Orientador: Renata Garcia Fonseca / Banca: Gelson Luis Adabo / Banca: Paulo Henrique dos Santos / Resumo: Apesar das restaurações em cerâmicas Y-TZP (Yttria tetragonal zirconia polycrystal) estarem sendo cada vez mais utilizadas na prática clínica devido às suas excelentes propriedades, tratamentos de superfície ainda são necessários para a melhoria de sua adesão com cimentos resinosos. Este estudo avaliou a influência da partícula e do momento do jateamento na caracterização superficial de uma cerâmica Y-TZP e na sua resistência de união com cimento resinoso. Espécimes de zircônia foram submetidos aos seguintes tratamentos com jateamento: partículas de Al2O3 de 50 μm; partículas de Al2O3 de 120 μm; partículas de Al2O3 de 30 μm modificadas por sílica (Rocatec Soft); e partículas de Al2O3 de 110 μm modificadas por sílica (Rocatec Plus). O jateamento foi realizado em três momentos diferentes: após a sinterização da zircônia (PÓS) (grupo controle); antes da sinterização da zircônia (PRÉ); e antes/após a sinterização (PP). A caracterização da superfície da zircônia incluindo rugosidade superficial (n=10), molhamento (n=10), microscopia eletrônica de varredura (n=2) e composição elementar (n=2) foi realizada. O teste de resistência de união ao cisalhamento (RC) (n=11) foi conduzido após a termociclagem dos espécimes (10000 ciclos - 5°C e 55°C). O modo de fratura foi analisado através de um estereomicroscópio (x 20). Rugosidade, molhamento e RC foram analisados através da ANOVA dois fatores e o teste de Tukey (α=,05). Nos grupos PRÉ e PP, a rugosidade aumentou de acordo com o tamanho da partícula. Independentemente da partícula, o grupo PÓS apresentou os menores valores de rugosidade, enquanto os grupos PRÉ e PP não apresentaram diferença significativa entre eles. De uma maneira geral, as partículas de Al2O3 de 120 μm e Rocatec Plus apresentaram os maiores e menores ângulos de contato. Com relação à partícula, os grupos PRÉ e PP exibiram o maior e o menor ângulo de contato... / Abstract: Despite Y-TZP (yttria tetragonal zirconia polycrystal) ceramic restorations became widely used in clinical practice due to its excellent properties, surface treatments are required for the improvement of the adhesion with resin cements. This study evaluated the influence of the particle and air abrasion moment on the surface characterization of a Y-TZP ceramic and its bond strength with a resin cement. Zirconia specimens were air-abraded with the following particles: 50 μm Al2O3 particles; 120 μm Al2O3 particles; 30 μm silica-coated Al2O3 particles (Rocatec Soft); and 110 μm silica-coated Al2O3 particles (Rocatec Plus). Air-abrasion was performed in 3 different moments: after zirconia sintering (AS)(control group); before zirconia sintering (BS); before and after zirconia sintering (BAS). The zirconia surface characterization including roughness (n=10), wettability (n=10), morphology (n=2) and elemental composition (n=2) was performed. The SBS test (n=11) was conducted after thermal cycling (10,000 cycles - 5ºC and 55ºC). Failure mode was determined with a stereomicroscope (×20). Roughness, wettability and SBS data were analyzed by two-way ANOVA and Tukey's test (α=.05). For BS and BAS, the roughness increased according to the increase in the particle size. AS showed the lowest roughness, while BS and BAS did not exhibit significant difference each other. In general, Rocatec Plus and 120 μm Al2O3 particles provided the lowest and the highest contact angle. BS and BAS exhibited the highest and the lowest contact angle. The particle as well as the air-abrasion moment did not promote regular morphological patterns. The additional presence of the Si element in the groups abraded with silica-modified Al2O3 particles was the only difference observed between these groups and those abraded with Al2O3 particles. For BS, the highest and the lowest SBS was provided by 120 μm Al2O3 particles and Rocatec Soft. For BAS and AS, the highest SBS... / Mestre

Orientador: Luiz Felipe Valandro / Co-orientador: Paulo Francisco Cesar / Banca: Marco Antonio Bottino / Banca: Renata Marques de Melo Marinho / Banca: Estevam Augusto Bonfante / Banca: Nelson Renato França Alves da Silva / Resumo: O objetivo deste trabalho é avaliar o efeito de dois diferentes métodos de deposição de sílica na superfície de uma cerâmica a base de zircônia estabilizada por ítria na adesão a um cimento resinoso e no limite de fadiga do material. A hipótese testada é que ambos os tratamentos de superfície promoverão aumento da adesão entre zircônia e cimento resinoso, e de que a adição de uma camada de sílica reduzirá a resistência à flexão biaxial de discos Y-TZP, antes e após ciclagem mecânica; já o jateamento aumentará a resistência da cerâmica nas duas condições, seguindo o mesmo padrão para o limite de fadiga. Para o teste de adesão, 45 barras receberam um dos seguintes tratamentos de superfície (n = 15): controle: grupo controle, sem tratamento adicional após sinterização; silicatização: jateamento com partículas de SiO2 30 μm (Rocatec Soft, 3M ESPE); glaze: aplicação de uma única camada de vidro amorfo (Glaze Vita Akzent - Vita Zanhfabrik) e condicionamento com HF por 1 min. As amostras foram cimentadas (cimentação resinosa) à secções de cerâmica de dissilicato de lítio e, após 2500 ciclos térmicos, o teste de resistência adesiva à tração foi executado. Para avaliação das propriedades mecânicas, corpos de prova em forma de disco da cerâmica VITA In-Ceram 2000 YZ cubes for InLab foram confeccionados de acordo com as normas do ensaio de flexão biaxial. Os tratamentos de superfície avaliados são: controle; silicatização; e Glaze/HF. Os corpos de prova foram submetidos a flexão biaxial antes e após ciclagem mecânica (2 x 106 ciclos, 100 N, biaxial, imersão em água 37 ºC, 4 Hz). O método de escada foi utilizado para determinação do limite de fadiga dos corpos de prova, com 102, 103, 104 e 105 ciclos. A resistência adesiva foi maior para o grupo silicatização, seguido pelo grupo Glaze/HF e por ultimo o grupo controle, o qual não resistiu à ciclagem térmica. A ciclagem mecânica.. / Abstract: The aim of this study is to evaluate the effect of different silica deposition methods on the surface of a zirconia ceramic on the adhesion to a resin cement and on the fatigue limit of the materials. The tested hypothesis is that surface treatments enhance the adhesion of resin cement to zirconia, and that the application of a silica layer reduces the flexural strength of zirconia discs, before and after mechanical cycling, and that air abrasion enhance the strength in both situations, following this patter also to fatigue limits. For the adhesive test, 45 bars received the following surface treatments (n = 15): control: without surface treatment after sintering; air-abrasion: 30 μm SiO2 particles (Rocated Soft, 3M ESPE); glaze: application of a thin layer of glaze (Glaze Vita Akzent - Vita Zanhfabrik), HF etching during 1 min plus silane. Samples were resin cemented to lithium dissilicate slices, and after 2,500 cycles of thermocycling, the tensile test was performed. Disc-shaped specimens were used for the evaluation of mechanical properties. The same surface treatments were performed on the tensile side of the samples. Specimens were submitted to biaxial flexural strength before and after mechanical cycling (2 x 106 cycles, 100 N, water immersion 37 ºC, 4 Hz). Stair case method was used to determine the fatigue limit of samples at 102, 103, 104 and 105 cycles. Adhesive strength was higher for air abraded group, compared to glaze group; control group did not survived thermocycling. Mechanical cycling had no effect on flexural strength. Air abrasion presented the highest values of flexural strength. Weibull analysis showed the highest m value for air abraded group without mechanical cycling, and the highest value was presented by glazed and mechanical cycled group. In stair case analysis, all groups presented a decrease in fatigue limit according to increase in number of cycles; air ... / Doutor

Orientador: Clovis Pagani / Banca: Ricardo Amore / Banca: Eduado Bresciani / Resumo: Os tratamentos de superfície convencionais realizados em cerâmicas feldspáticas são o condicionamento com ácido fluorídrico e a aplicação do silano. Porém em inúmeros estudos o condicionamento ácido tem sido questionado por sua toxidade química. Assim objetivou-se avaliar o efeito do tratamento térmico na cerâmica feldspática silanizada na adesão ao cimento resinoso. Por meio de um estudo in vitro foram seccionados 24 blocos de cerâmica feldspática sinterizada, com dimensões de 5 x 10 x 4 mm. Estes blocos foram divididos aleatoriamente em três grupos experimentais: G1 (HF + Silano); G2 (Silano + aquecimento 77 °C); G3 (HF+ Silano + aquecimento 77 °C). Os blocos cerâmicos foram cimentados a blocos de resina composta por meio de um cimento resinoso (Variolink, Ivoclair-Vivadent), posteriormente o conjunto foi cimentado a blocos idênticos de resina composta (Z-100, 3M-ESPE) e após a cimentação foram submetidos à ciclagem mecânica (10.000 ciclos 100 N). Após ciclagem foram seccionados em palitos de 1mm2 e submetido ao teste microtração a velocidade de 1 mm/min. Todos os corpos de prova foram analisados em estereomicroscópio com 20 x, para classificação das fraturas e apenas as amostras significativas em microscópio eletrônico de varredura com magnitudes com de 100 x, 300 x e 500 x. Os resultados obtidos foram submetidos à análise estatística Anova um fator e teste de Tukey (α = 0,05). A análise estatística demonstrou semelhança estatística (p - valor = 0,33)entre todos os grupos (G1 22,63 MPaA; G2 23,31 MPaA; G3 26,32 MPaA).A análise de falhas demonstrou predominância de falhas adesivas para todos os grupos. Conclui-se que o aquecimento do silano é efetivo para esta interface sendo possível eliminar o condicionamento com HF(ácido fluorídrico) / Abstract: The conventional surface treatment performed on feldspathic ceramic is the fluoridric acid etching and silane application. But in several studies the etching has been questioned for its chemical toxicity. Thus this study aimed to evaluate the effect of heat treatment on silanized feldspathic ceramic bond strength to resin cement. Through an in vitro study 24 feldspathic ceramic sintered blocks were sectioned; 5 x 10 x 4 mm of dimensions. These blocks were randomly divided into three experimental groups: G1 ( HF + silane ) ; G2 ( + Silane heating 77 °C); (G3 + Silane + HF + heating 77 °C). The ceramic blocks were cemented with resin blocks composed of resinous cement ( Variolink , IvoclairVivadent ) , the set was later cemented identical blocks of composite resin ( Z - 100 , 3M - ESPE ) , after cementation were subjected to cycling mechanical (10,000 cycles 100 N). After cycling were sectioned into sticks of 1mm2 and submitted to microtensile test with speed of 1 mm / min. Representative samples were analyzed with a stereomicroscope at 20 x and scanning electron microscope with magnitudes of 100 x, 300 x and 500 x. The results were statistically analyzed by ANOVA one factor and by Tukey test (α = 0.05). Statistical analysis showed (p - value = 0.33) statistical similarity between all groups (G1 22.63 mPa, mPa 23.31 G2, G3 26.32 mPa). The failure analysis showed predominance of adhesive failures for all groups. It can be concluded that heating the silane is effective for this interface it is possible to eliminate the etching with HF (Flouridric acid) / Mestre

Magister Artium - MA / My research considers the vessels of select women ceramists in and from rural KwaZulu-Natal and reflects on the changing contexts in which their work is utilized, consumed and displayed. The emphasis of my research is on the significance of ceramics in cultural practices and how this has changed or been maintained due to altered social and political circumstances and the changing dynamics of research. Additionally, when ceramic vessels are purchased by tourists, collectors and patrons they are subjected to a range of dialogues between maker and buyer. Finally, vessels may be selected to be displayed in exhibitions or held in collections of museums and galleries; once again, then they will be spoken about and they will speak to us on different terms. Each one of these movements in the life of a pot is reflected in the artist’s consideration of form, pattern, balance, shape, colour and symmetry of the vessels. Similarly, each one of these steps in the process engages with a different type of audience in a dynamic and significant way. I investigate how the authors of these vessels become involved in and negotiate a dialogue between themselves, their work and an exterior context that always projects its own voice about the artists and their work.

Thesis (Sc.D.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND SCIENCE. / Vita. / Bibliography: leaves 204-211. / by Thomas Dale Ketcham. / Sc.D.

No description available.

Lead-based and lead-free ferroelectric ceramic materials were prepared at low sintering temperatures with particular regard to their applications in thick film piezoelectric components. This project is focused on the development of processing methods and novel compositions to be used for thick film production by electrophoretic deposition (EPD) on heat-resistant alloys. Lead-based glasses and an oxide mixture (LiCO3, Bi2O3 and CuO), denoted LBCu, with low melting points were used as sintering aids for lanthanum-doped lead zirconate titanate (PLZT) ceramics. The required temperature to achieve dense ceramics was reduced from 1250 to 950 °C. It was found that the highest ferroelectric properties were obtained by the use of LBCu in comparison with those incorporating glass additives due to the shielding effect of the glass phase between the ferroelectric grains. However, the results of thick film preparation shown that the samples with glass additives were much smoother and relatively free of cracks up to 1000 ÂoC. In terms of lead-free ceramics, novel compositions were prepared, based on (Ba,Ca)(Zr,Ti)O3-(K0.5Bi0.5)TiO3 (BCZT-KBT) solid solutions having various Ca and Zr contents. The new solid solutions exhibited interesting features comprising core-shell type microstructures and relaxor ferroelectric behaviour in addition to reduced sintering temperatures and higher Curie point compared with BCZT ceramics. The required sintering temperature reduced to 1125 °C at 65% KBT, in comparison with 1500 °C for pure BCZT. The results showed that the compositional heterogeneity in the shell regions was reduced by air quenching, relative to that of the slow-cooled state, due to the retention of the more chemically-homogeneous high temperature state by the quenching process. The improvements were evident in increased polarisation, piezoelectric coefficient and depolarisation temperature values. However, the slow-cooled samples exhibited high reversible strain levels due to the presence of polar nanoregions (PNRs) in the ergodic state within the shell regions. Comparing the results obtained for two BCZT compositions, it was demonstrated that the stability of the ferroelectric tetragonal phase in slow-cooled BCZT-KBT samples was improved for the ceramic with lower Ca and Zr concentrations, denoted x=0.06, in comparison with that for higher levels, denoted x=0.15. Moreover, the electric field-induced ferroelectric state in the quenched ceramic with x=0.06 was found to be more stable during heating, giving rise to an enhanced depolarisation temperature.

Glass-ceramic composites and nanocrystalline glass-ceramics containing barium titanate (BT) or potassium sodium niobate (KNN) ferroelectric phases have been studied, with particular regard to their use as dielectric energy storage materials. Barium borosilicate glass (BBS) was used as a sintering aid for BT and KNN, producing glass-ceramic composites. The temperatures required to achieve densification were reduced from 1400 to 1200 °C for BCZT (Ca, Zr-doped BT) and 1170 to 1050 °C for KBN (Bi, Na, K, Zr-doped KNN) by the use of glass additives. An unexpected observation, found in both BCZT and KBN systems, was the heterogeneous dissolution of dopant elements into the glass, inducing additional anomalies in the relative permittivity-temperature relationships. For BCZT, the orthorhombic-tetragonal phase transformation temperature shifted upwards to ≈ 50 °C, which was attributed to modification of the Ca/Zr ratio by preferential dissolution of Ca into the glass phase. Similarly, for KBN the dopant elements appeared to be leached into the liquid phase during sintering, resulting in relative permittivity-temperature characteristics similar to those of pure KNN. A modified BBS glass having various KNN contents was prepared by the conventional melt-quenching method and then heat-treated to induce crystallisation, producing nanocrystalline glass-ceramics. It is shown that crystallisation of an intermediate barium niobate phase initiates at temperatures in the region of 650 °C; this is subsequently converted into perovskite KNN together with a second phase of Ba3Nb5O15 at temperatures from 700 to 800 °C. The final crystallite size was in the region of 30±7 nm. The highest dielectric energy storage density of 0.134(4) J cm-3 was obtained for a glass-modified BT ceramic at an electric field level of 5 kV mm-1. However, the energy storage efficiency of the BT-based ceramics was relatively poor and they displayed a general tendency for saturation, indicating potentially poor performance at higher field levels. On the other hand, the KNN-based ceramics exhibited slightly lower energy storage density values, up to 0.108(1) J cm-3, but with much improved linearity and energy storage efficiency. Therefore, the latter is considered to be more suitable as energy storage dielectrics. The BBS-KNN glass-ceramics yielded relatively low energy storage density, 0.035(2) J cm-3, but the dielectric linearity and storage efficiency were similar to or better than those of the KNN ceramics, indicating good potential for use as energy storage dielectrics at very high electric field levels as a result of their nanocrystalline microstructures.

Orientador: Maria Aparecida Zaghete Bertochi / Banca: Laudemir Carlos Varanda / Banca: Cauê Ribeiro de Oliveira / Resumo: As piezocerâmicas de chumbo a base de Pb(Zr1-xTix)O3 (PZT) sempre tiveram destaque devido às suas excelentes propriedades piezoelétricas. Suas aplicações como sensores, atuadores e capacitores tornaram essas cerâmicas um alvo de incessantes estudos. Entretanto, cresce a necessidade de substituí-las devido ao impacto ambiental causado pelo chumbo. Com este objetivo, pesquisas em busca de materiais alternativos vêm ganhando destaque na comunidade científica internacional. Nesse contexto, os únicos materiais que apresentaram características equiparáveis ao PZT foram os niobatos alcalinos texturizados. Entretanto, para a obtenção dessas cerâmicas texturizadas foi necessária a produção de templates de niobato de sódio (NaNbO3) por complexos processos de síntese, uma vez que estes não estão disponíveis comercialmente. Nessa linha de estudo, o presente projeto de pesquisa buscou a síntese de moldes (templates) de niobato de sódio e de potássio para texturização de cerâmicas livres de chumbo a base de niobatos alcalinos (NaKLiNbO3) por método "Templated Grain Growth" (TGG) e "Reactive Templated Grain Growth" (RTGG). Os templates foram produzidos por síntese hidrotérmica assistida por microondas (H-M), a 200ºC, e com variações de tempo, tipo de precursor de nióbio e concentração de reagentes. Os templates de NaNbO3 e KNbO3 foram produzidos através da reação entre um precursor de nióbio (Nb2O5 ou NH4.NbO.(C2O4)2.(H2O)2.(H2O)n) e o hidróxido do respectivo metal alcalino (NaOH ou KOH). O NaNbO3 foi produzido com ambos os precursores de nióbio, embora o oxalato amoniacal favoreça a cristalização de partículas cúbicas de maior tamanho (>4μm). Durante a síntese do NaNbO3, as análises de difratometria de raios X (DRX) e de microscopia eletrônica de varredura (MEV) mostraram que as microfibras de Na2Nb2O6.nH2O formadas são uma fase intermediária... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: PZT-based materials [Pb(Zr1-xTix)O3] are the most used piezoceramics around the world due to their excellent piezoelectric properties. Their applications as sensors, actuators and capacitors made these ceramics the center of unceasing studies. However, the necessity of substituting these materials has been increased mainly because of the environment impact caused by the lead element. With this objective, new researches aiming the discovery of alternative materials have been growth in the scientific community. In this context, the only materials which presented properties at the level of PZT were the texturized alkalines niobates. Nevertheless, to produce such texturized ceramics, the use of complexes methods of synthesis was necessary to create templates of sodium niobate (NaNbO3), once they are not commercially available. Therefore, this project attempted to produce templates of sodium and potassium niobates intending the texturization of alkaline niobate-based ceramics (NaKLiNbO3) by Templated Grain Growth (TGG) and Reactive Templated Grain Growth (RTGG) methods. The templates were produced by means of a microwave assisted hydrothermal synthesis (M-H), at 200ºC, by varying the time, type of niobium precursor and reactants concentrations. The templates of NaNbO3 e KNbO3 were produced through the reaction between a niobium precursor (Nb2O5 or NH4.NbO.(C2O4)2.(H2O)2.(H2O)n) and the hydroxide of the respective alkaline metal (NaOH or KOH). The NaNbO3 was synthesized by both niobium precursors, though the niobium ammoniacal oxalate promoted the formation of cubic particles of NaNbO3 with greater sizes (>4μm). During the synthesis of the NaNbO3, the analysis of X-ray diffratometry (XRD) and scanning electronic microscopy (SEM) indicated that the microfibers of Na2Nb2O6.nH2O are formed as an intermediary phase towards the NaNbO3 crystallization... (Complete abstract click electronic access below) / Mestre

Este estudo avaliou a influência da ciclagem térmica e mecânica, aliadas, na resistência ao cisalhamento da interface entre porcelana de cobertura e infraestruturas de diferentes sistemas totalmente. Também foi realizada a caracterização das interfaces por meio de análise de espectroscopia por energia dispersiva de Raios X (EDS). Foram testados sistemas totalmente cerâmicos a base de dissilicato de lítio (DL), zircônia tetragonal estabilizada por ítrio recoberta por estratificação (ZC) e por injeção (ZI) e alumina infiltrada por vidro (AI). Um grupo metalocerâmico a base de liga de CoCr foi testado como grupo controle. Vinte espécimes circulares de 6mm de diâmetro de cada sistema foram submetidos ao teste de resistência ao cisalhamento em máquina de ensaios mecânicos, sendo que metade destes (n=10) sofreram os procedimentos de ciclagem térmica e mecânica antes da realização dos testes. Os resultados foram analisados através do teste ANOVA a dois critérios (p<0,05) e utilizou-se teste de Tukey (p<0,05) para as comparações múltiplas. Análise das fratura foi realizada através de estereomicroscópio e MEV. A análise de EDS foi realizada ao longo da interface infraestrutura/porcelana de cobertura em um espécime de cada sistema seccionado longitudinalmente. As ciclagens térmica e mecânica aliadas não influenciaram na resistência ao cisalhamento dos sistemas testados. Houve, contudo, diferença estatística entre os sistemas testados. O grupo CoCr apresentou os maiores valores (34,72 ± 7,05 Mpa), seguido dos grupos DL (27,07 ± 5,28), ZI (23,58 ± 2,71), ZC (22,46 ± 2,08) e AI (18,15 ± 1,99). Os modos de fratura foram predominantemente adesivos para o grupo CoCr, coesivos na infraestrura para o grupo DL, coesivo na porcelana de cobertura para os grupos ZC e ZI, e mistos para o grupo AI. As análises de EDS mostraram haver uma zona de interação para todos os sistemas testados. Deste modo, é possível sugerir, através das análises de fratura e de EDS, que haja uma união química entre a porcelana de cobertura e infraestrutura nos diferentes sistemas testados e que as variações de resistência ao cisalhamento estão relacionadas a fatores intrínsecos ou na capacidade de molhamento da porcelana de cobertura. / The objective of this study was to evaluate the influence of thermal and mechanical cycling on the shear bond strength of different all-ceramic cores and veneering porcelain interfaces. It was also to characterize chemically the interfaces by energy dispersive spectroscopy (EDS). The allceramic systems tested were lithium dissilicate (DL), zirconia veneered by layering technic (ZC) or pressing technic (ZI) and glass infiltrated alumina (AI). A CoCr group was used as control. Twenty cylindrical specimens for each system were subjected to shear bond strength in a universal testing machine with a 0.5 mm/min crosshead speed. Half of the specimens (n=10) were thermal and mechanical cycled before shear bond strength was carried out. Mean shear bond strength (MPa) were analyzed with a 2-way analysis of variance and the Tukey test. Failures were classified with tereomicroscope and scanning electron microscope (SEM) analysis. In an addition, energy dispersive X-ray spectroscopy (EDS) analysis was performed from core/veneer interfaces. Thermal and mechanical cycling did not influence statistically on the shear bond strength for the systems evaluated. However, there was a statically significant difference between the systems evaluated. Control group (CoCr) presented the highest values (34,72 ± 7,05 Mpa), followed by DL (27,07 ± 5,28), ZI (23,58 ± 2,71), ZC (22,46 ± 2,08) e AI (18,15 ± 1,99). Thermal and mechanical cycling did not influence statistically on the shear bond strength for the systems evaluated. Failure modes were predominantly adhesive for CoCr group, cohesive in the core for DL, cohesive in veneer for groups ZC and ZI and mixed for AI. EDS analysis showed a interaction zone for all systems evaluated. Thus, it is possible to suggest, trough EDS analysis, that there is a chemical bond between core and veneer materials and that the shear bond strength variations can be related to intrinsic factors within veneering porcelain or to its wetting capacity.