Effect of CuO and MnO2 on sintering temperature, microstructure, and piezoelectric properties of 0.95(K0.5Na0.5)NbO3-0.05BaTiO3 ceramics

In this letter we report the effect of CuO and MnO₂ additives on the sintering behavior of 0.95(Na_0.5K_0.5)NbO₃-0.05BaTiO₃ ceramics. It was found that the composition corresponding to 0.95(Na_0.5K_0.5)NbO₃-0.05BaTiO₃ + 2.0 mol% CuO + 0.5 mol% MnO₂, sintered at 950 °C for 10 h, exhibited excellent piezoelectric properties corresponding to: k_p = 0.41, d₃₃ = 248 pC/N, Q_m = 305, ε₃^T/ε₀ = 1258, and T_c = 280 °C. These results indicate the prominence of this composition in lead-free systems.     

Synthesis and characterization of a new organic dihydrogenomonophosphate [3,5-(CH3O)2C6H3NH3]2(H2PO4)2

Chemical preparation, crystal structure, calorimetric studies and spectroscopic investigation are given for a new organic cation dihydrogenomonophosphate [3,5-(CH₃O)₂C₆H₃NH₃]₂(H₂PO₄)₂. This compound is triclinic with the following unit cell parameters: a=9.030(6) Å, b=16.124(5) Å, c=8.868(3) Å, α=75.04(3)°, β=110.71(4)°, γ=104.61(1)°, Z=4, V=1148.0(1) Å³, Z=2 and ρ_cal.=1.454 g cm⁻³. Crystal structure was solved and refined to R=0.04, 2752 independent reflections. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions parallel to planes, between which are located the organic groups. Solid-state and MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of the phosphorous and carbon signals to the independent crystallographic sites and to the various atoms of the organic groups.     

Sintering, microstructure and piezoelectric properties of CuO and SnO2 co-modified sodium potassium niobate ceramics

The CuO and SnO₂ co-modified Na_0.52K_0.48NbO₃ ceramics were prepared by a conventional mixed oxide method. Densification can be further improved but the grain growth is inhibited as a small amount of SnO₂ is added into 1% CuO doped Na_0.52K_0.48NbO₃. The results indicate that the physical and various electrical properties of CuO and SnO₂ doped Na_0.52K_0.48NbO₃ ceramics significantly depend on sintering conditions and the content of dopants. The ceramics doped with 1 mol% CuO and 1 mol% SnO₂ sintered at 1070 °C for 3 h show improved dielectric and piezoelectric properties: d₃₃ = 120 pC/N, k_p = 0.38, Q_m = 1040, ?_r = 710 and tanδ = 0.013 (1 kHz), in comparison with un-doped or CuO doped compositions.     

Processing, dielectric properties and impedance characteristics of Na0.5Bi0.5Cu3Ti4O12 ceramics

Na_0.5Bi_0.5Cu₃Ti₄O₁₂ (NBCTO) ceramics were prepared by conventional solid-state reaction method. The phase structure, microstructure and dielectric properties of NBCTO ceramics sintered at various temperatures with different soaking time were investigated. Pure NBCTO phase could be obtained with increasing the temperature and prolonging the soaking time. High dielectric permittivity (13,495) and low dielectric loss (0.031) could be obtained when the ceramics were sintered at 1000 °C for 7.5 h. The ceramics sintered at 1000 °C for 7.5 h also showed good temperature stability (−4.00 to −0.69%) over a large temperature range from −50 to 150 °C. Complex impedances results revealed that the grain was semiconducting and the grain boundaries was insulating. The grain resistance (R_g) was 12.10 Ω cm and the grain boundary resistance (R_gb) was 2.009 × 10⁵ Ω cm when the ceramics were sintered at 1000 °C for 7.5 h.     

Influence of sintering temperature on piezoelectric properties of (K0.5Na0.5)NbO3-LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ have been synthesized by traditional ceramics process without cold-isostatic pressing. The effect of the content of LiNbO₃ and the sintering temperature on the phase structure, the microstructure and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics were investigated. The result shows that the phase structure transforms from the orthorhombic phase to tetragonal phase with the increase of the content of LiNbO₃, and the orthorhombic and tetragonal phase co-exist in (K_0.5Na_0.5)NbO₃-LiNbO₃ ceramics when the content of LiNbO₃ is about 0.06 mol. The sintering temperature of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ decreases with the increase of the content of LiNbO₃. The optimum composition for (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics is 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃. The optimum sintering temperature of 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics is 1080 °C. Piezoelectric properties of 0.94 (K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics under the optimum sintering temperature are piezoelectric constant d₃₃ of 215 pC/N, planar electromechanical coupling factor k_p of 0.41, thickness electromechanical coupling factor k_t of 0.48, the mechanical quality factor Q_m of 80, the dielectric constant of 530 and the Curie temperature T_c = 450 °C, respectively. The results indicate that 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ piezoelectric ceramics is a promising candidate for lead-free piezoelectric ceramics.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Structure and electrical properties of (1 − x)Bi0.5Na0.5TiO3-xBi0.5K0.5TiO3 ceramics near morphotropic phase boundary

The binary lead-free piezoelectric ceramics with the composition of (1 − x)Bi_0.5Na_0.5TiO₃-xBi_0.5K_0.5TiO₃ were synthesized by conventional mixed-oxide method. The phase structure transformed from rhombohedral to tetragonal phase in the range of 0.16 ≤ x ≤ 0.20. The grain sizes varied with increasing the Bi_0.5K_0.5TiO₃ content. Electrical properties of ceramics are significantly influenced by the Bi_0.5K_0.5TiO₃ content. Two phase transitions at T_t (the temperature at which the phase transition from rhombohedral to tetragonal occurs) and T_c (the Curie temperature) were observed in all the ceramics. Adding Bi_0.5K_0.5TiO₃ content caused the variations of T_t and T_c. A diffuse character was proved by the linear fitting of the modified Curie-Weiss law. Besides, the ceramics with homogeneous microstructure and excellent electrical properties were obtained at x = 0.18 and sintered at 1170 °C. The piezoelectric constant d₃₃, the electromechanical coupling factor K_p and the dielectric constant ?_r reached 144 pC/N, 0.29 and 893, respectively. The dissipation factor tan δ was 0.037.     

Influence of Bi2O3 and CuO addition on low-temperature sintering and dielectric properties of Ba0.6Sr0.4TiO3 ceramics

In this study, we tried to lower the sintering temperature of Ba_0.6Sr_0.4TiO₃ (BST) ceramics by several kinds of adding methods of Bi₂O₃, CuO and CuBi₂O₄ additives. The effects of different adding methods on the microstructures and the dielectric properties of BST ceramics have been studied. In the all additive systems, the single addition of CuBi₂O₄ was the most effective way for lowering the sintering temperature of BST. When CuBi₂O₄ of 0.6 mol% was mixed with starting BST powders and sintered at 1100 °C, the derived ceramics demonstrated dense microstructure with a low dielectric constant (? = 4240), low dielectric loss (tan δ = 0.0058), high tunability (Tun = 38.3%) and high Q value (Q = 251). It was noteworthy that the sintering temperature was significantly lowered by 350 °C compared with no-additive system, and the derived ceramics maintained the excellent microwave dielectric properties corresponding to pure BST.     

SmAlO3-modified (K0.5Na0.5)0.95Li0.05Sb0.05Nb0.95O3 lead-free ceramics with a wide sintering temperature range

Lead-free ceramics (1 − x)(K_0.5Na_0.5)_0.95Li_0.05Sb_0.05Nb_0.95O₃-xSmAlO₃ (KNLNS-xSA) were prepared by conventional sintering technique. The phase structure, dielectric and piezoelectric properties of the ceramics were investigated. All compositions show a main perovskite structure, exhibiting room-temperature symmetries of tetragonal at x ≤ 0.0075, of pseudo-cubic at x = 0.0100. The Curie temperature of KNLNS-xSA ceramics decreases with increasing SmAlO₃ content. Moreover, the addition of SmAlO₃ can effectively broaden the sintering temperature range of the ceramics. The KNLNS-xSA ceramic with x = 0.0050 has an excellent electrical behavior of piezoelectric coefficient d₃₃ = 226 pC/N, planar mode electromechanical coupling coefficient k_p = 38%, dielectric loss tan δ = 3.0%, mechanical quality factor Q_m = 60, and Curie temperature T_C = 327 °C, suggesting that this material could be a promising lead-free piezoelectric candidate for piezoelectric applications.     

Ferroelectric properties of lithia-doped (Bi0.95Na0.75K0.20)0.5Ba0.05TiO3 ceramics

Lead-free piezoelectric (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics have been prepared by conventional process for different lithium substitutions. The SEM images show that the ceramics are well sintered at 1428 K. Dielectric and ferroelectric measurements have been performed. With the increasing of lithium substitution, the Curie temperature of the (Bi_0.95Na_0.75K_0.20−xLi_x)_0.5Ba_0.05TiO₃ ceramics shifts from 570 K to 620 K, but the maximum value of the dielectric constant decreases from 6700 to 4700 correspondingly. A relatively larger remanent polarization of 36.8 μC/cm² has been found in the x = 0.05 sample. The coercive field decreases as the lithium substitution amount increases. An optimized d₃₃ = 194 × 10^− 12 C/N and a relative dielectric constant ε_r = 1510 have been obtained in (Bi_0.95Na_0.75K_0.15Li_0.05)_0.5Ba_0.05TiO₃.     

Influences of poling condition and sintering temperature on piezoelectric properties of (Na0.5Bi0.5)1 − xBaxTiO3 ceramics

The structure, ferroelectric characteristics and piezoelectric properties of (Na_0.5Bi_0.5)_1 − xBa_xTiO₃ (x = 0.04, 0.06, 0.10) ceramics prepared by conventional solid state method were investigated. The influences of poling condition and sintering temperature on the piezoelectric properties of the ceramics were examined. The piezoelectric properties of the ceramics highly depend on poling field and temperature, while no remarkable effect of poling time on the piezoelectric properties was found in the range of 5-25 min. Compared with (Na_0.5Bi_0.5)_0.96Ba_0.04TiO₃ and (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃, the piezoelectric properties of (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ are more sensitive to poling temperature due to the relatively low depolarization temperature. Moderate increase of sintering temperature improved the poling process and piezoelectric properties due to the development of microstructural densification and crystal structure. With respect to sintering behavior and piezoelectric properties, a sintering temperature range of 1130-1160 °C was ascertained for (Na_0.5Bi_0.5)_0.90Ba_0.10TiO₃.     

Preparation and crystal structure of a new bismuth vanadate, Bi3.33(VO4)2O2

Single crystals of a new bismuth vanadate, Bi_3.33(VO₄)₂O₂ was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO₃·nH₂O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group (#2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) Å, α = 106.090(7), β = 94.468(7) and γ = 112.506(8)°, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO₄ tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 Å. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO₄.     

Dielectric properties of (1−x)(Mg0.95Co0.05)TiO3-xCaTiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of the (1−x)MgTiO₃-xCaTiO₃ ceramic system were investigated. With partial replacement of Mg by Co, dielectric properties of the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramics can be promoted. The microwave dielectric properties are strongly correlated with the sintering temperature. At 1275°C, the 0.95(Mg_0.95Co_0.05)TiO₃-0.05CaTiO₃ ceramics possesses excellent microwave dielectric properties: a dielectric constant ε_r of 20.3, a Q×f value of 107 000 ( at 7 GHz) and a τ_f value of −22.8 ppm/°C. By appropriately adjusting the x value in the (1−x)(Mg_0.95Co_0.05)TiO₃-xCaTiO₃ ceramic system, zero τ_f value can be achieved. With x=0.07, a dielectric constant ε_γ of 21.6, a Q×f value of 92 000 (at 7 GHz) and a τ_f value of −1.8 ppm/°C was obtained for 0.93(Mg_0.95Co_0.05)TiO₃-0.07CaTiO₃ ceramics sintered at 1275°C for 4 h.     

Effects of CuO doping on the electrical properties of 0.98K0.5Na0.5NbO3-0.02BiScO3 lead-free piezoelectric ceramics

CuO-doped 0.98K_0.5Na_0.5NbO₃-0.02BiScO₃ (0.98KNN-0.02BS-xCu) lead-free piezoelectric ceramics have been fabricated by ordinary sintering technique. The effects of CuO doping on the dielectric, piezoelectric, and ferroelectric properties of the ceramics were mainly investigated. X-ray diffraction reveals that the samples at doping levels of x ≤ 0.01 possess a pure tetragonal perovskite structure. The specimen doped with 1 mol% CuO exhibits enhanced electrical properties (d₃₃ ~ 207 pC/N, k_p ~ 0.421, and k_t = 0.424) and relatively high mechanical quality factor (Q_m = 288). These results indicate that the 0.98KNN-0.02BS-0.01Cu ceramic is a promising candidate for lead-free piezoelectric ceramics for applications such as piezoelectric actuators, harmonic oscillator and so on.     

Piezoelectric and dielectric properties of K0.5Na0.5NbO3-LiSbO3-BiScO3 lead-free piezoceramics

(1 − x) (0.95K_0.5Na_0.5NbO₃-0.05LiSbO₃)-xBiScO₃ lead-free piezoceramics have been fabricated by an ordinary pressure-less sintering process. The relationship between the BS content, phase structure, density, and piezoelectric properties and their temperature stability was discussed particularly. All compositions show a main perovskite structure, showing room-temperature symmetries of orthorhombic at x = 0, of tetragonal at 0.002 ≤ x ≤ 0.01. When 0.002 ≤ x ≤ 0.008, the ceramics have excellent electrical properties of d₃₃ = 265-305 pC/N, k_p = 45-54%, ?_r = 1346-1638, Curie temperature T_c = 315-370 °C and depolarizing temperature T_d = 315-365 °C, comparable to that of other KNN-based piezoceramics. The results indicate that the ceramics are promising lead-free piezoelectric materials.     

High piezoelectric d33 coefficient of lead-free (Ba0.93Ca0.07)(Ti0.95Zr0.05)O3 ceramics sintered at optimal temperature

Lead-free (Ba_0.93Ca_0.07)(Ti_0.95Zr_0.05)O₃ (BCZT) ceramics were prepared using a solid-state reaction technique. The structure and electrical properties were investigated with a special emphasis on the influence of sintering temperature. Crystalline structures and microstructures were analyzed by X-ray diffraction and scanning electron microscope (SEM) at room temperature. The BCZT ceramics sintered at 1450 °C show the highest densification and exhibit excellent piezoelectric properties of high piezoelectric coefficient d₃₃ = 387 pC/N, planar mode electromechanical coupling coefficient k_p = 44.2%, mechanical quality factor Q_m = 140 and Curie temperature T_c = 108 °C.     

Chemical preparation, crystal structure and characterization of the new sodium ytterbium cyclotriphosphate Na3Yb(P3O9)2·9H2O

Chemical preparation and crystal structure are reported for a new lanthanide cyclotriphosphate Na₃Yb(P₃O₉)₂·9H₂O. This salt crystallizes in the trigonal system, space group with the following parameters: a = 30.933(2), c = 12.8282(5) Å. The crystal structure was refined to R₁ = 0.0432 using 1782 reflections with I > 2 σ(I). In the Na₃Yb(P₃O₉)₂·9H₂O structure, the phosphoric ring anions, located around the axis are interconnected by YbO₈ dodecahedra and NaO₆ and NaO₇ polyhedra to build, around the threefold axis, large channels parallel to the c axis. All the nine water molecules in the present arrangement participate in the coordination spheres of the associated cations. The thermogravimetric analysis shows that the removal of these water molecules occurs in three stages between 305 and 736 K.The vibrational study by IR absorption spectroscopy of Na₃Yb(P₃O₉)₂·9H₂O is also reported.     

Structural characterization and AC conductivity of bis tetrapropylammonium hexachlorado-dicadmate, [N(C3H7)4]2Cd2Cl6

Synthesis, crystal structure, vibrational study, ¹³C, ¹¹¹Cd CP-MAS-NMR analysis and electrical properties of the compound [N(C₃H₇)₄]₂Cd₂Cl₆, are reported. The latter crystallizes in the triclinic system (space group , Z = 2) with the following unit cell dimensions: a = 9.530(1) Å, b = 11.744(1) Å, c = 17.433(1) Å, α = 79.31(1)°, β = 84.00(1)° and γ = 80.32(1)°. Besides, its structure was solved using 6445 independent reflections down to R = 0.037. The atomic arrangement can be described by alternating organic and inorganic layers parallel to the plan, made up of tetrapropylammonium groups and Cd₂Cl₆ dimers, respectively. In crystal structure, the inorganic layer, built up by Cd₂Cl₆ dimers, is connected to the organic ones through van der Waals interaction in order to build cation-anion-cation cohesion. Impedance spectroscopy study, reported in the sample, reveals that the conduction in the material is due to a hopping process. The temperature and frequency dependence of dielectric constants of the single crystal sample has been investigated to determine some related parameters to the dielectric relaxation.     

Dielectric and piezoelectric properties of Y2O3 doped (Bi0.5Na0.5)0.94Ba0.06TiO3 lead-free piezoelectric ceramics

Y₂O₃ doped lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (0-0.7 wt%) were synthesized by the conventional solid state reaction method, and the effect of Y₂O₃ addition on the structure and electrical properties was investigated. X-ray diffraction shows that Y₂O₃ diffuses into the lattice of (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ to form a solid solution with a pure perovskite structure. The temperature dependence of dielectric constant of Y₂O₃ doped samples under various frequencies indicates obvious relaxor characteristics different from typical relaxor ferroelectric and the mechanism of the relaxor behavior was discussed. The optimum piezoelectric properties of piezoelectric constant d₃₃ = 137 pC/N and the electromechanical coupling factor k_p = 0.30 are obtained at 0.5% and 0.1% Y₂O₃ addition, respectively.     

Effects of BiAlO3 on structure and electrical properties of K0.5Na0.5NbO3-LiSbO3 lead-free piezoceramics

(1−x)(0.948 K_0.5Na_0.5NbO₃-0.052LiSbO₃)-xBiAlO₃ (KNNLS-xBA) lead-free piezoceramics were synthesized by conventional solid state reaction method. The compositional dependence of phase structure and electrical properties of the ceramics was systemically studied. XRD patterns revealed that all the ceramic samples possessed pure perovskite structure. In addition, polymorphic phase transition (PPT) for the ceramics with BA doping could not be observed in the measuring range from room temperature to 500 °C. Within the studied range of BA addition, the ceramics with x = 0.002 represented a relatively desirable balance between the degradation of the piezoelectric properties, improvement in temperature stability and mechanical quality factor. It was found that the KNNLS-0.002BA ceramics exhibited optimum overall properties (d₃₃ = 233 pC/N, k_p = 35%, tanδ = 0.047, P_r = 27.3 μC/cm², Q_m = 56 and T_c = 349 °C), suggesting that this material should be a promising lead-free piezoelectric candidate for piezoelectric applications.