Y-TZP ceramic processing from coprecipitated powders: A comparative study with three commercial dental ceramics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Synthesis and stabilization of nanocrystalline zirconia with MSU mesostructure

In the presence of nonionic block-copolymer surfactant, nanocrystalline zirconia particles with MSU mesostrucmre were synthesized by a novel solid-state reaction route. The zirconia particles possess a nanocrystalline pore wall, which renders higher thermal stability compared to an amorphous framework. To further enhance its stability, laponite, a synthetic clay, was introduced. Laponite acts as an inhibitor to crystal a growth and also as a hard template for the mesostructure. High surface area and ordered pore structure were observed in the stabilized zirconia. The results show that the formation of the MSU structure is attributed to reverse hexagonal micelles, which are the products of the cooperative self-assembly of organic and inorganic species in the solid-state synthesis system with crystalline water and hygroscopic water present.

Study of porcelain-zirconia composites for dental applications

Materiais compósitos restauradores representam um dos mais bem sucedidos biomateriais na pesquisa moderna, na substituição do tecido biológico em aparência e função. Nesta linha, a porcelana feldspática tem sido largamente usada em odontologia devido suas interessantes qualidades como estabilidade de cor, propriedades estéticas, elevada durabilidade mecânica, biocompatibilidade, baixa condutividade térmica e elevada resistência ao desgaste. Entretanto, este material é frágil e pode falhar em ambiente oral devido ao micro-vazamento, baixa resistência à tração, descolagem ou fratura. Assim, para melhorar as propriedades mecânicas da porcelana, a zircônia parcialmente estabilizada com Ítria (Y-TZP) pode ser uma boa alternativa para fortalecer e produzir infraestruturas totalmente cerâmicas (coroas e próteses parciais fixas). Portanto, este estudo tem por objetivo avaliar as propriedades mecânicas e características microestruturais da porcelana reforçada com zircônia (3Y-TZP) em diferentes conteúdos e as variáveis que afetam as propriedades mecânicas destes materiais. O estudo de caracterização revelou que a zircônia comercial apresenta melhores resultados quando comparada com a zircônia sintetizada pelo CPM. Assim, os estudos seguintes utilizaram a zircônia comercial para todos os testes requeridos. As partículas de zircônia apresentam elevadas propriedades mecânicas quando comparadas a zircônia aglomerada. Os diferentes conteúdos revelam que as propriedades mecânicas dos compósitos aumentam com o aumento do conteúdo volumétrico até 30% vol.% (198,5Mpa), ou seja, maior resistência à flexão quando comparada com os outros compósitos. Do mesmo modo, a resistência ao desgaste para os compósitos com (30%, vol.% de zircônia) apresenta valores superiores quando comparado aos demais compósitos. Na adesão cerâmico-cerâmico a porcelana exibe elevada adesão para a superfície de zircônia porosa quando comparada a superfície rugosa. Os furos superficiais (PZ) e aplicação de compósitos com camada intermediária (RZI) na zircônia causam separadamente uma melhoria da resistência ao cisalhamento da zircônia-porcelana quando comparados as amostras convencionais de zircônia-porcelana (RZ), embora não sejam estatisticamente significativas (p>0.05). A presença de uma camada intermediaria produz um aumento significativo na força de ligação (~55%) em relação as amostras convencionais (RZ). Portanto, a correta a correta configuração e tratamento superficial podem produzir subestruturas com qualidade e força de ligação adequadas aos requisitos odontológicos.

Tetragonal-cubic phase boundary in nanocrystalline ZrO(2)-Y(2)O(3) solid solutions synthesized by gel-combustion

By means of synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy, we have detected, in a series of nanocrystalline and compositionally homogeneous ZrO(2)-Y(2)O(3) solid solutions, the presence at room temperature of three different phases depending on Y(2)O(3) content, namely two tetragonal forms and the cubic phase. The studied materials, with average crystallite sizes within the range 7-10 nm, were synthesized by a nitrate-citrate gel-combustion process. The crystal structure of these phases was also investigated by SXPD. The results presented here indicate that the studied nanocrystalline ZrO(2)-Y(2)O(3) solid solutions exhibit the same phases reported in the literature for compositionally homogeneous materials containing larger (micro)crystals. The compositional boundaries between both tetragonal forms and between tetragonal and cubic phases were also determined. (C) 2011 Elsevier B.V. All rights reserved.

Influence of titanium and lutetium on the persistent luminescence of ZrO2

Non-doped as well as titanium and lutetium doped zirconia (ZrO2) materials were synthesized via the sol-gel method and structurally characterized with X-ray powder diffraction. The addition of Ti in the zirconia lattice does not change the crystalline structure whilst the Lu doping introduces a small fraction of the tetragonal phase. The UV excitation results in a bright white-blue luminescence at ca. 500 nm for all the materials which emission could be assigned to the Ti3+ e(g) -> t(2g) transition. The persistent luminescence originates from the same Ti3+ center. The thermoluminescence data shows a well-defined though rather similar defect structures for all the zirconia materials. The kinetics of persistent luminescence was probed with the isothermal decay curve analyses which indicated significant retrapping. The short duration of persistent luminescence was attributed to the quasi-continuum distribution of the traps and to the possibility of shallow traps even below the room temperature. (C) 2012 Optical Society of America

Surface Segregation in Chromium-Doped Nanocrystalline Tin Dioxide Pigments

Surface properties play an important role in understanding and controlling nanocrystalline materials. The accumulation of dopants on the surface, caused by surface segregation, can therefore significantly affect nanomaterials properties at low doping levels, offering a way to intentionally control nanoparticles features. In this work, we studied the distribution of chromium ions in SnO2 nanoparticles prepared by a liquid precursor route at moderate temperatures (500 degrees C). The powders were characterized by infrared spectroscopy, X-ray diffraction, (scanning) transmission electron microscopy, Electron Energy Loss Spectroscopy, and Mossbauer spectroscopy. We showed that this synthesis method induces a limited solid solution of chromium into SnO2 and a segregation of chromium to the surface. The s-electron density and symmetry of Sn located on the surface were significantly affected by the doping, while Sn located in the bulk remained unchanged. Chromium ions located on the surface and in the bulk showed distinct oxidation states, giving rise to the intense violet color of the nanoparticles suitable for pigment application.

Structure of nanoporous zirconia-based powders synthesized by different gel-combustion routes

Zirconia-based ceramics that retain their metastable tetragonal phase at room temperature are widely studied due to their excellent mechanical and electrical properties. When these materials are prepared from precursor nanopowders with high specific surface areas, this phase is retained in dense ceramic bodies. In this work, we present a morphological study of nanocrystalline ZrO2-2.8 mol% Y2O3 powders synthesized by the gel-combustion method, using different organic fuels - alanine, glycine, lysine and citric acid - and calcined at temperatures ranging from 873 to 1173 K. The nanopore structures were investigated by small-angle X-ray scattering. The experimental results indicate that nanopores in samples prepared with alanine, glycine and lysine have an essentially single-mode volume distribution for calcination temperatures up to 1073 K, while those calcined at 1173 K exhibit a more complex and wider volume distribution. The volume-weighted average of the nanopore radii monotonically increases with increasing calcination temperature. The samples prepared with citric acid exhibit a size distribution much wider than the others. The Brunauer-Emmett-Teller technique was used to determine specific surface area and X-ray diffraction, environmental scanning electron microscopy and transmission electron microscopy were also employed for a complete characterization of the samples.

Analysis in vitro of the cytotoxicity of potential implant materials. I: Zirconia-titania sintered ceramics

Zirconia (ZrO(2)) is a bioinert, strong, and tough ceramic, while titania (TiO(2)) is bioactive but has poor mechanical properties. It is expected that ZrO(2)-TiO(2) mixed ceramics incorporate the individual properties of both ceramics, so that this material would exhibit better biological properties. Thus, the objective of this study was to compare the biocompatibility properties of ZrO(2)-TiO(2) mixed ceramics. Sintered ceramics pellets, obtained from powders of TiO(2), ZrO(2), and three different ZrO(2)-TiO(2) mixed oxides were used. Roughnesses, X-ray diffraction, microstructure through SEM, hardness, and DRIFT characterizations were performed. For biocompatibility analysis cultured FMM1 fibroblasts were plated on the top of disks and counted in SEM micrographs 1 and 2 days later. Data were compared by ANOVA complemented by Tukey`s test. All samples presented high densities and similar microstructure. The H(2)O content in the mixed ceramics was more evident than in pure ceramics. The number of fibroblasts attached to the disks increased significantly independently of the experimental group. The cell growth on the top of the ZrO(2)-TiO(2) samples was similar and significantly higher than those of TiO(2) and ZrO(2) samples. Our in vitro experiments showed that the ZrO(2)-TiO(2) sintered ceramics are biocompatible allowing faster cell growth than pure oxides ceramics. The improvement of hardness is proportional to the ZrO(2) content. Thus, the ZrO(2)-TiO(2) sintered ceramics could be considered as potential implant material. (C) 2010 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 94B: 305-311, 2010.

Development of zirconia-magnesia/zirconia-yttria composite solid electrolytes

Composite solid electrolytes were prepared by thoroughly mixing ZrO2:8 mol% MgO (Z8Mg) and ZrO(2):3 mol% Y(2)O(3) (Z3Y) ceramic powders followed by pressing and sintering at 1500 degrees C/1 h. The properties of the sintered pellets were studied by X-ray diffraction for evaluation of the structural phases by the Rietveld method, by high-temperature dilatometry for analysis of the thermal shrinkage/expansion behavior, and by impedance spectroscopy for determination of the oxide ion conductivity. The x(Z8Mg)+(1-x)(Z3Y) specimens, x= 0.2, 0.4, 0.5, 0.6, 0.8 and 1.0, are partially stabilized (monoclinic, cubic and tetragonal phases) with density >94% of the theoretical density and show thermal shock resistance and electrical conductivity values suitable for high-temperature oxygen gas detection. One-end closed tube samples of the composite solid electrolytes were assembled in Pt/Z8Mg+Z3Y/Cr+Cr(2)O(3)/Pt electrochemical cells for exposure to different levels of oxygen in the 1-850 ppm range. The total electrical conductivity increases for increasing the relative Z3Y content. Addition of Z3Y to Z8Mg (80 wt.%-20 wt.%) suppresses the electronic contribution to the electrical conductivity at 620 degrees C. (c) 2008 Elsevier B.V. All rights reserved.

Characterization of ceramic powders used in the inCeram systems to fixed dental Prosthesis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrical measurements in doped zirconia-ceria ceramics

Zirconia-ceria powders with 12 mol % of CeO2 doped with 0.3 mol% of iron, copper, manganese and nickel oxides were synthesized by the conventional mixed oxide method. These systems were investigated with regard to the sinterability and electrical properties. Sintering was studied considering the shrinkage rate, densification, grain size, and phase evolution. Small amount of dopant such as iron reduces sintering temperature by over 150degreesC and more than 98% of tetragonal phase was retained at room temperature in samples sintered at 1450degreesC against 1600degreesC to stabilize the tetragonal phase on pure ZrO2-CeO2 system. The electrical conductivity was measured using impedance spectroscopy and the results were reported. The activation energy values calculated from the Arrhenius's plots in the temperature range of 350-700degreesC for intragrain conductivities are 1.04 eV.

Synthesis of nanocrystalline tetragonal zirconia by a polymeric organometallic method

A polymeric precursor method based on the Pechini process was successfully used to synthesize zirconia-12 mol% ceria ceramic powders, the influence of the main process variables (citric acid-ethylene glycol ratio, citric acid-total oxides ratio and calcination temperature) on phase formation and powder morphology (surface area and crystallite size) were investigated. The thermal decomposition behavior of the precursor is presented. X-ray diffraction (XRD) patterns of powders revealed a crystalline tetragonal zirconia single-phase, with crystallite diameter ranging from 6 to 15 nm. The BET surface areas were relatively high, reaching 95 m(2) g(-1) Nitrogen adsorption/desorption on the powders suggested that nonaggregated powders could be attained, depending on the synthesis conditions. Copyright (C) 1999 John Wiley & Sons, Ltd.

Sintesi e caratterizzazione di nanopolveri composite allumina-zirconia

Il presente lavoro di tesi riguarda la sintesi di nanopolveri allumina-zirconia, seguendo tre differenti metodologie (sintesi per coprecipitazione, sintesi con il metodo dei citrati, sintesi idrotermale assistita da microonde) e il trattamento termico (calcinazione) delle polveri ottenute, mediante tecniche di riscaldamento convenzionali ed alternative (microonde). Lo scopo del lavoro è consistito nell’individuare, tra le tecniche esaminate, quella più idonea e conveniente, per la preparazione di nanopolveri cristalline 95 mol% Al2O3 – 5 mol% ZrO2 e nell’esaminare gli effetti che la calcinazione condotta con le microonde, ha sulle caratteristiche finali delle polveri, rispetto ai trattamenti termici convenzionali. I risultati ottenuti al termine del lavoro hanno evidenziato che, tra le tecniche di sintesi esaminate, la sintesi idrotermale assistita da microonde, risulta il metodo più indicato e che, il trattamento termico eseguito con le microonde, risulta di gran lunga vantaggioso rispetto a quello convenzionale. La sintesi idrotermale assistita da microonde consente di ottenere polveri nano cristalline poco agglomerate, che possono essere facilmente disaggregate e con caratteristiche microstrutturali del tutto peculiari. L’utilizzo di tale tecnica permette, già dopo la sintesi a 200°C/2ore, di avere ossido di zirconio, mentre per ottenere gli ossidi di alluminio, è sufficiente un ulteriore trattamento termico a basse temperature e di breve durata (400°C/ 5 min). Si è osservato, inoltre, che il trattamento termico condotto con le microonde comporta la formazione delle fasi cristalline desiderate (ossidi di alluminio e zirconio), impiegando (come per la sintesi) tempi e temperature significativamente ridotti. L’esposizione delle polveri per tempi ridotti e a temperature più basse consente di evitare la formazione di aggregati duri nelle nanopolveri finali e di contrastare il manifestarsi di fenomeni di accrescimento di grani, preservando così la “nanostruttura” delle polveri e le sue caratteristiche proprietà.

Removal torque of zirconia abutment screws under dry and wet conditions

The aim of this study was to verify whether screw abutment lubrication can generate higher preload values compared to non-lubricated screws, a titanium abutment was screwed onto an implant analog and scanned with the Procera System to generate 20 zirconia abutments. MKIII Brånemark implants were clamped to a precision torque device, and the abutments were distributed in dry and wet groups with 10 specimens each. In the wet groups, the inner threads of the implants were filled with artificial saliva. All abutments were fastened with a Torqtite screw under 32 Ncm. Ten detorque measurements were performed per group pushing the reverse button of the Torque controller soon after screw tightening with values registered. The mean detorque values were calculated and compared by a Student's t test (?=0.05). The wet condition presented significantly higher mean detorque than the dry condition (31.5 ± 1.2 versus 27.5 ± 1.5 Ncm, respectively; p=0.0000024). In conclusion, there was always a loss in the initial torque values when the removal torque was measured under both conditions. The wet condition presented higher mean torque than the dry condition. Better preload values were established in the wet group, suggesting that the abutment screw must be lubricated in saliva to avoid further loosening.