K_(0.5)Na_(0.5)NbO_3-La_2O_3无铅压电陶瓷性能的研究

采用传统周相反应法制备了K0.5Na0.5NbO3-xmol%La2O3(简称KNN-xLa)系列无铅压电陶瓷,研究了不同La2O3含量(x=0.0,0.05,0.15,0.25,0.35,0.5,1.0)样品的物相组成、显微结构、压电及介电性能.实验结果表明:La2O3的加入并没有改变陶瓷的相结构,体系仍为单一正交相钙钛矿结构.随着掺杂量x的增大样品的压电系数(d33)、机械品质因子(Qm)、平面机电耦合系数(kp)和样品密度(P)都呈现先增大后减少的变化趋势,而介质损耗(tan δ)呈现先变小后增大的变化趋势,烧成温度则随着x的增大而升高.当x=0.15时,材料的综合性能达到最佳,其中P=4.52 g/cm3,d33=120pC/N,Qm=130,kp=0.41,tan δ=0.021.此外,随着x的增大,居里温度Tc则呈现出先升高后降低的趋势,而正交相向四方相的转变温度To-t与Tc变化相反,且当x=0.15时,To-t=189℃,Tc=404℃.     

(Na1-xKx0.5)Bi0.5TiO3-xSrTiO3-0.3Mn陶瓷的性能研究

采用固相法制备了(Na1-x Kx)0.5Bi0.5TiO3-xSrnO3-0.3Mn系无铅压电陶瓷,研究了该系统的压电性能.XRD分析表明所得陶瓷样品在室温下均为三方、四方共存的钙钛矿结构,随着sr的增加三方相减少四方相增加.该体系样品具有优异的压电性能,在sr含量为0.02时,压电常数d33、平面机电耦合系数kp和厚度机电耦合系数Kt同时达到最大值,分别为171pC·N-1、33.1%和30.5%,sr具有"软性"添加物的作用.     

(K0.5Na0.5)(TaxNb1-x)O3无铅压电陶瓷的性能特征

采用传统电子陶瓷制备工艺制备了(K0.5Na0.5)(TaxNb1-x)O3无铅压电陶瓷。研究了不同Ta含量下(K0.5Na0.5)(TaxNb1-x)O3陶瓷的晶相组成及性能特征。结果表明,(K0.5Na0.5)(TaxNb1-x)O3陶瓷在低Ta含量时形成单一斜方相固溶体,但Ta含量达到0.08mol后则有K6Ta10.8O30次晶相产生。随着Ta的加入,陶瓷的体积密度逐渐增大,居里温度(Tc)逐渐降低。当Ta含量为0.08mol时陶瓷具有良好的铁电、压电性能和介电稳定性能,其压电常数d33为76pC/N。     

Ba(Zr_(0.055)Ti_(0945))O_3含量对[(Na_(0.80)K_(0.16)Li_(0.04))_(0.5)Bi_(0.5)]TiO_3陶瓷性能的影响

系统研究(1-y)[(Na0.80K0.16Li0.04)0.5Bi0.5]TiO3-yBa(Zr0.055Ti0.945)O3无铅压电陶瓷,获得压电应变常数高达185pC/N的0.94[(Na0.80K0.16Li0.04)0.5Bi0.5]-TiO3-0.06Ba(Zr0.055Ti0.945)O3压电陶瓷。样品的晶体结构为三方相、四方相共存,处于准同型相界(morphotropic phase boundary,MPB)附近。该类陶瓷室温MPB的摩尔(下同)含量为0.050y0.065。样品y=0.060在40°左右的(003)、(021)双峰与46.5°左右的(002)、(200)双峰分裂最明显。随着Ba(Zr0.055Ti0.945)O3含量的增加,铁电相-反铁电相相变温度(θd)升高、反铁电相-顺电相相变温度(θm)降低;θd和θm的温差越来越小,材料的弛豫性逐渐降低。     

Bi_(0.5)K_(0.5)TiO_3掺杂对0.945K_(0.5)Na_(0.5)NbO_3-0.045LiSbO_3无铅压电陶瓷结构性能的影响

采用传统固相合成法合成(1-x)(0.945K0.5Na0.5NbO3-0.045LiSbO3)-x(Bi0.5K0.5TiO3)(简记为(KNN-LS)(1-x)-BKTx))无铅压电陶瓷,研究不同BKT掺入量(x=0.000,0.005,0.010,0.015,0.020,0.025,0.030)对该体系陶瓷的微观结构和压电介电性能。结果表明:x≤0.025时,均可形成单一钙钛矿结构;与KNN-LS相比,体积密度(ρ)、机械耦合系数kp、kt显著提高;d33、介电损耗tanδ、机械品质因数Qm和次级相变温度降低;当x=0.020时,样品的整体性能达到最佳值:ρ=4.239g/cm3,d33=94pC/N,kp=30.9%,kt=20.7%,tanδ=0.024,相对介电常数εT33/ε0=2468,Qm=53.95,次级相变温度降至室温以下,温度稳定性好。     

稀土氧化物对Na_(0.5)Bi_(0.5)TiO_3基无铅压电陶瓷结构和性能的影响

综述了稀土氧化物在Na0.5Bi0.5TiO3(BNT)基无铅压电陶瓷中的应用现状和发展前景,并阐述了稀土氧化物在BNT基无铅压电陶瓷中的作用机理。     

Na0.5K0.44Li0.06Nb0.94Sb0.06O3无铅压电陶瓷的制备与性能研究

采用传统固相烧结法制备Na0.5 K0.44 Li0.06 Nb0.94 Sb0.06 O3无铅压电陶瓷,研究了烧结温度对陶瓷样品微观结构及电学性能的影响.研究结果表明:烧结温度在1020～1100℃范围内,样品均形成了单一的正交相钙钛矿结构,烧结温度对微观形貌和电学性能有较大影响;与纯KNN陶瓷相比,陶瓷的To-t和Tc均向低温方向移动;当烧结温度为1080℃时晶粒发育比较完全,To-t和Tc分别为45℃和345℃,同时表现出优异的电学性能:d33=200 pC/N,kp=0.365,tanδ=4.67％.     

Y_2O_3,Fe_2O_3掺杂(Na_(0.5)Bi_(0.5))TiO_3无铅压电陶瓷的研究

采用固相法制备了(Na0.5Bi0.5)TiO3+xmol%Y2O3+xmol%Fe2O3(0≤x≤1.25)(简称NBTYF)无铅压电陶瓷。XRD衍射结果表明,所有陶瓷样品均为单一的钙钛矿结构。SEM表明,掺杂后陶瓷的晶粒尺寸增大。介电温谱表明该体系陶瓷具有弛豫特性,随掺杂量的增加,退极化温度Td向低温方向移动,而居里温度Tc向高温方向移动。陶瓷的密度和压电常数d33和随x的增加先增大后减小,而机械品质因子Qm一直下降。当x=1.00时,该体系陶瓷具有最佳压电性能,d33=106pC/N,Qm=93,kp=16.08%,εr=594,tanδ=5.33%,ρ=5.699g/cm3。     

制备工艺对0.95(K_(0.5)Na_(0.5))NbO_3-0.05CaZrO_3基无铅陶瓷压电性能的影响

采用传统陶瓷工艺制备了0.95(K0.5Na0.5)NbO3-0.05CaZrO3无铅压电陶瓷。研究了烧结温度和极化工艺对陶瓷压电性能的影响。结果表明:随着烧结温度的提高,0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的体积密度增大,在1170℃时达到最大值,同时d33和kp,在此温度也分别达到他们的最大值210pC/N和0.40。极化工艺对0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的压电性能有明显的影响,0.95(K0.5Na0.5)NbO3-0.05CaZrO3陶瓷的最佳极化温度是70℃,最佳极化电场是4kV/mm。     

(Bi_(0.5)Na_(0.5))TiO_3-BaTiO_3系陶瓷的介电弛豫性能

采用传统压电陶瓷固相合成法制得了纯钙钛矿相的( 1 -x) (Bi0 5Na0 5 )TiO3 -xBaTiO3 (x=0 02, 0 04,0 06, 0 08, 0 10) (简写作BNBT)系无铅压电陶瓷。研究了1kHz条件下室温到400℃的温度范围内BNBT试样的介电温谱以及3种不同频率下(1、10、100kHz)BNBT-6试样的介电温谱,发现材料在研究组成范围内均为弛豫型铁电体。采用HRTEM研究了该系统的畴结构,表明BNBT钙钛矿结构铁电体的介电性能与复合离子的有序无序排列密切相关,纳米尺度有序微畴对介电弛豫起着重要作用。     

Photoluminescence and Temperature Dependent Electrical Properties of Er‐Doped 0.94Bi0.5Na0.5TiO3‐0.06BaTiO3 Ceramics

Er‐doped 0.94Bi_0.5Na_0.5TiO₃‐0.06BaTiO₃ (BNT‐6BT: xEr, x is the molar ratio of Er³⁺ doping) lead‐free piezoceramics with x = 0–0.02 were prepared and their multifunctional properties have been comprehensively investigated. Our results show that Er‐doping has significant effects on morphology of grain, photoluminescence, dielectric, and ferroelectric properties of the ceramics. At room temperature, the green (550 nm) and red (670 nm) emissions are enhanced by Er‐doping, reaching the strongest emission intensity when x = 0.0075. The complex and composition‐dependent effects of electric poling on photoluminescence also have been measured. As for electrical properties, on the one hand, Er‐doping tends to flatten the dielectric constant‐temperature (ε_r‐T) curves, leading to temperature‐insensitive dielectric constant in a wide temperature range (50°C–300°C). On the other hand, Er‐doping significantly decreases the ferroelectric‐relaxor transition temperature (T_F–R) and depolarization temperature (T_d), with the T_F–R decreasing from 76°C to 42°C for x = 0–0.02. As a result, significant composition‐dependent electrical features were found in ferroelectric and piezoelectric properties at room temperature. In general, piezoelectric and ferroelectric properties tend to become weaker, as confirmed by the composition‐dependent piezoelectric coefficient (d₃₃), planar coupling factor (k_p), and the shape of polarization‐electric field (P–E), current‐electric field (J–E), bipolar/unipolar strain‐electric field (S–E) curves. Furthermore, to understand the relationship between the T_F–R/T_d and the electrical properties, the composition of x = 0.0075 has been intensively studied. Our results indicate that the BNT‐6BT: xEr with appropriate Er‐doping may be a promising multifunctional material with integrated photoluminescence and electrical properties for practical applications.     

Microstructure and Electrical Properties of Nonstoichiometric 0.94(Na0.5Bi0.5+x)TiO3–0.06BaTiO3 Lead‐Free Ceramics

0.94(Na_0.5Bi_0.5+x)TiO₃–0.06BaTiO₃ (x = ?0.04, 0, 0.02; named NB_0.46T‐6BT, NB_0.50T‐6BT, NB_0.52T‐6BT, respectively) lead‐free piezoelectric ceramics were prepared via the solid‐state reaction method. Effects of Bi³⁺ nonstoichiometry on microstructure, dielectric, ferroelectric, and piezoelectric properties were studied. All ceramics show typical X‐ray diffraction peaks of ABO₃ perovskite structure. The lattice parameters increase with the increase in the Bi³⁺ content. The electron probe microanalysis demonstrates that the excess Bi₂O₃ in the starting composition can compensate the Bi₂O₃ loss induced during sample processing. The size and shape of grains are closely related to the Bi³⁺ content. For the unpoled NB_0.50T‐6BT and NB_0.52T‐6BT, there are two dielectric anomalies in the dielectric constant–temperature curves. The unpoled NB_0.46T‐6BT shows one dielectric anomaly accompanied by high dielectric constant and dielectric loss at low frequencies. After poling, a new dielectric anomaly appears around depolarization temperature (T_d) for all ceramics and the T_d values increase with the Bi³⁺ amount decreasing from excess to deficiency. The diffuse phase transition character was studied via the Curie–Weiss law and modified Curie–Weiss law. The activation energy values obtained via the impedance analysis are 0.69, 1.05, and 1.16 eV for NB_0.46T‐6BT, NB_0.50T‐6BT and NB_0.52T‐6BT, respectively, implying the change in oxygen vacancy concentration in the ceramics. The piezoelectric constant, polarization, and coercive field of the ceramics change with the variation in the Bi³⁺ content. The Rayleigh analysis suggests that the change in electrical properties of the ceramics with the variation in the Bi³⁺ amount is related to the effect of oxygen vacancies.     

Polarization behavior of` lead-free 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 thin films with enhanced ferroelectric properties

(Bi_0.5Na_0.5)TiO₃ based ferroelectric lead-free thin films have great potential for modern micro-devices. However, the multicomponent feature and volatile nature of Bi/Na makes the achievement of high quality films challenging. In this work, the morphotropic phase boundary composition, 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ thin films were successfully prepared by CSD method. Dense films with low dielectric loss and low leakage current density were obtained. A well-defined polarization hysteresis loop with a high remnant polarization was observed in the thin films. Moreover, the polarization behavior of the film at original state, under electric field and upon heating was investigated by PFM. A self-polarization and asymmetric domain switching behavior were observed. High temperature induced depolarization and the self-polarization recovered upon cooling. The thin films with good quality show a promising potential for the application in electrical devices, and the in-depth investigation of the polarization behavior improves the understanding of ferroelectric and piezoelectric properties of thin films.     

Giant electric field-induced strain at room temperature in LiNbO3-doped 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3

We report experimental investigation on the ferroelectricity and electric field-induced strain response in LiNbO₃-doped 0.94(Bi_0.5Na_0.5)TiO₃-0.06BaTiO₃ (BNT-BT) piezoelectric ceramics. At room temperature, a large strain of 0.6% (at 70 kV/cm) is achieved in the 2.5%-LiNbO₃-doped BNT-BT, higher than that of commercially-utilized Pb(Zr,Ti)O₃. The corresponding piezoelectric coefficient d^*₃₃ reaches 857 pm/V, which is high among these of BNT-based ceramics at room temperature. Further study indicates that the superior piezoelectric properties are realized at the ferroelectric-relaxor transition temperature T_F-R, which is pushed to room temperature with 2.5% LiNbO₃ doping. This indicates that large electromechanical response can be induced via delicate mixing of the ferroelectric rhombohedral phase and the polar nanoregions (PNRs) relaxor-ferroelectric tetragonal phase.     

Enhancement of pyroelectric properties of lead-free 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics by La doping

Lead-free 0.94NBT-0.06BT-xLa ceramics at x = 0.0–1.0 (%) were synthesized by a conventional solid-state route. XRD shows that the compositions are at a morphotropic phase boundary where rhombohedral and tetragonal phases coexist. With increasing La³⁺ content pyroelectric coefficient (p) and figures of merits greatly increase; however, the depolarization temperature (T_d) decreases. p is 7.24 × 10⁻⁴C m⁻² °C⁻¹ at RT at x = 0.5% and 105.4 × 10⁻⁴C.m^−2 °C⁻¹ at T_d at x = 0.2%. F_i and F_v show improvements at RT from 1.12 (x = 0%) to 2.65 (x10 ⁻¹⁰ m v⁻¹) (x = 0.5%) and from 0.021 to 0.048 (m².C⁻¹) respectively. F_i and F_v show a huge increase to 37.6 × 10⁻¹⁰ m v⁻¹ and 0.56 m² C⁻¹ respectively at T_d at x = 0.2%. F_C shows values of 2.10, 2.89, and 2.98 (x10⁻⁹C cm⁻² °C⁻¹) at RT at 33, 100 and 1000 (Hz) respectively. Giant pyroelectric properties make NBT-0.06BT-xLa at x = 0.2% and 0.5% promising materials for many pyroelectric applications.     

Y2O3掺杂对(Bi0.5Na0.5)0.94Ba0.06TiO3无铅压电陶瓷性能的影响研究

采用传统固相反应法制备了Y2O3掺杂(Bi0.5Na0.5)0.94Ba0.06TiO3(简写为BNBT6)陶瓷[简称为BNBT6-x(wt%)Y2O3陶瓷].研究了Y2O3 (0.2wt%～0.8wt%)掺杂对BNBT6陶瓷的结构、介电、压电、铁电性能的影响.结果表明,所有Y2O3掺杂陶瓷样品均形成了单一的钙钛矿结构;陶瓷的介电、压电、铁电性能受Y2O3掺杂的影响较为显著:当掺杂0.4wt%Y2O3时,10 kHz频率下测得的室温εr达到1530,且tanδ较小,为0.050,d33达到152 pC/N,kp=0.27,Qm=134.掺杂0.2wt%的Y2O3时BNBT6陶瓷的d33为145 pC/N,kp增大到0.29,Qm达到173,tanδ为0.053;掺杂适量Y2O3的BNBT6陶瓷铁电性能也得到改善.     

Tuning the electrocaloric effect in 0.94Bi0.5Na0.5TiO3-0.06BaTiO3 ceramics by relaxor phase blending

The pseudo-first-order phase transition in 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ceramics leads to a sharp increase in temperature change (ΔT) in the vicinity of the ferroelectric-to-relaxor transition temperature T_FR (~100 °C) [Appl. Phys. Lett. 110 (2017) 182904]. In this study, we add the 0.78Bi_0.5Na_0.5TiO₃-0.06BaTiO₃-0.16(Sr_0.7Bi_0.2)TiO₃ relaxor phase to the 0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃ ferroelectric matrix to tune its electrocaloric effect. The results show that the addition of the relaxor phase plays a vital role in phase and local-structure evolution. A transition occurs between the ferroelectric and ergodic relaxor phases when the mass fraction of the latter increases to 30% (x = 0.3), as verified by X-ray diffraction analysis, Raman spectroscopy, and polarization-electric field (P-E) hysteresis loops. Furthermore, addition of the relaxor phase reduces the T_FR from 76 °C at x = 0.1–55 °C at x = 0.2; however, this transition disappears at x = 0.3 and 0.4 composite. In-situ piezo-force microscopy (PFM) images illustrate that domains can be written into x = 0.1 and 0.2 ceramics with a valley in the piezoresponse curves. Increasing the temperature agitates the domain arrangement and decreases the contrast for PFM images; this indicates a gradual phase transition in the composite. The temperature corresponding to maximum ΔT exhibits a downward shift (0.58 K at 80 °C for x = 0.1 and 0.5 K at 65 °C for x = 0.2), while the temperature-ΔT curves are flat when x = 0.3 and 0.4. Moreover, the maximum ΔT shows a decrease with an increase in the relaxor phase content; this is believed to be related to a decrease in the latent heat due to a pseudo-first-order to second-order transition. Thus, we suggest that the incorporation of a relaxor phase into ferroelectric matrices is an effective technique to tune their electrocaloric effect and improve the thermal stability of ceramic composites.     

Giant electric field-induced strain and structure evolution of NaTaO3-modified 0.94(Bi0.5Na0.5)TiO3-0.06BaTiO3 Pb-free ceramics

To acquire giant electric field-induced strain in non-Pb materials is attracting a great deal of attention in the past decade. In the current investigation, the crystal and domain structures as well as the electrical performances of (1-x) (0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃)-xNaTaO₃ (BNBT-xNT) specimens were systematically studied to achieve enhanced strain. The introduction of NT makes the phase structure transit from rhombohedral-tetragonal to pseudo-cubic structure. The original domain structure of BNBT is destroyed, and the disorder degree of the local structure increases. Simultaneously, the remnant polarization, coercive field, and piezoelectric coefficients were significantly decreased. The transition from ferroelectric to ergodic relaxation can be effectively modified, thus lowering the transition zone to room temperature. Finally, the BNBT-3NT ceramics achieve marked strain coefficients at room temperature, with a maximum strain of 0.394% under 65 kV/cm and a d₃₃* of 606 pm/V.     

Large electrostrain and structural evolution in (1-x)[0.94Bi0.5Na0.5TiO3-0.06BaTiO3]-xAgNbO3 ceramics

A lead-free system formulated as (1-x)[0.94Bi_0.5Na_0.5TiO₃-0.06BaTiO₃]-xAgNbO₃ exhibits an electrostrain of 0.50% at 80 kV/cm and a maximum d₃₃^* of 721 pm/V at 60 kV/cm for x=0.3. The incorporation of AgNbO₃ shifts the relaxor-ferroelectric phase transformation temperature (T_F-R) to room temperature and lowers the energy barrier of the field-induced phase transformation. Furthermore, the in-situ electric field dependent high-energy synchrotron X-ray diffraction (SXRD) technique reveals that the sample x=0.03 transforms from dominant P4bm phase to a phase mixture of R3c + P4mm at 55 kV/cm during the electric field loading, and returns to initial dominant P4bm phase at 15 kV/cm during the unloading cycle of the electric field. Furthermore, it can be demonstrated that the electric field induced-phase transition in NBTBT-3AN occurs in the whole sample, rather than in the single direction of electric field. Therefore, the electrocstrain in NBTBT-3AN is more uniform, which would be beneficial to its actuator applications.     

Microstructure,dielectric, piezoelectric,and ferroelectric properties of fine-grained 0.94Na0.5Bi0.5TiO3-0.06BaTiO3 ceramics

For preparing fine-grained 0.94Na_0.5Bi_0.5TiO₃-0.06BaTiO₃ lead-free ferroelectric ceramics, the precursor powders were synthesized via sol-gel method and calcined at various temperatures. The precursor powders calcined at 520 °C, 550 °C, and 600 °C exhibit mean grain sizes of 30 ± 4 nm, 54 ± 3 nm, and 78 ± 5 nm, respectively. By optimizing the synthesis parameters, the fine-grained ceramics with high relative densities (>97%) and mean grain size around 100 nm were prepared. The ferroelectric, dielectric, and piezoelectric behavior were investigated. The ceramics prepared using the different precursor powders show different piezoelectric, ferroelectric, and dielectric behavior. The ceramic calcined at 550 °C and sintered at 900 °C exhibits the breakdown strength higher than 85 kV/cm, which exhibits the maximum polarization of 38.4 ± 0.3 μC/cm², remanent polarization of 20.6 ± 0.4 μC/cm².