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1.
Bi1-xSmxFeO3 (x?=?0.15–0.18) ceramics with high density were produced using spark plasma sintering. The effects of composition, synthesis conditions and temperature on the phase evolution were studied, using XRD, TEM and dielectric spectroscopy. The coexistence of the ferroelectric R3c, antiferroelectric Pnam and paraelectric Pnma phases was revealed, with relative phase fractions affected by both calcination conditions and Sm concentration. Experiments on powdered samples calcined at different temperatures up to 950?°C suggest higher calcination temperatures promote Sm diffusion, allowing samples to reach compositional homogeneity. The structural transitions from the Pnam and R3c phases to the Pnma phase were comprehensively investigated, with phase transition temperatures clearly identified. The dielectric permittivity, electrical resistivity and breakdown strength were increased upon Sm-substitution, while ferroelectric switching was suppressed. The polarization-electric field loop became increasingly narrow with increasing Sm-content, but double hysteresis loops, which may reflect a reversible antiferroelectric to ferroelectric transformation, were not observed.  相似文献   

2.
Multiferroic ceramics were prepared and characterized in (1?x)BiFeO3x(0.5CaTiO3–0.5SmFeO3) system by a standard solid‐state reaction process. The structure evolution was investigated by X‐ray diffraction and Raman spectrum analyses. The refinement results confirmed the different phase assemblages with varying amounts of polar rhombohedral R3c and nonpolar orthorhombic Pbnm as a function of the substitution content. In the compositions range of 0.2≤x≤0.5, polar R3c and nonpolar Pbnm coexisted, which was referred to polar‐to‐nonpolar morphotropic phase boundary (MPB). According to the dielectric and DSC analysis results, the ceramics with x≤0.2 changed to diffused ferroelectric, and the ferroelectric properties were enhanced significantly. Two dielectric relaxations were detected in the temperature range of 200‐300 K and 500‐700 K, respectively. The high‐temperature dielectric relaxation was attributed to the grain‐boundary effects. While the low temperature dielectric relaxation obtained in the samples with x=0.3‐0.5 was related to the charge transfer between Fe2+ and Fe3+. The magnetic hysteresis loops measured at different temperature indicated the enhanced magnetic properties in the present ceramics, which could be attributed to the suppressed cycloidal spin magnetic structure by Ti ions. In addition, the rare‐earth Sm spin moments might also affect the magnetic properties at relatively lower temperature.  相似文献   

3.
《Ceramics International》2015,41(6):7693-7697
(1−x)BaTiO3xBi(Mg1/2Ti1/2)O3 (BT–BMT, x=0–0.2, abbreviated as BT–BMT100x) ceramics were prepared by using a solid state reaction process. Their crystal structure, microstructure, conduction behavior, dielectric and tunability properties were investigated. It is found that the tetragonal phase and a pseudocubic phase coexist for x≤0.15 and transform to a pseudocubic phase at x=0.20. With the incorporation of BMT, BT–BMT becomes more insulating. The activation energies of the conduction are respectively 1.15(1) and 1.54(1) eV for grain and grain boundary of BT–BMT20. Furthermore, an abnormal nonlinear dielectric tunable behavior is observed. The dielectric permittivity first slightly increases until reaching the threshold electric field, and then suddenly decreases. This abnormal nonlinear dielectric behavior is attributed to the synergetic effects of the clamped oxygen vacancies and excessive aggregation of Bi at the grain boundaries.  相似文献   

4.
《Ceramics International》2020,46(14):22221-22229
The (La0.3Pr0.7)1-xCaxCrO3 (x = 0, 0.1, 0.3 and 0.5) ceramics have been synthesized by a sol-gel method. The compounds crystalize in orthorhombic structure with space group Pnma at room temperature. The magnetic measurements confirm that the materials form canted antiferromagnetic (AFM) ordering from 254.1, 231.2, 118.5, 49.3 K for the samples of x = 0, 0.1, 0.3 and 0.5, accompanied by a spin reorientation transition at 191.4, 145.1, 55.8, 38.9 K because of the Pr3+-Cr3+ interaction. Meanwhile, a positive exchange bias effect is observed due to the antiparallel coupling between the Pr3+ and the canted AFM structure of Cr3+. The Néel temperature, compensation temperature as well as the coupling strength of Pr3+-Cr3+ monotonously decrease with the increase of Ca2+ concentration. For the samples of x = 0.1 and 0.3, there exists a field induced Pr3+-Pr3+ AFM ordering. By means of dielectric measurements, large permittivity at room temperature and dielectric relaxation are observed in all the samples. The permittivity is decreased and dielectric relaxation moves to low temperature range with the increase of Ca2+ concentration. A relaxor-like ferroelectric transition is observed in the measuring temperature range in Ca2+ doped samples.  相似文献   

5.
Mutiferroic materials like bismuth ferrite BiFeO3 have attracted much interest in the last decade due to their promising potential for such applications as spintronics and magnetoelectric data storage devices. On the other hand, relaxor ferroelectrics have been intensively studied for their complex structures with quenched disorder and polar nanoregions which play an important role in their outstanding piezoelectric performance. Much less studied are the single-phase multiferroics that exhibit ferroelectric and/or magnetic relaxor behavior and the correlation between their structure and intricate magneto-electric interactions. In this work, we investigate the evolution of the structure and relaxor behavior in the solid solution between the complex perovskite multirelaxor Pb(Fe2/3W1/3)O3 [PFW] and canonical multiferroic BiFeO3 [BFO], (1-x)PFW-xBFO (with a solubility limit of x = 0.30). The temperature dependences of the dielectric permittivity and loss tangent measured in the frequency range from 100 Hz to 1 MHz indicate characteristic relaxor ferroelectric properties for compositions of x ≤ 0.15, with a frequency-dependent dielectric permittivity peak and its temperature, Tm, satisfying the Vogel-Fulcher law. Detailed studies of the evolution of the relaxor behavior with composition reveal that Tm decreases firstly with a small amount (x = 0.05) of BFO substitution and then increases with further increase of BFO concentration. The degree of relaxor character, as defined by ΔTm [Tm (1 MHz) - Tm (100 Hz)], increases monotonously with increasing BFO content, signifying an enhancement of relaxor behavior with BFO substitution, which is confirmed by the Lorenz-type quadratic variation of the static permittivity. A temperature - composition phase diagram is constructed in terms of the characteristic Burns temperature (TB) and freezing temperature (Tf), which delimits a paraelectric state (PE) above TB, a non-ergotic relaxor state (NR) below Tf, and an ergotic relaxor state (ER) in between. The observed enhancement of relaxor behavior is explained by an increase in the number and size distribution of polar nanoregions in the ER phase, resulting from increased compositional and charge disorders as a result of BFO substitution. The evolution of relaxor behavior and its microscopic mechanisms studied in this work are insightful for a better understanding the multirelaxor properties in multiferroics. Moreover, further substitution of BFO (x ≥ 0.2) flattens the permittivity curves and leads to a temperature-stable variation of high dielectric constant (≈ 103) in a wide temperature range, making the PFW-BFO solid solution attractive for such applications as high energy density capacitors.  相似文献   

6.
Dense nanocrystalline BaTiO3 ceramics are prepared in a single step by the Cold Sintering Process at 300 °C, under a uniaxial pressure of 520 MPa for 12 h using a molten hydroxide flux. Transmission electron microscopy reveals a dense microstructure with sharp grain boundaries. The average grain sizes are 75−150 nm depending on the flux amount. The dielectric permittivity is 700–1800 at room temperature at 106 Hz, with a dielectric loss, tan δ ∼ 0.04. The difference in permittivity and phase transition behavior are explained in terms of the intrinsic size effect of the BaTiO3. The nanocrystalline BaTiO3 ceramics still shows a macroscopic ferroelectric switching via a hysteresis loop. This work demonstrates that cold-sintering process could enable the densification of ferroelectric oxides in a single step. Futhermore, comparable dielectric properties to reported values for nanocrystalline grains are obtained, but at this time, with the lowest processing temperatures ever used.  相似文献   

7.
A route exploring the morphotropic phase boundaries (MPB) region in (Bi.5Na.5)TiO3-BaTiO3-(Bi.5K.5)TiO3 ternary system has been designed based on the phase diagram. X-ray diffraction (XRD) has been performed to determine the phases of the prepared samples. The dielectric, ferroelectric, and piezoelectric properties of [(1-x) 0.9363(Bi.5Na.5)TiO3–0.0637BaTiO3]-x(Bi.5K.5)TiO3 (BNKBT100x) ternary lead-free piezoelectric ceramics are investigated as the functions of x and sintering temperature. When x was varied from 0 to 0.11, the BNKBT100x ceramics show single perovskite structure sintered at 1130–1210?°C. These ceramics show large dielectric permittivity, small dielectric loss, and diffused phase transition behavior. Well-defined ferroelectric polarization-electric field (P-E) hysteresis loop and relative large piezoelectric and electromechanical coefficients are also found in these ceramics. When increasing x, the electrical performances first increase, then decrease. The same rule is found when varying the sintering temperature. The optimized composition and sintering temperature are finally obtained.  相似文献   

8.
Sol-gel method was used to prepare the Pr3+ ions-doped (1-x)Na0.5Bi0.5TiO3-xCaTiO3 (Pr-NBT-xCTO) (x?=?0, 0.04, 0.06, 0.08, 0.1, 0.12, and 0.16) thin films on Pt/Ti/SiO2/Si and fused silicon substrates. The structure phase of thin films was evolving from rhombohedral (R3c) to orthorhombic (Pnma) with increasing CTO content. Owing to the morphotropic phase boundary (MPB), the improved ferroelectric and dielectric properties were obtained at x?=?0.06–0.1. The MPB was formed from the concomitant phase of rhombohedral (R3c) and orthorhombic (Pnma). The Pr-NBT-0.08CTO thin film showed the best ferroelectric and dielectric properties, as well as strong relaxor behavior (the diffusion factor is γ?=?1.79). In addition, all the films exhibited strong red emission as excited by UV light, and wide optical band-gap (3.44–3.47?eV), which might be influenced by grain size and structural variation. Our results indicate that Pr-NBT-xCTO thin films may have potential applications in ferroelectric-luminescence multifunctional optoelectronic devices.  相似文献   

9.
This study reports on the synthesis of polycrystalline samples of (Na0.5Bi0.5)(1−x)BaxTi(1−x)(Fe0.5Nb0.5)xO3 with x=0, 0.025, 0.05, 0.075, and 0.1, using the solid-state reaction technique. It investigates the effects of the substitution of sodium and bismuth by barium in the A site and of titanium by iron and niobium in the B site with regard to the free NBT symmetry and dielectric properties were investigated. The crystallographic and dielectric properties were also investigated. The diffractograms showed that all the samples had a single phase character. The increase of ceramic lattice parameters induced an increase in the size of the perovskite lattice. This increase was caused by the increase of the radii of the A and B sites. Room temperature X-ray data revealed that the ceramic structures underwent a gradual distortion with the increase in the composition fraction. Dielectric permittivity was measured in the temperature range of 120–780 K with frequencies ranging from 1 to 103 KHz. Three anomalies, namely Td, T1 and Tm, were detected and noted to coexist at lower Td and Tm as the rate of substitutions increased. All the samples exhibited a diffuse phase transition and implied better dielectric permittivity maxima values at temperatures approaching room temperature, since the substitution rate values increased more than that of pure NBT. A relaxor behavior with ΔTm=14 K and ε'rmax=3876 at 1 kHz was observed for (Na0.5Bi0.5)0.9Ba0.1Ti0.9(Fe0.5Nb0.5)0.1O3 ceramic.  相似文献   

10.
Cold sintering process (CSP) offers a promising strategy for the fabrication of innovative and advanced high permittivity dielectric nanocomposite materials. Here, we introduce Ba(OH)2?8H2O hydrated flux as a new transient chemistry that enables the densification of BaTiO3 in a single step at a temperature as low as 150 °C. This remarkably low temperature is near its Curie transition of 125 °C, associated with a displacive phase transition. The cold sintered BaTiO3 shows a relative density of 95 % and a room temperature relative permittivity over 1000. This new hydrated flux permits the fabrication of a unique dense BaTiO3-polymer nanocomposite with a high volume fraction of ceramics ((1-x) BaTiO3x PTFE, with x = 0.05). The composite exhibits a relative permittivity of approximately 800, at least an order of magnitude higher than previous reports on polymer composites with BaTiO3 nanoparticle fillers that are typically well below 100. Unique high permittivity dielectric nanocomposites with enhanced resistivities can now be designed using polymers to engineer grain boundaries and CSP as a processing method opening up new possibilities in dielectric materials design.  相似文献   

11.
Multiferroics are materials that exhibit two or more primary ferroic properties within the same phase and have potential applications in sensors, spintronics and memory devices. Here, the dielectric, ferroelectric and magnetic properties of novel multiferroics derived from BaTi1?x(Fe0.5Nb0.5)xO3 (BTFN, 0.01 ≤ x ≤ 0.10) ceramics are investigated. Multiferroism in these ceramics is manifested by the coexistence of ferroelectric long-range ordering and antiferromagnetism. With increasing x-value, there is a structural evolution from a tetragonal perovskite to a mixture of tetragonal and cubic phases, accompanied by a decrease in the temperature of maximum permittivity. At room temperature, ferroelectric behaviour is evidenced by the presence of current peaks corresponding to domain switching in the current-electric field loops, while the observation of non-linear narrow magnetic hysteresis loops suggests dilute magnetism. The results indicate that in the x = 0.07 composition the antiferromagnetic order is established through an indirect super-exchange interaction between adjacent Fe ions.  相似文献   

12.
The Na0.47Bi0.47Ba0.06Ti1-xFexO3-Δ lead-free piezoelectric ceramics (BNBT-100xFe, x?=?0, 0.01, 0.02, 0.03) were synthesized by using the solid-state reaction technique. X-ray powder diffraction patterns demonstrate that the doping Fe2O3 has totally diffused into the crystal lattice of the ceramics and form a pure perovskite structure. Enhanced piezoelectric property is obtained at x?=?0.01, which is reflected on the enhanced remnant polarization (Pr) and a giant piezoelectric constant (d33) up to 168 pC/N. The increasing ferroelectric-to-relaxor phase transition temperature (TF-R) on dielectric permittivity curves suggest the enhanced ferroelectric characteristics with increasing the Fe3+ content. By using the complex ac impedance analysis, the grain, grain boundary and electrode effects are all detected at the appreciate composition. The resistivity behavior of the samples is sensitive to the doping Fe3+ concentration, and additionally, the oxygen vacancies play an important role in this characteristic.  相似文献   

13.
《Ceramics International》2017,43(12):8664-8676
Single-phase Ca1−3x/2TbxCu3Ti4−xTbxO12 (0.025≤ x≤0.075) (CTCTT) ceramics with a cubic perovskite-like structure and a fine-grained microstructure (1.6‒2.3 µm) were prepared using a mixed oxides method. The results revealed that mixed valence states of Cu2+/Cu+, Ti4+/Ti3+, and Tb3+/Tb4+ coexisted in CTCTT. A multiphonon phenomenon in the Raman scattering at 1148, 1323, and 1502 cm−1 was reported for undoped and doped CTTO. Tb was mainly incorporated in the interior of the CTCTT grains rather than on the surface. The dielectric permittivity of CTCTT (εr'RT =3590‒5200) decreased relative to CCTO (εr'RT =10240) at f =1 kHz, but the dielectric loss of CTCTT (the minimum value of tan δ=0.12 at RT) increased as a result of Tb doping. The defect chemistry of CTCTT is discussed. The internal barrier layers capacitance (IBLC) model was adopted for impedance spectroscopy (IS) analysis. The activation energies of the grain boundaries (Egb) and semi-conductive grains (Eg) for CTCTT were determined to be 0.52 eV and 104 meV, respectively. The IS and defect chemistry analyses confirmed that the decrease in the dielectric permittivity was mainly due to a decrease in conductivity in the semiconducting CTCTT grains caused by the acceptor effect of Tb4+ at the Ti site, which resulted in a decrease in the IBLC effect.  相似文献   

14.
(BaFe11.9Al0.1O19)1-x - (BaTiO3)x with x?=?0, 0.25, 0.5, 0.75 and 1 bicomponent ceramics has been prepared from single-phase compounds of BaFe11.9Al0.1O19 (x?=?0) (BFO) and BaTiO3 (x?=?1) (BTO) by a standard ceramic technique. The constituent materials have been chosen considering their perspective ferrimagnetic and ferroelectric properties, respectively for BFO and BTO. Moreover, Ba-hexaferrites are reported to exhibit ferroelectricity at room temperature as well, and the combination of two ferroelectric phases is of interest. Systematic investigations of the structural, magnetic and dielectrical properties versus chemical composition (x) have been performed. The ferrimagnetic phase transition temperature is almost independent of the BTO content, which is determined by intensity of the Fe3+-O2--Fe3+ indirect superexchange interactions in the BFO hexaferrite phase. However, the coercivity of composite samples is lower due to the contribution of the microstructure-dependent shape anisotropy to the total magnetic anisotropy energy. The permittivity vs. temperature behavior confirmed the existence of two ferroelectric phase transitions corresponding to structural phase transitions in BTO at ~ 400?K and BFO at ~ 700?K. It has been observed that the dielectrical properties of composite samples, including the temperatures of the phase transitions, critically depended on concentration x which affects the composite microstructure. This behavior has been discussed in terms of microstructure analysis and such parameters as the grain size, porosity and density.  相似文献   

15.
This study demonstrates the high energy-storage performance using 0.1 wt% MnO2–added 0.7(Bi1?xSmxFeO3)? 0.3(BaTiO3) (x = 0–0.3) ceramics through tailoring microstructures and polar order. Sequential structure transitions were identified from a co-occurrence of nonpolar pseudo-cubic Pm-3m and ferroelectric rhombohedral R3c symmetries to antipolar orthorhombic Pbam and nonpolar orthorhombic Pnma symmetries as Sm substitution increases. Recoverable energy densities (Wrec) of 4.5 J/cm3 and 4.1 J/cm3 with efficiencies (η) of 62.1% and 78.1% were achieved respectively for x = 0.15 and 0.2 at a field of 220 kV/cm. The improved energy storage is associated with microstructure modification and complex grain matrix, consisting of grain boundaries, nanocluster/nanomosaic structures, core-shell structures, and polar nanoregions. The nanocluster/nanomosaic structures may act as barriers to suppress polar order and enhance dielectric breakdown strength. This work provides an efficient route to utilize binary BiFeO3-BaTiO3 ceramics for electrical energy storage.  相似文献   

16.
《Ceramics International》2017,43(16):13349-13355
In this study, (Ta0.5Sm0.5)xTi1−xO2 (x = 0, 0.02, 0.06, 0.15) ceramics (referred to as TSTO) were fabricated by a standard solid-state reaction. As revealed by the X-ray diffraction (XRD) spectra, the TSTOs exhibit a tetragonal rutile TiO2 structure. All the TSTO ceramics display colossal permittivity (~ 102–105). Moreover, the optimal ceramic, (Ta0.5Sm0.5)0.02Ti0.98O2, exhibits high performance over a wide temperature range from 20 °C to 160 °C. At 1 kHz, the dielectric constant and dielectric loss are 2.30 × 104 and 0.11 at 20 °C; they are 3.85 × 104 and 0.64 at 160 °C. Dielectric and impedance spectra analyses for the TSTO ceramics indicate that the CP behavior over a broad temperature range in (Ta+Sm) co-doped TiO2 could be explained by the internal barrier layer capacitance (IBLC) model, which consists of semiconducting grains and insulating grain boundaries.  相似文献   

17.
《Ceramics International》2017,43(11):8378-8390
Dysprosium (Dy) substituted nickel ferrite (NiDyxFe2-xO4) powders with varying Dy content (x=0.0, 0.025, 0.05, 0.075, 0.1, 0.2) have been prepared by combustion method using DL-alanine fuel. Sintering characteristics of the powders and electrical properties of ceramics have been studied. Effective substitution of Dy3+ for Fe3+ is seen up to x=0.075 yielding improved properties, and a higher Dy content (x≥0.1) leads to partial substitution, disturbed stoichiometry, and diffusion of Dy to the grain boundaries and segregation as a secondary phase. Increasing Dy content reduces the crystallite size, powder particle size, and grain size in sintered ceramics, and the changing microstructural evolution is better resolved with back scattered electron imaging and compositional analysis. Raman spectroscopy confirms inverse spinel structure formation and substantiates the presence of secondary phase evidenced through X-ray diffraction and electron microscopy. A marginal increase in the electrical resistivity (ρdc) and magnetization are observed due to effectual substitution of Dy3+ for Fe3+ at the octahedral sites up to x=0.075. For x≥0.1, the increasing influence of highly resistive DyFeO3 secondary phase at the inter-granular boundaries leads to a rapid increase in resistivity and reduction in dielectric losses, and the magnetization is reduced due to the anti-ferromagnetic nature of the secondary phase (DyFeO3). Dense ceramics with high resistivity (~109 Ω cm), low dielectric loss (tan δ ~0.002) at 1 MHz, and high magnetization (50.07 emu/g) are obtained for an optimum Dy content of x=0.075. Dielectric response, complex impedance, and electrical modulus spectroscopy in the frequency range (10−2–106 Hz) reflect the changes in the microstructure, and suggests a non-Debye type relaxation.  相似文献   

18.
A series of textured (Nb0.5La0.5)xTi1-xO2 (x = 0, 0.0025, 0.005, 0.01) ceramics were sintered in a nitrogen environment after magnetic slip casting (12 T). Component x ranges from 0.0025 to 0.01 while the degree of orientation increases from 0.49 to 0.88. (Nb0.5La0.5)0.01Ti0.99O2 ceramics in the parallel magnetic field's plane have a high permittivity ɛr ≈ 1.6 × 104 and the ultralow dielectric loss tanδ ≈ 0.0038 at 104 Hz. The temperature coefficient value of η ≤ ± 7.1% between 218–473 K, fulfilling the X9R requirements. The giant permittivity properties of textured ceramics are mainly derived from internal barrier layer capacitor impacts, electron hopping, and electron-pinned defect-dipoles polarization. The microstructure evolution of sintered ceramics was modified by texturing in a magnetic field, leading to higher activation energies of dielectric relaxations and resistance of grain boundaries and grains. This excellent performance is expected to show great potential in electronic devices' miniaturization and high-density energy storage.  相似文献   

19.
A series of temperature‐stable microwave dielectric ceramics, (1?x)(Na0.5La0.5)MoO4x(Na0.5Bi0.5)MoO4 (0.0 ≤ x ≤ 1.0) were prepared by using solid‐state reaction. All specimens can be well sintered at temperature of 580°C–680°C. Sintering behavior, phase composition, microstructures, and microwave dielectric properties of the ceramics were investigated. X‐ray diffraction results indicated that tetragonal scheelite solid solution was formed. Microwave dielectric properties showed that permittivity (εr) and temperature coefficient of resonant frequency (τf) were increased gradually, while quality factor (Q × f) values were decreased, at the x value was increased. The 0.45(Na0.5La0.5)MoO4–0.55(Na0.5Bi0.5)MoO4 ceramic sintered at 640°C with a relative permittivity of 23.1, a Q × f values of 17 500 GHz (at 9 GHz) and a near zero τf value of 0.28 ppm/°C. Far‐infrared spectra (50–1000 cm?1) study showed that complex dielectric spectra were in good agreement with the measured microwave permittivity and dielectric losses.  相似文献   

20.
《Ceramics International》2016,42(3):4176-4184
The effect of the La3+ and Gd3+ co-doping on the structure, electric and magnetic properties of BiFeO3 (BFO) ceramics are investigated. For the compositions (x=0 and 0≤y≤0.15) in the perovskite structured LaxGdyBi1−(x+y)FeO3 system, a tiny residual phase of Bi2Fe4O9 is noticed. Such a secondary phase is suppressed with the incorporation of ‘La’ content (x). The magnitude of dielectric constant (εr) increases progressively by increasing the ‘La’ content from x=0 to 0.15 with a remarkable decrease of dielectric loss. For x=0.15, the system LaxGdyBi1−(x+y)FeO3 exhibits highest remanent magnetization (Mr) of 0.18 emu/g and coercive magnetic field (HC) of ~1 T in the presence of external magnetic field of 9 T at 300 K. The origin of enhanced dielectric and magnetic properties of LaxGdyBi1−(x+y)FeO3 and the role of doping elements, La3+, Gd3+ has been discussed.  相似文献   

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