Local atomic structure in tetragonal pure ZrO(2) nanopowders

The local atomic structures around the Zr atom of pure (undoped) ZrO(2) nanopowders with different average crystallite sizes, ranging from 7 to 40 nm, have been investigated. The nanopowders were synthesized by different wet-chemical routes, but all exhibit the high-temperature tetragonal phase stabilized at room temperature, as established by synchrotron radiation X-ray diffraction. The extended X-ray absorption fine structure (EXAFS) technique was applied to analyze the local structure around the Zr atoms. Several authors have studied this system using the EXAFS technique without obtaining a good agreement between crystallographic and EXAFS data. In this work, it is shown that the local structure of ZrO(2) nanopowders can be described by a model consisting of two oxygen subshells (4 + 4 atoms) with different Zr-O distances, in agreement with those independently determined by X-ray diffraction. However, the EXAFS study shows that the second oxygen subshell exhibits a Debye-Waller (DW) parameter much higher than that of the first oxygen subshell, a result that cannot be explained by the crystallographic model accepted for the tetragonal phase of zirconia-based materials. However, as proposed by other authors, the difference in the DW parameters between the two oxygen subshells around the Zr atoms can be explained by the existence of oxygen displacements perpendicular to the z direction; these mainly affect the second oxygen subshell because of the directional character of the EXAFS DW parameter, in contradiction to the crystallographic value. It is also established that this model is similar to another model having three oxygen subshells, with a 4 + 2 + 2 distribution of atoms, with only one DW parameter for all oxygen subshells. Both models are in good agreement with the crystal structure determined by X-ray diffraction experiments.

Interface excess and polymorphic stability of nanosized zirconia-magnesia

Controlling the phase stability of ZrO2 nanoparticles is of major importance in the development of new ZrO2-based nanotechnologies. Because of the fact that in nanoparticles the surface accounts for a larger fraction of the total atoms, the relative phase stability can be controlled throughout the surface composition, which can be toned by surface excess of one of the components of the system., The objective of this work is to delineate a relationship between surface excess (or solid solution) of MgO relative to ZrO2 and the polymorphic stability of (ZrO2)(1-x) - (MgO), nanopowders, where 0.0 <= x <= 0.6. The nanopowders were prepared by a liquid precursor method at 500 degrees C and characterized by N-2 adsorption (BET), X-ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS), and Raman spectroscopy. For pure ZrO2 samples, both tetragonal and monoclinic polymorphs were detected, as expected considering the literature. For MgO molar fractions varying from 0.05 to 0.10, extensive solid solution could not be detected, and a ZrO2 surface energy reduction, caused by Mg surface excess detected by XPS, promoted tetragonal polymorph thermodynamic stabilization with relation to monoclinic. For MgO molar fractions higher than 0.10 and up to 0.40, Mg solid solution could be detected and induced cubic phase stabilization. MgO periclase was observed only at x = 0.6. A discussion based on the relationship between the surface excess, surface energy, and polymorph stability is presented.

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.

Thermal behavior and decomposition kinetics of rifampicin polymorphs under isothermal and non-isothermal conditions

The thermal behavior of two polymorphic forms of rifampicin was studied by DSC and TG/DTG. The thermoanalytical results clearly showed the differences between the two crystalline forms. Polymorph I was the most thermally stable form, the DSC curve showed no fusion for this species and the thermal decomposition process occurred around 245 ºC. The DSC curve of polymorph II showed two consecutive events, an endothermic event (Tpeak = 193.9 ºC) and one exothermic event (Tpeak = 209.4 ºC), due to a melting process followed by recrystallization, which was attributed to the conversion of form II to form I. Isothermal and non-isothermal thermogravimetric methods were used to determine the kinetic parameters of the thermal decomposition process. For non-isothermal experiments, the activation energy (Ea) was derived from the plot of Log β vs 1/T, yielding values for polymorph form I and II of 154 and 123 kJ mol-1, respectively. In the isothermal experiments, the Ea was obtained from the plot of lnt vs 1/T at a constant conversion level. The mean values found for form I and form II were 137 and 144 kJ mol-1, respectively.

Erbium-activated silica-zirconia planar waveguides prepared by sol-gel route

Er(3+) doped (100-x)SiO(2)-xZrO(2) planar waveguides were prepared by the sol-gel route, with x ranging from 10 up to 30 mol%. Multilayer films doped with 0.3 mol% Er(3+) ions were deposited on fused quartz substrates by the dip-coating technique. The thickness and refractive index were measured by m-line spectroscopy at different wavelengths. The fabrication protocol was optimized in order to confine one propagating mode at 1.5 mu m. Photoluminescence in the near and visible region indicated a crystalline local environment for the Er(3+) ion. (c) 2007 Elsevier B.V. All rights reserved.

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.

EFFECT OF METAL PRIMERS ON MICROTENSILE BOND STRENGTH BETWEEN ZIRCONIA AND RESIN CEMENTS

Statement of problem. There are no established clinical procedures for bonding zirconia to tooth structure using resin cements. Purpose. The purpose of this study was to evaluate the influence of metal primers, resin cements, and aging on bonding to zirconia. Material and methods. Zirconia was treated with commercial primers developed for bonding to metal alloys (Metaltite, Metal Primer II, Alloy Primer or Totalbond). Non-primed specimens were considered as controls. One-hundred disk-shaped specimens (19 x 4 mm) were cemented to composite resin substrates using Panavia or RelyX Unicem (n=5). Microtensile bond strength specimens were tested after 48 hours and 5 months (150 days), and failure modes were classified as type 1 (between ceramic/cement), 2 (between composite resin/cement) or 3 (mixed). Data were analyzed by 3-way ANOVA and Multiple Comparison Tukey test (alpha=.05). Results. The interactions primer/luting system (P=.016) and luting system/storage time (P=.004) were statistically significant. The use of Alloy Primer significantly improved the bond strength of RelyX Unicem (P<.001), while for Panavia, none of the primers increased the bond strength compared to the control group. At 48 hours, Panavia had statistically higher bond strength (P=.004) than Unicem (13.9 +/- 4.4MPa and 10.2 +/- 6.6MPa, respectively). However, both luting systems presented decreasing, statistically similar; values after aging (Panavia: 3.6 +/- 2.2MPa; Unicem: 6.1 +/- 5.3MPa). At 48 hours, Alloy Primer/Unicem had the lowest incidence of type 1 failure (8%). After aging, all the groups showed a predominance of type 1 failures. Conclusions. The use of Alloy Primer improved bond strength between RelyX Unicem and zirconia. Though the initial values obtained with Panavia were significantly higher than RelyX Unicem, after aging, both luting agents presented statistically similar performances. (J Prosthet Dent 2011;105:296-303)

Thermal/mechanical simulation and laboratory fatigue testing of an alternative yttria tetragonal zirconia polycrystal core-veneer all-ceramic layered crown design

This study evaluated the stress levels at the core layer and the veneer layer of zirconia crowns (comprising an alternative core design vs. a standard core design) under mechanical/thermal simulation, and subjected simulated models to laboratory mouth-motion fatigue. The dimensions of a mandibular first molar were imported into computer-aided design (CAD) software and a tooth preparation was modeled. A crown was designed using the space between the original tooth and the prepared tooth. The alternative core presented an additional lingual shoulder that lowered the veneer bulk of the cusps. Finite element analyses evaluated the residual maximum principal stresses fields at the core and veneer of both designs under loading and when cooled from 900 degrees C to 25 degrees C. Crowns were fabricated and mouth-motion fatigued, generating master Weibull curves and reliability data. Thermal modeling showed low residual stress fields throughout the bulk of the cusps for both groups. Mechanical simulation depicted a shift in stress levels to the core of the alternative design compared with the standard design. Significantly higher reliability was found for the alternative core. Regardless of the alternative configuration, thermal and mechanical computer simulations showed stress in the alternative core design comparable and higher to that of the standard configuration, respectively. Such a mechanical scenario probably led to the higher reliability of the alternative design under fatigue.

Reliability of Metalloceramic and Zirconia-based Ceramic Crowns

Despite the increasing utilization of all-ceramic crown systems, their mechanical performance relative to that of metal ceramic restorations (MCR) has yet to be determined. This investigation tested the hypothesis that MCR present higher reliability over two Y-TZP all-ceramic crown systems under mouth-motion fatigue conditions. A CAD-based tooth preparation with the average dimensions of a mandibular first molar was used as a master die to fabricate all restorations. One 0.5-mm Pd-Ag and two Y-TZP system cores were veneered with 1.5 mm porcelain. Crowns were cemented onto aged (60 days in water) composite (Z100, 3M/ESPE) reproductions of the die. Mouth-motion fatigue was performed, and use level probability Weibull curves were determined. Failure modes of all systems included chipping or fracture of the porcelain veneer initiating at the indentation site. Fatigue was an acceleration factor for all-ceramic systems, but not for the MCR system. The latter presented significantly higher reliability under mouth-motion cyclic mechanical testing.

Oxide surface modification: Synthesis and characterization of zirconia-coated alumina

Four aluminas were used as Supports for impregnation with a zirconium oxide with the aim to achieve a coating, without phase separation, between Support and modifier. The Supports were impregnated with different concentrations Of zirconium aqueous resin, obtained through the polymeric precursor method. After impregnation the samples were calcined and then characterized by XRD, which led to identification of crystalline zirconia in different concentrations from each support used. Using a simple geometric model the maximum amount Of Surface modifier Oxide required for the complete coating of a support with a layer of unit cells was estimated. According to this estimate, only the support should be identified below the limit proposed and crystalline zirconium oxide Should be identified above this limit when a complete coating is reached. The results obtained From XRD agree with the estimated values and to confirm the coating, the samples were also characterized by EDS/STEM, HRTEM, XPS, and XAS. The results showed that the zirconium oxide oil the Surface of alumina Support reached the coating in the limit of 15 Zr nm(-2), without the formation of the ZrO(2) phase. (c) 2009 Elsevier Inc. All rights reserved.

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.

Effect of culture medium on biocalcification by Pseudomonas Putida, Lysinibacillus Sphaericus and Bacillus Subtilis

The objective of this study is to investigate the efficiency of calcium carbonate bioprecipitation by Lysinibacillus sphaericus, Bacillus subtilis and Pseudomonas putida, obtained from the Coleção de Culturas do Instituto Nacional de Controle de Qualidade em Saúde (INCQS), as a first step in determining their potential to protect building materials against water uptake. Two culture media were studied: modified B4 containing calcium acetate and 295 with calcium chloride. Calcium consumption in the two media after incubation with and without the bacterial inoculum was determined by atomic absorption analysis. Modified B4 gave the best results and in this medium Pseudomonas putida INQCS 113 produced the highest calcium carbonate precipitation, followed by Lysinibacillus sphaericus INQCS 414; the lowest precipitation was produced by Bacillus subtilis INQCS 328. In this culture medium XRD analysis showed that Pseudomonas putida and Bacillus subtilis precipitated calcite and vaterite polymorphs while Lysinibacillus sphaericus produced only vaterite. The shape and size of the crystals were affected by culture medium, bacterial strain and culture conditions, static or shaken. In conclusion, of the three strains Pseudomonas putida INQCS 113 in modified B4 medium gave the best results precipitating 96% of the calcium, this strain thus has good potential for use on building materials.

Crystallite size-dependent phases in nanocrystalline ZrO(2)-Sc(2)O(3)

ZrO(2)-10, 12 and 14 mol% Sc(2)O(3) nanopowders were prepared by using a nitrate-lysine gel-combustion synthesis. These materials were studied by synchrotron X-ray powder diffraction (SXPD) and Raman spectroscopy after calcination at different temperatures from 650 to 1200 degrees C, which led to samples with different average crystallite sizes, up to about 100 nm. The results from SXPD and Raman analyses indicate that, depending on Sc(2)O(3) content, the metastable t ''-form of the tetragonal phase or the cubic phase are fully retained at room temperature in nanocrystalline powders, provided an average crystallite sizes lower than similar to 30 nm. By contrast, powders with larger average crystallite sizes exhibit the stable rhombohedral, beta and gamma, phases and do not retain or very partially retain the metastable t '' and cubic ones.

Synchrotron X-ray powder diffraction and extended X-ray absorption fine structure spectroscopy studies on nanocrystalline ZrO(2)-CaO solid solutions

The crystal structure and the local atomic order of a series of nanocrystalline ZrO(2)-CaO solid solutions with varying CaO content were studied by synchrotron radiation X-ray powder diffraction and extended X-ray absorption fine structure (EXAFS) spectroscopy. These samples were synthesized by a pH-controlled nitrate-glycine gel-combustion process. For CaO contents up to 8 mol%, the t' form of the tetragonal phase (c/a > 1) was identified, whereas for 10 and 12 mol% CaO, the t '' form (c/a=1; oxygen anions displaced from their ideal positions in the cubic phase) was detected. Finally, the cubic phase was observed for solid solutions with CaO content of 14 mol% CaO or higher. The t'/t '' and t ''/cubic compositional boundaries were determined to be at 9 (1) and 13 (1) mol% CaO, respectively. The EXAFS study demonstrated that this transition is related to a tetragonal-to-cubic symmetry change of the first oxygen coordination shell around the Zr atoms.

High-temperature X-ray powder diffraction study of the tetragonal-cubic phase transition in nanocrystalline, compositionally homogeneous ZrO2-CeO2 solid solutions

Crystal structure of compositionally homogeneous, nanocrystalline ZrO2-CeO2 solutions was investigated by X-ray powder diffraction as a function of temperature for compositions between 50 and 65 mol % CeO2 center dot ZrO2-50 and 60 mol % CeO2 solid solutions, which exhibit the t'-form of the tetragonal phase at room temperature, transform into the cubic phase in two steps: t'-to-t '' followed by t ''-to-cubic. But the ZrO2-65 mol % CeO2, which exhibits the t ''-form, transforms directly to the cubic phase. The results suggest that t'-to-t '' transition is of first order, but t ''-to-cubic seems to be of second order. (C) 2008 International Centre for Diffraction Data.