Pb(Zn1/3Nb2/3)O3-Ba(Zn1/3Nb2/3)O3铁电陶瓷结构与性能的研究

采用固相反应的方法系统地研究了BZN稳定PZN基陶瓷的相结构与介电性能.随着BZN含量的增加,PZN-BZN陶瓷中钙钛矿相的稳定性增强,居里温度近似呈线性下降,室温介电常数和介质损耗随也显著降低,最小值分别为380和0.002.为获得100%钙钛矿结构的PZN基陶瓷所需BZN的最小用量为8mol%～10mol%,当BZN的mol%超过15mol%时,PZN基陶瓷中钙钛矿相所占的百分比不再受烧结工艺的影响,基本保持100%.1kHz时Pb0.9Ba0.1Zn1/3Nb2/3O3陶瓷的最大介电常数Kmax=8680,tgδ=0.02,相应的居里温度Tm为24℃.     

Dielectric properties of Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Dielectric properties of lead zinc niobate (PZN) ceramics modified by barium zinc niobate (BZN) and BaTiO₃ (BT) were investigated. By adding the modifier of BT and BZN, the stabilization of perovskite phase of PZN increased, but its Curie temperature decreased linearly with the amount of added modifier. Room temperature dielectric constant of PZN increased by addition of stabilizers up to 12 and 15 mol% of BZN and BT, respectively. The maximum room temperature dielectric constant was observed to be 7800 at 12 mol% of BZN, and 9800 at 15 mol% of BT, respectively.     

Effects of CaTiO3 on crystal structures and dielectric properties of Ba(Zn1/3Nb2/3)O3 ceramics via X-ray diffraction and Raman spectroscopy

Ba(Zn_1/3Nb_2/3)O₃–CaTiO₃ (BZN–CT) ceramics were synthesized at 1,395 °C for 4 h using a conventional solid-state sintering technique, with CT contents of 0, 30, 60, 75, and 90 wt%. Crystal structures were analyzed by X-ray diffraction, and vibrational modes were obtained by Raman spectroscopy to evaluate the correlation between crystal structures, dielectric properties, and phonon modes of these ceramics. Increasing CT content can remarkably affect the crystal structures and dielectric properties of BZN–CT ceramics. Crystal symmetries decrease with CT concentration from cubic to hexagonal structure. The lattice constant and the degree of order also change accordingly. The ordered phases transform from 1:1 to 1:2 ordered structure with changing crystal structures. The relationship between the Raman shifts, the FWHM values, and the dielectric properties were obtained by Raman spectral analyses.     

Low temperature hydrothermal synthesis of Ba(Mg1/3Ta2/3)O3 sol-derived powders

Powders of the microwave dielectric material barium magnesium tantalate Ba(Mg1/3Ta2/3)O3 have been produced by hydrothermal synthesis at moderately low temperatures (160 to 350°C). It was found that while it is relatively straightforward to produce the material in the desired perovskite phase at or below 200°C, the powder particles tend to be highly irregular in morphology with extremely small dimensions (of the order of 10 nm) and deficient in magnesium (with some precipitation of the excess magnesium as the hydroxide). The effects of both higher synthesis temperatures and different feedstock preparation were thus investigated with the aim of improving the precipitation of magnesium under hydrothermal conditions in order to produce a more homogeneous, stoichiometric powder and significant progress was made. It was found that when near-stoichiometric particles are formed, they adopt rounded morphologies and exhibit larger particle sizes (around 30–50 nm). These results show that the hydrothermal feedstock and the synthesis temperature used have a profound effect on particle stoichiometry, which in turn affects the growth morphology of the particles.     

Ba(Zn1/3Ta2/3)O3 ceramics reinforced high density polyethylene for microwave applications

The effect of Ba(Zn_1/3Ta_2/3)O₃ (BZT) ceramic filler on the dielectric, mechanical and thermal properties of high density polyethylene (HDPE) matrix have been investigated. The dispersion of BZT particles in the matrix was varied up to 0.45 volume fraction (V_f)_. The SEM images confirmed the increase in connectivity between the filler particles with the increase in filler loading. All the composites showed excellent densification (>99 %) with relatively low moisture absorption (<0.04 wt%). The dielectric properties of the composites were investigated at 1 MHz, 5 GHz and at 10 GHz. The relative permittivity and the dielectric loss were found to increase as a function of BZT loading. Different theoretical models were used to predict the relative permittivity at 10 GHz. Effective medium theory gave the best correlation with the experimental results. An enhancement in the thermal conductivity (TC) and a reduction in the coefficient of linear thermal expansion (CTE) were achieved with filler loading. A slight decrease in the tensile strength was also observed with BZT loading. At 10 GHz, 0.45 V_f BZT reinforced HDPE showed a low relative permittivity (ε_r = 8.2) and a low dielectric loss (tanδ = 1.6 × 10^?3) with good thermal (TC = 1.4 W m^?1 K^?1, CTE = 92 ppm/°C) and mechanical (tensile strength = 18 MPa) properties.     

Dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low temperatures

Dielectric characteristics of Ba(Mg_1/3Ta_2/3)O₃ ceramics (BMT ceramics) sintered at low temperatures with 2–3 wt% NaF additives were determined. A dielectric constant of 25 and extremely low dielectric loss (< 0.0001) were measured at 100 kHz and 1 MHz in BMT ceramics sintered under these conditions, and no frequency dependence of the dielectric constant was observed. This suggested that NaF as sintering additive had no harmful influence on the dielectric properties of the ceramics.     

Effects of non-stoichiometry and chemical inhomogeneity on the order-disorder phase formation in the complex perovskite compounds,Ba(Ni1/3Nb2/3)O3and Ba(Zn1/3Nb2/3)O3

The order-disorder phase formation of the complex perovskite compounds, Ba(Ni_1/3Nb_2/3)O₃ and Ba(Zn_1/3Nb_2/3)O₃, was investigated by various heat treatments. Heat-treated samples were characterized using X-ray diffraction, SEM, and EDS, interactively. On the basis of lattice parameter measurements, the defect concentration in the complex perovskite compounds was thought to control ordered or disordered phase formation. The chemical inhomogeneity in the calcined powder was responsible for the formation of a liquid phase in the non-equilibrium state. These compounds are postulated to melt incongruently above temperature at which the ordered phase forms. Irrespective of extended heat treatments, second phases were observed but could not be identified by XRD due to lack of information. The second phase in BNN was unreacted NiO with a small amount of barium and niobium, and the second phase in BZN was a pyrochlore-like compound of which the composition was BaNb = 11 with a small amount of zinc.     

Stabilization of the perovskite phase in Pb(Zn1/3, Nb2/3)O3 ceramics modified by Ba(Zn1/3, Nb2/3)O3 and BaTiO3

Stabilization of the perovskite phase in PZN-BT-BZN ceramics prepared by solid-state sintering was investigated. With the addition of BT and/or BZN, the amounts of perovskite phase in PZN ceramics increased, but the amount of pyrochlore phase decreased. Optimum calcination conditions for this system, to obtain PZN ceramics with the minimum amount of the pyrochlore phase, are a temperature range between 950 and 1000°C and a sintering time of 2–4 h. The perovskite phase of these systems could be 100% stabilized by the addition of more than 7 mol% BT, 8 and 10 mol% BTZN and BZN, respectively. This revised version was published online in November 2006 with corrections to the Cover Date.     

Raman spectroscopy and cathodoluminescence characteristics of order-disorder Ba(Zn1/3Ta2/3)O3 ceramics

The order-disorder transition in Ba(Zn_1/3Ta_2/3)O₃ (BZT) was characterized by using Raman spectroscopy, transmission electron microscopy (TEM), and cathodoluminescence (CL) microscopy. The 1:2 ordered structure of pure BZT ceramics was replaced by a 1:1 ordered structure at 1650 °C and the 1:1 ordered structure of BZT sintered at 1650 °C exhibited a 1:2 ordered structure when it was reannealed at 1500 °C for 12 h. The A_1g lines in the Raman spectrum of the sintered and reannealed samples were shifted to lower and higher wavenumbers, respectively. From the CL analysis, the 1:1 ordered BZT exhibited mainly three emission bands at around 533.2 (2.32 eV), 599.1 (2.07 eV), and 682.1 nm (1.81 eV), whereas the 1:2 ordered BZT exhibited mainly five bands at 346.4 (3.58 eV), 427.5 (2.90 eV), 520.9 (2.38 eV), 593.0 (2.09 eV), and 678.9 nm (1.82 eV). The strongest band originating from 2.32 to 2.38 eV was broadened, and the band center shifted towards a higher and lower wavelength in the 1:1 and 1:2 ordered BZT, respectively. Additional bands at around 346 and 427 nm in the grain interior of the annealed sample were strongly related to the 1:2 ordering of BZT.     

Microwave dielectric characteristics of Ba(Mg1/3Ta2/3)O3 ceramics sintered at low-temperatures

The microwave dielectric properties and microstructures of Ba(Mg_1/3Ta_2/3)O₃ (BMT) ceramics sintered at low temperatures with 2–3 wt.% NaF additives were investigated. BMT ceramics sintered at 1340 °C for 3–12 h showed dielectric constants (_r) of 25.5–25.7, Qf values of 41 500–50 400 GHz and temperature coefficients of the resonator frequency (τ_f) of 10.9–21.4 ppm °C⁻¹. The variation of sintering time almost had no effect on the dielectric constant. The Qf value increased and the τ_f decreased with increasing sintering time. The ordering degree of Mg²⁺ and Ta⁵⁺ at B-sites increased with increasing sintering time.     

Effect of Ba(Zn1/3Ta2/3)O3 and SiO2 ceramic fillers on the microwave dielectric properties of butyl rubber composites

Butyl rubber–Ba(Zn_1/3Ta_2/3)O₃ (BR–BZT) composites and butyl rubber–silica (BRS) composites were prepared by sigma mixing. The dielectric properties at 1 MHz and 5 GHz of BR–BZT and BRS composites were investigated as a function of ceramic loading and were found to be improved with filler loading. For a optimum BZT loading of 0.26 v_f, the BR–BZT composite have ε_r = 4.88, tanδ = 0.0022 (at 5 GHz), coefficient of thermal expansion (CTE) = 112 ppm/°C, thermal conductivity (TC) = 0.30 Wm^?1 K^?1 and water absorption = 0.047 vol%. The BRS composites attained ε_r = 2.79, tanδ = 0.0039 (at 5 GHz), CTE = 102 ppm/°C, TC = 0.40 Wm^?1 K^?1 and water absorption = 0.078 vol% for the same loading of silica. The stress–strain curves of both composites showed good flexibility of the composite. The measured relative permittivity and TC of both composites were compared with different theoretical approaches.     

Effect of Sn4+ B-Site Substitution on the Microstructure and Dielectric Properties of Ba(Mg1/3Ta2/3)O3 Microwave Ceramics

1.IntroductionRecent progress of microwave telecommunication de-mands the development and application of a variety ofmicrowave dielectric materials.The materials with highdielectric constant(ε),high quality factor(Q)and smalltemperature coefficient of resonant frequency(TCF)haveattracted the greatest interest of researchers.The com-pounds Ba(B'1/3B"2/3)O3(B'=Mg,Zn,Ni,etc.B"=Ta,Nb,etc.)with complex perovskite structure exhibit veryhigh Q value at microwave frequencies greaterthan10GHz.…     

Ba（Mg1／3Ta2／3）O3微波陶瓷的损耗研究

本工作用ＸＲＤ，ＥＰＭＡ，ＳＥＭ等测试技术计算和示出了用不同活性粉料制备的Ｂａ（Ｍｇ１／３Ｔａ２／３）Ｏ３微波陶瓷晶格中Ｂ位离子有序度和元素的面分布情况，对它们在Ｘ面下的电行为作了探讨。实验结果表明，ＢＭＴ陶瓷的微波损耗主要与其密度有序度和微观结构的均一度有关。     

Relaxor behavior in Ba(Zn1/3Nb2/3)O3-PbTiO3 new solid solution

Relaxor behavior has been found in a new solid solution between complex perovskite Ba(Zn(1/3)Nb(2/3))O(3) (BZN) and ferroelectric PbTiO(3) (PT), prepared by solid state reactions. A strong dispersion of the maximum of dielectric permittivity (epsilon(')) appears around the temperature of T(m), which shifts toward higher temperatures with increasing frequency. The variation of T(m) with frequency follows the Vogel-Fulcher relationship. The variation of 1/epsilon(') with temperature above Tm deviates from the Curie-Weiss law, but satisfies a Lorentz-type function. The relaxor behavior becomes weaker upon increasing PT-content.     

Effect of dopants on the low temperature microwave dielectric properties of Ba(Zn1/3Ta2/3)O3 ceramics

Ba(Zn_1/3Ta_2/3)O₃ has been prepared with different dopants that gave best microwave dielectric properties at room temperature. Effects of different dopants on the low temperature microwave dielectric properties of BZT were investigated. With decrease in temperature, loss tangent was found to decrease marginally and then increase at temperatures lower than 100 K. Increase in loss factor at lower temperatures were found to be less for dopants with smaller ionic radii. Dielectric constant was found to be almost independent of temperature. Temperature coefficient of resonant frequency slowly decreased from a positive value to negative value when temperature was lowered. Temperature at which τ_f becomes zero was found to vary for different dopants. There is a temperature stable region for tanδ, ɛ_r and τ_f which varies for different dopants.     

Influence of V2O5 additions to Ba(Mg1/3Ta2/3)O3 ceramics on sintering behavior and microwave dielectric properties

The microstructures and the microwave dielectric properties of barium magnesium tantalate ceramics prepared by conventional mixed oxide route have been investigated. The prepared Ba(Mg_1/3Ta_2/3)O₃ exhibited a mixture of cubic perovskite and a hexagonal superstructure with Mg and Ta showing 1:2 order in the B-site. It is found that low level doping of V₂O₅ (up to 0.5 wt.%) can significantly improve densification of the specimens and their microwave dielectric properties. The density of doped Ba(Mg_1/3Ta_2/3)O₃ ceramics can be increased beyond 95% of its theoretical value by 1500 °C-sintering, which is caused by the liquid-phase effect of V₂O₅ addition. The detected second phase Ta₂O₅ was mainly the result of V⁵⁺ substitution in the ceramics. Dielectric constant (ε_r) and temperature coefficient of resonant frequency (τ_f) were not significantly affected, while the unloaded quality factors Q were effectively promoted by V₂O₅ addition due to the increase in B-site ordering. The ε_r value of 24.1, Q×f value of 149,000 (at 10 GHz) and τ_f value of 7.2 ppm/°C were obtained for Ba(Mg_1/3Ta_2/3)O₃ ceramics with 0.25 wt.% V₂O₅ addition sintered at 1500 °C for 3 h.     

Effect of B2O3 additive on the sintering temperature and microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 ceramics

Journal of Materials Science: Materials in Electronics - This paper reported a research of the sinterability, microstructures, and microwave dielectric properties of Ba(Mg1/3Ta2/3)O3 (BMT) ceramics...     

Dielectric and ferroelectric properties of Bi(Zn1/2Ti1/2)O3-PbTiO3-PbZrO3 ternary ceramics

Ceramics of a new ternary solid solution system, xBi(Zn(1/2)Ti(1/2))O(3-yPbTiO(3)z)PbZrO(3) (xBZT-yPT-zPZ), with compositions along the solubility limit curve are prepared by solid-state reaction and sintering technique. Two morphotropic phase boundaries (MPBs) separating the orthorhombic and tetragonal (MPB(O-T)) phases and the tetragonal and rhombohedral (MPB(T-R)) phases, respectively, are observed with increasing z (0.10 ≤ x ≤ 0.21; 0 ≤ y ≤ 0.49). It is found that the transition from the ferroelectric to paraelectric phase becomes more diffuse with the addition of BZT into the PZT solid solution. Enhanced dielectric and ferroelectric properties appear at MPB(R-T), which exists over a wide composition region (0.45 ≤ z ≤ 0.6), as revealed by X-ray diffraction and dielectric measurements. The dielectric constant reaches a maximum value (ε' = 1250) on the tetragonal majority side of the MPB. The highest remnant polarization (P(r) = 34.2 μC/cm(2)) is found in the composition at the center of the MPB, where the rhombohedral and tetragonal phases coexist in almost equal quantities.     

Effect of lithium salts addition on sintering temperature, cationic ordering and dielectric properties of Ba(Mg1/3Ta2/3)O3 ceramic

The effect of different lithium salts (LiF, Li₂CO₃, LiNO₃) addition on sintering temperature, cationic ordering and dielectric properties of Ba(Mg_1/3Ta_2/3)O₃ ceramic has been investigated. This perovskite was synthesised by solid state reaction from BaCO₃, MgO and Ta₂O₅. It was shown that, by addition of LiNO₃, the sintering temperature was decreased to 1300°C (versus 1550°C–1600°C for the pure Ba(Mg_1/3Ta_2/3)O₃ ceramic) without altering dielectric properties at 1 MHz. A cationic ordering was also observed. Sintering with co-fired nickel electrodes in Ar/H₂ atmosphere was also successfully performed for Multi Layer Ceramic Capacitors applications.     

1 : 2 Long-range ordering and defect mechanism of WO3-doped perovskite Ba(Mg1/3Ta2/3)O3

The nature of the B-site cation ordering and the associated defect process necessary to stabilize the ordered domains were investigated using the WO₃-doped BaMg_1/3Ta_2/3O₃ BMT system as a typical example of BaB_1/3B_2/3O₃-type complex perovskites. It was shown that only the 1 : 2 long-range ordering of the B-site cation existed in both undoped and WO₃-doped BMT perovskites. The atomic defect mechanism associated with the stoichiometric 1 : 2 long-range ordering was systematically investigated. It is concluded that the substitution of W⁶⁺ for Ta⁵⁺ in the WO₃-doped BMT enhances the degree of the 1 : 2 long-range ordering and produces the positively charged W _Ta sites with a concomitant generation of tantalum vacancies V_Ta and mobile oxygen vacancies V _O for the ionic charge compensation.