Thesis (Ph. D.)--School of Dentistry and Dept. of Chemistry. University of Missouri--Kansas City, 2004. / "A dissertation in oral biology and chemistry." Advisor: J. David Eick. Typescript. Vita. Description based on contents viewed Feb. 23, 2006; title from "catalog record" of the print edition. Includes bibliographical references (leaves 137-145). Online version of the print edition.

Thesis (Ph.D. in Biochemistry, Biomolecular Structure Program) -- University of Colorado Denver, 2007. / Typescript. Includes bibliographical references (leaves 135-146). Online version available via ProQuest Digital Dissertations.

Purpose: Different methodology of adhesion have been tested in order to promote better bonding strength between dentinal substrate and composite resin. The increase of temperature associated with the solvent evaporation, it has been one of the ways of modifying the protocol in order to obtain better adhesion. Materials and Methods: For this study, were tested two different methodologies to increase adhesive temperature. The control group 1 (n=4) were tested under environmental temperature; group 2 (n=6) consisting of heating the adhesive in an experimental apparel before the adhesive to be applied and the group 3 (n=6) consisting in increasing of the temperature of the adhesive by application of warm air steam over adhesive applied on dentin. It was applied the tukey test at 5% probability. Results: The results of the study showed no statistically significant difference in comparison with the groups. (G1: 48,52ª, G2: 40,35ª, G3:47,21ª) Conclusion: This study concludes that the increase of temperature did not cause significant differences on bond strength. / Introdução: Na odontologia adesiva, diferentes metodologias tem sido testadas afim de promover melhor resistência de união entre os substratos dentina/resina. O aumento de temperatura, associado à evaporação de solventes, tem sido uma das maneiras de se modificar protocolo a fim de obter adesão mais satisfatória. Materiais e métodos: Para este trabalho, foram testadas duas metodologias diferentes de aquecimento do adesivo. Além do grupo controle (n=4), foram testados grupo temperatura (n=6) que consistiu no aumento da temperatura do adesivo antes de ser aplicado na dentina e o grupo ar quente (n=6) que consistiu no aquecimento do adesivo após a aplicação na dentina. Para avaliarmos a resistência de união, o ensaio de microtração foi escolhido. Após a realização do ensaio, foi aplicado o teste de tukey ao nível de 5% de probabilidade. Resultados: Os resultados do trabalho não demonstraram diferença estatisticamente significativa na comparação com os grupos (G1: 48,52ª, G2: 40,35ª, G3:47,21ª). Conclusão: Este trabalho conclui que o aumento de temperatura não promove ganhos significativos em qualidade adesiva.

Made available in DSpace on 2014-06-11T19:28:57Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-10Bitstream added on 2014-06-13T20:18:37Z : No. of bitstreams: 1 anchieta_rb_me_araca.pdf: 7195179 bytes, checksum: 1c86045d84983285e3b0998f11288632 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Introdução: Embora os sistemas adesivos autocondicionantes se caracterizem por desmineralizar e infiltrar a dentina simultaneamente, a presença de dentina alterada abaixo da camada híbrida tem sido reportada, sugerindo comportamento mecânico distinto. Proposição: Avaliar por meio do método dos elementos finitos tridimensional a influência da espessura da dentina parcialmente alterada no comportamento micromecânico de dois sistemas adesivos autocondicionantes. Materiais e Métodos: Foram elaborados 5 micro-modelos (M) simulando a interface dentina/adesivo (d/a) (82x41x41 μm), sendo: M1-representação da interface d/a baseada em sistema adesivo convencional de 2 passos; M2-representação de um sistema adesivo autocondicionante de 2 passos. Nos M3, M4 e M5 representação de um sistema adesivo autocondicionante de 1 passo, variando a espessura da camada de dentina parcialmente alterada em 0, 1,5 e 3 μm, respectivamente. Os modelos foram considerados isotrópicos, homogêneos e linearmente elásticos. A base de todos os modelos foi fixada nos eixos x, y e z, sendo aplicado um carregamento em tração (90º; 0,03 N) na face superior da resina composta. A análise numérica foi realizada para a obtenção da tensão principal máxima ( max). Resultados: o pico da max (MPa) foi encontrada no M5 (79,5), seguido do M4 (78,0) e do M3 (70). O topo dos tags foi o local mais solicitado em todos os modelos. Conclusão: O aumento da espessura da dentina parcialmente alterada aumentou a tensão na interface d/a; a ausência desta camada contribuiu para a menor concentração de tensão; o topo dos tags foi o local mais exigido na interface d/a. / Introduction: Although the self-etching adhesives are characterized by etching and infiltrating simultaneously the dentin, the presence of an altered dentin layer has been showed by literature, which might show specific mechanical behavior. Proposition: To evaluate through 3-D finite element analysis the influence of the partially altered dentin thickness on the micromechanical behavior of the self-etch adhesives. Materials and Methods: 5 micro-models (M) were developed for simulating the dentin/adhesive (d/a) interface (82x41x41 μm): M1-representation of the d/a interface based on 2 steps conventional adhesive system; M2-d/a interface based on 2 steps self-etch adhesive system M3, M4 and M5 – d/a interface based on all-in-one adhesive system, varying the thickness of the partially altered dentin (0, 1.5 and 3 μm, respectively). All the models were considered isotropic, homogeneous and lineally elastic. The bottom of all the models were constrained in the axes x, y and z. A tensile load (90o; 0.03N) was applied on the top of the composite resin. The numeric analysis was accomplished, being obtained the maximum principal stress ( max). Results: The pick of max (MPa) was found in M5 (79.5), followed by M4 (78.0) and M3 (70). The top of the resin tags was the most requested place in all models. Conclusion: The increase of the partially altered dentin thickness raised the max in the d/a interface; the absence of this layer contributed to the smallest tension concentration; the top of the tags showed higher stress concentration.

Les materiaux à forte mobilité comme l’InGaAs et le SiGe sont considérés comme des candidats potentiels pour remplacer le Si dans les circuits CMOS futurs. De nombreux défis doivent être surmontés pour transformer ce concept en réalité industrielle. Cette thèse couvre les principaux challenges que sont l’intégration de l’InGaAs sur Si, la formation d’oxydes de grille de qualité, la réalisation de régions source/drain auto-alignées de faible résistance, l’architecture des transistors ou encore la co-intégration de ces matériaux dans un procédé de fabrication CMOS.Les solutions envisagées sont proposées en gardant comme ligne directrice l’applicabilité des méthodes pour une production de grande envergure.Le chapitre 2 aborde l’intégration d’InGaAs sur Si par deux méthodes différentes. Le chapitre3 détaille le développement de modules spécifiques à la fabrication de transistors auto-alignés sur InGaAs. Le chapitre 4 couvre la réalisation de différents types de transistors auto-alignés sur InGaAs dans le but d’améliorer leurs performances. Enfin, le chapitre 5 présente trois méthodes différentes pour réaliser des circuits hybrides CMOS à base d’InGaAs et de SiGe. / High-mobility channel materials such as indium-galium-arsenide (InGaAs) and silicon-germanium(SiGe) alloys are considered to be the leading candidates for replacing silicon (Si) in future lowpower complementary metal-oxide-semiconductor (CMOS) circuits. Numerous challenges haveto be tackled in order to turn the high-mobility CMOS concept into an industrial solution. Thisthesis addresses the majors challenges which are the integration of InGaAs on Si, the formationof high-quality gate stacks and self-aligned source and drain (S/D) regions, the optimizationof self-aligned transistors and the co-integration of InGaAs and SiGe into CMOS circuits. Allinvestigated possible solutions are proposed in the framework of very-large-scale integration requirements.Chapter 2 describes two different methods to integrate InGaAs on Si. Chapter 3 detailsthe developments of key process modules for the fabrication of self-aligned InGaAs metal-oxidesemiconductorfield-effect transistors (MOSFETs). Chapter 4 covers the realization of varioustypes of self-aligned MOSFETs towards the improvement of their performance. Finally, chapter5 demonstrates three different methods to make hybrid InGaAs/SiGe CMOS circuits.

The aim of this study was to investigate how an experienced chemistry teacher gains and refines her pedagogical content knowledge (PCK) by cooperating with two grade 12 students (age 18) as coteachers while teaching chemical bonding in a grade 10 Upper secondary class. The study has been conducted from a sociocultural perspective, especially Vygotsky’s zone of proximal development (ZPD) (Vygotsky, 1978). Other theoretical concepts and models that has framed this study are Shulman´s Pedagogical content knowledge (PCK) and Pedagogical reasoning and action model (Shulman, 1986, 1987). When analysing the data, Magnusson, Krajcik, and Borko´s (1999) model of PCK and the 2017 Refined consensus model of PCK (Carlson, Daehler, et al., in press) was used. Empirical data was collected by video- and audio recorded lessons, coreflection sessions, coplanning sessions and interviews. During 10 weeks, about 28 hours of video and audio recordings was collected. Selected parts of the material were transcribed and analysed in order to answer two questions: (1) How can chemistry teachers refine their PCK when coteaching together with senior students in an Upper secondary science class? (2) How do Upper secondary senior student coteachers´ conceptual knowledge of representations and chemical bonding shape a teacher’s foundation of personal PCK (pPCK) when teaching chemical bonding in an Upper secondary science class? The results relating to research question one indicates that the coteachers contributed with their own learning experiences to help the teacher understand how students perceive difficult concepts. The coteachers were mediating between the teacher and the students, thus bridging the gap between the teacher and the students’ frames of references. The experienced chemistry teacher improved her understanding of students´ thinking about themselves as learners of chemical bonding. Regarding the second research question, the findings showed that the creative process of reconstructing concepts of chemical bonding in the coplanning sessions meant that these were a useful tool for developing new teaching strategies and to further develop representations such as drama to illustrate chemical bonding. Together, the teacher and student coteachers, constructed a new representation that better illustrated polar covalent bonding. Taken together, these results provide important insights into how the chemistry teacher´s pPCK was refined and how the coteachers contributed to improve instructional strategies.

La microélectronique cherche à produire des composants toujours plus performants. Un axe d'amélioration est l'intégration de plus de fonctionnalités dans un volume toujours plus compact. L'approche planaire classiquement utilisée jusqu'à présent atteint ses limites. Une solution à ce défi technologique est l'intégration 3D permettant d'empiler verticalement plusieurs circuits. Les étapes d'assemblage sont cruciales dans ces schémas d'intégration. Parmi les différentes techniques d'assemblage, le collage direct de couches minces métalliques est une alternative très intéressante. En effet, elle offre simultanément un lien mécanique et électrique vertical entre les couches actives de composants.Les propriétés microstructurales, physiques et chimiques des couches minces métalliques déposées ont été largement rapportées dans l'état de l'art antérieur. Cependant, elles n'ont jamais été étudiées dans l'environnement particulier du collage. Le but de notre étude est d'évaluer l'impact de cet environnement sur les couches minces métalliques assemblées pendant et après le procédé d'assemblage.Le collage direct consiste en la mise en contact de surfaces lisses à température ambiante et sous atmosphère ambiant afin de créer une adhérence entre elles. Puisque le collage n'est pas réalisé sous vide, des espèces adsorbées sont piégées à l'interface et une couche d'oxyde natif limite l'obtention du contact métal-métal. L'environnement de collage nous pousse donc à considérer ces différentes espèces qui interfèrent avec le procédé de collage et l'établissement du contact électrique.Dans cette étude, nous avons assemblé différents métaux dans différentes configurations de couches minces. Ainsi, les couches d'oxyde surfaciques ont été désignées comme influentes sur le comportement en adhésion des assemblages. Dans le cas précis du collage direct Cu-Cu, la réaction de l'eau interfaciale est primordiale au renforcement de la tenue mécanique dès la température ambiante. À plus haute température, la dissolution de l'oxyde piégé et la croissance de grain verticale sont des moteurs du scellement dépendant de phénomènes diffusifs. Il est apparu que les joints de grains sont des chemins de diffusion privilégiés dont le rôle dans la microstructure est majeur. Il a également mis en évidence que les couches de métaux réfractaires ne pouvaient pas être assemblées en utilisant les mêmes forces motrices que les métaux de transition dans la gamme de température considérée. La compréhension des différents mécanismes apporte un éclairage nouveau dans l'utilisation du collage direct dans les schémas d'intégration des composants de demain. / The semiconductor industry is driven by an increasing need of computation speed and functionalities. In the development of next generation devices the integration of more functionalities in an ever smaller volume becomes paramount. So far, classical planar integration was privileged but it is currently reaching its limits. One solution to this technological challenge is to consider the 3D dimension as pathway of integration. To ensure the vertical stacking of circuits, the development and control of assembly processes becomes crucial. Among the different techniques under development, direct bonding of metal thin films is a promising solution. It is a straightforward option that offers both a mechanical and an electrical link between the active strata.Microstructural, physical and chemical properties of deposited metal thin films were widely reported in previous state of art. However, they have not yet been studied in the specific bonding environment. The main goal of our study is to pinpoint the impact of this environment during and after the process of assembly.Direct bonding process consists in putting into contact smooth surfaces at room temperature and ambient air which in appropriate conditions leads to the establishment of attractive forces. Since bonding is not operated under vacuum, adsorbed species are trapped at the interface and the metal bonding suffers from the formation of native oxide. The encapsulation of these species as well as the native metal oxide interfere with the bonding process and the establishment of an electrical contact.In this study, various bonded structures have been realized using an extended set of metals in different thin film configurations. Metal oxide layers impact is clearly highlighted via the monitoring of adhesion properties of the assemblies. In the Cu-Cu direct bonding case, the interfacial water reaction is primordial in the strengthening of bonding toughness at room temperature. At higher temperature, oxide dissolution and vertical grain growth are driving forces in the sealing of bonding interface. The microstructure play a role in all these phenomena since grain boundaries are favorite diffusion pathway in thin films. Considering the temperature limitation imposed by the integration, we also highlight that refractory metal thin films needs another bonding approach compared to the transient metals. The understanding of bonding mechanisms throws new light on the use of direct bonding process in the realization of future electrical components.

Le collage direct consiste en la mise en contact de deux surfaces suffisamment lisses et propres pour créer une adhérence entre-elles, et ce sans apport de matière à l'interface des matériaux. Ce procédé est réalisable à l'échelle industrielle et compatible avec les procédés de la microélectronique. Il trouve son principal intérêt dans la réalisation de substrats innovants. Le plus célèbre d'entre eux est le substrat SOI (pour « Silicon On Insulator »). Depuis quelques années, une nouvelle voie s'est ouverte dans le collage direct en l'élargissant au collage de couches métalliques ce qui permet de répondre à de nouvelles applications en offrant par exemple conduction électrique et dissipation thermique. Ce travail de thèse a pour objectif d'analyser le comportement du collage direct de couches métalliques et de poser les premiers éléments de modélisation. La compréhension de ces fondamentaux est indispensable pour optimiser le procédé et permettre une intégration de cette technologie dans un grand nombre de dispositifs. Dans cette étude, des procédés de collage direct de couches de tungstène et de titane ont été développés à la lumière des pré-requis établis pour le collage direct. La caractérisation physico-chimique des interfaces de collage et de leur évolution en température ont permis de mettre en évidence le rôle clé de l'oxyde métallique. Il est montré que les mécanismes de collage sont gouvernés par des phénomènes de diffusion aux joints de grains et par l'instabilité de la couche d'oxyde piégée à l'interface de collage. Par ailleurs, les propriétés mécaniques et électriques des interfaces ont été étudiées. Enfin, la compréhension du comportement des interfaces en fonction de certains paramètres conduit à quelques recommandations pour réussir l'intégration du collage direct métallique. / Direct wafer bonding refers to a process by which two mirror-polished wafers are put into contact and held together at room temperature without any additional materials. This technology is feasible at an industrial scale and compatible with the microelectronic processes. Wafer bonding finds many interests applied to innovative substrates realization. Therefore the use of direct wafer bonding is growing and extending to various materials. Since few years direct bonding involving metallic layers presents many interests as it can offer, for example, vertical electrical conduction or heat dissipation. The aim of this work is to analyze the bonding behavior and to propose a first model describing the bonding driving forces. A precise understanding of these mechanisms is essential for the optimization and the technological integration of the process in various devices. In this study, tungsten and titanium bonding processes were developed. Physical and chemical bonding interfaces characterizations have highlighted the key role of the metallic oxide. We showed that bonding mechanisms are driven by grain boundary diffusion phenomena and the interface trapped oxide layer instability. Moreover, mechanical and electrical properties were also studied. Finally, the bonding behavior understanding in function of define parameters lead to some recommendations for the bonding process integration achievement.

Orientador: Marcelo Fava de Moraes / Banca: Victor Elias Arana Chavez / Banca: Matsuyoshi Mori / Banca: Silvio Issáo Myaki / Banca: Lafayette Nogueira Junior / Resumo: O objetivo deste estudo foi avaliar in vitro a resistência ao microcisalhamento de 5 sistemas adesivos ao esmalte, sendo 1 adesivo monocomponente (M), 2 primers autocondicionantes (P) e 2 adesivos autocondicionantes (A). Foram utilizadas 60 faces (vestibular ou lingual) de pré-molares, aplainadas com lixas d'água (400 e 600) e divididas aleatoriamente em 5 grupos (n=12), de acordo com o adesivo utilizado: SB2- Single Bond2 (M); CSE- Clearfil SE Bond (P); ADS- AdheSE (P); PLP- Adper Prompt L-Pop (A); XE3- Xeno III (A). Tubos de Tygon delimitaram a área de adesão em 0,8mm de diâmetro, para se obter os cilindros de resina composta (Z250). Após armazenamento em água destilada a 37ºC por 24h e termociclagem, foi realizado o teste de microcisalhamento (velocidade de 0,5mm/min).). Os dados foram submetidos aos testes de ANOVA e Tukey ('alfa'=5%). Os valores de média (MPa'mais ou menos'DP) e os resultados do teste de Tukey foram: SB2: 36,36('mais ou menos'3,34)a; ADS: 33,03('mais ou menos'7,83)a; XE3: 32,76('mais ou menos'5,61)a; CSE: 30,61('mais ou menos'6,68)a; PLP: 22,17('mais ou menos'6,05)b. Grupos com a mesma letra não apresentaram diferenças significantes. Pode-se concluir que não houve diferença estatística entre SB2, ADS, XE3 e CSE, apesar dos diferentes padrões de condicionamento destes adesivos. Apenas o PLP apresentou valores médios de adesão inferiores aos demais. / Abstract:The aim of this in vitro study was to evaluate the micro-shear bond strength of 5 adhesive systems to enamel, one single-bottle acid-etch adhesive (O), two selfetching primers (P) and two all-in-one self-etching adhesives (S). Sixty premolar enamel surfaces (buccal or lingual) were ground flat with 400- and 600-grit SiC papers and randomly divided into 5 groups (n=12), according to adhesive system: SB2 - Single Bond 2 (O); CSE - Clearfil SE Bond (P); ADS - AdheSE (P); PLP - Adper Prompt L-Pop (S); XE3 - Xeno III (S). Tygon tubing (internal diameter of 0,8mm) restricted the bonding area to obtain the resin composite (Z250) cylinders. After storage in distilled water at 37oC for 24h and thermocycling, micro-shear testing was performed (crosshead speed of 0.5mm/min). Data were submitted to one-way ANOVA and Tukey test ('alfa'=5%). Mean bond strength values (MPa'mais ou menos'SD) and the results of Tukey test were: SB2: 36.36('mais ou menos'3.34)a; ADS: 33.03('mais ou menos'7.83)a; XE3: 32.76('mais ou menos'5.61)a; CSE: 30.61('mais ou menos'6.68)a; PLP: 22.17('mais ou menos'6.05)b. Groups with the same letter were not statistically different. It can be concluded that no significant difference was there between SB2, ADS, XE3 and CSE, in spite of different etching patterns of these adhesives. Only PLP presented statistically lower bond strengths compared with others. / Doutor

The conformational energy differences have been determined for ethylene glycol, 2- chloroethanol, and 2,2- dichloroethanol in the neat liquid, DMSO, and H20 with Raman spectroscopy. Spectra in the 0-H valence region were utilized to determine the energy difference between interand intramolecularly hydrogen bonded species. It was found that the solvent effect on the relative stabilities of the gauche and trans rotamers of the alcohols differ significantly. The results also indicate that, unlike ethylene glycol, there is significant intramolecular hydrogen bond formation in the halogenated alcohols in the neat liquid phase. Stronger intramolecular hydrogen bond formation was observed in dichloroethanol than in 2-chloroethanol.