OBJECTIVES: Evaluate the effect of different veneering techniques, Y-TZP core thicknesses, and firing cycles with different heat rates and holding times on the mechanical properties of veneering porcelain. MATERIALS AND METHODS: Biaxial flexural strength and Thermal shock resistance tests were conducted to evaluate the mechanical properties of veneer porcelain. Core material, Y-TZP and two porcelain veneers, IPS e.max Ceram and VITA VM9, were used in this study. Vita YZ zirconia blocks were sectioned and sintered to provide slabs of 1.65, 3.25, and 6.50mm in thickness. Two techniques were used to fabricate VITA VM9 and e.max Ceram porcelain veneer porcelain discs, Hand Layered, mixing powder with manufacturer’s molding liquid, condensed in a mold, and Pressed, pressing powder uniaxially in a mold. A layer of carbon paint was applied to the zirconia to allow removal of the porcelain discs. For thermal shock test the veneering porcelain fired on the Y-TZP core with a wash layer. After the veneer discs were fabricated, they were sintered: (1) According to the manufacturer’s instructions; (2) Two different cycles with slower heat rate and longer holding than the recommended value. Biaxial flexural strength was determined using a universal mechanical tester. Thermal shock tests were performed using a Pober thermal shock device. Statistical analysis was conducted for all tests using ANOVA and Tukey post hoc test at p= 0.05. RESULTS: There was significant effect from changes of YZ Core thickness, firing cycle, and veneer technique on the mechanical properties of porcelain veneer. The veneering technique had the largest impact on the mechanical properties of veneer porcelain followed by firing cycle, followed by YZ core thickness. In using different firing cycles with different heat rates and holding times, slowing the heating rate had more influence on the mechanical properties of veneer porcelain. In measuring the surface temperature of the Y-TZP/VITA VM9 assembly, the specimen surface temperature was coincidental with the furnace programmed firing cycle using a slower heating rate firing cycle. CONCLUSIONS Veneering technique, slower heat rate firing cycle, and Y-TZP core thickness have significant impact on veneering porcelain mechanical properties. / 2018-09-28T00:00:00Z

OBJECTIVES: Objectives of this study were to evaluate and compare the failure load and mode of failure of aged (4 years) monolithic and veneered Y-TZP and glass ceramic subjected to static loading, cyclic loading, and thermo-cycling. MATERIALS AND METHODS: 2 ceramic materials were used: Vita In-Ceram YZ and IPS e. max CAD. Each material was designed into 60 veneered copings and 30 monolithic crowns (180 specimens). 10 specimens per group were loaded under compression using an Instron universal testing machine at a rate of 0.5 mm/minute until fracture. Another 10 specimens were subjected to cyclic loading (chewing simulation) in a water bath for 50,000 cycles at a frequency of 1 Hz at 30% of the mean failure load, and then were loaded under compression to fracture. Another 10 specimens were subjected to a thermo-cycling test, then loaded under compression to fracture. Data were analyzed using the ANOVA test at α=0.05. RESULTS: The mean failure load (standard deviation) values for veneered zirconia and e.max CAD copings and monolithic zirconia and e.max CAD crowns under static loading were: In-Ceram YZ 14830 N (2494), VM9 2491 N (1047), PM9 3909 N (783), IPS e.max CAD 4197 N (1011), IPS e. max Ceram 1206 N (296), IPS e.max press 2949 N (710). The values for veneered standard zirconia and e.max CAD copings and monolithic zirconia and e.max CAD crowns after cyclic fatigue were: In-Ceram YZ 11039 N (2720), VM9 2849 N (840), PM9 3170 N (1156), IPS e.max CAD 3539 N (526), IPS e. max Ceram 1291 N (1051), IPS e.max press 3093 N (742). For veneered standard zirconia and e.max CAD copings and monolithic zirconia and e.max CAD crowns after thermo- cycling: In-Ceram YZ 15695 N (1517), VM9 3177 N (816), PM9 2860 N (783), IPS e.max CAD 4265 N (681), IPS e. max Ceram 1149 N (375), IPS e.max press 2832 N (717). There was a significant difference in failure load between veneered and monolithic ceramic crowns subjected to static loading, cyclic loading, and thermo-cycling, and a significant difference in the mode of failure between veneered or monolithic crowns. CONCLUSIONS: 1. There was a significant difference in the static failure load of different veneered (Hand layered and pressed-on) YTZP zirconia and e.max CAD copings, monolithic YTZP zirconia, and e.max CAD Crowns, (p < 0.05). 2. The highest static failure loads were shown by high strength monolithic (In-Ceram YZ) material, which were more resistant to cyclic loading compared to other veneered and monolithic systems. 3. The failure load of IPS e.max ceram group was significantly the lowest compared to all other groups. 4. The failure load data for IPS e.max CAD and Vita In-Ceram YZ structures revealed a significant difference in the effect of these structures on the failure loads (p < 0.05). Comparing structures, monolithic Vita In-Ceram YZ crowns showed the highest failure load. 5. There was a significant difference in failure mode among various veneered and monolithic systems (p < 0.05). Only the variable treatment had no impact on the mode of failure of various veneered and monolithic systems (p > 0.05). / 2020-10-24T00:00:00Z

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-08-17T13:19:35Z No. of bitstreams: 1 CARLOS EDUARDO PEREIRA - TESE (PPGEQ) 2017.pdf: 6340687 bytes, checksum: a5c8d06008238c03161add19b46e0a44 (MD5) / Made available in DSpace on 2018-08-17T13:19:35Z (GMT). No. of bitstreams: 1 CARLOS EDUARDO PEREIRA - TESE (PPGEQ) 2017.pdf: 6340687 bytes, checksum: a5c8d06008238c03161add19b46e0a44 (MD5) Previous issue date: 2017-08-02 / A peneira molecular MCM-41 é considerada promissora como suporte para os óxidos metálicos em processo de refino de petróleo, adsorventes e catalisadores. Os catalisadores heterogêneos apresentam grande potencial de viabilizar a produção de biodiesel através da reação de transesterificação. A síntese da peneira molecular MCM-41 foi realizada a partir da água deionizada, brometo de cetiltrimetilamônio, hidróxido de amônio, etanol e ortossilicato de tetraetila. O óxido de zircônia foi obtido pelo método sol-gel a partir do oxicloreto de zircônio com hidróxido de amônio à temperatura ambiente e ativado por calcinação a 550 e 700°C. Em seguida o óxido de zircônia ativado foi sulfatado, seco e calcinado a 400 °C. A zircônia sulfatada foi incorporada a peneira molecular MCM-41 por impregnação via úmida, com diferentes proporções mássicas (10, 20, 30, 40, 50%). Verifica-se que a partir das análises de difração de raio X a formação da peneira molecular MCM-41 confirmou a estrutura hexagonal e a fase mesoporosa. Observou-se formação das fases, tetragonal e monoclínica do óxido de zircônia. Através da espectroscopia de absorção na região do infravermelho com transformada de Fourier foi possível detectar picos referentes a presença de íons sulfatos bidentados ligado a superfície da zircônia. As propriedades texturais apresentaram estruturas com poros bimodais após o processo de incorporação da zircônia sulfatada. As micrografias do óxido de zircônia ativadas a 550 e 700 °C apresentaram tricas em sua superfície antes e após de incorporação da zircônia sulfatada. O potencial catalítico foi avaliado na reação transesterificação do óleo de soja por rota metílica. O catalisador com óxido de zircônia ativado a 700 °C e sulfatado e incorporado a peneira molecular com 40% (em peso) apresentou maior conversão de ésteres metílicos 83,8%. No entanto, esta conversão não especifica o óleo obtido como biodiesel de acordo com a norma da Agência Nacional de Petróleo, Gás Natural e Combustíveis. Assim como o índice de acidez. Porém os resultados de densidade e viscosidade estão de acordo com a especificação estabelecida pelas normas. / The MCM-41 molecular sieve is considered promising as a support for the petroleum refining metal oxides, adsorbents and catalysts. Heterogeneous catalysts have great potential to make viable the production of biodiesel through the transesterification reaction. The synthesis of the MCM-41 molecular sieve was performed from deionized water, cetyltrimethylammonium bromide (CTABr), ammonium hydroxide (NH4OH), ethanol and tetraethyl orthosilicate (TEOS). The zirconium oxide was obtained by the sol-gel method from zirconium oxychloride with ammonium hydroxide at room temperature, the material was activated at 550 and 700 °C, and thereafter, sulphated. The material was then activated using the calcination process at 550 and 700 ° C and sulfated. The sulfation process was carried out with a 0.5 mol.L-1 sulfuric acid solution and allowed to stand for 30 minutes, dried for 12 h at 120 ° C and calcined at 400 ° C. The process of incorporation of ZS into the MCM-41 molecular sieve was done using different mass proportions (10, 20, 30, 40 and 50%) in relation to the mass of the MCM-41 molecular sieve, by wet method. It was verified from the analyzes of X-ray diffraction, the adsorption of nitrogen (BET method) and Fourier transform infrared spectroscopy (FTIR) the crystalline and textural properties which confirmed the molecular sieve obtainment and the presence of the tetragonal and monoclinic phases of the sulfated zirconia in the mesoporous structure. The micrographs of activated zirconium oxide at 550 and 700 °C and sulphated showed dispersed particles with the presence of cracks on its surface, after the incorporation there were no modifications in the structure. The catalytic activity was evaluated by the transesterification reaction of the soybean oil via the methyl route, using all the catalysts which were synthesized. The results showed that the catalyst 50_ZS/MCM-41_550 °C showed a greater conversion of methyl esters of 81.4% with the predominant tetragonal phase. The catalyst with the zirconium oxide activated at 700 °C obtained a conversion of 83.8% to the 40_ZS/MCM-41_700 °C catalyst, with the predominant monoclinic phase. However, the ester content of the oil samples was below the value established by the National Agency of Petroleum, Natural Gas and Fuels (ANP). The density and kinematic viscosity of the catalysts under study X_ZS/MCM-41 were in the range of the established standard. The acidity index was above the specified values, confirmed by the high percentage of free fatty acids in the oil.

Ceramics have been widely used for personnel and vehicle armour because of their desirable properties such as high hardness and low density. However the brittle nature associated with the ceramic materials, i.e. low toughness, reduces their ability to withstand multiple ballistic hits. The present work is focused on ceramic armour materials made from alumina and zirconia toughened alumina (ZTA). The effects of grain size and zirconia phase transformation toughening on the mechanical and high strain rate properties in both materials were investigated in detail. Alumina, 10%, 15% and 20% nano ZTA with 1.5 mol% yttria stabiliser were produced with various grain sizes. The processing of the materials started from suspension preparation, spray freeze drying of the suspension and die pressing to produce homogeneous green bodies with densities above 54%. Then, the green bodies were sintered using conventional single stage and/or two stage sintering to produce the samples with full density and a range of grain sizes (0.5 to 1.5 µm alumina grains and 60 to 300 nm zirconia grains). The effects of the processing conditions on the microstructures were studied and the optimum processing route for each sample was determined. The mechanical properties of the alumina and ZTA samples were investigated, including Vickers hardness, indentation toughness, 4-point bend strength and wear resistance. The results showed that, with an increasing amount of zirconia addition, evident increases of the toughness, strength and wear resistance properties were observed, whilst the hardness reduced slightly correspondingly. The effect of density and grain sizes on the hardness and toughness were studied as well: larger alumina grain size led to a higher hardness and negligible change in toughness, whilst the zirconia grain coarsening enhanced the phase transformation toughening effect and the samples displayed a higher toughness. In addition to the investigation of the mechanical properties, the alumina and nano ZTA samples were subjected to high strain rate testing, including split Hopkinson pressure bar (SHPB) (8-16 m/s) and gas gun impact testing (100-150 m/s). The high strain rate performances were compared in terms of their fracture behaviours, fragmentation process and fragment size distribution. Raman spectroscopy was used to measure the amount of zirconia phase transformation in ZTA samples after the high strain rate testing. The residual stress and dislocation density in alumina grains after testing were quantitatively measured using Cr3+ fluorescence spectroscopy. The results indicated that zirconia phase transformation can reduce the residual stress and dislocation densities in the ZTA samples, resulting in less damage, lower plastic deformation and less crack propagation. In addition, a nano zirconia material with 1.5 mol% yttria stabiliser (1.5YSZ) was subjected to a gas gun impact test with a very high impact speed (142 m/s); a deep projectile penetration was observed, due to the low hardness of the pure zirconia, whilst the sample stayed intact. The result further confirmed that the zirconia phase transformation toughening effect can improve the sample's high strain rate performance.

Aim: To evaluate the effect of different Ti-base abutment heights and cement type on the pullout retention of zirconia-based restorations. Methods: Identical crowns were designed in a CAD software to fit two different Tibase abutment heights, as follows (n=10/group): (i) 4-mm-height Ti-base abutment (Tall), and (ii) 2.5-mm-height Ti-base abutment (Short). Four cement types were selected: (i) Temporary cement (Provisional); (ii) Glass-ionomer cement (Meron); (iii) self-adhesive resin cement (U200), and (iv) conventional resin cement (Ultimate) with universal adhesive for treatment of titanium and zirconia substrates. Pull-out testing was performed in a universal testing machine. Data were statistically evaluated through two-way analysis of variance following post-hoc comparisons by Tukey test. Results: Tall Ti-base abutments demonstrated similar retention to short abutments when data is collapsed over cement (p>0.74). Data evaluation as a function of cement type demonstrated the superiority of resin-based cements relative to provisional and glass-ionomer groups (p<0.01). Retentiveness data as a function of both factors demonstrated similar force to dislodgment between tall and short abutments for all within cement comparisons (p>0.42), except for U200 (p=0.032). Also, tall abutments cemented with Ultimate evidenced higher pull out values than U200 (p=0.043), and both were significantly more retentive than tall provisional and meron (p<0.001). No significant difference was observed between U200 and Ultimate cements for short abutments (p=0.758), and both presented statistically higher pullout values than provisional and glass-ionomer (p=0.001). Conclusions: While Ti-base abutment height have not influenced zirconia superstructure retentiveness, resin-based cements significantly evidenced higher retention than glass ionomer and temporary cements. / Objetivo: Avaliar o efeito de diferentes alturas de interface de Titânio (Ti) e diferentes tipos de cimento na retenção de coroas de zircônia. Métodos: Coroas idênticas foram projetadas em um software de CAD capaz de adaptar duas alturas diferentes do pilar de interface de Ti: cada grupo foi composto de 10 amostras conforme se segue: (i) interface de Ti de 4 mm de altura (alto) e (ii) interface de 2,5 mm de altura (curto). Foram selecionados quatro tipos de cimento: (i) cimento temporário (Provisional); (ii) Cimento de ionômero de vidro (Meron); (iii) cimento resinoso auto-adesivo (U200) e (iv) cimento resinoso convencional (Ultimate) com adesivo universal para tratamento de substratos de titânio e zircônia. O teste de tração foi realizado em uma máquina de ensaio universal. Os dados foram avaliados estatisticamente através de análise de variância a dois critérios, após comparações pós-hoc pelo teste de Tukey. Resultados: As interfaces de Ti demonstraram retenção semelhante aos pilares curtos quando os dados foram colapsados sobre o cimento (p> 0,74). A avaliação dos dados em função do tipo de cimento demonstrou a superioridade dos cimentos à base de resina em relação aos grupos de cimentos temporário e de ionômero de vidro (p <0,01). Os dados de retenção em função de ambos os fatores demonstraram força semelhante ao deslocamento, entre pilares altos e curtos, para todos dentro das comparações de cimento (p> 0,42), exceto para U200 (p = 0,032). Além disso, os pilares altos cimentados com Ultimate evidenciaram maiores valores de tração do que os cimentados com U200 (p = 0,043), e ambos foram significativamente mais retentivos do que o pilar alto cimentado com cimento Provisional e o Meron (p <0,001). Não foi observada diferença significativa entre os cimentos U200 e Ultimate para pilares curtos (p = 0,758) e ambos apresentaram valores de tração estatisticamente mais elevados que os cimentos de ionômero de vidro e cimento temporário (p = 0,001). Conclusões: Embora a altura da interface de Ti não tenha influenciado a retenção das coroas de zircônia, os cimentos resinosos resultaram em maior retenção do que o ionômero de vidro e cimentos temporários.

Ce mémoire présente la synthèse et la caractérisation du matériau composite Ce-TZP/Al2O3 et l’étude de ce matériau dans une mise en forme par impression 3D de type stéréolithographie (SLA). Le matériau Ce-TZP présente une résistance au vieillissement en milieu aqueux (par transformation martensitique de la phase tétragonale vers la phase monoclinique) accrue en comparaison à Y-TZP. L’ajout d’alumine (Al2O3) comme seconde phase confère au matériau des propriétés mécaniques (résistance à la flexion en particulier) similaires à Y-TZP. La mise en forme par SLA offre la possibilité de fabriquer des objets avec des structures complexes tout en limitant l’utilisation et la perte de matière en comparaison à la fabrication soustractive, bien connue dans le domaine dentaire.Le composite Ce-TZP/Al2O3 a été synthétisé à partir d’une poudre Ce-TZP à laquelle est ajoutée de l’Al2O3 selon deux protocoles : la méthode Pechini modifiée et la méthode Isopropoxyde. Les études dilatométriques et microstructurales des composites ont montré que le matériau obtenu selon la méthode Isopropoxyde était plus homogène. Cette synthèse a donc été sélectionnée pour réaliser l’étude du frittage. Les conditions optimales résultants de cette étude (rampe de 300 °C/h, T°palier de 1500 °C pendant 1h, air), permettent d’atteindre une densité relative de l’ordre de 98% avec une taille de grains submicronique pour les deux phases.Des formulations photoréticulables sous exposition UV, chargées avec ce composite ainsi qu’avec le matériau de référence Y-TZP, ont été développées et étudiées afin de pouvoir mettre en forme ces matériaux par SLA. Avant utilisation dans le procédé, les formulations ont été caractérisées d’un point de vue rhéologique, thermique et également d’un point de vue de la réactivité sous exposition UV. Ces caractérisations ont permis de déterminer l’influence de la nature et de la taille des particules sur la réactivité principalement, paramètre également gouvernée par la composition des résines et notamment par le système amorceur, composé de un ou plusieurs photoinitiateur(s). Pour finir, les pièces fabriquées par SLA ont été frittées et caractérisées d’un point de vue mécanique et microstructural. / This thesis presents the synthesis and characterization of Ce-TZP/Al2O3 composite material and the study of this material in stereolithography process (SLA). Ce-TZP material exhibits an enhanced resistance to low temperature degradation (materialized by the tetragonal/monoclinic phase transformation) compared to Y-TZP. The addition of alumina (Al2O3) as a second phase gives to the material mechanical properties (especially flexural strength) similar to Y-TZP. SLA shaping offers the ability to make objects with complex structures while limiting the use and loss of material compared to subtractive manufacturing, well known in the dental field.The Ce-TZP/Al2O3 composite was synthesized from a Ce-TZP powder mixed with Al2O3 added according to two protocols: the modified Pechini method and the Isopropoxide method. The dilatometric and microstructural studies of the composites have showed that the material obtained by the Isopropoxide method was more homogeneous. This synthesis was therefore selected to carry out the sintering study. The optimal conditions resulting from this study (heating rate of 300 °C/h, T°soak of 1500 °C for 1h, air) allow to reach a relative density of 98 % with a submicron grain size for the two phases.Photocurable under UV exposure formulations, loaded with this composite as well as with the reference material Y-TZP, have been developed and studied in order to be able to shape these materials by SLA. Prior to use in the process, the formulations were characterized from a rheological, thermal and also from a viewpoint of reactivity under UV exposure. These characterizations made it possible to determine the influence of the nature and the size of the particles on the reactivity mainly, also governed by the composition of the resins and in particular by the initiator system, composed of one or more photoinitiator(s). Finally, the parts manufactured by SLA were sintered and characterized from a mechanical and microstructural point of view.

Os revestimentos poliméricos podem atuar como uma barreira física entre os íons agressivos e o substrato metálico. Porém, uma exposição prolongada pode causar danos ao revestimento polimérico, conduzir a uma redução contínua do efeito barreira e por consequência a perda da proteção contra a corrosão. A utilização de nano materiais pode atuar aumentando o efeito barreira, proporcionando um aumento no caminho de difusão dos íons agressivos e água até o substrato metálico. Nanopartículas de celulose apresentam elevada cristalinidade e razão de aspecto, excelentes propriedades mecânicas e são proveniente de fonte renovável. Por outro lado, a polianilina (PAni) vem sendo utilizada em revestimentos devido a elevação do potencial de corrosão dos aços devido o seu comportamento redox que proporciona a formação de uma camada de óxidos estável no substrato metálico. A aderência do revestimento polimérico é fundamental para que este possa atuar como revestimento protetor contra a corrosão. Com isso, um pré-tratamento superficial a base de ácido hexafluorzircônico e a utilização de organosilanos na resina epóxi, podem ser utilizados melhorando as propriedades de proteção contra a corrosão e de aderência. O objetivo deste estudo consistiu na obtenção de nanowhiskers de celulose (CNW) por moagem ultrafina através da celulose microcristalina (MCC) para posterior utilização em revestimento polimérico a base de resina epóxi. A CNW foi utilizada funcionalizada ou não com PAni SE (polianilina na forma condutora – sal de esmeraldina) em comparação a MCC nas mesmas condições. Foi avaliada a incorporação de silano aminopropiltrietoxisilano (APS) na resina epóxi e a utilização de uma camada de conversão de zircônia (Zr) aplicada ao substrato metálico. Os revestimentos poliméricos foram avaliados quanto a propriedades mecânicas e à proteção contra a corrosão. As imagens da microscopia de transmissão (TEM) mostram que é possível a obtenção da CNW por meio do processo de moagem, apresentando melhor estabilidade térmica em comparação a MCC. Os revestimentos poliméricos utilizando o silano APS e a camada de conversão de Zr apresentaram as melhores propriedades físicas e mecânicas. A interação entre a carga de reforço, a resina epóxi e a superfície metálica é um fator determinante na eficiência do revestimento polimérico, pois de acordo com a análise de migração subcutânea, a superfície do aço carbono, após 1000 h de exposição, não apresentou corrosão superficial. Com relação à proteção contra a corrosão, quando incorporado a CNW funcionalizada com PAni SE ao revestimento epóxi com APS e a camada de Zr, este apresentou os melhores resultados como constatado nas análises de névoa salina e espectroscopia de impedância eletroquímica (EIS). / Polymeric coatings can act as a physical barrier between the aggressive ions and the metal substrate. However, prolonged exposure can cause damage to the polymer coating and conduct to a continuous reduction in the barrier effect and result in the loss of protection against corrosion. The use of nanomaterials may act by increasing the barrier effect and providing an increased diffusion path of aggressive ions and water to the metal substrate. Cellulose nanoparticles have high crystallinity and aspect ratio, excellent mechanical properties and are derived from renewable sources. On the other hand polyaniline (PAni) has been used in coatings due to the increase of the corrosion potential of the steel due to redox behavior that results in the formation of a stable oxide layer on the metallic substrate. The adhesion of the polymeric coating is essential so that it can act as a protective coating against corrosion. With this, a superficial pre-treatment based on hexafluorzircônico acid and the use of organosilanes in the epoxy resin, can be used to improve the protection against corrosion properties and adhesion. The objective of this study was to obtain cellulose nanowhiskers (CNW) for ultrafine grinding through microcrystalline cellulose (MCC) for subsequent use in the polymer coating based on epoxy resin. The CNW was used functionalized or not with PAni SE (polyaniline in the conductive form - emeraldine salt) compared with MCC under the same conditions. The incorporation of silane aminopropyltriethoxysilane (APS) was evaluated in the epoxy resin and the use of a zirconia conversion layer (Zr) applied to the metal substrate. The polymeric coatings were evaluated for mechanical properties and corrosion protection. Transmission microscopy (TEM) show that obtaining the CNW through the ultrafine grinding process is possible, resulting in better thermal stability compared with MCC. Polymeric coatings using APS silane and Zr conversion coating had the best physical and mechanical properties. The interaction between the reinforcing filler, the epoxy resin and the metal surface is a determining factor in the efficiency of the polymeric coating, because according to the subcutaneous migration analysis, carbon steel surface after 1000 h of exposure, showed no corrosion superficial. With regard to protection against corrosion, when incorporated CNW functionalized with PAni SE to epoxy coating with APS and the Zr layer, showed the best results as found in salt spray tests and electrochemical impedance spectroscopy (EIS).

Electrophoretic deposition (EPD) has been used to produce the yttria-stabilized zirconia (YSZ) coatings on metal substrates. Sintering of YSZ with and without doping has been carried out at 1150 °C for 2hrs. The properties of these coatings have been examined in light of thermal barrier applications. For EPD, the green density increases with an initial increase in the HCl concentration and the EPD time. This suggests that particle packing was influenced by a time dependent re-arrangement, in addition to the initial suspension dispersion state. The green density peaks at a electrical conductivity of around 10×10-4 S/m achieved by an 0.5 mM HCl addition for the 20 g/l suspensions with the EPD time of around 8 ~10 minute. For sintered coatings, the HCl concentration had a marked effect on the neck size to grain size ratio of the 8 mol% yttria-stabilized zirconia (8YSZ) coatings. The presence of ZrCl4 and ZrOCl2, and a high concentration of oxygen vacancies at the grain boundaries are believed to promote neck growth in the early stage of sintering at 1150 °C. During sintering of 3 mol% and 8 mol% yttria-stabilized zirconia (3YSZ and 8YSZ) at 1150 ºC for 2hrs, the densification rate substantially increased with a small amount of Fe2O3 addition (0.5 mol%) to the 3YSZ/8YSZ deposits. A more pronounced graingrowth was present in the Fe2O3 doped 8YSZ deposits. The increased Zr4+ diffusion coefficient is mainly responsible to the rapid densification rate of the Fe2O3 doped 3YSZ/8YSZ deposits. A small grain growth observed in the Fe2O3 doped 3YSZ deposits is attributed to the Fe3+ segregation at grain boundary. A small amount of CeO2 doping was found to substantially inhibit the densification rate of the doped 3YSZ deposits with a minor grain growth. Fe2O3 doping reduced the thermal conductivities of 3YSZ/8YSZ. It is found that Rayleigh-type phonon scattering due to the mass difference alone is inadequate to explain the thermal conductivity of Fe2O3 doped YSZ systems. The lattice strain effects due to the ionic radius difference could more effectively reduce thermal conductivity of the Fe2O3-doped 3YSZ. A decrease in the growth rate of the TGO scale with the increasing Fe2O3 additions was observed for the oxidized FeCrAlY metal substrates with the Fe2O3-doped 3YSZ coating, which was found to be attributed to the early formation of the stable and dense α-Al2O3 phase due to the presence of Fe3+ ions.

Les maladies neurodégénératives sont en forte progression dans nos sociétés, mais elles sont également mieux connues et mieux soignées. Par exemple, la stimulation cérébrale profonde est de nos jours utilisée pour lutter contre des maladies comme la maladie de Parkinson. Pour cela, un boitier semblable à celui d'un pacemaker, placé sous la clavicule, est habituellement utilisé pour délivrer des impulsions électriques dans des zones spécifiques du cerveau grâce à des électrodes. Afin d'éviter certaines complications, un boitier ultrafin a été imaginé. Il peut être placé directement au niveau du crâne, au plus proche de la zone à traiter. Les matériaux composant ce boitier doivent présenter certaines caractéristiques. Nous avons choisi de travailler avec des feuilles de TA6V et de zircone yttriée et avons réalisé un assemblage hermétique par l'obtention d'une brasure fine en Ti2Ni.Les feuilles de zircone yttriée présentent des propriétés remarquables mais elles sont notoirement dégradées par un vieillissement hydrothermal. Une étude en vieillissement accéléré a été réalisée sur les feuilles de zircone telles que reçues mais également dans des conditions proches de l'utilisation. Le vieillissement mesuré est suffisamment limité pour envisager une utilisation in vivo, avec cependant une réserve concernant les zircones sous-stœchiométriques. Enfin, le profil de vieillissement et sa vitesse de progression ont pu être précisés.L'assemblage TA6V-zircone a été réalisé par brasage réactif in situ via l'apport initial en nickel pur et la création d'un joint de brasage en Ti2Ni. Le système TA6V-Ni-ZrO2 met en jeu plusieurs phénomènes, que nous avons cherché à déconvoluer : diffusion (solide et liquide), formation et croissance d'intermétalliques et réactions d'oxydo-réduction. La croissance des intermétalliques à partir du couple TA6V-Ni a été particulièrement étudiée. Cela a permis de relier certains événements à la température et de préciser les vitesses de croissance du Ti2Ni (selon son état physique). Grâce à l'ensemble des résultats, un procédé de brasage métal-céramique adapté aux matériaux ultrafins a été d'identifié et réalisé sur système avec succès. / Neurodegenerative diseases are increasingly present in our society but they are also better known and treated. For example, deep brain stimulation is nowadays used to treat diseases such as Parkinson disease. For this purpose, a pacemaker-like device localized in the infraclavicular region is commonly used to deliver electrical pulses in concerned area of the brain thanks to electrodes. In order to avoid some complications, an ultrathin housing was designed. It could be directly implanted under the scalp, close to the area to be treated. Materials of the housing have to be display some features. TA6V, yttria-stabilized zirconia sheets and a hermetic brazing with a Ti2Ni joint were selected to develop this housing.Yttria-stabilized zirconia sheets have remarkable properties but they undergo a degradation caused by hydrothermal aging. An accelerated aging study was done on pristine sheets but also under near-reality conditions. The observed aging is sufficiently limited to consider an in vivo application, subject to one reservation for the under-stoichiometric zirconia. Finally, the aging profile and the propagation rate were specified.The TA6V-zirconia joining was obtained by an in situ reactive brazing, thanks to a filler metal in pure nickel and the formation of a Ti2Ni joint. Several phenomena occur in the TA6V-Ni-ZrO2 system, which were separately studied: (solid and liquid) diffusion, formation and growth of intermetallic compounds and redox reactions. The intermetallic compounds growth from the TA6V-Ni couple was studied in detail. Thanks to all of the results, a metal-ceramic brazing process for ultrathin materials was identified and successfully achieved on our system.

Submitted by Maria Medeiros (maria.dilva1@ufcg.edu.br) on 2018-06-21T13:47:08Z No. of bitstreams: 1 VALÉRIA VITAL CORDEIRO - TESE (PPGCEMat) 2015.pdf: 2501691 bytes, checksum: b4f2ef7029d9c18c87c96cc0bbba39e8 (MD5) / Made available in DSpace on 2018-06-21T13:47:08Z (GMT). No. of bitstreams: 1 VALÉRIA VITAL CORDEIRO - TESE (PPGCEMat) 2015.pdf: 2501691 bytes, checksum: b4f2ef7029d9c18c87c96cc0bbba39e8 (MD5) Previous issue date: 2015-02-27 / CNPq / As indicações das cerâmicas odontológicas se devem as propriedades estéticas. O sistema CAD/CAM permite realizar restaurações cerâmicas, gerando uma elevada quantidade de resíduos, na forma de pó, durante o desbaste e fresa da peça cerâmica, que atualmente é descartado. Este trabalho tem por objetivo estudar o reaproveitamento dos resíduos de zircônia obtidos através do sistema CAD/CAM visando sua aplicação em prótese odontológica. Foi estudado o resíduo proveniente da fresagem de blocos comerciais de zircônia estabilizada com 3% de ítria (3Y-TZP), (sistema Zirkonzahn®), o resíduo caracterizado através da determinação da composição química, difração de raios X, determinação de tamanho de partículas e análise térmica diferencial/gravimétrica. O resíduo beneficiado seguiu duas rotas: desaglomeração em moinho de bolas e sem desaglomeração. Ambos os materiais foram utilizados para confecção de corpos de prova de zircônia queimados a 1180oC em seguida infiltrou-se o vidro de lantânio a 1140oC, os corpos para densificação e os corpos confeccionados extraídos das placas comerciais (Zirkonzahn®) foram queimados em temperaturas de 1300, 1400 e 1500oC após sinterização caracterizados com a determinação da porosidade aparente, microscopia eletrônica de varredura, resistência à flexão em três pontos e microdureza Vickers. Observou-se nos resultados que o resíduo é constituído por zircônia estabilizada com 3% de ítria (3Y-TZP) e matéria orgânica. A desaglomeração diminui o tamanho dos agregados e favoreceu o processo de sinterização, os corpos infiltrados não apresentam resistência adequada para infraestruturas, os corpos sinterizados a 1500oC apresentaram porosidade próxima da obtida pelos corpos de referência. A resistência e a microdureza dos corpos do resíduo atingiram o valor máximo de 1079 HV para os corpos com zircônia não desaglomerada (ZSD) e de 1523 HV para os corpos com zircônia desaglomerada (ZCD), após queima a 1500oC. / The use of ceramics in dental prosthesis is due to the aesthetic properties. The CAD/CAM system allows making ceramic restorations, generating a large amount of waste, in powder form, during the roughing and milling cutter of the ceramic piece, which currently is thrown away. The aim of this work is to study the reuse of the waste obtained from zirconia CAD/CAM system for its application in dental prosthesis. It was studied the residue from the milling of commercial stabilized zirconia blocks with 3% of yttria (3Y-TZP). The residue was characterized by chemical composition, X-ray diffraction, particle size and differential and gravimetric thermal analysis. The improvement residue followed two routes: deagglomeration in a ball mill and without deagglomeration. Both materials were used for preparation of specimens of zirconia. It were sintered at 1180oC then infiltrated with lanthanum glass at 1140oC. The infiltrated specimens and the specimens extracted from the commercial blocks (Zirkonzahn ®) were sintered at temperatures of 1300, 1400 and 1500oC.After sintering its were characterized by apparent porosity, scanning electron microscopy, flexural strength in three points and Vickers micro hardness. It was observed in the results that the residue consists of stabilized zirconia with 3% yttria (3Y-TZP) and organic matter. The deagglomeration decreases the size of the aggregates and favored the sintering process. The infiltrated specimens do not have adequate resistance to infrastructures, the sintered bodies to 1500oC presented close porosity obtained by the scanbodies. Resistance and micro hardness of bodies of waste reached the maximum value of 1079 HV for the bodies with no deagglomeration zirconia (ZSD) and 1523 HV for the bodies with zirconia desaglomerada (ZCD), after burning the 1500oC.