Phase transitions and phase diagram of the ferroelectric perovskite NBT-BT by anelastic and dielectric measurements

The complex elastic compliance and dielectric susceptibility of (Na_{0.5}Bi_{0.5})_{1-x}Ba_{x}TiO_{3} (NBT-BT) have been measured in the composition range between pure NBT and the morphotropic phase boundary included, 0 <= x <= 0.08. The compliance of NBT presents sharp peaks at the rhombohedral/tetragonal and tetragonal/cubic transitions, allowing the determination of the tetragonal region of the phase diagram, up to now impossible due to the strong lattice disorder and small distortions and polarizations involved. In spite of ample evidence of disorder and structural heterogeneity, the R-T transition remains sharp up to x = 0.06, whereas the T-C transition merges into the diffuse and relaxor-like transition associated with broad maxima of the dielectric and elastic susceptibilities. An attempt is made at relating the different features in the anelastic and dielectric curves to different modes of octahedral rotations and polar cation shifts. The possibility is also considered that the cation displacements locally have monoclinic symmetry, as for PZT near the morphotropic phase boundary.Comment: 11 pages, 9 figures, submitted to Phys. Rev.

Influence of chemically synthesized powder addition on K0.5Na0.5NbO3 ceramic's properties

A new strategy to produce lead-free K0.5Na0.5NbO3 (KNN) piezoceramics with reliable and improved piezoelectric performance is presented for the first time. KNN powders were synthesized using two distinct synthesis routes: a mechanochemical activation-assisted solid-state route (KNNSSR) and a sol-gel modified Pechini method (KNNchem). KNNchem powders were mixed with KNNSSR at different weight ratios (0, 3, 5, 10 and 20 wt%), and the mixtures were conventionally consolidated and sintered at 1130 degrees C for 2 h. It was found that KNNchem powders influence crystal phase, microstructure and piezoelectric properties of the sintered pellets. Gradually increasing KNNchem content promotes the conversion of the undesired phase present in KNNSSR into the stoichiometric one. It is also proved that the addition of KNNchem between 5 and 10 wt% improves piezoelectric properties, eventually leading to a d(33) piezoelectric charge constant value of 113-115 pC/N. These values are among the highest reported for undoped KNN ceramics obtained by conventional sintering

A glance at processing-microstructure-property relationships for magnetoelectric particulate PZT-CFO composites

In this work, we investigated the processing-microstructure-property relationships for magnetoelectric (ME) particulate composites consisting of hard ferromagnetic CoFe2O4 (CFO) particles dispersed in a Nb-doped PbZrxTi1-xO3 (PZT) soft ferroelectric matrix. Several preparation steps, namely PZT powder calcination, PZT-CFO mixture milling and composite sintering were tailored and a range of microstructures was obtained. These included open and closed porosities up to full densification, PZT matrices with decreasing grain size across the submicron range down to the nanoscale and well dispersed CFO particles with bimodal size distributions consisting of submicron and micron sized components with varying weights. All samples could be poled under a fixed DC electric field of 4 kV/mm and the dielectric, piezoelectric and elastic coefficients were obtained and are discussed in relation to the microstructure. Remarkably, materials with nanostructured PZT matrices and open porosity showed piezoelectric charge coefficients comparable with fully dense composites with coarsened microstructure and larger voltage coefficients. Besides, the piezoelectric response of dense materials increased with the size of the CFO particles. This suggests a role of the conductive magnetic inclusions in promoting poling. Magnetoelectric coefficients were obtained and are discussed in relation to densification, piezoelectric matrix microstructure and particle size of the magnetic component. The largest magnetoelectric coefficient ff33 of 1.37 mV cm-1 Oe-1 was obtained for submicron sized CFO particles, when closed porosity was reached, even if PZT grain size remained in the nanoscale

Tailoring α-alumina powder morphology through spray drying for cold consolidation by binder jetting

Our work describes an optimised procedure for granulating nanometric and fine micrometric particles by spray-drying to achieve ready-to-print α-Al2O3 powders. The study started by identifying raw materials suited for the process through complete characterisation of particles shape, size, and surface properties. Then, dispersion in diluted and concentrated water-based suspensions was achieved thanks to polyethyleneimine and the effect of gradual dispersant addition was assessed by determining ζ potential and aggregates size variation. Suspensions rheology was studied and modelled through Krieger-Dougherty equation to identify the maximum solid loading allowing sufficient feeding through the spray-dryer nozzle. Finally, optimisation of the granulation conditions was performed. The procedure has allowed to achieve size distributions with D90 &lt; 50 μm and Hausner ratio &lt;1.3 ensuring sufficient flowability. The granulated powders were printed and the porosity evolution of the samples after sintering was studied by mercury intrusion porosimetry and SEM analysis

Experimental approach for the study of SOFC cathodes

The suitability of impedance measurements in Solid Oxide Fuel Cells (SOFCs) is an important concern, especially in case of measuring separately the behaviour of one of the electrode when an overvoltage is applied. In this case a thin electrolyte-supported cell with the RE (Reference Electrode) coplanar with the WE (Working Electrode) is experimentally convenient, but many authors highlighted that incorrect results can be obtained if an inappropriate geometric configuration is used. In this work LSM cathodes ((La0.8Sr0.2)MnO3-x) were investigated in a Yttria-stabilised Zirconia (YSZ) electrolyte-supported cell, using an electrolyte 3 mm thick. Two types of cells were prepared: the first (Cell1) according to the geometric requirements suggested in literature: little WE (diameter 3 mm) aligned to the CE (Counter Electrode) and with equal Rpol(polarisation resistance) and time constant; RE co-planar around the WE and placed at a distance greater than three-electrolyte thicknesses from the WE; the second one (Cell2) equal to Cell1 but with a bigger WE (diameter 8 mm). Impedance measurements were carried out both in two- and three- electrode configuration, at OCV (Open Circuit Voltage) and under applied overpotentials. A preliminary comparison between the results extracted from Cell2 at two- and three- electrodes confirms that a thick electrolyte allows extracting suitable three-electrode impedance results in case of OCV and small overpotentials. On the other side, when an overpotential over 0.2 V is applied, a comparison between Cell1 and Cell2 gives quite different results. The investigation here presented considers also an experimental approach useful for the comprehension of the main phenomena governing the kinetic of the process

Efecto del campo el?ctrico en la estructura cristalina de cer?micas submicroestructuradas DE (1-X)(Bi0.5Na0.5)TiO3- X BaTiO3 con composici?n pr?xima a la frontera morfotr?pica

--El sistema (1-x)(Bi0.5Na0.5)TiO3 - x BaTiO3 (BNBT100x) presenta una frontera morfotr?pica [1] (MPB) por lo que se presenta como posible material piezoel?ctrico "lead-free". Muy recientemente se han puesto de manifiesto peculiaridades estructurales de este sistema cerca de la MPB. La naturaleza y el rol de ordenamientos at?micos locales diferentes del orden global y la posibilidad de simetr?as inferiores a la rombo?drica son temas de actualidad. Exploramos aqu? el gran potencial de la difracci?n en alta resoluci?n de radiaci?n sincrotr?nica y el ajuste por Rietveld de los difractogramas de alta resoluci?n completos [2], que permite una mejor caracterizaci?n de las fases presentes que en los habituales an?lisis de grupos de picos aislados. Se determina el efecto del campo el?ctrico aplicado en cer?micas submicro- estructuradas [3] de composiciones BNBT4 y BNBT6 obtenidas a partir de precursores nanom?tricos preparados mediante autocombusti?n de sol-gel. Los experimentos de difracci?n se desarrollaron en el sincrotr?n de Stanford (USA) con radiaci?n de 12 keV. Para todas las muestras analizadas se consider? el difractograma completo para un recorrido del vector de dispersi?n Q entre 0 y 6.4?-1. En todos los casos investigados, se esclareci? la ocurrencia de las fases tetragonal P4mm, rombo?drica R3c y/o monocl?nica Cc. Se dan resultados cuantitativos de ocurrencia, concentraciones relativas, forma y tama?o de part?culas y orientaciones preferente

Role of different solvents on the purification of as-synthesized nano-Ce1-xGdxO2-d powders

Ceria and rare earth-doped ceria powders have important applications in catalysis, gas sensoring, and electronics. Even if many authors report different methods for the synthesis of nano-sized doped-ceria only few of them give information about the necessary washing processes for the powder purification. The organics adsorbed on the as-synthesized particles surface strongly affect, in fact, the properties of the powder. In this work, CeO2 and Ce1-xGdxO2-d (x = 0.10, 0.20, 0.30) solid solutions were produced by polyol microwave assisted method. The amount of synthesis residues adsorbed on the as-synthesized powders was firstly evaluated. The purification ability of different solvents on the as-synthesized Ce0.80Gd0.20O1.90 was, then, accurately studied in order to obtain a clean powder without the need of any thermal treatments. The study shows that water purification allows to reduce the amount of the residues of synthesis leading to the production of nano-particles with a mono-dispersed distribution of dimensions

Synthesis of CeO2 nano-aggregates of complex morphology

Cerium oxide with spheric, flowerlike and needle-like shapes has been synthesized by a simple microwave assisted method using diethylene glycole in mild conditions. The effect of reaction temperature on the crystal structure and morphology were discussed. The structural evolutions and morphological characteristics of the nanostructures were investigated using X-ray diffractometery, scanning and trasmission electron microscopy, Fourier transform infrared spectroscopy, TGA/DSC and BET analysis. By changing experimental conditions pure CeO2 fluoritic phase or cerium formate with complex morphology were formed. High porosity CeO2 nanostructures, retaining the end-reaction morphology, was readily obtained by calcination of cerium precursor. This simple and economic soft chemical method leads to nanostructured-micrometric aggregates of cerium oxide with high specific surface area suitable for catalytic applications

Phase Transitions in Lead-free Piezoelectric Ceramics Monitored by the Resonance Method

AbstractFerroelectrics, like batio3 (bt) or binatio3 (bnt), were studied in the 1950s and are now revisited, due to the need for lead-free piezoceramics, according to worldwide directives for environmental protection. Poling some of these materials has shown a different physical mechanism than ferroelectric domain orientation, involving field-induced structural phase transitions from pseudo-cubic phases to ferro-piezoelectrically active ones. They also depolarize below the curie temperature due to a structural phase transition. Both poling and thermal depoling can be monitored by the measurement of the electromechanical resonances. Depoling of (1-x) bnt-xbt ceramics with x=0.04 (bnbt4) is here considered as a case study

Freeze cast porous membrane catalyst for hydrogen production via oxy-reforming

In this work, porous catalytic membrane with tailored microstructure has been developed for the production of hydrogen from the oxy-reforming process. Porous catalytic membranes have been produced by freeze-casting of ceria-based powders using camphene as solvent. The process parameters have been optimized in terms of type and amount of dispersant to obtain homogeneous and stable ceramic suspension suitable for the process, while the freezing temperature was chosen on the basis of the microstructure and porosity of the final samples. The obtained freeze cast sample produced showed very high levels of porosity (≈ 80%) and good gas permeability (1.0 × 10−11 m2). The ceria-based porous structure produced was finally evaluated as catalyst in high temperature oxy-reforming reaction for hydrogen production from methane showing high methane conversions (up to 90%) and hydrogen production. The use of a unique catalytic membrane other than pelleted catalysts allowed the obtaining of smooth thermal profiles without the evidence of endothermic or exothermic peaks