锑替代铋对铋锌铌陶瓷介电性能的影响

研究了Sb3＋替代Bi3＋对Bi2O3-ZnO-Nb2O5（BZN）系介质材料结构和性能的影响,并借助X射线、扫描电镜、LCR4284测试仪对其相结构和介电性能进行分析。研究结果表明,经Sb3＋替代的BZN陶瓷样品成瓷温度仍为1 000℃;随着Sb3＋替代量的增加,Bi2O3-ZnO-Nb2O5系介质材料的晶粒尺寸、介电常数、介电损耗都有所变化。当替代量x=0.4时,介电性能最佳,介电常数为184,介电损耗为0.001。     

Er3+替代Bi3+对Bi2(Zn1/3Nb2/3)2O7陶瓷烧结温度的影响

研究了Er3 替代Bi3 对Bi2(Zn1/3Nb2/3)2O7系介质材料结构和性能的影响,并借助X射线、扫描电镜、Agilent4284测试仪对其相结构和介电性能进行分析.研究结果表明:经Er3 替代的BZN陶瓷样品烧结温度升高(从960℃升高到1000℃);随着Er3 替代量的增加,Bi2(Zn1/3Nb2/3)2O7系介质材料的晶粒尺寸、介电常数、介电损耗都有所变化;当替代量x=0.1时,介电性能最佳,介电常数为78.7165,介电损耗为0.00134.     

Re‐entrant relaxor behavior in BaTiO3‐Bi(Zn2/3Nb1/3)O3 ceramics

The (1?x)BaTiO₃?xBi(Zn_2/3Nb_1/3)O₃ (x=0.10‐0.25) ceramics were fabricated via solid‐state reactions. Temperature‐dependent polarization measurement reveals that with the temperature lowering, the remnant polarization increases till a maximum value before it decreases, showing a reentrant phenomenon. Absence of apparent switching current peaks in the current density as a function of electric field should indicate the lack of a ferroelectric transition, which is further verified by the consistent macroscopic phase structure from the Raman spectra. An anomalous peak in the full width at half maximum of a deconvoluted mode at ~515 cm^?1 suggests the entering of a more disordered state of dipolar dynamics, which may be originated from the competition between the freezing of polar nanoregions and the random interacting fields.     

烧结温度对Bi2(Mg1/3Nb2/3)2O7介电陶瓷性能的影响

采用传统固相反应法制备了Bi2(Mg1/3Nb2/3)2O7(β-BMN)介电陶瓷,借助X射线衍射(XRD)研究了不同预烧温度合成β-BMN粉体的物相组成,借助扫描电镜(SEM)研究了不同烧结温度β-BMN的显微结构,考察了不同烧结温度和保温时间对β-BMN陶瓷性能的影响.结果表明:合成温度为850℃时已经完全形成主晶相(β-BMN).随着烧结温度的增加,样品的介质损耗(tanδ)先变小后增大,而相对介电常数(εr)先增大后减小.当烧结温度为1000℃保温5h时,得到的陶瓷的综合性能较佳:ρ=7.69g/cm3,εr=207,tanδ=0.00197.     

Ferroelectric to Relaxor Transition in BaTiO3–Bi(Zn2/3Nb1/3)O3 Ceramics

The (1?x)BaTiO₃–xBi(Zn_2/3Nb_1/3)O₃ (x = 0.01–0.30) ceramics were synthesized by solid‐state reactions. The solubility limit was determined to be x = 0.20. A systematic structural transition from a tetragonal phase (x ≤ 0.034), to a mixture of tetragonal and rhombohedral phases (0.038 ≤ x ≤ 0.20), and finally to a pseudocubic phase (x ≥ 0.22) at room temperature was identified. Dielectric measurement revealed a ferroelectric (x ≤ 0.04) to relaxor (x ≥ 0.06) transition with permittivity peak broadening and flattening, which was further verified by Raman spectroscopy and differential scanning calorimetry (DSC). Activation energies obtained from the Vogel–Fulcher model displayed an increasing trend from ~0.03 eV for x ~ 0.05, to unusually high values (>0.20 eV) for the compositions with x ≥ 0.15. With the increase in Bi(Zn_2/3Nb_1/3)O₃ content, the polarization hysteresis demonstrated a tendency from high nonlinearity to sublinearity coupled with the reduction in remnant polarization and coervice field. The deconvolution of the irreversible/reversible polarization contribution was enabled by first‐order reversal curve distributions, which indicates that the decreasing polarization nonlinearity with the increase in Bi(Zn_2/3Nb_1/3)O₃ concentration could be related with the change from the ferroelectric domain and domain wall contributions to the weakly coupled relaxor behaviors.     

High‐Performance Ferroelectric Solid Solution Crystals: Pb(In1/2Nb1/2)O3–Pb(Zn1/3Nb2/3)O3–PbTiO3

A series of regular shaped Pb(Zn_1/3Nb_2/3)O₃‐based ternary ferroelectric single crystals (1 ? x)Pb(In_1/2Nb_1/2)O₃–0.33Pb(Zn_1/3Nb_2/3)O₃–xPbTiO₃ (PIN–PZN–PT) have been grown by means of the top‐seeded solution growth method that prevented pyrochlore phase and promoted [001] or [111] growth. The nucleation and crystallization behavior of the Pb(Zn_1/3Nb_2/3)O₃‐based ferroelectric single crystals differed from other relaxor‐based ferroelectric single crystals was discovered. Di‐/piezo‐/ferro‐/pyroelectric properties were characterized systematically. The PIN–PZN–PT single crystals showed large coercive fields E_c, high Curie temperature T_C and high pyroelectric coefficient P, presenting similar performance but better thermal stability compared with the PZN–PT single crystals, and making it a promising material for transducers and IR detectors in a wider temperature range.     

Main Source of Microwave Loss in Transition‐Metal‐Doped Ba(Zn1/3Ta2/3)O3 and Ba(Zn1/3Nb2/3)O3 at Cryogenic Temperatures

Microwave resonator measurements were performed on high‐performance microwave ceramics Ba(Zn_1/3Ta_2/3)O₃ (BZT) and Ba(Zn_1/3Nb_2/3)O₃ (BZN) containing additives commonly used by commercial manufacturers (i.e., Co, Mn, and Ni). We find that the loss tangent, even in ambient magnetic fields, is dominated by electron paramagnetic resonance (EPR) absorption by exchange‐coupled 3d electrons in transition metal clusters at cryogenic temperatures. The large orbital angular momentum in Co²⁺ and Ni²⁺ ions of L = 3 causes strong anisotropic‐broadened dipolar interactions that extend EPR losses to zero applied field. This effect is greatest in BZN with Co concentrations greater than 0.5 mol%, dominating the losses at liquid nitrogen temperatures (77 K) and below. In samples containing Mn²⁺ ions with L = 0, the dipolar interactions and associated EPR losses in ambient fields are smaller. We show the magnetic‐field‐dependent changes in the EPR losses (i.e., tan δ) and magnetic reactive response (i.e., μ_r) are from the same mechanism, as they follow the Kramers–Kronig relation. Finally, we note that these materials can make ultra‐high Q passive microwave devices with externally controlled transfer functions, as the quality factor (Q) of the composition Ba(Co_1/15Zn_4/15Nb_2/3)O₃ at 77 K can be tuned from 1 100 to 12 000 at 10 GHz by applying practical magnetic fields.     

V2O5掺杂对(Bi1.5Zn1.0Nb1.5)O7介质陶瓷性能的影响

采用传统的固相反应法制备陶瓷试样,借助XRD,SEM和LCR测试仪,研究了V2O5掺杂对(Bi1.5Zn1.0Nb1.5)O7介质陶瓷的烧结特性和介电性能的影响.结果表明,掺杂适量V2O5后试样的烧结温度明显降低,相结构仍为立方焦绿石单相,且具有良好的介电性能:介电常数(εr)为135～154,介电损耗(tan δ)为0.0033～0.0007,频率温度系数(τf)为-442～-387(2MHz).     

添加剂对Ba(Zn1/3Nb2/3)O3-Sr(Zn1/3Nb2/3)O3陶瓷介电性能的影响

研究了MnCO3,BaZrO3对0.35Ba(Zn1/3Nb2/3)O3(BZN)-0.65Sr(Zn1/3Nb2/3)O3(SZN)陶瓷介电性能的影响.研究表明:添加MnCO3,BaZrO3时,对陶瓷的烧结均起促进作用,增大介电常数.加入1%(质量分数)的MnCO3可使陶瓷具有较小的介质损耗,同时MnCO3对陶瓷的介电常数温度系数具有正向调整作用.加入BaZrO3后通过生成液相而减少了第二相Ba5Nb4O15,BaNb2O6的生成.所制备的(0.35BZN0.65SZN)+0.1%MnCO3陶瓷的εr≈43.6,αe≈-8×10-6/K,tanδ＝0.6×10-4,且烧结温度低于1 300℃.     

ZnO-activated formation of phase pure perovskite Pb(In1/2Nb1/2)O3-Pb(Zn1/3Nb2/3)O3-PbTiO3 powder

This paper reports on the phase formation of perovskite Pb(In_1/2Nb_1/2)O₃-Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PIN-PZN-PT) powder when doped with 0.04 to 0.83 mol% ZnO. Air calcination of undoped powder mixtures for 4 hours at 800°C resulted in a mixture of Pb₂Zn_0.29Nb_1.71O_6.565 pyrochlore, PIN-PZN-PT perovskite, and In₂O₃. ZnO dopant concentrations as low as 0.04 mol% increased the rate of perovskite formation and resulted in near phase pure perovskite powder of 0.5 μm particle size when heated at 800°C in air. In all cases PbTiO₃ and Pb(In_1/2Nb_1/2)O₃ formed prior to PIN-PZN-PT formation. ZnO doping promotes perovskite phase formation by increasing the reactivity of the intermediate pyrochlore phase by substituting Zn²⁺ on Nb⁵⁺ sites and forming oxygen vacancies when heated in air. Heating in high resulted in an incomplete reaction and a mixture of perovskite and pyrochlore whereas low resulted in phase separation into a mixture of rhombohedral perovskite, tetragonal perovskite, and pyrochlore. The sensitivity clearly shows that oxygen vacancies due to ZnO-doping are critical for synthesis of phase pure PIN-PZN-PT powder.     

Low‐Temperature Sintering Li2MoO4/Ni0.5Zn0.5Fe2O4 Magneto‐Dielectric Composites for High‐Frequency Application

The coexistence of Li₂MoO₄ (LMO) and Ni_0.5Zn_0.5Fe₂O₄ (NZO) has been proven and their low‐temperature‐sintered magneto‐dielectric composites (1?x)LMO–xNZO (volume fraction factor x = 0.1, 0.3, 0.5, 0.7) were prepared by the conventional solid‐state reaction method and were sintered below 700°C. It is found that the optimal sample (x = 0.5) has good and relatively stable magneto‐dielectric performance in the frequency range from 10 MHz to 1 GHz with permittivity between 7.14 and 6.84, dielectric loss tangent between 0.09 and 0.02, and permeability between 5.23 and 3.30, magnetic loss tangent between 0.06 and 0.65, respectively. Furthermore, the verified chemical compatibility with silver indicates that the LMO–NZO ceramics are potential for low‐temperature cofired ceramic application and their multifunctional magneto‐dielectric properties also make them for potential applications in electronic devices.     

Structure,Microwave Dielectric Properties,and Low‐Temperature Sintering of Acceptor/Donor Codoped Li2Ti1−x(Al0.5Nb0.5)xO3 Ceramics

The structure, microwave dielectric properties, and low‐temperature sintering behavior of acceptor/donor codoped Li₂TiO₃ ceramics [Li₂Ti_1?x(Al_0.5Nb_0.5)_xO₃, x = 0–0.3] were investigated systematically. The x‐ray diffraction confirmed that a single‐phase solid solution remained within 0 < x ≤ 0.2 and secondary phases started to appear as x > 0.2, accompanied by an order–disorder phase transition in the whole range. Scanning electron microscopy observation indicated that the complex substitution of Al³⁺ and Nb⁵⁺ produced a significant effect on the microstructural morphology. Both microcrack healing and grain growth contributed to the obviously enhanced Q×f values. By comparison, the decrease of ε_r and τ_f values was ascribed to the ionic polarizability and the cell volume, respectively. Excellent microwave dielectric properties of ε_r ~ 21.2, Q×f ~ 181 800 GHz and τ_f  ~ 12.8 ppm/°C were achieved in the x = 0.15 sample when sintered at 1150°C. After 1.5 mol% BaCu(B₂O₅) additive was introduced, it could be well sintered at 950°C and exhibited good microwave dielectric properties of ε_r ~ 20.4, Q×f ~ 53 290 GHz and τ_f ~ 3.6 ppm/°C as well. The cofiring test of the low‐sintering sample with Ag powder proved its good chemical stability during high temperature, which enables it to be a promising middle‐permittivity candidate material for the applications of low‐temperature cofired ceramics.     

BaTiO3–Bi(Mg2/3Nb1/3)O3 Ceramics for High‐Temperature Capacitor Applications

Solid solutions of (1?x)BaTiO₃–xBi(Mg_2/3Nb_1/3)O₃ (0 ≤ x ≤ 0.6) were prepared via a standard mixed‐oxide solid‐state sintering route and investigated for potential use in high‐temperature capacitor applications. Samples with 0.4 ≤ x ≤ 0.6 showed a temperature independent plateau in permittivity (ε_r). Optimum properties were obtained for x = 0.5 which exhibited a broad and stable relative ε_r ~940 ± 15% from ~25°C to 550°C with a loss tangent <0.025 from 74°C to 455°C. The resistivity of samples increased with increasing Bi(Mg_2/3Nb_1/3)O₃ concentration. The activation energies of the bulk were observed to increase from 1.18 to 2.25 eV with an increase in x from 0 to 0.6. These ceramics exhibited excellent temperature stable dielectric properties and are promising candidates for high‐temperature multilayer ceramic capacitors for automotive applications.     

(Bi2-yCay)(Zn1/3 Ta2/3)2O7陶瓷的介电弛豫和介电性能

研究了(Bi2-yCay)(Zn1/3Ta2/3)2O7(0≤y≤1)材料的组成、结构与介电性能.当Ca含量增加时,材料的相结构由单斜焦绿石相转变为立方焦绿石相.样品在20～85℃,1 MHz时的介电常数温度系数由72×10-6/℃逐渐增加到470×10-6/℃,然后降为-100×10-6/℃,样品在微波频率下的品质因数Q值从1 250逐渐降低至40.在-60～160℃,观测到(Bi1.2Ca0.8)(Zn1/3Ta2/3)2O7样品出现介电弛豫现象.随着Ca含量的增加,介电损耗的弛豫峰向高温移动.比较了同为立方结构相的(Bi2-yCay)(Zn1/3Ta2/3)2O7(0.7＜y＜1)和(Bi1.5Zn0.5)(Zn0.5·Ta1.5)O7介电弛豫温区移动的差异并分析了其形成原因.     

Conduction Mechanisms in BaTiO3–Bi(Zn1/2Ti1/2)O3 Ceramics

Polycrystalline BaTiO₃–Bi(Zn_1/2Ti_1/2)O₃ (BT–BZT) ceramics have superior dielectric properties for high‐temperature and high‐energy density applications as compared to the existing materials. While it has been shown that the addition of BZT to BT leads to an improvement in resistivity by two orders of magnitude, in this study impedance spectroscopy is used to demonstrate a novel change in conduction mechanism. While nominally undoped BT exhibits extrinsic‐like p‐type conduction, it is reported that BT–BZT ceramics exhibit intrinsic n‐type conduction using atmosphere‐dependent conductivity measurements. Annealing studies and Seebeck measurements were performed and confirmed this result. For BT, resistivity values were higher for samples annealed in nitrogen as compared to oxygen, whereas the opposite responses were observed for BZT‐containing solid solutions. This suggests a fundamental change in the defect equilibrium conditions upon the addition of BZT to the solid solution that lowered the carrier concentration and changed the sign of the majority charge carrier. This is then also linked to the observed improvement in resistivity in BT–BZT ceramics as compared to undoped BT.     

High permittivity (1−x)Bi1/2Na1/2TiO3‐xPbMg1/3Nb2/3O3 ceramics for high‐temperature‐stable capacitors

(1?x)Bi_1/2Na_1/2TiO₃‐xPbMg_1/3Nb_2/3O₃[(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.     

Low-Temperature Sintering and Influence of the Process on the Dielectric Properties of Ba(Zn1/3Ta2/3)O3

By controlling the granulometric distribution of the powders, a density of >96% of the theoretical density has been attained for Ba(Zn1/3Ta2/3)O3 that has been sintered at a low temperature (1450°C) for a short soaking time (2 h). Attrition milling produces a very fine and monomodal powder that allows for good densification. The attrition conditions result from a compromise between granulometric distribution and the risk of pollution. We have found a great influence of the origin of the raw materials on the temperature coefficient of frequency, allowing a modulation in the range of 0-15 ppm/°C. Finally, we have studied the influence of each step of the process on the dielectric properties and identified the secondary phases that form with the evaporation of zinc: an eight-layered hexagonal perovskite and a tetragonal tungsten-bronze-type phase.     

Microstructures and Microwave Dielectric Properties of Ba((Co0.55Zn0.35Mg0.1)1/3Nb2/3)O3‐BaZrO3 Ceramics

Microstructures and microwave dielectric properties of (1?x)Ba((Co_0.55Zn_0.35Mg_0.1)_1/3 Nb_2/3)O₃‐xBaZrO₃ (x = 0.01, 0.02, 0.03, 0.04, 0.05, and 0.06) ceramics have been investigated. The 1:2 ordered structure remains in the solid solutions when x is less than 0.03, but the ordering is destabilized. While, the local ordering behavior, which generates from compositional inhomogeneous, is observed in the composition with x = 0.04, where the 1:1 ordered phase begins to form. For x = 0.05 and 0.06, the solid solutions are comprised of nanometer‐sized 1:1 and 1:2 ordered domains, those are dispersed in a disordered matrix. The lower Qf values of the as‐sintered ceramics mainly because of the lower ordering degrees. BaZrO₃ substitution decreases both the annealing time and temperature. The effects of annealing process upon the improvement of Qf values are significant for the lower substitution levels (x = 0.01 and 0.02), while only slight effects are determined for high substitution levels (x = 0.04, 0.05, and 0.06). The highest Qf value of 84,500 GHz is obtained for 1 mol% BaZrO₃ substituted composition, after annealing at 1300°C for 8 h.     

Determination of 1:2 Ordered Domain Boundaries in Ba[(Co,Zn, Mg)1/3Nb2/3]O3 Dielectric Ceramics

The boundaries of 1:2 ordered domains in Ba[(Co, Zn, Mg)_1/3Nb_2/3]O₃ perovskite ceramics are comprehensively studied by high‐resolution transmission electron microscopy (HRTEM) on the base of atomic position simulation. The atomic configurations for four types of twin boundaries are determined. A‐type and B‐type boundary, which lie along (001)_c and (110)_c planes, respectively, are conservative. C‐type boundary parallels to (111)_c plane, while Г‐type boundary is perpendicular to (111)_c plane. At C‐type and Г‐type boundary, atomic intersection leads to a buffer layer, among which the B‐site cations are generally disordered. The width of Г‐type boundary is larger than that of C‐type boundary, so is the perturbation to the system. The energy of four types of twin boundaries is proved to be “A‐type & B‐type < C‐type < Г‐type” according to the magnitude of the destabilization to the system. Single antiphase boundary (APB) is considered to be nonconservative. However, when combined with conservative twin boundary, an extra ordered structure with a periodicity of 1.24 nm along [001]_c direction and a periodicity of 0.87 nm along [110]_c direction forms. The boundary regions are indeed stabilized by the new superlattice.     

High‐Temperature Dielectric Relaxation in Pb(Mg1/3Nb2/3)O3–PbTiO3 Single Crystals

We reported the dielectric properties of Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ single crystal in the temperature range of 300–1073 K and the frequency range of 100 Hz–10 MHz. Our results showed the coexistence of both true‐ and pseudo‐relaxor behaviors in the crystal. The true relaxor behavior related to the paraelectric‐ferroelectric phase transition occurs at~423 K. The pseudo‐relaxor behavior appearing at~773 K was found to be related to oxygen vacancies. Further investigation reveals that the pseudo‐relaxor behavior has fine structure: it contains two oxygen‐vacancy‐related relaxation processes. The low‐temperature relaxation process is a dipolar relaxation created by the hopping motions of the oxygen vacancies, and the high‐temperature relaxation process is a Maxwell‐Wagner relaxation caused by the sample/electrode contacts.