valores dos módulos de elasticidade. Embora as microesferas de vidro tenham mostrado desempenhos melhores quanto às propriedades mecânicas dos compósitos quando comparados àqueles que continham vidro particulado proveniente das telas de monitores LCD, o material reaproveitado apresenta potencial econômico e mecânico para ser usado como carga em matriz de PA-6, respeitadas as limitações mecânicas do compósito obtido. / The current destination of end of life (or defective) computer Liquid Crystal Displays (LCDs) is incineration or to be discarded in landfills. However, the inorganic glass of the LCDs can be used as a filler in polymer matrices. In particular, Polyamide-6 (PA-6) is one of the most important engineering polymers in the market, due to its remarkably good mechanical properties, although presenting high hygroscopicity and low thermal stability. The presence of an inorganic filler in PA-6s can elevate its elastic modulus, while improving its thermal stability. Therefore, in this study, several properties of PA-6 composites reinforced with LCDs particulate glass where compared to PA-6 composites reinforced with industrial glass spheres, a widespread industrial filler. Samples were prepared in a laboratory twin-screw extruder followed by injection molding, and were submitted to tensile strength test, Izod-notched impact resistance test, scanning electron microscopy, X-ray diffraction, and thermal analyses (TG and DSC). The results indicated that all studied fillers caused reduction in the tensile strength of the PA-6 matrix and in its impact strength, although, in some cases, did not cause any significant reduction in the values of the elastic modulus. Composites containing glass microspheres showed a better performance in terms of mechanical properties when compared to the ones containing particulate glass from LCD screens. Nevertheless, the recycled glass material exhibits mechanical and economic potential to be used as filler for PA-6 matrix, once the mechanical properties limitations of the obtained composites are adequately considered.

Este trabalho tem por objetivo a comparação das propriedades da superfície da poliamida 6.6 tratada por plasma e por radiação ionizante, assim como determinar qual a melhor técnica e condição para ativação da superfície, visando a adesão da mesma e borracha poliacrílica utilizada na fabricação de retentores automotivos. O tratamento da poliamida 6.6 por plasma foi realizado utilizando um equipamento Electronic DIENER Plasma Surface- Technology LFG40, com gás nitrogênio à pressão de 1,40 kg/cm2. As amostras de poliamida 6.6 também foram tratadas por radiação ionizante, à pressão atmosférica e em vácuo, utilizando um acelerador industrial de elétrons, Dynamitron JOB 188, com dose de radiação de 5, 10, 20, 40, 50, 100, 200, 300, 400 e 500kGy com taxa de dose de 11,22 kGy/s para todas as doses e taxa de 11,22 kGy/s e 22,38 kGy/s para a dose de 20kGy. Após os processos de modificação da superfície da poliamida 6.6, parte das amostras não tratadas, tratadas por plasma e por radiação ionizante foram incorporadas à borracha poliacrílica, e outra parte foi destinada a caracterização da superfície utilizando as técnicas de MEV/EDS, FT-IR, PIXE/RBS, AFM e ângulo de contato. As amostras não tratadas e as amostras irradiadas não aderiram à borracha poliacrílica. As amostras tratadas por plasma aderiram à borracha poliacrílica com eficiência e apresentaram diferenças de rugosidade, nas análises de MEV e AFM, e aumento no ângulo de contato quando comparado com as amostras não tratadas. As amostras irradiadas não apresentaram diferenças significativas de propriedades nas análises utilizadas neste trabalho, quando comparadas com as amostras não tratadas. A radiação ionizante não foi eficiente na modificação da superfície da poliamida 6.6 para aderência à borracha poliacrílica. / This study aims to compare the surface properties of polyamide 6.6 plasma treatment and ionizing radiation, as well as determine the best technique and condition of the surface activation, adhesion of the same order and polyacrylic rubber used in manufacturing of automotive retainers. Treatment of polyamide 6.6 plasma was performed using an equipment \"Electronic Diener - Plasma - Surface-Technology LFG40\" with nitrogen gas at a pressure of 1.40 kg/cm2. Samples of polyamide 6.6 were also treated with ionizing radiation, atmospheric pressure and in vacuum, using an industrial electron accelerator, Dynamitron JOB 188 with radiation dose of 5, 10, 20, 40, 50, 100, 200, 300, 400 and 500kGy with a dose rate of 11.22 kGy/s for all doses and rate of 11.22 kGy/s and 22.38 kGy/s for a dose of 20kGy. After the processes of surface modification of polyamide 6.6, part of the untreated samples, treated by plasma and by ionizing radiation were incorporated into the polyacrylic rubber, and another part was designed to characterize the surface using the techniques of SEM / EDS, FT- IR, PIXE / RBS, AFM and contact angle. Untreated samples and the irradiated samples did not join the polyacrylic rubber. The samples treated by plasma joined the polyacrylic rubber efficiently and showed differences in roughness in SEM and AFM, and an increase in contact angle when compared with untreated samples. The irradiated samples showed no significant differences in the analysis of properties used in this study when compared with untreated samples. Ionizing radiation was not effective in surface modification of polyamide 6.6 for adherence with polyacrylic rubber.

Este trabalho tem por objetivo a comparação das propriedades da superfície da poliamida 6.6 tratada por plasma e por radiação ionizante, assim como determinar qual a melhor técnica e condição para ativação da superfície, visando a adesão da mesma e borracha poliacrílica utilizada na fabricação de retentores automotivos. O tratamento da poliamida 6.6 por plasma foi realizado utilizando um equipamento Electronic DIENER Plasma Surface- Technology LFG40, com gás nitrogênio à pressão de 1,40 kg/cm2. As amostras de poliamida 6.6 também foram tratadas por radiação ionizante, à pressão atmosférica e em vácuo, utilizando um acelerador industrial de elétrons, Dynamitron JOB 188, com dose de radiação de 5, 10, 20, 40, 50, 100, 200, 300, 400 e 500kGy com taxa de dose de 11,22 kGy/s para todas as doses e taxa de 11,22 kGy/s e 22,38 kGy/s para a dose de 20kGy. Após os processos de modificação da superfície da poliamida 6.6, parte das amostras não tratadas, tratadas por plasma e por radiação ionizante foram incorporadas à borracha poliacrílica, e outra parte foi destinada a caracterização da superfície utilizando as técnicas de MEV/EDS, FT-IR, PIXE/RBS, AFM e ângulo de contato. As amostras não tratadas e as amostras irradiadas não aderiram à borracha poliacrílica. As amostras tratadas por plasma aderiram à borracha poliacrílica com eficiência e apresentaram diferenças de rugosidade, nas análises de MEV e AFM, e aumento no ângulo de contato quando comparado com as amostras não tratadas. As amostras irradiadas não apresentaram diferenças significativas de propriedades nas análises utilizadas neste trabalho, quando comparadas com as amostras não tratadas. A radiação ionizante não foi eficiente na modificação da superfície da poliamida 6.6 para aderência à borracha poliacrílica. / This study aims to compare the surface properties of polyamide 6.6 plasma treatment and ionizing radiation, as well as determine the best technique and condition of the surface activation, adhesion of the same order and polyacrylic rubber used in manufacturing of automotive retainers. Treatment of polyamide 6.6 plasma was performed using an equipment \"Electronic Diener - Plasma - Surface-Technology LFG40\" with nitrogen gas at a pressure of 1.40 kg/cm2. Samples of polyamide 6.6 were also treated with ionizing radiation, atmospheric pressure and in vacuum, using an industrial electron accelerator, Dynamitron JOB 188 with radiation dose of 5, 10, 20, 40, 50, 100, 200, 300, 400 and 500kGy with a dose rate of 11.22 kGy/s for all doses and rate of 11.22 kGy/s and 22.38 kGy/s for a dose of 20kGy. After the processes of surface modification of polyamide 6.6, part of the untreated samples, treated by plasma and by ionizing radiation were incorporated into the polyacrylic rubber, and another part was designed to characterize the surface using the techniques of SEM / EDS, FT- IR, PIXE / RBS, AFM and contact angle. Untreated samples and the irradiated samples did not join the polyacrylic rubber. The samples treated by plasma joined the polyacrylic rubber efficiently and showed differences in roughness in SEM and AFM, and an increase in contact angle when compared with untreated samples. The irradiated samples showed no significant differences in the analysis of properties used in this study when compared with untreated samples. Ionizing radiation was not effective in surface modification of polyamide 6.6 for adherence with polyacrylic rubber.

A-102395 is a member of the capuramycin family of antibiotics which was isolated from the culture broth of Amycolatopsis sp. SANK 60206. A-102339 is structurally classified as a nucleoside antibiotic, which like all members of the capuramycin family, inhibits bacterial MraY (translocase I) with IC50 of 11 nM which is the lowest among the capuramycin family. A semisynthetic derivative of capuramycin is currently in clinical trials as an antituberculosis antibiotic, suggesting high potential for using A-102395 as a starting point for new antibiotic discovery. In contrast to other capuramycins, A-102395 has a unique arylamine-containing polyamide side chain. The biosynthetic gene cluster of A-102395 was previously identified and includes 35 putative open reading frames responsible for biosynthesis and resistance. Presently, there are no reports focused on the biosynthesis of this polyamide chain. Here we present the functional assignment and biochemical characterization of seven proteins, Cpr33-38 and Cpr12, that initiate the biosynthesis of the polyamide. Functional characterization of Cpr38, which has sequence similarity to the gene products encoded by pabA and pabB from E. coli, revealed that it functions as a 4-amino-4-deoxychorismate (ADC) synthase catalyzing a two-step reaction involving amidohydrolysis of L-Gln with ammonia channeled and incorporated into chorismic acid to generate ADC. Cpr12, encoded by a gene that was originally proposed to be outside the gene cluster and sharing similarity to proteins annotated as ADC lyase, was revealed to catalyze the elimination of pyruvate to form PABA. Cpr36 is demonstrated to function as a free-standingpeptidyl carrier protein (PCP), which is activated to form holo-protein from the apo-form. Cpr37, which belongs to the adenylation domain protein in the nonribosomal peptide synthase (NRPS), subsequently activates PABA and loads it to holo-Cpr36 Two proteins Cpr34 and Cpr35 work in concert to catalyze decarboxylative condensation between a thioester linked PABA and malonyl-S-acyl carrier protein (ACP) during aromatic polyketide biosynthesis catalyzed by type II polyketide synthases. Following condensation, Cpr33 acts as 3-oxoacyl-ACP reductase that catalyzes reduction to the β-hydroxythioester intermediate. In this scenario, hydride is predicted to be added to the re face to generate the S configuration resulting in the same stereochemical outcome as other 3-oxoacyl-ACP reductase (FabG) from bacterial type II fatty acid synthases.These findings are critical advancement for interrogating the biosynthesis of the unusual chemical components of the family of antibiotics of capuramycin.

La résistance à la rupture des polymères semi-cristallins est considérablement améliorée par l'incorporation de particules (sub)microniques qui cavitent et induisent une déformation plastique étendue de la matrice plutôt que sa rupture fragile. Nous nous sommes intéressés à plusieurs aspects de ce phénomène au travers de l'étude de systèmes de polyamide renforcé. Nous montrons que des particules nanostructurées de copolymères à blocs génèrent des renforcements remarquables sans la perte en rigidité obtenue avec des particules d'élastomère. Par ailleurs, la structuration de ces copolymères semble contrôler la coalescence et la fragmentation des particules lors de la dispersion. Plus généralement, des observations microscopiques et l'application de divers traitements thermomécaniques montrent que l'organisation cristalline de la matrice est déterminante pour le renforcement. A partir de ces résultats, nous proposons un modèle s'appuyant sur les approches physiques de la fracture des milieux hétérogènes qui explique l'origine physique d'un confinement critique de la matrice nécessaire pour obtenir la ductilité. La théorie proposée prévoit comment cette grandeur dépend de l'organisation cristalline, de la taille des particules ou de la température pour les systèmes de polyamide-12 étudiés et pour plusieurs autres systèmes de la littérature.

Létude a pour but de caractériser lévolution du comportement du Polyamide 11 au cours dun vieillissement thermo-mécanique de type fluage, et sintéresse en particulier à la fissuration fragile lente à 90°C.<br />En suivant lévolution de nombreux paramètres physico-chimiques, nous avons déterminé des conditions de vieillissement qui permettent dobtenir un matériau ayant des propriétés semblables à celles du matériau vieilli en service (transport de fluide).<br />La thèse démontre que le vieillissement influe fortement sur le comportement à la fissuration en fluage, et que le mécanisme dendommagement (multi-crazing) observé sur les éprouvettes est similaire à celui observé in-situ. <br />A partir des mécanismes observés, deux méthodes de détermination des durées de vie sont proposées. Dune part, à partir de courbes maîtresses présentées dans le cadre de la mécanique de la rupture en viscoplasticité avec utilisation du paramètre C*h, paramètre pertinent pour le PA11 à 90°C. Dautre part, à partir de critères locaux sur la base dune loi de comportement viscoplastique (modèle DDI). La pertinence de deux modèles dendommagement a été testée et discutée à partir dessais en mode mixte I+II.

Dans le procédé d'extrusion de tubes en polyamide 12, l'étape de calibration a une influence prépondérante sur les propriétés mécaniques résultantes. Lors de la calibration, le polymère fondu est tiré à travers un manchon cylindrique (calibre) situé dans un bac à eau sous vide. Le niveau de vide (dépression DP) est ajustable. Un débit d'eau (débit de suintement DSU) est appliqué à l'entrée du calibre et permet la formation d'un film d'eau qui lubrifie le contact tube/calibre. La calibration combine une trempe et un étirage des couches extérieures du tube, ce qui conduit à une orientation moléculaire importante dans cette zone (zone de peau). Par ailleurs, l'état de surface du tube est défini par les conditions de contact entre tube et calibre. La vitesse du polymère en entrée de calibre et l'épaisseur du film d'eau entre tube et calibre ont été mesurées. Nous avons ainsi montré qu'augmenter la lubrification dans le calibre amène à une diminution du taux d'étirage dans le calibre, taux noté DrCAL (rapport entre la vitesse de ligne et la vitesse en entrée de calibre). Niveau de lubrification et état de surface ont été corrélés par rugosimétrie. Par ailleurs, l'orientation des couches externes a été évaluée par des mesures de biréfringence. Une corrélation nette a été montrée entre la biréfringence en peau (DnPEAU) et DrCAL: réduire DrCAL conduit à une orientation plus faible en surface. Une modélisation thermomécanique a permis de déterminer la carte de température au cours du refroidissement, et de montrer de quelle manière les forces d'étirage se concentrent en peau lors de la cristallisation et génèrent des contraintes à l'origine de l'orientation dans le produit final. Enfin, DnPEAU et l'état de surface ont été reliés aux propriétés mécaniques: l'allongement à la rupture augmente lorsque l'orientation diminue et que le nombre de défauts de surface est limité. Connaissant les relations entre les paramètres du procédé, la structure des tubes, et les propriétés mécaniques, il est à présent possible d'adapter les paramètres de calibration de façon à augmenter le niveau de lubrification au sein du calibre et à réduire le taux d'étirage dans le calibre pour améliorer systématiquement les propriétés mécaniques résultantes.