Preparation, Characterization and Microwave Dielectric Properties of Ba (B1/2Nb1/2)03 [B' = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb and In] Ceramics

Microwave dielectric resonators (DRs) based on Ba(B1,2Nbi/2)03 [B' = La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Yb, and In] complex perovskites have been prepared by conventional solid state ceramic route. The dielectric properties (relative permittivity, Er; quality factor, Q; and resonant frequency, rr) of the ceramics have been measured in the frequency range 4-6 GHz using resonance methods. The resonators have relatively high dielectric constant in the range 36-45, high quality factor and small temperature variation of resonant frequency. The dielectric properties are found to depend on the tolerance factor (t), ionic radius (r), and lattice parameter (ap)

Photoacoustic Thermal Characterization of Porous Rare-Earth Phosphate Ceramics

The laser induced non-destructive photoacoustic technique has been employed to measure the thermal diffusivity of lanthanum phosphate ceramics prepared by the sol–gel route. The thermal diffusivity value was evaluated by knowing the transition frequency between the thermally thin to thermally thick region from the log–log plot of photoacoustic amplitude versus chopping frequency. Analysis of the data was carried out on the basis of the one-dimensional model of Rosencwaig and Gersho. The present investigation reveals that the sintering temperature has great influence on the propagation of heat carriers and hence on the thermal diffusivity value. The results were interpreted in terms of variations in porosity with sintering temperature as well as with changes in grain size.

Thermal characterization of nanocrystalline porous CePO4 ceramics

A laser-induced photoacoustic technique was employed to investigate thermal transport through nanocrystalline CePO4 samples prepared via the sol–gel route. Evaluation of thermal diffusivity was carried out using the one-dimensional model of Rosencwaig and Gersho for the reflection configuration of the photoacoustic method. Structural analyses of samples revealed that they are nanoporous in nature, possessing micron-sized grains. Analysis of results shows that thermal diffusivity value varies with sintering temperature. Results are explained in terms of the variation in porosity with sintering temperature and the effects of various scattering mechanisms on the propagation of phonons through the nanoporous ceramic matrix. Further analyses confirm that apart from porosity, grain boundary resistance and interface thermal resistance influence the effective value of thermal diffusivity of the samples under investigation.

Preparation and structural characterization of rare-earth doped lead lanthanum zirconate titanate ceramics

A new preparation route towards rare-earth (RE) doped polycrystalline lead lanthanum zirconate titanate (PLZT) ceramics (RE = Y(3+), Nd(3+), Yb(3+)), based on the use of doped lanthanum oxide or zirconia, is reported. Structural characterization by X-ray powder diffraction reveals that secondary phase formation can be substantially diminished in comparison to conventional preparation methods. The distribution of the rare-earth dopants was investigated as a function of concentration by static (207)Pb spin echo NMR spectra, using Fourier Transformation of Carr-Purcell-Meiboom-Gill spin echo trains. For the Nd- and Yb-doped materials, the interaction of the (207)Pb nuclei with the unpaired electron spin density results in significant broadening and shifting of the NMR signal, whereas these effects are absent in the diamagnetic Y(3+) doped materials. Based on different concentration dependences of the NMR lineshape parameters, we conclude that the structural role of the Nd(3+) dopants differs significantly from that of Yb(3+). While the Nd(3+) ions appear to be statistically distributed in the PLZT lattice, incorporation of Yb(3+) into PLZT appears to be limited by the appearance of doped cubic zirconia as a secondary phase. (C) 2009 Elsevier Masson SAS. All rights reserved.

Solid state NMR as a new approach for the structural characterization of rare-earth doped lead lanthanum zirconate titanate laser ceramics

To facilitate the design of laser host materials with optimized emission properties, detailed structural information at the atomic level is essential, regarding the local bonding environment of the active ions (distribution over distinct lattice sites) and their extent of local clustering as well as their population distribution over separate micro- or nanophases. The present study explores the potential of solid state NMR spectroscopy to provide such understanding for rare-earth doped lead lanthanum zirconate titanate (PLZT) ceramics. As the NMR signals of the paramagnetic dopant species cannot be observed directly, two complementary approaches are utilized: (1) direct observation of diamagnetic mimics using Sc-45 NMR and (2) study of the paramagnetic interaction of the constituent host lattice nuclei with the rare-earth dopant, using Pb-207 NMR lineshape analysis. Sc-45 MAS NMR spectra of scandium-doped PLZT samples unambiguously reveal scandium to be six-coordinated, suggesting that this rare-earth ion substitutes in the B site. Static Pb-207 spin echo NMR spectra of a series of Tm-doped PLZT samples reveal a clear influence of paramagnetic rare-earth dopant concentration on the NMR lineshape. In the latter case high-fidelity spectra can be obtained by spin echo mapping under systematic incrementation of the excitation frequency, benefiting from the signal-to-noise enhancement afforded by spin echo train Fourier transforms. Consistent with XRD data, the Pb-207 NMR lineshape analysis suggests that statistical incorporation into the PLZT lattice occurs at dopant levels of up to 1 wt.% Tm3+, while at higher levels the solubility limit is reached. (C) 2008 Elsevier Masson SAS. All rights reserved.

Solid state NMR characterization of lithium conducting ceramics

⁷Li solid state NMR has been used to characterize lithium aluminium titanium phosphate and lithium lanthanum titanate ceramics. Both materials have high ionic mobilities at room temperature and this is reflected in their static ⁷Li powder patterns. In the case of the phosphate based ceramic, a narrow Lorentzian peak is observed above 300 K, which narrows further with increasing temperature. The accompanying quadrupolar structure, with C_Q (quadrupolar coupling constant) ~ 40 kHz, suggests that the lithium ions are hopping rapidly between equivalent, high electric field gradient sites. The ²⁷Al and ³¹P magic angle spinning (MAS) spectra reveal an asymmetric phosphorus peak and two distinct aluminium resonances. The room temperature powder pattern of Li_0.33La_0.57TiO₃ shows a dipolar broadened peak which narrows quite suddenly at 310 K revealing quadrupolar satellites with C_Q ~ 900 Hz. A second lithium site is also observed in this material, as indicated by a further, weaker quadrupolar structure (C_Q ~ 40 kHz).

Fractal characterization of brittle fracture in ceramics under mode I stress loading

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

Evaluation of interface characterization and adhesion of glass ceramics to commercially pure titanium and gold alloy after thermal- and mechanical-loading

Objectives. This study evaluated the effect of thermal- and mechanical-cycling on the shear bond strength of three low-fusing glassy matrix dental ceramics to commercial pure titanium (cpTi) when compared to conventional feldspathic ceramic fused to gold alloy.Methods. Metallic frameworks (diameter: 5 min, thickness: 4 mm) (N = 96, n = 12 per group) were cast in cpTi and gold alloy, airborne particle abraded with 150 mu m aluminum oxide. Low-fusing glassy matrix ceramics and a conventional feldspathic ceramic were fired onto the alloys (thickness: 4mm). Four experimental groups were formed; Gr1 (control group): Vita Omega 900-Au-Pd alloy; Gr2: Ticeram-cpTi; Gr3: Super Porcelain Ti-22-cpTi and G4: Vita Titankeramik-cpTi. While half of the specimens from each ceramic-metal combination were randomly tested without aging (water storage at 37 C for 24h only), the other half were first thermocycled (6000 cycles, between 5 and 55 C, dwell time: 13 s) and then mechanically loaded (20,000 cycles under SON load, immersion in distilled water at 37 C). The ceramic-alloy interfaces were loaded under shear in a universal test machine (cross-head speed: 0.5 mm/min) until failure occur-red. Failure types were noted and the interfaces of the representative fractured specimens from each group were examined with stereo microscope and scanning electron microscope (SEM). in an additional study (N = 16, n = 2 per group), energy dispersive X-ray spectroscopy (EDS) analysis was performed from ceramic-alloy interfaces. Data were analyzed using ANOVA and Tukey's test.Results. Both ceramic-metal combinations (p < 0.001) and aging conditions (p < 0,001) significantly affected the mean bond strength values. Thermal- and mechanical-cycling decreased the bond strength (MPa) results significantly for Gr3 (33.4 +/- 4.2) and Gr4 (32.1 +/- 4.8) when compared to the non-aged groups (42.9 +/- 8.9, 42.4 +/- 5.2, respectively). Gr1 was not affected significantly from aging conditions (61.3 +/- 8.4 for control, 60.7 +/- 13.7 after aging) (p > 0.05). Stereomicroscope images showed exclusively adhesive failure types at the opaque ceramic-cpTi interfacial zone with no presence of ceramic on the substrate surface but with a visible dark titanium oxide layer in Groups 2-4 except Gr1 where remnants of bonder ceramic was visible. EDS analysis from the interfacial zone for cpTi-ceramic groups showed predominantly 34.5-85.1% O(2) followed by 1.1-36.7% Aland 0-36.3% Si except for Super Porcelain Ti-22 where a small quantity of Ba (1.4-8.3%), S (0.7%) and Sn (35.3%) was found. In the Au-Pd alloy-ceramic interface, 56.4-69.9% O(2) followed by 15.6-26.2% Si, 3.9-10.9% K, 2.8-6% Na, 4.4-9.6% Al and 0-0.04% Mg was observed.Significance. After thermal-cycling for 6000 times and mechanical-cycling for 20,000 times, Triceram-cpTi combination presented the least decrease among other ceramic-alloy combinations when compared to the mean bond strength results with Au-Pd alloy-Vita Omega 900 combination. (c) 2008 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Structural and dielectric characterization of praseodymium-modified lead titanate ceramics synthesized by the OPM route

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

Structural characterization of organometallic-derived 9.5/65/35 PLZT ceramics

This study consisted of an investigation of the influence of powder preparation on the phase and chemical compositions and microstructure of 9.5/65/35 PLZT materials sintered in an oxygen atmosphere. The powders with the formula Pb0.905La0.095(Zr0.65Ti0.35)(0.976)O-3+3.5 wt.% PbO were prepared by the polymeric organometallic precursor method (the Pechini method and the partial oxalate procedure). Phase composition was determined by X-ray diffraction of powder and EDS analysis, while grain size was determined based on the micrograph obtained from SEM. (C) 2001 Elsevier B.V. B.V. All rights reserved.

Characterization of bismuth titanate ceramics derived by mechanochemical synthesis

Bismuth titanate, Bi(4)Ti(3)O(12) (BIT) nanosized powders have been successfully synthesized via high energy mechanochemical activation. The phase formation of BIT, crystal structure, microstructure, crystallite size and specific surface area were followed by XRD, scanning electron microscopy (SEM) and the BET specific surface area measurements. The BIT milled 2 h shows the orthorhombic crystalline structure with small amount of amorphous phase. The microstructure of Bi(4)Ti(3)O(12) ceramics sintered at 1000 degrees C for 12h exhibit plate-like grain structure.

Structural and electrical characterization of semiconducting barium-lead-titanate ceramics

BaTiO3 is usually doped to achieve the temperature stability required by device applications, as well as to obtain a large positive temperature coefficient anomaly of resistivity (PTCR). Uniform distribution of dopants among the submicron dielectric particles is the key for optimal control of grain size and microstructure to maintain a high reliability. The system Ba0.84Pb0.16TiO3 was synthesized from high purity BaCO3, TiO2, PbO oxide powders as raw materials. Sb2O3, MnSO4 and ZnO were used as dopants and Al2O3, TiO2 and SiO2 as grain growth controllers. Phase composition was analyzed by using XRD and the microstructure was investigated by SEM. EDS attached to SEM was used to analyze phase composition specially related to abnormal grain growth. Electrical resistivities were measured as a function of temperature and the PTCR effect characterized by an abrupt increase on resistivity.

Synthesis and electrical characterization of tungsten doped Pb(Zr0.53Ti0.47)O-3 ceramics obtained from a hybrid process

Pure and W-doped PZT ceramics (PZT and PZTW) were prepared by a hybrid process consisting in the association of polymeric precursor and partial oxalate methods. The phase formation was investigated by simultaneous thermal analysis (TG/DSC) and X-ray diffraction (XRD). The effect of W doping PZT and their electrical properties was evaluated. Substitution of W by Ti leads to an increase of Curie temperature and broadening of dielectric constant. A typical hysteresis loop was observed at room temperature and the remnant polarization was increased with the content of W. (c) 2007 Elsevier B.V. All rights reserved.