Understanding the microwave dielectric properties of (Pb0.45Ca0.55)[Fe0.5(Nb1−xTax)0.5]O3 ceramics via the bond valence

Microwave dielectric properties of the (Pb_0.45Ca_0.55)[Fe_0.5(Nb_1−xTa_x)_0.5]O₃ ceramics were investigated in the range of 0.0⩽x(mol)⩽1.0. With increasing Ta₂O₅, the dielectric constant and the temperature coefficient of the resonant frequency (TCF) decreased, while the Q·f value of the specimens increased. The change of dielectric constant was evaluated by the correlation between ionic polarizability and bond valence. TCF of the specimens decreased with the tilting of oxygen octahedra due to an increase of bond valence of the B-site. The Q·f values were studied by infrared reflectivity spectra from 50 to 4000 cm⁻¹, and calculated by the Kramers-Kronig analysis and classical oscillator model. The specimens with 0.4 mol of Ta₂O₅ sintered at 1150 °C for 3 h showed ε_r of 82, Q·f of 7650, and TCF of −5 ppm/°C.     

Relationships between crystal structure and electrical properties of Li0.055[Agx(K0.5Na0.5)1−x]0.945(Nb1−yTay)O3 ceramics

Electrical properties of perovskite Li_0.055[Ag_x(K_0.5Na_0.5)_1?x]_0.945(Nb_1?yTa_y)O₃ (0.00 ≤ x ≤ 0.04, 0.01 ≤ y ≤ 0.09) ceramics were investigated based on the structural characteristics. A morphotropic phase boundary (MPB) between orthorhombic and tetragonal phase was detected through the entire range of compositions. With increasing of Ta⁵⁺ content, the dielectric constant (?_r), piezoelectric coefficient (d₃₃) and electromechanical coupling factor (k_p) of Li_0.055(K_0.5Na_0.5)_0.945(Nb_1?yTa_y)O₃ ceramics were increased up to y = 0.07 and then decreased, while mechanical quality factor (Q_m) was increased. However, the ?_r, d₃₃, k_p and Q_m of Li_0.055[Ag_x(K_0.5Na_0.5)_1?x]_0.945(Nb_0.07Ta_0.03)O₃ ceramics were not changed remarkably with Ag⁺ content. The dependence of temperature coefficient of k_p (TCk_p) on the oxygen octahedral distortion was also discussed by Raman-active vibrations modes.     

Structural properties of multiferroic 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectric multiferroics are very promising materials because of their practical applications and fundamental interests. The most widely studied magnetoelectric oxides are ABO₃ perovskites. In the paper structural properties of BiFeO₃ and Pb(Fe_0.5Nb_0.5)O₃ solid solution are described. The material crystallizes in rhombohedral R3c crystal structure which parameters are presented. Mössbauer spectroscopy was used to study local changes in an iron environment due to Fe/Nb substitution and hyperfine interaction parameters of different local surroundings of iron atoms are presented. The random distribution of B-site sublattice cations was confirmed. Ab initio calculations of the studied solid solution were conducted and theoretical crystal structure parameters were compared with the experimental data. The theoretical magnetic and electric properties are discussed. The local iron magnetic moments were estimated and their dependence on the local surrounding changes is shown. The calculated electrons densities and Bader's topological analysis were used to describe chemical bonding properties.     

Preparation and dielectric properties of (Sr1−xCax)Fe0.5Nb0.5O3; (x=0.0, 0.1, 0.2) ceramics

In the present work, strontium calcium iron niobate ((Sr_1?xCa_x)Fe_0.5Nb_0.5O₃; SCFN) (x=0, 0.1, and 0.2) powders were synthesized for the first time using a molten salt technique. The pure phase perovskite obtained at a relative low calcination temperature of 800 °C was characterized using the X-ray diffraction technique (XRD). SCFN ceramics were fabricated and their properties were investigated. The XRD data of the SCFN ceramics was consistent with an orthorhombic symmetry. However, the solubility of Ca in the SCFN ceramics had an upper limit at x=0.1. All ceramics showed a large dielectric constants. The Ca doping inhibited grain growth, but produced an improvement in dielectric–temperature stability. Furthermore, the doping reduced loss tangent, especially for the x=0.1 sample. These results suggest that the SCFN ceramics prepared from molten salt synthesis exhibit a good dielectric performances, compared to many high dielectric materials that have been prepared using the conventional method.     

Pb0.45Ca0.55(Fe0.5Nb0.5)0.9(Sn1-xZrx)O3微波陶瓷介电性能的研究

研究了B位Zr、Sn共掺杂对PCFN微波陶瓷相组成及介电性能的影响.发现总掺杂量为10mol%、Zr/Sn为11时,样品中出现了未知第二相.当Zr/Sn＜1时,样品的Q×f值随Zr含量的增加而降低,谐振频率温度系数随Zr含量的增加而增大;当Zr/Sn＞1时,样品的Q×f值随Zr含量的增加而增大,谐振频率温度系数随Zr含量的增加而降低.     

Large-strain 0.7Pb(ZrxTi1−x)O3–0.1Pb(Zn1/3Nb2/3)O3–0.2Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics for high-temperature application

0.7Pb(Zr_xTi_1−x)O₃–0.1Pb(Zn_1/3Nb_2/3)O₃–0.2Pb(Ni_1/3Nb_2/3)O₃ (0.7PZT–0.1PZN–0.2PNN, x = 0.44–0.47) piezoelectric powders and ceramics have been prepared through conventional solid-state reaction method. Outstanding piezoelectric and dielectric properties occurred at the morphotropic phase boundary (MPB), which was characterized by the X-ray diffraction spectrum. The MPB composition (x = 0.46) performed high d₃₃ value (641 pC/N), indicating that the system suited large-strain application. The field-induced strain reached 0.25% under a considerably low electric field (0.8 kV/mm) according to the bipolar strain *S–E loops. The effect of the grain size on the aging phenomenon and temperature stability has also been investigated. Due to higher Curie temperature and smaller grain size, the 0.7PZT–0.1PZN–0.2PNN ceramics maintained a high d₃₃ level after depoling treatment, revealing a superior strain capacity for high-temperature application.     

Magnetic and electrical properties of single-phase multiferroic (1-x)Pb(Zr0.52Ti0.48)O3–xPb(Fe0.5Nb0.5)O3 thin films prepared by sol-gel route

Single-phase multiferroic (1-x)Pb(Zr_0.52Ti_0.48)O₃-xPb(Fe_0.5Nb_0.5)O₃ (0≤x≤0.5) thin films were synthesized by sol-gel route and characterized to understand their structural, electrical, and magnetic properties. The films were thermally treated by conventional furnace (CFA) and rapid thermal annealing (RTA). A pyrochlore-free perovskite phase is stabilized only by RTA in samples with high Fe³⁺/Nb⁵⁺ content. The films displayed excellent dielectric and ferroelectric properties in the whole concentration range, with saturated hysteresis loops and remanent polarization values of ～15μC/cm². Films with x>0.3 showed ferromagnetic behavior at room temperature. Consequently, the multiferroic behavior in the films occurs in a different concentration range than that observed in bulk ceramics. The origin of the weak ferromagnetism is discussed.     

Temperature–field phase diagrams in Pb(Zn1/3Nb2/3)O3–4.5%PbTiO3 II

Temperature and field dependences of the dielectric constants under the DC biasing fields along the [011]- and [111]-directions in the cubic coordinate in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ were investigated. The temperature–field phase diagrams were constructed in the field range below 10 kV/cm. It was confirmed that in Pb(Zn_1/3Nb_2/3)O₃–4.5%PbTiO₃ the intermediate tetragonal phase as a ground state of the system exists even without the DC field, and the tetragonal phase disappears in the external field above 4 and 3 kV/cm along the [011]- and [111]-directions, respectively. The field-induced orthorhombic-phase in the field along the [011]-direction was also found.     

Orientation-dependent electrical property and domain configuration of Mn-doped Pb(In0.5Nb0.5)O3–PbTiO3 single crystal

Orientation dependence of electrical properties and domain configurations of 8 mol% Mn-doped rhombohedral PIN-PT (0.68Pb(In_0.5Nb_0.5)O₃–0.32Pb(Ti_0.92Mn_0.08)O₃) rhombohedral single crystals were investigated with an emphasis on studying the variations of coercive field (E_C), internal field (E_i) on domain patterns. Our results showed that for both [001] and [110]-oriented samples, the coercive field and internal field decreased with temperature (T) increasing in rhombohedral phase, and a peak appeared above rhombohedral-tetragonal phase transition temperature (T_RT). The abnormal peaks between T_RT and Curie temperature on E_C-T and E_i-T plots are explained by taking into consideration the ferroelectric phase transition and variation of defect polarization, which provides assistant comprehension on the dynamic of defect dipoles during phase transition at high temperature. Bubble- and ribbon-like domain patterns were observed in (001)- and (110)-plane, respectively, and smaller value of short-length correlation radius in (001)- plane indicates less aggregation of polar nanoregions in this crystallographic plane than that in (110)-plane.     

Phase evolution and strong temperature-dependent electrostrictive effect in (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 solid solutions

(1−x)Pb(Mg_1/3Nb_2/3)-xPbTiO₃ (PMN-xPT) ceramics with x ranging from 0.1 to 0.3 were synthesized by solid-state reaction method. X-ray diffraction, dielectric and ferroelectric property characterizations were systematically investigated. As x rises, the PMN-xPT transitions from a cubic to a rhombohedral phase, resulting in an enhancement in ferroelectricity. Our findings show that the electrostrain and longitudinal electrostrictive coefficient Q₃₃ both increase and then decrease within a critical region located between the depolarization temperature T_FR and T_m (corresponding to the maximum permittivity), demonstrating strong temperature-dependent characteristics. In x = 0.2, the maximum Q₃₃ of 0.0361 m⁴/C² is obtained, and a phase diagram of studied system is built. Our findings not only shed light on the phase evolution in this system but also reveal a strong temperature-dependent electrostrictive effect that can be used to improve electrostrains in PMN-based solid solutions if the critical region can be regulated to a suitable temperature region using engineering strategies.     

Electrical properties of [Li0.04(K0.5Na0.5)0.96−xAgx](Nb1−ySby)O3 ceramics

Dependence of electrical properties on the structural characteristics of Li_0.04(K_0.5Na_0.5)_0.96(Nb_1?ySb_y)O₃ (LKNNS (x = 0, 0.00 ≤ y ≤ 0.10)) and [Li_0.04(K_0.5Na_0.5)_0.96?xAg_x](Nb_0.925Sb_0.075)O₃ (LKNANS (0.01 ≤ x ≤ 0.05, y = 0.075)) were investigated. The oxygen octahedral distortion was dependent on Ag⁺ and/or Sb⁵⁺ content which affected to the phase transition temperature of LKNNS and LKNANS ceramics. The orthorhombic–tetragonal and tetragonal–cubic phase transition temperatures (T_O–T, T_C) of the specimens were decreased with increasing of average octahedral distortion. With increasing of Sb⁵⁺ content, the electromechanical coupling factor (k_p), piezoelectric constant (d₃₃) and dielectric constant (?_r) of the sintered specimens were increased up to y = 0.075, and then decreased. These results could be attributed to the shift of T_O–T to near room temperature for Li_0.04(K_0.5Na_0.5)_0.96(Nb_0.0925Sb_0.075)O₃.     

Dielectric and piezoelectric properties of Pb(Sc1/2Nb1/2)O3–Pb(Ni1/3Nb2/3)O3–PbTiO3 ternary ceramic materials

The dielectric and electrical properties of xPb(Sc_1/2Nb_1/2)O₃–yPb(Ni_1/3Nb_2/3)O₃–zPbTiO₃ (PSNNT 100x/100y/100z) ternary ceramic materials near the morphotropic phase boundary (MPB) were investigated. The MPB follows on almost linear region between PSNNT 58/00/42 and PSNNT 00/68/32 of the binary systems. The maximum electromechanical coupling factor kp=70·7% was found at PSNNT 36/26/38, where ε₃₃^T/ε₀=3019 and Tc=210°C were obtained. These values are similar to those of the Pb(Sc_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ system and better than those of PZT.     

Relaxation behavior in 0.24Pb(In1/2Nb1/2)O3–0.49Pb(Mg1/3Nb2/3)O3–0.27PbTiO3 ferroelectric single crystal

Dielectric relaxation properties of the ternary relaxor-based ferroelectric 0.24Pb(In_1/2Nb_1/2)O₃–0.49Pb(Mg_1/3Nb_2/3)O₃–0.27PbTiO₃ single crystal have been investigated as a function of temperature (300–570 K) in the frequency range from 100 Hz to 100 kHz. It was found that the variation of the permittivity maximum temperature T_m with frequency obeys the Vogel–Fulcher relationship. The high-temperature (T>T_m) side of the dielectric permittivity deviated from the Curie–Weiss law, but can be described by the Lorenz-type relationship. The coercive field obtained from the polarization hysteresis loops gradually decreases with increasing temperature, and the remnant polarization persists above T_m due to the existence of polar nanoregions (PNRs).     

Densification behavior and electrical properties of CuO-doped Pb(In1/2Nb1/2)O3–Pb(Mg1/3Nb2/3)O3–PbTiO3 ternary ceramics

CuO modified Pb(In_1/2Nb_1/2)O₃–Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PIN–PMN–PT) ternary relaxor based ferroelectrics with the composition near the morphotropic phase boundary were synthesized by two-step columbite precursor method. The introduction of CuO significantly improved the sinterability of PIN–PMN–PT ceramics, resulting in the full densification of samples at lower sintering temperatures. It also profoundly modified the crystal structure and fracture mode of the ceramics. Properly increasing CuO content led to the disappearance of rhombohedral-tetragonal phase transition, remarkably improved the Curie temperature (T_c), and made the ceramics more relaxorlike. The ternary ceramics doped with 0.25 wt% CuO possessed optimum piezoelectric properties (d₃₃=584 pC/N, d₃₃^*=948 pC/N, and k_p=0.68), high ferroelectric properties (E_c=9.9 kV/cm, and P_r=33.1 μC/cm²), low dielectric loss (tan δ=0.9%), and wider temperature usage range (T_c=225 °C). The obtained properties are much higher than those of previously reported PIN–PMN–PT based ceramics, indicating that CuO doped PIN–PMN–PT is a promising candidate for electromechanical applications with high performance and wide temperature/electric field usage ranges.     

Phase transitions and microwave dielectric behaviors of the (Bi1−xLi0.5xY0.5x)(V1−xMox)O4 ceramics

Microwave dielectric ceramics with intrinsic low sintering temperatures are potential candidates for low temperature co-fired ceramics technology. In the present work, the (Li_0.5Y_0.5)MoO₄ ceramic with tetragonal scheelite structures was selected to improve microwave dielectric properties of BiVO₄ ceramics. As proved by X-ray diffraction (XRD) results, scheelite structured solid-solution ceramics were formed with x value ≤0.1 in the (Bi_1−xLi_0.5xY_0.5x)(V_1−xMo_x)O₄. In situ XRD results further confirmed that the addition of (Li_0.5Y_0.5)MoO₄ also lowered transition temperature from distorted monoclinic to tetragonal scheelite structure. When x value increased further, zircon phase was detected by XRD. Room and high-temperature Raman spectra also supported the XRD results. Differences of thermal expansion coefficients of both monoclinic and tetragonal scheelite phases lead to an abnormality at phase transition temperature. Good microwave dielectric properties with permittivity above 70 and Qf (Q = quality factor = 1/dielectric loss and f = frequency) value above 8000 GHz were obtained in the (Bi_1−xLi_0.5xY_0.5x)(V_1−xMo_x)O₄ solid-solution ceramics with x value ≤0.1 sintered below 800°C. However, permittivity peak values at phase transition temperatures lead to large positive or negative temperature coefficient of resonant frequency, and this needs to be modified via composite technologies in the future.     

Reduced dielectric loss and strain hysteresis in (0.97−x)BiScO3–xPbTiO3–0.03Pb(Mn1/3Nb2/3)O3 piezoelectric ceramics

(0.97−x)BiScO₃–xPbTiO₃–0.03Pb(Mn_1/3Nb_2/3)O₃ (BS–PT–PMnN) ceramics were prepared by solid-state reaction method. X-ray diffraction analysis revealed that the morphotropic phase boundary (MPB) of BS–PT–PMnN ceramics located near x=0.58. The high Curie temperature (437 °C), large piezoelectric constant (300 pC/N), low dielectric loss (0.015) and small strain hysteresis (20%) were obtained for the MPB composition. Its dielectric loss and strain hysteresis were reduced down to one third and half those of pure BiScO₃–PbTiO₃ (BS–PT) ceramics, respectively. In addition, the maximum vibration velocity of the BS–PT–PMnN ceramics was 0.85 ms⁻¹, much superior to those of BS–PT (0.15 ms⁻¹) and modified PZT (0.4 ms⁻¹) ceramics. These results indicated BS–PT–PMnN ceramics were promising candidates for high temperature piezoelectric applications.     

Structure and microwave dielectric characteristics of Sr2[Ti1−x(Al0.5Nb0.5)x]O4 (x ≤ 0.50) ceramics

Sr₂[Ti_1−x(Al_0.5Nb_0.5)_x]O₄ (x = 0, 0.10, 0.25, 0.30, 0.5) ceramics were synthesized by a standard solid-state reaction process. Sr₂[Ti_1−x(Al_0.5Nb_0.5)_x]O₄ solid solutions with tetragonal Ruddlesdon-Popper (R-P) structure in space group I4/mmm were obtained within x ≤ 0.50, and only minor amount (1-2 wt%) of Sr₃Ti₂O₇ secondary phase was detected for the compositions x ≥ 0.25. The temperature coefficient of resonant frequency τ_f of Sr₂[Ti_1−x(Al_0.5Nb_0.5)_x]O₄ ceramics was significantly improved from 132 to 14 ppm/°C correlated with the increase in degree of covalency (%) with increasing x. The dielectric constant ɛ_r decreased linearly with increasing x, while high Qf value was maintained though it decreased firstly. The variation tendency of Qf value was dependent on the trend of packing fraction combined with the microstructure. Good combination of microwave dielectric properties was achieved for x = 0.50: ɛ_r = 25.1, Qf = 77 580 GHz, τ_f = 14 ppm/°C. The present ceramics could be expected as new candidates of ultra-high Q microwave dielectric materials without noble element such as Ta.     

The electrical properties of low-temperature sintered 0.07Pb(Sb1/2Nb1/2)O3-0.93Pb(ZrxTi1−x)O3 multilayer piezoceramic actuator

0.07Pb(Sb_1/2Nb_1/2)O₃-0.93Pb(Zr_xTi_1?x)O₃ (PSbN-PZT) piezoceramics were fabricated at a low firing temperature of 920 °C using the LiBiO₂, CuO and ZnO (LBCZ) sintering aids. The material samples exhibited excellent properties, including a converse piezoelectric coefficient d₃₃* of ~558 pm/V, a relative dielectric permittivity ε^T₃₃/ε₀ of ~1725, a planar coupling factor k_p of ~0.6 and a high Curie temperature T_c of ~308 °C, thus demonstrating the material suitability for use as a low-cost multilayer actuator. PSbN-PZT piezoceramic multilayer actuators with Ag/Pd internal electrodes were fabricated by tape casting method cofired at 920 °C. A large displacement of 1.45 μm was achieved in a single PSbN-PZT multilayer actuator (thickness = 2.0 mm) at the driving voltage of 125 V, while the displacement decreased ~27% under the mechanical stress of ~32 MPa. Good temperature stability was also exhibited in PSbN-PZT multilayer actuator, which was better than that of commercial PZT-5H ceramic. These results indicated that low-temperature fired PSbN-PZT multilayer actuator is a promising candidate device for commercial piezoactuator applications.