O3 Ceramics Research Articles

Multisource energy harvesting using (Ba,Ca)(Zr,Ti)O3 oscillating under temperature gradient

AbstractThe concept of multisource energy harvesting has attracted attention in order to harvest multiple types of energy in a single material. In this work, Pb‐free (Ba,Ca)(Zr,Ti)O3 (BCZT) ceramics were used to investigate a combination of piezoelectric and pyroelectric energy harvesting behavior. The temperature dependence of the permittivity and the pyroelectric coefficient was measured, and the pyroelectric properties of BCZT were expected to improve near its orthorhombic–tetragonal phase transition temperature TO–T (∼40°C). The output voltage and current were measured using a BCZT plate, where the BCZT was oscillated under a temperature gradient to apply mechanical stress and temperature fluctuation simultaneously. The measured output voltage from the combined piezo‐ and pyroelectric contributions at a frequency of 2 Hz and with a load resistance of 10 MΩ was 1.4 times higher than the sole piezoelectric output voltage. The resulting combined output voltage was confirmed by finite element simulation.

Impedance Spectroscopy of Lanthanum-Doped (Pb0.75Ba0.25)(Zr0.70Ti0.30)O3 Ceramics

This study examines the effects of La3+ doping on (Pb0.75Ba0.25)(Zr0.70Ti0.30)O3(PBZT) ceramics, which were synthesized using the conventional solid-state reaction method. X-ray diffraction analysis confirmed that the PBZT structure, including PBZT doped with La3+ at concentrations x = 1 at.% and x = 2 at.%, exhibited a rhombohedral (R3c) space group, while higher doping levels of x = 3 at.% and x = 4 at.% led to a dominant cubic (Pm-3m) phase with approximately 30% of a remnant rhombohedral component. Scanning electron microscopy (SEM, JEOL JSM-7100F TTL LV, Jeol Ltd., Tokyo, Japan) and energy dispersive X-ray spectroscopy (EDS) were utilized to investigate the structure and morphology of these ceramics. The findings indicated that the chemical composition of the ceramic samples closely corresponded to the initial stoichiometry of the ceramic powder. An increase in the amount of lanthanum results in a decrease in the average grain size of the ceramics. The electrical properties were further evaluated using complex impedance spectroscopy (IS) over a range of temperatures and frequencies, as well as temperature dependence of DC conductivity. The similarity in the changes in activation energy for DC conductivity and grain boundary conductivity, caused by lanthanum ion modification, allows for the conclusion that grain boundaries are the primary microstructural element responsible for conductivity in these materials.

Electrocaloric and pyroelectric properties of 0.6Ba0.85Ca0.15Zr0.10Ti0.90O3 –0.4BaTi0.89Sn0.11O3 ceramics

Electrocaloric and pyroelectric properties of 0.6Ba0.85Ca0.15Zr0.10Ti0.90O3 –0.4BaTi0.89Sn0.11O3 ceramics

Ta doping effect on microstructure and microwave dielectric properties of CoNb2O6‐based ceramics and mechanism study

AbstractAs communication technology continues to evolve, 5G technology is becoming more mature, and 6G technology is steadily advancing. Microwave equipment is moving toward high frequency, miniaturization, low loss and high temperature stability, and microwave dielectric ceramics have been deeply applied in this field. To elevate the Q × f value of CoNb2O6 system, Ta5+ was introduced into CoNb2O6, and CoNb2‐xTaxO6 (0.0 ≤ x ≤ 0.8) ceramics were prepared by the traditional solid‐phase method. By X‐ray diffraction, it was observed that at x = 0.8, in addition to a single niobium ferrite phase, information of tantalate phase also appeared. Raman spectral detection and group theory analysis indicate that Ag(2) and Ag(3) modes are the dominant Raman vibrations at ≈873 cm−1. Furthermore, the polarization rate affects the εr value, and the bond energy of Nb/Ta‐O and the recovery force characterized by the average deformation of the [Nb/TaO6] octahedron are the key elements influencing the temperature coefficient of the resonance frequency (τf). The internal strain, ordered induced size, and chemical bonding valence of ionic valence states are the key factors that can increase the Q × f value. Moreover, the introduction of ions with lower electronegativity leads to an enhanced electronic compensation of oxygen vacancies, which also reduces the dielectric loss. This paper enriches the theory related to low dielectric loss and shows that CoNb1.8Ta0.2O6 (εr = 21.4832, Q × f = 100723 GHz, τf = ‐61.38 ppm/°C) ceramics with superior microwave dielectric properties are expected to be used in wireless communication devices.

Resolving the Role of Configurational Entropy in the Optimization of Mechanical, Thermal, and Microwave Dielectric Properties of SrLa(Al0.50-xGaxZn0.125Mg0.125Ti0.25)O4 Ceramics.

The demand for high-performance microwave dielectric ceramics has surged with the proliferation of fifth-generation (5G) communication networks. In this work, SrLa(Al0.50-xGaxZn0.125Mg0.125Ti0.25)O4 (x = 0-0.20) ceramics were designed by leveraging the unique properties of SrLaAlO4 ceramics and high-entropy engineering. The effects of configurational entropy (Sconf = 1.23R - 1.54R) on the mechanical, thermal, and microwave dielectric properties of SrLa(Al0.50-xGaxZn0.125Mg0.125Ti0.25)O4 ceramics were investigated. X-ray diffractometer and transmission electron microscope analyses confirmed that each composition belonged to the tetragonal structure with a space group of I4/mmm. Significant improvements in Vickers hardness were observed with increasing Sconf, reaching 8.05 GPa at Sconf = 1.54R compared to 5.64 GPa in SrLaAlO4 ceramics. Additionally, the increasing entropy showed great potential in reducing the thermal expansion coefficient (CTE) from 12.32 to 11.49 ppm/°C. The optimal quality factor (Q × f) of 98,000 GHz was achieved at Sconf = 1.37R, attributed to the optimization of intrinsic lattice energy and infrared-damped modes. The temperature coefficient of resonant frequency (τf) was successfully modified toward zero due to entropy-driven CTE and structural modifications. Excellent microwave dielectric properties with εr = 22.5, Q × f = 98,000 GHz, and τf = -2.0 ppm/°C were obtained at Sconf = 1.37R. This work highlights the potential of entropy-engineering in developing high-performance microwave dielectric ceramics, offering a promising pathway for the advancement of 5G communication components.

Effect of unsaturated or saturated ferroelectric polarization on electrocaloric effect

The pursuit of high-efficiency and zero-emission refrigeration technologies has spurred interest in electrocaloric (EC) refrigeration utilizing ferroelectric (FE) materials, where accurate characterization of the EC effect is crucial for comprehending its underlying physical mechanisms and for developing high-performance EC materials. In this study, we investigate the influence of unsaturated vs saturated FE polarization characteristics on EC effects using Pb0.99Nb0.02[(Zr0.6Sn0.4)0.85Ti0.15]0.98O3 ceramics. Direct EC measurement reveals that unsaturated loops can introduce substantial errors and even fake negative EC effects when employing the Maxwell approach for indirect EC measurement. In contrast, relatively accurate indirect EC results can be obtained using saturated FE hysteresis loops. Furthermore, it also highlights the necessity for saturated polarization conditions to achieve optimal EC performance in FEs. This work not only emphasizes the importance of carefully selecting polarization data for indirect EC measurements, but also presents a universal strategy to enhance EC effects in various materials.

Enhanced energy storage properties of BaTiO3 ceramics: Effect of doping Bi(Mg0.25Zn0.25Ti0.5)O3 on microstructure, dielectric and ferroelectric properties

(1-x) BaTiO3 – x Bi(Mg0.25Zn0.25Ti0.5)O3 (x = 0.00, 0.06, 0.12, 0.20,molar ratio) ceramics were prepared by solid sintering method. The effects of Bi(Mg0.25Zn0.25Ti0.5)O3 (BMZT) doping on microstructure, dielectric, ferroelectric and energy storage properties of BaTiO3 (BTO) were studied. With BMZT addition, the sintering temperature gradually decreases, the grain size reaches a minimum at x = 0.12 and the phase structure changes from tetragonal to cubic. And dielectric properties changed from temperature-dependent to temperature-insensitive. Additionally, higher cubic phase content induced slim polarization and electric field (P-E) loop and low remnant polarization (Pr). Therefore, 0.88 BaTiO3 - 0.12 Bi(Mg0.25Zn0.25Ti0.5)O3 ceramics achieved recoverable energy storage density (Wrec) of 702.7 mJ/cm3 and high energy efficiency of 87.3 % under electric field of 93 kV/cm. It exhibited optimum properties, including a minimum grain size (0.620 μm), superior dielectric properties (εr = 1811.3, tanδ = 0.0552 at 1150 °C), a high maximum polarization strength (14.3 μC/cm2), and the maximum dielectric breakdown strength (93 kV/cm), as identified in the present study. It simultaneously maintains high energy storage density and efficiency over a wide electric field range and large temperature range (room temperature - 90 °C). Thus (1-x) BaTiO3 – x Bi(Mg0.25Zn0.25Ti0.5)O3 ceramics are a promising material for energy storage applications.

Spin-reorientation transition and exchange-bias effect in CeFe0.5Cr0.5O3 ceramics

The polycrystalline CeFe0.5Cr0.5O3 ceramics were synthesized by the solid-state method, whose structural and magnetic properties were systematically studied. With the interaction between Ce and Fe/Cr ions, a first-order spin-reorientation transition from Γ4 to Γ1 is observed over a wide temperature interval in CeFe0.5Cr0.5O3, which is remarkably sensitive to applied magnetic field. Interestingly, the exchange-bias effect is found in CeFe0.5Cr0.5O3 ceramics during the spin-reorientation transition, ascribed to the paramagnetic/antiferromagnetic system presented by the two interacting magnetic sublattices (Ce and Fe/Cr). The coexistence of spin-reorientation transition and exchange-bias effect is promising to expand the practical application of CeFe0.5Cr0.5O3 ceramics in multifunctional spintronics.

High-performance electric energy storage in BiFeO3–Ba(Ti0.8Zr0.2)O3 relaxor ferroelectric ceramics

Perovskite relaxor ferroelectrics have been widely developed for energy storage applications due to their exceptional dielectric properties. This work explores the energy storage performance, thermal stability, and structural evolution in (1-x)BiFeO3–x Ba(Ti0.8Zr0.2)O3 ceramics (x = 0.3, 0.4, 0.5, and 0.6) via modulating Ba(Ti0.8Zr0.2)O3 (BZT) concentration. An enhancement of breakdown electric field from 120 kV/cm at x = 0.3–220 kV/cm at x = 0.5 can be attributed to increased grain boundaries and nanodomains as electric barriers to inhibit charge mobility. A high recoverable energy density of 5.9 J/cm3 and a high energy efficiency of 86.2 % were achieved at x = 0.5 and 0.6, respectively. The structure shifts from ferroelectric rhombohedral R3c symmetry toward a coexistence of nonpolar symmetries (including tetragonal P4/mmm, cubic Pm-3m, and orthorhombic Pbnm) with increasing BZT. The integration of BZT in BiFeO3 demonstrates to break the long-range order and promote the formation of polar nanoregions and nanodomains, leading to a high-efficiency energy storage.

Low-temperature sintering BCZT-Dy ceramics with low strain hysteresis for actuator application

Ba(Cu0.5W0.5)O3 (BCuW)-doped [(Ba0.85Ca0.15)1-xDyx](Zr0.1Ti0.9)O3 (BCZT-xDy, x = 0.001, 0.03) ceramics were prepared by conventional ceramic processing via low-temperature sintering technique. Rather pure perovskite structure and densified morphology with irregular nearly spherical-shape grains are achieved in all ceramics due to liquid-phase sintering. All BCuW-doped BCZT-xDy ceramics present apparent dielectric frequency dispersion and relaxor ferroelectric characteristic due to ion substitution and adding BCuW. The ceramics prepared at optimized sintering temperatures have rather large strain and small strain hysteresis, showing prospect application in piezoelectric high-precision actuators.

Impacts of P-site non-stoichiometry on the structure and properties of BaZnP2O7 ceramics

In this work, a series of P5+-enriched BaZnP2+xO7 ceramics were synthesized using the solid-state method at temperatures ranging from 825°C to 925°C. All ceramics exhibited a single triclinic phase. A suitable excess of P5+ promoted grain growth and densification, which also affected εr and Q×f. Subsequently, the relationship between total lattice energy and Q×f was explored, as well as the connection between total bond energy and τf. At 850°C, the BaZnP2.01O7 ceramics achieved a relative density of 97.7 % and demonstrated optimal properties: εr∼8.78, Q×f∼149,008 GHz, τf∼-28.92 ppm/°C. These ceramics present an outstanding combination of low εr, high Q×f and low sintering temperature, indicating their potential for application in Low-Temperature Co-fired Ceramics (LTCC) technology.

Innovative binary Na0·5Bi0·5TiO3-based composite ceramics with excellent comprehensive energy storage performances under low electric fields

The insufficient energy storage properties (ESPs) of lead-free dielectric ceramics at low electric fields (E) hinder their applications in the integrated and miniaturized electronic equipment. From this perspective, a synergetic tactic for enhancing the ESPs of (1-x) (Na0·5Bi0.5)0.75Sr0·25TiO3-xCa(Mg1/3Ta2/3)O3 ceramics at low E is proposed by constructing composite ceramics in combination with the design of average ionic polarizability. Consequently, the best recorded ESPs (recoverable energy density Wrec ∼ 6.7 J/cm3 and energy efficiency η ∼ 92.5 %) contrasted to other lead-free ceramics at the same E (260 kV/cm) are attained in the x = 0.15 ceramics. This is owing to the improved breakdown E caused by the second phase Bi4Ti3O12 and the retentive high-polarization characteristic of matrix. In addition, rapid discharge time (∼66.8 ns), excellent thermal (30–130 °C) and frequency (1–100 Hz) stability are also achieved. Hence, the present work offers an innovative insight into the optimization of comprehensive ESPs for dielectric ceramics at low E.

Modulation of solid solution in MgxMn1−xAl2xFe2(1−x)O4 spinel ceramics for multifunctional devices

AbstractSolid solution modulation is an ideal method for combining the advantages of different parent compounds while mitigating their disadvantages. Here, we investigated the thermal sensitivity, magnetic properties, and microwave absorption of MgxMn1−xAl2xFe2(1−x)O4 (0.2 ≤ x ≤ 0.8) spinel solid solution ceramics for application in multifunctional devices. The electrical transport and magnetic properties can be modulated by adjusting the solution ratio. The ceramics exhibit negative temperature coefficient characteristic. The B‐values from 5065–8056 K, suggesting accurate temperature measurements over a wide temperature range. As a type of soft magnetic material, it has a narrow hysteresis loop and high resistivity. Vector network analyzer studies indicate Mg0.2Mn0.8Al0.4Fe1.6O4 could be a candidate for microwave absorption in S‐band. This study successfully extends the applicability of MgxMn1−xAl2xFe2(1−x)O4 ceramics for high‐temperature thermistors and also confirms potential for multifunctional device.

Effects of electrical and mechanical properties of Ba0.92Ca0.08Zr0.05Ti0.95O3 ceramics with lanthanum dopants

Element doping is one of the important approaches to improve the performance of lead-free piezoelectric ceramics. In this study, Ba0·92Ca0·08Zr0·05Ti0·95O3-xLa (BCZT-xLa) piezoelectric ceramics were prepared by sol–gel method. The effects of La3+ contents on the phase structure, mechanical properties, and electrical properties of BCZT-xLa ceramics were investigated. Results showed that La3+ could affect the properties of ceramics by adjusting the concentration of oxygen vacancies and microstructure. When the La3+ contents were 0.008, the ceramics showed the best performance (the maximum permittivity was 8736.27, the remnant polarisation was 9.69 μC/cm2 and the coercive field was 3.44 kV/cm). The influences of Vickers hardness on ceramics were investigated using various La3+ contents. The lattice energy and oxygen vacancies were the main factors for the change in Vickers hardness. With an increment of x, the Vickers hardness values decreased from 6.271 GPa to 1.438 GPa. This study could provide a reference for BCZT piezoelectric ceramics doped with rare earth elements.

Low field assisted electrocaloric effect and energy storage responses through optimization of morphotropic phase boundary by sintering temperature for lead-free Ba0.95Ca0.05Sn0.09Ti0.91O3 ceramics

The development of lead-free ferroelectric materials is highly desired for next-generation energy storage and superior electrocaloric effect (ECE) applications. However, one of the significant challenges in lead-free dielectric materials is to obtain enhanced ECE and energy storage density at lower applied electric fields, needed for realization of sustainable and efficient energy solutions. Herein, the sol-gel elaborated lead-free Ba0.95Ca0.05Sn0.09Ti0.91O3 ceramics have been synthesized and sintered at temperatures 1100 and 1200 ˚C. The sample sintered at 1200 ˚C exhibits low field assisted improved ∆T ∼ 0.42 K and ∆S ∼ 0.52 J/kg/K values and are closely associated with presence of MPB and relaxor characteristics. The enhanced recoverable energy density (Wrec) and total energy density (Wtot) are also obtained as 79 mJ/cm3 and 87 mJ/cm3 for the same sample sintered at 1200 ˚C with excellent conversion efficiency of 91 % under a very low applied electric field of 30 kV/cm. The results demonstrate that the optimization of sintering temperature significantly affects the MPB evolution, microstructure and emergence of relaxor characteristics owing to vibrant polar-nano regions that result in enhanced ECE and energy storage characteristics. The present work would be beneficial for advancement of lead-free ferroelectric materials as an efficient electrocaloric cooling and sustainable green energy solutions.

Strain evolution from the ferroelectric to the relaxor state in (0.67 - x)BiFeO3-0.33BaTiO3-xBi(Mg0.5Zr0.5)O3 lead-free ceramics.

The BiFeO3-BaTiO3 solid solution exhibits enhanced electric properties due to its modified phase structure with relaxor characteristics and reduced leakage current. Despite these advancements, the underlying mechanism behind the phase transition from a ferroelectric to a relaxor state in BF-BT ceramics remains largely unexplored. Here, the evolution of strain in (0.67 - x)BiFeO3-0.33BaTiO3-xBi(Mg0.5Zr0.5)O3 ceramics is investigated, with a focus on the strain transition from a ferroelectric to a relaxor phase. A strengthening of relaxor behavior is observed in the modified rhombohedral (R) and pseudocubic (PC) phase structure, resulting in optimal strain (Suni = 0.25%, Spos = 0.24%) at x = 0.04. The enhanced strain is attributed to the promotion of domain switching and the presence of strong random fields, with polar nanoregions integrating into a long-range ordered matrix. Furthermore, a gradual increase in strain with rising temperature is noted, driven by increased polarization and the expansion of ferroelectric domains. This study underscores the critical role of structural modifications in augmenting the electric response of BF-BT ceramics, thereby advancing the development of lead-free piezoelectric materials.

High-performance PSZT-PSMI-PSZS ceramics: Piezoelectric and ferroelectric insights for advanced applications

High-performance ferroelectric materials have garnered increased attention due to their exceptional dielectric, piezoelectric, and electrostrictive properties. A solid-state reaction method was used to prepare the perovskite Pb(1-x)Smx[(Zr0.52Ti0.48)0.9(Mo1/3In2/3)0.05(Zn1/3Sb2/3)0.05]O3 (where x = 0, 0.02, 0.04, 0.06, and 0.08) ceramics, abbreviated PSZT-PSMI-PSZS. Energy-dispersive X-ray spectroscopy (EDX) and Fourier-transform infrared (FT-IR) spectroscopy were employed to verify the elemental composition and molecular structure, respectively. The results showed good agreement between nominal and measured compositions, and indicated structural changes post-calcination, suggesting successful formation of the perovskite phase. Piezoelectric properties were evaluated, revealing the highest piezoelectric coefficient (d33 = 310 pC/N) at x = 0.02, attributed to optimal morphological features and the morphotropic phase boundary effect. This sample also demonstrated the highest electromechanical coupling factors (kp = 60 %, k31 = 35 %) and the largest impedance resonance frequency difference (Δf = 15.05 kHz). Ferroelectric testing indicated excellent ferroelectric characteristics, with the maximum remanent polarization (Pr = 17.71 μC/cm2) and saturation polarization (Ps = 22.75 μC/cm2) observed at x = 0.02, along with the lowest coercive field (Ec = 10.16 kV/cm). Additionally, this composition exhibited the highest unipolar strain (Smax = 0.17 %) and the inverse piezoelectric coefficient (d∗33 = 427.57 p.m./V). This comprehensive analysis emphasizes the potential of Sm-doped PZT-PMI-PZS ceramics for advanced piezoelectric and ferroelectric applications, particularly at a doping concentration of x = 0.02, where the materials exhibited excellent electrical and mechanical properties.

Effects of CeO2 doping on the mechanical, infrared radiative, and thermophysical properties of Pr2Zr2O7 ceramics for potential thermal protective coatings

A series of Ce4+-doped Pr2Zr2O7 ceramics were produced using a solid reaction method to utilize novel ceramic materials as potential candidates for thermally protective coatings. The effects of Ce4+ doping on the phase composition and mechanical, infrared radiative, and thermophysical properties were studied in detail. The results indicated the good phase stability and sintering resistance of the Pr2(Zr1−xCex)2O7 ceramics. Moreover, Ce4+-doped Pr2Zr2O7 bulk materials exhibited higher infrared emissivity (0.904) at wavelengths of 3–5 μm and 1000 °C for Pr2(Zr0.5Ce0.5)2O7) owing to the introduction of impurity energy levels. Pr2(Zr0.7Ce0.3)2O7 exhibited an appropriate average coefficient of thermal expansion of 12.4 × 10−6 K−1 and a low thermal conductivity of 1.14 W m−1 K−1 at 1000 °C, owing to the reduction of lattice energy and the presence of more oxygen vacancies and substitution atoms.

A high-power piezoelectric ceramic with great electrical properties and temperature stability

Lead-based Pb(Zr, Ti)O3 ceramics have been widely used in high-power piezoelectric applications, but its stable operation at high temperature is still a grand challenge. In this work, the third element Pb(Mn1/3Sb2/3)O3 (PMS) was incorporated into Pb(Zr0.48Ti0.52)O3 (PZT) to design the xPb(Mn1/3Sb2/3)O3-(1-x)Pb(Zr0.48Ti0.52)O3 (PMS-PZT) ternary ceramics through the phase diagram. The ceramics with morphotropic phase boundary (MPB) structure and uniform grain size were fabricated successfully. The dielectric, ferroelectric and piezoelectric properties of the ceramics were probed respectively. Excellent piezoelectric properties (Qm=1595, kp=0.61, d33=318pC/N, tanδ=0.60 %, Tc=300℃) were obtained in 0.075PMS-0.925PZT ceramic, which can be attributed to its MPB structure and the pinning effect of defect dipoles on domain rotation. Moreover, the T-phase dominated 0.075PMS-0.925PZT ceramic obtains great temperature stability with a low variation of resonant frequency below 2.2 % and no variation of non-resonant frequency in the temperature range from 25°C to 175°C. These results make the ceramic as a good candidate for piezoelectric frequency applications that require constant performance within a wide temperature range.

Ultrahigh Energy Storage in (Ag,Sm)(Nb,Ta)O3 Ceramics with a Stable Antiferroelectric Phase, Low Domain-Switching Barriers, and a High Breakdown Strength.

AgNbO3 (AN) antiferroelectrics (AFEs) are regarded as a promising candidate for high-property dielectric capacitors on account of their high maximum polarization, double polarization-electric field (P-E) loop characteristics, and environmental friendliness. However, high remnant polarization (Pr) and large polarization hysteresis loss from room-temperature ferrielectric behavior of AN and low breakdown strength (Eb) cause small recoverable energy density (Wrec) and efficiency (η). To solve these issues, herein, we have designed Sm3+ and Ta5+ co-doped AgNbO3. The addition of Sm3+ and Ta5+ reduces the tolerance factor, polarizability of B-site cations, and domain-switching barriers, enhancing AFE phase stability and decreasing hysteresis loss. Meanwhile, adding Sm3+ and Ta5+ leads to decreased grain sizes, increased band gap, and reduced leakage current, all contributing to increased Eb. As a benefit from the above synergistic effects, a high Wrec of 7.24 J/cm3, η of 72.55%, power density of 173.73 MW/cm3, and quick discharge rate of 18.4 ns, surpassing those of many lead-free ceramics, are obtained in the (Ag0.91Sm0.03)(Nb0.85Ta0.15)O3 ceramic. Finite element simulations for the breakdown path and transmission electron microscopy measurements of domains verify the rationality of the design strategy.