Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Pour conférer au caoutchouc naturel de meilleures propriétés mécaniques, quand il s’agit d’applications industrielles spécifiques telles que le pneumatique, il est mélangé entre autres à des charges renforçantes. L’objectif de cette thèse est double : nous nous sommes premièrement intéressés à l’élaboration d’un nouveau type de charges hybrides, composées d’une partie minérale (silice) et organique (polymère). La stratégie que nous avons développée consiste à synthétiser des nanoparticules hybrides de morphologie contrôlée par polymérisation en émulsion ensemencée et à les agréger a posteriori. Nous avons également réalisé l’étude des propriétés mécaniques d’élastomères chargés avec les charges hybrides obtenues. / It’s necessary to use filler to give better mechanical properties to the natural rubber when it is used in the making of tires. The objective of this thesis is twofold: firstly we have developed a new type of fillers composed of mineral part (silica) and organic part (polymer). The strategy that we developed is to synthesize hybrid nanoparticles of controlled morphology by seeded emulsion polymerization and to aggregate them subsequently. The second objective was to study the mechanical properties of elastomers filled with the obtained hybrid entities.

Im ersten Teil dieser Arbeit wurden die Synthesen und photophysikalischen Eigenschaften mehrerer Donor-Akzeptor-substituierter Übergangsmetallkomplexe des Typs [(C^N)2Ir(N^N)][PF6] vorgestellt. Das Ir(III) wurde mit Lochleitern wie Carbazol (CZ) und Triarylamin (TAA), die über eine Methyl- und Ethylbrücke mit dem cyclometallierten C^N-Liganden Phenylpyrazol (ppz) und Phenylpyridin (ppy) verbunden waren, verknüpft. Zweizähnige neutrale N^N- und P^P-Liganden wie 2,2’-Bipyridyl (bpy), 3,4,7,8-Tetramethyl-1,10-phenanthrolin (tmp) und cis-1,2-Bis(diphenylphosphino)ethylen (bdppe) wurden als Akzeptoren ausgewählt.Um die Eigenschaften in Vergleich setzen zu können, wurden die entsprechenden Referenzverbindungen ohne Lochleiter hergestellt. Alle Carbazol-Komplexe, bis auf die bdppe-Verbindungen, zeigen Emission und transiente Absorption ähnlich denen ihrer Referenzverbindungen, was sie für Anwendungen in der OLED-Forschung interessant macht. Untersuchungen an LECs (lichtemittierende elektrochemische Zellen) zeigen eine rotverschobene Lumineszenz. Die Triarylamin-Komplexe zeigen keine Emission bei RT, allerdings weisen diese eine intensive, blauverschobene und langlebige Lumineszenz bei 77 K in einer festen Matrix auf. Die transienten Absorptionsspektren unterscheiden sich stark von denen der Referenzverbindungen. Sie weisen charakteristische Merkmale von den Spektren der isolierten Radikalanionen und Radikalkationen auf, was durch spektroelektrochemische Messungen bewiesen wurde. Daraus kann geschlossen werden, dass es sich bei dem angeregten Zustand um einen ladungsgetrennten (CS) Zustand handelt, wo die positive Ladung am Triarylamin-Donor und die negative Ladung am N^N-Akzeptor sitzt. Die Abklingzeiten der angeregten Zustände verlaufen biexponentiell, was ein Hinweis auf das Vorhandensein zweier angeregter Zustände, dem 1CS und 3CS Zustand, ist. Um dieses Verhalten zu untersuchen, wurden verschieden substituierte bpy-Komplexe synthetisiert und analysiert. Temperaturabhängige Messungen der transienten Absorption zeigten, dass alle Ratenkonstanten temperaturunabhängig sind, mit Ausnahme des OMe-substituierten Komplexes. Die Gleichgewichtskonstante K = k1 / k2 ist nahezu eins für alle Komplexe. Bei dem OMe-Komplex sinkt sie mit steigender Temperatur. Eine Auftragung der Ratenkonstanten gegen die Energiedifferenzen, die durch cyclovoltammetrische Messungen erhalten wurden, zeigte, dass alle Konstanten mit steigender Donorstärke am bpy-Liganden abfallen. DFT-Rechnungen an der OMe-Verbindung sind noch in Arbeit. Im zweiten Teil dieser Arbeit wurden neutrale Ir(III) und Pt(II) Komplexe des Typs [(O^O)Ir(N^N)2] und [(O^O)Pt(N^N)] vorgestellt. Hier wurde TAA mit Acetylacetonat (acac) direkt, oder über eine CH2-Brücke verbunden, um den Einfluss der Art der Verbrückung auf die photophysikalischen Eigenschaften zu beobachten. Als zweizähniger N^N-Ligand wurde 2,2’-Bipyridyl (bpy) gewählt. Auch hier wurden alle entsprechenden Referenzverbindungen ohne Triarylamin als Vergleich hergestellt. Zudem wurde der homoleptische fac Ir(N^N)3 Komplex mit Triarylamin, welches über eine Methyl- und Ethylbrücke an Phenylpyrazol angeknüpft wurde, synthetisiert. Die Synthese des Ir(III)-Komplexes mit TAA substituiertem acac-Liganden verknüpft über eine CH2-Brücke konnte nicht hergestellt werden. Alle neutralen TAA-substituierten -diketonato Pt(II) und Ir(III) Komplexe zeigen keine Lumineszenz, außer dem Pt(II)-Komplex mit CH2-Gruppe. Dieser zeigt angeregte Zustände die in guter Übereinstimmung mit den Emissionslebenszeiten bei RT sind. Diese sind ähnlich denen der Referenz, was auf einen 3Pt(N^N)(O^O)- Zustand schließen lässt. Die Komplexe ohne CH2-Brücke zeigen zudem keine transiente Absorption was auf ein Charge-Transfer-Quenching aufgrund der direkten Verknüpfung zwischen Donor und Akzeptor zurückzuführen sein könnte. Der homoleptische fac Ir(N^N)3 Komplex weist weder Emission bei RT, noch transiente Absorption auf. Bei 77 K ist eine stark strukturierte Emission mit einer Abklingzeit von 14 s zu beobachten. Verglichen mit dem literaturbekannten Vergleichskomplex ist die Emission auf die Bevölkerung eines 3Ir(ppz)3-Zustandes zurückzuführen. Unsere Ergebnisse sind grundlegend für die Synthese weiterer Verbindungen mit stärkeren Akzeptoren, wie z. B. Naphthalenimid, um längerlebige ladungsgetrennte Zustände zu erhalten. Diese könnten Anwendung als Photosynthesiser in Solarzellen und anderen optoelektronischen Bauteilen finden. Zudem sind weiter Untersuchungen an LECs und OLEDs für die Carbazol-Komplexe noch immer von Interesse, um das Ausmaß der Triplett-Triplett-Annihilierung zu quantifizieren. / In the first part of this work we presented the synthesis and photophysical properties of a series of transition metal donor-acceptor Ir(III)complexes of the type [(C^N)2Ir(N^N)][PF6]. The Ir(III) was connected with hole conducting donor-moieties like carbazole (CZ) and triarylamine (TAA) linked via a methylene and ethylene bridge to the cyclometalating C^N ligands phenylpyrazole (ppz) and phenylpyridine (ppy). Bidentate N^N and P^P ligands like 2,2’-bipyridyl (bpy), 3,4,7,8-tetramethyl-1,10-phenanthroline (tmp) and cis-1,2-bis(diphenylphosphino)ethylene (bdppe) were used as acceptor units. In order to analyse the influence of the electron density of the bpy ligand, TAA-complexes with acceptor- and donor-substituted bpy acceptor units were synthesised. Therefore, 4,4’-dinitro-2,2’-bipyridyl, 4,4’-dichloro-2,2’-bipyridyl, 4,4’-dimethoxy-2,2’-bipyridyl and 4,4’-dimethylamino-2,2’bipyridyl were used as neutral N^N ligands. In order to compare the photophysical properties, all reference compounds without hole conducting component were syntesised. All the carbazole compounds, except the bdppe complexes, exhibit emission and transient absorption properties similar to their reference compounds that make them interesting for OLED (organic light emitting device) applications. LEC (light emitting electrochemical cell) studies show a red shifted luminescence. The triarylamine compounds do not luminesce at RT but they exhibit an intense, blue-shifted and long-lived luminescence at 77 K in a rigid matrix. The transient absorption spectra differ strongly from that of their reference compounds. The spectra display characteristic features of the spectra of the isolated radical anions and cations supported by spectroelectrochemical measurements. Thus, it can be assumed that the transient states are charge separated (CS) states in which the positive charge is localised at the TAA donor units and the negative charge at the N^N acceptor units. The decays of the transient states are biexponentially what indicates the presence of two transient states, the 1CS and the 3CS state. To understand this behaviour the differently substituted bipyridyl-complexes were synthesised and analysed. Temperature dependent transient absorption measurements showed that all rate constants are indepentend of the temperature, except for the complex with OMe subsituents at the bpy ligand. The equilibrium constant K = k1 / k2 is nearly one for all complexes. For the OMe-compound it decreases with increasing temperature. Plotting the rate constants vs. the free energy differences (determined by cyclovoltammetry measurements) shows that all constants are decreasing with increasing donor strength of the bpy ligand. DFT calculations on the OMe-compound are already in work. In the second part of this work, neutral Ir(III) and Pt(II) complexes of the type [(O^O)Ir(N^N)2] and [(O^O)Pt(N^N)] were introduced. There, TTA was connected directly or via a CH2 bridge to acectylacetonate (acac = O^O) in order to probe the influence of the different kinds of connection on the photophysics of the complexes. As the bidentate N^N ligand 2,2’-bipyridyl (bpy) was chosen. All the corresponding reference compounds without triarylamine were obtained in order to compare with the TAA substituted analoga. Furthermore, the homoleptic fac Ir(N^N)3 complex with triarylamine connected via a methylene and ethylene bridge to phenylpyrazole as introduced in the first part of this work was synthesised. The synthesis of the Ir(III) compound with the TAA substituted acac ligand connected via the CH2 group was not successful. All the neutral triarylamine-substituted -diketonato Pt(II) and Ir(III) complexes do not luminesce at RT, except the Pt(II)-complex with CH2 bridge. This compound shows transient state characteristics that are in good agreement with the luminescence lifetimes at RT and that are similar to the reference compound, what suggests to a 3Pt(N^N)(O^O) state. The complexes without the CH2 bridging unit show no transient signals what may be caused by charge-transfer quenching due to the direct linkage between donor and acceptor unit. The homoleptic fac Ir(N^N)3 complex exhibits no emission at RT and no transient signals. At 77 K it shows a highly structured emission with 14 s lifetime. Compared to the literature-known reference compound this emission is caused by the population of a 3Ir(ppz)3 state. Our findings are important for designing complexes with stronger acceptor units (i.e. naphthaleneimide) for long CS states lifetimes to be used as photosynthesisers in solar cells and other optoelectronic devices. Besides, LEC and OLED studies on the carbazole complexes are still of interest to analyse the degree of triplet-triplet-annihiliation in these devices.

Com hipóteses de simetria plana e que a distribuição inicial de cargas, ocupa totalmente a amostra (tocando os dois eletródios), estudou-se o problema do movimento de carga espacial livre (M.C.E.L.) monopolar, em sólidos isolantes, submetidos à uma d.d.p. conhecida. Utilizando o método das características, reduziu-se o problema à um sistema de duas equações diferenciais ordinárias,de ia. ordem. O método foi aplicado para as distribuições linear, exponencial e p ~ x -1/2 , sob condições de curto circuito. são apresentados gráficos relativos à evolução temporal do perfil da densidade de cargas e da corrente externa. Estes resultados são comparados com outros obtidos por um cálculo aproximado, baseado em princípios variacionais . / Assuming planar symmetry and an arbitrary charge distribution that spreads through the sample, the one-carrier free - space-charge motion is studied in insulators solids. Using the method of characteristics we can reduce the problem t o the resolution of a system of two ordinary first order differential equations. Results are applied for linear, exponential and S.C.L. current charge distributions , under short-circuit conditions, The charge distribution for several times and the discharge currents are presented. The results are compared with those coming from an approximated method, based on variational principles.

Submitted by Jadson Francisco de Jesus SILVA (jadson@uefs.br) on 2018-01-22T22:31:41Z No. of bitstreams: 1 PROFLETRAS UEFAS JUCELMA SACRAMENTO ALVES .pdf: 15349749 bytes, checksum: f1351347dbf4cbb51a6d0a759155b473 (MD5) / Made available in DSpace on 2018-01-22T22:31:41Z (GMT). No. of bitstreams: 1 PROFLETRAS UEFAS JUCELMA SACRAMENTO ALVES .pdf: 15349749 bytes, checksum: f1351347dbf4cbb51a6d0a759155b473 (MD5) Previous issue date: 2016-12-20 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / This work does not have the aim of revolutionize the teaching of Portuguese language in the classes of Elementary School II, although it intends to offer a tool so that the subjects of the intervention can rethink the way of learning and socializing the linguistic-discursive constructions. For this, we work with the discursive genre charge because it is a multimodal genre that combines verbal language (the word) with nonverbal language (the image). Besides the multimodality that makes up the chargic text, our option for the textual genre charge is justified by discourses full of meanings and interspersed by humor. For a systematized work with the genre, a didactic sequence was developed and applied, whose objective was to verify the knowledge that the student already possessed, assisting in the development of fundamental skills to increase the reading competence of the multimodal text. Our work is divided in nine stages, dealing with conceptions of language and language, discursive genres, reading of images, methodological approach, workshop description and data analysis respectively. / Este Trabalho n?o tem o objetivo de revolucionar o ensino de l?ngua portuguesa nas turmas do Ensino Fundamental II, embora pretenda oferecer uma ferramenta para que os sujeitos da interven??o possam repensar a forma de aprender e socializar as constru??es lingu?stico-discursivas. Para isso trabalhamos com o g?nero discursivo charge por se tratar de um g?nero multimodal que alia a linguagem verbal (a palavra) com a linguagem n?o verbal (a imagem). Al?m da multimodalidade que comp?e o texto ch?rgico nossa op??o pelo g?nero textual charge justifica-se pelos discursos plenos de significados e entremeados pelo humor. Para um trabalho sistematizado com o g?nero foi desenvolvida e aplicada uma sequ?ncia did?tica cujo objetivo foi verificar o conhecimento que o aluno j? possu?a, auxiliando no desenvolvimento de habilidades fundamentais para amplia??o da compet?ncia leitora do texto multimodal. Nosso trabalho divide-se em nove etapas abordando concep??es de l?ngua e linguagem, g?neros discursivos, leitura de imagens, abordagem metodol?gica, descri??o das oficinas e an?lise de dados respectivamente.

A novel application of ionic liquid as a charge carrier for the analysis and detection of neutral organometallic complexes using a mass spectrometer has been presented. The mass spectrometer detects only charged compounds which raise a difficulty in analyzing a neutral molecule that lacks a basic site to associate with charge. Therefore, an effective way of providing charge has always been an area of keen interest in the field of mass spectrometry. Ionic liquids have a very fascinating property of forming a cation-? interaction with other molecules to give a charged complex. In order to take advantage of this, it is important to know the geometric structure of the complex. Advanced methodologies like hydrogen-deuterium exchange and computational calculations have been used assisting in better understanding of the structure of the ionic liquid complexes.

This study explores an innovative approach to control the droplet size distribution produced by an electrospray with the intention of eventually being able to deliver precisely controlled quantities of precursor materials for nanofabrication. The technique uses a thermionic cathode to charge the droplets in excess of the Rayleigh limit, leading to droplet breakup or fission. The objective of these experiments was to assess whether the proposed technique could be used to produce a new droplet size distribution with a smaller mean droplet diameter without excessively broadening the distribution. An electrospray was produced in a vacuum chamber using a dilute mixture of ionic liquid. During their transit from the capillary source to a diagnostic instrument, the resulting droplets were exposed to an electron stream with controlled flux and kinetic energy. The droplets were sampled in an inductive charge detector to characterize changes in the size distribution. A positively biased anode electrode was used to collect electron current during droplet exposure. This collected current was used as the primary control variable and used as a measure of the electron flux. The anode bias voltage was a secondary control variable and used as a measure of the electron energy. In a series of seven tests, two sets showed evidence of fission having occurred resulting in the formation of two droplet populations after electron bombardment. Three sets of results showed evidence of a single droplet population after electron bombardment, but shifted to a smaller mean diameter, and one set of results was inconclusive. Because of the large standard deviation in the droplet diameter distributions, the two cases in which a second population was evident were the strongest indication that droplet fission had occurred.

Thesis. 1978. M.S.--Massachusetts Institute of Technology. Dept. of Mechanical Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Anthony H. Wexler. / M.S.

Choy, Chun Wing = 皺摺界面和柱形微粒群的靜電共振 / 蔡振榮. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references (leaves 53-56). / Text in English; abstracts in English and Chinese. / Choy, Chun Wing = Zhou zhe jie mian he zhu xing wei li qun de jing dian gong zhen / Cai Zhenrong. / Chapter 1 --- Introduction --- p.1 / Chapter 1.1 --- Electric field near corrugated interfaces --- p.1 / Chapter 1.2 --- Electrostatic resonances of cylindrical clusters --- p.2 / Chapter 1.3 --- Objective of the thesis --- p.4 / Chapter 2 --- Review on Green Function Formalism --- p.5 / Chapter 2.1 --- Integral equation formalism --- p.5 / Chapter 2.2 --- Periodic corrugated interfaces --- p.8 / Chapter 2.3 --- Solution by mode expansion --- p.11 / Chapter 2.4 --- Numerical Results --- p.12 / Chapter 3 --- Electric Field at the Interface --- p.15 / Chapter 3.1 --- Formalism --- p.15 / Chapter 3.2 --- Numerical Results --- p.18 / Chapter 3.3 --- Effective medium approximation --- p.22 / Chapter 3.4 --- Discussion --- p.24 / Chapter 4 --- Application of GFF in cylindrical clusters --- p.26 / Chapter 4.1 --- Review of Bergman's spectral representation --- p.26 / Chapter 4.2 --- Extension of Bergman's spectral representation using Green Function Formalism --- p.29 / Chapter 4.3 --- Finding pole spectrum using Green Function Formalism --- p.31 / Chapter 4.4 --- Numerical Results --- p.34 / Chapter 4.4.1 --- Two approaching cylinders --- p.34 / Chapter 4.4.2 --- Three cylinders arranging in a horizontal array --- p.40 / Chapter 4.4.3 --- Three cylinders arranging in an equilateral triangle --- p.42 / Chapter 4.4.4 --- Three cylinders arranging in an isosceles triangle --- p.46 / Chapter 5 --- Summary --- p.51 / Bibliography --- p.53 / Chapter A --- Multiple image method to a pair of cylinders --- p.57 / Chapter A.1 --- Dipole factor of a pair of cylinders --- p.57 / Chapter A.2 --- Spectral representation --- p.58 / Chapter B --- Illustration of Bergman-Milton Spectral Representation --- p.60 / Chapter B.1 --- Series combination --- p.61 / Chapter B.2 --- Parallel combination --- p.62

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