Structure,electrical, and thermal expansion properties of PZnTe–PZT ternary system piezoelectric ceramics

xPb(Zn_0.5Te_0.5)O₃–(1?x)Pb(Zr_0.5Ti_0.5)O₃ (PZnTe–PZT) ceramics were prepared by the solid‐state reaction method. The phase structure, microstructure, ferroelectric and dielectric properties and thermal expansion properties were systematically investigated. X‐ray diffraction analysis showed the morphotropic phase boundary (MPB) existed at the composition of x = 0.08, which was the coexistence of the rhombohedral phase and the tetragonal phase. The grain size of ceramics decreased rapidly from 10‐20 μm to 1‐3 μm when the PZnTe was added in. The PZnTe–PZT ceramics at the MPB composition showed the largest high field effective piezoelectric coefficient and the lowest strain hysteresis H. The dielectric permittivity and phase transition temperature exhibited strongly compositional dependence. A good linear relation was shown in T_m temperature vs x content and a DPT behavior was found in xPZnTe–(1?x)PZT (x = 0.02‐0.08). The thermal expansion properties showed a low thermal expansion coefficient in the low temperature while a high thermal expansion coefficient in the high temperature. Besides, the thermal expansion curve also showed the characteristic of DPT in PZnTe–PZT ceramics.     

The Composition and Temperature‐Dependent Structure Evolution and Large Strain Response in (1−x)(Bi0.5Na0.5)TiO3−xBa(Al0.5Ta0.5)O3 Ceramics

The (1?x) (Bi_0.5Na_0.5)TiO₃?xBa(Al_0.5Ta_0.5)O₃((1?x)BNT‐xBAT) lead‐free piezoceramics was fabricated using a conventional solid‐state reaction method. The temperature and composition‐dependent strain behavior, dielectric, ferroelectric (FE), piezoelectric, and pyroelectric properties have been systematically investigated to develop lead‐free piezoelectric materials with large strain response for actuator application. As the BAT content increased, the FE order is disrupted resulting in a degradation of the remanent polarization, coercive field, and the depolarization temperature (T_d). A large strain of 0.36% with normalized strain d₃₃* = 448pm/V was obtained for the optimum composition x = 0.045 at room temperature. The bipolar and unipolar strains for the compositions x = 0.035 and x = 0.04 reach almost identical maximum values when the temperature is in the vicinity of their respective depolarization temperature (T_d). The Raman‐spectra analysis, macroscopic properties, thermal depolarization results, and temperature‐dependent relationships of both polarization and strain demonstrated that the origin of the large strain response for this investigated system is attributed to a field‐induced relaxor to FE phase transformation.     

Origin of ferroelectric P‐E loop in cubic compositions and structure of poled (1‐x)Bi(Mg1/2Zr1/2)O3‐xPbTiO3 piezoceramics

Structural analysis of electrically poled samples of polycrystalline, (1‐x)Bi(Mg_1/2Zr_1/2)O₃‐xPbTiO₃ piezoceramics across morphotropic phase boundary reveals electric field‐induced cubic to tetragonal phase transition and significant domain reorientation in tetragonal and two‐phase compositions. The c‐axis domain elongation is observed for tetragonal compositions after poling. The morphotropic phase boundary composition, having coexisting cubic and tetragonal phases in the unpoled state, exhibits alteration in relative proportion of the two phases, in addition to domain extension and reorientation along c‐axis. For the morphotropic phase boundary composition, the tetragonality (c/a) is enhanced with significantly large c‐axis strain (~0.92%) in tetragonal phase after poling. Origin of ferroelectric P‐E loop in cubic compositions is linked with the electric field‐induced phase transition.     

Temperature dependence of field‐responsive mechanisms in lead zirconate titanate

An electric field loading stage was designed for use in a laboratory diffractometer that enables in situ investigations of the temperature dependence in the field response mechanisms of ferroelectric materials. The stage was demonstrated by measuring PbZr_1?xTi_xO₃ (PZT) based materials—a commercially available PZT and a 1% Nb‐doped PbZr_0.56Ti_0.44O₃ (PZT 56/44)—over a temperature range of 25°C to 250°C. The degree of non‐180° domain alignment (η₀₀₂) of the PZT as a function of temperature was quantified. η₀₀₂ of the commercially available PZT increases exponentially with temperature, and was analyzed as a thermally activated process as described by the Arrhenius law. The activation energy for thermally activated domain wall depinning process in PZT was found to be 0.47 eV. Additionally, a field‐induced rhombohedral to tetragonal phase transition was observed 5°C below the rhombohedral‐tetragonal transition in PZT 56/44 ceramic. The field‐induced tetragonal phase fraction was increased 41.8% after electrical cycling. A large amount of domain switching (η₀₀₂=0.45 at 1.75 kV/mm) was observed in the induced tetragonal phase.     

A novel room-temperature synthesis technique for producing high-density Ba1-xSrxTiO3 and PbZryTi1-yO3 composites

The ability to synthesize capacitors at room temperature has great cost-saving potential compared to energy-intensive conventional sintering techniques which involve extended periods at high temperature. In this work, several compositions in the Ba_1-xSr_xTiO₃ (BST) and PbZr_yTi_1-yO₃ (PZT) series were synthesized conventionally and densified via a room-temperature fabrication (RTF) process. The BST and PZT particles were coated and mixed with an aqueous solution of Li₂MoO₄ (LMO), which acts as a binder. The novel techniques presented in this work, including the usage of a vacuum-assisted pellet die and a bath sonicator in combination, were designed to increase the density of the resultant pellets. Relative densities as high as 96.1% were achieved for BST x = 0.5, 96.9% for BST x = 0.45%, and 95.1% for PZT y = 0.5 RTF pellets using LMO as a binder. These composites are the densest room-temperature fabricated composites reported to date. In addition, the effect of mixing particles with two different size distributions was analyzed for composites produced with PZT particles. The dielectric properties of all these dense RTF composites were measured at temperatures ranging from 150 °C to ? 60 ℃ and compared with those of conventionally sintered electroceramics with the same compositions.     

Effect of ZnO nano-particulate modification on properties of PZT–BLT ceramics

This research was conducted to study the effect of ZnO nano-particulate modification on properties of Pb(Zr_0.52Ti_0.48)O₃ (PZT)–(Bi_3.25La_0.75)Ti₃O₁₂ (BLT) ceramics prepared by a mixed-oxide solid-state sintering method. ZnO nano-particulate was added into PZT–BLT ceramics to obtain PZT–BLT/xZnO (x = 0, 0.1, 0.5 and 1.0 wt%). The PZT–BLT/xZnO ceramics were investigated in terms of phase, microstructure, physical, electrical, and mechanical properties. Tetragonality of PZT–BLT crystal structure tended to increase with increasing ZnO content. ZnO addition obviously increased the density of PZT–BLT ceramics while the grain size slightly decreased. Intergranular fracture mode was observed for pure PZT–BLT ceramic while the samples contained ZnO nano-particles showed a mixed-mode inter-/trans-granular fracture. Addition of ZnO also affected hardness and fracture toughness values. Addition of ZnO nano-particulate into PZT–BLT ceramics was found to improve room temperature dielectric constant but did not have a significant effect on ferroelectric properties. These observed results were expected to be caused by the behaviors similar to a donor-doped system.     

High Power Performance of Manganese‐Doped BNT‐Based Pb‐Free Piezoelectric Ceramics

Electromechanical properties and high power characteristics of Pb‐free hard piezoelectric ceramics in the (BiNa_0.88K_0.08Li_0.04)_0.5 (Ti_1?xMn_x)O₃ (x = 0, 0.014, 0.015, and 0.016) system were studied. Mn doping resulted in a considerable enhancement of mechanical quality factor Q_m and vibration velocity. The lowest mechanical and dielectric losses were achieved in 1.5 mol% Mn‐doped ceramics with a planar Q_m of about 970 and tanδ of 0.89%. The heat dissipation and resonance frequency shift under high drive condition were remarkably suppressed upon Mn doping. The maximum vibration velocity was increased from 0.28 m/s in undoped ceramic to 0.6 m/s in 1.5 mol% Mn‐doped composition. The results of this study revealed that Mn‐doped BNT‐based piezoelectrics exhibited a superior high power performance compared to their lead‐based counterparts such as PZT4 and PZT8 ceramics.     

Investigation on the Electric‐Induced Light Scattering of PLZT Transparent Ceramics

Transparent ceramics of Pb_1?xLa_x(Zr_1?yTi_y)_1?x/4O₃ (PLZT) were fabricated by the two‐stage sintering method. The electric‐induced light scattering phenomenon for two compositions of PLZT ceramics was investigated. It was found that the composition with relatively bigger ferroelectric domains exhibits a relatively smaller light scattering driving field, but simultaneously a lower transparency in the original state. The dielectric properties, ferroelectric hysteresis loops, and ferroelectric domain structures of the two compositions were studied which are consistent with the electric‐induced light scattering results.     

High permittivity (1−x)Bi1/2Na1/2TiO3‐xPbMg1/3Nb2/3O3 ceramics for high‐temperature‐stable capacitors

(1?x)Bi_1/2Na_1/2TiO₃‐xPbMg_1/3Nb_2/3O₃[(1?x)BNT‐xPMN] ceramics have been fabricated via a conventional solid‐state method for compositions x ≤ 0.3. The microstructure, phase structure, ferroelectric, and dielectric properties of ceramics were systematically studied as high‐temperature capacitor materials. XRD pattern certified perovskite phase with no secondary phase in all compositions. As PMN concentration increased, the phase of (1?x)BNT‐xPMN ceramics transformed from ferroelectric to relaxor gradually at room temperature, with prominent enhancement of dielectric temperature stability. For the composition x = 0.2, the temperature coefficient of capacitance (TCC) was <15% in a wide temperature range from 56 to 350°C with high relative permittivity (>3300) and low dielectric loss (<0.02) at 150°C, which indicated promising future for (1?x)BNT‐xPMN system as high‐temperature stable capacitor materials.     

Piezoelectric Properties of a Pioneering 3‐1 Type PZT/Epoxy Composites Based on Freeze‐Casting Processing

Lead zirconate titanate (PbZr_1 ? xTi_xO₃, PZT)/epoxy composites with one‐ dimensional epoxy in PZT matrix (called 3‐1 type piezocomposites) have been fabricated by tert‐butyl alcohol (TBA)‐based directional freeze casting of PZT matrix and afterward infiltration of epoxy. The composites with PZT volume fraction ranging from 0.36 to 0.69 were obtained by adjusting initial solid loading in freeze‐casting slurry. The effect of poling voltage on piezoelectric properties of the composites was studied for various volume fraction of PZT phase. With the increasing of PZT volume fraction, relative permittivity (ε_r) increased linearly and piezoelectric coefficient (d₃₃ and d₃₁) increased step by step. The resultant composites with 0.57 PZT volume fraction possessed the highest hydrostatic piezoelectric strain coefficient (d_h) value (184 pC/N), voltage coefficient (g_h) value (13.6 × 10^?3 V/m Pa), and hydrostatic figure of merit (HFOM) value (2168 × 10^?15 Pa^?1).     

Structures and Properties of Pb(Zr0.5Ti0.5)O3−Pb(Zn1/3Nb2/3)O3− Pb(Ni1/3Nb2/3)O3 Ceramics for Energy Harvesting Devices

Piezoelectric ceramics with large energy density coefficient d₃₃·g₃₃ value have been found suitable for piezoelectric energy harvesting applications. In this study, the phase structures and piezoelectric properties of xPb(Zr_0.5Ti_0.5)O₃?yPb(Zn_1/3Nb_2/3)O₃?(1?x?y)Pb(Ni_1/3Nb_2/3)O₃ (xPZT?yPZN?(1?x?y)PNN) ceramic were investigated with systematically varying PZN and PNN components. The ternary phase diagram of PZT?PZN?PNN system was illustrated and the composition region of morphotropic phase boundary (MPB) was determined. Piezoelectric and dielectric measurements verify that the materials in MPB region all present large d₃₃ and d₃₃·g₃₃ values. In particular, very high d₃₃·g₃₃ coefficients of 20162.2 × 10^?15 m²/N and 21026.3 × 10^?15 m²/N are observed from samples 0.75PZT?0.15PZN?0.1PNN and 0.8PZT?0.05PZN?0.15PNN with compositions located on the rhombohedral phase side near MPB because the dielectric coefficient ε₃₃^T/ε₀ decreases faster than the d₃₃ coefficient at this side.     

Crack‐tip toughness of lead‐free (1−x)(Na1/2Bi1/2)TiO3–xBaTiO3 piezoceramics

Crack opening displacements were evaluated on semi‐elliptical indentation cracks in lead‐free (1?x)(Na_1/2Bi_1/2)TiO₃–xBaTiO₃ piezoceramics and a commercially available PZT ceramic. The observed crack‐tip toughness of NBT‐xBT was found to be substantially higher than for PZT. Two evaluations for the crack opening displacement were demonstrated and contrasted: A more elaborate three‐term‐approximation and a pragmatic utilization of the Irwin parabola.     

Effect of Samarium substitution on dielectric properties of (Pb)(Zr, Ti, Fe, Nb)O3 type ceramic system

The influence of Samarium substitution on the dielectric properties of modified PZT composition with representative formula [Pb_1−xSm_xZr_0.588Ti_0.392Fe_0.01Nb_0.01O₃] system is reported. Samarium (Sm) was varied from 0 to 0.01/FU in the present system in a step of 0.0025. The samples were prepared by the traditional solid state reaction process. XRD analysis showed all the samples to be single phase with tetragonal structure. Dielectric properties were studied in detail as a function of frequency and temperature (from room temperature (RT) 30 to 400 °C). All compositions show phase transition and the transition temperature (T_C) is found to decrease with increase in Sm substitution. Room temperature dielectric constant shows an increasing trend while loss improves with Sm doping.     

Influence of composition on the unipolar electric fatigue of Ba(Zr0.2Ti0.8)O3‐(Ba0.7Ca0.3)TiO3 lead‐free piezoceramics

The lead‐free (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ system is considered as promising candidate for the replacement of lead‐based piezoceramics in actuation applications, during which electric fatigue is a major concern. This issue was addressed in this work, where the unipolar fatigue resistance of three (1?x)Ba(Zr_0.2Ti_0.8)O₃‐x(Ba_0.7Ca_0.3)TiO₃ compositions with different crystallographic structures (rhombohedral, orthorhombic, and tetragonal) was evaluated. Strain asymmetry and development of an internal bias field were observed in all compositions. The decrease in the remanent polarization and the large signal piezoelectric coefficient after 10⁷ unipolar cycles was found to lie between 6%‐12% and 2%‐13%, respectively. The most pronounced fatigue was observed for the orthorhombic composition, which has the largest extrinsic contribution to strain. On the other hand, the best fatigue resistance was observed for the tetragonal composition, which has a predominantly intrinsic strain response. The correlation of fatigue resistance with strain mechanism was corroborated with determination of the Rayleigh parameters and changes in the domain morphology after cycling as confirmed by piezoresponse force microscopy.     

Novel magnetoelectric composites of cobalt iron alloy and barium titanate

Magnetoelectric barium titanate ceramics with embedded cobalt iron alloy particles (Co_1/3Fe_2/3)_x–(BaTiO₃)_(1?x), with x=0.2, 0.4, and 0.6, were prepared by a polyol‐mediated synthesis with subsequent sintering in a reducing forming gas atmosphere. The samples were characterized by XRD and SEM/EDX measurements. The sizes of the Co_1/3Fe_2/3 grains increase with x. Impedance spectroscopy showed a behavior similar to pure BaTiO₃, in particular the occurrence of the ferroelectric‐paraelectric phase transition, and high permittivities for the sample with x=0.6, that is, near the percolation threshold. The samples exhibit soft ferromagnetic properties with large saturation magnetizations of 2.5 μ_B/atom and narrow hystereses. Detailed magnetoelectric investigations revealed a unique DC‐field dependence of α_ME for all three compositions. Most remarkably, the sample with x=0.4 possesses a broad ME hysteresis and an inversion of the sign of α_ME at 5 kOe.     

Electric Field‐Induced Phase Transition Behaviors,Thermal Depolarization,and Enhanced Pyroelectric Properties of (Pb0.97La0.02)(ZrxSn0.89−xTi0.11)O3 Ceramics

(Pb_0.97La_0.02)(Zr_xSn_0.89?xTi_0.11)O₃ (x = 0.60, 0.62, 0.64, 0.66, 0.68, 0.70, 0.72, and 0.74) ceramics with the compositions in tetragonal antiferroelectric (AFE) region, near the morphotropic phase boundary, were prepared by using the conventional solid‐state reaction process. Their electric field‐induced phase transitional behaviors, composition‐ and temperature‐dependent dielectric, depolarization, and pyroelectric properties were investigated systematically. The AFE to ferroelectric phase switching field E_A‐F decreased with increasing x, while depolarization temperature T_d increased with a linear relationship of T_d = 842x‐483. Enhanced pyroelectric coefficient with a value of 12.1 μC/cm²/K was obtained at 88°C for the ceramics with x = 0.68, which was four times larger than the reported values. Composition‐dependent pyroelectric response over 24°C–140°C was realized by changing x from 0.60 to 0.74. The results also suggested that the enhanced pyroelectric response near T_d was accompanied by a release of large P_r, caused by an induced ferroelectric to AFE phase transition.     

Effect of Ga2O3 on Sintering and Phase Stability of Sc2O3‐Doped Tetragonal Zirconia Prepared via Aqueous Solution Route

The effects of the presence of Ga₂O₃ on low‐temperature sintering and the phase stability of 4, 5, and 6 mol% Sc₂O₃‐doped tetragonal zirconia ceramics (4ScSZ, 5ScSZ, and 6ScSZ, respectively) were investigated. A series of zirconia sintered bodies with compositions (ZrO₂)_0.99?x(Sc₂O₃)_x(Ga₂O₃)_0.01, x = 0.04, 0.05, and 0.06 was fabricated by sintering at 1000°C to 1500°C for 1 h using fine powders that were prepared via the combination of homogeneous precipitation method and hydrolysis technique using monoclinic zirconia sols synthesized through the forced hydrolysis of an aqueous solution of zirconium oxychloride at 100°C for 168 h. The presence of 1 mol% Ga₂O₃ was effective in reducing sintering temperature necessary to fabricate dense bodies and enabled to obtain dense sintered bodies via sintering at 1100°C for 1 h. The phase stability, that is, low‐temperature degradation behavior of the resultant zirconia ceramics was determined under hydrothermal condition. The zirconia ceramics codoped with 1 mol% Ga₂O₃ and 6 mol% Sc₂O₃ (1Ga6ScZ) fabricated via sintering at 1300°C for 1 h showed high phase stability without the appearance of monoclinic zirconia phase, that is the tetragonal‐to‐monoclinic phase transformation was not observed in the 1Ga6ScZ after treatment under hydrothermal condition at 150°C for 30 h.     

Characterization of the High‐Temperature Ferroelectric (100−x−y)BiScO3–(x)Bi(Zr0.5Zn0.5)O3–(y)PbTiO3 Perovskite Ternary Solid Solution

Ternary compositions based on Bi(B′B″)O₃–PbTiO₃‐type compounds have been investigated for high‐temperature piezoelectric applications. Compositions in the ternary were chosen to be near the binary morphotropic phase boundary (MPB) composition of BiScO₃–PbTiO₃ (BS–PT). Ternary compositions in (100?x?y)BiScO₃–(x)Bi(Zr_0.5Zn_0.5)O₃–(y)PbTiO₃ [(100?x?y)BS–xBZZ–yPT] have been investigated with x ≤ 7.5. For compositions with x > 10, the Curie temperature (T_C) decreased below 400°C. Dielectric, piezoelectric, and electromechanical properties were characterized as a function of temperature, frequency, and electric field. Small additions of BZZ were shown to increase the electromechanical properties with only a small loss in T_C. The electromechanical properties were temperature stable up to the depoling temperature. The most promising composition exhibited a T_C of 430°C, piezoelectric coefficient (d₃₃) of 520 pC/N, and a planar coupling factor (k_p) of 0.45 that remained unchanged up to depoling temperature at 385°C.     

Strain and Fracture of a Ceramic Based on Lanthanum Chromite

The bending behavior of a ceramic — a lanthanum chromite-based solid solution La_{1 – x} Ca_xCrO₃ (x = 0.025) doped with 5 – 40 wt.% Y₂O₃ — is studied in the temperature range of 20 – 1400°C. At 20°C the composition with 5 – 10 wt.% Y₂O₃ is strained inelastically and exhibits relatively superior mechanical properties in comparison to compositions containing 20 – 40 wt.% Y₂O₃. These compositions are prone to brittle fracture within the linear elastic strain. Based on the strain and fracture characteristics of lanthanum chromite at 20°C, its mechanical behavior at high temperatures is predicted.     

Relaxor Characteristics of the Phase Transformation in (1 − x)BaTiO3–xBi(Zn1/2Ti1/2)O3 Perovskite Ceramics

The single‐phase solid solutions of the (1 ? x)BaTiO₃–(x)Bi(Zn_1/2Ti_1/2)O₃ (BT–BZT) where x = 0.02–0.15 were prepared to investigate dielectric properties. Crystal structure of samples was obtained by using an X‐ray diffraction technique and Raman spectroscopy. For compositions with x ≤ 0.08, the solid solutions exhibited clear tetragonal symmetry and transitioned to pseudocubic symmetry as the content of BZT increased. The dielectric response exhibited a sharp phase transition within the BT‐rich region and the composition 0.92BT–0.08BZT was characterized by the onset of relaxor characteristics. As the concentration of BZT increased, the phase transition exhibited broader and more diffuse behavior. The polarization as a function of electric field (P–E) of these solid solutions also exhibited the same trend. The BT‐rich compositions showed a normal ferroelectric P–E response with a decrease in loop area as the BZT content increased. The composition at x = 0.08 exhibited a pinched hysteresis loop and with further increase in BZT content, the P–E response was characterized by slim loops.