BiCoO3-doped (K0.475Na0.475Li0.05)(Nb0.8Ta0.2)O3 lead-free piezoelectric ceramics

(1--x)(K_0.475Na_0.475Li_0.05)(Nb_0.8Ta_0.2)O₃--xBiCoO₃ (KNLNT--BC) lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. Effects of the BC content on the phase structure, microstructure and electrical properties of KNLNT--BC ceramics were investigated. XRD patterns reveal that all the ceramic samples are in the pure perovskite-type structure, and the phase structure changes from the tetragonal to pseudo-cubic phase with the increase of the BC content. After the substitution of BC, the grain size is significantly reduced and relaxer behaviors are induced. By adding a small amount of BC to KNLNT ceramics, piezoelectric properties are improved, while further addition of BC makes the piezoelectric properties deteriorate markedly. The optimized electrical properties at x = 0.005 are as follows: d₃₃ = 194 pC/N, k_p = 0.44.     

烧结方式对(K,Na,Li)(Nb,Sb,Ta)O3压电陶瓷的微观结构和物理性能的影响

(K,Na)NbO₃基陶瓷(KNLNST陶瓷)是一类很有发展潜力的无铅压电材料, 目前对其进行两步烧结相关的研究还很少。本工作分别采用普通烧结(Conventional Sintering, CS)和两步烧结(Two-step Sintering, TSS)制备了(K_0.4425Na_0.52Li_0.0375)(Nb_0.8825Sb_0.08Ta_0.0375)O₃陶瓷, 并进行微观结构与物性的对比研究。TSS可将(K,Na)NbO₃基陶瓷的相对密度ρ°由CS时的95.0%提高至97.0%, 压电系数d₃₃由CS时的363 pC/N增大到387 pC/N。两种烧结方式制备的KNLNST陶瓷的微观组织结构和电畴结构有着很大的差异。KNLNST-CS陶瓷的晶粒尺寸较小而且分布较为均匀, 极化后多数晶粒的电畴图案为简单的平行条纹。KNLNST-TSS陶瓷的晶粒尺寸则大小分布不均匀, 极化后许多大晶粒中呈现带状条纹内部又存在着精细的平行条纹的电畴图案。     

Piezoceramics Properties as a Function of the Structure in the System (K,Na,Li)(Nb,Ta,Sb)O3

The influence of the sintering conditions and stoichiometry on the crystalline symmetry and electrical properties of the system (K_0.44+xNa_0.52Li_0.04)(Nb_0.86Ta_0.10Sb_0.04)O_3+x/2, with x = -0.06, 0.00, and 0.04, has been evaluated. By lowering the concentration of K cations, a faster stabilization of the tetragonal phase is reached. Increasing the sintering time also leads to the stabilization of the tetragonal phase at room temperature, as evidenced by Raman spectroscopy, thus improving the piezoelectric properties of these materials. The Raman spectra versus temperature showed 2 anomalies at temperatures of ~70 and ~270 to 330degC, associated with polymorphism and the ferro-paraelectric phase transitions, respectively. Active Raman scattering modes are observed above Curie temperature, indicating that the symmetry is not cubic but pseudocubic. This pseudocubic phase is associated with relaxor diffuseness, attributed to composition fluctuations. In addition, the piezoelectric properties were correlated with the tetragonality of the system, showing a linear dependence between the piezoelectric properties and the tetragonality ratio. The ceramics with c/a = 1.011 ratio exhibit enhanced electrical properties, d₃₃ ~255 pC/N and k_p ~0.47.     

BaZrO3掺杂对(K0.49Na0.51)0.98Li0.02(Nb0.77Ta0.18Sb0.05)O3无铅压电陶瓷的结构与电性能的影响

采用固相反应法制备了(K_0.49Na_0.51)_0.98Li_0.02(Nb_0.77Ta_0.18Sb_0.05)O₃-xBaZrO₃ (NKNLST-xBZ, x = 0~0.020 mol)无铅压电陶瓷, 系统研究了BaZrO₃的掺杂量对陶瓷的压电、介电、机电和铁电性能的影响。结果表明: 随着BaZrO₃掺杂量x的增加, 陶瓷的晶体结构由正交相向四方相转变, 在x=0.005~0.008区间出现正交相与四方相两相共存的区域, 在此区域内陶瓷的晶粒变得细小且均匀, 介电损耗tanδ大幅降低, 压电常数d₃₃和平面机电耦合系数k_p增加。该体系陶瓷的介电常数ε T 33 /ε0则随着BaZrO₃的增加持续增加, 相变温度则向低温方向移动。当x=0.005时, 该组成陶瓷具有最佳的综合性能: 压电常数d33=372 pC/N, 平面机电耦合系数kp=47.2%, 介电损耗tanδ=3.1%, 以及较高的介电常数ε^T₃₃ /ε₀=1470和居里温度T_c=208℃。     

(K0.44,Na0.52,Li0.04) (Nb0.84,Ta0.10,Sb0.06)O3 Ferroelectric Ceramics

Recent progress in (K_0.44,Na_0.52,Li_0.043-based ceramics (KNN) with special emphasis on (K_0.44,Na_0.52,Li_0.040.84,Ta_0.10,Sb_0.06))O₃ (KNN-LT-LS) is reviewed concisely. The base KNN and its compositional derivatives are analyzed in terms of dopant-property relationships, which are then extended to the ternary derivatives. The effects of processing conditions such as humidity, precursor purity, and oxygen partial pressure during sintering are elaborated on from a phenomenological perspective. It is also shown that the spontaneous polarization is sensitive to the processing route chosen for synthesis (mixed oxide versus perovskite routes). Special attention is devoted to the discussion of the morphotropic phase boundary (MPB) dilemma in the KNN-LT-LS system, where it is shown that the origin of high piezoelectric activity is actually due to a polymorphic transition at room temperature. It is shown that prototype transducers based on pure and 1 mol% Ba²⁺ doped KNN-LT-LS exhibit performance metrics comparable to those fabricated using PZT-5H. Overall, KNNLT- LS ceramics show great promise for lead-free applications, although issues such as temperature dependence of properties and strong sensitivity to processing conditions remain as the 2 major challenges.     

Sintering behavior and microwave dielectric properties of Bi3(Nb1−xTax)O7 solid solutions

Solid solutions of Bi₃(Nb_1−xTa_x)O₇ (x = 0.0, 0.3, 0.7, 1) were synthesized using solid state reaction method and their microwave dielectric properties were first reported. Pure phase of fluorite-type could be obtained after calcined at 700 °C (2 h)⁻¹ between 0 ≤ x ≤ 1 and Bi₃(Nb_1−xTa_x)O₇ ceramics could be well densified below 990 °C. As x increased from 0.0 to 1.0, saturated density of Bi₃(Nb_1−xTa_x)O₇ ceramics increased from 8.2 to 9.1 g cm⁻³, microwave permittivity decreased from 95 to 65 while Q_f values increasing from 230 to 560 GHz. Substitution of Ta for Nb modified temperature coefficient of resonant frequency τ_f from −113 ppm °C⁻¹ of Bi₃NbO₇ to −70 ppm °C⁻¹ of Bi₃TaO₇. Microwave permittivity, Q_f values and τ_f values were found to correlate strongly with the structure parameters of fluorite solid solutions and the correlation between them was discussed in detail. Considering the low densified temperature and good microwave dielectric proprieties, solid solutions of Bi₃(Nb_1−xTa_x)O₇ ceramics could be a good candidate for low temperature co-fired ceramics application.     

Ferroelectric, dielectric and piezoelectric properties of potassium lanthanum bismuth titanate K0.5La0.5Bi4Ti4O15 ceramics

The Aurivillius type bismuth layer-structured compound potassium lanthanum bismuth titanate (K_0.5La_0.5Bi₄Ti₄O₁₅) is synthesized using conventional solid-state processing. The phase analysis is performed by X-ray diffraction (XRD) and the microstructural morphology is conducted by scanning electron microscopy (SEM). The ferroelectric, dielectric and piezoelectric properties of K_0.5La_0.5Bi₄Ti₄O₁₅ (KLBT) ceramics are investigated in detail. The remnant polarization (P_r) and coercive field (E_c) are found to be 8.6 μC cm⁻² and 60 kV cm⁻¹, respectively. The Curie temperature T_c and piezoelectric coefficient d₃₃ are 413 °C and 18 pC N⁻¹, respectively.     

Mn-doped perovskite-type oxide LaFeO3 as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Perovskite oxides based on the alkaline earth metal lanthanum for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolytes are promising catalysts, but their catalytic activity and stability remain unsatisfactory. Here, we synthesized a series of LaFe_1−xMn_xO₃ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) perovskite oxides by doping Mn into LaFeO₃ (LF). The results show that the doping amount of Mn has a significant effect on the catalytic performance. When x = 0.5, the catalyst LaFe_0.5Mn_0.5O₃ (LFM) exhibits the best performance. The limiting current density in 0.1 mol·L⁻¹ KOH solution is 7 mA·cm⁻², much larger than that of the commercial Pt/C catalyst (5.5 mA·cm⁻²). Meanwhile, the performance of the doped catalyst is also superior to that of commercial Pt/C in terms of the long-term durability. The excellent catalytic performance of LFM may be ascribed to its abundant O²⁻/O⁻ species and low charge transfer resistance after doping the Mn element.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Domain size dependence of d33 piezoelectric properties for barium titanate single crystals with engineered domain configurations

Engineered domain configuration was induced into barium titanate (BaTiO₃) single crystals, and the d₃₃ piezoelectricity was investigated as a function of domain size. First, for the BaTiO₃ single-domain crystals, piezoelectric constant d₃₃ along [1 1 1]_c direction was calculated as 224 pC/N. Prior to the domain engineering, the dependence of domain configuration on the temperature and the electric-field was investigated, and above Curie temperature (T_c), when the electric-field over 6 kV/cm was applied along [1 1 1]_c direction, the fine engineered domain configuration appeared. On the basis of the above information, the 33 resonators with different domain sizes were successfully prepared. Their piezoelectric measurement revealed that the d₃₃ of the 33 resonators with fine engineered domain configurations was higher than that of BaTiO₃ single-domain crystals. Moreover, d₃₃ increased with decreasing domain sizes. The highest d₃₃ of 289 pC/N was obtained in the BaTiO₃ crystal with a domain size of 13 μm.     

Structure and electrical properties of (100)-oriented Pb(Zn1/3Nb2/3)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films on La0.7Sr0.3MnO3 electrode by chemical solution deposition

(100)-oriented 0.462Pb(Zn_1/3Nb_2/3)O₃–0.308Pb(Mg_1/3Nb_2/3)O₃–0.23PbTiO₃ (PZN-PMN-PT) perovskite ferroelectric thin films were prepared on La_0.7Sr_0.3MnO₃/LaAlO₃ (LSMO/LAO) substrate via a chemical solution deposition route. The perovskite LSMO electrode was found to effectively suppress the pyrochlore phase while promote the growth of the perovskite phase in the PZN-PMN-PT film. The film annealed at 700 °C exhibited a high dielectric constant of 2130 at 1 kHz, a remnant polarization, 2P_r, of 29.8 μC/cm², and a low leakage current density of 7.2 × 10^− 7 A/cm² at an applied field of 200 kV/cm. The ferroelectric polarization was fatigue-free at least up to 10¹⁰ cycles. Piezoelectric coefficient, d₃₃, of 48 pm/V was also demonstrated. The results showed that much superior properties could be achieved with the PZN-PMN-PT thin films on the solution derived LSMO electrode than on Pt electrode by sputtering.     

(1-x)K0.48Na0.52NbO3-xBi0.45Nd0.05(Na0.92Li0.08)0.5ZrO3无铅压电陶瓷相结构及压电性能

为了在获得较高压电性能的同时又不大大降低陶瓷的居里温度(T_C), 设计和制备了Bi_0.45Nd_0.05(Na_0.92Li_0.08)_0.5ZrO₃改性的K_0.48Na_0.52NbO₃系无铅压电陶瓷((1-x)KNN-xBNNLZ), 研究了BNNLZ含量对KNN基无铅压电陶瓷相结构和电学性能的影响。研究结果表明, 所有陶瓷样品均具有较高的居里温度T_C(>300℃)。随着BNNLZ含量的增加, 陶瓷的正交-四方相变温度(T_O-T)不断向低温方向移动, 而三方-正交相变温度(T_R-O)不断向高温方向移动, 最终在陶瓷中形成了三方-四方(R-T)共存相, R-T共存相处于0.05<x<0.07范围。BNNLZ的加入引起陶瓷相结构的演化改变导致压电常数(d₃₃ )、介电常数(ε_r )、剩余极化强度 (P_r )和机电耦合系数(k_p )都先增大后减小, 当x=0.06时陶瓷具有最佳压电性能: d₃₃=313 pC/N, k_p=42%, P_r=25.48 μC/cm², ε_r=1353, tanδ=2.5%, T_C=327℃。     

Ag-assisted CeO2 catalyst for soot oxidation

In this work, the Ag loaded Ce-based catalyst was synthesized (by the sol−gel method) and its performance was studied by TG, H₂-TPR, XRD, SEM, TEM, BET and XPS. The results show that Ag nanoparticles be successfully loaded onto the CeO₂ surface and the relative content of Ag nanoparticles is about 10.22 wt.% close to the theoretical value (10%). XPS shows that Ag nanoparticles induce a great number of oxygen vacancies in the CeO₂ lattice through the electronic transfer, and H₂-TPR indicates that the Ag-assisted CeO₂ catalyst exhibits a better reduction performance and Ag nanoparticles can promote O⁻ transform into O²⁻. The catalytic activity for soot oxidation was studied by TG under air atmosphere and the activity was found to be obviously enhanced when Ag nanoparticles be load on the surface of CeO₂ (T₁₀ = 386 °C, T₉₀ = 472.5 °C, T_m = 431 °C). The reaction mechanism was also presented and O₂⁻ species is regarded as the determinant factor for the catalytic activity.     

Ba(Ti0.96Sn0.04)O3陶瓷的物性研究

采用传统固相反应法制备了Ba(Ti_0.96Sn_0.04)O₃无铅压电陶瓷, 对其压电性能、介电性能、铁电性能和微观结构等进行了研究。研究发现, 原料以及制备工艺对Ba(Ti_0.96Sn_0.04)O₃陶瓷的压电性质具有较大的影响。与BaTiO₃陶瓷相比, Ba(Ti_0.96Sn_0.04)O₃陶瓷的正交-四方相变温度T_O-T得到了一定的提高, 并且T_O-T附近的热滞只有1.8℃。陶瓷的微观形貌呈现出较为复杂的畴结构, 主要以90°平行带状畴为主, 偶尔有少量不同构型的180°畴。电滞回线呈现为理想的近似矩形饱和形状的曲线, 剩余极化强度P_r为18.9 μC/cm², 矫顽场E_c为 2.5 kV/cm。此外, 非180°畴的翻转是引起陶瓷逆压电常数d₃₃^*的主要因素, 其值可达550 pm/V。     

25 MHz ultrasonic transducers with lead- free piezoceramic, 1-3 PZT fiber-epoxy composite, and PVDF polymer active elements

This paper presents the fabrication and characterization of single-element ultrasonic transducers whose active elements are made of lead-free piezoceramic, 1-3 PZT/polymer composite and PVDF film. The lead free piezoelectric KNNLT- LS(K_0.44Na_0.52Li_0.04)(Nb_0.84Ta_0.10S_0.06b)O₃ powders and ceramics were prepared under controlled humidity and oxygen flow rate during sintering. Due to its moderate longitudinal piezoelectric charge coefficient (175 pC/N) and k_t of 0.50, the KNN-LT-LS composition may be a good candidate for highfrequency transducer applications. PZT fibers with 25 μm diameter formed by the viscose suspension spinning process were incorporated into epoxy to fabricate 1-3 composites with the averaged k_t = 0.64 and d₃₃ = 400 pC/N. Using KNN-LS-LT ceramic, 1-3 PZT fiber composite, and PVDF film, 3 different unfocused single element transducers with center frequencies of 25 MHz were fabricated. The acoustic characterization of the transducers demonstrated that wideband and low insertion loss could be obtained employing KNN-LS-LT ceramic. The ?6 dB bandwidth and insertion loss were 70% and ?21 dB, respectively. In comparison, the insertion loss of the ceramic transducer was much smaller than those made with 1-3 composite and PVDF film. This was attributed to closer electrical impedance match to 50 Ω and higher thickness coupling coefficient of the ceramic transducer.     

Influence of A-site nonstoichiometry on sintering, microstructure and electrical properties of (Bi0.5Na0.5)TiO3 ceramics

Lead-free (Bi_0.5Na_0.5)_1+xTiO₃ ceramics (x = −0.02, −0.01, −0.005, 0, 0.005 and 0.01) were prepared by ordinary sintering. The effect of A-site stoichiometry on the densification, microstructure, dielectric properties, high-temperature impedances, and piezoelectric properties was explored. It was found that the high conductivity of (Bi_0.5Na_0.5)TiO₃ (BNT) ceramics should be mainly attributed to the formation of A-site cation vacancies during sintering. Improved physical and electrical properties can be achieved in the sample with A-site cation excess. The control of the stoichiometry proves to be an effective way to improve BNT ceramics for possible application.     

Mo--V--Nb--O-based catalysts for low-temperature selective oxidation of Cα--OH lignin model compounds

Mo–V–Nb tri-component oxide catalysts were prepared and firstly used for the selective oxidation of C_α−OH lignin compounds. The catalytic performance of the composite oxides was obviously enhanced due to the synergistic effects of Mo and V elements. Mo_5−xV_xO₁₄ phase with a variable Mo/V ratio provided suitable active sites for the oxidative dehydrogenation (ODH) of C_α−OH lignin model compound. The optimized Mo–V–Nb molar composition was confirmed as Mo_0.61V_0.31Nb_0.08O_x/TiO₂, which exhibited the prominent catalytic activity with the turnover frequency of 1.04×10⁻³ mmol· g(cat)⁻¹·s⁻¹. Even at room temperature, the catalysts showed highly-efficient ODH reaction activities. The active phase for selective oxidation reaction and the inhibiting effect of α-MoO₃ phase were also discussed in the study.     

BiAlO3掺杂PZT陶瓷的高压电性能和低电场应变滞后

铅基压电陶瓷因其优异的压电性能, 被广泛应用于压电器件。其中, 压电驱动器要求压电陶瓷具有较高压电性能并且在电场下具有较高的电致应变和较小的应变滞后。本研究通过施主-受主共掺, 得到高压电性能和低电场应变滞后的PZT陶瓷。采用传统固相反应法制备了(1-x)(Pb_0.95Sr_0.05)(Zr₅₃Ti₄₇)O₃-xBiAlO₃+0.2%MnO₂陶瓷(掺杂量为质量百分数), 并对其微观结构和压电性能进行了研究。结果表明：BiAlO₃掺杂量较少时, 陶瓷中缺陷偶极子的“钉扎”效应使得陶瓷畴壁转动困难, 陶瓷压电性能较弱, 应变滞后也较小。随BiAlO₃掺杂量增加, 缺陷偶极子“钉扎”效应减弱, 陶瓷的压电性能和应变滞后随之提高。本实验得到的性能最优组分为x=1.75%, 该组份陶瓷的压电系数d₃₃=504 pC/N, 机电耦合系数k_p=0.71, 机械品质因数Q_m=281, 居里温度T_C=312 ℃, 在10 kV/cm电场下的应变滞后仅为15%, 并且还具有较好的温度稳定性, 是一种具有应用价值的压电驱动器用压电陶瓷材料。     

Er3+ 掺杂对Bi3Ti1.5W0.5O9-Bi4Ti3O12 共生无铅压电陶瓷性能的影响

用传统固相法制备了Bi_7-x Er _x Ti_4.5W_0.5O₂₁(BTW-BIT-xEr³⁺,x=0.05、0.10、0.15、0.25、0.35)共生铋层结构无铅压电陶瓷,用BTW-BIT-xEr³⁺的XRD和SEM表征其相结构和形貌,研究了Er³⁺掺杂对其上转换发光性能和电学性能的影响。结果表明：在这种陶瓷中生成了铋层状结构的单一晶相。在980 nm光波激发下所有组分的上转换荧光谱中都能清晰地观察到两个绿光和一个红光发射峰,峰的中心分别位于532 nm、548 nm和660 nm处。改变掺杂Er³⁺离子浓度可调节其强度比。根据BTW-BIT-0.15Er³⁺样品在532 nm和548 nm绿光的光强比拟合了290~440 K的温度灵敏度,结果表明440 K处的灵敏度最大为0.0023 K^-1。Er³⁺离子替代BTW-BIT-xEr³⁺伪钙钛矿层的Bi³⁺使氧空位浓度的降低,降低了高温介电损耗,提高了激活能和压电常数。BTW-BIT-0.15Er³⁺陶瓷的综合电学性能最优,分别为d₃₃=14 pC/N、T_c=697℃,tanδ=0.53%、Q_m=2055。这种陶瓷材料具有最优的发光性能和良好的热稳定性。     

CaxSr1-xBi2Nb2O9无铅压电陶瓷制备及其高温稳定性研究

采用传统固相法制备了Ca_xSr_1-xBi₂Nb₂O₉ (x=0、0.10、0.25、0.40)无铅压电陶瓷, 研究了Ca²⁺掺杂量对其微观结构、电学性能及其高温稳定性的影响。掺入Ca²⁺并未改变SrBi₂Nb₂O₉陶瓷的晶体结构; 随着Ca²⁺掺杂量的增加, 陶瓷晶粒由片状向长条状转变; 陶瓷的矫顽场(E_c)下降, 剩余极化强度(P_r)先增大后减小; 陶瓷的居里温度由450℃升高到672℃。当x=0.10时, 陶瓷具有较好的综合性能: 2P_r=14.8 μC/cm², d₃₃=22 pC/N, T_c=488℃; 当退火温度达到400℃时, 压电常数d₃₃仍达到20 pC/N, 说明该材料具有较好的温度稳定性, 可以在400℃的高温环境中应用。