Haixue Yan

THE CONTRIBUTION OF ELECTRICAL CONDUCTIVITY, DIELECTRIC PERMITTIVITY AND DOMAIN SWITCHING IN FERROELECTRIC HYSTERESIS LOOPS

Triangular voltage waveform was employed to distinguish the contributions of dielectric permittivity, electric conductivity and domain switching in current-electric field curves. At the same time, it is shown how those contributions can affect the shape of the electric displacement — electric field loops (D–E loops). The effects of frequency, temperature and microstructure (point defects, grain size and texture) on the ferroelectric properties of several ferroelectric compositions is reported, including: BaTiO3; lead zirconate titanate (PZT); lead-free Na0.5K0.5NbO3; perovskite-like layer structured A2B2O7 with super high Curie point (Tc); Aurivillius phase ferroelectric Bi3.15Nd0.5Ti3O12; and multiferroic Bi0.89La0.05Tb0.06FeO3. This systematic study provides an instructive outline in the measurement of ferroelectric properties and the analysis and interpretation of experimental data.

Thermal depoling of high Curie point Aurivillius phase ferroelectric ceramics

The thermal depoling behavior of several different Aurivillius phase ferroelectric ceramics has been studied. This includes two-layer (CaBi2Nb2O9,Ca0.9Ba0.1Bi2Nb2O9,Bi3NbTiO9,Bi3Nb1.2Ti0.8O9), three-layer (Bi4Ti3O12), and four-layer [CaBi4Ti4O15,Ca0.94(Na,Ce)0.03Bi4Ti4O15] compounds. All of them have a high Curie point (Tc⩾675°C). The orthorhombic structured materials show good resistance to thermal depoling up to temperatures close to their Curie points. However, Bi4Ti3O12, which has a monoclinic structure, shows a significant reduction in d33 well before its Curie point. The monoclinic distortion produces more non-180° ferroelectric domain structures, and it is the thermal instability of these that accounts for their thermal depoling behaviour. Excess Nb doping of Bi3NbTiO9 produces a significant reduction in its resistance to thermal depoling, suggesting that the doping produces a lowering of the crystallographic symmetry.

Unfolding grain size effects in barium titanate ferroelectric ceramics

Grain size effects on the physical properties of polycrystalline ferroelectrics have been extensively studied for decades; however there are still major controversies regarding the dependence of the piezoelectric and ferroelectric properties on the grain size. Dense BaTiO3 ceramics with different grain sizes were fabricated by either conventional sintering or spark plasma sintering using micro- and nano-sized powders. The results show that the grain size effect on the dielectric permittivity is nearly independent of the sintering method and starting powder used. A peak in the permittivity is observed in all the ceramics with a grain size near 1 μm and can be attributed to a maximum domain wall density and mobility. The piezoelectric coefficient d33 and remnant polarization Pr show diverse grain size effects depending on the particle size of the starting powder and sintering temperature. This suggests that besides domain wall density, other factors such as back fields and point defects, which influence the domain wall mobility, could be responsible for the different grain size dependence observed in the dielectric and piezoelectric/ferroelectric properties. In cases where point defects are not the dominant contributor, the piezoelectric constant d33 and the remnant polarization Pr increase with increasing grain size.

Dielectric relaxation, lattice dynamics and polarization mechanisms in Bi0.5Na0.5TiO3-based lead-free ceramics

In 0.95[0.94Bi0.5Na0.5TiO3-0.06BaTiO3]-0.05CaTiO3 ceramics, the temperature TS (dielectric permittivity shoulder at about 125 °C) represents a transition between two different thermally activated dielectric relaxation processes. Below TS, the approximately linear decrease of the permittivity with the logarithm of frequency was attributed to the presence of a dominant ferroelectric phase. Above TS, the permittivity shows a more complicated dependence of the frequency and Raman modes indicate a sudden increase in the spatial disorder of the material, which is ascribed to the presence of a nonpolar phase and to a loss of interaction between polar regions. From 30 to 150 °C, an increase in the maximum polarization with increasing temperature was related to three possible mechanisms: polarization extension favoured by the simultaneous presence of polar and non-polar phases; the occurrence of electric field-induced transitions from weakly polar relaxor to ferroelectric polar phase; and the enhanced polarizabili...

A-Site (MCe) Substitution Effects on the Structures and Properties of CaBi4Ti4O15 Ceramics

We investigated the effect of A-site compound substitution on the structures and properties of Ca0.8(MCe)0.1Bi4Ti4O15 (M denotes Li, Na and K) ceramics. The samples were prepared by the conventional ceramic technique. Sintering characteristics of Ca0.8(MCe)0.1Bi4Ti4O15 and CaBi4Ti4O15 ceramics were discussed. X-ray powder diffraction patterns of the three modified CBT-based compounds show a single phase of bismuth oxide layer type structure with m=4. The hysteresis loops of polarization versus electric field of the four compounds were also measured. A-site compound substitution improves the piezoelectric properties and the high-temperature resistivity of these materials. A-site (LiCe) and (KCe) substitution not only improves the Curie temperature but also decreases the temperature coefficient of dielectric constant (TKe). Among the three modified ceramics, only the Curie temperature of Ca0.8(NaCe)0.1Bi4Ti4O15 is lower than that of CaBi4Ti4O15; however, its TKe is the lowest. As a result, all the three modified CBT-based ceramics were found to be excellent high-temperature piezoelectric materials.

Effects of A-Site (NaCe) Substitution with Na-Deficiency on Structures and Properties of CaBi4Ti4O15-Based High-Curie-Temperature Ceramics

Three kinds of bismuth-layer-structured ferroelectric (BLSF) ceramics, CaBi4Ti4O15 (CBT), Ca0.8(CeNa)0.1Bi4Ti4O15 (CNBT), and Na-deficient Ca0.8(Ce0.1Na0.05\Box0.05)Bi4Ti4O15 [CN\BoxBT] (where \Box represents vacancies) were prepared by a conventional ceramic technique. X-ray powder diffraction showed that their crystal structures are a single phase of BLSF with m=4. Sintering characteristics of the three ceramics were also discussed. Scanning electron microscope (SEM) micrographs of CN\BoxBT showed that the grain is platelike. The A-site (NaCe) substitution can improve the piezoelectric constant d33 and high-temperature resistivity with decreasing Curie temperature. The modification by A-site (NaCe) substitution with Na-deficiency is more pronounced than CNBT, which not only leads to a very high piezoelectric constant d33 and high-temperature resistivity but also increases the Curie temperature. The reason for the high Tc (Tc=866°C) of CN\BoxBT is considered to be internal stress. As a result, Na-deficient CN\BoxBT ceramic is found to be an excellent high-temperature piezoelectric material.

Structural and chemical stability of multiwall carbon nanotubes in sintered ceramic nanocomposite

Abstract Abstract The structural and chemical stability of multiwall carbon nanotubes (MWNTs) in ceramic nanocomposites prepared by spark plasma sintering was studied. High resolution electron microscopy, X-ray diffraction and Raman spectroscopy were used to evaluate any degradation of the MWNTs. They were found to be well preserved in alumina after sintering up to 1900°C/100 MPa/3 min. In boron carbide, structural degradation of MWNTs started from ∼1600°C when sintered for 20 min. Multiwall carbon nanotubes maintained their high aspect ratio and fibrous nature even after being sintered in boron carbide at 2000°C for 20 min. However, no Raman vibrations of MWNTs were observed for nanocomposites processed at temperatures <2000°C, which indicates that they were severely degraded. Structural preservation of MWNTs in ceramic nanocomposites depends on the ceramic matrix, sintering temperature and dwell time. Multiwall carbon nanotubes were not preserved for matrices that require high sintering temperatures (>1600°C) and longer processing times (>13 min).

Reversibility in electric field-induced transitions and energy storage properties of bismuth-based perovskite ceramics

The effects of temperature and electric field-induced structural modifications on the energy storage properties of 0.95[0.94Bi0.5Na0.5TiO3–0.06BaTiO3]–0.05K0.5Na0.5NbO3 (BNT–BT–5KNN) ceramics were investigated. X-ray diffraction performed on unpoled and poled ceramics in the temperature range 25–500 °C suggested an increment in the rhombohedral phase intensity peaks and in the tetragonal distortion after electrical poling. The rhombohedral phase content reduced with increasing temperature in both unpoled and poled ceramics. In the unpoled ceramic, the rhombohedral phase eventually disappeared, while it survived in the poled specimen up to 500 °C. The stabilization of the rhombohedral ferroelectric phase by dc poling produced remarkable differences in the temperature dependence of permittivity, loss, current–polarization–electric field loops and energy density. As a consequence of a reversible transition induced by an alternating electric field, competitive energy densities (0.39–0.51 J cm−3 in the range 25–175 °C) with those of lead-based and lead-free bulk ceramics recently developed was obtained, indicating bismuth-based perovskites as potential lead-free systems for energy storage applications.

High energy density in silver niobate ceramics

Solid-state dielectric energy storage is the most attractive and feasible way to store and release high power energy compared to chemical batteries and electrochemical super-capacitors. However, the low energy density (ca. 1 J cm−3) of commercial dielectric capacitors has limited their development. Dielectric materials showing field induced reversible phase transitions have great potential to break the energy storage density bottleneck. In this work, dense AgNbO3 ceramic samples were prepared successfully using solid state methods. Ferroelectric measurements at different temperatures reveal evidence of two kinds of polar regions. One of these is stable up to 70 °C, while the other remains stable up to 170 °C. The associated transition temperatures are supported by second harmonic generation measurements on poled samples and are correlated with the occurrence of two sharp dielectric responses. The average unit cell volume is seen to increase with increasing DC field and has been interpreted in terms of increasing levels of structural disorder in the system. At a high electric field the structure becomes ferroelectric with high polarization. This field induced transition exhibits a recoverable energy density of 2.1 J cm−3, which represents one of the highest known values for lead-free bulk ceramics.

High-strength nanograined and translucent hydroxyapatite monoliths via continuous hydrothermal synthesis and optimized spark plasma sintering

The synthesis of high-strength, completely dense nanograined hydroxyapatite (bioceramic) monoliths is a challenge as high temperatures or long sintering times are often required. In this study, nanorods of hydroxyapatite (HA) and calcium-deficient HA (made using a novel continuous hydrothermal flow synthesis method) were consolidated using spark plasma sintering (SPS) up to full theoretical density in ∼5 min at temperatures up to 1000°C. After significant optimization of the SPS heating and loading cycles, fully dense HA discs were obtained which were translucent, suggesting very high densities. Significantly high three-point flexural strength values for such materials (up to 158 MPa) were measured. Freeze-fracturing of disks followed by scanning electron microscopy investigation revealed selected samples possessed sub-200 nm sized grains and no visible pores, suggesting they were fully dense.