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1.
Often, addition of BiMO3 to BaTiO3 (BT) leads to improvement in resistivity with a simultaneous shift to n‐type conduction from p‐type for BT. In considering one specific BiMO3 composition, that is, Bi(Zn1/2Ti1/2)O3 (BZT), several prospective candidates for the origin of this n‐type behavior in BT‐BZT were studied—loss of volatile cations, oxygen vacancies, bismuth present in multiple valence states and precipitation of secondary phases. Combined x‐ray and neutron diffraction, prompt gamma neutron activation analysis and electron energy loss spectroscopy suggested much higher oxygen vacancy concentration in BT‐BZT ceramics (>4%) as compared to BT alone. X‐ray photoelectron spectroscopy and x‐ray absorption spectroscopy did not suggest the presence of bismuth in multiple valence states. At the same time, using transmission electron microscopy, some minor secondary phases were observed, whose compositions were such that they could result in effective donor doping in BT‐BZT ceramics. Using experimentally determined thermodynamic parameters for BT and slopes of Kröger‐Vink plots, it has been suggested that an ionic compensation mechanism is prevalent in these ceramics instead of electronic compensation. These ionic defects have an effect of shifting the conductivity minimum in the Kröger‐Vink plots to higher oxygen partial pressure values in BT‐BZT ceramics as compared to BT, resulting in a significantly higher resistivity values in air atmosphere and n‐type behavior. This provides an important tool to tailor transport properties and defects in BT‐BiMO3 ceramics, to make them better suited for dielectric or other applications.  相似文献   

2.
The dependence of energy storage properties on grain size was investigated in BaTiO3‐based ferroelectric ceramics. Modified BaTiO3 ceramics with different grain size were fabricated by two‐step sintering method from BaTiO3 powders doped with Al2O3 and SiO2 by aqueous chemical coating. For samples doped with ZnO sintering aid in addition to Al2O3‐SiO2, the density and breakdown strength increased significantly. In general, samples with smaller grains have lower polarization but higher energy storage efficiency. Al2O3‐SiO2‐ZnO‐doped samples with average grain size of 118±2 nm have an energy density of 0.83±0.04 J/cm3. Obvious segregation of doping elements in second phase and grain boundary was observed by TEM‐EDS. Impedance spectroscopy further explains the relationship between microstructure and properties. Compared to common energy storage ceramics, the grain size of this low‐cost ceramics sintered at relatively low temperature is small, and the pilot scale production has been well completed. All these features make the utilization in multilayer devices and industrial mass production possible. In addition, the obtained rules are helpful in further development of energy storage ceramics.  相似文献   

3.
Effects of quenching process on dielectric, ferroelectric, and piezoelectric properties of 0.71BiFeO3?0.29BaTiO3 ceramics with Mn modification (BF–BT?xmol%Mn) were investigated. The dielectric, ferroelectric, and piezoelectric properties of BF–BT?xmol%Mn were improved by quenching, especially to the BF–BT?0.3 mol%Mn ceramics. The dielectric loss tanδ of quenched BF–BT?0.3 mol%Mn ceramics was only 0.28 at 500°C, which was half of the slow cooling one. Meanwhile, the remnant polarization Pr of quenched BF–BT?0.3 mol%Mn ceramics increased to 21 μC/cm2. It was notable that the piezoelectric constant d33 of quenched BF–BT?0.3 mol%Mn ceramics reached up to 191 pC/N, while the TC was 530°C, showing excellent compatible properties. The BF–BT?xmol%Mn system ceramics showed to obey the Rayleigh law within suitable field regions. The Rayleigh law results indicated that the extrinsic contributions to the dielectric and piezoelectric responses of quenched BF–BT?xmol%Mn ceramics were larger than the unquenched ceramics. These results presented that the quenched BF–BT?xmol%Mn ceramics were promising candidates for high‐temperature piezoelectric devices.  相似文献   

4.
Lead‐free 0.955K0.5Na0.5Nb1‐zTazO3‐0.045Bi0.5Na0.5ZrO3+0.4%MnO ceramics (abbreviated as KNNTaz‐0.045BNZ+0.4Mn) were prepared by a conventional solid‐state sintering method in a reducing atmosphere (oxygen partial pressure of 1 × 10?10 atm). All ceramics with a pure perovskite structure show the two‐phase coexistence zone composed of rhombohedral and tetragonal phase. Ta5+ ions substitute for Nb5+ ions on the B‐site, which results in a decrease in the R phase fraction in the two‐phase coexistence zone. The R‐T phase transition temperature moves to room temperature due to the substitution of Nb5+ ions by Ta5+ ions. A complex domain structure composed of small nano‐domains (~70 nm) formed inside large submicron domains (~200 nm) exists in KNNTa0.02‐0.045BNZ+0.4Mn ceramics, which can induce a strong dielectric‐diffused behavior and improve the piezoelectric properties. The temperature stability for the reverse piezoelectric constant for the KNNTaz‐0.045BNZ+0.4Mn ceramics can be improved at = 0.02. Excellent piezoelectric properties (d33 = 328 pC/N, and  = 475 pm/V at Emax = 20 kV/cm) were obtained for the KNNTa0.02‐0.045BNZ+0.4Mn ceramics.  相似文献   

5.
In this study, we reported a new BaTiO3–Na0.5Bi0.5TiO3–Nb2O5–Mn2O3/Fe2O3/Co3O4/In2O3 X8R system with high dielectric constant (>2100) at room temperature. The impacts of oxygen vacancy ( ) on dielectric, electrical conductivity, and ferroelectric properties were systematically studied. The Curie point is largely depended on the concentration, which can be confirmed by the dielectric behavior and A1g octahedral breathing modes in Raman spectrum. In addition, the activation energy of diffusion is greatly reduced with the increase in concentration. It was found that the remnant polarization and coercive field were both decreased with increasing concentration, due to the facilitated defect dipoles reorientation and domain switching.  相似文献   

6.
Lead‐free MnO‐doped 0.955K0.5Na0.5NbO3‐0.045Bi0.5Na0.5ZrO3 (abbreviate as KNN‐0.045BNZ) ceramics have been prepared by a conventional solid‐state sintering method in reducing atmosphere. The MnO addition can suppress the emergence of the liquid phase and improve the homogenization of grain size. All ceramics sintered in reducing atmosphere show a two‐phase coexistence zone composed of rhombohedral (R) and tetragonal (T) phase. MnO dopant results in the content increase in R phase and slight increase in Curie temperature TC. For KNN‐0.045BNZ ceramics, Mn2+ ions preferentially occupy the cation vacancies in A‐site to decrease oxygen vacancy concentration for 0.2%‐0.4% MnO content, whereas Mn2+ ions substitute for Zr4+ ions in B‐site to form oxygen vacancies at  0.5. The defect dipole is formed at the moderate concentration from 0.5 to 0.6, which can provide a preserve force to improve the temperature stability of piezoelectric properties for kp and . The Mn0.4 ceramics show excellent electrical properties with quasistatic piezoelectric constant d33 = 300 pC/N, electromechanical coupling coefficient kp = 51.2%, high field piezoelectric constant  = 430 pm/V (at Emax = 25 kV/cm) and TC = ~345°C, insulation resistivity ρ  =  6.13 × 1011 Ωcm.  相似文献   

7.
Ferroelectric phase coexistence was constructed in (1?x)BaTiO3xCaSnO3 lead‐free ceramics, and its relationship with the piezoelectricity of the materials was investigated to ascertain potential factors for strong piezoelectric response. It is found that the addition of CaSnO3 caused a series of phase transitions in the (1?x)BaTiO3xCaSnO3 ceramics, and a ferroelectric coexistence of rhombohedral, orthorhombic, and tetragonal phases is formed at = 0.08, where the ceramics exhibit the lowest energy barrier and consequently facilitate the polarization rotation and extension, resulting in the optimal piezoelectricity of d33 and kp values of 550 pC/N and 0.60, respectively. Our study provides an intuitive insight to understand the origin of high piezoelectricity in the ceramics with the coexistence of multiferroelectric phases.  相似文献   

8.
As part of a continued push for high permittivity dielectrics suitable for use at elevated operating temperatures and/or large electric fields, modifications of BaTiO3 with Bi(M)O3, where M represents a net‐trivalent B‐site occupied by one or more species, have received a great deal of recent attention. Materials in this composition family exhibit weakly coupled relaxor behavior that is not only remarkably stable at high temperatures and under large electric fields, but is also quite similar across various identities of M. Moderate levels of Bi content (as much as 50 mol%) appear to be crucial to the stability of the dielectric response. In addition, the presence of significant Bi reduces the processing temperatures required for densification and increases the required oxygen content in processing atmospheres relative to traditional X7R‐type BaTiO3‐based dielectrics. Although detailed understanding of the structure–processing–property relationships in this class of materials is still in its infancy, this article reviews the current state of understanding of the mechanisms underlying the high and stable values of both relative permittivity and resistivity that are characteristic of BaTiO3‐Bi(M)O3 dielectrics as well as the processing challenges and opportunities associated with these materials.  相似文献   

9.
With the fast charge-discharge speed and ultrahigh power density, electrostatic energy storage materials offer great potential in the applications for pulsed power systems. As a very important member of structural ceramics, 3Y-TZP (3 mol% Y2O3 doped tetragonal zirconia polycrystals) has shown extraordinary mechanical properties. However, the research on their energy storage performance is still lacking. Herein, a ferroelectric phase, BaTiO3 (BT), was introduced and demonstrated to improve the dielectric properties and energy storage performance of 3Y-TZP ceramic matrix via the conventional solid-state reaction method. With increasing the BT content from 0 to 15 mol%, the permittivity of the composite ceramics could be effectively increased from 40.2 to 64.1 measured at 1 kHz. Simultaneously, the dielectric loss could be effectively decreased by depressing the response of charged defects, which was further interpreted by the thermally stimulated depolarization current technique. Meanwhile, the breakdown strength showed a typical increase-then-decrease trend with increasing BT content, and reached their maximum values when doped with 7 mol% BT. Together with the enhancement of dielectric properties, the 7 mol% BT-doped 3Y-TZP ceramics exhibited a maximum energy storage density of 0.42 J/cm3, which was approximately 150% larger than that of the pure 3Y-TZP ceramics.  相似文献   

10.
In the present work, it is shown how the controlled porosity can be exploited to obtain a compromise between a reduced permittivity down to a few hundreds and maintaining a high tunability level as in the dense material, to fulfill requirements for tunable applications. Nb‐doped Pb(Zr,Ti)O3 ceramics with porosity in the range 5%‐30% have been prepared by direct sintering method. X‐ray diffraction analysis and Rietveld refinement indicated a co‐existence of tetragonal and monoclinic phases in the porous ceramics. Dielectric properties revealed a gradual reduction in permittivity when increasing the porosity level, while maintaining low dielectric losses below 3%. The ferroelectric switching behavior is also influenced by the porosity level: a continuous reduction in the saturation and remnant polarization is observed with increasing porosity. The nonlinear dielectric properties of all the investigated ceramics preserve a high level of tunability in comparison with one of the dense material, irrespective of the porosity level, while zero field permittivity was decreased below 1000. An optimum behavior is found for the ceramic sample with 25% porosity, which shows a high tunability, smaller losses, and moderate dielectric constant (ε ~600).  相似文献   

11.
The influence of temperature on the variation in dielectric nonlinearity and domain structures was investigated for the (Ba0.95Ca0.05)(Ti0.83Zr0.17)O3 (BCTZ)‐based multilayer ceramic capacitor that shows a diffuse phase transition. Whereas the dielectric constant (εr) vs temperature shows a broadened maximum peak at low ac driving field, such a peaked behavior disappears at high ac driving field due to an abrupt increase in dielectric constants at low temperatures. Such low temperature effect can be associated with an enhanced spontaneous polarization (PS) and a significant increase in irreversible domain wall contribution to polarization representing normal ferroelectric behavior based on the Preisach analysis. No ferroelectric domain contrasts were observed at room temperature through transmission electron microscopy. However, they appeared and became more and more distinct with the decrease in temperature, and the crystal structure also changed from cubic to rhombohedral with increased lattice constants. It demonstrates that the dramatic increase in the dielectric nonlinearity with decreasing temperatures originates from the corresponding changes in domain and crystal structure, where the polar‐micro‐regions of BCTZ at room temperature change to normal ferroelectric domains at low temperatures.  相似文献   

12.
(1?x)Bi1/2Na1/2TiO3xPbMg1/3Nb2/3O3[(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.  相似文献   

13.
A new lead‐potassium‐free ceramic of (0.9‐x)NaNbO3‐0.1BaTiO3‐xNaSbO3 (NN‐BT‐xNS) was successfully prepared via a solid‐state reaction method. The microstructure, phase structure, dielectric, ferroelectric, and piezoelectric properties were investigated as a function of NS content. The substitution of NS for NN was found to dramatically change the grain morphology from cube‐like grains typical for alkaline niobate‐based ceramics to conventional sphere‐like grains especially for Pb‐based perovskite ceramics. A normal to relaxor ferroelectric phase transformation was accompanied by a tetragonal (T) to rhombohedral (R) phase transition. A composition‐temperature phase diagram demonstrated a vertical morphotropic phase boundary between T and R phases in the composition range of x=0.03‐0.04, where optimum electrical properties of d33=252 pC/N, kp=36%, Qm=168, =2063, and Tc=109°C were obtained in the x=0.035 ceramic sintered at 1260°C. Particularly, excellent temperature insensitivity of small‐signal piezoelectric properties suggested large application potentials in various actuators and sensors in comparison with other typical lead‐free materials.  相似文献   

14.
The improved dielectric properties and voltage‐current nonlinearity of nickel‐doped CaCu3Ti4O12 (CCNTO) ceramics prepared by solid‐state reaction were investigated. The approach of A′‐site Ni doping resulted in improved dielectric properties in the CaCu3Ti4O12 (CCTO) system, with a dielectric constant ε′≈1.51×105 and dielectric loss tanδ≈0.051 found for the sample with a Ni doping of 20% (CCNTO20) at room temperature and 1 kHz. The X‐ray photoelectron spectroscopy (XPS) analysis of the CCTO and the specimen with a Ni doping of 25% (CCNTO25) verified the co‐existence of Cu+/Cu2+ and Ti3+/Ti4+. A steady increase in ε′(f) and a slight increase in α observed upon initial Ni doping were ascribed to a more Cu‐rich phase in the intergranular phase caused by the Ni substitution in the grains. The low‐frequency relaxation leading to a distinct enhancement in ε′(f) beginning with CCNTO25 was confirmed to be a Maxwell‐Wagner‐type relaxation strongly affected by the Ni‐related phase with the formation of a core‐shell structure. The decrease of the dielectric loss was associated with the promoted densification of CCNTO and the increase of Cu vacancies, due to Ni doping on the Cu sites. In addition, the Ni dopant had a certain effect on tuning the current‐voltage characteristics of the CCTO ceramics. The present A′‐site Ni doping experiments demonstrate the extrinsic effect underlying the giant dielectric constant and provides a promising approach for developing practical applications.  相似文献   

15.
x% mol MnO2‐doped Ba0.925Ca0.075TiO3 ceramics (abbreviated as BCT‐Mnx, x=0‐1.5) were synthesized by conventional solid‐state reaction method. The effects of MnO2 addition and (Ba+Ca)/Ti mole ratio (A/B ratio) on the microstructure and electrical properties of the ceramics were investigated. The internal bias filed Ei was determined from the asymmetrical polarization hysteresis loops and found to increase with the doping concentration of MnO2. High mechanical quality factors (Qm>1200) and low dielectric loss (tanδ<0.5%) were found in the BCT‐Mn0.75 and BCT‐Mn1.0 ceramics with Ei>3 kV/cm, meanwhile, the piezoelectric and electromechanical properties were found to decrease compared with the pure BCT, exhibiting a typical characteristic of “hard” behavior. Of particular interest is that the microstructure of BCT‐Mn0.75 ceramics could be controlled by changing the A/B ratio, where enhanced piezoelectric coefficient d33 on the order of 190 pC/N was obtained in the BCT‐Mn0.75 ceramics with A/B=1.01 due to its fine‐grained microstructure, with yet high Qm, being on the order of 1000. The high d33 and Qm in MnO2‐doped BCT ceramics make it a promising candidate for high power piezoelectric applications.  相似文献   

16.
Low‐power plasma‐sprayed Cr/Al2O3 coatings have been developed for their potential application as broad bandwidth, thin thickness, lightweight, and strong microwave‐absorbing materials. The dielectric and microwave absorption properties of the as‐sprayed coatings were studied in the X‐band (from 8.2 to 12.4 GHz). High complex permittivity of the coatings was obtained because of a large number of internal boundaries and the conductive networks. Meanwhile, a significant enhancement of microwave absorption properties of the coating was achieved due to the enhanced interfacial polarization and conductance loss. The reflection loss (RL) <?10 dB of the Al2O3–15Cr coating was obtained from 9.8 to 11.4 GHz by choosing an appropriate coating thickness, and an optimal minimum reflection loss (RLmin) of ?45.35 dB was achieved at 10.3 GHz with a thin thickness of 1.32 mm.  相似文献   

17.
We report a novel strategy to improve the dielectric properties of the biferroic YCrO3 ceramic compound through interface conduction control by means of an insulating Al2O3 using a core‐shell design. The YCrO3 particles were covered with several layers of insulating Al2O3 using the atomic layer deposition technique to produce the core‐shell structure. TEM images reveal homogeneous and well‐defined Al2O3 coatings of ~8, ~60, and ~130 nm thickness. XRD shows the Al2O3‐shell to be amorphous. The dielectric characteristics of the sintered nano‐composite were investigated in the 100 Hz–1 MHz frequency range and temperature between 300 and 580 K. As the Al2O3‐shell thickness covering the YCrO3 particles is increased, a decrease of the dielectric permittivity, loss tangent and AC conductivity values was found in the whole range of temperatures and frequencies. Furthermore, the rounded hysteresis loop, typical of conductive ceramic is restored as the insulating Al2O3 layer becomes thicker. This behavior is explained because the insulating Al2O3‐shell acts as internal barrier layer localizing the surface charges on the sintered grain boundaries. This fact was confirmed by Electron Beam Induced Current technique where a clear contrast at the grain boundaries confirms the charge localization at the YCrO3/Al2O3 interface. These results also reveal that the Al2O3‐shell induces another conductive mechanism when the insulating Al2O3 layer becomes thicker. Nonetheless, this new strategy is an effective approach to suppress the parasitic conductivity in polycrystalline multiferroic ceramics and increasing thus the multifuncionality.  相似文献   

18.
Sr- and Ba titanate particles doped with Nb, Mn, and Ce were produced via a wet-chemical precipitation process based on salt solutions and metal chlorides around Al2O3 flake-like particles. In a calcination process at high temperatures, a shell of doped oxides is formed that is responsible for the unusual electrical properties. The particles were investigated via scanning electron microscope (SEM) and transmission electron microscope which showed homogeneously covered Al2O3 particles. X-ray diffraction exposed secondary phases besides BaTiO3 and SrTiO3 because of the high solubility of Ba(OH)2 and Sr(OH)2 in water and a resulting shortfall of earth alkaline metal. The oxidation states of the doping elements were determined via X-ray photoelectron spectroscopy. Composite materials prepared from this filler and silicone rubber showed typical nonlinear voltage-current (U-I) characteristics, which are of special interest for high voltage engineering. The filler was evenly distributed within the matrix without settling while cross-linking of the polymer, which was shown in an SEM-backscattered electron image. The nonlinearity coefficient α, which is an important factor for field grading applications, was determined for different materials and reached a value of up to 7.  相似文献   

19.
Lead‐free MnO‐doped 0.955K0.5Na0.5NbO3‐0.045Bi0.5Na0.5ZrO3 (Abbreviated as KNN‐0.045BNZ) ceramics have been prepared by the conventional solid‐state sintering method in reducing atmosphere ( = 1 × 10?10 atm) and air. For ceramics sintered in reducing atmosphere, only Mn2+ ions exist in ceramics who preferentially occupy the cation vacancies in A‐site at = 0.2‐0.4, whereas Mn2+ ions substitute for Zr4+ ions in B‐site to form defects () at > 0.4. For ceramics sintered in air, mixed Mn2+, Mn3+, and Mn4+ ions coexist here. The Mn2+ ions preferentially occupy the cation vacancies in A‐site at = 0.2‐0.4 and then Mn2+ ions substitute for Zr4+ ions in B‐site at > 0.4. Meanwhile, the Mn3+ ions and Mn4+ ions substitute for Nb5+ ions in B‐site to form defects () at = 0.2‐0.8. The (, , and ) dipolar defects show a positive dipolar defect contribution (DDC) to the , whereas the dipolar defects () show a negative DDC to the . The dipolar defects ( ‐ and ) can help improve the temperature stability of . The 0.4% MnO‐doped KNN‐0.045BNZ ceramics sintered in reducing atmosphere show excellent piezoelectric constant d33 = 300 pC/N and 0.2% MnO‐doped KNN‐0.045BNZ ceramics sintered in air possess optimal piezoelectric constant d33 = 290 pC/N.  相似文献   

20.
Dielectric materials with high power and energy densities are desirable for potential applications in advanced pulsed capacitors. Computational material designs based on first‐principles calculations provide a “bottom‐up” method to design novel materials. Here, we present a first‐principles effective Hamiltonian simulation of perovskite ferroelectrics, Ba1‐xSrxTiO3, for energy storage applications. The effects of different chemical compositions, temperatures, and external electric fields on the ferroelectric hysteresis and energy storage density of Ba1‐xSrxTiO3 were investigated. The Curie temperature was tuned from 400 to 100 K by doping Sr in the BaTiO3 lattice. At a constant temperature, the ferroelectric hysteresis became slimmer as the Sr content increased, and the energy storage efficiency increased. For the same chemical composition, the energy storage density increased as the temperature increased. For the composition x = 0.4, a discharged energy density of ~2.8 J/cm3 with a 95% efficiency was obtained in an external electric field of 350 kV/cm, and a discharged energy density of 30 J/cm3 with a 92% efficiency was obtained in an external electric field of 2750 kV/cm. The energy storage property predictions and new material designs have potential to create experimental and industrial products with higher energy storage densities.  相似文献   

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