Spontaneous long and short-range ferroelectric ordering in Pb(0.55)La(0.30)TiO(3) ceramics

In this work, we investigated the temperature dependence of short and long-range ferroelectric ordering in Pb(0.55)La(0.30)TiO(3) relaxor composition. High-resolution x-ray powder diffraction measurements revealed a clear spontaneous macroscopic cubic-to-tetragonal phase transition in the PLT relaxor sample at similar to 60 K below the maximum of the dielectric constant peak (T(m)). Indeed, the x-ray diffraction (XRD) data showed that at 300 K (above T(m) but below the Burns temperature, T(B)) the long-range order structure corresponds to a macroscopic cubic symmetry, space group number 221 (Pm-3m), whereas the data collected at 20 K revealed a macroscopic tetragonal symmetry, space group number 99 (P4mm) with c/a=1.0078, that is comparable to that of a normal ferroelectric. These results show that for samples with tetragonal composition, the long-range ferroelectric order may be recovered spontaneously at cryogenics temperatures, in contrast to ferroelectric samples with rhombohedral symmetry. On the other hand, x-ray absorption spectroscopy investigations intriguingly revealed the existence of local tetragonal disorder around Ti atoms for temperatures far below T(m) and above T(B), for which the sample presents macroscopic tetragonal and cubic symmetries, respectively. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3431024]

The role of oxygen vacancy in the photoluminescence property at room temperature of the CaTiO(3)

In this paper, electron paramagnetic resonance, photoluminescence (PL) emission, and quantum mechanical calculations were used to observe and understand the structural order-disorder of CaTiO(3), paying special attention to the role of oxygen vacancy. The PL phenomenon at room temperature of CaTiO(3) is directly influenced by the presence of oxygen vacancies that yield structural order-disorder. These oxygen vacancies bonded at Ti and/or Ca induce new electronic states inside the band gap. Ordered and disordered CaTiO(3) was obtained by the polymeric precursor method. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3190524]

Luminescent and thermo-optical properties of Nd(3+)-doped yttrium aluminoborate laser glasses

In this work we performed a thorough spectroscopic and thermo-optical investigation of yttrium aluminoborate glasses doped with neodymium ions. A set of samples, prepared by the conventional melt-quenching technique and with Nd(2)O(3) concentrations varying from 0.1 to 0.75 mol %, were characterized by ground state absorption, photoluminescence, excited state lifetime measurements, and thermal lens technique. For the neodymium emission at 1064 nm ((4)F(3/2) -> (4)I(11/2) transition), no significant luminescence concentration quenching was observed and the experimental lifetime values ranged around 70 mu s. The obtained values of thermal conductivity and diffusivity of approximately 10.3 x 10(-3) W / cm K and 4.0 x 10(-3) cm(2) / s, respectively, are comparable to those of commercial laser glasses. Moreover, the fluorescence quantum efficiency of the glasses, calculated using the Judd-Ofelt formalism and luminescence decay, lies in the range from 0.28 to 0.32, larger than the typical values obtained for Nd(3+) doped YAl(3)(BO(3))(4) crystals. (c) 2009 American Institute of Physics. [DOI: 10.1063/1.3176503]

Internal Residual Stresses in Sintered and Commercial Low Expansion Li(2)O-Al(2)O(3)-SiO(2) Glass-Ceramics

We performed Synchrotron X-ray diffraction (XRD) analyses of internal residual stresses in monolithic samples of a newly developed Li(2)O-Al(2)O(3)-SiO(2) (LAS) glass-ceramic produced by sintering and in a commercial LAS glass-ceramic, CERAN (R), produced by the traditional crystal nucleation and growth treatments. The elastic constants were measured by instrumented indentation and a pulse-echo technique. The thermal expansion coefficient of virgilite was determined by high temperature XRD and dilatometry. The c-axis contracts with the increasing temperature whereas the a-axis does not vary significantly. Microcracking of the microstructure affects the thermal expansion coefficients measured by dilatometry and thermal expansion hysteresis is observed for the sintered glass-ceramic as well as for CERAN (R). The measured internal stress is quite low for both glass-ceramics and can be explained by theoretical modeling if the high volume fraction of the crystalline phase (virgilite) is considered. Using a modified Green model, the calculated critical (glass) island diameter for spontaneous cracking agreed with experimental observations. The experimental data collected also allowed the calculation of the critical crystal grain diameters for grain-boundary microcracking due to the anisotropy of thermal expansion of virgilite and for microcracking in the residual glass phase surrounding the virgilite particles. All these parameters are important for the successful microstructural design of sintered glass-ceramics.

Identification of Elastic, Dielectric, and Piezoelectric Constants in Piezoceramic Disks

Three-dimensional modeling of piezoelectric devices requires a precise knowledge of piezoelectric material parameters. The commonly used piezoelectric materials belong to the 6mm symmetry class, which have ten independent constants. In this work, a methodology to obtain precise material constants over a wide frequency band through finite element analysis of a piezoceramic disk is presented. Given an experimental electrical impedance curve and a first estimate for the piezoelectric material properties, the objective is to find the material properties that minimize the difference between the electrical impedance calculated by the finite element method and that obtained experimentally by an electrical impedance analyzer. The methodology consists of four basic steps: experimental measurement, identification of vibration modes and their sensitivity to material constants, a preliminary identification algorithm, and final refinement of the material constants using an optimization algorithm. The application of the methodology is exemplified using a hard lead zirconate titanate piezoceramic. The same methodology is applied to a soft piezoceramic. The errors in the identification of each parameter are statistically estimated in both cases, and are less than 0.6% for elastic constants, and less than 6.3% for dielectric and piezoelectric constants.

Evaluation of the physical and chemical properties of two commercial and three experimental root-end filling materials

Objective. The aim of this study was to evaluate the pH, calcium release, setting time, and solubility of two commercially available mineral trioxide aggregate (MTA) cements (white MTA Angelus and MTA Bio), and of three experimental cements (light-cured MTA, Portland cement with 20% bismuth oxide and 5% calcium sulfate, and an epoxy resin-based cement). Study design. For evaluation of pH and calcium ion release, polyethylene tubes with 1.0 mm internal diameter and 10.0 mm length were filled with the cements and immediately immersed in flasks containing 10 mL deionized water. After 3, 24, 72, and 168 hours, the tubes were removed and the water from the previous container was measured for its pH and calcium content with a pH meter and an atomic absorption spectrophotometer. For analysis of the setting time, Gilmore needles weighing 100 g and 456.5 g were used, in accordance with the American Society for Testing and Materials specification no. C266-03. Solubility of each cement was also tested. Results. All the cements were alkaline and released calcium ions, with a declining trend over time. After 3 hours, Portland cement + bismuth oxide and MTA Bio had the highest pH and light-cured MTA the lowest. After 1 week, MTA Bio had the highest pH and light-cured MTA and epoxy resin-based cement the lowest. Regarding calcium ion release, after 3 hours, Portland cement + bismuth oxide showed the highest release. After 1 week, MTA Bio had the highest. Epoxy resin-based cement and light-cured MTA had the lowest calcium release in all evaluation periods. Regarding setting times, white MTA Angelus and MTA Bio had the shortest, Portland cement + bismuth oxide had an intermediate setting time, and the epoxy resin-based cement had the longest. The materials that showed the lowest solubility values were the epoxy resin-based cement, Portland cement + bismuth oxide, and light-cured MTA. The highest solubility values were presented in white MTA Angelus and MTA Bio. Conclusions. The white MTA Angelus and MTA Bio had the shortest setting times, higher pH and calcium ion release, and the highest solubility. In contrast, the epoxy resin-based cement and light-cured MTA showed lower values of solubility, pH, and calcium ion release. (Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2010; 110: 250-256)

Evaluation of the radiopacity of some commercial and experimental root-end filling materials

Objective. The aim of the present study was to evaluate the radiopacity of 5 root end filling materials (white MTA Angelus, MTA Bio, light-cured MTA, Sealepox RP, and Portland cement clinker with bismuth oxide and calcium sulfate). Method. Five specimens, 10 mm in diameter and 1 mm in thickness according to specification ISO 6876: 2001 were fabricated from each material and radiographed using Insigth occlusal films close to a graduated aluminum step-wedge (2 to 16 mm in thickness). Radiographs were digitized and compared to the aluminum step-wedge. The radiographic density data were converted into millimeters of aluminum (mm Al), using the Digora 1.51 software. Results were evaluated statistically using the analysis of variance (ANOVA) followed by Tukey test. The level of significance was set at 5% (P<.05%). Results. Radiopacity values ranged from 1.21 mm Al (light-cured MTA) to 6.45 mm Al (MTA Angelus). Comparison between materials showed significant difference (P<.05) between MTA Angelus and all other materials, between Sealepox RP and MTA Bio, and between light-cured MTA and Portland cement clinker. Light-cured MTA was significantly less radiopaque than all other materials. No significant difference (P>.05) was found between MTA Bio and Portland cement clinker. Conclusions. All retrograde filling materials evaluated showed greater radiopacity than dentin. All the materials, except light-cured MTA met the minimum radiopacity standards of 3 mm Al recognized by the ISO 6876: 2001 and ADA n.57. (Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2009; 108: e35-e38)

Radiopacity of Portland Cement Associated With Different Radiopacifying Agents

This study evaluated the radiopacity of Portland cement associated with the following radiopacifying agents: bismuth oxide, zinc oxide, lead oxide, bismuth subnitrate, bismuth carbonate, barium sulfate, iodoform, calcium tungstate, and zirconium oxide. A ratio of 20% radiopacifier and 80% white Portland cement by weight was used for analysis. Pure Portland cement and dentin served as controls. Cement/radiopacifier and dentin disc-shaped specimens were fabricated, and radiopacity testing was performed according to the ISO 6876/2001 standard for dental root sealing materials. Using Insight occlusal films, the specimens were radiographed near to a graduated aluminum stepwedge varying from 2 to 16 mm in thickness. The radiographs were digitized and radiopacity compared with the aluminum stepwedge using Digora software (Orion Corporation Soredex, Helsinki, Finland). The radiographic density data were converted into mmAl and analyzed statistically by analysis of variance and Tukey-Kramer test (alpha = 0.05). The radiopacity of pure Portland cement was significantly lower (p < 0.05) than that of dentin, whereas all cement/radiopacifier mixtures were significantly more radiopaque than dentin and Portland cement alone (p < 0.05). Portland cement/bismuth oxide and Portland cement/lead oxide presented the highest radiopacity values and differed significantly from the other materials (p < 0.05), whereas Portland cement/zinc oxide presented the lowest radiopacity values of all mixtures (p < 0.05). All tested substances presented higher radiopacity than that of dentin and may potentially be added to the Portland cement as radiopacifying agents. However, the possible interference of the radiopacifiers with the setting chemistry, biocompatibility, and physical properties of the Portland cement should be further investigated before any clinical recommendation can be done. (J Endod 2009,35:737-740)

Radiopacity Evaluation of Calcium Aluminate Cement Containing Different Radiopacifying Agents

Introduction: The aim of this study was to evaluate the radiopacity of calcium aluminate cement (Endo Binder) with 3 different radiopacifiers (bismuth oxide, zinc oxide, or zirconium oxide) in comparison with gray mineral trioxide aggregate (GMTA), white MTA, and dental structures (enamel and dentin). Methods: Eighteen test specimens of each cement with thicknesses of 0.5, 1.0, 1.5, 2.0, 2.5, and 3.0 mm (n = 3) were made by using a stainless steel matrix and were adapted to a standardizing device (8 x 7 cm) with a graduated aluminum stepwedge varying from 2.0-16.0 mm in thickness. To compare the radiopacity of the cements with that of dental structures, slices of first molars with a thickness increasing from 0.5-3.0 mm were obtained and placed on the standardizing device. One occlusal radiograph for each tested cement was taken, with exposure time of 0.1 seconds and focus-film distance of 20 cm. Films were processed in an automatic device, and the mean radiopacity values were obtained by using a photodensitometer. Results: Mean values showed that the thicker the specimen was, the greater was its radiopacity. Only EndoBinder + bismuth oxide (EBBO) and GMTA demonstrated radiopacity values greater than 3.0 mm of the aluminum scale for all thicknesses. When zinc oxide was used as radiopacifier agent, EndoBinder only reached the desired radiopacity with a thickness of 2.0 mm, and with zirconium oxide it was 2.5 mm. Conclusions: Bismuth oxide was the most efficient radiopacifier for EndoBinder, providing adequate radiopacity in all studied thicknesses, as recommended by ISO 6876, being similar to GMTA. (J Endod 2011;37: 67-71)

Pressure-induced electrical and structural anomalies in Pb(1-x)Ca(x)TiO(3) thin films grown at various oxygen pressures by chemical solution route

Lead calcium titanate (Pb(1-x)Ca(x)TiO(3) or PCT) thin films have been thermally treated under different oxygen pressures, 10, 40 and 80 bar, by using the so-called chemical solution deposition method. The structural, morphological, dielectric and ferroelectric properties were characterized by x-ray diffraction, FT-infrared and Raman spectroscopy, atomic force microscopy and polarization-electric-field hysteresis loop measurements. By annealing at a controlled pressure of around 10 and 40 bar, well-crystallized PCT thin films were successfully prepared. For the sample submitted to 80 bar, the x-ray diffraction, Fourier transformed-infrared and Raman data indicated deviation from the tetragonal symmetry. The most interesting feature in the Raman spectra is the occurrence of intense vibrational modes at frequencies of around 747 and 820 cm(-1), whose presence depends strongly on the amount of the pyrochlore phase. In addition, the Raman spectrum indicates the presence of symmetry-breaking disorder, which would be expected for an amorphous (disorder) and mixed pyrochlore-perovskite phase. During the high-pressure annealing process, the crystallinity and the grain size of the annealed film decreased. This process effectively suppressed both the dielectric and ferroelectric behaviour. Ferroelectric hysteresis loop measurements performed on these PCT films exhibited a clear decrease in the remanent polarization with increasing oxygen pressure.

In situ X-ray diffraction studies of phase transition in Pb1-x La x Zr0.40Ti0.60O3 ferroelectric ceramics

The temperature dependence of the crystalline structure and the lattice parameters of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric ceramic system with 0.00 x 0.21 was determined. The samples with x 0.11 show a cubic-to-tetragonal phase transition at the maximum dielectric permittivity, Tmax. Above this amount and especially for the x = 0.12 sample, a spontaneous phase transition from a relaxor ferroelectric state (cubic phase) to a ferroelectric state (tetragonal phase) is observed upon cooling below the Tmax. Unlike what has been reported in other studies, the x = 0.13, 0.14, and 0.15 samples, which present a more pronounced relaxor behavior, also presents a spontaneous normal-to-relaxor transition, indicated by a cubic to tetragonal symmetry below the Tmax. The origin of this anomaly has been associated with an increase in the degree of tetragonality, confirmed by the measurements of the X-ray diffraction patterns. The differential thermal analysis (DSC) measurements also confirm the existence of these phase transitions.

Nanograined Ferroelectric Ceramics Prepared by High-Pressure Densification Technique

For the first time, nanograined Pb(1-1.5x)La(x)TiO(3) ferroelectric ceramics, with x=0.2, were produced by a process based on a high-pressure densification technique (HPD) that eliminates the need of high-temperature sintering. Our results showed the production of workable dense ceramics with average grain size around 100 nm and free from secondary phase. Regarding the dielectric measurements, the samples showed satisfactory dielectric losses as well as remarkable diffusivity in the dielectric curves. Moreover, ferroelectric hysteresis measurements showed that samples produced by the HPD technique can stand high electric fields necessary to switch the polarization and thus to induce piezoelectric activity. Our results demonstrated clearly the viability of the proposed method to produce nanograined ferroelectric bulk ceramics, then opening the possibility of developing new technologies.

Photoluminescent behavior of SrZrO(3)/SrTiO(3) multilayer thin films

A detailed investigation was made into the origin of photoluminescence in an alternate multilayer system of SrZrO(3) (SZO) and SrTiO(3) (STO) thin films. XRD and room-temperature PL studies revealed a high consistency with respect to improved crystallization at elevated temperatures. The photoluminescence behaviour of SZO/STO multilayered system consists in the superposition of independent photoluminescence emissions of both STO and SZO films. Based on the present results and on previous experimental and theoretical data, we propose that the origin of the photoluminescence emission results from structural disorder generated by the presence of distortions in the ideal constituent clusters of these materials. (c) 2009 Elsevier B.V. All rights reserved.

Microstructural, structural and dielectric properties of Er(3+)-modified BaTi(0.85)Zr(0.15)O(3) ceramics

The (micro)structural and electrical properties of undoped and Er(3+)-doped BaTi(0.85)Zr(0.15)O(3) ceramics were studied in this work for both nominal Ba(2+) and Ti(4+) substitution formulations. The ceramics were produced from solid-state reaction and sintered at 1400 degrees C for 3 h. For those materials prepared following the donor-type nominal Ba(1-x)Er(x)(Ti(0.85)Zr(0.15))O(3) composition, especially, Er(3+) however showed a preferential substitution for the (Ti,Zr)(4+) lattice sites. This allowed synthesis of a finally acceptor-like, highly resistive Ba(Ti,Zr,Er)O(3-delta)-like system, with a solubility limit below but close to 3 cat.% Er(3+). The overall phase development is discussed in terms of the amphoteric nature of Er(3+), and appears to mainly or, at least, partially also involve a minimization of stress effects from the ion size mismatch between the dopant and host cations. Further results presented here include a comparative analysis of the behavior of the materials` grain size, electrical properties and nature of the ferroelectric-to-paraelectric phase transition upon variation of the formulation and Er(3+) content. (C) 2008 Elsevier Ltd. All rights reserved.

Effect of pH on the production of dispersed Bi4Ge3O12 nanoparticles by combustion synthesis

This paper reports the production of bismuth germanate ceramic scintillator (Bi4Ge3O12) by combustion synthesis (SHS) method, focusing on the influence of the synthesis parameters on the crystalline phases and agglomeration of the nanoparticles. The synthesis and sintering conditions were investigated through thermal analysis, X-ray diffraction as function of temperature, dilatometry and scanning electron microscopy. Well-dispersed Bi4Ge3O12 powder was accomplished by the combustion of the initial solution at pH 9, followed by low temperature calcination and milling. Sintered ceramics presented relative density of 98% and single crystalline Bi4Ge3O12 phase. The luminescent properties of the ceramics were investigated by photo- and radio- luminescence measurements and reproduced the typical Bi4Ge3O12 single-crystal spectra when excited with UV, beta and X-rays. The sintered ceramics presented light output of 4.4 x 10(3) photons/McV. (c) 2008 Published by Elsevier Ltd.