Ferroelectric and electromechanical performance of diverse engineered states of Mn-doped 0.75Pb(Mg1/3Nb2/3)O3-0.25PbTiO3 ceramics

The materials processing history has a great influence on their properties and finally determines their application effect. In this paper, the ferroelectric, polarization-switching current, and strain properties of Mn-doped 0.75Pb(Mg_1/3Nb_2/3)O₃-0.25PbTiO₃ ceramics were studied in fresh state, aged state, and poled state, respectively. Compared with the symmetric polarization-electric-field (P-E) hysteresis loops, current-density-electric-field (J-E) curves, and bipolar electric-field-induced strain (S-E) curves in fresh state samples, asymmetric P-E loops, J-E curves, and bipolar S-E curves were obtained in poled state samples. Well-aged-state samples exhibit double hysteresis P-E loop, four peaks J-E curves, and symmetric S-E curves without negative strain. The symmetry-conforming short-range order (SC-SRO) principle of point defects and internal electric field E_i is employed to clarify the different phenomenon of three states. Results indicated that randomly oriented defect polarization P_D in aged samples can reverse the spontaneous polarization P_S back and result in the double hysteresis P-E loop and four peaks J-E curves. The oriented P_D and resulting E_i in poled-state samples will lead to the asymmetric loops and strain memory effect.     

High dielectric permittivity and electrostrictive strain in a wide temperature range in relaxor ferroelectric (1-x)[Pb(Mg1/3Nb2/3)O3-PbTiO3]-xBa(Zn1/3Nb2/3)O3 solid solutions

High electric field-induced strain with ultralow hysteresis, which is often generated based on electrostrictive effects in ferroelectric materials, is highly desired due to its potential applications in high-precision displacement actuators. In this paper, (1-x)[Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃]-xBa(Zn_1/3Nb_2/3)O₃ [(1-x)(PMN-PT)-xBZN] ceramics were fabricated by a solid-state reaction method. The effect of Ba(Zn_1/3Nb_2/3)O₃ (BZN) content on dielectric and electrostrictive properties in relaxor ferroelectric PMN-PT solid solutions was investigated in detail by dielectric spectra, polarization-electric field (P-E) hysteresis loops and strain-electric field (S-E) curves. With an increasing BZN content, the temperature stability of the dielectric permittivity of (1-x)(PMN-PT)-xBZN is improved due to the formation of two coexistent phases. A high electrostrictive strain (~0.17% at 60?kV/cm) with an ultralow hysteresis (<10%) characteristic is obtained in a composition where x?=?0.1725. The strain versus polarization (S-P) curves measured from 30?°C to 130?°C can be well fitted based on a quadratic relation, suggesting the dominating role of the electrostrictive effect. The longitudinal electrostrictive coefficient Q₃₃ for this system ranges from 0.0254?m⁴/C² to 0.0318?m⁴/C². Our results suggest that (1-x)(PMN-PT)-xBZN ferroelectric ceramics are potential candidates for applications in capacitors and high-precision displacement actuators.     

Structural and electrical properties of 0.56Pb(Ni1/3Nb2/3)O3-0.10Pb(Zn1/3Nb2/3)O3-0.34PbTiO3 ceramics prepared by different ceramic processings

The ternary system of 0.56Pb(Ni_1/3Nb_2/3)O₃-0.10Pb(Zn_1/3Nb_2/3)O₃-0.34PbTiO₃ (0.56PNN-0.10PZN-0.34PT) ceramics were prepared by conventional solid-state reaction method via straight mixed oxide method, columbite precursor method and B-site oxide mixing route. X-ray diffraction (XRD) measurement demonstrated that both the tetragonal and rhombohedral phases coexist in the B-site oxide mixing route prepared ceramics accompanied by the largest content of perovskite phase of 95.18%. The 0.56PNN-0.10PZN-0.34PT ceramics prepared by the straight mixed oxide method and the B-site oxide mixing route exhibit rather homogeneous microstructure. As a comparison, in the columbite precursor method prepared ceramics nebulous granules and octahedral or other polyhedral morphology grains are observed. All the sintered ceramics exhibit diffused ferroelectric phase transition where the dielectric response peaks are broad, diffused and strongly frequency dependent. However, the temperature of dielectric maximum (T_m) increases greatly from 398.0 K of the 0.56PNN-0.10PZN-0.34PT ceramics prepared by the B-site oxide mixing route to 423.3 K of the ones prepared by the straight mixed oxide method. Saturated and symmetric P-E hysteresis loops are observed in all the sintered ceramics, where the B-site oxide mixing route prepared ceramics exhibit large value of remanent polarization (P_r) of 17.13 μC/cm² and the least value of coercive field (E_c) of 11.99 kV/cm. Piezoelectric constant (d₃₃) exhibits the largest value of 449 pC/N for the ceramics prepared by the B-site oxide mixing route. Such results are related to the phase composition, density and porosity of the ceramics.     

Correlations between the crystal structure and microwave dielectric properties in Ce2[Zr1-xMx]3(MoO4)9 (M = Mn1/3Nb2/3, Mn1/3Ta2/3) solid-solution ceramics

Ce₂[Zr_1-xM_x]₃(MoO₄)₉ (M = Mn_1/3Nb_2/3, Mn_1/3Ta_2/3; x = 0.02, 0.04, 0.06, 0.08 and 0.10) (abbreviated as CZ_1-xN_x and CZ_1-xT_x) ceramics were prepared through the solid-state reaction method. Effects of (Mn_1/3Nb_2/3)⁴⁺ and (Mn_1/3Ta_2/3)⁴⁺ ions on the sintering characteristics, crystal structures, microwave dielectric properties and infrared vibrational modes were studied in detail. X-ray diffraction (XRD) results reveal the formation of solid solutions for all components. Based on the chemical bond theory and Rietveld refinement, intrinsic structure parameters including the polarizability (P), the packing fraction (P.F.) and the octahedral distortion (Δ_octa.), and bond parameters including the lattice energy (U), bond energy (E) and thermal expansion coefficient (α) were calculated. Interestingly, the Ce–O bond plays a major role in the bond ionicity (f_i), while Mo–O bond dominates the contributions in the lattice energy (U), bond energy (E) and thermal expansion coefficient (α). In addition, these parameters are used to explain the variations of the microwave dielectric properties of ceramics either changing the doping contents or replacing different ions at x = 0.06. Furthermore, far infrared (FIR) spectra uncover that the phonon modes provide the major polarization contribution of 68.59% in the CZ_0.9T_0.1 ceramic, implying that the main contribution to ε_r stems from the ionic polarization instead of the electronic polarization. Typically, the optimum microwave dielectric properties are achieved for the CZ_0.9N_0.1 and CZ_0.9T_0.1 ceramics with ε_r = 10.76, Q × f = 85,893 GHz (at 9.52 GHz), τ_f = −14.83 ppm °C⁻¹ and ε_r = 10.72, Q × f = 87,355 GHz (at 9.81 GHz) and τ_f = −8.68 ppm °C⁻¹, respectively. Notably, the CZ_0.9T_0.1 ceramic has a markedly increased Q × f while maintaining a good τ_f = −8.68 ppm °C⁻¹ and a low sintering temperature of 700 °C.     

Low temperature synthesis and dielectric, ferroelectric and piezoelectric study of microwave sintered BaTiO3 ceramics

Barium titanate (BaTiO₃/BT) ferroelectric system was synthesized in single perovskite phase at low temperature by using powders derived from modified solid state reaction (MSSR) and sintered by microwave (MW) processing routes. Conventional calcination temperature was optimized at 900 °C for 4 h. MW sintering of BT samples was carried out at 1100 °C for 30 min to get dense (98% density) ceramics. Room temperature (RT) dielectric constant (?_r) and dielectric loss (tan δ) at 1 kHz frequency of MW sintered BT samples was found to be ∼2500 and 0.03, respectively. Saturated polarization vs. electric field (P-E) loops with remnant polarization (P_r) ∼6 μC/cm² and coercive field (E_c) ∼1.45 kV/cm confirmed the ferroelectric nature of MW sintered BT samples. Piezoelectric coefficient from strain vs. electric field (S-E) loops study was found to be 335 pm/V.     

Composition dependent structure,dielectric and energy storage properties of Pb(Tm1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3 antiferroelectric ceramics

In order to stabilize the perovskite structure and improve the storage energy density (U) of Pb(Tm_1/2Nb_1/2)O₃ (PTmN) based materials, Pb(Mg_1/3Nb_2/3)O₃ (PMN) was introduced into PTmN to form binary (1-x)PTmN-xPMN solid solution ceramics. The XRD patterns show that all the compositions belong to orthorhombic phase with space group Pbnm. The Curie temperature (T_C) gradually decreases while the dielectric constant (ε') increases for (1-x)PTmN-xPMN with increasing PMN content. The ε' of each composition above T_C obeys the Curie-Weiss law. The appearance double hysteresis loop confirms the antiferroelectric nature of (1-x)PTmN-xPMN (x = 0.02–0.18) ceramics. With the increase of PMN concentration, the maximum polarization slowly increases from 8.58 μC/cm² to 29.5 μC/cm² while the threshold electric field (E_A-F) gradually declines from 290 kV/cm to 120 kV/cm. The maximum of U (3.12 J/cm³) is obtained in 0.92PTmN-0.08PMN ceramic with moderate E_A-F = 220 kV/cm, which makes (1-x)PTmN-xPMN ceramics safe in practical application.     

Investigation of ternary system Pb(Sn,Ti)O3-Pb(Mg1/3Nb2/3)O3 with morphotropic phase boundary compositions

(1 − x)Pb(Sn_1−yTi_y)O₃-xPb(Mg_1/3Nb_2/3)O₃ (x = 0.1-0.4, y = 0.45-0.65) ternary system was prepared using two-step columbite precursor method. Phase structure of the synthesized ceramics was studied by using X-ray powder diffraction and the morphotropic phase boundary (MPB) curve of the ternary system was confirmed. The isothermal map of Curie temperature (T_C) in the phase diagram was obtained based on the dielectric-temperature measurements. The coercive field E_C and internal bias field E_i were found to increase with increasing PT content, while decrease with increasing PMN content. The optimum properties were achieved in the MPB composition 0.8Pb(Sn_0.45Ti_0.55)O₃-0.2Pb(Mg_1/3Nb_2/3)O₃, with dielectric permittivity ?_r, piezoelectric coefficient d₃₃, planar electromechanical coupling k_p, mechanical quality factor Q_m and T_C of being on the order of 3040, 530pC/N, 55.5%, 320 and 190 °C, respectively, exhibiting potential usage for high power application.     

Temperature‐Dependent Scaling Behavior of Dynamic Hysteresis in Pb(Zr,Ti)O3 Ceramics

The dynamic hysteresis scaling behaviors of Nb‐doped Pb(Zr_0.52Ti_0.48)O₃ ceramics have been investigated as a function of electric field amplitude (E₀) and frequency (f) at different temperatures (T). The loop area <A> of saturated loops is found to follow various power laws as <A> ∝ E₀^0.3065 at fixed f and <A> ∝ f ^0.0120 at fixed E₀. Furthermore, the linear scaling relation <A> = k₃ f^αE₀^β + b₃ is estimated under various temperatures. The exponents α (=0.01) and β (=0.10) are T‐independent, whereas the slopes k₃ and y‐intercepts b₃ are T‐dependent because the increasing temperature in the same phase range only decreases the threshold field of the reversal rather than change the dynamic reversal process.     

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.     

Fabrication and electrical properties of Pb(Co1/3Nb2/3)O3 ceramics

Pb(Co_1/3Nb_2/3)O₃ (PCN) ceramics have been produced by sintering PCN powders synthesized from lead oxide (PbO) and cobalt niobate (CoNb₂O₆) with an effective method developed for minimizing the level of PbO loss during sintering. Attention has been focused on relationships between sintering conditions, phase formation, density, microstructural development, dielectric and ferroelectric properties of the sintered ceramics. From X-ray diffraction analysis, the optimum sintering temperature for the high purity PCN phase was found at approximately 1050 and 1100 °C. The densities of sintered PCN ceramics increased with increasing sintering temperature. However, it is also observed that at very high temperature the density began to decrease. PCN ceramic sintered at 1050 °C has small grain size with variation in grain shape. There is insignificant change of dielectric properties with sintering temperature. The P–E hysteresis loops observed at −70 °C are of slim-loop type with small remanent polarization values, which confirmed relaxor ferroelectric behavior of PCN ceramics.     

Large electric-field-induced strain in B-site complex-ion (Fe0.5Nb0.5)4+-doped Bi1/2 (Na0.82K0.12)1/2TiO3 lead-free piezoceramics

In order to obtain a new system of (Bi_1/2Na_1/2)TiO₃ (BNT) based lead-free incipient piezoceramics with large strain for practical applications of actuators, we investigated the effect of B-site complex-ion (Fe_0.5Nb_0.5)⁴⁺ (FN)-doped Bi_1/2 (Na_0.82K_0.12)_1/2TiO₃ ceramics on the phase structure, dielectric, ferroelectric, piezoelectric and electric-field-induced strain properties. All samples exhibited single perovskite phase with pseudocubic symmetry. The room temperature electric-field-induced polarization (P-E) and strain (S-E) hysteresis loops indirectly illustrated ferroelectric-to-relaxor (FE-RE) phase transition. The increasing content of FN doping decreased the FE-RE phase transition temperature, T_F-R to below room temperature and induced the reversible FE-RE phase transition, giving rise to a large strain of 0.462% with a normalized strain, d^*₃₃ of 660 pm/V at a critical composition of x = 5. A fluctuation of the dielectric curve for BNKT-5 mol% FN ceramics in the spectra around 80 °C before and after polarization suggested that the large strain response can be induced via delicate mixing of the FE and RE phase.     

Effects of melt structure on non‐isothermal crystallization behavior of isotactic polypropylene nucleated with α/β compounded nucleating agents

In this study, the effects of melt structure (tuned by controlling the fusion temperature T_f) on non‐isothermal crystallization and subsequent melting behaviors of isotactic polypropylene (iPP) nucleated with α/β compounded nucleating agents (α/β‐CNAs) have been further investigated. The results show that under all cooling rates studied (2–40°C/min), the crystallization temperature on cooling curves increased gradually with decrease of T_f, meanwhile, when T_f was in temperature range of 166°C–179°C where ordered structures survived in the melt (defined as Region II), crystallization activation energy ΔE was found to be evidently lower compared with that when T_f > 179°C or T_f < 166°C. The results of subsequent heating showed that occurrence of Ordered Structure Effect can be observed at all the cooling rates studied; the location of the Region II was constant when cooling rate varied; Low cooling rate encouraged formation of more β‐phase triggered by ordered structure. Moreover, the role of ordered structure on β‐α recrystallization was comparatively studied by tuning the end temperature of recooling (T_end) after held at T_f, and it was found that ordered structure encouraged the formation of β‐phase with high thermal stability at low temperature part of Region II, while enhanced the β‐crystal with relatively low thermal stability at high temperature part of Region II. POLYM. ENG. SCI., 57:989–997, 2017. © 2016 Society of Plastics Engineers     

Field and Frequency Dependence of the Dynamic Hysteresis in Lead Zirconate Titanate Solid Solutions

Dynamic hysteresis of Nb‐doped Pb(Zr_1?xTi_x)O₃ (PZT, 0.20 ≤ x ≤ 0.60) ceramics were studied systemically at different field (E) and frequency (f). The hysteresis loops were strongly dependent on E and f. The measured coercive fields (E_c0) were far lower than the calculated values based on the Landau–Ginzburg theory, and increased dramatically from the rhombohedral phase to the tetragonal phase while had less variation with composition in the same phase. With increasing E or f for each composition, three types of loops were observed: linear, minor, and saturated loops. The cross fields (E₀), cross polarizations (P₀), and hysteresis areas (<A>) showed different variation regularities with f. Similar varying curves were observed for all PZT ceramic samples by normalizing E₀, P₀, and <A> with E/E_c0, which indicated the same polarization switching for different domain structures. Further analyses revealed that the switching processes can be divided into three stages: space charge polarization, domain switching, and steady state. The first and second stage occurred at ~0.5 and ~1.5 E/E_c0, respectively. These results would be very helpful to further understand the polarization switching of ferroelectric ceramics.     

The influence of axial pressure on relaxor properties of BaBi2Nb2O9 ceramics

On the basis of our studies it results that dielectric properties of BaBi₂Nb₂O₉ ceramics are sensitive to axial pressure applied. The pressure causes an increase of dispersion in the real part of dielectric permittivity ?′(T,f) and a rise in the temperature T_m at which the maximum in ?′(T,f) dependence occurs. The applied pressure induces in the ?′(T) dependence an additional step-like anomaly, which appears at the temperature T_A < T_m. The applied pressure shifts both T_m and T_A at the same rate, i.e. dT_A/dX = dT_m/dX = +14 °C/kbar at high axial pressure range, above the threshold pressure X_thresh. The Vogel–Fulcher relationship is employed to determine the axial pressure influence on relaxor properties of BBN ceramics. The simulated order parameter q takes non-zero values below Burn‘s temperature T_B, where the polar clusters appear on cooling. For pressures higher than 0.8 kbar, the T_B changes at the rate dT_B/dX = −200 °C/kbar. The decrease in the difference between Burn's T_B and the freezing T_f temperatures induced by the applied axial pressure is observed. This could be ascribed to the narrowing of temperature range of relaxor behavior.     

The electrocaloric effect of Ba1-xLaxTi0.9Sn0.1O3 ceramics with excellent temperature stability near room temperature

The Ba_1-xLa_xTi_0.9Sn_0.1O₃ ceramics (x = 0, 0.006, 0.007, 0.008) were prepared by the traditional solid-state reaction method. The influence of La³⁺ on the phase, dielectric properties, ferroelectric properties, and electrocaloric effect (ECE) was analyzed in detail. The results of refinement show that all ceramics are multiphase coexistence at room temperature, including the cubic phase, the tetragonal phase, and the orthogonal phase. With the increase of La³⁺, the polar phases decrease but the non-polar phase increases, which is the main reason for the decline in adiabatic temperature change (ΔT). The analysis of dielectric properties and ferroelectric properties demonstrate that the diffuse phase transition is strengthened by introducing La³⁺. It also means that polar nanoregions (PNRs) might be formed. Therefore, the temperature stability of the Ba_1-xLa_xTi_0.9Sn_0.1O₃ ceramics in a wide temperature range near room temperature is improved. Simultaneously, the PNRs provide additional entropy to improve ECE. A higher ΔT = 0.88 K is obtained under 60 kV/cm for x = 0.007, which also possesses excellent temperature stability in the temperature range of 298 K–378 K. The doping of La³⁺ also improves the electric field threshold of the electrocaloric strength (ΔT_max/ΔE) and stabilizes the ΔT_max/ΔE under a higher electric field, which is conducive to improving ECE under a higher electric field and providing another possible solution for promoting the practical application of ECE.     

Correlation between structural,ferroelectric, piezoelectric and dielectric properties of Ba0.7Ca0.3TiO3-xBaTi0.8Zr0.2O3 (x = 0.45, 0.55) ceramics

We report on the correlation between structural, ferroelectric, piezoelectric and dielectric properties of the (1-x)Ba_0.7Ca_0.3TiO₃-xBaTi_0.8Zr_0.2O₃ (x?=?0.45, 0.55; abbreviated as 55BCT30 and 45BCT30) ceramics close to morphotropic phase boundary (MPB) region. The 55BCT30 and 45BCT30 ceramics were synthesized by the standard, high-temperature solid state ceramic method. X-ray diffraction (XRD) along with Rietveld refinement indicate that the 55BCT30 ceramics exhibit rhombohedral (R, space group R3m), orthorhombic (O, space group Amm2) and tetragonal (T, space group P4mm) phases while 45BCT30 ceramics exhibit only T and O phases. The temperature dependent Raman spectroscopy measurements confirm the structure and phase transformations observed from XRD. All the ceramics are chemically homogeneous and exhibit a dense microstructure with a grain size of 5–7?µm. The presence of polarization-electric field and strain-electric field hysteresis loops confirm the ferroelectric and piezoelectric nature of the ceramics. The polarization current density-electric field curves show the presence of two sharp peaks in opposite directions indicating the presence of two stable states with opposite polarity. Higher values of direct piezoelectric coefficient (d₃₃ ~?360 pC/N) were observed due to the existence of low energy barrier near MPB region and polymorphism. The 55BCT30 ceramics exhibit a higher value of electrostrictive coefficient (Q₃₃ ~?0.1339?m⁴/C²) compared to the well-known lead-based materials. The temperature dependent dielectric measurements indicate the O to T phase transition for 55BCT30 and 45BCT30. These ceramics exhibit a Curie temperature (T_c) of 380?K with a dielectric maximum of ~ 4500.     

Enhancement in dielectric and ferroelectric properties of lead free Bi0.5(Na0.5K0.5)0.5TiO3 ceramics by Sb-doping

Lead free piezoelectric Bi_0.5(Na_0.5K_0.5)_0.5TiO₃ (pure and 1 wt.%, 2 wt.%, 4 wt.% Sb-doped) ceramics were synthesized away from its MPB. The crystalline nature of the BNKT ceramic was studied by XRD and SEM. Depolarization temperature (T_d) and transition temperature (T_c) were observed through phase transitions in dielectric studies which were found to increase after Sb-doping, thus increasing its usable temperature range. In the study of relaxation behavior, the activation energy for relaxation was found to be 0.33, 0.43, 0.57 and 0.56 eV for pure and Sb-doped samples, respectively. All samples were found to exhibit normal Curie-Weiss law above their T_c. Doping of Sb was found to restrain the diffused character of the pure sample. In P-E loop, Sb-doping was found to increase the ferroelectric properties.Pure and Sb-doped BNKT ceramics exhibited high values of piezoelectric charge coefficient (d₃₃) as 115, 121, 129 and 100 pC/N, respectively.     

Ferro-/pyroelectric response of 0.57BF-0.31PMN-0.12PT ternary ceramic far away from morphotropic phase boundaries

A ternary BiFeO₃-Pb(Mg_1/3Nb_2/3)O₃-PbTiO₃ (BF-PMN-PT) solid solution with a composition far away from morphotropic phase boundaries (MPB) has been synthesized by solid-state reaction method. XRD analysis revealed a pure perovskite phase without any trace of pyrochlore phase. The system exhibited a broad phase transition with transition temperature T_c ~ 285 °C. The hysteresis loop of the ceramics displayed high remanent polarization (Pr ~ 41.23 μC/cm²) and coercive field (E_c ~ 35.41 kV/cm). The true-remanent polarization after removing the non-remanent components was evaluated by remanent hysteresis and PUND tasks, which revealed the actual usable polarization component for memory devices. Time-dependent compensated plots confirmed the resistive-leakage free characteristic of the BF-PMN-PT ceramics which makes them useful for application in devices like actuators where the electric field is switched at different rates. Fatigue test showed the ferroelectric parameters (switching and non-switching polarization values) do not vary over 10⁷ cycles which is important especially in electromechanical transducers and memory devices. A large piezoelectric charge coefficient (d₃₃ ~ 115 pC/N) was observed for the investigated ceramics.     

The kinetic study of the curing reaction of mono- and di-epoxides obtained during the reaction of divinylbenzene and hydrogen peroxide with acid anhydrides

In this paper, the non-isothermal differential scanning calorimetry (DSC) was employed to investigate the cure process and to determine the kinetic parameters of the curing reactions of mono- and di-epoxides with maleic and glutaric anhydrides. The epoxides were obtained during the epoxidation process of commercially available divinylbenzene by using 60% hydrogen peroxide as the oxidant in the presence of organic solvents and magnesium oxide as the catalyst. It was found that the cure process of epoxides with maleic anhydride was described through higher values of enthalpy of polymerization (ΔH_R) and lower temperatures of the cure initiation (T_onset), the peak maximum temperature (T_max) and the final cure temperature (T_end). It can be considered to accelerate the rate of reaction and lead to an excellent network structure when maleic anhydride was used as curing agent. The kinetic analysis was firstly computed using a model free-estimation of the activation energy (Friedman, Ozawa-Flynn-Wall methods) and then the multivariate non-linear regression with a 6th degree Runge-Kutta process in a modified Marquardt procedure was employed to calculate the corresponding kinetic parameters (E_i, n_i, A_i) using the nth-order reaction f(α). The unbranched three-step process of the nth-order reaction f(α) for each step was the best to describe the cure process of mono- and di-epoxide with acid anhydrides. The determined values of the activation energies were in the range 64.7-105.2 kJ/mol for epoxides/glutaric anhydride system and 64.7-82.7 kJ/mol when maleic anhydride was used as hardening agent.     

Preparation,structure, and electric properties of the Pb(Zn1/3Nb2/3)O3–Pb(Yb1/2Nb1/2)O3–PbTiO3 ternary ferroelectric system ceramics near the morphotropic phase boundary

Ceramics of the xPb(Zn_1/3Nb_2/3)O₃–(1 ? x ? y)Pb(Yb_1/2Nb_1/2)O₃–yPbTiO₃ (PZN–PYN–PT) ternary system were synthesized using a modified two-step columbite precursor method which can effectively suppress the pyrochlore phase. A morphotropic phase boundary (MPB) region, separating tetragonal and rhombohedral phases in the ternary systems has been determined. The electric properties of the compositions near MPB region were investigated. Dielectric response exhibits relaxor-like characteristics with broad dielectric peaks and dispersive dielectric behavior with respect to frequency and temperature. The phase diagram of the 0.45PZN–(0.55 ? y)PYN–yPT pseudo-binary system in the composition range of 0.15 < y < 0.35 was established based on dielectric measurements. The optimal properties were achieved in the MPB composition of 0.52PZN–0.21PYN–0.27PT with piezoelectric coefficient d₃₃, dielectric permittivity ε′, planar electromechanical coupling k_p, dielectric loss tan δ, coercive field E_c, remnant polarization P_r, and T_C being of 558 pC/N, 2065, 62%, 0.2%, 19.88 kV/cm, 31.44 μC/cm² and 259.5 °C, respectively, showing potential usage in high-temperature electromechanical applications.