Dielectric,ferroelectric and field-induced strain response of lead-free BaZrO3-modified Bi0.5Na0.5TiO3 ceramics

Lead-free piezoelectric ceramics (1 − x)Bi_0.5Na_0.5TiO₃–xBaZrO₃ (BNT–BZ100x, with x = 0–0.10) were prepared using a conventional solid-state reaction method. The crystal structure, microstructure, dielectric, ferroelectric, and piezoelectric properties of BNT–BZ100x ceramics were studied as functions of different BZ content. X-ray diffraction patterns revealed that the BZ completely diffused in the BNT lattice in the studied composition range. An appropriate amount of BZ addition improved the dielectric, ferroelectric, and piezoelectric properties of BNT ceramics. The remanent polarization (P_r) and piezoelectric constant (d₃₃) increased from 22 μC/cm² and 60 pC/N for pure BNT to 30 μC/cm² and 112 pC/N for x = 0.040, respectively. In addition, electric field-induced strain was enhanced to its maximum value (S_max = 0.40%) with normalized strain (d*₃₃ = S_max/E_max = 500 pm/V) at an applied electric field of 8 kV/mm for x = 0.055. The enhanced strain can be attributed to the coexistence of ferroelectric and relaxor ferroelectric phases.     

Na0.25K0.25Bi0.5TiO3无铅压电陶瓷的介电特性研究

用固相反应法制备了Na0.25K0.25Bi0.5TiO3(NKBT50)陶瓷,研究了该陶瓷在室温至400℃温度范围内的介电性能.发现该陶瓷的介电温谱与烧结气氛、极化状态有关.在空气中烧结的未极化样品在70℃附近存在介电和损耗峰,而极化后及在氧气氛中烧结的样品并不存在该介电、损耗峰.分析认为70℃的介电和损耗峰与氧空位形成的缺陷偶极子的极化弛豫有关.热激电流显示,陶瓷的去极化温度为225℃,与此相对应的介电、损耗峰也与氧空位有关.     

溶胶-凝胶法制备的高压电常数（Bi0.5Na0.5）1－xBaxTiO3系无铅压电陶瓷

测量了使用溶胶-凝胶工艺制备的(Bi0.5Na0.5)1-xBaxTiO3(x=0.00，0.04，0.06，0.08,0.12)系陶瓷的介电、压电、铁电和热释电性能.由于使用了溶胶-凝胶工艺制备的粉料，因此所有样品的压电性能都得到了较大提高.其中(Bi0.5Na0.5)0.94Ba0.06TiO.3系陶瓷具有该系列最大的压电常数，d33=173×10-12C/N，与传统工艺相比，d33提高了近40%.同时，在一定范围内，随Ba含量的增加，材料的剩余极化Pr和矫顽场Ec逐渐减小，退极化温度逐渐降低.对于(Bi0.5Na0.5)0.94Ba0.06TiO.3系陶瓷，剩余极化和矫顽场分别为25μC/cm2和28kV/cm，退极化温度约为80℃. 关键词： 溶胶-凝胶 压电常数 剩余极化 矫顽场     

Enhanced piezoelectric properties near the morphotropic phase boundary in lead-free (1-x)(Bi0.5K0.5)TiO3-xBi(Ni0.5Ti0.5)O3 ceramics

Lead-free piezoelectric ceramics of the composition (1-x)(Bi_0.5K_0.50)TiO₃-xBi(Ni_0.50Ti_0.50)O₃ or (1-x)BKT-xBNiT (when x = 0–0.20 mol fraction) were prepared by a conventional mixed-oxide method and sintered at 1050 °C for 4 h. The effects of BNiT content on the phase equilibria, and the dielectric, ferroelectric and piezoelectric properties were systematically investigated. High density sintered specimens (5.71–6.12 g/cm³) were obtained for all compositions. X-ray diffraction patterns showed that all BKT-BNiT samples exhibited a single perovskite phase which confirms that BNiT and BKT formed a solid solution up to x = 0.20. A morphotropic phase boundary (MPB) separating a BKT-rich tetragonal phase and a BNiT pseudo-cubic phase was identified over the compositional range 0.05 < x < 0.10, where enhanced electrical properties were observed. The optimum dielectric properties (ε_r = 1710, tanδ = 0.036), ferroelectric properties (P_r = 16.6 μC/cm², E_c = 22.5 kV/cm and R_sq = 0.86) and piezoelectric properties (d₃₃ = 288 pC/N, S_max = 0.22% and d^*₃₃ = 313 pm/V) were observed with a relatively high T_m ∼ 304 °C within this MPB region. Overall, these results indicate that the BKT-BNiT ceramic system is a promising lead-free piezoelectric candidate for further development for actuator applications.     

钛酸铋钠系铁电体的相变研究

研究了(Na0.5Bi0.5)TiO3,(Na0.5Bi0.5)(1-x)BaxTiO3和(Na0.5Bi0.5)(1-x)SrxTiO3陶瓷的介电温谱,确认了该系列材料在520℃以下的高、低温两种介电反常和存在于这一温度区间的巨大热滞现象.发现该类材料只存在对应于低温介电反常的介电损耗峰,而对于高温介电峰则无对应的损耗峰.同时,常温时材料的结构特征对于其介电温谱的特征影响较小,但施加偏置场却可明显改变材料的介电温谱特征:1)可使得材料的热滞现象几乎消失;2)适当偏置场下材料升降温介电曲线可与零偏场下介电 关键词： 钛酸铋钠 热滞 相变 极性微区     

(Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free ceramics with simultaneous addition of CeO2 and La2O3

(Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (BNBT-6) with simultaneous addition of 0.5 mol% CeO₂ and 0.25, 0.5 and 0.75 mol% La₂O₃, respectively, was prepared by a conventional ceramic fabrication technique. An addition of 0.5 mol% CeO₂ together with 0.5 mol% La₂O₃ enhanced the piezoelectric and dielectric constant of BNBT-6 ceramics significantly. At room temperature, this composition exhibits a high piezoelectric constant (d₃₃=162×10^-12 C/N) and relatively low dielectric loss (cos=2.0%) at 1 kHz. X-ray diffraction pattern shows that the coexistence of tetragonal and rhombohedral phases in the BNBT-6 composition was not changed by adding CeO₂+La₂O₃, and they diffused into the BNBT lattice during sintering. SEM observation indicates that a small amount of CeO₂+La₂O₃ almost does not affect the microstructure. PACS 77.65.Bn; 77.84.Dy; 77.22.-d     

铌酸钾钠基无铅压电陶瓷的X射线衍射与相变分析

分析了斜方相、四方相铌酸钾钠基无铅压电陶瓷材料的结构和X射线衍射图谱的特点. 对于铌酸钾钠基压电材料斜方相结构, 从构成晶胞的一个单斜原胞进行分析, 计算出X射线衍射谱上每个衍射角附近的衍射峰数目和相对强度. 提出了2θ在20°—60°范围内根据(1 0 2)衍射峰(52°附近)和(1 2 1)衍射峰(57°附近)劈裂的数目区分斜方和四方相的新方法. 对于多晶陶瓷粉末, 可以更简便的由22°(或45°)附近前后峰的相对高低来判断斜方、四方相. 关键词： 铌酸钾钠 无铅压电陶瓷 X射线衍射 相变     

Transverse piezoelectric properties of Mn-doped Bi0.5Na0.5TiO3 thin films

Lead-free (Bi_0.5Na_0.5)(Ti_1-xMn_x)O₃ (BNTMn-x; x = 0, 0.0025, 0.0050, 0.0100) thin films were fabricated using a chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrate. The effect of Mn substitution on crystal structures, surface morphologies, and ferroelectric and transverse piezoelectric properties of BNTMn-x thin films was investigated. The 0.5 mol% Mn-doped (Bi_0.5Na_0.5)(Ti_0.995Mn_0.005)O₃ thin film exhibited a well-saturated ferroelectric P-E hysteresis loop at room temperature. A remnant polarization (P_r) of 16 μC/cm² was obtained for the BNTMn-0.0050 film at an applied electric field of 400 kV/cm. In addition, a 1.12-μm-thick BNTMn-0.0050 film was applied as a cantilever. The Pt/BNTMn-0.0050/Pt/TiO₂/SiO₂/Si unimorph cantilever exhibited a high transverse piezoelectric coefficient ($e_{31}^1$) of 2.43 C/m².     

The effect of CuO and NiO doping on dielectric and ferroelectric properties of Na0.5Bi0.5TiO3 lead-free ceramics

In the present work, lead-free piezoelectric ceramics (Na_0.5Bi_0.5)TiO₃ –xCuO–yNiO (for x = 0.0, 0.02, 0.04 and 0.06) have been prepared by a conventional solid-state reaction method. An investigation of CuO and NiO doping in bismuth sodium titanate (BNT) and a study of the structure, morphology, and dielectric and ferroelectric properties of the NBT–CuNi system have been conducted. Phase and microstructural analysis of the (Na_0.5Bi_0.5)TiO₃ (NBT) based ceramics has been carried out using X-ray diffraction and scanning electron microscopy (SEM) techniques. Field emission scanning electron microscopy (FE-SEM) images showed that inhibition of grain growth takes place with increasing Cu and Ni concentration. The results indicate that the co-doping of NiO and CuO is effective in improving the dielectric and ferroelectric properties of NBT ceramics. Temperature-dependent dielectric studies have also been carried out at room temperature to 400 °C at different frequencies. The NBT ceramics co-doped with x = 0.06 and y = 0.06 exhibited an excellent dielectric constant ?_r = 1514. The study suggests that there is enormous scope of application of such materials in the future for actuators, ultrasonic transducers and high-frequency piezoelectric devices.     

Temperature dependent of thermal expansion and ferroelectric properties for BiAlO3-modified BaTiO3 lead-free ceramics

Perovskite structure (1 − x)BaTiO₃–xBiAlO₃ (BT–xBA, x = 0.05, 0.08 and 0.1, corresponding to BT–5BA, BT–8BA and BT–10BA, respectively) ceramics were prepared by a solid state reaction route. Crystal structure of BT–xBA ceramics was determined by using XRD. Dielectric properties were studied as a function of temperature at different frequencies, which indicated that the phase transition temperature (T_m) decreased with increasing x. With increasing temperature, thermal expansion dl/l increased while thermal expansion coefficient α had weak concentration dependence. The Burns temperature was much higher than the transition temperature T_m for the BT–5BA and BT–10BA ceramics. Polarization hysteresis loops (P–E), electrostrictive (S–E) and S versus P² (S–P²) at different temperatures were displayed. P_max slightly decreased due to thermally activated leakage current, meanwhile, S_max decreased at above T_m with the contribution of ferroelectric domain reorientation decreased. The electrostrictive coefficient Q value was clearly larger than that of lead-based electrostrictors at room temperature. Furthermore, it exhibited a slim loop with negligible hysteresis and a subtle linear feature at higher temperature.     

Bi-fluctuation in Na0.5Bi0.5TiO3 ferroelectric ceramics with abnormal relaxor behaviour

ABSTRACT

The existence of Bi-fluctuation dispersing in Na_0.5Bi_0.5TiO₃ (NBT) relaxor ferroelectric is hinted in other recent studies. However, this fluctuation has not been directly observed yet. We introduce the Bi-rich nano-regions with different sizes in a series of NBT ceramics by the slight excess of Bi³⁺ content. The crystal symmetries of the Bi-rich nano-regions and the NBT matrix are rhombohedral. The lattice parameters of the nano-regions are larger than those of the matrix in NBT ceramics, which were confirmed by the X-ray diffraction Rietveld refinement, TEM techniques and first-principles calculation. Also, the disorder-induced nano-regions appearing as Bi-fluctuation are associated with the complex phase transitions and the high-frequency relaxor behaviour of NBT suggested by the dielectric measurements and Raman spectra.     

Influence of the dc and ac field intensity on electric permittivities of (Na0.5Bi0.5)0.88Ba0.12TiO3 ceramics

The electric permittivity measurements under different ac or dc field amplitudes on lead-free (Na_0.5Bi_0.5)_0.88Ba_0.12TiO₃ ceramics were performed. A significant increase or decrease in permittivities was observed with increasing ac or dc fields intensity, respectively. It was found that temperature T _m decreases or increases with increasing ac or dc fields, respectively. When ac field amplitude increased, stronger frequency relaxation around T _m and greater shift in T _m was observed. This was in opposite to the effect of dc field intensity. The obtained results were discussed in terms of polar region behaviour in external electric fields.     

Synthesis and physical properties of Ca- and Ta-modified (K,Na)NbO3 lead-free piezoelectric ceramics

Polycrystalline samples of lead-free Ca and Ta co-substituted potassium sodium niobate (K_0.5Na_0.5NbO_3, KNN) ceramics have been prepared by solid state reaction technique. X-ray diffraction showed formation of a single-phase perovskite structure with orthorhombic symmetry. Substitution inhibits the grain growth, improves densification and decreases the ferro-paraelectric phase transition temperature. Temperature dependent dielectric permittivity studies demonstrate significant decrease in peak-permittivity values in the substituted samples. Bulk longitudinal piezoelectric coefficient is significantly enhanced, up to ～155 pC/N for (K_0.48Na_0.48Ca_0.02)(Nb_0.85Ta_0.15O₃) as compared to 95 pC/N for pristine KNN ceramic. Local piezoelectric properties have been observed by piezoresponse force microscopy (PFM) technique. Distinct piezocontrast was studied in both vertical and in-plane modes of PFM for all samples. The samples exhibit self-polarization effect in the unpoled state and effective local vertical piezoelectric coefficient was the largest in Ca and Ta co-substituted sample whereas the in-plane piezoelectric coefficient was maximum for Ca-substituted KNN sample. These studies are important for using substituted lead free KNN materials in various piezoelectric applications.     

Lead‐free piezoelectric (Na0.5Bi0.5)0.94TiO3–Ba0.06TiO3 nanofiber by electrospinning

Lead‐free (Na_0.5Bi_0.5)_0.94TiO₃–Ba_0.06TiO₃ (NBT‐BT6) nanofibers were synthesized by the sol–gel process and electrospinning, and a butterfly‐shaped piezoelectric response was measured by scanning force microscopy. NBT‐BT6 nanofibers with perovskite phase were formed, after being cleaned at 700 °C for 1 hour, and the diameters are in the range of 150 nm to 300 nm. The average value of the effective piezoelectric coefficient d₃₃ is 102 pm/V. The high piezoelectricity may be attributed to the easiness for the electric field to tilt the polar vector of the domain and to the increase of the possible spontaneous polarization direction. There is a potential for the application of NBT‐BT6 nanofibers in nanoscale piezoelectric devices. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structural,ferroelectric, optical properties of A-site-modified Bi0.5(Na0.78K0.22)0.5Ti0.97Zr0.03O3 lead-free piezoceramics

We reported the role of A-site modification on the structural, ferroelectric, optical and electrical field-induced strain properties of Bi_0.5(Na_0.78K_0.22)_0.5Ti_0.97Zr_0.03O₃ lead-free piezoceramics. The Li⁺ ions with concentration from 0 to 5 mol% were used to substitute at A-site. There was no phase transition when Li⁺ ions was added up to 5 mol%. The electric field-induced strain (S_max/E_max) values increased from 600 to 643 pm/V for 2 mol% Li⁺-added which results from distortion both rhombohedral and tetragonal phase structures. The band gap reduced from 2.88 to 2.68 eV and the saturation polarization decreased from 46.2 to 26.1 μC/cm² when Li⁺ ions concentration increased from 0 to 5 mol% respectively. We expect that this work could be helpful for further understanding the role of A-site dopants in comparison with B-site modification in lead-free Bi_0.5(Na,K)_0.5TiO₃-based ceramics.     

Influence of sintering conditions on structural,thermal, electric and ferroelectric properties of Na0.5Bi0.5TiO3 ceramics

Na_0.5Bi_0.5TiO₃ ceramics were prepared by a conventional solid-state reaction method and by a hot-pressing route. The influence of sintering conditions on structural, thermal, dielectric and ferroelectric properties of these ceramics was investigated. All obtained samples exhibited a single perovskite phase. It was shown that the sintering conditions significantly influence the properties under investigation. This includes changes in the value of the electric permittivity ? and dielectric loss tanδ, a shift of T_m and T_d and change of the ferroelectric properties. These effects are mainly related to volatility of the Na and Bi components during the sintering process along with formation of their compensating charge defects, which leads to local structure change.     

Relaxor properties of Nb-modified (Ba0.8Sr0.2)TiO3 ceramics

Nb-doped (Ba_0.8Sr_0.2)TiO₃ ceramics were prepared using conventional mixed-oxide processing technique. Permittivity and loss factor were investigated as a function of temperature for various frequencies of the measuring field. The obtained results confirmed the relaxor ferroelectric behaviour of the studied ceramics, i.e. a strong frequency dispersion of the permittivity maximum and a visible shift of its temperature with frequency. Analysis of real part of permittivity allowed us to determine the value of the freezing temperature characterising the relaxor ferroelectrics. The physical processes, responsible for the relaxor behaviour of the studied ceramics are discussed.     

High-temperature impedance spectroscopy of BaFe0.5Nb0.5O3 ceramics doped with Bi0.5Na0.5TiO3

Bi_0.5Na_0.5TiO₃ (BNT)-doped BaFe_0.5Nb_0.5O₃ (BFN) ceramics were synthesized by a two-step solid-state reaction. Temperature dependence of dielectric properties measured at different frequencies was investigated over broad temperature and frequency ranges. Impedance spectroscopy and universal dielectric response were employed to study the relaxation behavior and conductivity mechanism of the ceramics in a frequency range from 40 Hz to 100 MHz and a temperature range from 300 K to 800 K. The complex plane impedance data revealed the bulk and grain boundary contributions toward conductivity processes in the form of semicircular arcs. The high-temperature conductivity of ceramics is attributable to thermally activated second ionized oxygen vacancy.