Effects of the sintering atmosphere on Nb-based dielectrics

The effects of a forming atmosphere on the stability, the sintering and the dielectric properties of Ba₅Nb₄O₁₅, BaNb₂O₆, ZnNb₂O₆ and Zn₃Nb₂O₈ ceramics were investigated, because of the primary importance of the sintering atmosphere in relation to copper sintering. These Nb-based materials were sintered in air and in Ar/H₂10%. Zn-containing samples are very sensitive to the reductive atmosphere. ZnO volatilises at 800–850 °C and the resulting compound does not exhibit the expected properties. BaNb₂O₆ and Ba₅Nb₄O₁₅ are more stable in term of relative weight loss. Nevertheless, the phase analysis reveals a modification of the BaNb₂O₆ phase, what induces the degradation of the dielectric property stability versus temperature. The properties of Ba₅Nb₄O₁₅ are not modified by a sintering in reductive atmosphere. A relative permittivity of 38.8, a permittivity temperature coefficient of −150 ppm °C⁻¹ and an insulating resistivity of 10^10.9 Ω cm were obtained for this latter.     

Effects of chemical additives on high-field electromechanical properties of PMN–PT–BT ceramics

A chemical additive method using sol–gel reactions was used to modify the composition and resultant properties of a commercially available 0.96(0.91Pb(Mg_1/3Nb_2/3)O₃–0.09PbTiO₃)–0.04 BaTiO₃ (PMN–PT–BT) ceramic. Without an additional ball-mixing process, several combinations of minor additives such as Fe, Ba, Sr, Zn, and Ti were incorporated by the chemical method. Weak- and high-field characteristics including dielectric properties, induced strain and polarization, and associated hystereses were evaluated for the samples sintered at 1200 °C for 4 h. All properties were found to depend on the chemical additives and temperature. Especially, the temperature dependence of high-field characteristics revealed different behavior from that reported for conventionally prepared samples. For example, the samples containing 0.5 wt.% SrO, 0.5 wt.% ZnO, and 0.5 wt.% TiO₂ did not exhibit a transition to piezoelectric behavior at the temperature expected from the dielectric measurements. Overall, the coating process has been successfully used to modify, and in some cases, enhance the high-field characteristics of PMN-based ceramics for electromechanical uses.     

Phase equilibria and dielectric properties of Bi3+(5/2)xMg2−xNb3–(3/2)xO14−x cubic pyrochlores

Subsolidus pyrochlores with the proposed formula, Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) were successfully synthesised at the firing temperature of 1025 °C using conventional solid-state reaction. The excess Bi³⁺ charge was offset by removal of relative proportion of Mg²⁺ and Nb⁵⁺ together with creation of oxygen non-stoichiometry in order to preserve electroneutrality of the system. These samples were crystallised in cubic structure with space group of Fd3m, No. 227 and their refined lattice parameters were in the range of 10.5706 (3)–10.5797 (7) Å. The surface morphologies of the samples as confirmed by scanning electron microscopy analysis were of irregular shaped grains while their crystallite sizes of ~30–85 nm were calculated using the Scherrer equation and the Williamson–Hall method. No thermal event was discernable indicating these pyrochlores were thermally stable within a studied temperature range of ~30–1000 °C. The recorded dielectric constants of Bi_3+(5/2)xMg_2−xNb_3−(3/2)xO_14−x (0.14≤x≤0.22) subsolidus pyrochlores were generally above ~160 and their dielectric losses were in the order of 10⁻⁴–10⁻³ at the frequency of 1 MHz and temperature of ~30 °C. Meanwhile, these ceramic samples also exhibited negative temperature coefficient of relative permittivity between −528 and −742 ppm/°C in the temperature range of ~30–300 °C.     

The phase structure and electric properties of low-temperature sintered (K,Na)NbO3-based piezoceramics modified by CuO

0.25 wt% CuO-doped (Li,K,Na)(Nb,Ta)O₃–AgSbO₃ lead-free piezoceramics with pure perovskite structure were successfully prepared at a sintering temperature below 1000 °C. The sintering temperature of KNN-based piezoceramics was effectively reduced by about 100 °C due to the enhanced densification process induced by the addition of CuO. Besides, the acceptable sintering temperature window was broadened by the addition of CuO. It is found that the CuO-doped samples show slightly higher tetragonal–orthorhombic phase transition point (T_T−O) but a lower Curie point (T_c), compared to undoped ones. The KNN-based piezoceramics became “hard” as CuO was added, supported by an increase of Q_m. Fairly good electrical properties of d₃₃^*=383 pm/V, ε_r=860, Q_m=188 and T_c=215 °C could be obtained in dense CuO-modified KNN-based piezoceramics sintered at 970 °C, demonstrating promising potential in practical applications.     

Low-temperature sintering of (K,Na)NbO3-based lead-free piezoceramics with addition of LiF

Dense Li/Ta-codoped KNN-based piezoceramics with d₃₃^* up to 375 pm/V were successfully fabricated by conventional sintering at a temperature as low as 900 °C by using LiF as a sintering additive. The reduction of densification temperature up to 200 °C was realized by a transient liquid phase sintering mechanism, consequently no grain boundary phase was observed in the sintered samples. It was found that the addition of LiF could further shift down the tetragonal–orthorhombic transition point (T_T-O), indicating that a small amount of Li⁺ could diffuse into the A-site of KNN matrix. The introduction of LiF enhanced the linearity of strain curves of the ceramics, which is unambiguously in favor for the actuator application. The present work reveals that low-temperature sintered LiF-doped KNN-based piezoceramics demonstrates promising potential in multilayer-structured actuator applications.     

Noncentrosymmetric phase of submicron NaNbO<Subscript>3</Subscript> crystallites

The temperature and pressure characteristics of a noncentrosymmetric crystal modification of NaNbO₃ were studied by Raman spectroscopy. A transition towards the bulk-like structure of NaNbO₃ occurs in the temperature range from 280 to 360 °C. High-pressure Raman spectroscopy revealed successive pressure-induced phase transitions at around 2, 6.5 and 10 GPa. Raman scattering profiles recorded above 7 GPa correspond to those reported for the bulk. The temperature-induced spectral changes were completely reversible between −150 and 450 °C. Those induced by pressure were almost reversible from ambient pressure up to 15.9 GPa. Piezoresponse force microscopy demonstrated the occurrence of piezoelectric activity for submicron NaNbO₃ crystals with particle size ranging from 200 to 400 nm. The noncentrosymmetric crystallographic structure plays a critical role for the enhancement of piezoelectricity.     

Lead-free NaNbO3-based ferroelectric perovskites and their polar polymer-ceramic composites: Fundamentals and potentials for electronic and biomedical applications

Ferroelectric lead-free NaNbO₃-based ceramics are the most promising candidates to a wide range of advanced technological applications as sensors, transducers and actuators. In special, (K,Na)NbO₃ (KNN) and (Ba,Na)(Ti,Nb)O₃ (BTNN) show interesting structural properties, including morphotropic phase boundaries regions that lead to exceptional dielectric, piezoelectric and ferroelectric responses. Also, the biocompatibility of these compounds allows their application as biomedical sensors, medical devices, and bone tissue replacement. In this way, high impact applications can be achieved with ferroelectric lead free NaNbO₃ – based (NN-based) ceramics. In this review, we will explore the strategies for the improvement of ferroelectric, dielectric and structural properties reviewing the effects of the synthesis process, microstructure and chemical composition of lead-free complex perovskite ceramics, specially KNN and BTNN, as well as, PVDF-KNN and PVDF-BTNN polymer-ceramic and the (PVDF-TrFE)-KNN copolymer-ceramic composites to provide new insights and research opportunities for the development and improvement of fundamental properties of such systems considering their potential for technological applications, especially for the biological ones.     

PSN掺杂对锆钛酸铅特性的改善

研究了通过掺杂Ｐｂ（Ｓｎ１／３Ｎｂ２／３Ｏ３［ＰＳＮ］对Ｐｂ（ＴｉｙＺｒ２）Ｏ３系陶瓷热稳定性及老化特性的改善,试验表明加入一定量的ＰＳＮ组成的陶瓷体系,居里温度提高,高温下的热稳定性和老年特性均得以改善,满足了高温下高性能的压电换能元件的需要。     

Sintering behavior and microwave dielectric properties of Bi2O3–ZnO–Nb2O5-based ceramics sintered under air and N2 atmosphere

The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi₂(Zn_1/3Nb_2/3)₂O₇ (BZN) and Bi₂(Zn_1/3Nb_2/3−xV_x)₂O₇ (BZNV, x = 0.001) sintered under air and N₂ atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V₂O₅ and N₂ atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N₂ atmosphere with _r = 76.1, Q = 850 and Q_f = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with _r = 76.7, Q = 890 and Q_f = 3580 GHz. The temperature coefficient of resonant frequency τ_f was not obviously influenced by the different atmospheres. For BZN ceramics the τ_f was −79.8 ppm/°C while τ_f is −87.5 ppm/°C for BZNV ceramics.