Dielectric and Ferroelectric Characterization of Na(Ta,Nb)O<Subscript>3</Subscript> Solid Solution Ceramics

Ceramics in the Na(Ta_{1 − x}Nb_x)O₃ system were prepared by a solid state reaction approach, and their dielectric characteristics were evaluated together with the structures. The complete solid solution with orthorhombic structures was observed in the present system, and three supposed phase transitions at about 475, 580 and 650^∘C were observed by DTA. Only one dielectric anomaly was observed at high temperature for x = 0.2 and 0.4, and alternative dielectric anomaly (a diffused dielectric peak) was observed around 170 and 380^∘C for x = 0.6 and 0.8, respectively. The compositions of 0.6 and 0.8 are weakly ferroelectric and those of 0.2 and 0.4 are supposed to be antiferroelectric at room temperature.     

Piezoelectric Properties of 0.2[Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)]-0.8[PbTiO<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript>] Ceramics Sintered at a Low Temperature with the Aid of Li<Subscript>2</Subscript>O

The dielectric and piezoelectric properties of 0.2Pb(Mg_1/3Nb_2/3)O₃-0.8Pb(Zr_0.475Ti_0.525)O₃ (abbr. as PMNZT) ceramics were measured. Extremely low sintering temperatures of 950^∘C using liquid-phase sintering aid of Li₂O is achieved which was very useful for multi-layered applications. X-ray study shows the splitting of rhombohedral (200) in pure PMNZT to (002) and (200) peaks in Li₂O doped samples. 10 times higher dielectric constant was achieved in Li₂O doped samples to compare to pure ones although the Curie temperature (T_c = 322^∘C) of Li₂O doped PMNZT ceramics was not changed. The value of k_p and k₃₃ increased up to 0.1 wt% of Li₂O and saturating thereafter.     

Mechanical and electrical properties of Bi<Subscript>1.5-x</Subscript>La<Subscript>x</Subscript>Zn<Subscript>0.92</Subscript>Nb<Subscript>1.5</Subscript>O<Subscript>6.92</Subscript> pyrochlore ceramics

BiFeO₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (BF-PMN-PT) ternary ceramics with pure perovskite phase were prepared through a two-step solid reaction method. Based on structural analysis, the ternary phase diagram of BF-PMN-PT solid solution at room temperature has been established. The Curie temperature T_C, remnant polarization P_r and piezoelectric constant d₃₃ vary in the range of 138 to 225 °C, 15.12 to 23.65 μC/cm² and 129 to 276 pC/N, respectively. The coercive field Ec increases gradually from 5.77 to 29.56 kV/cm upon PT content increasing. The magnetic study suggests that the magnetism turns from diamagnetism for PMN-PT to paramagnetism for BF-PMN-PT by adding BiFeO₃ into PMN-PT and adding more content of BF does not change the paramagnetism further.     

The Effect of Cobalt Oxide Addition on the Conductivity of Ce<Subscript>0.9</Subscript>Gd<Subscript>0.1</Subscript>O<Subscript>1.95</Subscript>

The conductivity of cobalt oxide doped Ce_0.9Gd_0.1O_1.95 (CGO10) of various doping concentrations, sintering temperatures, dwell times, and cooling rates was investigated by 4-point DC conductivity measurements. In cobalt oxide doped CGO10, an enhanced total conductivity occuring with a low activation energy of 0.54 eV was detected below 250^∘C in quenched samples. If the same samples were cooled down slowly, only the ionic conductivity of undoped CGO with an activation energy of 0.8 eV was found. The increased conductivity is attributed to a percolating network of an electronically conducting grain boundary phase rich in CoO, which can be retained by quenching from temperatures between 900 and 1000^∘C.     

Development and Electromechanical Properties of Multimaterial Piezoelectric and Electrostrictive PMN-PT Monomorph Actuators

Monolithic multimaterial monomorphs, comprised of varying ratios of piezoelectric 0.65Pb(Mg_1/3 Nb_2/3)O₃-0.35PbTiO₃ to electrostrictive 0.90Pb(Mg_1/3Nb_2/3)O₃-0.10PbTiO₃, have been co-fired at 1150^∘C. The relative permittivity, displacement, and polarization hysteresis were investigated for varying ratios of piezoelectric to electrostrictive material. The permittivity of the 1:1 multimaterial monomorphs followed the dielectric mixing laws, showing a dielectric constant of 5,500 at room temperature. The P-E hysteresis loop of the 1:1 sample exhibited a maximum and remnant polarization slightly less than the piezoelectric PMN-PT 65/35, but higher than the electrostrictive PMN-PT 90/10. Displacement was found to be higher for the 3:1 monolithic monomorph actuators, reaching 76 μ m at 6 kV/cm. The results indicate that by minimizing the electrostrictive layer thickness the tip displacement can be substantially increased while maintaining a lower hysteresis than that of the purely piezoelectric counterpart.     

Influence of substitution on dielectric diffuseness in Ba<Subscript>(1-x)</Subscript>Bi<Subscript>(2+2x/3)</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> ceramics prepared by chemical precursor decomposition method

Barium bismuth niobate, Ba_(1-x)Bi_(2+2x/3)Nb₂O₉ (BBN with x = 0.0, 0.1, 0.2, 0.3, 0.4) ceramic powders in the nanometer range were prepared by chemical precursor decomposition method (CPD). The single phase layered perovskite was prepared throughout the composition range studied. No intermediate phase was found during heat treatment at and above 600°C. The crystallite size and the particle size, obtained from XRD and TEM respectively, were in the range of 15–30 nm. The addition of Bi₂O₃ substantially improved the sinterability associated with high density (96%) which was otherwise difficult in the case of pure BaBi₂Nb₂O₉ (BBN x = 0.0). The sintering was done at 900°C for 4 h. The relative permittivity of BBN ceramics at both room temperature and in the vicinity of the temperature of maximum permittivity (T_m) has increased significantly with increase in bismuth content and loss is also decreased to a certain level of bismuth doping. T_m increased with increase in Bi₂O₃. The diffuseness (γ) in the phase transition was found to increase from 1.54 to 1.98 with the increase in Ba²⁺ substitution level from x = 0.0 to x = 0.3.     

Properties of Cu,Ni, and V doped-LaCrO <Subscript>3</Subscript> interconnect materials prepared by pechini,ultrasonic spray pyrolysis and glycine nitrate processes for SOFC

The ceramic interconnect,La_0.8Sr_0.05Ca_0.15(Cr_{1 −x} , B_x)O₃ (B = Cu, Ni, V, x = 0.02, 0.1, 0.5) (LSCCB) powders were prepared by Pechini method, Ultrasonic Spray Pyrolysis (USP) and Glycine Nitrate Process (GNP). Nano sized powders were synthesized by GNP and their chemical compositions were confirmed by ICP analysis. The electrical conductivities of LSCCCu, LSCCNi, and LSCCV samples were 34 S/cm, 48 S/cm, and 22 S/cm at 800^∘C in air, respectively. Among the LSCCB powders, the LSCCNi sample shows highest relative density and electrical conductivity. In a low oxygen partial pressure, however, LSCCV sample was more stable. The perovskite phase of the composition LSCCV sample is of large practical interest for interconnects in SOFC because of the stability in low oxygen partial pressure.     

Co-Precipitation Method for the Preparation of Nanocrystalline Ferroelectric SrBi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> Ceramics

A simple co-precipitation technique had been successfully applied for the preparation of pure ultrafine single phase SrBi₂Nb₂O₉. Ammonium hydroxide and ammonium oxalate were used to precipitate Sr^{2 +}, Bi³⁺ and Nb⁵⁺ cations simultaneously. No pyrochlore phase was found while heating powder at 850C and pure SrBi₂Nb₂O₉ (SBN) phase was formed as revealed by the X-ray diffraction (XRD) studies. Particle size and morphology was studied by transmission electron microscopy (TEM). The room temperature dielectric constant at 1 kHz is 100. The ferroelectric hysteresis loop parameters of these samples were also studied.     

Sinterability,Mechanical, Microstructural,and Electrical Properties of Gadolinium-Doped Ceria Electrolyte for Low-Temperature Solid Oxide Fuel Cells

In this study, we report key functional properties of gadolinium-doped ceria (Gd_0.1Ce_0.9O_1.95, GDC) sintered at low temperatures as well as single-cell electrochemical performance of a single-cell prepared there of. GDC solid solutions were sintered at various temperatures ranging 1100–1400^∘C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), density measurements, mechanical strength tests and electrical conductivity measurements. The dry-pressed GDC disc sample sintered at 1100^∘C was found to have 96% of the theoretical density and higher sintering temperatures led to higher densities. SEM micrographs of the fracture and plan surfaces of the sintered discs established the absence of any open pores. The sample sintered at 1100^∘C exhibited high electrical conductivity of 0.027 S/cm at 650^∘C. The mechanical strength of the sintered samples was determined to be in the range of 150–175 MPa. Greater than 96% of theoretical density, good mechanical strength, and high electrical conductivity of GDC disc samples sintered at 1100^∘C established the viability of low-temperature processing of GDC for its use as an SOFC electrolyte. Accordingly, a single-cell was prepared by co-sintering of GDC electrolyte and LSCF-GDC cathode at 1100^∘C and subsequent firing of CuO-GDC anode at 900^∘C. The electrochemical performance of the cell was evaluated in H₂ fuel at 650^∘C.     

Microwave Dielectric Properties of CuO-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-Doped ZnNb<Subscript>2</Subscript>O<Subscript>6</Subscript> Ceramics with Low Sintering Temperature

Microwave dielectric properties of low temperature sintering ZnNb₂O₆ ceramics doped with CuO-V₂O₅-Bi₂O₃ additions were investigated systematically. The co-doping of CuO, V₂O₅ and Bi₂O₃ can significantly lower the sintering temperature of ZnNb₂O₆ ceramics from 1150 to 870C. The secondary phase containing Cu, V, Bi and Zn was observed at grain boundary junctions, and the amount of secondary phase increased with increasing CuO-V₂O₅-Bi₂O₃ content. The dielectric properties at microwave frequencies (7–9 GHz) in this system exhibited a significant dependence on the relative density, content of additives and microstructure of the ceramics. The dielectric constant ( _r) of ZnNb₂O₆ ceramics increased from 21.95 to 24.18 with increasing CuO-V₂O₅-Bi₂O₃ additions from 1.5 to 4.0 wt%. The quality factors (Q× f) of this system decreased with increasing CuO-V₂O₅-Bi₂O₃ content and ranged from 36118 to 67100 GHz for sintered ceramics, furthermore, all Q× f values of samples with CuO-V₂O₅-Bi₂O₃ additions are lower than that of un-doped ZnNb₂O₆ ceramics sintered at 1150C for 2 h. The temperature coefficient of resonant frequency ( _f) changed from –33.16 to –25.96 ppm/C with increasing CuO-V₂O₅-Bi₂O₃ from 1.5 to 4.0 wt%     

Electrical conductivity of the Al-stabilized La<Subscript>2/3</Subscript>TiO<Subscript>3</Subscript>

A-site deficient lanthanum titanate (La_2/3TiO₃) materials with perovskite structure are attractive due to their electrical applications such as ion conductors and dielectrics. However, its stability at room temperature in air is obtained only if Na or Li etc. is incorporated into La site or Al into Ti site. In this study, the electrical conductivities of La_0.683(Ti_0.95Al_0.05)O₃ have been measured in oxygen partial pressure (Po₂) between 1 and 10⁻¹⁸ atm at 1000~1400°C. The electrical conductivity exhibited −1/4, −1/6 and −1/5 dependence (log σ ∝ log , n = −1/4, −1/6, −1/5) depending upon temperature and Po₂. The defect model explaining the observation was proposed and discussed. The chemical diffusion coefficient was estimated from the electrical conductivity relaxation.     

Tunable Dielectric Characteristics of 0.9Pb(Fe<Subscript>1/2</Subscript>Nb<Subscript>1/2</Subscript>)O<Subscript>3</Subscript>/0.1CaTiO<Subscript>3</Subscript>

Tunable dielectric characteristics of 0.9Pb(Fe_1/2Nb_1/2)O₃/0.1CaTiO₃ relaxor ferroelectric ceramics were investigated as the function of DC bias field and temperature. High tunability (more than 20%) was obtained in the present ceramics under a relatively weak DC bias field (1.4 kV/cm). The value of tunability changed from negative to positive with increasing DC field. For the simulation of the dielectric constant under DC bias field, modified model needs to be constructed for the relaxor ferroelectrics. The dielectric constant curve as a function of temperature without and under DC field was well fitted using the equation of diffuse phase transition. The lower ε_max, higher T_max and higher diffuseness parameter under DC field were observed and only the lower ε_max contributed to positive tunability.     

Studies on Electrical Properties and Magnetoelectric Effect of (x)Ni0.8Cu0.2Fe2O4 + (1?x)Ba0.8Pb0.2Ti0.8Zr0.2O3 Composites

Materials consisting of piezomagnetic and piezoelectric phases viz. Ni_0.8Cu_0.2Fe₂O₄ and Ba_0.8Pb_0.2 Ti_0.8Zr_0.2O₃ have been prepared by standard ceramic method. The presence of two phases in the composites has been confirmed by XRD. Variation of the dielectric constant with frequency in the range 100–1 MHz has been studied at room temperature and the variation of dielectric constant with temperature at set frequencies (1 kHz, 10 kHz, 100 kHz and 1 MHz) has been studied. The dielectric relaxation was observed for the compositions with tetragonal structure whereas normal behaviour was observed for cubic structure. All the samples have shown linear magnetoelectric conversion in the presence of a static magnetic field. The dc resistivity (ρ_DC) was studied as a function of temperature in the range 300–773^∘K. The variation of resistivity with temperature shows metal/seconductor behaviour.     

Piezoelectric properties of a Ba(Zr0.075Ti0.925)O3 single crystal induced by poling treatment

Piezoelectric properties in a Ba(Zr_0.075Ti_0.925)O₃ single crystal were investigated with a consideration that its phase transition lies on room temperatures and the transition can affect piezoelectric properties. The poling treatments were carried with bias fields ranging 2.2 kV/cm∼11 kV/cm at room temperature. The crystal possesses the phase transition from orthorhombic to rhombohedral, lying on room temperature. At 37^∘C, the crystal exhibited the excellent piezoelectric properties, a d₃₁ coefficient of over 500 pC/N and a k₃₁ coefficient of 0.38, being caused by the phase transition.     

In-Plane 90<Superscript>∘</Superscript> Rotation of Lamellar Domains in PbTiO<Subscript>3</Subscript> Grains Revealed by Piezoresponse Force Microscopy

Nanoscale switching of the lamellar 90^∘ domains ({a-a} domains) of PbTiO₃ grains in the surface of sol-gel-derived PbTiO₃/Pb(Zr_0.58Ti_0.42)O₃/PbTiO₃ thin films is studied by three-dimensional piezoresponse force microscopy. It is demonstrated that the lamellar domain pattern in the PbTiO₃ grains can be rotated 90^∘ in the plane of film by the electric field at the tip. It is found that the rotation of lamellar domain pattern involves transverse growth of the existing embedded a-a domain nucleus, whose domain walls are perpendicular to the surrounding ones. During the transverse growth, the existing 90^∘ domains extend along length direction and penetrate into neighboring domain walls, while formation of new 90^∘ domain walls was mediated by the nanoscale 45^∘ tilted spike domains.     

Dielectric Properties and Sintering Characteristics of CaTiO<Subscript>3</Subscript>-(Li<Subscript>1/2</Subscript>Nd<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript> Ceramics

The dielectric properties and the sintering effect upon microstructure of (1–x) CaTiO₃-x(Li_1/2Nd_1/2)-TiO₃ Ceramics are investigated in this paper. Nd³⁺ and Mg^{2 +} ions co-substitution for Ca^{2 +} on A site improves the sintering characteristic of CaTiO₃ ceramics with forming orthorhombic perovskite structure. The structure of (1 – x) CaTiO₃-x(Li_1/2Nd_1/2)TiO₃ changes from orthorhombic to tetragonal as (Li_1/2Nd_1/2)TiO₃ addition increasing. Limited solubility of (Li_1/2Nd_1/2)TiO₃ in CaTiO₃ forming a part solid solution compound achieves the adjustment of for CaTiO₃ at low sintering temperature. The proper dielectric properties with = 78, tan = 0.0006, = +7 ppm/C are obtained for 0.8Ca_0.67(Nd,Mg)_0.22TiO₃-0.2(Li_1/2Nd_1/2)TiO₃ ceramics.     

Defects and Transport in Langasite II: Donor-doped (La<Subscript>3</Subscript>Ga<Subscript>4.75</Subscript>Nb<Subscript>0.25</Subscript>SiO<Subscript>14</Subscript>)

The electrical conductivity of Nb doped langasite (La₃Ga_4.75Nb_0.25SiO₁₄) was examined as a function of temperature and oxygen partial pressure by complex impedance spectroscopy. A pO₂-independent regime was found at high pO₂ followed by a pO₂^{− 1/6} dependent regime at low pO₂. A defect model consistent with these results was derived in which the electron density n is fixed by the density of ionized Nb donors at high pO₂ and by the generation of oxygen vacancies at low pO₂. The temperature and oxygen partial pressure dependence of the electron density was obtained independently by thermoelectric power measurements. The Nb donor ionization energy was determined to be 1.52 ± 0.06 eV, confirming Nb to be a deep donor in langasite. By combining conductivity and thermoelectric power data, an expression for the electron mobility given by μ_e = 1.1× 10^{− 2}exp( ) was obtained. After evaluating the temperature dependent conductivity data under reducing conditions, in light of the defect model, a value for the reduction enthalpy (E_r = 6.57 ± 0.24 eV) was derived.     

Morphology of PZT-PMN Films Grown from Airflow

Lead zirconate titanate-lead magnesium niobate (PZT-PMN) films with thicknesses in the range 5 to 200 μm were fabricated by deposition from airflow at room temperature. Precursor powders of PZT and PMN were mixed in a ball mill and entrained in an airflow generated by a commercial jet-mill (Micron-Master 02-506). Films were grown at a rate of 1 μm/minute onto the Ni and tungsten carbide substrates exposed to the air-powder mixture. Unfired, poled PZT-PMN films provided an audio acoustic response and form translucent 20–30 μm thick layers. Full density of the air-flow deposited materials has been achieved at temperatures 450°C lower than that typical for ball milled bulk PZT-PMN ceramics. After sintering for 2 hours at 850°C PZT-PMN ceramics with relative density of 99.5%, ? ～ 2170, tan δ ～ 0.009 @1 kHz and acceptable piezoelectric properties was obtained. Films sintered 2 hours at 1000°C showed remnant polarization P _r = 26 μC/cm², P _s = 36 μC/cm² @95 kV/cm, and 50 Hz ac electric breakdown field as high as 120–170 kV/cm. Unusual grain morphology governs improved sinterability and enhanced properties of ferroelectric ceramics. Optical and AFM micrographs revealed needle-like grains preferentially oriented parallel to the air-powder stream. As-deposited films were found to be very non-uniform across the thickness: glass-like and with tensile strain on the contact surface. This strain is released and film microcrystalline structure becomes uniform in annealed film.     

Piezoelectric properties and domain structure of the orthorhombic (K,Na,Li)(Nb,Ta,Sb)O3 single crystal

ABSTRACT

In this work, (K,Na,Li)(Nb,Ta,Sb)O₃ (KNLNTS) crystal is in the orthorhombic phase at room temperature. The orthorhombic-tetragonal phase transition temperature is 50.0°C, and the Curie temperature T_C of the tetragonal-cubic phase transition temperature is 253.8°C. The crystal is poled, the defects were “pinned” in specific position, and has positive effect in domain wall motions and better ferroelectric property (P_r is 6.49 µC/cm², E_c is 6.66 kV/cm). The domain configrations of the crystal were studied by means of a polarizing light microscopy (PLM), with poling along [100]_C direction.     

Formation of a KNbO<Subscript>3</Subscript> single crystal using solvothermally synthesized K<Subscript>2-m</Subscript>Nb<Subscript>2</Subscript>O<Subscript>6-m/2</Subscript> pyrochlore phase

A K_2-mNb₂O_6-m/2 single crystal with a pyrochlore phase formed when the Nb₂O₅?+?x mol% KOH specimens with 0.6?≤?x?≤?1.2 were solvothermally heated at 230 °C for 24 h. They have an octahedral shape with a size of 100 μm, and the composition of this single crystal is close to K_1.3Nb₂O_5.65. The single-crystal KNbO₃ formed when the single-crystal K_2-mNb₂O_6-m/2 was annealed at a temperature between 600 °C and 800 °C with K₂CO₃ powders. When annealing was conducted at 600 °C (or with a small amount of K₂CO₃), the KNbO₃ single crystal has a rhombohedral structure that is stable at low temperatures (< ? 10 °C). The formation of the rhombohedral KNbO₃ structure can be explained by the presence of the K⁺ vacancies in the specimen. The KNbO₃ single crystal with an orthorhombic structure formed when the K_2-mNb₂O_6-m/2 single crystal was annealed at 800 °C with 20 wt% of K₂CO₃.