The lithium disilicate (LS2) glass system provides the basis for a large number of useful glass-ceramic products. Microwave processing of materials such as glass-ceramics offers unique benefits over conventional processing techniques. Variable frequency microwave (VFM) processing is an advanced processing technique developed to overcome the hot spot and the arcing problems in microwave processing. In general, two main questions are addressed in this dissertation: 1. How does microwave energy couple with a ceramic material to create heat? and, 2. Is there a "microwave effect" and if so what are the possible explanations for the existence of that effect? The results of the present study show that VFM processing was successfully used to crystallize LS2 glass at a frequency other than 2.45 GHz and without the aid of other forms of energy (hybrid heating). Crystallization of LS2 glass using VFM heating occurred in a significantly shorter time and at a lower temperature as compared to conventional heating. Furthermore, the crystallization mechanism of LS2 glass in VFM heating was not exactly the same as in conventional heating. Although LS2 crystal phase (Orthorhombic Ccc2) was developed in the VFM crystallized samples as well as in the conventionally crystallized samples as x-ray diffraction (XRD) confirmed, the structural units of SiO4 tetrahedra (Q species) in the VFM crystallized samples were slightly different than the ones in conventionally crystallized samples as the Raman spectroscopy revealed. Moreover, the observed reduction in the crystallization time and apparent temperature in addition to the different crystallization mechanism observed in the VFM process both provided experimental evidence to support the presence of the microwave effect in the LS2 crystallization process. Also, the molecular orbital model was successfully used to predict the microwave absorption in LS2 glass and glass-ceramic. This model was consistent with experiments and indicated that microwave-material interactions were highly dependent on the structure of the material. Finally, a correlation between the Fourier transform infrared reflectance spectroscopy (FTIRRS) peak intensities and the volume fraction of crystals in partially crystallized LS2 glass samples was established. / Ph. D.

The goal of this research was to create a microstructure graded glass-ceramic and investigate the resulting properties as a function of crystallization processing. The desired glass-ceramic was a lithium disilicate material that has a crystallization gradient across the sample, leading to functionally graded properties as a result of the microstructure gradient. Samples were prepared by melting and pouring glass at 1400°C, annealing at 400°C for 48 hours, and nucleating at 480°C for 2 hours. To ensure that crystallization would not occur homogeneously throughout the sample, a temperature gradient was imposed during crystallization. Samples were crystallized on a self-constructed resistance wire furnace that was open to air. Several crystallization processing parameters were tested, including high temperature for a short time and low temperature for a long time. Samples were ground and polished to 0.25 microns before characterization methods were performed. Scanning electron microscopy (SEM) showed the microstructure transition across the sample cross section, with crystals present on the crystalline side and only nuclei present on the glassy side. Raman spectroscopy showed a transformation of the characteristic spectra across the sample cross section, with defined, high-intensity peaks on the crystalline side and broad, low-intensity peaks on the glassy side. Microhardness showed a slight transition in hardness values across the sample cross section, however the variability was too great to draw any conclusions. The characterization methods showed that the desired material was created and the resulting properties were a function of the crystallization processing parameters. / Master of Science

Syfte Syftet med föreliggande studie var att undersöka böjhållfastheten hos IPS e.max CAD före och efter termocykling med 10 000 respektive 15 000 cykler. Material och metod Trettio provkroppar framställdes från fem stycken IPS e.max CAD LT-block. Provkropparna var indelade i två testgrupper (GT10 och GT15), och en kontrollgrupp (GK), á 10 provkroppar i varje. Provkropparna utformades enligt måtten L 17,9 ± 0,03 mm x B 2,5 ± 0,03 mm x H 2,5 ± 0,03 mm. Samtliga provkroppar kristalliserades och grupp GK förvarades i rumstemperatur, resterande två grupper, GT10 och GT15 termocyklades i 10 000 respektive 15 000 cykler.Därefter utfördes ett trepunkts böjhållfasthetstest. Resultaten analyserades med One-way ANOVA, Tukey’s test med signifikansnivån α= 0,05 i statistikprogrammet SPSS. Resultat Resultaten visade att det inte fanns någon signifikant skillnad mellan grupp GK och GT10 (p>0,05) respektive mellan grupp GT10 och GT15 (p>0,05). Grupp GT15 hade högst medelvärde (516 MPa) och grupp GK hade lägst medelvärde (450 MPa). Signifikant skillnad fanns mellan grupp GK och GT15 (p<0,05). Grupp GT15 hade en signifikant högre böjhållfasthet (~470-637 MPa) jämfört med grupp GK (~406-494 MPa). Slutsats Inom föreliggande studies begränsningar kan följande slutsatser dras: Termocykling med 10 000 cykler påverkar inte böjhållfastheten, däremot ger ökat antal cykler (15 000) högre böjhållfasthet. / Purpose  The purpose of the present study was to investigate the flexural strength of IPS e.max CAD beforeand after thermal cycling with 10,000 and 15,000 cycles, respectively.  Material and method  Thirty specimens were prepared from five IPS e.max CAD LT blocks, divided into two test groups (GT10 and GT15), and one control group (group GK) (n=10). The specimens were designed with the dimensions L 17.9 ± 0,03 mm x W 2.5 ± 0,03 mm x H 2.5 ± 0,03 mm. All specimens were crystallized and group GK was kept in room temperature, the remaining two groups, GT10 and GT15 were thermocycled with 10,000 and 15,000 cycles respectively. A three-point flexural strength test was performed. The results were analyzed with One-way ANOVA, Tukey's test with a significance level α = 0.05 in the statistical program SPSS.  Results  The results showed that there was no significant difference between groups GK and GT10 (p> 0.05), and between groups GT10 and GT15 (p> 0.05). It was also observed that group GT15 had the highest average (516 MPa) and group GK had the lowest average (450 MPa). There was a significant difference between groups GK and GT15 (p <0.05). Group GT15 had a significantly higher flexural strength (~ 470-637 MPa) compared to group GK (~406-494 MPa).  Conclusion  Within the limitations of the present study, the following conclusions can be drawn:Thermal cycling comprising 10,000 cycles do not affect the flexural strength, however, increasing the number of cycles (15,000) will give higher flexural strength.

Objective: The primary objective of this study was to evaluate the roughness of CAD/CAM blocks of lithium disilicate glass-ceramic (IPS e.max CAD, Ivoclar Vivadent®, Schaan, Liechtenstein), before and after surface treatment with hydrofluoridric acid 10% and after silane coating by Atomic Force Microscopy and Optical Microscopy. The average size of silane as well as its fit to the valleys after acid etching was also studied. Methods: Ten specimens of CAD/CAM blocks of lithium disilicate glass-ceramic were analyzed by Atomic Force Microscopy. Before surface treatment with hydrofluoridric acid 10%, the specimens were also analyzed by Atomic Force Microscopy. All specimens were also analyzed by Optical Microscopy after the application of a layer of silane. Free software Gwyddion version 2.51 was used on data processing. The 3D surface measurements were: root mean square roughness, average roughness, maximum peak height, maximum pit depth, maximum height, Skewness and Kurtosis of surface and profile roughnesses. Images provided by Optical Microscopy were used to calculate the size of the silane particle, also using the free software Gwyddion version 2.5.1. Non-parametric tests were done by the free software R version 3.5.1. Results: Surface roughness and profile roughness were numerically different, but both increased after acid etching. All the skewness measurements concentrated around zero, indicating a more symmetrical behavior after acid conditioning. Silane cross-sectional area measured from 0,0374m² to 0,424351m² and its radius ranged from 0,115m to 0,3675m and could fit in on about 77,5% of the conditioned surface valleys. Significance: Roughness surface and silane layer are important factors to the bond strength between ceramic and resin cements, ensuring the success of restorative treatment. / Objetivo: O principal objetivo deste estudo in vitro foi analisar a rugosidade de superfície de blocos de CAD/CAM de cerâmica de dissilicato de lítio, antes e depois do condicionamento com ácido fluorídrico a 10% durante 20 segundos e após a aplicação de uma camada de silano, usando a Microscopia de Força Atômica e Microscopia Óptica. A média do tamanho do silano e como eles se ajustam nos vales da superfície condicionada também foram estudados. Metodologia: 10 amostras confeccionadas por blocos para CAD/CAM de cerâmica de dissilicato de lítio foram analisadas por um microscópio de força atômica. Depois do tratamento de superfície com ácido fluorídrico a 10% durante 20 segundos, os espécimes foram novamente analisados por Microscopia de Força Atômica. Todas as amostras foram analisadas em microscópio óptico depois da aplicação de uma camada de silano. O software Gwyddion (versão 2.5.1) foi usado para o processamento de dados. As medidas obtidas para as imagens 3D das superfícies foram: raiz quadrada média da rugosidade, rugosidade média, altura do pico mais alto, profundidade do vale mais baixo, máxima altura, assimetria e curtose, tanto para a análise de superfície quanto para a análise do perfil. As imagens obtidas pela Microscopia Óptica foram usadas para calcular o tamanho da partícula de silano, também usando o software Gwyddion (versão 2.5.1.). Testes não-paramétricos foram calculados pelo software R (versão 3.5.1). Resultados: As rugosidades da superfície e do perfil foram numericamente diferentes, mas ambas aumentaram após o condicionamento ácido. A assimetria concentrou-se próxima a zero, indicando um comportamento mais simétrico após o condicionamento. A área da secção transversal do silano mede entre 0,0374m² a 0,424351m² e o seu raio mediu entre 0,115m a 0,3675m. Esse tamanho de partícula pode ser acomodado em 77,5% dos vales presentes nas superfícies condicionadas. Significância: A rugosidade e a camada de silano são fatores importantes para o aumento da união entre a cerâmica e o cimento resinoso, assegurando o sucesso do tratamento restaurador.

Made available in DSpace on 2017-07-21T19:25:45Z (GMT). No. of bitstreams: 1 Ivan Mathias.pdf: 11996423 bytes, checksum: f3bdcfad9b494e72052f6a36c4a749d4 (MD5) Previous issue date: 2015-04-01 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / In this work two vitreous systems are studied, the lithium disilicate (LS2) and sodiumcalcium-silica with stoichiometry 2Na2O.CaO.3SiO2 (2N1C3S) and the glassceramics formed from these by heat treatment. Several properties were determined for the two systems as a function of crystallized volume fraction, from glass to fully crystallization (100%), highlighting the fracture toughness and the brittle-ductile transition, with the last two determined only for the LS2 glass-ceramic. Hardness and elastic modulus were obtained for the two glass-ceramics and their values increase with the crystallized volume fraction in the glass ceramic, with the exception of hardness of 2N1C3S, which has its maximum for the crystallized volume fraction of 9%. Thermal expansion coefficients were determined and are larger in the LS2 glassy phase and in the 2N1C3S crystalline phase, thereby generating mean residual stresses obtained by Selsing model of -76 MPa for the LS2 (compression in the crystal) and 232 MPa for the 2N1C3S (traction in the crystal). The indentation fracture toughness was also determined for the two systems using the Anstis' and Niihara's models. The results show an increase of indentation fracture toughness with the crystalline volume fraction for LS2 glass-ceramic and also a dependence with indentation load. As for the 2N1C3S glass-ceramic, indentation fracture toughness are reduced at intermediate crystalline fractions, which is attributed to residual stresses arising from the difference between the thermal expansion mismatch between the glass and the crystalline phases. LS2 glass-ceramic flexural strength increases with the crystalline fraction, from 103 ± 3 MPa for the glass to 260 ± 20 MPa for the fully crystallized sample. Without the removal of the crystallization surface layer, this value rises to 290 ± 20 MPa. The increase in flexural strength in the first 20% of the crystallized fraction is more pronounced. As the size of the precipitates was kept constant, this increase can be related only to the increase in the crystallized fraction. The residual stress in the matrix, the critical radius of spontaneous cracking of the crystals and the crack mean free path between the precipitates were considered in the analysis of the increase in flexural strength. The existence of pores in the samples was a factor that limited its resistance. The fracture toughness (KDTIC) a function of the crystallized fraction was determined for LS2 glassceramics using the double torsion technique. It was found that KDTIC increases with the crystallized fraction, from 0.75 MPa.m1/2 for the glass to about 3.50 ± 0.05 MPa.m1/2 for the fully crystallized sample, a significant increase of approximately five times. Several factors were analyzed as possible causes of the increase in KDTIC. The experimental data are better adjusted with a recently proposed model with one adjustable parameter that relates the ratio of the crystal and glass areas to the crystallized volume fraction. The brittle-ductile transition (BDT) of LS2 glass and glass-ceramic samples (39% crystallized volume fraction) were determined for three different strain rates. BDT temperatures were determined for each strain rate.Activation energies of BDT for the glass and glass-ceramic were obtained, which were 5.2 ± 0.2 eV and 7 ± 2 eV. It was found that BDT activation energy in glass resembles the activation energy of the LS2 viscous flow, thus concluding the BDT in LS2 is governed by viscous flow of the glass matrix. Finally, the fact of the activation energy of the glass ceramic be larger than the glass was attributed to the fact that the viscosity of the vitreous matrix is "hindered" by the presence of crystalline precipitates. A viscosity model of a rigid spheres composite was used as an analogy to explain this observation. / No presente trabalho são estudados dois sistemas vítreos, o dissilicato de lítio (LS2) e o soda-cal-sílica de estequiometria 2Na2O.CaO.3SiO2 (2N1C3S), bem como os vitrocerâmicos formados a partir destes através de tratamentos térmicos. Diversas propriedades foram determinadas para os dois sistemas em função da fração cristalizada, desde vidro até os 100%, com destaque para a tenacidade à fratura e a transição frágil-dúctil, sendo estas últimas determinadas somente para o LS2. Dureza e módulo de elasticidade foram obtidos para os dois sistemas e seus valores aumentam com a fração volumétrica cristalizada no vitrocerâmico, com exceção da dureza no 2N1C3S, que tem seu máximo para a fração cristalizada de 9%. Os coeficientes de expansão térmica foram determinados e são maiores na fase vítrea do LS2 e na fase cristalina do 2N1C3S, gerando assim tensões residuais médias obtidas pelo modelo de Selsing de -76 MPa para o LS2 (compressiva no cristal) e 232 MPa para o 2N1C3S (trativa no cristal). A tenacidade à fratura por indentação (KC) foi determinada também para os dois sistemas, sendo utilizados os modelos de Anstis e Niihara. Os resultados mostram um aumento com a fração cristalina para o LS2 e também uma dependência com a carga utilizada no teste. Já para o 2N1C3S, os valores de KC sofrem uma redução em frações cristalinas intermediárias, comportamento atribuído às tensões residuais oriundas da diferença entre os coeficientes de expansão térmica e anisotropias elásticas do material. Os ensaios de resistência à flexão mostraram que para o LS2 a resistência aumenta com a fração cristalina, passando de 103 ± 3 MPa para o vidro para 260 ± 20 MPa para a amostra totalmente cristalizada. Se não removermos a camada de cristalização superficial, este valor sobe para 290 ± 20 MPa. O aumento da resistência à flexão nos primeiros 20% da fração cristalizada é mais pronunciado. Como o tamanho dos precipitados foi mantido constante, esse aumento pode ser relacionado apenas ao aumento na fração cristalizada. A tensão residual na matriz, o raio crítico dos cristais para trincamento espontâneo e o livre caminho médio da trinca entre os precipitados foram considerados na análise do aumento da resistência à flexão. A existência de poros nas amostras foi um fator que limitou a sua resistência. Caso amostras sem poros fossem feitas, um aumento em torno de 20 a 30% da resistência seria obtido. A tenacidade à fratura (KDTIC) foi determinada para o LS2 pela técnica de torção dupla em função da fração cristalizada. Foi verificado que KDTIC aumenta com a fração cristalizada, passando de 0,75 MPa.m1/2 para o vidro para cerca de 3,50 ±0,05 MPa.m1/2 para a amostra totalmente cristalizada, um aumento significativo de aproximadamente cinco vezes. Diversos fatores foram apontados como possíveis causas do aumento da tenacidade e foi verificado que os fatores considerados de forma isolada não são suficientes para descrever completamente o aumento na tenacidade. Os dados experimentais são melhor ajustados com um modelo de um parâmetro de ajuste recentemente proposto que relaciona a razão entre as áreas dos cristais e do vidro na superfície de fratura com a fração cristalizada. A transição frágil-dúctil (TFD) de amostras vítreas e vitrocerâmica (39% fração cristalizada) de LS2 foram determinadas para três taxas de deformação. Foram determinadas as temperaturas de TFD para cada uma das taxas e foi verificada uma dependência com a taxa de deformação. Foram calculadas as energias de ativação para a TFD no vidro e vitrocerâmico, sendo elas de 5,2 ± 0,2 eV e 7 ± 2 eV. Verificou-se que a energia de ativação da TFD no vidro se assemelha a energia de ativação do escoamento viscoso do LS2, concluindo assim que a TFD no LS2 é governada pelo escoamento viscoso da matriz vítrea. Por fim, o fato da energia de ativação do vitrocerâmico ser maior que do vidro foi atribuída ao fato de que a viscosidade da matriz vítrea seria "dificultada" pela presença dos precipitados cristalinos. Um modelo de viscosidade de um compósito com esferas rígidas foi utilizado como analogia para explicar essa observação.