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De par leur présence à l’interface entre plusieurs domaines linguistiques (phonologie, morpho-syntaxe, sémantique ou pragmatique), les déterminants ont depuis longtemps suscité l’intérêt des chercheurs en acquisition. On trouve ainsi de nombreux travaux portant notamment sur les contraintes phono-prosodiques, lexico-syntaxiques, sémantiques ou pragmatiques à l’œuvre dans le processus d’acquisition de ces formes, mais peu d’entre eux ont cherché à proposer une analyse combinée de ces facteurs, en tenant compte à la fois des morphèmes adultes et des formes de transition (omissions et fillers). Nous avons donc souhaité, dans le cadre de ce travail, décrire l’émergence des déterminants et de leurs proto-formes en essayant de saisir, dans une perspective multidimensionnelle intégrant à la fois des facteurs distributionnels et fonctionnels, quels facteurs influencent le plus ce processus, et à quelles périodes.Cette thèse repose sur l’analyse d’un corpus longitudinal de quatre enfants, âgés de 1;6 pour le plus jeune lors de la première séance sélectionnée à 3;5 pour le plus âgé lors de la dernière. Nous avons repéré au sein de ce corpus tous les noms produits par les enfants ainsi que les formes les précédant et chaque syntagme a fait l’objet d’une analyse phono-prosodique, lexico-syntaxique, sémantique, pragmatique et discursive.Les résultats montrent d’une part que tous les facteurs distributionnels peuvent - à des degrés différents - influencer la production des formes pré-nominales, et d’autre part, que les usages que les enfants font des formes témoignent d’une sensibilité précoce à certains contrastes pragmatico-discursifs. Toutefois, aucun des facteurs pris séparément n’a permis de rendre compte de l’intégralité des productions des enfants. L’analyse conjointe de ces facteurs distributionnels et fonctionnels a confirmé les tendances dégagées au préalable et a mis en évidence l’influence d’un ensemble de facteurs (et en particulier, phono-prosodique, syntaxique et pragmatique) plus que d’un facteur unique ou prédominant tout au long du processus d’acquisition des déterminants. / Given their presence at the crossroads of different linguistic fields (phonology, morphosyntax, semantics or pragmatics), determiners have for a long time aroused the interest of language acquisition researchers. We thus find several studies dealing with the phono-prosodic, lexical and syntactic, semantic or pragmatic constraints involved in the acquisition of determiners. But only few of them have provided a combined analysis of all these factors, considering both adult morphemes and transitional forms (omissions and filler syllables). Our study aims to describe the emergence of filler syllables and determiners and understand - in a multidimensional perspective examining simultaneously distributional and functional factors - which factors may affect the acquisition process, and over which periods of time.Our study is based on a corpus of four children, aged from 1;6 for the youngest in the first selected session to 3;5 for the eldest in the last session. We first identified all the noun phrases produced in the data and each occurrence was then analysed according to phono-prosodic, lexical, syntactic, semantic, pragmatic and discursive factors.Our results show that each distributional factor may influence, at different degrees, the production of pre-nominal forms and that children’s use of forms shows early sensitivity to pragmatic factors. However, none of the factors taken separately have accounted for all of the children’s productions. An additional combined analysis of both distributional and functional factors has supported the initial trends and highlighted the influence of a series of factors (and in particular, phono-prosodic, syntactic and pragmatic), more than a single and predominant one throughout the acquisition process of determiners.

Compression Resin Transfer Molding (CRTM) is an advanced liquid molding process for producing continuous fiber-reinforced composite parts in relatively large dimensions and with high fiber volume fractions. This thesis investigates this process for the purpose of producing continuous fiber reinforced composites with particle fillers. In many composites, fillers are used within the resin for various reasons such as cost reduction and improvement of properties. However, the presence of fillers in a process involving resin impregnation through a fibrous medium can result in a composite with non-homogeneous microstructure and properties. This work aims to model the resin impregnation and particle filtration during injection and compression stages of the process. For this purpose, a previously developed particle filtration model is adapted to CRTM. An appropriate commercial software tool is used for numerical solution after a survey of available packages. The process is analyzed based on the developed model for various process scenarios. The results of this study aim to enhance the understanding of particle-filled resin impregnation and particle filtration phenomena in the CRTM process and are likely to be used towards designing optimum process configurations for a desired outcome in the future.

New processes for the production of polymeric dispersions with high solids content and low viscosity were developed, investigated and characterized. The specifications required for the desired application of paper coating, which constitutes one of the major innovative aspects of this thesis, requires in average particle sizes smaller than 200 nm. This particle size is significantly smaller than obtained in previous work in this area. The main objective of this project was to increase the solids content of existing products from ~50 to ~60 wt% while keeping the viscosity at low levels (< 1200 mPa•s at 20 s-1). In order to produce high solids content latexes with low viscosity, bimodal particle size distributions were resorted to. To obtain highest packing fraction, the small particle size population should be about 7 times smaller than the large particles, bringing the size of the small particles to less than 30 nm. Modified (micro)emulsion processes were developed in order to produce small particle size latex with reduced surfactant concentration and increased solids content. The large particle population was developed using a semi-batch emulsion polymerization process, simulating a product that is commercially available (~52 wt% solids content and viscosity of ~500 mPa•s at 20 s-1). To increase the solids content of this product up to 60 wt%, a second population of small particles was created using two approaches. In the first approach, the small particles were generated in situ using the modified (micro)emulsion approaches developed previously. This process resulted in latexes of ~ 60% solids content and viscosities lower than 500 mPa•s at 20 s-1. In the second approach, the second population of particles was created by the addition of seeds by using small cross-linked particles as pseudo inert-fillers. This process resulted in products with ~58% solids and viscosities lower than 1400 mPa•s at 20 s-1. The slightly decreased solids content and increased viscosity relative to the previous approaches is due to the difficulty in producing cross-linked seeds with particle sizes smaller than 30 nm at an acceptable concentration, causing deviations from ideal conditions. / Thesis (Ph.D, Chemical Engineering) -- Queen's University, 2011-05-03 13:58:44.22

L’étude s’inscrit dans le cadre d’un projet Européen 3Dice, dont l’objectif est d’améliorer la fiabilité mécanique d’un composant microélectronique innovant. La miniaturisation du composant induit des difficultés lors de la caractérisation mécanique. Le développement de méthodes de caractérisation est nécessaire. La flexibilité du composant microélectronique est de plus en plus demandée. Les joints de connexion subissent souvent un pré-chargement. La tolérance du joint aux pré-chargements est intéressante à étudier. Cette thèse s’est déroulée autour de ces deux problématiques. Les méthodes de caractérisation de la couche mince métallique, la résine chargée en silice et le joint de connexion sont développées. L’étude de la fatigue du joint de connexion est effectuée. / This work is a part of an European fund project ‘3Dice’ which aims to improve the mechanical reliability of an innovated microelectronic product. The miniaturization of microelectronic component causes the difficulties to determine mechanical properties of materials involved. The development of experimental methods for microelectronic materials’ characterization is necessary. The flexibility of the products is an additional requirement recently in microelectronic field. The solder joint’s tolerance to the pre-load is interesting to investigate. The thesis is carried out based on these two topics. The characterization methods of thin film, resin with fillers and solder joint are developed. The fatigue behavior of solder joint is investigated under different displacement ratios.

Made available in DSpace on 2014-10-09T12:26:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:59Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:26:24Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:59Z (GMT). No. of bitstreams: 0 / Com o propósito de melhorar a estabilidade dimensional, melhorar propriedades de resistência elétrica, mecânica, ao calor entre outras dos polímeros, novas cargas e reforços são testados com esse propósito. As cargas mais utilizadas, para propiciar as características mencionadas anteriormente, são as fibras de vidro e de carbono, as cargas minerais como o carbonato de cálcio precipitado, o talco e a micro esfera de vidro. O objetivo principal deste trabalho foi estudar as potencialidades da cinza da casca de arroz (CCA) como uma carga, já que ela é constituída em 96% de dióxido de silício e compará-la com o talco que é a carga mineral mais utilizada. Estes estudos foram realizados a partir da elaboração de um composto formado pela cinza da casca de arroz refinada e a poliamida 6 (PA 6) que é um dos principais plásticos de engenharia com aplicações em todas as áreas produtivas. As amostras foram injetadas e irradiadas em um acelerador de elétrons. Posteriormente suas propriedades mecânicas e térmicas foram medidas. Também foram injetadas peças automotivas para verificar a processabilidade da PA 6 com CCA. Os resultados mostraram que a utilização da cinza da casca de arroz como carga para compostos de poliamida 6 é tecnicamente e economicamente viável. A irradiação do composto estudado (PA 6 com 30% de cinza da casca de arroz) não trouxe melhorias significativas nas propriedades mecânicas e térmicas avaliadas. / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

La synthèse d'acide polyamique (APA) comportant des blocs élastomères de type oligo-oxyéthylène et -oxypropylène et des polyimides correspondants (PEI) a été étudiée et leurs propriétés de perméation gazeuse déterminées pour He, N2, O2, H2, CH4 et CO2. Il a été montré que la présence de la phase élastomère augmentait de façon très importante les coefficients de perméabilité au gaz comparativement aux polyimides aromatiques conventionnels. La perméabilité du CO2, augmentée de façon préférentielle par rapport celles de tous les autres gaz, conduit à des sélectivités idéales tout à fait remarquables, en particulier vis-à-vis de N2 (≈40). L’incorporation de nanoparticules de silice dans les PEI (de 1 à 15% en masse) a été effectuée lors de l’étape de cyclo-déshydratation de l'APA, soit par ajout de silice hydrophobes (16 nm) ou hydrophiles (12 nm), soit par méthode Sol-Gel à partir de précurseurs alcoxysilanes (TMOS et TEOS). L'influence des charges SiO2 sur les propriétés de perméation gazeuse a été étudiée par la méthode du temps de retard (time-lag) essentiellement sur la série préparée avec des particules préformées. On a observé que les nano-charges de silice ne semblent pas interférer dans le processus de cyclisation et que les propriétés mécaniques sont renforcées ; la perméabilité aux gaz varie surtout selon la quantité de charges incorporées mais aucune augmentation spectaculaire de perméabilité n’a pu être observée. On peut en déduire que, vraisemblablement, c’est la phase élastomère qui est le lieu d’incorporation des particules de SiO2. Ces résultats montrent l’intérêt des membranes PEI et PEI/SiO2 dans des applications industrielles de séparation de gaz, notamment pour la séparation de mélanges CO2/N2 / The synthesis of polyamic acids (PAA) with oligo-oxyethylene and -oxypropylene rubbery blocks and the related polyimides (PEI) has been studied and their gas permeation properties determined for He, N2, O2, H2, CH4 and CO2. It was shown that the rubbery phase dramatically increased the gas permeability coefficients compared to conventional aromatic polyimides. The permeability of CO2 is preferentially increased in comparison to all other gases, leading to remarkable ideal selectivities, especially for the N2 mixture (≈40). The incorporation of silica nanoparticles in PEI (from 1 to 15 wt%) was carried out during the cyclo-dehydration of the PAA by adding fumed hydrophobic (16 nm) or hydrophilic (12 nm) silica, or by Sol-Gel approach using alkoxysilane precursors (TMOS and TEOS). The effect of SiO2-fillers on the properties of gas permeation has been studied by the time-lag method mainly on the series prepared with fumed silica. It was observed that nano-particles of silica do not seem to disturb the PAA cyclization process and that the mechanical properties are improved; the gas permeability varies essentially depending on the amount of fillers incorporated but no spectacular increase in permeability could be shown due to the nano-particles amounts. Apparently, it can be deduced that it is the rubbery phase which accommodates the SiO2 particles. These results showed the value of PEI and PEI/SiO2 membranes in industrial applications of gas separation, especially for the separation of CO2/N2 mixtures

This diploma thesis deals with 1) the preparation of biodegradable polymer films based on polyhydroxyalkanoates (PHA) and 2) their modification by lignin as an active additive. The motivation for this work was to prepare active packaging material for food packaging. Polymer films were prepared by blending of neat crystalline poly(3hydroxybutyrate) (P3HB) and amorphous polyhydroxyalkanoate (PHA). The lignin was isolated from grape seeds derived from grape pomace. The solubility of lignin in chloroform was improved by acetylation. The properties of the isolated lignin were determined by elemental analysis, ash content, and infrared spectroscopy (FTIR). Lignin was used as an active additive for the modification of polymeric films prepared by solution casting of P3HB or P3HB blended with amorphous polyhydroxyalkanoate. The effect of different concentrations of lignin in the range of 1 to 10 % was tested. The lignin type and concentration had a different influence on the final thermal and mechanical behaviour of polymeric films. Lignin increased the values of the Young modulus and tensile strength of the prepared films. Differential scanning calorimetry data confirmed that lignin positively modified crystallization kinetics of P3HB. Thermogravimetry was used to analyse the thermal stability of PHA films. Lignin markedly increased the thermal stability of PHA films. However, acetylated lignin harms the mechanical properties of films. Moreover, this work showed that lignin isolated from grape seeds and added into PHA films proved its high antioxidant capacity. PHA films with lignin displayed much better gas barrier properties compared with PHA films without lignin. The prepared bioactive PHA films fulfil the requirements for sustainable food packaging with high antioxidant capacity and excellent gas barrier properties.