Nanozirconia ceramics have great potential to be used in a range of applications from dental implants to petrochemical valves due to their enhanced mechanical properties and superior hydrothermal ageing resistance. Unlike conventional ceramic components that are normally produced in large quantities with low costs using various conventional dry forming or wet forming methods, industry scale processing of nanoceramics has not yet been achieved. Concentration and granulation of nanostructured 3 mol% yttria stabilised zirconia via a spray freeze drying (SFD) technique was investigated to determine whether large scale dry forming of nanoceramics would be possible. Commercial nanosuspension with a primary particle size of 16 nm was concentrated to 55 wt% solids content using an electrosteric dispersant, β-alanine, whilst retaining low viscosities of ~20 mPa s at a 200 s-1 shear rate. The nanosuspensions concentrated using the β-alanine also displayed good ageing resistance and it has been proven that a large scale vacuum assisted rotary evaporator can be used to perform concentration in industry.

abstract: The release of organophosphorus compounds (OPs) and subsequent exposure to these compounds is of concern to humans and the environment. The goal of this work was to control the concentrations of gaseous OPs through interaction with sorbent oxides. Experimental and computational methods were employed to assess the interactions of dimethyl phosphite (DMHP), dimethyl methylphosphonate (DMMP), dimethyl ethylphosphonate (DMEP), diethyl ethylphosphonate (DEEP), and triethyl phosphate (TEP) with amorphous silica (a-silica), ã-alumina, and monoclinic zirconia (m-zirconia) for applications in air pollution control. Interactions of the selected OPs with a-silica were chosen as a baseline to determine the applicability of the computational predictions. Based on the a-silica results, computational methods were deemed valid for predicting the trends among materials with comparable interactions (e.g. -OH functionality of a-silica interacting with the phosphonyl O atoms of the OPs). Computational evaluations of the interactions with the OPs were extended to the oxide material, m-zirconia, and compared with the results for ã-alumina. It was hypothesized that m-zirconia had the potential to provide for the effective sorption of OPs in a manner superior to that of the a-silica and the ã-alumina surfaces due to the surface charges of the zirconium Lewis acid sites when coordinated in the oxidized form. Based on the computational study, the predicted heats of adsorption for the selected OPs onto m-zirconia were more favorable than those that were predicted for ã-alumina and a-silica. Experimental studies were carried out to confirm these computational results. M-zirconia nanoparticles were synthesized to determine if the materials could be utilized for the adsorption of the selected OPs. M-zirconia was shown to adsorb the OPs, and the heats of adsorption were stronger than those determined for commercial samples of a-silica. However, water interfered with the adsorption of the OPs onto m-zirconia, thus leading to heats of adsorption that were much weaker than those predicted computationally. Nevertheless, this work provides a first investigation of m-zirconia as a viable sorbent material for the ambient control of the selected gaseous OPs. Additionally, this work represents the first comparative study between computational predictions and experimental determination of thermodynamic properties for the interactions of the selected OPs and oxide surfaces. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Available commercial ceramic brackets are made of alumina either monocrystalline or polycrystalline. One major drawback of these brackets is fracture during archwire torsion or tipping. Another drawback is that each type comes in one shade only: transparent or translucent. Objectives: To fabricate orthodontic brackets from different esthetic materials and evaluate their mechanical properties; to introduce extremely low profile miniature zirconia brackets and evaluate their torsional fracture strength; also, to fabricate brackets in shades comparable to natural tooth shades, and compare them to commercial ceramic brackets under different lights. Materials and Methods: CAD/CAM technology was used to mill brackets from: ParadigmTM MZ100 and LavaTM Ultimate resin composite; Mark II feldspathic porcelain; and In-Ceram® YZ zirconia. The brackets were subjected to two separate tests (torque and tipping). The average moments necessary to fracture the brackets were determined and compared to those of commercial alumina brackets, Mystique® MB and Resolve®. Also, miniature zirconia brackets were fabricated and subjected to torsion till failure. Static fatigue test was performed on standard YZ, MZ100, and Mystique brackets. Brackets were fabricated using CAD/CAM in shade A3 materials: MZ100; Lava Ultimate; and Mark II. Zirconia and alumina brackets were also fabricated and colored. Adobe Photoshop software was used to determine ΔE values between the brackets and A3 acrylic teeth from digital images taken under three different lights (daylight, fluorescent, and incandescent). The shaded brackets were compared to commercial alumina brackets: Inspire ICETM; Radiance PlusTM; Avex® CX; and Mystique® MB. Results: Standard zirconia brackets had the highest torsional and tipping strength among the tested esthetic brackets. Miniature zirconia brackets showed comparable or even statistically significantly higher resistance to archwire torsion than commercial alumina brackets. Standard zirconia brackets showed the highest survival rate of 83%. Under daylight, Radiance Plus and Lava Ultimate brackets had the smallest mean ΔE values. Lava Ultimate brackets had the smallest mean ΔE under fluorescent and incandescent light. Conclusions: Esthetic brackets can be fabricated in extremely low profile and smaller dimensions from zirconia with fracture strength comparable to the bulkier commercial alumina brackets. Also, brackets can be produced in natural tooth shades enhancing their esthetic appearance. / 2018-09-28T00:00:00Z

Orientador: Alvaro Della Bona / Coorientador: Tarcísio José Arruda Junior / Coorientador: John Robert Kelly / Banca: Alexandre Luiz Souto Borges / Banca : Rubens Nisie Tango / Banca : Liliana Gressler May / Banca : Mario Alexandre Coelho Sinhoreti / Resumo: Esse estudo avaliou o desenvolvimento de tensões dentro da porcelana de restaurações metalo-cerâmicas (MC) e de zircônia-porcelana (ZC) como resultado de diferentes taxas de resfriamento a partir de temperaturas acima da transição vítrea (Tg). Restaurações unitárias (coroas) foram fabricadas com 1 ou 2 mm de espessura de porcelana. Termopares foram posicionados nas superfícies de cimentação (T1) e oclusal (T4) e inseridos na interface (T2) e dentro da porcelana (T3). Para o resfriamento rápido, o forno foi aberto imediatamente após o tempo de sinterização e desligado. O resfriamento lento foi obtido pela abertura do forno quando a 50°C abaixo da Tg. Modelos axi-simétricos foram construídos para simulação de tensões térmicas tempo-dependentes usando análise de elementos finitos (AEF). Equações de temperatura em função do tempo obtidas por termopares foram inseridas no modelo como condições das margens. A mudança do coeficiente de expansão térmica, densidade, módulo de cisalhamento, capacidade térmica e da Tg de acordo com a taxa de resfriamento foi considerada para simulação do comportamento da porcelana em temperaturas acima da Tg (visco-elástico). O comportamento dos materiais de infra-estrutura e da porcelana abaixo da Tg foi considerado elástico. A taxa de resfriamento na faixa de temperatura próxima a Tg foi 20°C/min e 900°C/min para resfriamento lento e rápido. Durante o resfriamento lento, os diferentes termopares mostraram temperaturas similares em ambas as coroas. Gradientes de temperatura foram observados no resfriamento rápido da coroa ZC (T1-T4 = 100°C) e, em menor magnitude, para a MC (T1-T4 = 30°C). Os resultados de AEF mostraram diferenças de tensão... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This study evaluated the development of transient and residual stresses within the porcelain of veneered restorations (zirconia- and metal-based) as a result of different cooling rates from temperatures above the glass transition temperature (Tg). All-ceramic (porcelain on zirconia-based ceramic) and porcelain-fused-to-metal (PFM) molar crowns were fabricated with 1 mm or 2 mm porcelain thickness. Thermocouples were attached to intaglio (T1) and occlusal (T4) surfaces and embedded within the ceramics interface (T2) and inside the porcelain (T3) to acquire temperature readings by time. For fast cooling, the furnace was opened immediately after the holding time and switched off afterward. Slow cooling was determined by opening the furnace when it reached 50 °C bellow the Tg. Axially-symmetric crown-like models were constructed to perform a simulation of time-dependent thermal stresses using finite element analyses (FEA). Time-dependent temperature equations from thermocouples were set as boundary conditions for surfaces of the model. Coefficient of thermal expansion, density, shear modulus, heat capacity and Tg dependency on cooling rate were considered for the porcelain simulation (visco-elastic above Tg). Porcelain below the Tg and the framework materials were considered to behave elastically. The cooling rates at Tg range were 20 °C/min and 900 °C/min for slow and fast cooling. During slow cooling, different thermocouples showed similar temperatures for both zirconia and metal crowns. Remarkable temperature gradients were observed for the fast cooled all-ceramic crown (T1-T4 = 100 °C) and, of lower magnitude, for PFM (T1-T4 = 30 °C). FEA results showed differences... (Complete abstract click electronic access below) / Doutor

Made available in DSpace on 2014-06-11T19:35:02Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-02-01Bitstream added on 2014-06-13T20:45:49Z : No. of bitstreams: 1 benetti_p_dr_sjc.pdf: 1295026 bytes, checksum: 84c067e5318d9cb1124bfd1cbcf324f7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Esse estudo avaliou o desenvolvimento de tensões dentro da porcelana de restaurações metalo-cerâmicas (MC) e de zircônia-porcelana (ZC) como resultado de diferentes taxas de resfriamento a partir de temperaturas acima da transição vítrea (Tg). Restaurações unitárias (coroas) foram fabricadas com 1 ou 2 mm de espessura de porcelana. Termopares foram posicionados nas superfícies de cimentação (T1) e oclusal (T4) e inseridos na interface (T2) e dentro da porcelana (T3). Para o resfriamento rápido, o forno foi aberto imediatamente após o tempo de sinterização e desligado. O resfriamento lento foi obtido pela abertura do forno quando a 50°C abaixo da Tg. Modelos axi-simétricos foram construídos para simulação de tensões térmicas tempo-dependentes usando análise de elementos finitos (AEF). Equações de temperatura em função do tempo obtidas por termopares foram inseridas no modelo como condições das margens. A mudança do coeficiente de expansão térmica, densidade, módulo de cisalhamento, capacidade térmica e da Tg de acordo com a taxa de resfriamento foi considerada para simulação do comportamento da porcelana em temperaturas acima da Tg (visco-elástico). O comportamento dos materiais de infra-estrutura e da porcelana abaixo da Tg foi considerado elástico. A taxa de resfriamento na faixa de temperatura próxima a Tg foi 20°C/min e 900°C/min para resfriamento lento e rápido. Durante o resfriamento lento, os diferentes termopares mostraram temperaturas similares em ambas as coroas. Gradientes de temperatura foram observados no resfriamento rápido da coroa ZC (T1-T4 = 100°C) e, em menor magnitude, para a MC (T1-T4 = 30°C). Os resultados de AEF mostraram diferenças de tensão... / This study evaluated the development of transient and residual stresses within the porcelain of veneered restorations (zirconia- and metal-based) as a result of different cooling rates from temperatures above the glass transition temperature (Tg). All-ceramic (porcelain on zirconia-based ceramic) and porcelain-fused-to-metal (PFM) molar crowns were fabricated with 1 mm or 2 mm porcelain thickness. Thermocouples were attached to intaglio (T1) and occlusal (T4) surfaces and embedded within the ceramics interface (T2) and inside the porcelain (T3) to acquire temperature readings by time. For fast cooling, the furnace was opened immediately after the holding time and switched off afterward. Slow cooling was determined by opening the furnace when it reached 50 °C bellow the Tg. Axially-symmetric crown-like models were constructed to perform a simulation of time-dependent thermal stresses using finite element analyses (FEA). Time-dependent temperature equations from thermocouples were set as boundary conditions for surfaces of the model. Coefficient of thermal expansion, density, shear modulus, heat capacity and Tg dependency on cooling rate were considered for the porcelain simulation (visco-elastic above Tg). Porcelain below the Tg and the framework materials were considered to behave elastically. The cooling rates at Tg range were 20 °C/min and 900 °C/min for slow and fast cooling. During slow cooling, different thermocouples showed similar temperatures for both zirconia and metal crowns. Remarkable temperature gradients were observed for the fast cooled all-ceramic crown (T1-T4 = 100 °C) and, of lower magnitude, for PFM (T1-T4 = 30 °C). FEA results showed differences... (Complete abstract click electronic access below)

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Submitted by LIECA HASSEGAWA KAVASHIMA null (lie-ca@hotmail.com) on 2016-11-07T22:26:34Z No. of bitstreams: 1 Lieca Hassegawa Kavashima - Dissertação - Mestrado.pdf: 7864947 bytes, checksum: 6b3f02c88be52df0bcf622c6caeaba96 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-11-10T16:51:24Z (GMT) No. of bitstreams: 1 kavashima_lh_me_bauru.pdf: 7864947 bytes, checksum: 6b3f02c88be52df0bcf622c6caeaba96 (MD5) / Made available in DSpace on 2016-11-10T16:51:24Z (GMT). No. of bitstreams: 1 kavashima_lh_me_bauru.pdf: 7864947 bytes, checksum: 6b3f02c88be52df0bcf622c6caeaba96 (MD5) Previous issue date: 2016-09-23 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / A zircônia tetragonal policristalina estabilizada com ítria ou zircônia Y-TZP, atualmente é utilizada como biomaterial na odontologia, para a confecção de próteses por meio da tecnologia CAD/CAM, a partir de blocos comerciais pré-sinterizados. A cerâmica Y-TZP é biocompatível, bioinerte e apresenta estética e propriedades mecânicas adequadas à aplicação. Contudo, as características mecânicas podem variar de acordo com o método de fabricação podendo estar sujeita à falhas por fratura frágil causada por defeitos oriundos das etapas de conformação, pré-sinterização, usinagem da prótese ou sinterização. Dessa forma, o objetivo do presente trabalho foi avaliar o processamento cerâmico e determinar as propriedades mecânicas da zircônia Y-TZP. Os blocos foram conformados por prensagem uniaxial e isostática a 200 MPa, pré-sinterizados com diferentes parâmetros (900°C e 950°C) de temperatura, submetidos a ensaio de microdureza Vickers e usinados por CAD/CAM para confecção de próteses. O material pré-sinterizado foi cortado em barras, sinterizado e submetido aos ensaios mecânicos para a determinação da resistência à flexão, módulo elástico dinâmico e estático. Os resultados indicaram que o processo térmico de pré-sinterização com patamar a 950°C proporcionou material adequado ao manuseio e usinagem CAD/CAM com microdureza similar aos materiais disponíveis comercialmente. Os valores de módulo de elasticidade do material após a sinterização final, determinados pelos métodos dinâmicos e estático, entre 205,7 e 231,9 GPa, estão próximos aos relatados na literatura (entre 200 e 220 GPa). As análises estatísticas pelo método ANOVA (p>0,05) e testes de Tukey-Kramer demonstraram que o processo de pré-sinterização não exerceu influência na resistência mecânica após a sinterização final. Assim, o processo de fabricação estudado neste trabalho apresentou parâmetros que possibilitaram a confecção de próteses odontológicas, por meio da tecnologia CAD/CAM, obtendo materiais com propriedades mecânicas adequadas à confecção de copings odontológicos. / The polycrystalline tetragonal yttria stabilized zirconia or Y-TZP zirconia is currently used as a biomaterial in dentistry for the manufacture of prostheses by means of the CAD / CAM technology with pre-sintered commercial blocks. Y-TZP ceramic is biocompatible, bioinert and presents aesthetic features and appropriate mechanical properties for the application. However, the mechanical characteristics can vary according to the manufacturing method and may be subjected to failure by brittle fracture caused by defects originated from forming, pre-sintering, prosthesis machining or sintering. Thus, the goal of this work was to evaluate the ceramic processing and determine the mechanical properties of the Y-TZP zirconia. Blocks were formed by uniaxial and isostatic compression at 200 MPa, pre-sintered with different temperature parameters (900°C and 950°C), subjected to Vickers microhardness test and machined by CAD / CAM for prostheses manufacture. The pre-sintered material was cut into bars, sintered and submitted to mechanical tests in order to determine flexural strength, static and dynamic elastic modulus. Results showed that the pre-sintering thermal process with 950°C as a baseline provided a suitable material handling and machining CAD / CAM with a microhardness similar to the materials commercially available. The Young’s modulus values of the material after the final sintering, determined by the dynamic and static methods were found between 205.7 and 231.9 GPa are close to those reported in the literature (between 200 and 220 GPa). The statistical analyses via ANOVA (p> 0.05) method and Tukey-Kramer tests showed that the pre-sintering process had no influence on the mechanical resistance after the final sintering. Therefore, the manufacturing process studied in this work presented parameters that enabled the manufacture of dental prostheses by means of the CAD / CAM technology, obtaining materials with suitable mechanical properties to dental copings confection.

abstract: Nanoporous crystalline oxides with high porosity and large surface areas are promising in catalysis, clean energy technologies and environmental applications all which require efficient chemical reactions at solid-solid, solid-liquid, and/or solid-gas interfaces. Achieving the balance between open porosity and structural stability is an ongoing challenge when synthesizing such porous materials. Increasing porosity while maintaining an open porous network usually comes at the cost of fragility, as seen for example in ultra low density, highly random porous aerogels. It has become increasingly important to develop synthetic techniques that produce materials with these desired properties while utilizing low cost precursors and increasing their structural strength. Based on non-alkoxide sol-gel chemistry, two novel synthetic methods for nanoporous metal oxides have been developed. The first is a high temperature combustion method that utilizes biorenewable oil, affording gamma alumina (Al2O3) with a surface area over 300 cm3/g and porosity over 80% and controllable pore sizes (average pore width 8 to 20 nm). The calcined crystalline products exhibit an aerogel-like textural mesoporosity. To demonstrate the versatility of the new method, it was used to synthesize highly porous amorphous silica (SiO2) which exhibited increased mechanical robustness while achieving a surface area of 960 m2/g and porosity of 85%. The second method utilizes sequential gelation of inorganic and organic precursors forming an interpenetrating inorganic/organic gel network. The method affords yttria-stabilized zirconia with surface area over 90 cm3/g and porosity over 60% and controllable pore sizes (average pore width 6 to 12 nm). X-ray diffraction, gas sorption analysis, Raman spectroscopy, nuclear magnetic resonance spectroscopy and electron microscopy were all used to characterize the structure, morphology, and the chemical structure of the newly afforded materials. Both novel methods produce products that show superior pore properties and robustness compared to equivalent commercially available and currently reported materials. / Dissertation/Thesis / Ph.D. Chemistry 2012

Materiais com gradiente funcional (MGF), a base de aço inoxidável e cerâmica têm despertado interesse em diversas áreas tecnológicas: estrutural, térmica, elétrica, biomédica e militar, e têm inspirado pesquisadores a combinar propriedades e características que não estão presentes em peças convencionais. Têm sido também considerados como uma alternativa na preparação de partes de motores de alta eficiência, ferramentas de corte e revestimentos estruturais para reatores químicos. A incorporação de metal e cerâmica em uma estrutura graduada permite a integração de muitas propriedades desejáveis que combinam ambas vantagens do metal e a cerâmica. Os componentes cerâmicos são capazes de suportar altas temperaturas e possuem alta resistência à corrosão, enquanto os componentes metálicos apresentam uma alta resistência à tração e alta ductilidade, e portanto são menos susceptíveis a fratura catastrófica. Neste trabalho, compósitos com níveis variáveis de aço inoxidável 316L e zircônia estabilizada com ítria, obtidos pelo processo de moagem de alta energia, foram preparados e caracterizados para determinar o comportamento térmico de cada composição, com o objetivo de planejar a sinterização dos MGFs com gradação de composição química. Difração de raios-x (DRX), análises de dilatometria e calorimetria exploratória diferencial (DSC) foram realizadas para os materiais compósitos com proporções diferentes de aço inoxidável e de zircônia, com o objetivo de analisar a influência da composição, como da taxa de aquecimento no comportamento dos compósitos selecionados durante a sinterização. Além disso, foram construídos por metalurgia do pó e caracterizados três peças de MGF. As peças de MGFs foram caracterizadas no microscópio óptico e microscópio eletrônico de varredura (MEV). Microanálise química foi feito pela técnica de espectroscopia de energia dispersiva (EDS) para o MGF1 e EDS - Line scan analysis das peças MGF2 e MGF3. Finalmente, as fases presentes nas peças foram medidas pela técnica de penetração Vickers. Os resultados dos ensaios dilatométricos para compósitos com teores de zircônia superiores a 50% e com taxas de aquecimento de 5ºC/min e 10ºC/min até 1200ºC, apresentaram uma contração linear maior em torno a 900ºC, e para composições com taxa de aquecimento de 15ºC/min em torno a 1000ºC, indicando que o processo de densificação se inicio a temperaturas inferiores que as outras composições observadas nas curvas dilatométricas para essas mesmas taxas de aquecimento. Os DSC dos compósitos apresentaram uma mudança correspondente à precipitação dos carbetos de cromo próprios do aço inox austenítico. A adição de zircônia ao aço inoxidável inibiu a precipitação dos carbetos, indicado pelo aparecimento de um pico nas amostras composta somente pelo aço inoxidável. / Functionally graded materials (FGM) based on stainless steel and ceramics has aroused interest in many technological areas: structural, thermal, electrical, biomedical and military, and has inspired researchers to combine properties and features which are not present in conventional samples, and is considered to be an alternative in the preparation of high efficient motors parts, cutting tools and structural coatings for chemical reactors. The incorporation of metal and ceramic in a graduated structure allows the integration of many desirable properties that combine advantages of metallic and ceramic materials. Ceramic components are capable of withstanding high temperatures and have high corrosion resistance, while the metallic components provide a higher mechanical resistance, in particular ultimate tensile strength and ductility, and therefore less susceptible to catastrophic fracture. In this work, composites with variable levels of 316L Stainless Steel and Yttria Stabilized Zirconia, obtained by high-energy milling process, were prepared and characterized, in order to determine the thermal behavior of each composition, with the aim of planning the sintering of a FGM with gradation of chemical composition. X-rays diffractometry (XRD), dilatometric analyses and differential scanning calorimetry (DSC) were performed for composites materials with distinct proportions of Stainless Steel and Zirconia, with the objective of analyzing the influence of the composition, as the heating rate the behavior of Stainless Steel/Zirconia layers during sintering. Additionally, were built by powder metallurgy and characterized three samples of FGM. The samples of MGFs were characterized in the optical microscope and scanning electron microscope (SEM). Chemical microanalysis was done by the technique of energy dispersive spectroscopy (EDS) of FGM1 and EDS-Line Scan Analysis of samples and FGM2 and FGM3. Finally, the phases present in the samples were measured by Vickers penetration technique. The results of dilatometric tests for composites with levels higher than zirconia to 50% and heating rates of 5°C/min and 10ºC/min up to 1200°C showed a greater linear shrinkage around 900ºC, and compositions at a heating rate of 15°C/min to about 1000°C, indicating that the densification process is starting at temperatures below that observed in other compositions dilatometric curves for these same heating rates. The DSC of the composites showed a change corresponding to the chrome carbides precipitation own austenitic stainless steel. The zirconia addition to stainless steel inhibited the carbides precipitation, indicated by the appearance of a peak in the samples composed only of stainless steel.