Ce travail apporte une meilleure compréhension des propriétés diélectriques des gels isolants dans le contexte particulier de son utilisation en électronique de puissance. Différentes techniques de mesures qui, pour la plupart ont été développées dans la caractérisation des liquides isolants (visualisation de streamers, détection optique des décharges, mesure de la charge apparente) ont été utilisées. Une méthode optique permettant des mesures de décharges partielles sous tension nonsinusoïdale (ondes à front raide) a été développée. Des décharges dans des cavités et les décharges attribuées à l'effet couronne ont été identifiées. Un régime de décharges réversibles et un régime de dégradation où les propriétés d'auto-cicatrisation du matériau sont réduites ont été mis en évidence. La fréquence des décharges augmente considérablement avec la température. Elles pourraient contribuer à l'accélération du vieillissement des assemblages à long terme. Les décharges partielles apparaissent plus facilement sous tension impulsionnelle qu'en alternatif. La visualisation des phénomènes générés sous champ élevé (génération et propagation de “streamers”) permet de mieux caractériser les mécanismes mis en jeu. Les mesures conventionnelles de décharges partielles en alternatif selon la norme CEI ne sont pas pertinentes dans le cas de la caractérisation du gel sous contraintes impulsionnelle. Une étude du claquage du gel silicone dans diverses configurations d'électrodes (tailles, formes) en fonction de la température et de la forme de l'onde de tension montre qu'il dépend de la surface des électrodes. Le gel se rapproche beaucoup plus d'un liquide non polaire que d'un solide.

Purpose: Contact lens (CL) materials, modalities of wear and replacement, and care systems have changed considerably since the early studies of CL compliance were first conducted. Silicone hydrogel (SiHy) and daily disposable (DD) lenses are now the most popular lenses worn worldwide and the care systems that are currently available for them have been designed to be straightforward to use. The purpose of this research was to investigate patient knowledge of and compliance with the use of these contemporary CLs and care products, to determine whether non-compliant CL wearers experience ocular complications relating to lens wear more frequently and are more likely to discontinue lens wear, and to try to determine the factors that may constrain or enable patients to follow recommendations for appropriate lens wear and care. Methods: There are many ways in which compliance can be assessed in health care. Several different methodologies were employed during this research: A questionnaire was administered to just over 100 current lens wearers to determine whether photographic aids would help them to recognize which products they were using. More than 500 contact lens (CL) wearers were recruited by their eye care practitioners (ECPs) and mailed a questionnaire designed to evaluate their compliance with contact lens wear and care and to determine whether they had experienced any contact lens related complications which may have occurred as a result of non-compliance. Close to 5000 Current and lapsed CL wearers in Canada were recruited using Facebook to take part in an on line survey investigating CL wearing experiences during 2008 – 2010 and to establish the percentage of participants who temporarily and permanently discontinued CL wear during the period surveyed, the reasons for discontinuation and whether compliance with lens wear and care may have played a role. ECPs and patients independently completed more than 2000 linked questionnaires evaluating their contact lens wear and care. In addition the frequency with which patients attended their ECP’s office for eye examinations was assessed to determine whether there was a relationship between this and their patients’ compliance. More than 800 daily disposable contact lens (DDCL) wearers in four countries completed an online questionnaire designed to investigate how frequently they reused their lenses, the reasons for reuse and how the lenses were stored between uses. Quantitative (online questionnaire) and qualitative (focus groups) research methods were used to explore in detail the lens wear and care habits of adapted contact lens wearers in an attempt to seek a better understanding of what enables and constrains patient compliance with appropriate lens wear and lens care. Results: The rates of non-compliance with the wear of contemporary CLs were found to be similar to those previously reported. Non-compliance with recommendations for CL replacement was shown to be associated with a higher rate of CL related problems. CL wearers continue to “drop-out” for reasons of discomfort and dryness with their lenses but the drop out rates were not found to be different between compliant and non-compliant CL wearers. Patients who were non-compliant with lens replacement were found to attend their ECP’s offices less frequently. Wearers of DDCLs were the most compliant with lens replacement; however, some did report reusing these lenses and sleeping overnight in them. Focus group participants were able to provide a greater insight into why non-compliant behaviour occurs in CL wearers with the most frequently occurring themes identified as the “consequences” that may occur if patients are non-compliant with one or more aspects of their contact lens wear and the importance of receiving “instructions” regarding the most appropriate way to wear and care for their lenses. Most of the themes that emerged from this qualitative research study were both constraints to, and enablers of, compliance. Conclusions: Compliance with contemporary CLs and care products remains poor. Non-compliant behaviour can result in serious complications and patients may not always be aware of this. Careful counseling and education on the risks associated with CL wear is required to provide patients with a better lens wearing experience and continued successful contact lens wear. ECPs and the contact lens industry can hopefully apply this greater understanding of why patients fail to wear and care for their lenses as they should and to help them develop strategies and tools to aid compliance and success in contact lens wear.

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Ein Dielektrischer Elastomer Aktuator (DEA) ist ein dehnbarer Kondensator, der aus einem Elastomerfilm besteht, der sich zwischen zwei flexiblen Elektroden befindet. Bei Anlegen einer elektrischen Spannung, ziehen sich die Elektroden aufgrund elektrostatischer Wechselwirkungen an, wodurch das Elastomer in z-Richtung zusammengepresst wird und sich dementsprechend in der x-,y-Ebene ausdehnt. Hierdurch werden Aktuationsbewegungen erreicht, welche sehr präzise über die Spannung gesteuert werden können. Zusätzlich sind DEAs kostengünstig, leicht und aktuieren geräuschlos. DEAs können beispielsweise für Produkte im medizinischen Bereich oder für optischer Komponenten genutzt werden. Ebenso kann aus diesen Bauteilen Strom erzeugt werden. Das größte Hindernis für eine weite Implementierung dieser Materialien liegt in den erforderlichen hohen Spannungen zum Erzeugen der Aktuationsbewegung, welche sich tendenziell im Kilovolt-Bereich befinden. Dies macht die Elektronik teuer und die Bauteile unsicher für Anwender. Um geringere Betriebsspannungen für die DEAs zu erreichen, sind signifikante Materialverbesserungen - insbesondere des verwendeten Elastomers - erforderlich. Um dies zu erreichen, können die dielektrischen Eigenschaften (Permittivität) der Elastomere gesteigert und/oder deren Steifigkeit (Young-Modul) gesenkt werden. In der vorliegenden Arbeit konnte die Aktuationsleistung von Silikonfilmen durch die Addition organischer Dipole erheblich verbessert werden. Hierfür wurde ein Verfahren etabliert, um funktionalisierte Dipole kovalent an das Polymernetzwerk zu binden. Dieser als "One-Step-Verfahren" bezeichnete Ansatz ist einfach durchzuführen und es werden homogene Filme erhalten. Die Dipoladdition wurde anhand verschiedener Silikone erprobt, die sich hinsichtlich ihrer mechanischen Eigenschaften unterschieden. Bei maximalem Dipolgehalt verdoppelte sich die Permittivität aller untersuchten Silikone und die Filme wurden deutlich weicher. Hierbei war festzustellen, dass die Netzwerkstruktur der verwendeten Silikone einen erheblichen Einfluss auf die erreichte Aktuationsdehnung hat. Abhängig vom Netzwerk erfolgte eine enorme Steigerung der Aktuationsleistung im Bereich von 100 % bis zu 4000 %. Dadurch können die Betriebsspannungen in DEAs deutlich abgesenkt werden, so dass sie tendenziell bei Spannungen unterhalb von einem Kilovolt betrieben werden können. / Dielectric elastomer actuators (DEAs) are compliant capacitors consisting of an elastomer film between two flexible electrodes. When a voltage is applied the electrostatic attraction of the electrodes leads to a contraction of the polymer in the z-direction and to a corresponding expansion in the x,y-plane. DEAs show high actuation strains, which are very accurate and adjustable by the applied voltage. In addition these devices are low-cost, low-weight and the actuation is noise-free. DEAs can be used for medical applications, optical components or for energy harvesting. The main obstacle for a broad implementation of this technology is the high driving voltage, which tends to be several thousand volts. For this reason the devices are unsafe for users and the needed electronic components are expensive. A significant improvement of the materials - especially of the used elastomer - is necessary to lower the actuation voltages. This can be achieved by improving the dielectric properties (permittivity) of the elastomer and/or by lowering it's stiffness (Young's modulus). In this work the actuation performance of silicone lms was improved significantly by the addition of organic dipoles. A simple procedure was developed, in which functionalized dipoles were bound to the polymer matrix, leading to homogenous and transparent films. This so-called "one-step-film-formation" was tested on various silicones with different mechanical properties. For the highest dipole content the permittivity of all tested silicones was doubled and the modified films showed a substantially lower stiffness. It was proven that the structure of the macromolecular network has a clear impact on the achievable actuation properties. For the highest dipole contents the actuation performance increased remarkably by 100 % up to 4000 % in respect to the investigated network. The addition of organic dipoles to the elastomer enables a signicant reduction of the needed driving voltage for DEAs below one kilovolt.

Purpose: Contact lens (CL) materials, modalities of wear and replacement, and care systems have changed considerably since the early studies of CL compliance were first conducted. Silicone hydrogel (SiHy) and daily disposable (DD) lenses are now the most popular lenses worn worldwide and the care systems that are currently available for them have been designed to be straightforward to use. The purpose of this research was to investigate patient knowledge of and compliance with the use of these contemporary CLs and care products, to determine whether non-compliant CL wearers experience ocular complications relating to lens wear more frequently and are more likely to discontinue lens wear, and to try to determine the factors that may constrain or enable patients to follow recommendations for appropriate lens wear and care. Methods: There are many ways in which compliance can be assessed in health care. Several different methodologies were employed during this research: A questionnaire was administered to just over 100 current lens wearers to determine whether photographic aids would help them to recognize which products they were using. More than 500 contact lens (CL) wearers were recruited by their eye care practitioners (ECPs) and mailed a questionnaire designed to evaluate their compliance with contact lens wear and care and to determine whether they had experienced any contact lens related complications which may have occurred as a result of non-compliance. Close to 5000 Current and lapsed CL wearers in Canada were recruited using Facebook to take part in an on line survey investigating CL wearing experiences during 2008 – 2010 and to establish the percentage of participants who temporarily and permanently discontinued CL wear during the period surveyed, the reasons for discontinuation and whether compliance with lens wear and care may have played a role. ECPs and patients independently completed more than 2000 linked questionnaires evaluating their contact lens wear and care. In addition the frequency with which patients attended their ECP’s office for eye examinations was assessed to determine whether there was a relationship between this and their patients’ compliance. More than 800 daily disposable contact lens (DDCL) wearers in four countries completed an online questionnaire designed to investigate how frequently they reused their lenses, the reasons for reuse and how the lenses were stored between uses. Quantitative (online questionnaire) and qualitative (focus groups) research methods were used to explore in detail the lens wear and care habits of adapted contact lens wearers in an attempt to seek a better understanding of what enables and constrains patient compliance with appropriate lens wear and lens care. Results: The rates of non-compliance with the wear of contemporary CLs were found to be similar to those previously reported. Non-compliance with recommendations for CL replacement was shown to be associated with a higher rate of CL related problems. CL wearers continue to “drop-out” for reasons of discomfort and dryness with their lenses but the drop out rates were not found to be different between compliant and non-compliant CL wearers. Patients who were non-compliant with lens replacement were found to attend their ECP’s offices less frequently. Wearers of DDCLs were the most compliant with lens replacement; however, some did report reusing these lenses and sleeping overnight in them. Focus group participants were able to provide a greater insight into why non-compliant behaviour occurs in CL wearers with the most frequently occurring themes identified as the “consequences” that may occur if patients are non-compliant with one or more aspects of their contact lens wear and the importance of receiving “instructions” regarding the most appropriate way to wear and care for their lenses. Most of the themes that emerged from this qualitative research study were both constraints to, and enablers of, compliance. Conclusions: Compliance with contemporary CLs and care products remains poor. Non-compliant behaviour can result in serious complications and patients may not always be aware of this. Careful counseling and education on the risks associated with CL wear is required to provide patients with a better lens wearing experience and continued successful contact lens wear. ECPs and the contact lens industry can hopefully apply this greater understanding of why patients fail to wear and care for their lenses as they should and to help them develop strategies and tools to aid compliance and success in contact lens wear.

Choosing the right solvent is critical for many industrial applications. A useful property for selection of solvents is their solubility parameters. This concept of solubility parameters is central to this thesis and has been used in two different case studies of material treatment applications. Silicone rubber (crosslinked poly(dimethyl siloxane), PDMS) has many favorable material properties making it useful in biomedical devices. However, a limiting aspect of its material properties is a hydrophobic surface. The aim of this work was to prepare a hydrophilic PDMS material while retaining the transparency of the material. To do this, PDMS was combined with a hydrophilic polymer, polyvinylpyrrolidone (PVP) in an interpenetrating polymer network (IPN). A two-step IPN synthesis method was developed and it was found that the solvent used for polymerization of PVP had a significant influence on the water-wettability and the transparency of the PVP/PDMS IPN. Several different analytical techniques were used for determining the degree of phase separation in the PVP/PDMS IPN. It was found, by using microscopy techniques, that the PVP phase domains varied between 200 nm up to a few micrometers, and the size of the phase domains was correlated to the solvent used for polymerization of the IPN. The second topic for which solvent effects were explored was for the use of mesoporous silica particles as potential drug delivery devices. In the present work a drug molecule, ibuprofen, was loaded into mesoporous silica particles using different solvents, and in addition adsorption isotherms were established in each solvent. The maximum loading of ibuprofen in the mesoporous material was achieved when using a nonpolar solvent, in particular liquid carbon dioxide was successfully used. One of the advantages of using liquid carbon dioxide is that no solvent residues are left in the final material, which is important for pharmaceutical applications. Furthermore, it was concluded that ibuprofen was stored in an X-ray amorphous form in the mesoporous particles. Release studies in water showed a rapid release of ibuprofen from the mesoporous silica particles, while the dissolution of samples with crystalline ibuprofen was slower. This was verified to be an effect of a larger exposed ibuprofen area in the ibuprofen-loaded mesoporous silica particles, and it was concluded that the intrinsic dissolution rate for the samples were identical.

Thesis (Ph.D. in Pharmaceutical Sciences) -- University of Colorado Denver, 2007. / Typescript. Includes bibliographical references (leaves 133-143). Online version available via ProQuest Digital Dissertations.

O núcleo metálico fundido (NMF), dentre outras funções, visa suportar a restauração que o sobrepõe. Muitas são as técnicas que podem ser utilizadas para a obtenção deste núcleo; o importante, porém, para manutenção da integridade dental, é a sua perfeita adaptação intra-radicular. Este trabalho apresenta um método para moldagem de condutos radiculares utilizando, como suporte intra-radicular, agulha hipodérmica. Foram realizados tratamentos endodônticos em 10 dentes humanos uniradiculares e, após o preparo, o conduto foi moldado (dupla impressão) com siliconas polimerizadas por condensação e adição, pela técnica indireta, utilizando dois tipos de suporte intra-radicular (pinjet e agulha hipodérmica). Foram obtidos 4 moldes de cada dente (interagindo material x técnica) totalizando 40 modelos, sobre os quais foram encerados os núcleos. Após a fundição, a adaptação dos núcleos foi analisada segundo dois métodos: radiográfico e microscópico. No primeiro, os dentes foram radiografados com os NMFs em posição e as imagens digitalizadas foram analisadas em computador (software ImageLab). Para avaliação microscópica, os dentes foram seccionados longitudinalmente, os núcleos foram adaptados no interior do canal e a adaptação foi verificada em microscópio de dupla coordenada, em que era calculada a porcentagem do conduto ocupada pelo NMF. Constatou-se que houve diferença estatisticamente significante (2 way ANOVA - Bonferroni - p<0.05) entre as médias dos valores de adaptação obtidos em função da técnica (agulha x pinjet) utilizando a silicona polimerizada por adição, nos dois métodos de avaliação. Não houve diferença estatisticamente significante em relação aos materiais de moldagem utilizados. Concluiu-se que a técnica utilizando agulha hipodérmica apresentou melhor fidelidade de reprodução permitindo melhor adaptação do NMF, quando utilizada a silicona polimerizada por adição. / Post and core aim to support the crown, being necessary a perfect intraradicular adaptation. There are several techniques that can be used to obtain cores, however, in order to maintain dental integrity, it is important to achieve a perfect intra-radicular adaptation. This study presents an inedited and innovator method for molding root canals using hypodermic needle as intra-radicular support. Endodontic treatment was done in 10 uniradicular human teeth and, after the preparation, root canals were molded (double print) with condensation cure silicone and addition cure silicone by indirect technique, using two types of intra-radicular supports (Pinjet and hypodermic needle). Four molds were obtained from each tooth (interacting material X technique) totalizing 40 models, on which the cores were polished. After fusion, the adaptation of cores was analyzed according to two methods: radiographic and microscopic. In the first, teeth were radiographed with the core in position and the digitalized images were analyzed through ImageLab software. For microscopic evaluation, teeth were longitudinally sectioned, the cores were adapted into root canals, and the adaptation was verified in microscope of double coordinate. The occupation percentage of core into root canal was calculated. A significant statistical difference (two-way ANOVA and Bonferroni\'s - p<0.05) was found between mean values of adaptation considering the molding technique (needle x pinjet) using the addition silicon in the two evaluated methods. There was no significant statistical difference regarding the utilized materials. It was concluded that the hypodermic needle technique had better fidelity of reproduction, permitting a good adaptation of cores, regardless of the material utilized.

Dans cette thèse à l’interface entre élasticité et capillarité, nous présentons tout d’abord une instabilité élastique, le claquage, revisitée dans un contexte élastocapillaire. En déposant une goutte d’eau sous une lamelle flambée en position basse, nous parvenons à déclencher une instabilité de claquage à contresens de la gravité. Cette démonstration de la prédominance des effets capillaires à petite échelle s’accompagne d’une étude des positions d’équilibre et de la stabilité de systèmes goutte-lamelle. Nous démontrons l’influence importante de la taille et de la position de la goutte le long de la lamelle, puis étendons notre étude au cas de bulles ou de gouttes condensées à partir de vapeur d’eau. Enfin, nous nous intéressons à l’aspect dynamique de l’instabilité, qui est dictée principalement par l’élasticité, y compris dans le cas élastocapillaire.Nous mettons ensuite en évidence un phénomène surprenant : la dynamique de descente d’une goutte d’eau sur un élastomère silicone présente deux régimes successifs, caractérisés par deux vitesses différentes. Nous montrons que les chaînes libres non réticulées présentes dans l’élastomère sont à l’origine de cette dynamique inattendue. La goutte est progressivement recouverte par des chaînes de silicone, et sa vitesse change brutalement lorsqu’une concentration surfacique critique est atteinte, ce qui se traduit par une transition brutale de tension de surface. Nous nous intéressons aux vitesses de gouttes dans les deux régimes ainsi qu’aux échelles de temps mises en jeu lors de l’extraction de chaînes non réticulées, et montrons que l’extraction de ces chaînes se produit au niveau de la ligne triple. / This thesis focuses on interactions between liquids and elastic solids. We first revisit the snap-through instability from an elastocapillary point of view, showing that capillary forces are able to counterbalance gravity by inducing snap-through with a droplet deposited below a downward buckled elastic strip clamped at both ends. Equilibrium, stability, and dynamics of drop-strip systems are investigated, demonstrating the influence of droplet size and droplet position along the buckled strip, and showing that capillarity is driving the system toward instability but elasticity is ruling the subsequent dynamics. Spin-off versions of the experiment are also designed, including a humidity-controlled mechanical switch and upscaled experiments using soap bubbles.We then focus on interactions between silicone elastomers and aqueous droplets to understand the mechanisms underlying an unexpected two-regime droplet dynamics observed on vertical silicone elastomer plates. After demonstrating that this two-regime dynamics is due to the presence of uncrosslinked oligomers in the elastomer, we show that the speed transition coincides with a surface tension transition. A quantitative study of the droplets speeds in the two regimes is performed, and the timescale needed for uncrosslinked oligomers to cover the water-air interface is investigated both for sessile and moving droplets. We eventually show that uncrosslinked chains are extracted from the elastomer at the water - air - silicone elastomer triple line, and demonstrate that extraction occurs in various setups such as partially immersed silicone elastomer plates or air bubbles sliding up PDMS planes immersed in a water bath.