Yttria stabilized Zirconia (8YSZ) is an extensively used solid electrolyte, which finds applications in electrochemical sensors, solid oxide fuel cells and gate oxide in MOSFETs. Recent studies report that YSZ thin films are better performers than their bulk counterparts, in terms of ionic conductivity even at moderate temperatures. YSZ thin films also attract attention with the scope of device miniaturization. However, most of the studies available in the literature on YSZ thin films focus mainly on their electrical characterization. In this work, YSZ thin films were deposited, characterized and possible use of sensors were evaluated. In the present work, 8 mol% yttria stabilized zirconia thin films were deposited using RF magnetron reactive sputtering under different deposition conditions. Films with thicknesses ranging from few tens to few hundreds of nanometres were deposited. The deposited films were subjected to morphological, structural, compositional and electrical characterizations. Deposition and annealing conditions were optimized to obtain dense, stoichiometric and crystalline YSZ thin films. The ionic conductivity of 200 nm nanocrystal line thin film was found to be two orders of magnitude higher than the bulk. The ionic conductivity increased with the decrease in film thickness. Compositional analyses of a set of YSZ thin films revealed free surface yttrium segregation. The free surface segregation of dopants can locally alter the surface chemistry and influence the oxygen transfer kinetics across the electrode-electrolyte interface. Although number of reports are available on the segregation characteristics in YSZ bulk, no reports are available on yttria segregation in YSZ thin film. Hence, this work reports detailed investigations on the free surface yttria segregation in YSZ thin films using angle resolved X-ray photoelectron spectroscopy (XPS). Influence of annealing temperature, film thickness, annealing time, and purity on the segregation concentration was determined. It was found that the most important factor that determines the segregation was found to be the target purity. The segregation depth profile analysis showed that the segregation layer depth was proportional to segregation concentration. Free surface segregation reduced the ionic conductivity of the YSZ thin films roughly about a factor. However, segregation did not affect the film’s morphology, grain size, crystallinity and activation energy. The difference in ionic conductivity observed in the segregated and clean YSZ films suggests that dopant free surface segregation could also be one of the reasons for the variable ionic conductivity reported in the literature. For using YSZ in miniaturized devices, micro-structuring of YSZ is important. It has been reported that the wet etching techniques available for YSZ were not repeatable and do not etch annealed YSZ samples. Reactive ion etching (RIE) is better suited for YSZ patterning due to its capability to offer high resolution, easy control and tenable anisotropic/isotropic pattern transfer for batch processing. Although reports are available on the dry etching of zirconia and yttria thin films, no studies were reported on the dry etching of YSZ thin films. In this work, inductively coupled reactive ion etching (ICP-RIE) using fluorine and chlorine chemistries were employed to etch YSZ thin films. Optimized etching conditions were identified by varying different process parameters like, type of gas, gas flow rate, RF power, ICP power, chamber pressure and carrier wafer in the ICP-RIE process. Optimized conditions were chosen by examining the etch depth, composition analyses before and after etch using XPS, selectivity towards SiO2 (which is the most common buffer layer) and surface roughness. Etch chemistries involved in a particular plasma (SF6, Cl2 and BCl3) were discussed with the help of surface composition and etch thicknesses. The results showed that etching YSZ with BCl3 plasma at optimized conditions yielded best results through oxygen-scavenging mechanism. A maximum etch rate of 53 nm/min was obtained in BCl3 plasma using PECVD Si3N4 carrier wafer at an ICP power of 1500 W, RF power of 100 W, chamber pressure of 5 mTorr with 30 sccm BCl3 flow. Sensing devices were designed by employing YSZ thin film as solid electrolyte and nickel oxide and gold thin film as sensing and reference electrodes, respectively to evaluate the possible use of YSZ thin film in miniaturized NO2 sensor. The electrodes were deposited in inter-digitated pattern. Two types of electrodes were designed with different number of fingers in symmetric and asymmetric configurations. The NO2 sensing was performed in the concentration range of 25 to 2000 ppm at three different temperatures, 673, 773 and 873 K in mixed potential and impedance metric modes. The mixed potential type measurements were carried out only for asymmetric cell in two different electrode configurations. The impedance metric type measurements were carried out for both symmetric and asymmetric cells in two different electrode configurations. Preliminary NO2 sensing experiments in both the types of measurements revealed that in devices with electrodes having more fingers were better in performance. In mixed potential type sensors, sensitivity was measured as the amount of voltage generated when the sensor was exposed to a test gas. The generated voltage was found to be proportional to the logarithm of NO2 concentration in the entire measurement range (50 to 2000 ppm) with the regression fitting parameter, adj.R2 around 0.97 to 0.99 in all the cases. A maximum potential of 271 mV was measured with 2000 ppm NO2 at 873 K. The response and recovery times of the sensors were sensitive to the operating temperature. In impedance metric mode, the sensitivities were measured as the variation in the low frequency phase angle (∆ φ) when the gas concentration is changed. The frequency range of the measurement was from 0.01 Hz to100 kHz. The response time in the impedance metric sensors was comparable to that of mixed potential sensors. But the recovery time in impedance metric sensors was much was slower than the mixed potential type for all the concentrations. The sensors showed linear response only in a narrow range of 50 to 500 ppm with regression fitting value, R2 around 0.98 in all the cases. Above 500 ppm, the sensitivity value was observed to be saturated. From the gas sensing studies performed on the miniaturized sensors, it was found that the mixed potential type sensing mode is better than the impedance metric type in YSZ thin film based devices. However detailed interference gas studies were needed before drawing any conclusion. In summary, the studies presented in the work have contributed to the understanding of free surface yttria segregation behaviour in YSZ thin films. Micromachining conditions were optimized for both pristine and annealed YSZ thin films. Suitability of YSZ thin film based miniaturized NO2 gas sensor was evaluated.

Mesoscale optical phenomena occur when light interacts with a number of different types of materials, such as biological and chemical systems and fabricated nanostructures. As a framework, mesoscale optics unifies the interpretations of the interaction of light with complex media when the outcome depends significantly upon the scale of the interaction. Most importantly, it guides the process of designing an optical sensing technique by focusing on the nature and amount of information that can be extracted from a measurement. Different aspects of mesoscale optics are addressed in this dissertation which led to the solution of a number of problems in complex media. Dynamical and structural information from complex fluids—such as colloidal suspensions and biological fluids—was obtained by controlling the size of the interaction volume with low coherence interferometry. With this information, material properties such as particle sizes, optical transport coefficients, and viscoelastic characteristics of polymer solutions and blood were determined in natural, realistic conditions that are inaccessible to conventional techniques. The same framework also enabled the development of new, scale-dependent models for several important physical and biological systems. These models were then used to explain the results of some unique measurements. For example, the transport of light in disordered photonic lattices was interpreted as a scale-dependent, diffusive process to explain the anomalous behavior of photon path length distributions through these complex structures. In addition, it was demonstrated how specialized optical measurements and models at the mesoscale enable solutions to fundamental problems in cell biology. Specifically, it was found for the first time that the nature of cell motility changes markedly with the curvature of the substrate that the cells iv move on. This particular work addresses increasingly important questions concerning the nature of cellular responses to external forces and the mechanical properties of their local environment. Besides sensing of properties and modeling behaviors of complex systems, mesoscale optics encompasses the control of material systems as a result of the light-matter interaction. Specific modifications to a material’s structure can occur due to not only an exchange of energy between radiation and a material, but also due to a transfer of momentum. Based on the mechanical action of multiply scattered light on colloidal particles, an optically-controlled active medium that did not require specially tailored particles was demonstrated for the first time. The coupling between the particles and the random electromagnetic field affords new possibilities for controlling mesoscale systems and observing nonequilibrium thermodynamic phenomena

In the last decade new materials appeared that are candidates to be used as an electrolyte in a Solid Oxide Fuel Cell, SOFC. Some materials show high ionic conductivity but lack in important properties, such as mechanical stability or chemical compatibility with other materials in the fuel cell. Scandia Stabilised Zirconia, SSZ, became a possibility when the scandia price dropped with the opening of the Chinese and Russian markets. In the starting system Ce[subscript(x)]Y[subscript(0.2-x)]Sc₀.₆Zr₃.₂O[subscript(8-δ)], (0≤x≤0.2), scandia is introduced to improve conductivity and stabilise the cubic phase; yttria is introduced to fully stabilise the cubic phase and ceria to enhance conductivity lost with the introduction of yttria. The aim of this project is to develop a reliable new method to produce quality ceramics that are not strongly composition dependent, then to prepare a range of compositions and compare intrinsic properties without having to be concerned that poor sintering dominates conduction properties. This project can be divided in two sections, the first section the powder production method, the characteristics of the powders and its final products are in focus. In the second section the relation between electric characteristics and microstructure of the material is reported. In the first section, the effect of different compositions of the system Ce[subscript(x)]Y[subscript(0.2-x)]Sc₀.₆Zr₃.₂O[subscript(8-δ)], (0≤x≤0.2) is studied, in terms of structure, phase and microstructure. The nature, size and shape of the powders are discussed, and their effect on the final product. The sol-gel and combustion method gives the formation of hard agglomerates (shells), during the combustion, a wide range of grain sizes, between less than 1µm and 200 µm, and the formation of grains with non spherical shape. In this project, the sol-gel and combustion process and solid state method are also compared. In the second section of this project, AC Impedance measurements, as a function of temperature, oxygen partial pressure and time are discussed. The Arrhenius plot for all compositions shows two regions (high and low temperature) and the change of region occurs at 580 °C. At low temperatures there is a slight difference between compositions but this difference is less at high temperatures. The obtained ionic conductivity, at 350 °C, varies from 3.84×10⁻⁶ to 5.53×10⁻⁵ S/cm; at 700 °C, ionic conductivity from 0.013 to 0.044 S/cm. At low temperatures, the activation energy associated with bulk process is generally lower than grain boundary process; for example, the composition Ce₀.₁Y₀.₁Sc₀.₆Zr₃.₂O₇.₆₅ has an activation energy, for the bulk process, of 1.05 eV and an activation energy, for the grain boundary process, of 1.17 eV. For compositions with higher ceria content, activation energy, for bulk and grain boundary, have similar values. The AC impedance as function of oxygen partial pressure show that the amount of ceria introduced as an effect on the conductivity at low oxygen partial pressure. For the sample with no ceria in its composition, Y₀.₂Sc₀.₆Zr₃.₂O₇.₆₀, the conductivity does not vary significantly as the oxygen partial pressure is decreased; for oxygen partial of 0.21 atm, conductivity is 0.018 S/cm and when oxygen partial pressure is approximately 10⁻²⁴ atm conductivity is 0.018 S/cm. For the sample with a higher content of ceria, Ce₀.₁₂Y₀.₀₈Sc₀.₆Zr₃.₂O₇.₆₆, there is a decrease in conductivity while oxygen partial pressure decreases; and there is also the appearance of a semi-circle for lower oxygen partial pressures. For oxygen partial pressure approximately 0.21 atm, conductivity is 0.019 S/cm, but when oxygen partial pressure is decreased to 10⁻²⁴ atm conductivity decreases to 0.011 S/cm. AC impedance measurements as a function of annealing time at 600 °C were performed. Total conductivity is fairly stable, for all compositions, until 1800 hours but after this time, conductivity slowly decreases. Some compositions show a second semi-circle in the AC impedance spectra, either from the beginning, time equals 0 hours, or after some working hours. Here, the changes in conduction and conduction processes with time are discussed.

Ce travail de thèse est une approche originale de la compréhension des mécanismes physico-chimiques s'opérant à l'interface des restaurations céramo-céramiques par la microscopie confocale Raman. Il est scindé en trois parties. La première partie expose les caractéristiques d'une chape céramique à noyau zircone (Y-TZP) recouverte d'une céramique feldspathique. Les principaux facteurs responsables de la qualité de l'interface ont été recherchés par une revue de littérature. Le principe de la microscopie confocale Raman a été décrit. La seconde partie est la mise au point des méthodes d'analyse spectrale et d'imagerie Raman, en surface et en profondeur, sur matériaux isolés et à l'interface. La répartition des phases cristallines ou amorphes a été estimée de part et d'autre de cette dernière. La composition chimique élémentaire des composants et une ligne de balayage par traversée de l'interface ont été obtenues par spectroscopie dispersive en énergie (EDS). Le troisième chapitre explore les changements chimiques et morphologiques de l'interface sous différents procédés de fabrication : avec ou sans l'utilisation d'un Liner, avec ou sans utilisation d'une cuisson de régénération de l'Y-TZP. Les images Raman ont été traitées par la fonction d'analyse K-Means Cluster. Une cartographie de la distribution des éléments chimiques a été effectuée par EDS. / This thesis is an original approach to the understanding of the physical and chemical mechanisms operating at the interface of core-veneer all-ceramic restorations by confocal Raman microscopy. It is divided into three sections. The first part describes the characteristics of a zirconia core (Y-TZP) layered with feldspathic ceramic. The main factors affecting the interface have been investigated in the literature review. The principle of confocal Raman microscopy is described. The second part describes the development of spectral analysis and Raman imaging methods, on both the surface and at depth, on isolated materials and at the interface. The allocation of crystalline or amorphous phases was estimated around the interface. The elemental chemical analysis of the components and scanning line through the interface were obtained using energy dispersive X-ray spectroscopy (EDS). The third section explores the chemical and morphological changes of the interface under different manufacturing methods : with or without an optional liner material between the two components and with or without the use of a regeneration firing of the Y-TZP core. Raman images were processed by K-Means Cluster analysis function. The elemental distribution around the interface was estimated using EDS.

Devido à crescente utilização de componentes cerâmicos como estruturas de suporte para restaurações sobre implantes e a ausência de resultados conclusivos, em longo prazo, sobre a influência deste tipo de material no processo de formação e manutenção do biofilme oral e saúde dos tecidos peri-implantares, este estudo teve por objetivo investigar o perfil microbiano do biofilme formado sobre próteses unitárias de implantes com conectores de zircônia (Zr) ou titânio (Ti) e sua implicação clínica nos tecidos de suporte ao longo de 3 anos de função. Vinte indivíduos saudáveis participaram do estudo e foram reabilitados com implantes dentários e coroas protéticas unitárias cimentadas sobre conectores de zircônia (n=10; região anterior de maxila) ou conectores de titânio (n=10; região posterior da mandíbula). Amostras de biofilmes supra e subgengival, e dados de indicadores clínicos (profundidade e sangramento à sondagem, recessão gengival e nível ósseo marginal) foram coletados dos sítios peri-implantares e dentes contralaterais em 4 períodos distintos, na instalação da prótese (T0) e após 12 (T1), 24 (T2) e 36 (T3) meses de função mastigatória. Trinta e sete espécies microbianas foram identificadas e quantificadas pelo método de hibridização DNA-DNA Checkerboard. Os dados foram submetidos à análise estatística não-paramétrica de regressão linear mista (Brunner and Langer nonparametric analysis of longitudinal data in factorial experiments) e múltiplas comparações foram realizadas por meio do teste de Friedman-Conover, corrigido por Benjamini-Hockberg False Discovery Rate (FDR). Para análise da reabsorção óssea marginal foi utilizado o teste Two-Way ANOVA. Todas as análises foram realizadas com um nível de significância de 5%. O perfil microbiano detectado nos implantes restaurados com conectores de zircônia, titânio e seus respectivos dentes contralaterais foi semelhante a partir do período de 12 meses de investigação. Espécies patogênicas e não-patogênicas foram detectadas nos biofilmes supra e subgengival dos dois substratos, com um aumento significante da quantificação das espécies ao longo do tempo. Apesar do perfil semelhante, os substratos investigados influenciaram na quantidade total de micro-organismos identificados (p<0,05). Os conectores de Zr apresentaram maior quantificação de genomas totais nas amostras subgengivais quando comparadas aos conectores de Ti (p<0,05). A profundidade de sondagem reduziu nos implantes com Zr após 12 meses, enquanto nos implantes com Ti aumentou no mesmo período (p<0,05). O sangramento à sondagem e a recessão gengival aumentaram ao longo do tempo para Zr e Ti. Não houve diferença significante nos valores da reabsorção óssea marginal, entre os dois materiais, após 36 meses (p>0,05). De modo geral, pode-se concluir que o perfil microbiano dos biofilmes supra e subgengival dos implantes com Zr ou Ti foi semelhante, com um aumento da quantificação das espécies ao longo do tempo. A microbiota investigada neste estudo parece não ter influenciado os indicadores clínicos ao longo dos 36 meses de acompanhamento. Os resultados clínicos sugerem a manutenção da saúde dos tecidos peri-implantares nos diferentes substratos investigados / Due to the increasing use of ceramic abutments as support structures for implant restorations and the lack of long-term conclusive results on the influence of this type of material on the oral biofilm formation and maintenance of peri-implant tissue health, the purpose of this study was to investigate the microbial biofilm profiles of single-implant restorations using zirconia (Zr) or titanium (Ti) abutments and their clinical implications in the supporting tissues over a 3-year period. Twenty healthy subjects participated in the study and were rehabilitated with single-unit implant restorations cemented on zirconia (n = 10; anterior maxilla) or titanium abutments (n = 10; posterior mandible). Supra and subgingival biofilm samples, and clinical parameters data (probing depth and bleeding on probing, gingival recession and marginal bone level) were collected from the peri-implant sites and contralateral teeth at 4 different time-periods, at the prosthesis installation (T0) and after 12 (T1), 24 (T2) and 36 (T3) months of loading. Thirty-seven microbial species were identified and quantified by DNA-DNA Checkerboard hybridization method. The data were submitted to Brunner and Langer nonparametric analysis of longitudinal data in factorial experiments followed by Friedman-Conover multiple comparisons test, corrected by Benjamin-Hockberg False Discovery Rate (FDR). Two-Way repeated ANOVA was used to analyze marginal bone resorption. Statistical significance was set at 0.05 probability level. The microbial profiles detected in the implants restored with zirconia or titanium abutments and their respective contralateral teeth were similar from the 12-month follow-up. Pathogenic and non-pathogenic species were detected in the supra and subgingival biofilms of the two substrates, with a significant increase in the microbial counts over time. Despite the similar profile, the investigated substrates influenced the total amount of microorganisms identified (p <0.05). The Zr abutments presented higher total genome counts in the subgingival samples when compared to Ti abutments (p <0.05). The probing depth reduced in the implants with Zr after 12 months, whereas in the implants with Ti increased in the same period (p <0.05). Bleeding on probing and gingival recession increased over time for both Zr and Ti. There was no significant difference in marginal bone resorption values between the two materials after 36 months (p>0.05). Overall, it can be concluded that the microbial profile of supra and subgingival biofilms of the implants with Zr or Ti was quite similar, and the microbial counts increased over time. The microbiota investigated in this study does not seem to have influenced the clinical parameters during the 36 months of follow-up. The clinical results suggest the maintenance of peri-implant tissue health in the different substrates investigated

O objetivo deste estudo foi confeccionar uma nova macroestrutura de implantes de Zircônia (Y- TZP) e Titânio (Grau 4) e posteriormente avaliar comparativamente a transmissão de força e a resistência flexural, submetidos à fadiga mecânica e termomecânica. Foram obtidos 33 implantes de Zircônia e de titânio Grau 4. As tensões geradas em torno dos implantes foram observadas em 3 espécimes inicialmente por meio de análise fotoelástica, com forca de 200N aplicada no longo eixo dos implantes. Em seguida, os implantes foram incluídos em resina de poliuretano (F-16, AXSON Technologies) com inclinação de 30° e aleatoriamente separados em grupos (n=10),, segundo o tipo de tratamento a que foram submetidos: Controle (sem tratamento) (Zr e Ti), fadiga mecânica (ZrM e TiM) e fadiga termomecânica (ZrTM e TiTM). A máquina de fadiga mecânica foi programada para aplicar carga de 133 N, com frequência de120 ciclos por minuto (2 Hz), totalizando 2.000.000 ciclos em cada espécime. A ciclagem térmica foi configurada com a temperatura mínima entre 2o a 5oC e temperatura máxima entre 50° a 55° C com exposição de 30 segundos para cada faixa e 5 segundos para troca dos líquidos. Após o ensaio de fadiga mastigatória, todos os grupos foram submetidos ao ensaio de tensão flexural. Os resultados foram submetidos à análise estatística (2-way ANOVA, teste de Bonferroni, p<0,05) e verificou-se que nao houve diferença estatisticamente significante na quantificação da transmissão de força entre os implantes de Zircônia e Titânio. Os implantes de Titânio apresentaram maior resistência flexural, com diferença estatisticamente significante (p<0.05) em relação aos implantes de Zircônia. Concluiu-se que foi possível obter um design de implante de zircônia compatível com as condições de forças aplicadas em ambiente bucal. A fadiga mecânica e termomecânica não influenciaram a resistência flexural dos implantes de Titânio nem dos implantes de Zircônia. / The aim of this study was to develop a new Zirconia (Y-TZP) and Titanium (Grade 4) implant macrostructure to make an accurate comparative evaluation of the stress transmission and flexural strength after both materials were subjected to mechanical and thermomechanical fatigue. Thirty three Zirconia and Titanium Grade 4 implants were obtained. A force of 200N was applied to the long axis of the implants and the distribution of the generated stress around implants was initially observed in three specimens by photoelastic analysis. Then, the implants were embedded in polyurethane resin (F-16, AXSON Technologies) with an inclination of 30°and randomly divided into groups (n = 10), according to the type of treatment they were subjected to: Control (no treatment ) (Zr and Ti), mechanical fatigue (ZRM and TiM) and thermomechanical fatigue (ZrTM and TiTM). The mechanical fatigue testing machine was programmed to apply a load of 133 N, with a frequency of 120 cycles per minute (2 Hz) and a total of 2,000,000 cycles in each specimen. The thermocycling was set with the minimum temperature between 2°-5°C and maximum temperature between 50°-55°C with 30 seconds exposure for each track and 5 seconds for the exchange of fluids. Following the fatigue test (chewing simulation), all groups were subjected to flexural strength test. The data were subjected to statistical analysis (2-way ANOVA, Bonferroni test, p <0.05) and the results showed no statistically significant difference between Zirconia and Titanium implants\'s stress transmission values. Titanium implants showed higher flexural strength, which was statistically significant (p <0.05) compared with Zirconia implants. It was concluded that it was possible to obtain a Zirconia implant design compatible with the forces applied in the oral environment. Moreover, the mechanical and thermomechanical fatigue had no influence on the flexural strength of both Titanium and Zirconia implants.

OBJETIVO: Verificar, através da análise por elementos finitos, a influência do formato da infraestrutura e protocolo de resfriamento nas tensões térmica residuais (TTR) e nas tensões após carregamento oclusal de coroas com infraestrutura de zircônia YTZ-P. MÉTODOS: Foram construídos modelos 3D de coroa em segundo molar inferior com dois diferentes formatos de infraestrutura: uniforme (IU) e anatômico (IA). Análise da transferência de calor foi conduzida com dois protocolos de resfriamento: lento (RL) e rápido (RR). Os dados de temperatura foram utilizados na análise da tensão térmica, na qual foi considerada a mudança do coeficiente de contração térmico linear e do módulo de elasticidade da porcelana próximo a sua Tg. Sobre os modelos com tensões térmicas residuais foi simulado o carregamento oclusal: 400 N distribuídos em 2 áreas de 1 mm2 nas cúspides vestibulares. Foram analisadas as distribuições das tensões máxima principal (1) e mínima principal (3) residuais (após resfriamento) e finais (após carregamento oclusal) na porcelana de cobertura. RESULTADOS: Os modelos com RL apresentaram maiores tensões de tração (1 positiva) e de compressão (3 negativa), além de amplas áreas com ausência de tração (1 negativa) na oclusal e na cervical. Nos modelos com RR as mesmas áreas eram isentas de compressão (3 positiva). Ao comparar as infraestruturas no RL, o modelo com IA apresentou maior área com ausência de tração, menor pico 1 (IA: 27,6 MPa; IU: 32,8 MPa) e maior pico de 3 (IA: -61,2 MPa; IU: -46,8 MPa). Com o carregamento oclusal, notou-se, de modo geral, um pequeno aumento das tensões de tração na face lingual e diminuição da tração na região cervical da face vestibular, para ambos os formatos de infraestrutura. CONCLUSÃO: A distribuição observada nos modelos resfriados rapidamente tende a oferecer menos proteção à propagação de trincas, pois na face oclusal foram geradas regiões sem compressão. Os modelos com IA, quando resfriados lentamente, apresentaram distribuição de tensões, antes e após carregamento oclusal, que pode diminuir o risco de lascamento da porcelana. / OBJECTIVE: To analyze, using a 3D finite element model, the residual thermal stress distribution and occlusal stress distribution in a veneered zirconia crown regarding the framework design and cooling protocol. METHODS: 3D models of second lower molar veneered zirconia crowns were built with two different core designs: uniform (U) or anatomic (A). Heat transfer analyses were conducted with two cooling protocols: slow (S) and fast (F). The output of temperatures was used to calculate thermal stresses. The non-linear increase in porcelain modulus and coefficient of thermal expansion close to its Tg was taken into account. An occlusal load (400 N in two 1 mm2 contact area at the buccal cusps) was applied in the pre-stressed model. The maximum (1) and minimum (3) principal stresses at the porcelain were analyzed. RESULTS: Slowly cooled models showed higher tensile (positive 1) and compressive stresses (negative 3). In addition, tension-free zones were shown in their occlusal and cervical regions, while compression-free zones were shown in the same regions of rapidly cooled models. Regarding the framework design, the anatomic model showed larger tension-free zones at the occlusal face, lower 1 peak (A: 27.6 MPa; U: 32.8 MPa) and higher 3 peak (A: -61.2 MPa; U: -46.8 MPa). After occlusal loading, the tensile stress values increased in the lingual face and decreased in the cervical of buccal face, but the general pattern of residual thermal stress distribution was maintained. CONCLUSION: The stress distribution of rapidly cooled models is less prone to protect the porcelain from crack propagation, because of the compression-free zones in the occlusal and cervical regions. The anatomic design in slowly cooled models showed stress distribution more favorable to prevent porcelain chipping.

O objetivo do estudo foi avaliar a resistência de união à zircônia após diferentes tratamentos de superfície e o comportamento mecânico de pilares e coroas de zircônia associados aos mesmos tratamentos. Na primeira fase, 95 discos em zircônia foram obtidos e divididos em cinco grupos (n = 19): GC (grupo controle, sem nenhum tipo de tratamento); GAL (jateamento com partículas de Al2O3 antes da sinterização); GALS (jateamento com partículas de Al2O3 após sinterização); GRO (silanização com sistema Rocatec antes da sinterização) e GROS (silanização com sistema Rocatec após sinterização). Três amostras de cada grupo tiveram a superfície analisada em MEV e MCVL. Dez amostras de cada grupo foram submetidas a ensaio de microcisalhamento e as seis restantes foram submetidas à análise de interface por meio de MEV. A análise estatística utilizou modelo de regressão linear com efeitos mistos e teste de Tukey (p < 0,01). Na segunda fase, 70 pilares do tipo hexágono externo foram obtidos em zircônia e associados a coroas totais com copings de zircônia. Os conjuntos análogo-pilar-coroa também foram divididos em cinco grupos (n=14) e submetidos aos mesmos tratamentos previamente descritos. Ainda, foram realizadas mensurações para verificação da adaptação dos copings sobre os pilares e rugosidade superficial dos discos, copings e pilares em MCVL. Foi realizado ensaio de fadiga mecânica dos conjuntos com carga progressiva de 80, 120, 160, 200, 240, 280 e 320 N, frequência de 5 Hz, totalizando 20.000 ciclos em cada estágio. A ciclagem térmica foi realizada com temperaturas entre 5º C e 55º C. Após os ensaios mecânicos, os resultados foram submetidos à análise estatística (probabilidade de sobrevida, teste de Log-Rang, p < 0,05) Os resultados apontaram que o grupo ROS apresentou valores de resistência de união significativamente superiores (p < 0,01) e que a rugosidade superficial foi semelhante para discos e copings (p = 0,22) e para discos e pilares (p = 0,96), e diferente entre copings e pilares (p < 0,01). A desadaptação marginal foi maior para o grupo RO (p < 0,01) e a probabilidade de sobrevida dos conjuntos foi similar para todos os grupos testados (p = 0,57). Concluiu-se que a utilização do Rocatec aumenta os valores de resistência de união à zircônia, não compromete o comportamento mecânico do material e sua utilização é viável em peças já sinterizadas. / The aim of this study was to evaluate the bond strength to zirconia after different surface treatments and to evaluate the mechanical behavior of zirconia abutments and crowns associated with these treatments. In the first phase, 95 discs in zirconia were obtained and divided into five groups (n = 19): GC (control group, without any treatment), GAL (air particle abrasion with Al2O3 particles before sintering), GALS (air particle abrasion with Al2O3 particles after sintering), GRO (silanization with Rocatec system before sintering) and GROS (silanization with Rocatec system after sintering). Three samples of each group had the surfaces analyzed in SEM and CLSM. Ten samples of each group were subjected to microshear test and the other remaining six had their interface examined by SEM. The statistical analysis used a linear regression model with mixed effects and Tukey test (p <0.01). In the second stage, 70 external hex abutments were obtained in zirconia and associated with crowns and zirconia copings. The analog-abutment-crown assemblies were also divided into five groups (n = 14) and subjected to the same treatments described previously. Measurements to verify the adaptation of copings on the abutments and surface roughness of the discs, copings and abutments were performed in CLSM. A fatigue test was carried with progressive load of 80, 120, 160, 200, 240, 280 and 320 N, frequency of 5 Hz and 20,000 cycles at each stage. Thermal cycling was performed with temperatures between 5° C and 55° C. After mechanical tests, the results were subjected to statistical analysis (survival probability, Log-Rang test, p <0.05) The results showed that the ROS group had significantly higher bond strength values (p < 0.01) and that the surface roughness was similar for discs and copings (p = 0.22) and for discs and abutments (p = 0.96), and was different between copings and abutments (p < 0.01). The marginal gap was higher for RO group (p < 0.01) and the survival probability of the sets was similar for all tested groups (p = 0.57). It was concluded that the use of Rocatec increases the bond strength values to zirconia, does not compromise the mechanical behavior of the material and its use is now feasible in sintered parts.

Neste trabalho investigou-se a influência da adição dos ânions cloreto, fluoreto e sulfato nas propriedades físico-químicas de nanopós de zircônia sintetizada pelo método Pechini. Análises de fluorescência de Raios-X, difração de Raios-X, espectroscopia no infravermelho, área de superfície específica, espectroscopia Raman, microscopia eletrônica de varredura, análise termogravimétrica, calorimetria diferencial por varredura, amplitude sônica eletrocinética e dilatometria foram realizadas para caracterizar os pós sintetizados. Os resultados obtidos mostraram que o tratamento térmico realizado para a obtenção dos pós retirou os ânions cloreto e fluoreto da composição química final da zircônia enquanto o ânion sulfato permaneceu. Mesmo sendo retirados os ânions cloreto e fluoreto influenciaram no processo de cristalização da zircônia modificando o tamanho de cristalito obtido. A permanência do ânion sulfato na composição química da zircônia se deve à maior energia de ligação com o cátion Zr 4+ assim, observou-se uma maior influência deste ânion no processo de cristalização. Isso permitiu a formação de cristalitos menores e a estabilização da fase tetragonal da zircônia. Em todos os casos, as análises mostraram que a influência dos ânions se deu por segregação dos mesmos na superfície da zircônia o que, principalmente no caso do ânion sulfato, tende a reduzir a energia da superfície da zircônia através do aumento da área de superfície específica. Verificou-se também que o ânion sulfato pode ser retirado da superfície da zircônia através da lavagem do pó em meio básico. Esse procedimento permitiu aumentar a área de superfície específica e tende a melhorar sua sinterabilidade. / In this study was investigated the influence of the addition of the chloride, fluoride and sulfate anions in the physico-chemical properties of zirconia nanopowders synthesized by the Pechini method. Analyses of X-ray fluorescence, X-ray diffraction, infrared spectroscopy, specific surface area, Raman spectroscopy, scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, electrokinetic sonic amplitude and dilatometry were performed to characterize the synthesized powders. The results showed that the heat treatment performed to obtain the powders removed the chloride and fluoride anions from the final chemical composition of the zirconium whereas the sulfate anion anion remained. Despite the chloride and fluoride anions removal, they influenced the crystallization process of the zirconium, modifying the size of the crystallite obtained. The permanence of the sulfate anion in the chemical composition of the zirconia is due to the higher binding energy with the Zr 4 + cation, thus it was observed a greater influence of that anion in the crystallization process. That allowed the formation of smaller crystallites and the stabilization of the tetragonal phase of the zirconia. In all of the cases, the analyses showed that the influence of the anions occurred by their segregation on the surface of the zirconia which, particularly in the case of the sulfate anion, tends to reduce the surface energy of the zirconium by increasing the specific surface area. It was also found that the sulfate anion can be removed from the surface of the zirconia by washing the powder in a basic medium. That procedure increased the specific surface area and it tends to improve its sinterability.

OBJETIVOS:1a etapa: validar teste de cisalhamento utilizando um novo dispositivo de padronização através da comparação dos valores de resistência de união (RU) entre a zircônia com dois tratamentos de superfície e um cimento resinoso, aos resultados obtidos com testes de cisalhamento convencional e microcisalhamento; 2a etapa: avaliar o efeito dos primers metálicos à base de MDP por meio da RU entre zircônia Y-TZP e diferentes tipos de cimentos resinosos (de ativação química, duais e auto-adesivo); 3a etapa: avaliar o efeito de dois lasers Nd:YAG e Er:YAG e do jateamento com óxido de alumínio (JAT) na superfície da zircônia Y-TZP antes da sua sinterização final e da abrasão triboquímica mais silano (controle positivo) após a sinterização final, por meio da resistência à flexão (RF), rugosidade superficial (RS) e RU; 4a etapa: avaliar a estabilidade da união entre a zircônia e um cimento resinoso com um primer à base de MDP e de um laser de alta potência após a termociclagem. Os tratamentos superficiais utilizados nesta etapa foram escolhidos com base nos resultados da 2a e 3a etapas. MATERIAL E MÉTODOS: para os testes de RU foram confeccionados corpos de prova de Y-TZP com dimensões 6x6x3mm, e para o teste de RF 2,5x4,5x20 mm. Para 1a etapa os tratamentos de superfície foram JAT+Signum Ziconia Bond (SZB Heraeus), abrasão triboquímica foi realizada Rocatec (ROC 3M Espe), o silano utilizado foi RelyX Ceramic Primer (3M Espe) e os cimentos resinosos: Panavia F (Kuraray), NX3 (Kerr), seT (SDI), Multilink (Ivoclair). Durante a 3a etapa a abrasão triboquímica foi realizada ROC, o laser Nd:YAG (Power Laser ST6, Lares Research - 1,2W, 10 Hz) e Er:YAG (Kavo Key II, KaVo Co. - 120 mJ, 6 Hz). O teste de cisalhamento com dispositivo de padronização foi o método de avaliação da RU utilizado para as 2a, 3a e 4a etapas. Os dados dos testes de RU, RG foram analisados pela ANOVA e Tukey (=0,05) e RF por Kruskall-Wallis (=0,05). RESULTADOS: 1a etapa: pelo teste de microcisalhamento os materiais se comportaram da seguinte forma: JAT+SZB>ROC>CO, sendo que para os outros dois testes de cisalhamento o seguinte ranqueamente foi obtido: JAT+SZB=ROC>CO. 2a etapa: o SZB apresentou maiores valores de RU para todos os cimentos quando comparados aos grupos controle. O ZP aumento os valores para o cimento Panavia F e NX3. Já o AP aumentou os valores para o cimento seT. 3a etapa: para o teste de RU o JAT e Er:YAG resultaram em valores similares ao ROC, sendo que Nd:YAG resultou em maiores valores comparado ao ROC. Quando avaliados por RS: Nd:YAG>Er:YAG>JAT>ROC; já para RF: ROC>JAT=Nd:YAG= Er:YAG. 4a etapa: Após o teste de cisalhamento os seguinte ranqueamento foi obtido: Nd:YAG 24h>Nd:YAG termociclado=SZB 24h>SZB termociclado. CONCLUSÕES: Uma vez que o teste de cisalhamento com dispositivo de padronização mostrou resultados similares ao teste de cisalhamento convencional pode ser um método viável para avaliação da RU. O tratamento com Nd:YAG antes da sinterização final se mostrou efetivo nos valores de RU. / OBJECTIVES: first stage: validate shear test using a new device for standardized by comparing the values of bond strength (BS) with conventional shear test and microshear test, between zirconia and a resin cement with two surface treatments. Second stage: evaluate the effect of metal primers based on MDP by BS between YTZP and different types of resin cements. Third stage: evaluate Y-TZP surface treatments effect of two lasers (Nd:YAG and Er:YAG) and two sandblasting procedures, with Al2O3 (JAT) before final sintering and tribochemical slicatization after the final sintering, through the flexural resistance (FR) surface roughness (SR) and BS. Fourth stage: evaluate the bonding stability between zirconia and resin cement using a MDP-based primer or a high power laser, after thermal cycling. MATERIAL AND METHODS: BS Y-TZP specimens were prepared with dimensions of 6x6x3mm, and for FS test with 2,5x4,5x20 mm. In the first stage the surface treatments of the specimens were JAT+ Signum Ziconia Bond (SZB - Heraeus), tibochemical silicatization using Rocatec (ROC - 3MEspe) and control (CO - without treatment). In the second stage the primers used were Alloy-Primer (AP - Kuraray), SZB, Z-Prime Plus (ZP - Bisco), and the resin cements: Panavia F (Kuraray), NX3 (Kerr), set (SDI), Multilink (Ivoclair). During the third stage the tribochemical silicatization was perfomed using ROC. The shear bond strength device standardized was used to evaluate the BS of second, third and fourth stage. Test data for BS, SR were analyzed by ANOVA and Tukey test ( = 0.05) and FS by Kruskall-Wallis test ( = 0.05). RESULTS: first Stage: the microshear test groups behave as follow: JAT+SZB> ROC>CO, and for the other two shear tests following the ranking were obtained: JAT+SZB=ROC>CO. Second stage: the SZB showed higher BS for all cements when compared to control groups. The ZP values increased for Panavia F and NX3. AP values increased only for the seT cement. Third stage: BS values for JAT and Er:YAG were similar to ROC, and Nd:YAG was higher compared to the ROC. When evaluated by SR: Nd:YAG> Er:YAG>JAT> ROC, while for FS: ROC> JAT = Nd:YAG = Er:YAG. Fourth stage: after the shear test the following ranking was obtained: Nd:YAG 24h> Nd:YAG thermocycled = SZB 24h> SZB thermocycled. CONCLUSIONS: shear bond strength test with standardized device showed similar result to the conventional shear bond strength, and it can be considered a viable method for evaluating the BS. Treatment with Nd:YAG before the final sintering was effective in BS.