A aplicação de uma ou mais camadas de tinta sobre as superfícies metálicas é a maneira mais comum e eficaz de proteger os substratos metálicos contra o fenômeno da corrosão. No entanto, os sistemas de pintura podem vir a falhar precocemente por diferentes motivos, causando um ataque corrosivo inesperado no metal a ser protegido. Por esta razão, o processo de repintura em estruturas metálicas é realizado frequentemente para garantir a integridade da estrutura pintada e aumentar sua vida útil. Como o processo de repintura gera impactos econômicos e ambientais, sistemas de pintura capazes de sofrerem uma reparação sem a necessidade de uma intervenção humana, precisam ser desenvolvidos. O encapsulamento de agentes de reparação, com propriedades de formação de filme, em microcápsulas poliméricas é uma excelente alternativa para que os sistemas de pintura se autorreparem, aumentando os intervalos de repintura. Após o processo de encapsulamento, as microcápsulas contendo o agente de reparação são incorporadas na preparação da tinta, para que o sistema de pintura seja aplicado sobre a estrutura metálica. Este tipo de aditivação confere ao revestimento a propriedade de autorreparação, pois quando o sistema de pintura é danificado as microcápsulas são rompidas e liberam o agente de reparação no local danificado, protegendo novamente o substrato metálico. Neste trabalho foi desenvolvido um sistema autorreparador monocomponente, através do microencapsulamento de uma resina a base de éster de epóxi, pelo método de polimerização in-situ. Também foi desenvolvido um sistema autorreparador bicomponente, através do microencapsulamento de uma resina a base de epóxi, pelo método de emulsão e polimerização in-situ de ureia-formaldeído-melamina e do seu endurecedor a base de poliamida, pelo método de extração de solvente em paredes de poliestireno. Foi realizado um planejamento estatístico para estudar a emulsão precursora das microcápsulas de poli(ureia-formaldeído-melamina) contendo o sistema monocomponente, onde foram estudados: o tipo e a velocidade de agitação, a presença de cloreto de sódio na formulação, o uso de uma sonda ultrassônica após a etapa de dispersão, a concentração de tensoativo na formulação e o tensoativo utilizado. Como variáveis de resposta foram determinadas: a estabilidade visual das emulsões e o diâmetro das gotículas formadas. A melhor condição de emulsificação determinada foi utilizada para a obtenção das microcápsulas de poli(ureia-formaldeídomelamina) contendo a resina éster de epóxi e das microcápsulas de poli(ureiaformaldeído-melamina) contento a resina epóxi. Entre as condições de emulsificação estudadas, apenas a condição utilizando o tensoativo goma arábica possibilitou a obtenção das microcápsulas de poli(ureia-formaldeído-melamina) na faixa de diâmetro desejada. O método escolhido para o encapsulamento do endurecedor possibilitou a obtenção de microcápsulas de poliestireno, porém com uma baixa capacidade de armazenamento. A liberação dos agentes de reparação encapsulados foi observada pela microscopia óptica e comprovada pela técnica de espectroscopia na região do infravermelho (FTIR) e pela técnica de espectroscopia Raman. Os aditivos autorreparadores desenvolvidos (mono e bicomponente) foram adicionados separadamente em uma tinta epóxi, nas proporções mássicas em base seca de 10 e 15 %. O sistema de pintura foi aplicado em um esquema de três camadas e o aditivo de autorreparação foi incorporado na primeira e/ou segunda camada aplicada. O sistema de pintura contendo o aditivo autorreparador monocomponente apresentou um aspecto visual melhor do que o sistema de pintura contendo o aditivo autorreparador bicomponente, porém o sistema bicomponente forneceu melhores propriedades de aderência, de impermeabilidade, anticorrosivas e de autorreparação à tinta aditivada. As medidas com as técnicas eletroquímicas de espectroscopia de impedância eletroquímica (EIE) e de varredura com eletrodo vibratório (SVET) comprovaram que os dois aditivos desenvolvidos proporcionaram o efeito autorreparador aos sistemas de pintura aditivados, quando estes foram danificados mecanicamente com uma microbroca ou com um estilete. Ensaios acelerados de corrosão em câmara de névoa salina e ensaios de exposição ao intemperismo natural mostraram que os aditivos desenvolvidos promoveram uma proteção adicional ao aço carbono, quando o sistema de pintura foi danificado mecanicamente. / The application of one or more coating layers on the metallic surfaces is the most common and effective way to protect metallic substrates against corrosion. Nevertheless, the coating layer may fail early for different reasons, leading to an unexpected corrosive attack on the protected metal. For this reason, the coating repair process is performed to ensure the integrity during the service life of the coated metallic structures. Due to the fact that coating repair process generates economic and environmental impacts; there is a great need for the development of systems capable to repair themselves, without human intervention. The encapsulation of repairing agents, with film forming properties, in polymeric microcapsules is an excellent alternative to the coating self-repair, decreasing the coating repair process frequency. After the encapsulation process, the microcapsules containing the repair agent are incorporated into the paint preparation and the coating system could be applied normally to the metallic surface. This kind of additivation confers to the coating the self-healing property, because when the coating system is damaged the microcapsules suffers a rupture and release the repair agent into the damaged site, protecting the metallic substrate from corrosion. In this work, a mono-component self-healing system was developed, through the microencapsulation of an epoxy ester resin, by the in-situ polymerization method. A bi-component self-healing system was also developed, by the microencapsulation of an epoxy resin, through the emulsion and in-situ polymerization method and by the microencapsulation of a polyamide hardener, by the double emulsion and solvent extraction method. A factorial design was developed to study the precursor emulsion of the poly (urea-formaldehyde-melamine) microcapsules containing the monocomponent system, where the studied factors were: the type and speed of the agitation, the presence of sodium chloride in the formulation, the use of an ultrasonic probe after the emulsification, the surfactant type and concentration. The analyzed response variables were: the visual stability of the emulsions and the mean diameter of the formed droplets. The best obtained emulsification conditions were employed to produce the poly(urea-formaldehyde-melamine) microcapsules containing the epoxy ester resin and poly(urea-formaldehyde-melamine) microcapsules containing the epoxy resin. Among the studied emulsification conditions, only using arabic gum surfactant the poly (urea-formaldehyde-melamine) microcapsules were obtained. The selected method for the hardener encapsulation was efficient to obtain polystyrene microcapsules, but with low loading capacity. The release of the encapsulated repair agents was observed by optical microscopy and confirmed by infrared spectroscopy (FTIR) technique and Raman spectroscopy technique. The developed self-healing additives (mono and bicomponent) were added separately in an epoxy commercial coating, using the dry mass ratios 10% and 15 %. The coating system was applied in a three layer coating system and the self-healing additive was incorporated into the first and/or second layer. The coated samples containing the mono-component additive had a better visual appearance than the bi-component additive system; nevertheless the bi-component system provided better adhesion, impermeability, anti-corrosion and self-healing properties to the doped coating. The electrochemical impedance spectroscopy (EIS) and scanning vibrating electrode technique (SVET) measurements proved that the two developed additives provided self-healing properties to the doped coating systems, when they were mechanically damaged with a micro drill or a blade. Accelerated corrosion tests in the salt spray chamber and natural atmospheric corrosion tests showed that the developed additives provided an additional protection to the carbon steel, when the coating system has been mechanically damaged.

Neste trabalho foi realizado o estudo térmico, cinético e dielétrico durante a cura de um compósito constituído de uma matriz de resina epóxi-anidrido e de talco como carga modificadora das características dielétricas e mecânicas da matriz polimérica. Foram analisadas também as propriedades dinâmicas mecânicas e morfológicas dos compósitos completamente curados. O interesse na investigação das características térmicas, cinéticas e dielétricas visou encontrar correlação entre essas características e as propriedades dinâmicas mecânicas finais dos compósitos. Foram estudados os compósitos com diferentes concentrações de carga, variando de 0 a 10% m/m, utilizando as técnicas de calorimetria exploratória diferencial (DSC), de análise dielétrica (DEA), análise termomecânica dinâmica (DMTA) e análise por microscopia eletrônica de varredura (MEV). Os resultados da análise DSC foram analisados por método isotérmico (modelo de Sourour-Kamal modificado) e por método dinâmico (modelo isoconversional). Os resultados da análise da cura dos compósitos mostraram que a concentração da carga retarda o processo de cura, conforme observado pela análise dielétrica; a temperatura de transição vítrea do compósito curado apresentou valores mínimos nas concentrações de 7 e 10%, enquanto que a análise térmica dinâmica previu que a energia de ativação aumenta com o grau de conversão. Os resultados da análise termomecânica dinâmica mostraram o aumento no módulo de armazenamento a 25ºC de 2,1 GPa (0% talco) a 3,3 GPa (10% talco), indicando haver o efeito reforçador do talco sobre a matriz polimérica. As micrografias dos compósitos foram um excelente recurso para estudar suas morfologias e se correlacionam com os resultados cinéticos e mecânicos. / In this work we performed the thermal, kinetics, dielectrical and morphological studies on the curing of a hybrid composite material composed of epoxy-anhydride matrix and talc as modifier agent of the dielectrical and mechanical properties of the polymer matrix. It also was studied the dynamic mechanical properties of the full-cured composite materials. This investigation aimed to correlate the thermal, kinetics, and dielectrical characteristics of the curing material with their final mechanical properties. Composite materials with different talc concentrations were studied in the range from 0% up to 10% w/w, employing the Differential Scanning Calorimetry (DSC), the Dielectric Analysis (DEA), Dynamic Mechanical Thermal Analysis (DMTA) and Microscopy Electron Scanning (SEM) techniques. The DSC experimental results were analyzed through the isothermal method (Modified Sourour-Kamal model) and the dynamic method (Isoconversional model). The cure analysis results of the composite specimens showed the talc acting as a cure retardant as observed from DEA results; the glass transition temperature of the full-cured composite materials showed minimum values at talc concentrations of 7 and 10%, while the dynamic thermal analysis predicted the activation energy is increasing with the conversion degree. The DMTA results exhibited the storage modulus at 25ºC increases from 2.1 GPa for the matrix without talc up to 3.3 GPa at 10% talc concentration composite, thus indicating the reinforcement role of the talc on the polymer matrix. The composites micrographs were an excellent resource for study their morphologies and for correlation of kinetics and mechanical results.

Compósitos desenvolvidos a partir da incorporação de rejeitos industriais além de serem mais uma opção disponível às mais diversas aplicações, podem promover a redução de passivos ambientais gerados durante anos. Visando atender à essas questões, foram desenvolvidos compósitos com matriz de resina epóxi carregados com rejeito de scheelita nas proporções de 1%, 5%, 10%, 20 % e 30%. Para tanto, o rejeito de scheelita foi, inicialmente, caracterizado por meio de FRX, DRX e MEV. Já a resina epóxi foi analisada por meio de FTIR antes e após a cura. Duas condições de cura foram adotadas para a confecção dos corpos de prova, uma realizada somente a temperatura ambiente e outra executada à temperatura ambiente com uma etapa de pós cura térmica realizada a 80°C por 5 horas. Os corpos de prova foram moldados por casting em molde de silicone e as proporções foram calculadas em volume. A massa específica dos compósitos foi determinada. Para caracterizar o desempenho mecânico das composições foram realizados ensaios de tração e ensaios de dureza os quais evidenciaram que as frações de carga mineral influenciam positivamente o módulo de elasticidade e a dureza e afetam negativamente a resistência à tração. Os parâmetros Ra, Rq e Rz foram medidos e considerados na caracterização do acabamento superficial. Ensaios de deslizamento com a configuração pino contra disco foram realizados para caracterizar o desempenho tribológico dos compósitos que geraram respostas de coeficiente de atrito e profundidade da trilha do desgaste. Os corpos de prova em forma de disco foram confeccionados com os diferentes compósitos e como pinos foram utilizadas esferas de aço AISI 52100. O compósito com 10% de carga apresentou o melhor desempenho tribológico com coeficiente de atrito variando entre 0,1 e 0,4 e profundidade da trilha do desgaste entre 25 e 50 µm. As imagens de MEV realizadas nas superfícies de ruptura dos corpos de prova de tração e nas superfícies desgastas dos discos utilizados nos ensaios pino contra disco revelaram desprendimento de material e partículas soltas sugerindo baixa adesão interfacial carga/matriz. De modo geral, as respostas obtidas estão de acordo com o que expressa a literatura. / Composites that incorporate industrial waste are an option for a wide range of applications and can also reduce the environmental passive generated over years. To address these issues, composites of epoxy resin loaded Scheelite Tailings in proportions of 1%, 5%, 10%, 20% and 30% were developed. For this, the Scheelite Tailings was characterized by XRF, XRD and SEM. The epoxy resin was analyzed by FTIR before and after curing. Two curing conditions were used for the preparation of the test specimens, at ambient temperature and the other at room temperature with a post-curing step at 80 ° C for 5 hours. The specimens were molded by casting in silicone mold and the proportions were calculated by volume. The specific mass was determined. The mechanical performance of the compositions was characterized by tensile and hardness tests which, the results showed that the mineral filler fractions generate positive effect on the Young\'s modulus and hardness and negative effect on the tensile strength. The parameters Ra, Rq and Rz were measured and considered as characterization of the surface finishing. Sliding tests with the pin on disk configuration were performed to characterize the tribological performance of the composites that generated friction coefficient responses and depth of the wear track. The disk specimens were made with the different compositions and the pins were AISI 52100 steel balls. The composite with 10% of scheelite tailings presented the best tribological performance with coefficient of friction varying between 0.1 and 0.4 and depth of the wear track between 25 and 50 50 µm. The SEM images performed on the tensile test specimen rupture surfaces and on the wear surfaces of the disks used in the pin to disk tests indicate release of material and loose particles suggesting low interfacial adhesion of mineral filler/matrix. In general, the answers obtained are in agreement with what is expressed in the literature.

The focus of this study is mono-layer polymer light emitting diode (PLED). The emitting layer is poly-p-phenylenebenzobisoxazole (PBO). PBO is a fully conjugated heterocyclic aromatic rigid-rod polymer. Anode is indium-tin-oxide (ITO). Cathode is aluminum (Al). We used UV epoxy resin to package PLED devices, then measured current-voltage response, electroluminescence (EL) emission, and device lifetime. We demonstrate that the packaged mono-layer PBO LED reduced its demise from water and oxygen. Device lifetime increased from 1 hour to several hundred hours. At a larger bias voltage or current, emission intensity and device efficiency became higher. But decay rate increased leading to shortened device lifetime. Device temperature appeared linearly with current density. A red shift of the EL emission was observed. The £fmax. of emission spectra moved from 534 nm (initial) to 582 nm (after 100 hrs). After thermal annealing at 120¢J for ten hours, threshold voltage increased from 5 V to 12 V, current density decreased to several 10 mA/cm2, luminous intensity improved several ten times to 10-2 cd/m2, emission color changed from yellow-green to orange, luminous efficiency improved from 10-7 to 10-4 cd/A, but device lifetime declined to less than 20 hrs.

Poly-p-phenylenebenzobisoxazole (PBO) and carbon nanotube (CNT) contain fully conjugated rod like backbone entailing excellent mechanical properties, thermo -oxidative stability and solvent resistance. Rigid-rod PBO is commonly processed by dissolving in methanesulfonic acid or Lewis acid. A CNT of multi-wall carbon nanotube (MWNT) was dissolved in a Lewis acid solution of PBO for dispersion, and then spun for thin film. MWNT concentration in the films was from zero up to 5 wt. %. Compared to that of pure PBO film, all PBO/MWNT composite films retained same but enhanced UV-Vis absorption peaks, according to MWNT concentration, showing that PBO and MWNT did not have overlapping electron orbitals affecting their energy gaps. The composite films were excited at 325 nm using a He-Cd laser for photoluminescence (PL) emission. All PL spectra had maximum intensity at 540 nm indicative of yellow-green light emission. The composite films were fabricated as light emitting diodes using indium-tin-oxide/glass as substrate and anode, as well as vacuum evaporated Al as cathode for respectively hole and electron injectors. In these light emitting devices, MWNT doped PBO would decrease threshold voltage for about 2 V. Up to 0.1 wt. % of MWNT, the device emission current was increased two orders of magnitude than those of the devices without MWNT. Further increase of MWNT caused a successive decrease in electroluminescence emission intensity attributed to a quench effect from aggregations of MWNTs. UV epoxy resin was applied to package the mono-layer and bilayer PBO light emitting devices. The UV epoxy resin had some gas release during encapsulation. The devices were packaged with vacuum and without vacuum encapsulation. It was demonstrated that the device encapsulation reduced its demise from water and oxygen. The vacuum encapsulation could remove gaseous volatile of the device to inhibit oxygen and moisture to prolong device lifetime. The main degradation of light emitting device was the oxidization of cathode. The interactions between nitrogen of PBO and H2O caused the formation of hydrogen bonding at room temperature. Oxygen and moisture diffused into PBO polymer and were suspected to form mid-gap state for the polymer. The mid energy band disappeared upon heat treatment before encapsulation. A device under a higher bias voltage was found to have a shorter lifetime, but a larger EL emission intensity. The EL emission intensity was not a constant under a constant current bias. The vacuum encapsulated device had two or twenty times lifetime than, respectively, the device encapsulation without vacuum evacuation or in ambient conditions. The sandwich structure of ITO/PBO/Al had no observable photovoltaic effect due to insufficient exciton separation into electrons and holes. Poly(2,3-dihydro thieno-1,4-dioxin):polystyrenesulfonate (PEDOT:PSS), a hole transferring medium, was spun into a thin-film between PBO and indium-tin-oxide to facilitate photovoltaic (PV) effect by forming a donor-acceptor interlayer to separate and to transport photoinduced charges. Optimum PBO thickness for the PV heterojunctions was about 71 nm at which the hole transferring PEDOT:PSS generated the maximum short circuit current (Isc) at a thickness of 115 nm. By using a layer of lithium fluoride (LiF) as an electron transferring layer adhering to Al cathode, the most open circuit voltage (Voc) and the maximum short circuit current (Isc) were achieved with a LiF thickness of 1-2 nm due to possible electric dipole effect leading to an increase of Voc from 0.7 V to 0.92 V and of Isc from about 0.1

Polymer-clay nanocomposites have received a lot of attention because of outstanding improvements in properties when compared with neat polymeric materials. The aim of this study was to prepare epoxy-clay nanocomposites by mixing organically modified montmorillonite with an epoxy resin and to investigate the effects of clay content on the mechanical, thermal and flammability properties of the resultant nanocomposites. The production of the epoxy-clay nanocomposites was accomplished by in-situ polymerization. In the nanocomposite synthesis, organically modified clay content was varied from 1 wt.% to 9 wt.%. Araldite LY556 epoxy resin, Aradur 918 anhydride hardener, and DY070 imidazole type accelerator were used in the epoxy system. Closite 30B, an organoclay modified with methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium chloride (MT2EtOH), was used as the clay material. X-ray diffraction results showed that d-spacing between the platelets of organoclay increased from 1.80 nm to 4.4 nm. The microstructures of nanocomposites were investigated by scanning electron microscopy (SEM). The SEM micrographs indicated that at 1 wt.% clay loading, no clay aggregates were observed. On the other hand, beyond 1 wt.% clay loading, formation of clay agglomerations was observed. Tensile strength and tensile strain values of nanocomposites decreased with clay loading. The tensile strength value of neat epoxy resin decreased from 55 MPa to 29 MPa with 9 % clay loading. On the other hand, Young&amp / #8217 / s modulus increased with clay content and a maximum value was obtained at 5 wt. % clay loading. At 9 % clay loading, Young&amp / #8217 / s modulus value was 26 % higher than that of the neat epoxy resin. Impact strength property had a minimum value at 7 wt. % clay content. Flexural strength and flexural strain at break property behaved in a similar trend. They had a minimum value at 5 % clay loading. At this clay loading, flexural strength value became approximately 43 % lower compared to the flexural strength of the neat epoxy resin. On the other hand, at 9 wt.% clay loading flexural modulus value increased approximately 48 % compared to the pure epoxy resin. Up to 7 wt.% clay ratio, initial decomposition temperature of epoxy resin was slightly improved. Also, according to TGA results, amount of char formation increased with clay loading. DSC results indicate that Tg of the cured nanocomposite resins decreased from 147 oC to 129 oC with 9 wt. % clay loading. The flammability of neat epoxy resin was not significantly affected with Cloisite 30B addition.

Carbon nanotubes (CNTs) are a relatively new allotrope of carbon that possess very unique and exciting physical characteristics. However, much is still unknown regarding their physical structure and chemical reactivity. The focus of this dissertation is to utilize the chemical modification of these filamentous carbon structures as a probe to investigate the structure and reactivity of carbon nanotubes. Also discussed is the ability of CNTs, once chemically modified, to interact with specific polymer matrices and how the addition of modified and unmodified CNTs affects the physical properties of these matrices.

Polymer/clay nanocomposites consisting of an epoxy resin matrix filled with organoclays have been investigated. The main objective of this study was to determine which combination of components led to the greatest enhancement in properties of the epoxy resin. Exfoliation of the clay was desired, as exfoliated nanocomposites are known to exhibit great improvements in mechanical properties [1]. The epoxy resins studied were di-functional DGEBA and tetra-functional TGDDM. The epoxy resin was cured with three different hardeners, these included: the high functionality amine hardener, TETA, and two anhydride hardeners, accelerated MTHPA and pure HHPA. The three organoclays used, contained alkylammonium cations and were also compared to the unmodified clay. Morphology was investigated by XRD and TEM, and the flexural properties of the resulting nanocomposites were studied. The effect that the addition of an organoclay has on the cure of the epoxy resin was investigated using MDSC. Both the temperatures required to cure the resin with, and without, the clay, and any changes in the total heat flow that occurred were studied. The Tg++ of the cured nanocomposites was also measured using MDSC. The heat flow results indicated that the clays added to the epoxy resins act as a physical barrier, which prevents the resin from reaching full cure. In the higher functional resin, the addition of clay resulted in a significant decrease in the total heat flow, suggesting that a large amount of epoxy remains uncured, and, as a result, there should be a reduction in the amount of cross-linking. The lower cross-link density led to a significantly lower Tg and the mechanical properties were also poorer. The reactivity of the hardener towards the resin was found to have the greatest impact on the cured nanocomposite morphology. Intragallery polymerisation occurring at a faster rate than the extragallery polymerisation causes exfoliation. In order to achieve a balance that favours intragallery polymerisation, it was found that the curing reaction was required to be catalysed by the alkylammonium cation of the organoclay, and not catalysed by other means. The DGEBA cured with HHPA provided the largest layer expansion in the clay structure due to the alkylammonium cation catalysing the anhydride ring-opening reaction. The effect was not seen with TGDDM due to the tertiary amine in its structure. The accelerator within the MTHPA assisted extragallery polymerisation of the resin and the TETA cured readily without additional catalysis.

Made available in DSpace on 2016-08-03T16:31:16Z (GMT). No. of bitstreams: 1 Miller Zaroni Santoro.pdf: 2303143 bytes, checksum: c5e5ddd496f8c0c48e1af99dfe38af5b (MD5) Previous issue date: 2011-04-29 / The aim of this study was to compare the forces of deflection in vitro between aesthetic and wire NiTi wires, to check the maximum force and plateau region and determine its correlation with the diameter of the wire with and without coating. Ten trials were conducted in seven brands of bows pre-skirted, six-wire aesthetic (InVu (I), Optis (O), Flexy Super Elastic Esthetic (FSEE), Orthocosmetic Elastinol (OE), Niticosmetic (N), and Pro Form Coated Nitanium (PFCN)) and a superelastic NiTi wire (Nitinol Super Elastic (NSE), applying The test is three-point bending, associated with universal machine EMIC. We developed a device with ceramic brackets (Transcend), whose strings were arrested for elastic modular, and obtained the values of the force deflection at 3.0, 2.0 and 1.0 mm. The diameter of the wires with and without coating were measured using digital especímetro Micromaster. The analysis of variance with a criterion (p <0.05) showed significant difference between the wires and post-hoc Tukey test determined that the force at 3mm deflection for wire O<OE=PFCE<FSEE=NSE<I. The paired t-test compared the strength of deflection (2-1mm) in the plateau region and showed that the wires O, FSEE and N showed constant forces. The wire N showed the largest diameter among the samples, while NSE wires and O, minors. The Pearson correlation coefficient showed that there was a correlation between the diameter of the wire and the force of deflection. It can be concluded that there are differences between the forces produced by the wires and aesthetic that force is directly proportional to the diameter of the uncoated wire for all peaks, ie the larger the diameter, the greater the force produced. / O objetivo do presente estudo consistiu em comparar as forças de deflexão in vitro entre fios estéticos e fio NiTi, para verificar a força máxima e da região platô e determinar sua correlação com o diâmetro do fio com e sem revestimento. Foram realizados dez ensaios de sete marcas comerciais de arcos précontornados, sendo seis fios estéticos (Invu (I), Optis (O), Flexy Super Elastic Esthetic (FSEE), Niticosmetic (N), Orthocosmetic Elastinol (OE) e Pro Form Coated Nitanium (PFCN)) e um fio NiTi superelástico (Nitinol Super Elastic (NSE)), aplicando-se o teste de curvatura de três pontos, associado a máquina de ensaios universal EMIC. Desenvolveu-se um dispositivo com braquetes cerâmicos (Transcend), cujos fios foram presos por elásticos modulares, sendo obtidos os valores da força de deflexão em 3,0, 2,0 e 1,0mm. O diâmetro dos fios com e sem revestimento foram mensurados com o especímetro digital Micromaster. A análise de variância a um critério (p<0,05) mostrou diferença significante entre os fios e o teste post-hoc de Tukey determinou que a força de deflexão em 3mm para o O<OE=PFCE<FSEE=NSE<I. O teste t-pareado comparou a força de deflexão (2-1mm) na região platô e mostrou que os fios O, FSEE e N apresentaram forças constantes. O fio da N apresentou o maior diâmetro entre as amostras, enquanto que os fios NSE e O, os menores. O Coeficiente de Correlação de Pearson mostrou que houve correlação entre o diâmetro do fio e a força de deflexão. Pode se concluir que há diferenças entre as forças produzidas pelos fios estéticos e que a força é diretamente proporcional ao seu diâmetro do fio com e sem revestimento para todas as deflexões, ou seja, quanto maior o diâmetro, maior a força produzida.

As resinas termorrígidas são uma classe de polímeros que devido à reação de reticulação deveriam apresentar uma única cadeia molecular de peso infinito, no entanto, questionamentos sugerem que a formação da rede tridimensional é não-homogênea. Atualmente, devido aos avanços obtidos pela nanotecnologia, torna-se possível uma abordagem diferenciada na modificação química de polímeros como a resina epoxídica. Neste trabalho, foram preparados nanocompósitos adicionando diferentes teores do oligômero poliédrico de silsesquioxano (POSS) n-fenilaminopropil na resina epoxídica. Foi substituindo 1, 5 e 10 por cento em massa (% m.) do agente de reticulação trietilenotetramina (TETA) por POSS. Esta modificação foi realizada com o objetivo de promover maior concentração de interligações nas interfaces das regiões nodulares, descritas como imperfeições ou descontinuidades que ocorrem pela cura não-homogênea da resina. Através da morfologia e da análise do teor de gel, foi evidenciada boa dispersão e melhoria na homogeneidade da rede tridimensional da resina acima de 5 % m. de POSS e aumento da fração gel nos nanocompósitos comparados com a resina epoxídica pura. Na realização de análises de difração de raio-x (DRX) foi visto que a adição do POSS aumentou a distância média entre as cadeias da resina. Foi realizada análise dinâmico-mecânica (DMA) no modo não-isotérmico e por varredura de frequência no modo isotérmico. Pelo modo não-isotérmico os resultados demonstraram que o POSS deslocou a Tg para temperaturas maiores e não alterou significativamente a densidade de ligações cruzadas da resina epoxídica. O modo isotérmico foi utilizado para a determinação de parâmetros das equações de Williams-Landel-Ferry (WLF) e Vogel-Fulcher-Tammann (VFT). Foi calculada a distribuição dos espectros de relaxação H(t) e retardação L(t) molecular através dos módulos de armazenamento e perda obtidos pelo modo isotérmico no DMA. Os parâmetros WLF e VFT demonstraram que a incorporação do POSS ao mesmo tempo em que aumentou a Tg, reduziu a energia de ativação de movimentação segmentar e tornou a resina epoxídica mais forte estruturalmente. A redução da energia de ativação foi associada com a redução das forças de interação intermolecular, enquanto que a redução da fragilidade foi associada ao fato do POSS ser capaz de interligar as interfaces de regiões nodulares. Os espectros H(t) e L(t) mostraram que o pico de relaxação associado aos nódulos formados no processo de reticulação desapareceu. A determinação da capacidade calorífica (Cp) e do excesso de entropia (Sex) através de análises de calorimetria exploratória diferencial modulada (MDSC) demonstrou que o POSS é capaz de minimizar as flutuações de calor ao longo da microestrutura da resina epoxídica. A minimização das flutuações térmicas e a alteração dos tempos de relaxação demonstram que a adição do POSS é eficiente em termos de minimização de imperfeições na microestrutura da resina epoxídica. / The thermosetting resins are a class of polymers that due to the crosslinking reaction should present a single chain with infinite molecular weight; however, questions suggest that the formation of three-dimensional network is non-homogeneous. Today, due to advancements in nanotechnology, became possible a differentiated approach in the chemical modification of polymers such as epoxy resin. In this work, nanocomposites with different contents of the polyhedral oligomeric silsesquioxane (POSS) n-phenylaminopropyl in epoxy resin were prepared. It was substituted 1, 5 and 10 weight percent (wt%) of the crosslinking agent, triethylenetetramine (TETA), for POSS. This modification was performed in order to promote greater concentration of interconnections at the interfaces of the regions described as nodular imperfections or discontinuities that arise due to inhomogeneous cure of the resin. Through the morphology and the gel content analysis was observed good dispersion and improvements in the uniformity of three-dimensional network of the resin up till 5 wt% of the POSS and increase in the gel fraction of the nanocomposites compared with pure epoxy resin. X-ray diffraction (XRD) showed that the POSS promoted an increase in distance between chains of the resin. Dynamic-mechanical analysis (DMA) was performed in non-isothermal mode and a frequency sweep in the isothermal mode. By non-isothermal mode the results showed that the POSS shifted the Tg to higher temperatures and does not modify the crosslink density. The isothermal mode was used to determine the parameter of the Williams-Landel-Ferry (WLF) and Vogel-Fulcher-Tammann (VFT) equations. The distribution of the relaxation H(t) and retardation L(t) spectra was calculated through the storage (E') and loss (E'') modulus obtained by the DMA isothermal mode. The WLF and VFT parameters showed that the incorporation of POSS at the same time increased the Tg reduced the activation energy of segmental motion and made the epoxy resin structurally stronger. The reduction in the activation energy was associated with reduced intermolecular forces whereas the decrease in the structural fragility is associated with the fact that the POSS be able to interconnect the interfaces of the nodular regions. The H(t) and L(t) spectra showed that the nodules formed in the crosslinking process disappeared. The determination of the heat capacity (Cp) and excess entropy (Sex), analyzed by modulated differential scanning calorimetry (MDSC), showed that POSS is capable of minimizing fluctuations of heat along the microstructure of the epoxy resin. The reduction of thermal fluctuations and change in the relaxation times shows that the POSS addition is efficient to minimize imperfections in the microstructure of the epoxy resin.