Piezoelectric K0.5Na0.5NbO3 Ceramics Textured Using Needlelike K0.5Na0.5NbO3 Templates

Improved performance by texturing has become attractive in the field of lead‐free ferroelectrics, but the effect depends heavily on the degree of texture, type of preferred orientation, and whether the material is a rotator or extender ferroelectric. Here, we report on successful texturing of K_0.5Na_0.5NbO₃ (KNN) ceramics by alignment of needlelike KNN templates in a matrix of KNN powder using tape casting. Homotemplated grain growth of the needles was confirmed during sintering, resulting in a high degree of texture parallel to the tape casting direction (TCD) and the aligned needles. The texture significantly improved the piezoelectric response parallel to the tape cast direction, corresponding to the direction of the strongest <001>_pc orientation, while the response normal to the tape cast plane was lower than for a nontextured KNN. In situ X‐ray diffraction during electric field application revealed that non‐180° domain reorientation was enhanced by an order of magnitude in the TCD, compared to the direction normal to the tape cast plane and in the nontextured ceramic. The effect of texture in KNN is discussed with respect to possible rotator ferroelectric properties of KNN.     

Growth of (Na0.5K0.5)NbO3 single crystals by abnormal grain growth method from special shaped nano-powders

Using the composite powders of (Na_0.5K_0.5)NbO₃ (NKN) nano-particles and nano-rods as starting materials, the NKN single crystals were prepared by abnormal grain growth (AGG) method. The morphology evolution and the formation mechanism in the crystal growth process were investigated in detail. The results revealed that the average size and the apparent quantity of abnormal grains increased gradually with the increase of sintering temperature. The biggest NKN single crystals with size of about 3 mm were obtained at 950 °C for 2 h. Though the nano-particles and nano-rods have the same composition, the driving forces are distinctively different due to the diversity of grain morphology. The nano-rods have the large driving forces especially at high sintering temperature, which plays a dominant role in facilitating the formation of NKN single crystals during AGG process.     

Microstructural changes in (K0.5Na0.5)NbO3 ceramics sintered in various atmospheres

(K_0.5Na_0.5)NbO₃ is a potential lead-free piezoelectric ceramic, but often suffers from abnormal grain growth. Previous work on BaTiO₃ and SrTiO₃ has shown that abnormal grain growth can be suppressed by controlling the sintering atmosphere. In the present work, (K_0.5Na_0.5)NbO₃ was sintered in atmospheres ranging from O₂ to H₂ and the effect on grain growth behaviour studied. Sintering in reducing atmospheres causes a delay in the onset and a reduction in the amount of abnormal grain growth. The effect of sintering atmosphere on grain growth behaviour can be explained using the 2D nucleation-controlled theory of grain growth. Changes in the grain shape during sintering in reducing atmospheres indicate a reduction in the edge free energy of (K_0.5Na_0.5)NbO₃ caused by an increase in the concentration of oxygen vacancies. This decreases the critical driving force necessary for rapid grain growth and causes a transition from abnormal to pseudo-normal followed by abnormal grain growth.     

Crystal growth and ferroelectric property of Na0.5K0.5NbO3 and Mn-doped Na0.5K0.5NbO3 crystals grown by floating zone method

Na_0.5K_0.5NbO₃ (NKN) and Mn-doped NKN crystals, which are one of the promising candidates of lead-free piezoelectric materials, were grown by using a floating zone (FZ) method. The resulting crystal growth was compared with crystal growth that resulted from using a flux method in a previous study. In the crystal grown by FZ method under where the growth rate was controlled to 3 mm/h, thin layers formed parallel and perpendicular directions to the growth direction. In the crystal grown by FZ method, the crystal structure could not be classified as having the orthorhombic lattice of Amm2, which was observed in the crystal grown using a flux method. It was found that doped Mn was substituted in the perovskite-type lattice of NKN. Pure NKN crystals showed 90° domains that had a zig-zag shape, whereas Mn-doped NKN crystals were aligned to the domain layers in straight lines. It was confirmed that Mn-doped NKN crystal showed a square P–E hysteresis loop.     

Thermal stability and local atomic structure of (Na0.5K0.5)NbO3 doped BaTiO3 ceramics

Dielectric properties of x(Na_0.5K_0.5)NbO₃–(1−x)BaTiO₃ (x=0.00 and 0.06) specimens were investigated in terms of changes in local atomic structure, according to the phase transition by elevating the overall temperature. A 0.06(Na_0.5K_0.5)NbO₃–0.94BaTiO₃ (NKN–BT) specimen exhibited enhanced temperature stability along with an increased dielectric constant. The degree of reduction in tetragonality (c/a) at the Curie temperature was smaller in NKN–BT compared to that in pure BaTiO₃, as calculated by Rietveld refinement. From a comparison of the pre-edge region in the Ti K-edge, it was determined that the off-center displacement of the Ti atom was also raised to 13.4% through NKN substitution, with a change in local orientation from the [001] to the [111] directions. The substitution by NKN, which has a different ionic radius and electrical charge compared with BaTiO₃, causes structural distortion of the TiO₆ octahedra in the NKN–BT lattice, resulting in local polarization. These structural changes lead to the temperature stability of the dielectric constant and an overall improvement in the electrical properties of BaTiO₃.     

Dielectric,ferroelectric and field-induced strain behavior of K0.5Na0.5NbO3-modified Bi0.5(Na0.78K0.22)0.5TiO3 lead-free ceramics

Lead-free piezoelectric (1 ? x)Bi_0.5(Na_0.78K_0.22)_0.5TiO₃–xK_0.5Na_0.5NbO₃ (BNKT–xKNN, x = 0–0.10) ceramics were synthesized using a conventional, solid-state reaction method. The effect of KNN addition on BNKT ceramics was investigated through X-ray diffraction (XRD), dielectric, ferroelectric and electric field-induced strain characterizations. XRD revealed a pure perovskite phase with tetragonal symmetry in the studied composition range. As the KNN content increased, the depolarization temperature (T_d) as well as maximum dielectric constant (?_m) decreased. The addition of KNN destabilized the ferroelectric order of BNKT ceramics exhibiting a pinched-type hysteresis loop with low remnant polarization (11 μC/cm²) and small piezoelectric constant (27 pC/N) at 3 mol% KNN. As a result, at x = 0.03 a significant enhancement of 0.22% was observed in the electric field-induced strain, which corresponds to a normalized strain (S_max/E_max) of ～434 pm/V. This enhancement is attributed to the coexistence of ferroelectric and non-polar phases at room temperature.     

Screening Sintering Aids for (K0.5Na0.5)NbO3 Ceramics

Searching for suitable sintering aids for ceramic materials is important and tedious work. In this study, we introduce a simple and effective method, named liquid phase screening method (LPSM), for rapidly screening sintering aids for KNN ceramics. By measuring the structure and properties, we demonstrated that the suitable sintering aids for KNN can be quickly determined by LPSM. The new sintering aids found by this method, GeO₂ and borax which have not been reported before, lead to improved properties.     

Low-Temperature Sintering of (K0.5Na0.5)NbO3 Piezoelectric Ceramics

(K_0.5Na_0.5)NbO₃ piezoelectric ceramics can be sintered at a temperature as low as 750 °C for 5 h by incorporating Li₂CO₃ + Bi₂O₃ + ZnO as the sintering aid, whereas the conventional sintering temperature is around 1,100 °C. The optimal “soft” piezoelectric properties are obtained for ceramics sintered at 850 °C for 5 h. The dielectric permittivity (ε), piezoelectric coefficient (d ₃₃), electromechanical coupling (k _p) and mechanical quality factors (Q _m) of (K, Na)NbO₃ modified with 5.5 wt% sintering aids are 1,436, 90 pC/N, 0.3 and 10, respectively. These values are similar to the values obtained for (K_0.5Na_0.5)NbO₃ ceramics sintered above 1,100 °C. The underlying mechanism for abrupt change of dielectric permittivity is explained.     

聚合物前驱体法低温制备铌酸钾钠超细粉体

以柠檬酸为配位剂与金属离子配合,水作为溶剂,乙二醇为酯化剂,通过聚合物前驱体法制备(K0.5Na0.5)NbO3粉体.研究了柠檬酸(CA)和乙二醇(EG)的用量和pH值对溶胶性能的影响.采用XRD和TG-DSC研究了(K0.5Na0.5)NbO3晶相的形成过程,用SEM对所制得粉体的表面形貌进行了分析.结果表明:当前驱体溶胶的pH值为7.5,n(CA):n(metalion)=3:1,n(CA):n(EC)=1:2时,可以获得稳定性好的溶胶.凝胶前驱体在加热过程中先反应生成NaNbO3和K2Nb8O21,然后二者固相反应形成K0.5Na0.5NbO3.大部分晶粒呈方形的粒状,少数颗粒呈长柱状.讨论了晶粒形貌的形成原因.     

Grain size control of lead-free Li0.06(Na0.5K0.5)0.94NbO3 piezoelectric ceramics by Ba and Ti doping

In this study, Ba- and Ti-doped Li_0.06(Na_0.5K_0.5)_0.94NbO₃ [(1 ? x)Li_0.06(Na_0.5K_0.5)_0.94NbO₃–xBaTiO₃ (x = 0–0.07)] ceramics were prepared by using conventional solid state reaction method, and the microstructure and electric properties of these samples were investigated. The grain size distribution of non-doped Li_0.06(Na_0.5K_0.5)_0.94NbO₃ ceramics was relatively wide. The microstructure was composed of grains ranging 1.1–5.0 μm in size. However, with increasing Ba and Ti content, the grain size distribution became narrow and the average grain size decreased from 2.0 to 0.9 μm in size. In particular, the microstructure of x = 0.07 sample was composed of grains ranging 0.5–2.2 μm in size. As a result, the frequency dispersion of dielectric constant for the (1 ? x)Li_0.06(Na_0.5K_0.5)_0.94NbO₃–xBaTiO₃ (x = 0–0.07) ceramics was reduced and the mechanical quality factor Q_m was enhanced with increasing Ba and Ti content.     

铜掺杂对(Na0.5K0.5)NbO3无铅压电陶瓷性能的影响

采用传统固相反应法对(Na0.5K0.5)NbO3压电陶瓷进行铜掺杂改性研究。使用SEM、XRD并结合常规压电陶瓷性能测试手段对该体系的显微结构、压电性能等进行表征。研究结果表明:CuO的掺入使材料出现“硬化”现象,即材料的压电系数d33、平面机电耦合系数Kp和介电损耗tanδ下降了,机械品质因子Qm大大提高;CuO掺入量在1%mol时各项性能最佳。另外,从SEM图片中可以看出:(Na0.5K0.5)NbO3压电陶瓷材料的平均晶粒尺寸随着CuO掺入量的增加明显变大。这表明CuO有烧结助熔作用,能降低烧成温度。     

(1-x)KNN-xNKBT无铅压电陶瓷的结构及其电性能研究

采用传统固相法制备了(1-x)K0.5Na0.5NbO3-x(Na0.8K0.2)0.5Bi0.5TiO3(x=0-5%)无铅压电陶瓷,研究了(Na0.8K0.2)0.5Bi0.5TiO3的不同引入量对其物相结构、显微形貌、介电性能以及压电性能的影响。结果表明:所有样品都具有钙钛矿结构;随着x的增加,室温下样品从正交相逐渐向四方相过渡并且居里温度向低温方向移动,样品的压电常数d33与机电耦合系数kp均先升高后降低。该体系多晶型转变PPT位于2%≤x≤3%,当x=3%时,样品的压电性能达到最佳,其中:d33=189pC/N,kp=41%,Qm=96,tanδ=0.028。     

Donor doping of K0.5Na0.5NbO3 ceramics with strontium and its implications to grain size,phase composition and crystal structure

In this study, the particular effects of A-site donor doping, such as crystal-structure change, the secondary-phase formation and the grain-size decrease, in a lead-free piezoceramic material K_0.5Na_0.5NbO₃ (KNN) doped with Sr²⁺, were investigated. Extended X-ray absorption fine structure (EXAFS) analyses proved that Sr occupies the perovskite A-sublattice, and locally modifies the KNN monoclinic structure to cubic. Introducing Sr into the A-sublattice, as well as accounting for the charge-compensating A-site vacancies in the starting composition, causes increasing lattice disorder and microstrain, as determined from a Rietveld refinement of the synchrotron X-ray diffraction data. Above 2% Sr the system segregates the A-site vacancies in a secondary phase in order to release the chemical pressure, as revealed by Raman spectroscopy. All these effects result in an increasing number of low-angle grain boundaries that limit the grain growth and finally lead to a significant grain-size decrease.     

BiFeO_3掺杂改性铌酸钾钠无铅压电陶瓷

采用传统固相法制备了(1–x)(K0.5Na0.5)NbO3-xBiFeO3[(1–x)KNN-xBF]无铅压电陶瓷,研究了不同BF含量(x=0,0.175%,0.5%,1%,2%,3%,摩尔分数)样品的物相组成、显微结构及电性能。结果表明:当x≤3%时,得到了纯钙钛矿结构的(1–x)KNN-xBF陶瓷。与纯KNN相比,在0x≤1%时,(1–x)KNN-xBF样品的密度(ρ)、压电常数(d33)、平面机电耦合系数(kp)和机械品质因子(Qm)都显著增大;当1%x≤3%时,ρ,d33,kp和Qm又迅速降低;在x=1%时达到最大值。x=1%时,(1-x)KNN–xBF材料的综合性能最好,其中ρ=4.42g/cm3,d33=172pC/N,kp=0.45,介电损耗tanδ=0.021,相对介电常数εr=759和Qm=138;同时表现出较好的抗老化性能。     

Development of texture in Bi0.5Na0.5TiO3 prepared by reactive-templated grain growth process

The effect of sodium concentration on texture development in Bi_0.5Na_0.5TiO₃ [BNT] bulk ceramics was examined. The 〈1 0 0〉-textured specimens were prepared by the reactive-template grain growth process using platelike Bi₄Ti₃O₁₂ particles. Texture did not extensively develop in stoichiometric and Na-deficient BNT, but excess Na promoted extensive texture development together with densification. The role of excess Na was discussed based on the formation of a liquid phase.     

Composition,microstructure and electrical properties of K0.5Na0.5NbO3 ceramics fabricated by cold sintering assisted sintering

In this paper, cold sintering was served as a forming method to assist the conventional sintering, which is so-called cold sintering assisted sintering (CSAS) method. Lead-free K_0.5Na_0.5NbO₃ piezoelectric ceramics were prepared by the CSAS method, and the effects of the different procedures on the sintering behaviors and electrical properties of KNN ceramics were studied. Compared with conventional sintering (CS), cold sintering process can induce potassium-rich phase on the KNN particle surface, and remarkably increase both the green and sintering density of KNN ceramics. Meanwhile, the potassium-rich phase would transform to K₄Nb₆O₁₇ second phase on the grain surface, and subsequently suppress the volatilization of potassium element. The sinterability and electrical properties were greatly improved, and KNN piezoelectric ceramics with high performance can be manufactured in a wide sintering temperature range (1055 °C–1145 °C), which proves that CSAS has the potential to be an excellent sintering technique for producing KNN based ceramics.     

钛酸铋钠钾锂无铅陶瓷的柠檬酸制备技术

以钠、钾、锂的碳酸盐为原料，采用柠檬酸盐-凝胶法制备了Biol5（Na1-x-y，LixKy）0.5TiO3无铅压电陶瓷，研究了影响凝胶合成的各种工艺条件，利用TG-DTA，SEM，XRD，纳米粒度分析等技术分析了凝胶预烧温度及预烧粉体的粒度分布。研究结果表明：柠檬酸与金属离子的物质的量比、溶液浓度、pH是影响前驱液与凝胶形成的主要因素；用柠檬酸盐一凝胶法合成的Bi0.5（Na1-x-y，LixKy）TiO3粉体粒度细小均匀，合成温度低；陶瓷的压电常数d33可达138pC／N，其平面机电耦合系数kp为0．30。     

Fine structural analysis and phase transition behavior for Li-modified Na0.5K0.5NbO3 lead-free piezoelectric ceramics

The fine crystal structure of Li_x(Na_0.5K_0.5)_1?xNbO₃ ceramics has been studied by means of Nb-K edge extended X-ray absorption fine structure (EXAFS) and X-ray internal strain measurement technique in the vicinity of the compositions showing a polymorphic phase boundary (PPB) between orthorhombic and tetragonal structures. The anisotropic distortion of the NbO₆ octahedral initially occurred when x was increased from 0.050 to 0.053, prior to the completion of the phase transition from orthorhombic to tetragonal symmetry. EXAFS clearly revealed that the bond distance of Nb–O1 with [0 0 1] configuration was increased, and that of Nb–O2 with [1 1 0] configuration was oppositely decreased in the NbO₆ octahedral. In the vicinity of the PPB compositions, the internal strain η_(0 1 1) also increased from 4.5 × 10^?3 to the maximum value of 12.0 × 10^?3 in the narrow x range from 0.040 to 0.055, then decreased to 3.2 × 10^?3 at x = 0.06. On the other hand, the η_(1 0 0) increases from 1.5 × 10^?3 to the maximum value of 2.9 × 10^?3 in the next narrow x range from 0.055 to 0.060. The variation of η_(1 0 0) differed in Li dependence from that of η_(0 1 1), which indicates that a large anisotropic strain remains in the crystal lattice in the PPB compositions.     

High‐Performance (Na0.5K0.5)NbO3 Thin Film Piezoelectric Energy Harvester

The pseudocubic structure of a (Na_0.5K_0.5)NbO₃ (NKN) film grown on a Pt/Ti/SiO₂/Si substrate changed to an orthorhombic structure when the film was transferred onto a polyimide substrate. Piezoelectric constant for the transferred NKN film increased considerably from 74 ± 11 to 120 ± 18 pm/V because the crystal structure of the film had changed from pseudocubic to orthorhombic. A gold interdigitated electrode was deposited onto the transferred NKN film to synthesize a NKN piezoelectric energy harvester. The NKN piezoelectric energy harvester was poled before bending under a 100 kV/cm DC electric field across the electrodes. When a strain of 0.85% and a strain rate of 4.05%/s were applied to the NKN piezoelectric energy harvester, it produced a maximum output voltage of 1.9 V and a current of 38 nA, corresponding to a power density of 2.89 μW/cm³.