Phase Structure, Microstructure, and Electrical Properties of Sb-Modified (K, Na, Li) (Nb, Ta) O3 Piezoelectric Ceramics

Lead-free (K_0.44Na_0.52Li_0.04)(Nb_{0.80− x} Ta_0.20Sb _x )O₃ piezoelectric ceramics were prepared by the ordinary sintering method. The much higher Pauling electronegativity of Sb compared with Nb makes the ceramics more covalent. By increasing x from 0.00 to 0.06, the phase structure of the ceramics changed from the tetragonal to the pseudocubic phase, and both the bands in the Raman scattering spectra shifted to lower frequency numbers. The grain growth of the ceramics was improved by substituting Sb⁵⁺ for Nb⁵⁺. By increasing x , the dielectric properties were optimized and the variation of dielectric constants before and after poling became smaller. Only the tetragonal–cubic phase transition was observed above room temperature in all the ɛ_r– T curves. The degree of diffuseness increased from 1.29 at x =0.00 to 1.96 at x =0.06, indicating that the ceramics at x =0.06 changed to an approximate ideal relaxor ferroelectric. The temperature dependences of f _r and k _p became better by increasing x properly. Significantly, the ceramics with x between 0.00 and 0.04 had high density and outstanding electrical properties ( d ₃₃=241–272pC/N, k _p=0.42–0.52, ɛ_r=1258–1591, tan δ=0.015–0.025, T _c=280°–355°C, E _c=10.62–12.60 kV/cm, and P _r=16.19–20.13 μC/cm²). Besides, the underlying mechanism for variations of the electrical properties due to Sb⁵⁺ substitution was explained in this work.     

Effects of La on Dielectric and Piezoelectric Properties of Pb1−xLa2x/3(Nb0.95Ti0.0625)2 O6 Ceramics

Ceramics with the chemical compositions of Pb_{1− x} La_{2 x /3}(Nb_0.95Ti_0.0625)₂O₆ (0≤ x ≤0.060) (PLTN) were prepared by the conventional solid-state reaction method. X-ray diffraction analysis indicated that Ti and La doping not only decreased the rhombohedral–tetragonal phase transformation temperature, but also stabilized the orthorhombic phase of PLTN ceramics. All ceramics sintered at 1190°–1250°C had shown the pure orthorhombic ferroelectric phase. La doping suppresses grain growth and inhibits the formation of pores and cracks, resulting in an increase in relative density up to 97%. The amount of La doping to PLTN ceramics obviously affect ceramics' piezoelectric constant ( d ₃₃) and dielectric loss (tanδ). The sample with x =0.015 possesses high Curie temperature ( T _c=560°C), low dielectric loss (tanδ=0.0054), and excellent piezoelectric constant ( d ₃₃=92 pC/N), presenting a high potential to be used in high-temperature applications as piezoelectric transducers.     

Piezoelectric Properties of (1−x)(Na0.5K0.5)NbO3–xAgSbO3 Lead-Free Ceramics

(1− x )(Na_0.5K_0.5)NbO₃– x AgSbO₃ lead-free piezoelectric ceramics were prepared by normal sintering. The effects of the AgSbO₃ on the phase structure and piezoelectric properties of the ceramics were systematically studied. These results show that the AgSbO₃-modified (K_0.50Na_0.50)NbO₃ lead-free piezoelectric ceramics form stable solution with orthorhombic structure, and the Curie temperature and the polymorphic phase transition of the ceramics decreased with increasing AgSbO₃. The result shows that the piezoelectric properties of the ceramics strongly depend on the AgSbO₃. The ceramics with x =0.05 possess optimum properties ( d ₃₃=192 pC/N, k _p=43%, T _c=348°C, T _o−t =145°C, ɛ_r∼632, and tan δ∼3.5%). These results indicate that the ceramic is a promising candidate material for lead-free piezoelectric ceramics.     

Phase Transformation and Tunable Piezoelectric Properties of Lead-Free (Na0.52K0.48−xLix)(Nb1−x−ySbyTax)O3 System

Lead-free (Na_0.52K_{0.48− x} )(Nb_{1− x − y} Sb _y )O₃- x LiTaO₃ (NKNS–LT) piezoelectric ceramics have been fabricated by ordinary sintering. A special attention was paid to the composition design through which the dielectric and piezoelectric properties of the (Li, Ta, Sb) modified NKN systems were significantly promoted. A property spectrum was generated with a particular discussion on the relationship between the Sb content, the LT content, the polymorphic phase transition, and the electrical properties and their temperature stability. Excellent and tunable electrical properties of d ₃₃=242–400 pC/N, k _p=36%–54%,     , and T _c=230°–430°C demonstrate a tremendous potential of the compositions studied for device applications.     

Phase Structure and Electrical Properties of (K0.48Na0.52)(Nb0.95Ta0.05)O3-LiSbO3 Lead-Free Piezoelectric Ceramics

(1− x )(K_0.48Na_0.52)(Nb_0.95Ta_0.05)O₃– x LiSbO₃ [(1− x )KNNT− x LS] lead-free piezoelectric ceramics were prepared by the conventional solid-state sintering method. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phases was identified in the composition range of 0.03< x <0.05. The ceramics near the MPB exhibit a strong compositional dependence and enhanced electrical properties. The (1− x )KNNT– x LS ( x =0.04) ceramics exhibit good electrical properties ( d ₃₃=250 pC/N, k _p=45.1%, k _t =46.3%, T _c=348°C, T _{o − t} =74°C, P _r=25.9 μC/cm², E _c=10.7 kV/cm, ɛ_r∼1352, tan δ∼3%). These results show that (1− x )KNNT– x LS ceramic is a promising lead-free piezoelectric material.     

Effect of BiScO3 and LiNbO3 on the Piezoelectric Properties of (Na0.5K0.5)NbO3 Ceramics

Lead-free potassium sodium niobate-based piezoelectric ceramics (1− y )(Na_{0.5−0.5 x} K_{0.5−0.5 x} Li _x )NbO₃− y BiScO₃ (  y =0.01, x= 0–0.06) have been prepared by an ordinary sintering process. The XRD analysis showed that the structure changes from orthorhombic to tetragonal with the increase of x (at y =0.01, abbreviated as KNNBSL100 x ). At room temperature, the polymorphic phase transition from the orthorhombic to the tetragonal phase was identified at approximately 0.02≤ x ≤0.04. The piezoelectric and ferroelectric properties were significantly enhanced. The temperature dependences of the relative permittivity revealed that the Curie temperature was increased with the addition of LiNbO₃. These solid solution ceramics are promising as potential lead-free candidate materials.     

K/Na Ratio Dependence of the Electrical Properties of [(KxNa1−x)0.95Li0.05](Nb0.95Ta0.05)O3 Lead-Free Ceramics

[(K _x Na_{1− x} )_0.95Li_0.05](Nb_0.95Ta_0.05)O₃ (K _x NLNT) ( x= 0.40–0.60) lead-free piezoelectric ceramics were prepared by conventional solid-state sintering. The effects of K/Na ratio on the dielectric, piezoelectric, and ferroelectric properties of the K _x NLNT ceramics were studied. The experimental results show that the electrical properties strongly depend on the K/Na ratio in the K _x NLNT ceramics. The K _x NLNT ( x =0.42) ceramics exhibit enhanced properties ( d ₃₃∼242 pC/N, k _p∼45.7%, k _t∼47%, T _c∼432°C, T _o−t =48°C, ɛ_r∼1040, tanδ∼2.0%, P _r∼26.4 μC/cm², E _c∼10.3 kV/cm). Enhanced electrical properties of the K _x NLNT ( x =0.42) ceramics could be attributed to the polymorphic phase transition near room temperature. These results show that the K _x NLNT ( x =0.42) ceramic is a promising lead-free piezoelectric material.     

Effect of V2O5 Doping on the Sintering and Dielectric Properties of M-Phase Li1+x−yNb1−x−3yTix+4yO3 Ceramics

The effect of the addition of V₂O₅ on the structure, sintering and dielectric properties of M -phase (Li_{1+ x − y} Nb_{1− x −3 y} Ti _x +4 _y )O₃ ceramics has been investigated. Homogeneous substitution of V⁵⁺ for Nb⁵⁺ was obtained in LiNb_{0.6(1− x )}V_{0.6 x} Ti_0.5O₃ for x ≤ 0.02. The addition of V₂O₅ led to a large reduction in the sintering temperature and samples with x = 0.02 could be fully densified at 900°C. The substitution of vanadia had a relatively minor adverse effect on the microwave dielectric properties of the M -phase system and the x = 0.02 ceramics had [alt epsilon]_r= 66, Q × f = 3800 at 5.6 GHz, and τ_f= 11 ppm/°C. Preliminary investigations suggest that silver metallization does not diffuse into the V₂O₅-doped M -phase ceramics at 900°C, making these materials potential candidates for low-temperature cofired ceramic (LTCC) applications.     

Phase Transitional Behavior and Piezoelectric Properties of Lead-Free (Na0.5K0.5)NbO3–(Bi0.5K0.5)TiO3 Ceramics

(1− x )(Na_0.5K_0.5)NbO₃–(Bi_0.5K_0.5)TiO₃ solid solution ceramics were successfully fabricated, exhibiting a continuous phase transition with changing x at room temperature from orthorhombic, to tetragonal, to cubic, and finally to tetragonal symmetries. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal ferroelectric phases was found at 2–3 mol% (Bi_0.5K_0.5)TiO₃ (BKT), which brings about enhanced piezoelectric and electromechanical properties of piezoelectric constant d ₃₃=192 pC/N and planar electromechanical coupling coefficient k _p=45%. The MPB composition has a Curie temperature of 370°–380°C, comparable with that of the widely used PZT materials. These results demonstrate that this system is a promising lead-free piezoelectric candidate material.     

Microstructure and Electrical Properties of [(K0.50Na0.50)0.95−xLi0.05Agx](Nb0.95Ta0.05)O3 Lead-Free Ceramics

[(K_0.50Na_0.50)_{0.95− x} Li_0.05Ag _x ](Nb_0.95Ta_0.05)O₃ (KNLNANT- x ) lead-free piezoelectric ceramics were prepared by normal sintering. Effects of the Ag content on the microstructure and electrical properties of KNLNANT- x ceramics were systematically investigated. It is found that the ceramics with x =0.03 exhibit relatively good electrical properties along with high Curie temperature: ( d ₃₃∼252 pC/N, T _c∼438°C, k _p∼45.4%, P _r∼30.1 μC/cm², E _c∼13.8 kV/cm, ɛ_r∼1030, and tan δ∼2.6%). The related mechanism for enhanced electrical properties of the ceramics was also discussed. These results show that KNLNANT-0.03 ceramic is a promising candidate material for high temperature lead-free piezoelectric ceramics.     

Effects of V Substitution on Dielectric and Polarization Properties for Sr0.5Bi2.25Na1.25(Nb3−xVx)O12 Ceramics

The effects of V substitution for Nb on the dielectric and polarization properties of Sr_0.5Bi_2.25Na_1.25(Nb_{3− x} V _x )O₁₂ ceramics were investigated in this study. From the X-ray powder diffraction results, no secondary phase was detected in the composition range of 0–0.075. The remanent polarizations ( P _r) of the samples in the composition range of 0–0.03 were improved by the V substitution for Nb and the highest P _r value of approximately 15 μC/cm² was obtained at x =0.03; it was noted that the V substitution for Nb was effective in improving the P _r values in this ceramics. On the other hand, the coercive fields ( E _c) of the samples were on the order of approximately 40 kV/cm in such a composition range. Moreover, the anomalous variations in the dielectric constant were observed in the composition range of 0–0.075. Also, it was observed that the dielectric loss increased drastically at the temperature of approximately 500°C.     

Processing and Electrical Properties in Lead-Based (Pb(Mg1/3Nb2/3)O3, Pb(Yb1/2Nb1/2)O3, PbTiO3) Systems

Lead-based ferroelectric (FE) ceramics exhibit superior electromechanical properties; therefore, there has been an increased focus on developing new lead-based FE materials with high Curie temperature ( T _c) and enhanced properties. The aim of this study was to investigate new compositions in the Pb(Mg_1/3Nb_2/3)O₃–Pb(Yb_1/2Nb_1/2)O₃–PbTiO₃ ( PMN–PYbN–PT) system to enhance the electromechanical properties while increasing the T _c and lowering the sintering temperature. The 0.575[0.5PMN–0.5PYbN]–0.425PT composition at PMN/PYbN (50/50) mole ratio were prepared by reactive sintering PMNT and PYbNT powder mixtures at 950°–1200°C for 4 h. PMNT and PYbNT powders were calcined via the columbite method. Samples were prepared by cold isostatic pressing at 80 MPa. Dense and fully perovskite 0.575[0.5PMN–0.5PYbN]–0.425PT ceramics were fabricated at 975°C for 4 h, and these samples displayed a remnant polarization ( P _r) of 32 μ C/cm², coercive field ( E _c) of 17 kV/cm, and a piezoelectric charge coefficient ( d ₃₃) of 475 pC/N. It is proposed that this ternary system can be tailored for various applications.     

Microstructure and Electrical Properties of (K, Na, Li)NbO3–Pb(Zr,Ti)O3 Piezoelectric Ceramics

A new type (1− x )(K_0.485Na_0.485Li_0.03)NbO₃– x Pb(Zr_0.53Ti_0.47)O₃ piezoelectric ceramics was fabricated by conventional ceramics sintering technique. Their microstructure and electrical properties of the ceramics were also studied. X-ray diffraction and scanning electron microscopy patterns indicate that all ceramics samples exhibit a pure perovskite and highly dense structure, and the coexistence of the tetragonal and orthorhombic phases is formed; The ceramic with x =0.75 exhibits the following excellent properties: d ₃₃=363 pC/N, k _p=63%, Q _m=142, ɛ_r=1590, tan δ=1.70%, P _r=28.6 μC/cm², E _c=0.89 kV/mm, T _c=295°C. These results indicate that the ceramic is a promising candidate for piezoelectric ceramics in practical applications.     

BiScO3 Doped (Na0.5K0.5)NbO3 Lead-Free Piezoelectric Ceramics

Lead-free potassium sodium niobate-based piezoelectric ceramics (1− x )(Na_0.5K_0.5)NbO₃– x BiScO₃ (KNN–BS) ( x =0∼0.05) have been prepared by an ordinary sintering process. Single perovskite phase of KNN–BS exhibits an orthorhombic symmetry at x <0.015 and pseudocubic symmetry at x >0.02, separating by a MPB at 0.015≤ x ≤0.02. Piezoelectric and ferroelectric properties are significantly enhanced in the MPB, which are as follows: piezoelectric constant d ₃₃=203 pC/N, planar coupling coefficient k _p=0.36, remnant polarization P _r=24.4 μC/cm². These solid solution ceramics look promising as a potential lead-free candidate materials.     

Microwave Dielectric Properties of CaTiO3-CaAl1/2Nb1/2O3 Ceramics Doped with Li3NbO4

The microwave dielectric properties of CaTi_{1− x} (Al_1/2Nb_1/2) _x O₃ solid solutions (0.3 ≤ x ≤ 0.7) have been investigated. The sintered samples had perovskite structures similar to CaTiO₃. The substitution of Ti⁴⁺ by Al³⁺/Nb⁵⁺ improved the quality factor Q of the sintered specimens. A small addition of Li₃NbO₄ (about 1 wt%) was found to be very effective for lowering sintering temperature of ceramics from 1450–1500° to 1300°C. The composition with x = 0.5 sintered at 1300°C for 5 h revealed excellent dielectric properties, namely, a dielectric constant (ɛ_r) of 48, a Q × f value of 32 100 GHz, and a temperature coefficient of the resonant frequency (τ_f) of −2 ppm/K. Li₃NbO₄ as a sintering additive had no harmful influence on τ_f of ceramics.     

Structure and Microwave Dielectric Properties of Hexagonal Ba[Ti1−x(Ni1/2W1/2)x]O3 Ceramics

Microwave dielectric ceramics with the composition of Ba[Ti_{1− x} (Ni_1/2W_1/2) _x ]O₃ ( x =0.4–0.6) were prepared by a solid-state reaction method. The evolution of the crystalline phases was investigated by X-ray powder diffraction analysis. A cubic-to-hexagonal phase transition occurred between 1000° and 1300°C. The phase transition is irreversible; thus, the hexagonal phase remains stable at room temperature. The X-ray powder diffraction data for x =0.5 were refined using the Rietveld method. It was identified as a h -BaTiO₃-type hexagonal perovksite with the space group of P 6₃/ mmc . It also reveals that random occupancy of Ti⁴⁺ and W⁶⁺ ions occurs in the B-site substructures, whereas Ni²⁺ ions exclusively occupy the octahedral site in the corner-sharing octahedron. The dielectric properties of dense-sintered ceramics were characterized at microwave frequencies. With an increase in x from 0.4 to 0.6, the Q × f value increased from 26 700 to 42 000 GHz, whereas ɛ_r decreased from 29.8 to 20.0, and τ_f from +6.5 to −9.9 ppm/°C.     

Microstructure, Piezoelectric, and Ferroelectric Properties of Bi2O3-Added (K0.5Na0.5)NbO3 Lead-Free Ceramics

Lead-free piezoelectric (K_0.5Na_0.5)NbO₃– x wt% Bi₂O₃ ceramics have been synthesized by an ordinary sintering technique. The addition of Bi₂O₃ increases the melting point of the system and improves the sintering temperature of (K_0.5Na_0.5)NbO₃ ceramics. All samples show a pure perovskite phase with a typical orthorhombic symmetry when the Bi₂O₃ content <0.7 wt%. The phase transition temperature of orthorhombic–tetragonal ( T _{O − T} ) and tetragonal–cubic ( T _C) slightly decreased when a small amount of Bi₂O₃ was added. The remnant polarization P _r increased and the coercive field E _c decreased with increasing addition of Bi₂O₃. The piezoelectric properties of (K_0.5Na_0.5)NbO₃ ceramics increased when a small amount of Bi₂O₃ was added. The optimum piezoelectric properties are d ₃₃=140 pC/N, k _p=0.46, Q _m=167, and T _C=410°C for (K_0.5Na_0.5)NbO₃–0.5 wt% Bi₂O₃ ceramics.     

Effect of MnO2 Addition on the Structure and Electrical Properties of Pb(Zn1/3Nb2/3)0.20(Zr0.50Ti0.50)0.80O3 Ceramics

Pb(Zn_1/3Nb_2/3)_0.20(Zr_0.50Ti_0.50)_0.80O₃ ceramics of pure perovskite structure were prepared by the two-stage method with the addition of 0–3.0 wt% MnO₂ and their piezoelectric properties were investigated systematically. The MnO₂ addition influences in a pronounced way both the crystal structure and the microstructure of the materials. The materials are transformed from the tetragonal to the rhombohedral structure, and the grain size is enhanced when manganese cations are added. The distortion of crystal structure for samples with MnO₂ addition can be explained by the Jahn–Teller effect. The values of electromechanical coupling factor ( k _p) and dielectric loss (tan δ) are optimized for 0.5-wt%-MnO₂-doped samples ( k _p= 0.60, tan δ= 0.2%) and the mechanical quality factor ( Q _m) is maximized for 1.0-wt%-MnO₂-doped samples ( Q _m= 1041), which suggests that oxygen vacancies formed by substituting Mn³⁺ and Mn²⁺ ions for B-site ions (e.g., Ti⁴⁺ and Zr⁴⁺ ions) in the perovskite structure partially inhibited polarization reversal in the ferroelectrics. The ceramics with 0.50–1.0 wt% MnO₂ addition show great promise as practical materials for piezoelectric applications.     

Electromechanical Properties of Pb(Yb1/2Nb1/2)O3-PbZrO3-PbTiO3 Ceramics

The electromechanical and electric-field-induced strain properties of x Pb(Yb_1/2Nb_1/2)O₃· y PbZrO₃·(1− x − y )PbTiO₃ ( x = 0.12, 0.25, 0.37; y = 0.10–0.40) ceramics have been studied systematically as a function of Pb(Yb_1/2Nb_1/2)O₃ (PYN) content and PbZrO₃/PbTiO₃ (PZ/PT) ratio. In addition, the effect of MnO₂ on the electromechanical properties of 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ was also investigated. The maximum transverse strain values of 1.6 × 10⁻³ for x = 0.12, 1.45 × 10⁻³ for x = 0.25, and 1.36 × 10⁻³ for x = 0.37 were obtained at the compositions which were regarded as the morphotropic phase boundary (MPB). The transverse strain was maximized at the MPB composition. The value of the maximum electromechanical coupling coefficient was 0.69 for y = 0.40 and x = 0.12 composition. In the 0.12Pb(Yb_1/2Nb_1/2)O₃·0.40PbZrO₃·0.48PbTiO₃ composition, the temperature of the maximum dielectric constant decreased and the grain size increased with an addition of MnO₂. The electromechanical coupling coefficient decreased while the mechanical quality factor rapidly increased with an addition of MnO₂. These resulted mainly from the acceptor effect of manganese ions that were produced by doping MnO₂ into the perovskite structure.     

Glass-Forming Ability and Crystallization Tendency Evaluated by the DTA Method in the Na2O–B2O3–Al2O3 System

In order to evaluate the crystallization tendency of glasses, the ratio of the crystallization temperature to the liquidus temperature ( T _c/ T _L) was obtained by DTA measurement for the Na₂O–B₂O₃ and Na₂O–B₂O₃–Al₂O₃ systems. The critical cooling rate for glass formation ( Q *) was also measured. The measurements were performed in the composition range of (100 − x )Na₂O–( x )B₂O₃, ( x = 25–35 and 60–100 mol%), and (100 − y )0.5Na₂O·0.5B₂O₃−( y )Al₂O₃, ( y = 6–34 mol%). The relationship between T _c/ T _L and Q * was discussed. A linear relationship between T _c/ T _L and log Q * for these systems was found. Furthermore, the relationship between T _c/ T _L and Q * was verified by computer simulation based on the crystallization kinetics of glass or supercooled liquid.