Microwave-assisted sintering and improved dielectric,ferroelectric properties of 0.5[(Ba0.7Ca0.3)TiO3]–0.5[Ba(Zr0.2Ti0.8)O3] lead-free ceramics

0.5[(Ba_0.7Ca_0.3)TiO₃]–0.5[Ba(Zr_0.2Ti_0.8)O₃] lead-free ceramics were synthesised by coprecipitation method and sintered by fast microwave sintering (MWS) and by conventional sintering (CS) at 1200°C. After being sintered with the two different methods, the materials were characterised for structural, microstructural, frequency and temperature-dependent dielectric properties, Raman spectroscopy, and ferroelectric measurements. Results are compared and discussed in the present paper. X-ray diffraction confirms the presence of the tetragonal and rhombohedral phases in the composites sintered by both methods. The ferroelectric to paraelectric transition temperature (Tc) is increased in microwave-sintered composite. Diffuse constant (γ) values show BCT–BZT ceramics to be neither normal ferroelectrics nor relaxor ferroelectrics. Raman spectra confirm phase transition in the ceramic samples. Saturation polarisation (Ps) values are 7.62 and 4.28?µC?cm^?2 and nearly equal remanant polarisation (Pr) values were observed for BCT–BZT composite sintered with MWS and CS, respectively.     

Processing mediated enhancement of ferroelectric and electrocaloric properties in Ba(Ti0.8Zr0.2)O3–(Ba0.7Ca0.3)TiO3 lead-free piezoelectrics

High-performance Ba(Ti_0.8Zr_0.2)O₃–(Ba_0.7Ca_0.3)TiO₃ (BCZT) fiber crystals were grown using laser-heated pedestal growth (LHPG) for a systematic investigation of processing effects on structure and physical properties. By changing the growth rate (200−5 mm/h), fiber crystals with varying stoichiometry were realized: controlled composition, Ba_0.872Ca_0.128Ti_0.925Zr_0.075O_3-δ, for the optimized crystal (5 mm/h), relative to the ceramic sample (SS) synthesized by the ceramic method. SS and optimized fibers exhibited larger energy storage densities of 700 and 868 mJ/cm³, respectively. Electrocaloric (EC) measurements by direct and indirect methods yielded ΔT of 1.3 K & 0.95 K and EC responsivity (ΔT/ΔE) of 0.3 and 0.43 K mm/kV for SS and 5 mm/h respectively, at 30 kV/cm, at least two-folds higher compared to 200 mm/h fiber. The EC responsivity of our samples is comparable to that of Pb(Mg,Nb)O₃ crystals. These results demonstrate that BCZT has potential application as EC elements when the composition is controlled by fine-tuning of growth parameters.     

Aging effect in Er3+-doped 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 ceramics

Usually, aging in poled ferroelectrics leads to degradation of certain physical properties. In this study, we found a remarkable aging effect in tetragonal Er³⁺-doped 0.5Ba(Zr_0.2Ti_0.8)O₃–0.5(Ba_0.7Ca_0.3)TiO₃ (BZT-BCT) ceramics after poling. It is observed that the domains can spontaneously rotate to keep their spontaneous polarization direction similar to that of the poling electric field during aging for the poled ceramics. Furthermore, compared with freshly poled ceramics, the thermally stimulated current (TSC) peak of the aged ones shifts toward a higher temperature (10°C). And the temperature of the TSC peak in the aged ceramics is exactly equal to their Curie temperature. Such features indicate that aging for the poled ceramics could stabilize the alignment of ordered ferroelectric domains. Additionally, a downward TSC peak above Curie temperature is obtained in both poled and aged ceramics, demonstrating that poling and aging can lead to ordered alignment of defect dipoles. The aging mechanism of poled Er³⁺-doped BZT-BCT ceramics has proposed and discussed in this article.     

Fabrication of lead-free Ba(Zr0.2Ti0.8)O3–(Ba0.7Ca0.3)TiO3 nanoparticles and the application in flexible piezoelectric nanogenerator

Recently, flexible nanogenerators have attracted much attention due to the continuous demand of portable electronic devices. Thus, in our present work, a flexible piezoelectric nanogenerator (pNG) was fabricated by mixing 0.5Ba(Zr_0.2Ti_0.8)O₃-0.5(Ba_0.7Ca_0.3)TiO₃ nanoparticles (BCTZ NPs) and a PDMS polymer matrix. The flexible device exhibited excellent performance with maximum open-circuit voltage of 0.6 V and short-circuit current of 7.5 nA. BCTZ NPs were prepared by a reaction between a metallic salt and a metallic oxide in a solution of composite-hydroxide eutectic. XRD pattern showed BCTZ NPs to have pure perovskite structure. In this paper, the structure, morphology of the BCTZ NPs, and electric property of the BCTZ-based pNG were systematically studied. With the advantages of small-size, environmentally friendly, high flexibility, and high-sensitivity to external vibration, BCTZ will open up a range of new applications.     

ZrO2掺杂对(Ba0.9Ca0.1)TiO3陶瓷性能的影响

采用新型溶胶凝胶制粉技术和传统陶瓷工艺相结合,对(Ba0.9Ca0.1)TiO3陶瓷进行ZrO2掺杂,对陶瓷晶相特征及铁电、介电、压电性能进行了研究。结果表明,ZrO2的加入对(Ba0.9Ca0.1)TiO3陶瓷的铁电性能略有改善,Curie峰前移和展宽,提高了介电常数ε和介电损耗tanδ,压电常数d33却降低了。当ZrO2掺杂量为0.14mol时,陶瓷的介电常数有最大值2559.43,介电损耗有最小值0.027,此时压电常数为35。     

Origin of superior dielectric and piezoelectric properties in 0.4Ba(Zr0.2Ti0.8)O3–0.6(Ba0.7Ca0.3)TiO3 at intermediate grain sizes

Grain size effect is one of the most important issues to develop next-generation multilayer microdevices. In this work, the tetragonal 0.4Ba(Zr_0.2Ti_0.8)O₃–0.6(Ba_0.7Ca_0.3)TiO₃ (BZT–60BCT) ceramics with a wide grain size from 2.1 to 24 μm were successfully prepared by using ultrafine nano powder and two-step sintering. The results demonstrate that critical/intermediate grain size of dielectric constant ε_r and piezoelectric constant d₃₃ appears at ∼12.9 μm. It was found that the presence of large lattice tetragonality, and enhanced domain wall motion induced by domain coexistence between submicron and nano size in sample with a grain size of ∼12.9 μm, resulting in the superior dielectric and piezoelectric properties. These findings and analyses of the origin of superior dielectric and piezoelectric properties at intermediate grain size have important practical implications in the design of high-performance piezoelectric ceramics.     

Synthesis and Characterization of Lead-Free Ferroelectric 0.5[Ba(Zr0.2Ti0.8)O3]–0.5[(Ba0.7Ca0.3)TiO3]—Polyvinylidene Difluoride 0–3 Composites

0.5[Ba(Zr_0.2Ti_0.8)O₃]–0.5[(Ba_0.7Ca_0.3)TiO₃]/[BZT–BCT]–polyvinylidene difluoride/[PVDF] 0–3 composites were prepared by uniaxial hot-press method for different volume fractions of BZT–BCT ceramic powder in a PVDF polymer matrix. The structural, microstructural and dielectric properties were investigated and discussed. There was an increase in relative permittivity (ε_r) and dielectric loss (tan δ) of the composites with increase in the volume fraction of the ceramics. At room temperature and at 1 kHz frequency, 0.25[BZT–BCT]–0.75[PVDF] composite showed a highest relative permittivity (ε_r) ~41.     

Ba(Zr0.3Ti0.7)O3薄膜的结构及性能

用溶胶-凝胶法分别在Pt/Ti/SiO2/Si和LaNiO3/Pt/Ti/SiO2/Si衬底上制备了锆钛酸钡[Ba(Zr0.3Ti0.7)O3,BZT]薄膜.相结构及介电性能研究表明:衬底和薄膜厚度对BZT薄膜性能具有显著影响.制备在LaNiO3/Pt/Ti/SiO2/Si衬底上的BZT薄膜具有(100)面的择优取向,其介电常数及介电损耗则随着薄膜厚度的增加而降低.对制备在Pt/Ti/SiO2/Si衬底上的BZT薄膜,在薄膜厚度低于500nm时,其介电常数随薄膜厚度增加而增加,大于500nm时又有所减小.     

Dielectric properties and relaxor behavior of high Curie temperature (Ba0.85Ca0.15)(Zr0.1Ti0.9)O3–Bi(Mg0.5Ti0.5)O3 Lead-free ceramics

The (1?x)(Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃?xBi(Mg_0.5Ti_0.5)O₃ [(1?x)BCZT–xBMT, x=0.1–0.7] lead-free solid solution ceramics were prepared by the conventional mixed oxide method. The phase structure was investigated by X-ray diffraction and results show that a single perovskite phase was obtained in all of these samples, suggesting that the added BMT diffused into BCZT to form a solid solution. Dense ceramics with relative densities >95% were obtained, and a small amount of BMT (≤50 mol%) acted as grain growth promoter, had an evident effect on grain size growth. Further increase of the BMT content inhibited the grain growth of BCZT samples. Temperature dependence of the dielectric properties showed that all the BCZT–BMT solid solution ceramics exhibited relaxor-like characteristics. With increasing BMT content, the Curie temperature was first increased and then decreased, giving a maximum value of 218 °C for the 0.4BCZT–0.6BMT composition. Furthermore, stable dielectric constants and low losses were obtained with 0.5≤x≤0.7 in the wide temperature range, indicating that the system possess potential for high-temperature application.     

Two–step processing of thermoelectric (Ca0.9Ag0.1)3Co4O9/nano–sized Ag composites with high ZT

A two–step processing method, spark plasma sintering (SPS) combined with a heat–treatment, was used to fabricate (Ca_0.9Ag_0.1)₃Co₄O₉/nano–sized Ag composites. Sliver within the lattice generated hole carriers, and silver along the grain boundaries improved the transport path of the charge carriers. Samples sintered using SPS at different temperatures had very different thermoelectric properties. The results showed that when the sample was sintered at 1233 K, the maximum power factor reached 0.43 mW/(m·K²) along with an electrical resistivity of 8.61 mΩ·cm and a Seebeck coefficient of 196.90 μV/K, and the corresponding lattice thermal conductivity was 1.86 W/(m·K). This study shows how to improve the properties and broaden the application of Ca₃Co₄O₉ thermoelectric ceramics.     

ZrO2掺杂对(Ba0.9Ca0.1)TiO3陶瓷性能的影响

采用新型溶胶凝胶制粉技术和传统陶瓷工艺相结合，对（Ba0.9Ca0.1）TiO3陶瓷进行ZrO2掺杂，对陶瓷晶相特征及铁电、介电、压电性能进行了研究，结果表明，ZrO2的加入对（Ba0．9Ca0．1）TiO3陶瓷的铁电性能略有改善，Curie峰前移和展宽，提高了介电常数ε和介电损耗tanδ，压电常数d33却降低了。当ZrO2掺杂量为0.14mol时，陶瓷的介电常数有最大值2559．43，介电损耗有最小值0.027，此时压电常数为35。     

Strong photoluminescence and piezoelectricity properties in Pr-doped Ba(Zr0.2Ti0.8)O3–(Ba0.7Ca0.3)TiO3 ceramics: Influence of concentration and microstructure

(Ba_0.85Ca_0.15)_1−xPr_x(Zr_0.1Ti_0.9)O₃ (where 0 < x < 0.01, abbreviated as BCZT:xPr) ceramics were fabricated by conventional solid-state reaction method. The influence of dopant concentration and microstructure on photoluminescence, ferroelectric, and piezoelectric properties was systematically investigated. The results showed that the photoluminescence spectra of the samples exhibited strong green (530 nm) and red (602 nm) emissions upon excitation of the 430 nm to 500 nm light, which couples well with to the emission band of the commercial blue light-emitting diodes chips. The emission intensities were strongly dependent on the dopant concentration and crystallite size, which reached the optimal value when the crystallite size and dopant concentration were 8 μm and 0.002 mol, respectively. Meanwhile, a large piezoelectric response with d₃₃ = 325 pC/N was obtained for BCZT:0.002Pr near the morphotropic phase boundary. Therefore, the Pr-doped BCZT materials, simultaneously exhibiting excellent luminescent properties and high piezoelectric properties, may have significant technological promise in novel multifunctional devices.     

Ca含量对(Ba1-xCax)(Ti0.9Zr0.1)O3无铅压电陶瓷性能的影响

采用传统的固相法制备(Ba1-xCax)(Ti0.9Zr0.1)O3(简称BCTZ)无铅压电陶瓷.借助扫描电镜(SEM)和X射线衍射仪(XRD)等测试方法研究了Ca含量对所制备BCTZ无铅压电陶瓷显微结构和压电介电性能的影响.结果表明:随着Ca含量的增加,(Ba1-xCax)(Ti0.9Zr0.1)O3无铅压电陶瓷的晶粒尺寸先增大后减小,所制备的BCTZ陶瓷的物相都是钙钛矿结构,没有杂相;随着Ca含量的增加,BCTZ陶瓷压电常数(d33),介电常数(εr),机电耦合系数(kp)分别先增加后降低,而介质损耗(tanδ)先减小后增大.当Ca含量(x)为0.15mol时,在1450℃烧结制得的(Ba1-xCax)(Ti0.9Zr0.1)O3无铅压电陶瓷性能最佳:压电常数(d33)为363pC/N,机电耦合系数(kp)为39.63％,介电常数(εr)为4184,介质损耗(tanδ)为1.08％.     

High thermal stability of electric field-induced strain in (1−x)(Bi0.5Na0.5)TiO3-xBa0.85Ca0.15Ti0.9Zr0.1O3 lead-free ferroelectrics

In ferroelectric materials high electric field-induced strain (EFIS) with good thermal stability is of much interest from both fundamental research and potential applications. Here we propose a strategy to achieve high thermally stable EFIS based on electrostrictive effect and thermal stability of polarization. According to this strategy, we synthesized (1−x)(Bi_0.5Na_0.5)TiO₃-xBa_0.85Ca_0.15Ti_0.9Zr_0.1O₃ (BNT-xBCZT) ferroelectric ceramics in order to tailor the thermal stability of dielectric permittivity, polarization and EFIS. A dielectric platform with a wide temperature region is induced by increasing x from 0.24 to 0.36 gradually. From 30 °C to 150 °C, a variation of 20% polarization results in a change of 36% EFIS, suggesting a good thermal stability as expect. Temperature-insensitive electrostrictive coefficient Q₃₃ ranges from 0.0264 m⁴/C² to 0.0314 m⁴/C². These results not only prove the effectiveness of this strategy, but also suggest that this strategy can be applied to other ferroelectric materials to improve the thermal stability.     

Ba0.98Bi0.02(Ti0.9Zr0.1)1-xCuxO3陶瓷的介电弛豫特征

采用固相反应法制备Ba0.98Bi0.02(Ti0.9Zr0.1)1-xCuxO3(x=0,0.01,0.02,0.03,摩尔分数)陶瓷.X射线衍射分析结果表明:所有样品均为四方晶体结构,摩尔分数为2%的Cu2+能够完全溶入Ba0.98,Bi0.02(Ti0.9Zr0.1)03陶瓷晶格中.Ba0.98Bi0.02(Ti...     

Structural,dielectric and ferroelectric properties of Ba1−x(Bi0.5Na0.5)xTiO3 ceramics

Lead free Ba_1?x(Bi_0.5Na_0.5)_xTiO₃ (x=0, 0.02, 0.04, 0.06, 0.08, 0.1) ferroelectric ceramics were synthesized by conventional solid state reaction technique. Sintering was done at 1200 °C for 2 h in air atmosphere. The final products have tetragonal symmetry with decreasing c/a ratio confirmed by X-ray diffraction analysis. The grain size varies between 300 nm to 1000 nm for x=0 to 0.1. With increase in Bi_0.5Na_0.5TiO₃ [BNT] content, the room temperature permittivity decreases whereas the Curie temperature (T_c) increases and its highest value was found to be 155 °C for 10 mol% of BNT addition. The ceramics show stable and low dielectric loss characteristics. The remnant polarization (P_r) and the coercive field (E_c) increases monotonously with increase in BNT content. The highest value of 2P_r (=17 μC/cm²) and 2E_c (=22 Kv/cm) was obtained for x=10 mol% BNT addition.     

Effect of Ba nonstoichiometry on the phase composition,microstructure, chemical stability and electrical conductivity of BaxCe0.7Zr0.1Y0.1Yb0.1O3−δ (0.9≤x≤1.1) proton conductors

The perovskite proton conductors Ba_xCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ (x=0.9, 0.94, 0.98, 1.0, 1.03, 1.06, and 1.1) have been successfully prepared by the conventional solid state reaction route. X-ray diffraction (XRD) patterns of the samples indicate that Ba_xCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ (x≥1.0) samples possess a single phase orthorhombic structure, but a secondary phase (Y,Ce)O_2−δ exists in Ba_xCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ (x<1.0) samples. SEM photographs show that the grain size of Ba_xCe_0.7Zr_0.1Y_0.1Yb_0.1O_3−δ increases and the porosity decreases with Ba²⁺ content varying from x=0.9 to 1.1. Because of ZnO addition as sintering aid, the sintering temperature of the samples reduces from 1550 °C to 1250 °C. The chemical stability of the samples against CO₂ decreases with the increase in Ba content from x=0.9 to 1.1. All the samples show a excellent stability against water vapor at 850 °C. The conductivities of the samples increase and the activation energies reduce with the increase in Ba content. The present results suggest that it is very important to control the stoichiometry of cations to obtain desired perovskite type high temperature proton conductors.     

Tuning the dielectric,ferroelectric and electromechanical properties of Ba0.83Ca0.10Sr0.07TiO3–MnFe2O4 multiferroic composites

We report the successful synthesis of Ba_0.83Ca_0.10Sr_0.07TiO₃–MnFe₂O₄ multiferroic composites showing significant improvement in electromechanical and magnetoelectric properties. All the composite samples have formed a diphasic perovskite-ferrite composite without the presence of any impurity or intermediate phase. The bare as well as composite samples have shown classical dielectric behavior even at higher ferrite substituted samples. The electrical characteristics of composite samples have shown slight deterioration, which is mainly attributed to non-ferroelectric MnFe₂O₄. However, the composites still exhibit high enough piezoelectric behavior and the modification in the electromechanical response of composites is mainly caused by a change in applied stress with MnFe₂O₄ addition. The M-H loops of composites have demonstrated a ferrimagnetic behavior with a substantial increase in saturation magnetization on increasing the ferrite concentration. Further, the composites have shown better coupling between the ferroelectric and ferrimagnetic phases, which has resulted in an improved magnetoelectric characteristic. The role of oxygen vacancies on ferroelectric and magnetic properties of prepared composites has been systematically studied.     

Investigation of crystal structure,dielectric properties,impedance spectroscopy and magnetic properties of (1-x)BaTiO3 – (x)Ba0.9Ca0.1 Fe12O19 multiferroic composites

Composites having composition (1-x)BaTiO₃?(x)Ba_0.9Ca_0.1Fe₁₂O₁₉ (x = 0.10, 0.20, 0.30) were synthesized by conventional solid-state reaction technique. X-ray diffraction (XRD) was used to examine the phase formation. Rietveld refinement has been done using the FullProf suite which predicted the dual phase symmetry consisting hexagonal (P63/mmc) and tetragonal (P4mm) phases in the prepared composites. The dielectric properties of the obtained composites were investigated at different temperatures as a function of frequency in the range of 100 Hz to 7 MHz. The dielectric constant increases with an increase in Ca doped barium ferrite content. The composites showed usual dielectric dispersive behaviour with increasing frequency. The conduction mechanism and dielectric relaxation were examined by complex impedance spectroscopy (CIS). Nyquist plots of all composites showed two semicircles and their centers lied below the real axis. Magnetic characterization was performed by using a vibrating sample magnetometer (VSM) up to a field of 15 kOe at room temperature. The hysteresis loops reveal the ferromagnetic nature of the composites. The values of saturation magnetization, magnetic moment per formula unit, and corresponding coercivity increases with ferrite content and are maximum at x = 0.3. AC conductivity also increases with ferrite content. The variation of frequency exponent ‘n' of the power-law with temperature suggests that the overlapping large polaron tunneling (OLPT) model is appropriate to explain the mode of conduction in all samples.     

α-Bi2O3/β-Ni(OH)2 composites: Effective solar light photocatalysts for organic pollutants degradation

α-Bi₂O₃/β-Ni(OH)₂ composites exhibited perfect photocatalytic properties for organic pollutants degradation under sunlight irradiation. Pure α-Bi₂O₃ and β-Ni(OH)₂ were prepared by coprecipitation method and then mechanically mixed in different proportions to form α-Bi₂O₃/β-Ni(OH)₂ composites. The XRD and FTIR analyses have well emphasized the formation of monoclinic α-Bi₂O₃ and hexagonal β-Ni(OH)₂ phases with high crystallinity. The SEM micrographs of α-Bi₂O₃ and β-Ni(OH)₂ powders displayed a rod and sheet shaped grains, respectively. The band gap of the pure α-Bi₂O₃ was estimated to be 2.87 eV. Pure β-Ni(OH)₂ revealed three absorption bands in the UV–visible light region. α-Bi₂O₃/β-Ni(OH)₂ composites have a more intense absorption in the visible light region compared to pure α-Bi₂O₃ sample. Modification of α-Bi₂O₃ by β-Ni(OH)₂ induced a superior photocatalytic activity especially at β-Ni(OH)₂ content of 12 wt% in α-Bi₂O₃ (BN-12 composite). This composite showed high efficiencies of 99%, 96%, 91% and 90% for methylene blue, Congo red, methyl orange and 4-niropheniol degradation in 80, 80, 180 and 300 min under sunlight irradiation, respectively. The remarkable photocatalytic activity of the α-Bi₂O₃/β-Ni(OH)₂ composite was attributed to the new states in charge separation, charge transportation and the intensive absorption of visible light. α-Bi₂O₃/β-Ni(OH)₂ composite (BN-12) has a great potential in removing of cationic and anionic dyes beside phenolic compounds from wastewater.