Lead-free NKN-5LT piezoelectric materials for multilayer ceramic actuator

As a candidate for lead-free piezoelectric materials, Li₂O excess 0.95(Na_0.5K_0.5)NbO₃–0.05LiTaO₃ (NKN-5LT) ceramics were developed by conventional sintering process. Sintering temperature was lowered by adding Li₂O as a sintering aid. Abnormal grain growth in NKN-5LT ceramics was observed with varying Li₂O content. In the 1 mol% Li₂O excess NKN-5LT samples sintered at 1000°C for 4 h in air, electromechanical coupling factor and piezoelectric constant of NKN-5LT ceramics were found to reach the highest values of 0.37 and 250 pC/N, respectively. Lead-free piezoelectric ceramic, Li₂O excess NKN-5LT, multilayer ceramic actuators (MLCA) were fabricated. 10?×?10?×?1 mm³ size MLCAs were fabricated by conventional tape casting method. The displacement of Li₂O excess NKN-5LT MLCA with 3 mm thickness was ~1 μm at 150 V.     

Effect of composite electrode thickness on the electrochemical performances of all-solid-state li-ion batteries

Several ceramic half-cells with differing electrode composite thicknesses but identical formulations were assembled using the spark plasma sintering (SPS) technique, in order to conduct comparable investigations of their kinetic limitations. The SPS technique was used to assemble the composite electrode and the electrolyte together within a few minutes. NASICON-type Li_1.5Al_0.5Ge_1.5(PO₄)₃ (LAGP) ceramic was used as solid electrolyte, as it offers high ionic conductivity (3 × 10^?4 S.cm^?1 at 25 °C) with a Li⁺ transport number of 1. LiFePO₄ active material was used as a model material; it offers an average flat potential of 3.45 V vs Li⁺/Li and a reasonably high theoretical capacity of 170 mAh.g^?1. Surface capacity values (from 0.8 to 3.5 mAh.cm^?2), which are proportional to electrode thickness, remained quite close to the initial values after more than 20 cycles, even for a 325 μm thick electrode (3.5 mAh.cm^?2). The overpotential in the flat plateau region was proportional to the current density used, which means that it was dependent only on the cell’s ohmic drop. Performances were not limited by the ion transport into the solid electrolyte and composite electrode volume - as in classical Li-ion batteries - since the transport number of LAGP is one. Therefore, very thick electrode-enabling batteries with high-surface capacity can be considered.     

Optimization of the thermoelectric properties of Bi<Subscript>2</Subscript>O<Subscript>2</Subscript>Se ceramics by altering the temperature of spark plasma sintering

The n-type polycrystalline Bi₂O₂Se ceramics were fabricated by solid state reaction and SPSed at different temperatures (873–973 K). The grains of the sample grow up gradually and the grain size enlarges from about 200 nm to micrometer level with the increase of sintering temperature. The highest electrical conductivity of 6.23 S/cm is obtained for the sample sintered at 898 K which benefits from grain orientation along (00l) plane and the highest measured density. The electrical transport properties tend to decline with further increase of the sintering temperature due to the decrease of density and the orientation degree. The maximum power factor of 78.39 μWK^?2m^?1 is obtained at 773 K. The thermal conductivity is intrinsically suppressed owing to the layered crystal structure of Bi₂O₂Se and fine grains within the nanometer size. The ZT value reaches 0.09 at 773 K for the sample SPSed at 898 K and the optimal temperature during the SPS process has been determined.     

Piezoelectric properties of Li, Sb, and Ta co-doped (K,Na)NbO3 ceramics with fine grain size sintered by SPS method

(Na_0.52?K_0.44Li_0.04)(Nb_0.86Ta_0.06Sb_0.08)O₃ (LTS-KNN) nano-powders with the size of 11–34 nm were prepared by a sol–gel method. Using the nano-powders, LTS-KNN ceramics with fine grain size of 200–400 nm and high density were fabricated by spark plasma sintering. The satisfied piezoelectricity is obtained, such as d ^* ₃₃?~?481 pm/V, d ₃₃?~?296 pC/N, K _p?~?49.7 %, ε ₃₃ ^T /ε ₀?~?920, tanδ?~?0.025 at 1 kHz and relative density is 99.4 %, respectively. It is shown that nano-powders are suitable to prepare fine-grained potassium-sodium niobate ceramics with satisfied properties.     

Sintering and dielectric properties of Bi1.5ZnNb1.5O7 cubic pyrochlore ceramics via high-energy milling technology

The dense Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics is synthesized by high-energy milling technology from the coarse Bi_1.5ZnNb_1.5O₇ cubic pyrochlore powders prepared by solid state route. The sintering and dielectric properties of the Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics are investigated, which show that the sintering temperature of the prepared ceramics could be effectively lowered to 800°C and the bulk density reach 6.889 g/cm³ approximately 97% of the theoretical density of Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics. The excellent dielectric properties of the ceramics sintered at 850°C has been obtained with the relative permittivity of 160 and the dielectric loss of 10^?4. This route would be a low-cost and mass production for lowering the sintering temperature of the Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramics without sintering aids.     

Microstructure and electrical properties of the rare-earth doped 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 piezoelectric ceramics

Phase structure, microstructure, piezoelectric and dielectric properties of the 0.4 wt% Ce doped 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ (Ce-BNT6BT) ceramics sintered at different temperatures have been investigated. The powder X-ray diffraction patterns showed that all of the Ce-BNT6BT ceramics exhibited a single perovskite structure with the co-existence of the rhombohedral and tetragonal phase. The morphologies of inside and outside of the bulk indicated that the different sintering temperatures did not cause the second phase on the inside of bulk. However, the TiO₂ existed on the outside of the bulk due to the Bi₂O₃ and Na₂O volatilizing at higher temperature. The ceramics sintered at 1,200 °C showed a relatively large remnant polarization (P _r) of about 34.2 μC/cm², and a coercive field (E _c) of about 22.6 kV/cm at room temperature. The permittivity ? _r of the ceramics increased with the increasing of sintering temperature in antiferroelectric region, the depolarization temperature (T _d) increased below 1,160 °C then decreased at higher sintering temperature. The resistivity (ρ) of the Ce-BNT6BT ceramics increased linearly as the sintering temperature increased below 1,180 °C, but reduced as the sintering temperature increased further. A maximum value of the ρ was 3.125?×?10¹⁰ ohm m for the Ce-BNT6BT ceramics sintered at 1,180 °C at room temperature.     

Lithium ion conduction in Li5La3Ta2O12 and Li7La3Ta2O13 garnet-type materials

Electrical properties of the lithium garnets Li₅La₃Ta₂O₁₂ (L5LTO) and Li₇La₃Ta₂O₁₃ (L7LTO) are reported over a wide frequency range from 10 MHz to 0.1 Hz at different temperatures. The structural properties are characterized by powder X-ray diffraction, Scanning electron microscopy with energy dispersive X-ray spectroscopy and Fourier transformation Infrared spectroscopy. By means of the frame work of classical brick layer model (BLM) and of a finite element approach, the ion transport properties of grain and grain boundary for the lithium garnets were analyzed. The specific grain conductivity of 5.0?×?10^?6?S/cm at 40 °C is found for both lithium garnets. Specific grain conductivities and grain boundary conductivities are thermally activated, with activation energies found to be in the range of 0.55–0.61 eV. The total conductivity is found to be depending on the ion conduction of grain boundary. The information on the fraction of contact area α_contact between grains <0.25 is obtained by the finite element approach for Li₇La₃Ta₂O₁₃.     

Microelectrodes for local conductivity and degradation measurements on Al stabilized Li<Subscript>7</Subscript>La<Subscript>3</Subscript>Zr<Subscript>2</Subscript>O<Subscript>12</Subscript> garnets

The attractiveness of Li₇La₃Zr₂O₁₂ (LLZO) cubic based garnets lies in their high ionic conductivity and the combination of thermal and electrochemical stability. However, relations between composition and conductivity as well as degradation effects are still not completely understood. In this contribution we demonstrate the applicability of microelectrodes (Ø = 20–300 μm) for electrochemical impedance spectroscopy (EIS) studies on LLZO garnets. Microelectrodes allow to obtain local information on the ionic conductivity. A comparison between the overall performance of the sample (3.3 × 10^?4 S cm^?1) and local measurements revealed differences in conductivity with a maximum of the locally measured values of 6.3 × 10^?4 S cm^?1 and a minimum of 2.6 × 10^?4 S cm^?1. One reason behind these conductivity variations is most probably a compositional gradient in the sample. In addition, microelectrodes are very sensitive to conductivity changes near to the surface. This was used to investigate the effect of moisture in ambient air on the conductivity variations of LLZO. Substantial changes of the measured Li-ion transport resistance were found, particularly for smaller microelectrodes which probe sample volumes close to the surface.     

Normal sintering and electric properties of (K,Na,Li)(Nb,Sb)O3 lead-free piezoelectric ceramics

0.94(K₀₅Na_0.5)NbO₃?0.03LiNbO₃?0.03LiSbO₃ (KNLNS) lead-free piezoelectric ceramics were prepared by conventional mixed oxide route with normal sintering method. The samples were sintered at different temperatures with KNLNS powder atmosphere to prevent volatilization of alkali metal oxides at high temperature. The effects of sintering temperature on the density, structure and electric properties of KNLNS ceramics were studied. X-ray diffraction (XRD) results showed that the crystal structure of the crushed KNLNS ceramic powders were pure perovskite phase with tetragonal phase structure when sintered at T????1080°C. However a K₃Li₂Nb₅O₁₅ phase with tetragonal tungsten bronze structure began to appear when the sintering temperature was higher than 1080°C. The optimum sintering temperature was 1080°C which was determined by measuring the density of the samples. Scanning electron microscope (SEM) observation indicated that the sintering temperature had a great effect on the microstructure of the samples. The KNLNS ceramics under the optimum sintering temperature showed excellent electric properties: ???=?4.29 g/cm³, ?? _r?=?826, tan???=?0.049, d ₃₃?=?190 pC/N, k _p?=?0.30, and T _c?=?385°C. The results show that the KNLNS ceramics are promising candidate for lead-free piezoelectric ceramics.     

Effects of cobalt addition on structural,thermal and electrical properties of praseodymium-yttrium co-doped barium cerates

Effects of cobalt addition on structural, thermal and electrical properties of praseodymium-yttrium co-doped barium cerates have been investigated. Relative densities >98 % have been achieved after sintering at 1400 °C or 1500 °C for only 1 h. All studied compounds are stable in ambient air up to the measured 900 °C and, in reducing atmosphere (both wet and dry 5 % H₂-Ar) up to the measured 800 °C. The Co-free sample (BaCe_0.7Y_0.2Pr_0.1O_3-δ) exhibits the highest conductivity of 1.21?×?10^?2 S cm^?1 at 700 °C in air while the corresponding cobalt containing sample (BaCe_0.7Y_0.175Pr_0.1Co_0.025O_3?δ) has a conductivity of 9.85?×?10^?3 S cm^?1 at 700 °C in air. Cobalt addition allows the ability to retain much larger amounts of water to be retained as suggested by the higher conductivities obtained in wet hydrogen compared to the values in dry reducing atmosphere. This latter phenomenon is of special interest as it suggests the possibility of higher ionic conductivities in water-containing atmosphere and would benefit to intermediate- and high-temperature solid oxide fuel cells and/or electrolysers. The thermal expansion coefficients for the Co-free and Co-containing samples were around 12.0?×?10^?6 K^?1 between 25 and 1000 °C.     

Effect of Zn2SnO4 on the sintering and electrical properties of SnO2 ceramics

SnO₂ ceramics with relative density about 98 % were obtained based on the addition of Zn₂SnO₄. The shrinkage of the ceramic samples increased sharply and got a saturated value about 13.3 % with doping more than 0.2 mol% Zn₂SnO₄. In the dielectric spectra, no relaxation peaks were observed and no deep trap states could be detected from 50–300 °C and 40–5 M?Hz. Thus, the oxygen vacancies may not be necessary for the densification of SnO₂ ceramics during sintering process. For all the samples, nonlinear electrical properties were observed and the breakdown electrical fields are in good agreement with the barrier height. With increasing Zn₂SnO₄ content, the activation energies E _a for O^? or O^2? adsorbed at grain boundary decreased and the doping of Zn₂SnO₄ may be an important reason for the improve of grain conductivity and formation of Schottky barrier.     

Sintering and varistor behaviour of SnO2-Zn2SnO4 composite ceramics

Densified SnO₂-Zn₂SnO₄ composite ceramics were prepared by conventional ceramic processing and the sintering, electrical properties were investigated. The X-ray diffraction results and sintering curves showed that the pellets pressed by ZnO and SnO₂ mixed powders began to shrink after Zn₂SnO₄ was synthesized at about 950 °C. The results suggest that the densification of SnO₂-Zn₂SnO₄ composite ceramics cannot be attributed to the oxygen vacancies created by acceptor doping as traditional viewed. The measurement of J-E curves showed that the SnO₂-Zn₂SnO₄ composite ceramics have good nonlinear properties (α?~?3.9–4.5) without any other doping. Another interesting result is that the composite ceramics have low breakdown electrical field (E _B?~?10 V/mm) with high relative dielectric constant (1 kHz, ε _r?~?6?×?10³). Further studies demonstrate that the varistor behavior is also a grain boundary barrier effect and the barrier height is about 0.84 eV.     

Ionic conduction and crystal structure of aluminum doped NASICON-type LiGe<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript> glass-ceramic crystallized at different times and temperatures

In this communication, NASICON-type glass-ceramic (lithium germanium phosphate, LiGe₂(PO₄)₃) was prepared as lithium super ionic conductor using aluminum as dopant for ionic conduction improvement. The solid solution was Li_1?+?xAl_xGe_2-x(PO₄)₃ (x?=?0.5) that Ge⁴⁺ ions were partially substituted by Al³⁺ ions in crystal structure. Initial glasses were converted to glass-ceramics at different times and temperatures for maximum ionic conduction achievement. The crystals were characterized by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy-Dispersive X-ray spectroscopy (EDX), Differential Scanning Calorimetry (DSC) and Complex Impedance Spectroscopy (CIS) methods. The maximum lithium ion conductivity for glass-ceramic, 5.32?×?10^?3 S/cm at 26 °C was obtained for specimen crystallized at 850 °C for 8 h with minimum activation energy of 0.286 eV. Increasing the crystallization temperature results in secondary phase formation in grain boundary and increasing in crystallization time results in microcracks formation in specimen. Both phenomena decreased the ionic conductivity.     

Low-temperature sintering and microwave dielectric properties of Mg4Nb2O9 ceramics

The effects of V₂O₅ and Li₂CO₃ on the sinterability and microwave dielectric properties of Mg₄Nb₂O₉ (MN) ceramics were investigated. With addition of 1.5wt% V₂O₅, the dielectric constant (?) and Q·? value of MN ceramics sintered at 1,000 °C are comparable to those of pure MN sintered at 1,400 °C. The good results are because of the enhancement of the density by liquid sintering at the lower temperatures. With the mixtures of V₂O₅ and Li₂CO₃, the sintering temperature of MN was further reduced to 925 °C at the expense of the quality factor (Q·?) value. Typically, ? of 13.7 and Q·? value of 78,000 GHz were obtained for the specimens with mixtures of 1.5wt% V₂O₅ and 1.5wt% Li₂CO₃ and sintered at 925 °C for 5 h.     

Low-temperature sintering of Li2O-doped BaTiO3 lead-free piezoelectric ceramics

Low-temperature sintering of BaTiO₃ ceramics using Li₂O as sintering aids was investigated with a special influences of Li₂O content (0–4?mol%) and sintering temperature (1000–1100°C) on crystalline structure and electrical properties. The sinterability of BaTiO₃ ceramics significantly improved by adding Li₂O, whose densification sintering temperature reduced from 1300°C to 1000°C. XRD pattern indicated that BaTiO₃-xLi₂O samples were single phase with a tetragonal symmetry as x?=?0–0.3?mol%, while the samples became an orthorhombic symmetry as x?=?0.5–4?mol%. The densification sintering temperature in which samples showed relative density higher than 90?% decreased with increasing Li₂O content. A maximum d ₃₃ value (200 pC/N) was obtained for the BaTiO₃-0.5?mol%Li₂O sample sintered at 1050°C, which is attributed to a vicinity of the phase transition and the high density. Adding Li₂O not only reduced the sintering temperature but also obtained the acceptable piezoelectric properties, which will make BaTiO₃ become a kind of promising and practical lead-free piezoelectric ceramics.     

Thermoelectric properties of Bi3+ substituted Co-based misfit-layered oxides

Highly densified (Ca_1?x Bi _x )₃Co₄O₉ thermoelectric ceramics with a layered structure were prepared by a sol–gel method followed by spark plasma sintering (SPS). Thermoelectric (TE) properties of the complex oxide ceramics were measured from room temperature to 700 °C. The results show that Bi³⁺ substitution leads to an increase in both electrical conductivity and Seebeck coefficient simultaneously. Bi³⁺ doped samples also show a lower thermal conductivity than undoped samples. The dimensional figure of merit ZT value of (Ca_0.95 Bi_0.05)₃Co₄O₉ samples is 0.25 at 700 °C.     

Effect of CuO addition on sintering temperature and piezoelectric properties of 0.05Pb(Al0.5Nb0.5)O3−0.95Pb(Zr0.52Ti0.48)O3+0.7 wt.% Nb2O5 + 0.5 wt.% MnO2 ceramics

Effect of CuO addition on piezoelectric properties of 0.05Pb(Al_0.5Nb_0.5)O₃?0.95Pb(Zr_0.52Ti_0.48)O₃+0.7 wt.% Nb₂O₅ + 0.5 wt.% MnO₂ (PAN-PZT) ceramics was studied to decrease the sintering temperature below 900°C for LTCC. The PAN-PZT ceramics sintered at 1200°C had piezoelectric properties of d ₃₃ = 340 pC/N, k _p = 61.6%, Q _m = 1,725, and density of 7.5 g/cm³. The addition of CuO significantly decreased the sintering temperature due to the formation of liquid phase containing a binary combination of PbO and CuO in grain boundary. Piezoelectric properties of d ₃₃ = 361 pC/N, k _p = 57%, Q _m = 145, and density of 7.8 g/cm³ were achieved at sintering temperature of 900°C. The CuO doped PAN-PZT ceramics show high density and d ₃₃ at low sintering temperature though its electromechanical quality factor abruptly decreases due to the CuO additive effect.     

Lead-free Na0.5K0.5NbO3 piezoelectric ceramics fabricated by spark plasma sintering: Annealing effect on electrical properties

Niobate ceramics such as NaNbO₃ and KNbO₃ have been studied as promising Pb-free piezoelectric ceramics, but their sintering densification is fairly difficult. In the present study, highly dense Na_0.5K_0.5NbO₃ ceramics with submicron grains were prepared using SPS, whose density was raised to 4.47 g/cm³ (>99% of the theoretical density) at 920 °C. Reasonably good ferroelectric and piezoelectric properties were obtained in the SPSed Na_0.5K_0.5NbO₃ ceramics after annealing in air. The effect of annealing time on the electrical properties was investigated to determine optimal processing condition. The piezoelectric parameter (d ₃₃) of the Na_0.5K_0.5NbO₃ ceramics annealed properly reached 148 pC/N.     

Bulk dense nanocrystalline BaTiO3 ceramics prepared by novel pressureless two-step sintering method

In this paper, we investigate preparation of bulk dense nanocrystalline BaTiO₃ ceramics using an unconventional two-step sintering strategy, which offers the advantage of not having grain growth while increasing density from about 73 to above 99.6%. Isothermal and constant grain size sintering have been carried out to high density in pure BaTiO₃ system. The kinetics of this method is also discussed, which exploits the different kinetics between densification diffusion and grain boundary mobility. Using this method, bulk dense ceramics with a grain size of 8–10 nm was obtained successfully at a very low sintering temperature.     

Piezoelectric characteristics of low temperature sintering Pb(Ni1/3Nb2/3)O3–Pb(Zr1/2Ti1/2)O3 ceramics as a function of Pb(Mn1/3Sb2/3)O3 substitution

In this study, in order to develop the composition ceramics for multilayer ceramic for ultrasonic nozzle and ultrasonic actuator application, Pb(Mn_1/3Sb_2/3)O₃ (abbreviated as PMS) substituted Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (abbreviated as PNN-PZT) ceramics were fabricated using two-stage calcinations method and Li₂CO₃, Na₂CO₃ and ZnO as sintering aids, and their piezoelectric and dielectric characteristics were investigated. With the increase of the amount of PMS substitution, electromechanical coupling factor (k _p), and mechanical quality factor (Q _m) of specimens showed the maximum value at 3 mol% substituted specimen while dielectric constant (? _r) was decreased. At the sintering temperature of 900 °C, the density, ? _r, k _p, and Q _m of 3 mol% PMS substituted PNN-PZT composition ceramics showed the optimal values of 7.92 [g/cm³], 959, 0.584, and 1003, respectively, for low loss multilayer piezoelectric actuator application.