Effects of ZnO on the piezoelectric properties of Pb(Mn1/3Sb2/3)O3-Pb(Zr,Ti)O3 ceramics

Perovskite-type 0.05 Pb(Mn_1/3Sb_2/3)O₃-0.95 Pb(Zr_0.5Ti_0.5)O₃ (PMS-PZT) was synthesized by conventional bulk ceramic processing technique. ZnO as a dopant up to 0.5 mol% was incorporated into the PMS-PZT system, and the effects on piezoelectric properties were investigated. Pyrochlore phase was not detected to form during the synthesis of the PMS-PZT system with 0∼0.5 mol% ZnO addition. The highest density of 7.92 g/cm³ was obtained when sintered at 1200°C for 2 hrs. Piezoelectric properties as a function of ZnO content were evaluated using a gain phase analyzer. Piezoelectric charge constant (d₃₁) and piezoelectric voltage output coefficient (g₃₁) increased up to −130 pC/N and −24.9 × 10³Vm/N, respectively, with increasing ZnO content. Mechanical quality factor (Q _m) was shown to reduce considerably with increasing ZnO content. When 0.3 mol% of ZnO was added into the system, electromechanical coupling factor (k _p) and relative dielectric constant () reached to the maximum of 56% and 1,727, respectively.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Piezoelectric and dielectric characteristics of low temperature sintering Pb(Ni1/3Nb2/3)O3-Pb(Mn1/3Nb2/3)O3-Pb(Zr1/2Ti1/2)O3 ceramics for multilayer piezoelectric actuator

In this study, in order to develop the composition ceramics for multilayer piezoelectric actuator, PNN substituted PMN-PZT ceramics were fabricated using Li₂CO₃ and Na₂CO₃ as sintering aids, and their piezoelectric and dielectric characteristics were investigated. With the increase of the amount of PNN substitution, dielectric constant (εr), electromechanical coupling factor (k _p), and piezoelectric constant (d ₃₃) of specimens showed the maximum value at each sintering temperature, and crystal structure changed from tetragonal to rhombohedral. At the sintering temperature of 950^∘C, the density, εr, k _p, d ₃₃, Q_m and Tc of 12 mol% PNN substituted PMN-PNN-PZT composition ceramics showed the optimal values of 7.79 g/cm³, 1160, 0.599, 419pC/N, 894 and 332^∘C, respectively, for low loss multilayer piezoelectric actuator application.     

Dielectric properties and morphotropic phase boundaries in the xPb(Zn1/3Nb2/3)O3−(1−x)Pb(Zr0.5Ti0.5O3 pseudo-binary system

Ceramics in the xPb(Zn_1/3Nb_2/3)O₃−(1−x)Pb(Zr_0.5Ti_0.5)O₃ [xPZN–(1−x)PZT] solid solution system are expected to display excellent dielectric, piezoelectric, and ferroelectric properties in compositions close to the morphotropic phase boundary (MPB). The dielectric behavior of ceramics with x = 0.1−0.6 has been characterized in order to identify the MPB compositions in this system. Combined with X-ray diffraction results, ferroelectric hysteresis measurements, and Raman reflectivity analysis, it was consistently shown that an MPB exists between x = 0.2 and x = 0.3 in this binary system. When x ≤ 0.2, the tetragonal phase dominates at ambient temperatures. In the range of x ≥ 0.3, the rhombohedral phase dominates. For this rhombohedral phase, electrical measurements reveal a profound frequency dispersion in the dielectric response when x ≥ 0.6, suggesting a transition from normal ferroelectric to relaxor ferroelectric between 0.5 ≤ x ≤ 0.6. Excellent piezoelectric properties were found in 0.3PZN–0.7PZT, the composition closest to the MPB with a rhombohedral structure. The results are summarized in a PZN–PZT binary phase diagram.     

Microwave dielectric properties of Ca[(Li1/3Nb2/3)1−x Tix]O3−δ ceramics with glass

The effect of the addition of glass on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−x Ti_x]O_3−δ(CLNT) was investigated. Addition of glass (B₂O₃-ZnO-SiO₂-PbO system) improved the densification and reduced the sintering temperature from 1150^∘C to 900^∘C of Ca[(Li_1/3Nb_2/3)_1−x -Ti_x]O_3−δ microwave dielectric ceramics. As increasing glass contents from 10 wt% to 15 wt%, the dielectric constants (ε_r) and bulk density were increased. The quality factor (Q⋅f₀), however, was decreased slightly. The temperature coefficients of the resonant frequency (τ_f) shifted positive value as increasing glass contents over Ti content is 0.2 mol. The dielectric properties of Ca[(Li_1/3Nb_2/3)_0.75Ti_0.25]O_3−δ with 10 wt% glass sintered at 900^∘C for 3 h were ε_r = 40 Q·f₀ = 11500 GHz, τ_f = 8, ppm/°C. The relationship between the microstructure and dielectric properties of ceramics was studied by X-ray diffraction (XRD), and scanning electron microscope (SEM).     

Effects of Al2O3 on the piezoelectric properties of Pb(Mn1/3Nb2/3)O3-PbZrO3-PbTiO3 ceramics

Piezoelectric properties of Al₂O₃-doped Pb(Mn_1/3Nb_2/3)O₃-PbZrO₃-PbTiO₃ ceramics were investigated. The constituent phases, microstructure, electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants were analyzed. Diffraction peaks for (002) and (200) planes were identified by X-ray diffractometer for all the specimens doped with Al₂O₃. The highest sintered density of 7.8 g/cm³ was obtained for 0.2 wt% Al₂O₃-doped specimen. Grain size increased by doping Al₂O₃ up to 0.3 wt%, and it decreased by more doping. Electromechanical coupling factor, dielectric constant, piezoelectric charge and voltage constants increased by doping Al₂O₃ up to 0.2 wt%, and it decreased by more doping. This might result from the formation of oxygen vacancies due to defects in O^{2 −} ion sites and the substitution of Al³⁺ ions.     

Application of spark plasma sintering for growing dense Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 single crystal by solid-state crystal growth

This study examined the effect of spark plasma sintering (SPS) on the densification behavior and resulting dielectric and piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ ceramics with a 5 mol% excess of PbO. Through normal sintering at 1200^∘C, the density of the specimen reached only 92% of the theoretical density (TD). However, with the SPS treatment, the density of the PMN-PT ceramics increased to more than 99% of the TD at 900^∘C, and maintained over 98% of the TD during subsequent heat-treatment at 1200^∘C for 10 h. The increased density of the Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ ceramics resulted in an improvement in the dielectric and piezoelectric properties. The SPS treatment was also successfully applied to the densification of a PMN-PT single crystal grown on a BaTiO₃ seed crystal using a solid-state crystal growth (SSCG) process.     

Piezoelectric properties of a Ba(Zr0.075Ti0.925)O3 single crystal induced by poling treatment

Piezoelectric properties in a Ba(Zr_0.075Ti_0.925)O₃ single crystal were investigated with a consideration that its phase transition lies on room temperatures and the transition can affect piezoelectric properties. The poling treatments were carried with bias fields ranging 2.2 kV/cm∼11 kV/cm at room temperature. The crystal possesses the phase transition from orthorhombic to rhombohedral, lying on room temperature. At 37^∘C, the crystal exhibited the excellent piezoelectric properties, a d₃₁ coefficient of over 500 pC/N and a k₃₁ coefficient of 0.38, being caused by the phase transition.     

Dielectric and piezoelectric properties of La2O3 doped (Bi0.5Na0.5)0.92(Ba0.8Sr0.2)0.08 TiO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (Bi_0.5Na_0.5)_0.92(Ba_0.8Sr_0.2)_0.08 TiO₃+x mol% La₂O₃(x = 0, 0.1, 0.3, 0.5, 0.8) were synthesized by conventional solid state reaction. The crystal structure of all compositions is mono-perovskite ascertained by XRD. The grain size decreased and diffuse phase transition behavior was more evident with the increasing amount of La₂O₃. The piezoelectric constant d₃₃ and the electromechanical coupling factor k_p showed the maximum value of 165 pC/N and 0.322 at 0.3% and 0.1% La₂O₃ addition, respectively, and rapidly decreased when La₂O₃ addition over 0.5%. The loss tangent tanδ linearly increased and the mechanical quality factor Q_m linearly decreased with the increasing amount of La₂O₃.     

Investigation of La-doped 0.25Pb(Zn1/3Nb2/3)O3-0.75Pb(ZrxTi1-x)O3 ceramics near morphotropic phase boundary

La-doped 0.25Pb(Zn_1/3Nb_2/3)O₃-0.75Pb(Zr_xTi_1-x)O₃ (x = 0.51–0.57) ceramics were prepared by a conventional mixed oxide method. The piezoelectric and dielectric properties of various compositions near the morphotropic phase boundary (MPB) were investigated. The MPB was determined by X-ray diffraction (XRD) patterns. The optimal properties were obtained in the specimen with Zr/Ti = 53/47: d₃₃ = 570 pC/N, k_p = 0.60, ε_r = 3900, tgδ = 1.9%, T_c = 204°C, P_r = 35.21 μC/cm², E_c = 11.62 kV/cm, which means it is a good candidate for applications.     

Piezoelectric properties and dielectric behavior of Bi1/2Na1/2[Ti1−x (Sb1/2Nb1/2) x ]O3 lead-free piezoelectric ceramics

New lead-free piezoelectric ceramics of ABO₃ perovskite type, Bi_1/2Na_1/2[Ti_1−x (Sb_1/2Nb_1/2) _x ]O₃, were synthesized by conventional solid state reaction. The effect of the replacement of complex ions of (Sb_1/2Nb_1/2)⁴⁺ in the B cationic site on structural and electrical properties was investigated. The XRD analysis showed that all samples exhibited a single phase of perovskite structure. Piezoelectric and dielectric measurement revealed that the substitution of (Sb_1/2Nb_1/2)⁴⁺ ions lead to an increase in piezoelectric constant(d ₃₃), electromechanical coupling factor(k _t), relative dielectric constant(ɛ _r),and loss tangent (tanδ), while excess of (Nb_1/2Sb_1/2)⁴⁺ ions results in a decrease in d ₃₃, k _t, ɛ _r, but an increase in tanδ. Temperature dependence of dielectric constant ɛ _r measurement indicated these compounds were relaxor ferroelectric. At low frequency and high temperature, dielectric constant increased sharply attributed to the superparaelectric clusters after (Sb_1/2Nb_1/2)⁴⁺ ions substitution.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Effect of Sb2O3 addition on the varistor characteristics of ZnO-Bi2O3-ZrO2-MtrO (Mtr = Mn, Co)

Effect of Sb₂O₃ addition on the varistor characteristics of pyrochlore-free ZnO-Bi₂O₃-ZrO₂-M_trO (M_tr = Mn, Co) system previously proposed has been studied. With Sb₂O₃ up to 0.1 mol%, a gradual enhancement of densification and the grain growth inhibition were seen in the system sintered between 900 and 1200^∘C. In X-ray diffraction patterns, small amount of pyrochlore appeared in the specimens doped with Sb₂O₃ (>0.06 mol%), which is thought responsible for the sintering behavior. Enhanced values of non linear coefficient (α) were obtained in ZnO-Bi₂O₃-ZrO₂ (ZBZ) doped with 0.001 mol% Sb₂O₃, but was leveled off at higher concentrations. In ZBZ added with M_trO (M_tr = Mn, Co), significant increase of nonlinear coefficient (α > 30) along with low leakage current (I _L ≪ 100 μA/cm²) was attained. The α-enhancement effect of Sb₂O₃, however, was not observed in high-α ZBZ added with M_trO. As for degradation, addition of a trace amount (0.001 mol%) of Sb₂O₃ to ZBZM_tr was efficient, especially in I _L.     

Effect of sintering temperature on piezoelectric and dielectric properties of 0.98(Na0.5K0.5)NbO3-0.02Li(Sb0.17Ta0.83)O3+0.01wt%ZnO ceramics

We studied sintering temperature to enhance the piezoelectric and dielectric properties of 0.98(Na_0.5?K_0.5)NbO₃-0.02Li(Sb_0.17Ta_0.83)O₃?+?0.01wt%ZnO (hereafter NKN-LST+ZnO) lead free piezoelectric ceramics. The synthesis and sintering method were the conventional ceramic technique and sintering was executed at 1080?～?1120°C. We found that optimal sintering temperature and NKN-LST+ZnO ceramics showed the highest piezoelectric properties and dielectric properties at the optimal sintering temperature. The NKN-LST+ZnO ceramics sintered at 1090°C show a superior performance with piezoelectric constant d ₃₃?=?185 pC/N, k _p?=?0.36, ε ₃₃ ^T /ε₀?=?491 respectively. These results reveal that NKN-LST+ZnO ceramics are promising candidate materials for lead-free piezoelectric application.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with B2O3 and CuO additions

The low sintering temperature and the good dielectric properties such as high dielectric constant (ε _r ), high quality factor (Q × f), and small temperature coefficient of resonant frequency (TCF) are required for the application of chip passive components in wireless communication low temperature co-fired ceramics (LTCC). In the present study, the sintering behaviors and dielectric properties of Ba₃Ti₅Nb₆O₂₈ ceramics were investigated as a function of B₂O₃-CuO content. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250^∘C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ε _r of 37, TCF of −12 ppm/^∘C. The addition of B₂O₃-CuO was revealed to lower the sintering temperature of Ba₃Ti₅Nb₆O₂₈, 900^∘C and to enhance the microwave dielectric properties: Q × f of 32,500 GHz, ε _r of 40, TCF of 9 ppm/^∘C. From the X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Effect of B2O3 and CuO on the sintering temperature and microwave dielectric properties of the BaTi4O9 ceramics

The effect of B₂O₃ and CuO on the sintering temperature and microwave dielectric properties of BaTi₄O₉ ceramics was investigated. The BaTi₄O₉ ceramics were able to be sintered at 975^∘C when B₂O₃ was added. This decrease in the sintering temperature of the BaTi₄O₉ ceramics upon the addition of B₂O₃ is attributed to the formation of BaB₂O₄ second phase whose melting temperature is around 900^∘C. The B₂O₃ added BaTi₄O₉ ceramics alone were not sintered below 975^∘C, but were sintered at 875^∘C when CuO was added. The formation of BaCu(B₂O₅) second phase could be responsible for the decrease in the sintering temperature of the CuO and B₂O₃ added BaTi₄O₉ ceramics. The BaTi₄O₉ ceramics containing 2.0 mol% B₂O₃ and 5.0 mol% CuO sintered at 900^∘C for 2 h have good microwave dielectric properties of ε_r = 36.3, Q× f = 30,500 GHz and τ_f = 28.1 ppm/^∘C     

Morphotropic phase boundary and electrical properties of lead-free bismuth sodium lanthanum titanate—barium titanate ceramics

The important properties of lead-free piezoelectric ceramics have been investigated from Bismuth Sodium Lanthanum Titanate and Barium Titanate system: (1 − y)(Bi_0.5Na_0.5)_{(1 − 1.5x)}La _x TiO₃(BNLT)—yBaTiO₃(BT) where x = 0.017 and y = 0 − 0.2, respectively. The morphotropic phase boundary (MPB) was found to be around y = 0.1 by the x-ray diffraction and dielectric measurement at various amount of BT. The temperature dependence of dielectric constant (ε _r ) at various value of y showed the diffuse phase transition exhibiting the relaxor type ferroelectrics. The degree of diffuseness increased at a high doping content of about y = 0.15 where the second phase transition (T₂) of the ferroelectric to antiferroelectric phase disappeared. Moreover, this sample had the maximum piezoelectric coefficient (d ₃₃) of about 112 pC/N with relatively low dielectric constant. The optimum sintering temperatures and the microstructures of the dense BNLT-BT ceramics were also examined.     

Characteristic of grain oriented (Bi0.5Na0.5)TiO3-BaTiO3 ceramics

Dielectric and piezoelectric properties of grain oriented (Bi_0.5Na_0.5)TiO₃-BaTiO₃ ceramics were investigated in a process that the templated grain growth and hot pressing methods were employed. A ceramic composition in Bi-based perovskite structure family, (Bi_0.5Na_0.5)TiO₃-BaTiO₃, was chosen as a matrix material and plate shaped SrTiO₃ as a template. To examine the combined process effect on piezoelectric properties, three processes, conventional solid reaction, templated grain growth and the combine treatment of templated grain growth and hot-pressing, were compared. Specimen processed by templated grain growth and hot pressing methods exhibited better piezoelectric coefficient, d ₃₁ (−79.6 pC/N) and electromechanical coefficient, k ₃₃ (0.35) than those of the other specimens, fabricated by solid reaction and templated grain growth, respectively. The improved properties were attributed to reduction of pore existing in matrix, which is related to abnormal grain growth from SrTiO₃ template and its resultant heterogeneous shrinkage.     

Dielectric and piezoelectric properties of KCT added (Li0.02(Na0.56 K0.46)0.98(Nb0.81Ta0.15Sb0.04)O3 ceramics

In this study, [Li_0.02(Na_0.56 K_0.46)_0.98](Nb_0.81Ta_0.15Sb_0.04)O₃ + x mol% K_5.4Cu_1.3Ta₁₀O₂₉ ceramics were fabricated by conventional solid-state solution processes. Then, their dielectric and piezoelectric properties were investigated. Sinterability of all samples was enhanced because K_5.4Cu_1.3Ta₁₀O₂₉ (abbreviated as KCT) acted as sintering aids. As the result of XRD, phase structure showed orthorhombic symmetry when KCT ≤ 0.2 mol%. Whereas, the phase structure changed from orthorhombic symmetry to tetragonal symmetry when KCT?≥?0.4 mol%. The results suggest that the orthorhombic and tetragonal phases co-exist in the composition ceramics with 0.2 mol% < KCT < 0.4 mol% at room temperature. The effects of the addition of KCT on the dielectric and piezoelectric properties were investigated. As the result, excellent properties of density=4.81[g/cm³], electromechanical coupling factor (k_p)=0.48 and piezoelectric constant(d₃₃)=252[pC/N] were obtained in the composition ceramics with 0.4 mol%KCT.     

Phase Transformation and Temperature Dependence of Relative Permittivity for A-site Substituted Sr(Y0.5Ta0.5)O3Perovskites

A-site cation substitution with Ba²⁺ or Ca²⁺ ions was made for the ordered complex perovskite Sr(Y_0.5Ta_0.5)O₃ to correlate the structure evolution and the change in the temperature coefficient of relative permittivity (TC_r) with the cation substitution. The crystal symmetry of the solid solutions at room temperature changed as monoclinic rhombohedral cubic with the corresponding A-site cation species of Ca²⁺ Sr²⁺ Ba²⁺. On heating, the rhombohedral phase of Sr(Y_0.5Ta_0.5)O₃ was firstly transformed to the cubic phase with a lower symmetry (F43m or F432) at 1000°C and further to the ideal cubic phase (Fm3m) at 1300°C. The similar phase transformation behavior at elevated temperatures was observed for each of the Ba²⁺-substituted perovskites, both the phase transformation temperatures being lowered with increasing Ba²⁺ content. TC_r of the ordered perovskites monotonously increased over the temperature range where the phase transformation regions from monoclinic to rhombohedral or from rhombohedral to cubic (F43m or F432) occurred. On the other hand, a subtle symmetry change in the cubic phase from F43m (F432) to Fm3m caused a remarkable change in the TC_r from positive to negative at the transformation temperature. These results suggested that the positive TC_r is essentially correlated to the relaxation of the tilting of the BO₆ octahedra in the perovskite structure on heating.