Solvent suspensions of a high performance polymer, Polyamide-imide (PAI) are widely used in magnetic wire coatings. Here we investigate the effect that the introduction of montmorillonite (MMT) has on PAI. MMT was introduced into an uncured PAI suspension; the sample was then cured by step-wise heat treatment. Polarized optical microscopy was used to choose the best suitable MMT for PAI matrix and to study the distribution of MMT in PAI matrix. Concentration dependent dispersion effect was studied by x-ray diffraction (XRD) and was confirmed by Transmission electron microscopy (TEM). Differential scanning Calorimetry (DSC) and Thermogravimetric analysis (TGA) was used to study impact of MMT on glass transition temperature (Tg) and degradation properties of PAI respectively. Micro-hardness testing of PAI nanocomposites was also performed. A concentration dependent state of dispersion was obtained. The glass transition (Tg), degradation and mechanical properties were found to correlate to the state of dispersion.

Cette recherche s’inscrit dans un contexte d’amélioration des performances et du confort des vêtements textiles d’intervention contre le feu et la chaleur. L’objectif est de réduire le poids total des équipements de protection individuelle (EPI), en remplaçant leur structure actuelle par un tissu complexe de type « Spacer Fabric », qui résulte de l’assemblage de deux couches, aux propriétés différentes, par un fil de liage. Ces travaux de thèse se concentrent sur le développement du fil de liage et peuvent se définir comme une étude de faisabilité visant à prouver la possibilité de filer des monofilaments de « gros » diamètre (200 – 300 μm) à partir d’une solution de polyamide-imide Kermel®. Pour mener ce projet à terme, un dispositif expérimental de filage par coagulation a été développé. Entièrement automatisé, il permet aussi bien l’étude de l’influence des paramètres de filage sur la qualité des monofilaments obtenus, que la simulation d’une production de type industriel. Pour répondre à notre problématique, cet outil de prototypage a été appliqué au développement des monofilaments souhaités. Un plan d’expériences a été construit, comprenant quatre facteurs : le diamètre d’extrusion, la concentration en solvant du bain de coagulation et les taux d’étirage appliqués dans le bain et dans l’air. Cette étude expérimentale a mis en évidence l’importance de la maîtrise de la cinétique de coagulation, avec une influence hautement significative des facteurs diamètre d’extrusion et concentration du bain de coagulation, notamment sur l’évolution du taux de vide des monofilaments obtenus. / This research aims to improve the performance and the comfort requirements of textile protective clothing against heat and flames. The main purpose is to reduce the weight of such personal equipment by replacing their current structure with complex woven “Spacer Fabric”, composed of an assembly of two textile layers, having different properties, and linked by a binder yarn. These works particularly focus on the development of this binder yarn and consist in a feasibility study to demonstrate the possibility to demonstrate the possibility to spun monofilaments having a large diameter (200 – 300 μm) from a polyamide-imide solution (Kermel®). A dedicated experimental wet-spinning device has been designed to carry out this project. Such fully automated machine enables to conduct detailed studies concerning the influence of multiple spinning parameters on the physical properties of the manufactured monofilaments, therefore providing a simulation of an industrial production of such fibers. Hence, this prototyping tool has been used to develop monofilaments addressing the initially stated issue. A four factor Design of Experiments has been built to investigate the effects and combinations between the following parameters: extrusion diameter, concentration of the coagulation bath, drawing rates applied in the bath and in the air. The derived results mainly showed the importance of controlling the coagulation kinetic. Moreover, highly significant influences of both extrusion diameter and concentration of coagulation bath factors have been highlighted, especially concerning the evolution of the void fraction of the monofilaments.

Ce travail de thèse a consisté à améliorer certaines propriétés de revêtements fonctionnels à base de polychlorure de vinyle (PVC) plastifié et de polyamide-imide (PAI) par incorporation de nanocharges inorganiques préformées, lamellaires ou divisées. La compatibilisation des nanocharges avec la matrice dans laquelle elles ont été incorporées s’est avérée indispensable pour obtenir des films nanocomposites avec une distribution homogène et un état de dispersion le plus fin possible. Différentes stratégies de compatibilisation ont été étudiées, comme la physisorption, la chimisorption, l’intercalation ou encore la chélation d’agents compatibilisants judicieusement choisis et adaptés à chacun des systèmes. Les nouvelles nanocharges ainsi modifiées ont été caractérisées en vue de leur introduction dans la matrice. Les films nanocomposites « compatibilisés » ont été élaborés en voie solvant et/ou par polymérisation in-situ, suivie d’une gélification physique pour le PVC ou d’une réticulation chimique pour le PAI. La caractérisation morphologique des films, réalisée par DRX et MEB/MET, ainsi que les propriétés thermiques et thermomécaniques des films, évaluées par ATG, DSC et DMA, mettent en évidence l’importance de deux paramètres : la chimie de surface des nanocharges, à l’origine des interactions interfaciales nanocharge/polymère, et le procédé d’élaboration du nanocomposite. / This study aims at improving some properties of functional PVC- and PAI- based coatings by adding preformed inorganic lamellar or spherical nanofillers. The compatibilization of nanofiller with the polymer matrix in which they are introduced, is required in order to obtain nanocomposite films with an homogeneous distribution and a dispersion state as fine as possible. Different compatibilization strategies, well-suited for each system, have been studied: compatibilizer physisorption, chemisorption, intercalation or chelation. The new modified nanofillers have been characterized before their introduction into the matrix. Various strategies have been considered to obtain the “compatibilized” nanocomposite films such as the solution mixing and/or the in-situ polymerization, followed by a physical gelation or curing step for PVC- or PAI-based nanocomposites, respectively. The morphological characterization of the films, through XRD and SEM/TEM analysis, and the thermal and thermomecanical properties, evaluated by TGA, DSC and DMA, underlined the importance of two parameters: the nanofiller surface chemistry, responsible for the nanofiller/polymer interfacial interactions, and the elaboration process of the nanocomposite.

Ce travail de thèse a consisté à améliorer certaines propriétés de revêtements fonctionnels à base de polychlorure de vinyle (PVC) plastifié et de polyamide-imide (PAI) par incorporation de nanocharges inorganiques préformées, lamellaires ou divisées. La compatibilisation des nanocharges avec la matrice dans laquelle elles ont été incorporées s'est avérée indispensable pour obtenir des films nanocomposites avec une distribution homogène et un état de dispersion le plus fin possible. Différentes stratégies de compatibilisation ont été étudiées, comme la physisorption, la chimisorption, l'intercalation ou encore la chélation d'agents compatibilisants judicieusement choisis et adaptés à chacun des systèmes. Les nouvelles nanocharges ainsi modifiées ont été caractérisées en vue de leur introduction dans la matrice. Les films nanocomposites " compatibilisés " ont été élaborés en voie solvant et/ou par polymérisation in-situ, suivie d'une gélification physique pour le PVC ou d'une réticulation chimique pour le PAI. La caractérisation morphologique des films, réalisée par DRX et MEB/MET, ainsi que les propriétés thermiques et thermomécaniques des films, évaluées par ATG, DSC et DMA, mettent en évidence l'importance de deux paramètres : la chimie de surface des nanocharges, à l'origine des interactions interfaciales nanocharge/polymère, et le procédé d'élaboration du nanocomposite.

Made available in DSpace on 2016-12-08T17:19:37Z (GMT). No. of bitstreams: 1 1_Introducao.pdf: 64784 bytes, checksum: a1b19b41bade65db44f4ab7b4a5561dc (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Polyamide-imide (PAI) is a polymer widely used in magnet wires for electrical applications due to combination of their mechanical, electrical and thermal properties. This polymer can be improved by the addition of inorganic moieties, among them silsesquioxanes, forming organic/inorganic hybrids. This dissertation presents the preparation of hybrid polymers PAI/copolysilsesquioxane (PAI/coPSQ), where the matrix of polyamide-imide (PAI) is prepared from the condensation of trimellitic anhydride (TMA) and diphenylmethane-4 ,4-diisocyanate (MDI), and the copolysilsesquioxane is prepared by the sol-gel method from alkoxide precursors, in this case, 3-aminopropyltriethoxysilane (APES) and phenyltrietoxisilane (PTES). The methods for obtaining the hybrid PAI/coPSQ by simple mixing and in situ reaction were evaluated. The hybrid polymers were characterized by their spectroscopic characteristics, morphology, electrical, mechanical and thermal properties. The PAI/coPSQs coatings prepared with APES-rich coPSQ presented gelatinization due to high crosslinking generated by the polymer chains of PAI and the amine groups of PSQ. The method of in situ reaction mixture was more efficient in the generation of hybrid PAI/coPSQ, minimizing the occurrence of gelatinization. The SEM and AFM confirmed the absence of separation between the organic and inorganic phases and the FTIR and NMR 13C and 29Si analysis confirmed the formation of a Si-O-Si network. PAI/coPSQ hybrid samples showed no significant changes of Tg, while PAI/PTES hybrid obtained by polycondensation of PTES presented a decrease of Tg. PAI/PSQs hybrids were analyzed by thermogravimetry and showed a small improvement in thermal resistance. The results of nanoindentation tests confirmed the influence of adding coPSQ to increase hardness and elastic modulus of PAI films, while the average performance of dielectric strength showed trends of increasement. / O polímero poliamida-imida (PAI) é amplamente utilizado em fios esmaltados para aplicações elétricas devido ao balanço de suas propriedades mecânicas, elétricas e térmicas. Este polímero pode ser melhorado pela adição de cargas inorgânicas em sua matriz, dentre elas os silsesquioxanos, formando híbridos orgânicos/inorgânicos. O presente trabalho apresenta o preparo de polímeros híbridos PAI/copolissilsesquioxano (PAI/coPSQ), onde a matriz de poliamida-imida (PAI) é preparada a partir da reação de condensação entre o anidrido trimelitico (TMA) e o difenilmetano-4,4-diisocianato (MDI), e o copolissilsesquioxano é preparado pelo método sol-gel a partir de precursores alcóxidos, neste caso o 3-aminopropiltrietoxissilano (APES) e o feniltrietoxissilano (PTES). Foram avaliadas as metodologias de obtenção do híbrido PAI/coPSQ por mistura simples e por reação in situ. Os polímeros híbridos foram caracterizados quanto às suas características espectroscópicas e morfológicas, propriedades elétricas, mecânicas e térmicas. Os vernizes de PAI preparados com coPSQs ricos em APES apresentaram gelatinização devido ao alto grau de reticulação gerado pelas ligações cruzadas entre as cadeias poliméricas do PAI e os grupos amínicos. O método de mistura por reação in situ mostrou-se mais eficiente na geração do híbrido PAI/coPSQ, minimizando a ocorrência de gelatinização. As análises morfológicas confirmaram a ausência de separação entre as fases orgânica e inorgânica e as análises de FTIR e NMR 13C e 29Si confirmaram formação da rede Si-O-Si. As amostras híbridas PAI/coPSQ não apresentaram alterações significativas de Tg, enquanto que o híbrido PAI/PTES obtido pela policondensação somente do PTES apresentou grande diminuição de Tg. Os híbridos PAI/PSQs apresentaram uma pequena melhoria na estabilidade térmica analisada por termogravimetria. Os resultados do ensaio de nanoindentação confirmaram a influência da adição do coPSQ para o aumento da dureza e do módulo de elasticidade dos filmes de PAI, enquanto que os resultados médios da propriedade de rigidez dielétrica apresentaram tendência de aumento.

There is currently a high demand for electric power from renewablesources. One source that remains relatively untapped is the motionof ocean waves. Anders Hagnestål has been developing a uniquelyefficient and simplified design for a point-absorb buoy generator byconverting its linear motion directly into alternating electric power usinga linear PM engine. To test this method, a smaller prototype isbuilt. Its characteristics present some unusual challenges in the designand construction of its winding.Devices of this type typically use relatively low voltage (690V typicallyfor a wind turbine, compared to the 10kV range of traditionalpower plants). To achieve high power, they need high current, whichin turn requires splitting the conductors in the winding into isolatedparallel strands to avoid losses due to eddy currents and current crowding.However, new losses from circulating currents can then arise. Inorder to reduce said losses, the parallel conductors should be transposedin such a way that the aggregate electromotive force the circuitsthat each pair of them forms is minimized.This research and prototyping was performed in absence of advancedindustrial means of construction, with limited space, budget,materials, manpower, know-how, and technology. Manual ingenuityand empirical experimentation were required to find a practical implementationfor: laying the cables, fixing them in place, transferringthem to the machine, stripping their coating at the ends and establishinga reliable connection to the current source.Using theoretical derivations and FEM simulation, a sufficientlygood transposition scheme is proposed for the specific machine thatthe winding is built for. A bobbin replicating the shape of the enginecore is built to lay down the strands.The parallel strands are then organized each into their respectivebobbin, with a bobbin rack and conductor funneling device being designedand constructed to gather them together into a strictly-organizedbundle. An adhesive is found to set the cables in place.Problems with maintaining the orientation and configuration of thecables in the face of repeated torsion are met and solved. A chemicalsolution is used to strip the ends of the conductors, and a reliableconnection is established by crimping the conductors into a bi-metalCu-Al lug.ivIn conclusion, the ideal transposition schemes required to cancelout circulating currents due to magnetic flux leakage are impossibleto put in practice without appropriate technological means. The feasibletransposition scheme turns out to be a simple mirroring of conductors’positions, implemented by building each half of the windingseparately around replicas of the core and then connecting them usingcrimping lugs. / Efterfrågan på el från förnybara källor är hög och inget tyder på att det kommer ändras den närmsta tiden. En källa till förnybar el som än idag står relativt orörd är den där man använder energin från havsvå- gor. Det är denna förnybara källa Anders Hagnestål haft i åtanke när han nu bygger en unikt effektiv generator med syftet att i ett senare skede utvinna el med hjälp av flytande punktabsorberande vågkraft- system. Generatorn är av den linjära typen och omvandlar det punk- tabsorberande systemet rörelse till el. För att testa denna generator- modell så påbörjades bygget av två fullskaliga prototyper 2017. Denna uppsats behandlar specifikt arbetet med generatorlindningen till pro- totyperna och innefattar processen från design till själva byggnatio- nen. Lindingen består av flertalet mindre och isolerade lindningsleda- re med uppgift att bland annat minska skinneffekt och virvelströms- förluster. När man använder denna metod så uppkommer dock ett nytt problem vilket härstammar från att lindningsledarna är samman- kopplade i vardera ända och bildar på så sätt n slutna strömkretsar. Konsekvensen kan vara stora förluster från cirkulerande strömmar på grund av det magnetiska ströflöde som finns runt järnkärnan som lindningen omsluter. Utgångspunkten för att minimera dessa cirkule- rande strömmar är att transponera alla lindningsledare på ett sätt så att den resulterande elektromotoriska spänningen för varje strömkrets blir så liten som möjligt. Med hjälp av förenklade modeller samt FEM simuleringar så bestämdes ett lämpligt sätt att transponera lindningstrådarna utifrån oli- ka kriterier. Lösningen blev att lindningstrådarna endast transponera- des en gång med en så kallad 180 grader transponering. Detta ger en tillräckligt god minimering av de cirkulerande ström- marna, men den stora fördelen med denna lösning är att det är möjligt att linda maskinen med de små resurser projektet hade tillgång till, dock var detta till en stor nackdel då väldigt mycket tid gick till att hitta egna tillvägagångsätt för att utföra byggandet av lindningen på ibland okonventionella sätt.