ZnO-activated formation of phase pure perovskite Pb(In1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3 powder

This paper reports on the phase formation of perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) powder when doped with 0.04 to 0.83 mol% ZnO. Air calcination of undoped powder mixtures for 4 hours at 800°C resulted in a mixture of Pb₂Zn_0.29Nb_1.71O_6.565 pyrochlore, PIN-PZN-PT perovskite, and In₂O₃. ZnO dopant concentrations as low as 0.04 mol% increased the rate of perovskite formation and resulted in near phase pure perovskite powder of 0.5 μm particle size when heated at 800°C in air. In all cases PbTiO₃ and Pb(In_1/2Nb_1/2)O₃ formed prior to PIN-PZN-PT formation. ZnO doping promotes perovskite phase formation by increasing the reactivity of the intermediate pyrochlore phase by substituting Zn²⁺ on Nb⁵⁺ sites and forming oxygen vacancies when heated in air. Heating in high resulted in an incomplete reaction and a mixture of perovskite and pyrochlore whereas low resulted in phase separation into a mixture of rhombohedral perovskite, tetragonal perovskite, and pyrochlore. The sensitivity clearly shows that oxygen vacancies due to ZnO-doping are critical for synthesis of phase pure PIN-PZN-PT powder.     

Effect of strontium substitution on the structure and dielectric properties of unfilled tungsten bronze Ba4-xSrxSmFe0.5Nb9.5O30 ceramics

The effects of Sr²⁺ substitution for Ba²⁺ on phase structure, microstructure, dielectric and electric properties for Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2, 3 and 4) ceramics were systematically researched. X-ray diffraction patterns show that Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ (x = 0, 1, 2 and 3) ceramics are tetragonal tungsten bronze compound with a space group of P4bm, while the sample for x = 4 is an orthorhombic structure compound. The result can be corroborated by the analysis of Raman spectroscopy. As the Sr²⁺ contents increase from 0 to 3, the full width at half maximum of Raman lines of all samples increase gradually, indicating that the degree of lattice distortion increase. All tetragonal tungsten bronze ceramics exhibited a broad permittivity peaks, accompanied by frequency dispersion, indicating all samples are relaxor. The electrical properties of BSSFN ceramics were further studied by complex impedance spectroscopy. XPS spectrum shows that Fe²⁺ and Fe³⁺ coexist in Ba_4-xSr_xSmFe_0.5Nb_9.5O₃₀ ceramics, and their proportion varies with the concentration of Sr²⁺.     

Effect of MnO2 on the microstructure and electrical properties of 0.83Pb(Zr0.5Ti0.5)O3-0.11Pb(Zn1/3Nb2/3)O3-0.06Pb(Ni1/3Nb2/3)O3 piezoelectric ceramics

A sample of 0.83Pb(Zr_0.5Ti_0.5)O₃-0.11Pb(Zn_1/3Nb_2/3)O₃-0.06Pb(Ni_1/3Nb_2/3)O₃ (PZNNT) to which MnO₂ was added, with a high mechanical quality factor (Q_m) and a good transduction coefficient (d₃₃×g₃₃), were systematically investigated. Based on the SEM analysis there existed two kinds of “secondary phases”, Rich Ti and Rich Zn phases, which arose due to the B-site substation of PZNNT-based ceramics by manganese ions. One phase was due to the Mn³⁺ replacing the Ti⁴⁺ to create oxygen vacancies and induce the hardening effect. Another phase was due to the Mn²⁺ replacing the Zn-site to stabilize the perovskite phase. When the addition of MnO₂ reached the solubility limit of 1.5 mol% in the PZNNT-based ceramics, the sample showed optimal electrical properties (Q_m=357, d₃₃×g₃₃=9859 × 10⁻¹⁵ m²/N, k_p=0.56), which suggested its potential application for piezoelectric energy harvesting in larger field excitation environments.     

Synthesis of Zn3Nb2O8 ceramics using a simple and effective process

Synthesis of Zn₃Nb₂O₈ ceramics using a simple and effective reaction-sintering process was investigated. The mixture of ZnO and Nb₂O₅ was pressed and sintered directly without any prior calcination. Single-phase Zn₃Nb₂O₈ ceramics could be obtained. Density of these ceramics increased with soaking time and sintering temperature. A maximum density 5.72 g/cm³ (99.7% of the theoretical density) was found for pellets sintered at 1170 °C for 2 h. Pores were not found and grain sizes >20 μm were observed in pellets sintered at 1170 °C. Abnormal grain growth occurred and grains >50 μm could be seen in Zn₃Nb₂O₈ ceramics sintered at 1200 °C for 2 h and 1200 °C for 4 h. Reaction-sintering process is then a simple and effective method to produce Zn₃Nb₂O₈ ceramics for applications in microwave dielectric resonators.     

Elimination of pyrochlore phase in high-concentration Sm3+-doped PMN-PT piezoelectric ceramics by excessive MgO

Undesirable pyrochlore phase often appears in Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PMN-PT)-based ceramics with high rare-earth ion (RE³⁺) doping concentration, which greatly limits their development. In this study, 0–5 mol% Sm³⁺-doped Pb(Mg_1/3Nb_2/3)O₃-29PbTiO₃ (PMN-29PT:0-5Sm) ceramics were first synthesized using traditional precursor method. In the X-ray diffraction spectra and scanning electron microscope images of PMN-29PT:3-5Sm ceramics, the diffraction peaks of pyrochlore phase and pyrochlore grains with octahedral morphology were observed, respectively. The reason for the appearance of the pyrochlore phase is that Sm³⁺ doping causes the Nb-rich regions. To eliminate the pyrochlore phase, PMN-29PT:3-5Sm ceramics were resynthesized by an improved precursor method in which an excess of 4 mol% MgO was added to the reactants before pre-sintering. After adding an excess of 4 mol% MgO, the concentration ratio of Nb⁵⁺ and Mg²⁺ in the pyrochlore grains returned to the value in the perovskite grains, and the pyrochlore phase was transformed into the perovskite phase PMN. The dielectric, ferroelectric, and electromechanical properties were compared before and after eliminating the pyrochlore phase. The results show that the comprehensive performance of the ceramics is improved after eliminating the pyrochlore phase.     

The Influence of La Doping and Heterogeneity on the Thermoelectric Properties of Sr3Ti2O7 Ceramics

La‐doping mechanisms and thermoelectric properties of Sr₃Ti₂O₇ Ruddlesden–Popper (RP) ceramics sintered under air and flowing 5% H₂ at 1773 K for 6 h have been investigated. Changes in lattice parameters and conductivity revealed a limited interstitial anion mechanism (~1 at.%) based on La³⁺ + ½O^2?→Sr²⁺, which resulted in insulating samples when processed in air. In contrast, electronic donor‐doping (La³⁺ + e^? → Sr²⁺) and oxygen loss [O^2? → ½ O₂ (g) + 2 e^?] are the dominant mechanism(s) in 5% H₂‐sintered ceramics with a solution limit of ~5 at.%. The increased solubility limit is attributed to the formation of Ti³⁺ during reduction, which compensates for the extra positive charge associated with La on the A‐site and also to the occurrence of oxygen loss due to the reducing conditions. For 5% H₂‐sintered samples, an insulating surface layer was formed associated with SrO volatilization and oxygen uptake (during cooling) from the sintering. Unless removed, the insulating layer masked the conductive nature of the ceramics. In the bulk, significantly higher power factors were obtained for ceramics that were phase mixtures containing highly conductive perovskite‐based (Sr,La)TiO_3?δ (ST). This highlights the superior power factor properties of reduced perovskite‐type ST phases compared to reduced RP‐type Sr₃Ti₂O₇ and serves as a precaution for the need to identify low levels of highly conducting perovskite phases when exploring rare‐earth doping mechanisms in RP‐type phases.     

Influence of Nb2O5 addition on dielectric properties and diffuse phase transition behavior of BaZr0.2Ti0.8O3 ceramics

Nb₂O₅ doped Ba(Zr_0.2Ti_0.8)O₃ (short as BZT20) ceramics were prepared by a mixed-oxide method using a high-energy planetary ball mill and the influence of Nb₂O₅ addition on microstructure, dielectric properties and diffuse phase transition behavior of BZT20 ceramics were investigated. It was demonstrated that Nb⁵⁺entered the B-site of BZT20 ceramic and substituted for Ti⁴⁺, which caused the expansion and distortion of crystal lattice. BZT20 ceramics doped with 0.2 mol% Nb₂O₅ showed excellent dielectric property and lower diffusivity with ε_m=37,823 and γ=1.49. We supposed that the increase of dielectric constant and decrease of diffuseness parameter with increasing Nb₂O₅ content were caused by lattice disorder and unbalancing of cations induced by the substitution of Ti⁴⁺ by Nb⁵⁺ in the B sites of BZT20 ceramics. The Curie temperature decreased with the increase of Nb₂O₅ content, which can be attributed to enlarged distortion energy of the Nb doped BZT20 structure. Besides, grain size effect on the dielectric property and diffuse phase transition behavior of Nb₂O₅ doped BZT20 ceramics was also investigated.     

Identification of Substitution Mechanism in Group VIII Metal Oxides Doped Pb(Zn1/3Nb2/3)O3–PbZrO3–PbTiO3 Ceramics with High Energy Density and Mechanical Performance

Group VIII metal oxides, that is, Fe₂O₃, Co₂O₃, and NiO have been introduced to 0.2Pb(Zn_1/3Nb_2/3)O₃–0.8Pb(Zr_0.50Ti_0.50)O₃ (PZN–PZT) to deterministically identify the substitution mechanism and meantime to tailor mechanical and piezoelectric properties in obtaining energy harvesting materials. On the basis of the X‐ray diffraction and Raman analysis, it is clear that the group VIII metal oxides induce a phase transformation from the morphotropic phase boundary to the tetragonal phase side, and the corresponding grain size increases accordingly. It is reasonable to deduce that two types of substitution behaviors coexist in the group VIII metal oxides added PZN–PZT system. Due to the mixed valence of +2 and +3, the foreign doping ions prefer to enter the B site in the perovskite structure, not only substituting for Ti⁴⁺, Zr⁴⁺, and Nb⁵⁺ ions in the inequivalence replacement but also substituting for Zn²⁺ ions in the equivalence replacement. The proposed complex substitution mechanisms can give the full explanation about the grain growth phenomena and the variation in mechanical and electric properties in the modified PZN–PZT system. At the same doping level of 0.3 mol%, the maximum transduction coefficient (d₃₃·g₃₃ = 13120 × 10^?15 m²/N) and good fracture toughness (K_IC = 1.32 MPa m^1/2) are obtained in Co₂O₃ added 0.2PZN–0.8PZT ceramics, which shows great promise as practical materials for energy harvesting device applications.     

Correlation between the structure and modified microwave dielectric characteristics of Zr4+ substituted Ni0.4Zn0.6Ti(1-x)ZrxNb2O8 ceramics

Microwave ceramics are an important classes of materials that are used in microwave communication systems, especially in the area of 5G wireless communication and the internet of things. In this work, to improve the Q×f values and enhance the temperature stability of Ni_0.4Zn_0.6TiNb₂O₈ ceramics, the influence of the substitution of Zr⁴⁺ ions at the Ti site in Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics was investigated. The Q×f value increases from 32114 GHz to 45733 GHz and the τ_f value changes from 38.1 ppm/°C to 3 ppm/°C with a slight Zr⁴⁺ ion substitution (x = 0.1). Meanwhile, the sample with the Zr⁴⁺ ion substitution (x = 0.3) that was sintered at 1120 °C shows a very high Q×f value of 92078 GHz. Furthermore, the XRD results reveal that the phase and structure of the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics change with the different Zr⁴⁺ ion contents. The substitution of the Zr⁴⁺ ion can promote the sintering process for the Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics and restrain the Ni_0.5Ti_0.5NbO₄ phase formation. The results obtained from Ni_0.4Zn_0.6Ti_(1-x)Zr_xNb₂O₈ ceramics can offer useful information for the study and application of high-frequency microwaves.     

The effect of B-site substitution on the structural evolution and electrical properties of lead-free (K,Na)NbO3 ceramics

Lead-free (K_0.49Na_0.51)(Nb_1−xSb_x)O₃ piezoelectric ceramics were prepared via the conventional sintering method and the effect of the substitution of Nb with Sb on the phase structure, microstructure and electrical properties of the prepared (K_0.49Na_0.51)(Nb_1−xSb_x)O₃ ceramics was systematically investigated. The prepared ceramics exhibited a single-phase perovskite structure which changed from a standard orthorhombic structure to a pseudocubic structure as x was increased from 0 to 0.1. X-ray diffraction patterns and Raman spectra obtained for the prepared ceramics clearly revealed that the degree of structural symmetry increased with x. Substituting an appropriate amount of Sb⁵⁺ for Nb⁵⁺ was found to improve the microstructure and thereby enhance the piezoelectric/ferroelectric properties. Further increasing the Sb content resulted in a decrease of the average grain size and a deterioration of the performance. The peak values of the piezoelectric constant d₃₃ (182 pC/N) and the electromechanical coupling coefficient k_p (41%) were obtained for the ceramic with x=0.06.     

Structural characteristics and optical properties of lead-free Bi(Zn1/2Ti1/2)O3-BaTiO3 ceramics

The xBi(Zn_1/2Ti_1/2)O₃-BaTiO₃ (xBZT-BT) ceramics, where x (mol) =0, 0.03, 0.06, 0.09, and 0.12, have been prepared by a solid-state reaction method. The phase transition, microstructure and optical properties were investigated. X-ray diffraction patterns indicate that the as-prepared samples have a polycrystalline perovskite structure. For x<0.06, the xBZT-BT ceramics exhibit clear tetragonal symmetry, and transform to rhombohedral phase as 0.06< x≤0.12. Coexistence of both tetragonal phase and rhombohedral phase is observed for x=0.06. The lattice strain is estimated by the Williamson-Hall analysis model, which suggests that the incorporation of substitution ions into the host lattice produces the inner stress field gives rise to structure distortions. The Raman scattering spectra corroborate the decrease in tetragonality with increasing the x, where the characteristic variation of phonon modes indirectly reveal the incorporation of Bi(Zn_1/2Ti_1/2)O₃. Furthermore, the optical band gaps of xBZT-BT ceramics show a non-linear change, which can be explained by the crystal field theory and phase structure effect.     

Composition design,phase transitions and electrical properties of Sr2+-substituted xPZN–0.1PNN–(0.9−x)PZT piezoelectric ceramics

The influences of PZN content and Sr²⁺ substitution on the structure and electrical properties of Pb(Zn_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr_0.52Ti_0.48)O₃ (abbreviated as PZN–PNN–PZT) piezoelectric ceramics were studied. All as-prepared PZN–PNN–PZT ceramics presented single phase of perovskite structure, while higher PZN contents favored rhombohedral symmetry and larger grain size. Meanwhile, with the increase in Sr²⁺ content, the phase structure changed from a mix of tetragonal and rhombohedral symmetries to a pure rhombohedral symmetry. Although the ferroelectric Curie temperature (T_C) was decreased with increasing the PZN and Sr²⁺ contents, the piezoelectric constant (d₃₃) exhibited the opposite trend. As a result, optimum comprehensive electrical properties were obtained in the 0.1PZN–0.1PNN–0.8PZT composition with 10 mol% Sr²⁺ substitution: d₃₃~800 pC/N, k_p ~0.65, ɛ_r~4081, T_C~176 °C, P_r~30.92 µC/cm². Thus, the 10 mol% Sr²⁺-substituted 0.1PZN–0.1PNN–0.8PZT ceramic is a promising candidate for high performance applications.     

Effects of Mg Substitution on Order/disorder Transition,Microstructure, and Microwave Dielectric Characteristics of Ba((Co0.6Zn0.4)1/3Nb2/3)O3 Complex Perovskite Ceramics

Effects of Mg substitution on order/disorder transition, microstructure, and microwave dielectric characteristics of Ba((Co_0.6Zn_0.4)_1/3Nb_2/3)O₃ complex perovskite ceramics have been investigated. The ordered complex perovskite solid solutions are obtained in Ba((Co_0.6?x/2Zn_0.4?x/2Mg_x)_1/3Nb_2/3)O₃ ceramics (x = 0, 0.1, 0.2, and 0.3), and the ordering degree in the as‐sintered dense ceramics increases with increasing Mg‐substitution amount. The significantly improved Qf value is obtained in the present ceramics with increasing x, whereas the dielectric constant decreases slightly together with some increase of temperature coefficient of resonant frequency. The best combination of microwave dielectric characteristics is obtained in the composition of x = 0.3: ε_r = 33.7, Qf = 93 800 GHz, and τ_f = 9.6 ppm/°C. In the Mg‐substituted compositions, clear domain boundaries are obtained and the domain size increases as x increases, the highest Qf value is obtained when the domain size is about 40–60 nm in the ceramics with x = 0.3. The increased ordering degree and the fine ordering domain structure are considered to primarily contribute to the significant increase of Qf value in the Mg‐substituted Ba((Co_0.6Zn_0.4)_1/3Nb_2/3)O₃ complex perovskite ceramics.     

Piezoelectric properties and microstructures of ZnO-doped Bi0.5Na0.5TiO3 ceramics

This article studies the microstructure and piezoelectric properties of a ceramic lead-free NBT under different amount of ZnO doping. X-ray diffraction shows that Zn²⁺ diffuses into the lattice of (Bi_0.5Na_0.5)TiO₃ to form a solid solution with a pure perovskite structure. By modifying the zinc oxide content, the sintering behavior of (Bi_0.5Na_0.5)TiO₃ ceramics was significantly improved and the grain size was increased. The piezoelectric coefficient d₃₃ for the 1.0 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1050 °C was found to be 95 pC/N, and the electromechanical coupling factor k_p = 0.13. However, the piezoelectric coefficient d₃₃ for the 0.5 wt.% ZnO-doped (Bi_0.5Na_0.5)TiO₃ ceramics sintered at 1140 °C was found to be 110 pC/N, and the electromechanical coupling factor k_p = 0.17.     

Structural and relaxor behavior in lead-free (Ba0.8Sr0.2)Ti1−x(Zn1/3Nb2/3)xO3 ceramics

The Solid solutions of (1−x)Ba_0.8Sr_0.2TiO₃−xBa(Zn_1/3Nb_2/3)O₃ (BST–BZN) with 0.025≤x≤0.15 were prepared by a high temperature solid-state reaction technique. The effects of the Ba(Zn_1/3Nb_2/3)O₃ addition on the phase composition in the B site on structural and dielectric properties was investigated. The room temperature X-ray diffraction analyses of all ceramics revealed a perovskite phase with a composition dependent symmetry. The temperature and frequency dependence of the dielectric permittivity and losses have been explored. While ceramics of compositions x≤0.05 showed normal ferroelectric behavior, while ceramics with x≥0.1 were of relaxor type. It was found that degree of diffuseness and the relaxor effect increased, whereas the transition temperature (T_C or T_m) decreased when both zinc and niobium were introduced in the Ba_0.8Sr_0.2TiO₃ lattice. For the composition with x≥0.1, the frequency depend on T_m, satisfying the Vogel–Fulcher formula, which indicates a relaxor bahavior.     

Densification and properties of oxygen sintered CuO-doped PIN-PMN-PT ceramics

Relationships between sintering temperature and annealing atmosphere on microstructure and dielectric, ferroelectric, and piezoelectric properties of reactively sintered CuO-doped Pb(In_1/2Nb_1/2)O₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PMN-PT) ceramics were investigated. Uniform 2−3 μm grain size, dense CuO-doped PIN-PMN-PT ceramics are obtained when oxygen sintered versus a bimodal grain size microstructure when sintered in air. Oxygen sintered ceramics have excellent properties including d₃₃ = 300–315 pC/N, E_C = 7.7–8 kV/cm, and tan δ < 1.5%. The MPB region was mapped for ternary compositions doped with 0.5 mol% CuO and sintered in O₂. MPB 25PIN-40PMN-35PT demonstrated the maximum piezoelectric properties with d₃₃ = 565 +/− 23 pC/N and k_p = 0.64 +/− 0.01. Sintering from 1050 °C to 1200 °C increased the coercive field from 8.5 to 11.5 kV/cm and reduced dielectric losses from tan δ = 1.8% to 0.8% by facilitating diffusion of CuO into the lattice and creating domain wall pinning defect dipoles as evidenced by an increase in the internal field bias of P-E loops.     

Enhancing piezoelectricity of PLZT ceramics by bismuth stearate coating via water-soluble defatted powder injection molding

Lead zirconate titanate-based piezoelectric ceramics (Pb_0·91La_0·06(Zr_0·58Ti_0.42)_0.975Nb_0·02O₃, PLZT) were prepared by water-soluble defatted powder injection molding using bismuth stearate as surfactant. The effects of bismuth stearate surfactant amount on the feed viscosity, water degreasing rate and electrical properties were studied. The results showed that the bismuth stearate coating reduces agglomeration between the PLZT powders and decreases the viscosity of the feed. During sintering, bismuth stearate is decomposed into bismuth oxide, which acts as sintering aid to increase the density of the sintered bismuth stearate-coated PLZT ceramics. Bi³⁺ dissolves into the perovskite crystal lattice, which increases the tetragonality factor and the content of tetragonal phase, and improves the dielectric, ferroelectric and piezoelectric properties of the bismuth stearate-coated PLZT ceramics. This study provides a novel modification method for the production of injection molded ceramics using a water-soluble binder system.     

Investigations of the divalent metal ions Zn2+, Co2+, Ni2+ doped ultra-wide temperature stable BBNN system

Multi-component BaTiO₃–Bi_0.5Na_0.5TiO₃–Nb₂O₅ (BBNN) system doped with divalent metal ions (Zn²⁺, Co²⁺, Ni²⁺) was prepared by the conventional solid–state method.The X-ray diffraction patterns revealed all samples exhibited perovskite (P4mm) single phase. The dielectric properties and micro-mechanisms were discussed and validated. Novel theories, based on the characteristics of the different kinds of dielectric polarization, are proposed to explain the dielectric anomalies in the dielectric system. The relationships between microstructure and the dielectric properties were investigated systematically for the first time. The samples doped with 15 mol% Zn²⁺/Co²⁺presented good dielectric properties of an ultra-broad temperature stable range (from −50 and >300), high dielectric constant (ε~1925 for Zn²⁺/ ε~1341 for Co²⁺) and low dielectric loss (tan δ<0.02) were obtained. These features made the ceramics system have high practical values for miniaturization and harsh environments applications.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Structure,microstructure and electrical properties of Cu2+ doped (K,Na,Li)(Nb,Ta,Sb)O3 piezoelectric ceramics

This work studies the effects of copper doping on the properties of the (K_0.44Na_0.52Li_0.04)(Nb_0.86Ta_0.10Sb_0.04)O₃ piezoelectric ceramic material. Cu²⁺ incorporation into the perovskite structure produces a transformation of the crystalline lattice from tetragonal to orthorhombic symmetry together with an increase of the secondary phase. The grain size of the ceramic samples is increased due to the formation of a liquid phase during sintering, which increases with the Cu²⁺ content. EDS analysis reveals that the secondary-phase regions present a Cu and Nb-rich composition, indicating that the Cu-excess accommodates through the formation of this secondary phase. Cu-doping induces a rapid increase of the orthorhombic–tetragonal phase transition temperature, while the tetragonal–cubic phase transition temperature is decreased, the latter becoming more diffuse with the increase of Cu content. The piezoelectric properties of the material are reduced with the copper concentration, whereas the mechanical quality factor increases by a factor of nearly four.