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.     

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。     

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.     

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.     

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.     

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.     

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.     

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℃.     

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.     

Low‐Temperature Sintering Microwave Characteristics of B2O3‐doped CaLa4Ti4O15 Dielectric Ceramics

Preparation and microwave dielectric properties of B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics have been investigated. X‐ray diffraction data show that CaLa₄Ti₄O₁₅ ceramic has a trigonal structure coupled with a second phase of CaLa₄Ti₅O₁₇. The CaLa₄Ti₄O₁₅ ceramic with addition of 0.5 wt% B₂O₃, sintered at 1220°C for 4 h, exhibits microwave dielectric properties with a dielectric constant of 45.8, Q × f value of 24,000 GHz, and temperature coefficient of resonant frequency (τ_f) of ?19 ppm/^°C. B₂O₃‐doped CaLa₄Ti₄O₁₅ ceramics, which have better sintering behavior (decrease in sintering temperature ~ 330°C) and dielectric properties than pure CaLa₄Ti₄O₁₅ ceramics, are candidates for applications in microwave devices.     

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.     

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.     

Properties of Low‐Temperature Sintering PNN–PMW–PSN–PZT Piezoelectric Ceramics with Ba(Cu1/2W1/2)O3 Sintering Aids

Piezoelectric ceramics Pb(Ni_1/3Nb_2/3)O₃–Pb(Mg_1/2W_1/2)O₃–Pb(Sb_1/2Nb_1/2)O₃–Pb(Zr_0.39Ti_0.61)O₃ with Ba(Cu_1/2W_1/2)O₃ sintering aids were fabricated using economical industrial oxide powders and their piezoelectric, dielectric, and ferroelectric properties were investigated in order to develop low‐temperature sintering ceramics for multilayer piezoelectric actuators. A quadratic formula and the Curie–Weiss law reveal that the ceramics are typical displacive‐type ferroelectric relaxors. The ceramics sintered as low as 900°C have good piezoelectric properties of d₃₃ = 551 pC/N, k_p = 0.52, ε_r = 3583, tgδ = 0.02, and T_C = 161°C, which is much promising to manufacture multilayer piezoelectric transducers.     

Sr(Ga0.5Nb0.5)1−xTixO3 Low‐Loss Microwave Dielectric Ceramics with Medium Dielectric Constant

The microwave dielectric properties of Sr(Ga_0.5Nb_0.5)_1?xTi_xO₃ (x = 0, 0.1, 0.2 and 0.3) ceramics have been investigated together with their microstructures. Single‐phase solid solutions are achieved in this series of ceramics. The ordering features are comprehensively analyzed by transmission electron microscopy and Raman spectroscopy. Local 1:1 ordering in B‐site leads to a double‐cubic structure with space group , while Ti substitution disrupts this 1:1 ordering between Ga and Nb, and the metastable ordering between Ti and (Ga + Nb) is speculated to form due to their large size difference. The dielectric constant and temperature coefficient of resonant frequency increase nonlinearly as x increases, while the Qf value decreases gradually. The variation trend of Qf value is mainly attributed to the intrinsic loss because of the increasing vibrational anharmonicity by Ti substitution. The ordering transition from short coherence, long‐range ordering to short‐range ordering with increasing Ti content has an agreeable and weak effect on the Qf value. The best combination of microwave dielectric properties is achieved for the composition of x = 0.3: ε_r = 46.6, Qf = 42 200 GHz and τ_f = 5.0 ppm/°C.     

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.     

Phase‐Composition‐Dependent Piezoelectric and Electromechanical Strain Properties in (Bi1/2Na1/2)TiO3–Ba(Ni1/2Nb1/2)O3 Lead‐Free Ceramics

New lead‐free perovskite solid solution ceramics of (1 ? x)(Bi_1/2Na_1/2)TiO₃–xBa(Ni_1/2Nb_1/2)O₃[(1?x)BNT–xBNN,x = 0.02–0.06) were prepared and their dielectric, ferroelectric, piezoelectric, and electromechanical properties were investigated as a function of the BNN content. The X‐ray diffraction results indicated that the addition of BNN has induced a morphotropic phase transformation from rhombohedral to pseudocubic symmetry approximately at x = 0.045, accompanying an evolution of dielectric relaxor behavior as characterized by enhanced dielectric diffuseness and frequency dispersion. In the proximity of the ferroelectric rhombohedral and pseudocubic phase coexistence zone, the x = 0.045 ceramics exhibited optimal piezoelectric and electromechanical coupling properties of d₃₃~121 pC/N and k_p~0.27 owing to decreased energy barriers for polarization switching. However, further addition of BNN could cause a decrease in freezing temperatures of polar nanoregions till the coexistence of nonergodic and ergodic relaxor phases occurred near room temperature, especially for the x = 0.05 sample which has negligible negative strains and thus show the maximum electrostrain of 0.3% under an external electric field of 7 kV/mm, but almost vanished piezoelectric properties. This was attributed to the fact that the induced long‐range ferroelectric order could reversibly switch back to its original ergodic state upon removal of external electric fields.     

High strain (0.4%) Bi(Mg2/3Nb1/3)O3‐BaTiO3‐BiFeO3 lead‐free piezoelectric ceramics and multilayers

The relationship between the piezoelectric properties and the structure/microstructure for 0.05Bi(Mg_2/3Nb_1/3)O₃‐(0.95‐x)BaTiO₃‐xBiFeO₃ (BBFT, x = 0.55, 0.60, 0.63, 0.65, 0.70, and 0.75) ceramics has been investigated. Scanning electron microscopy revealed a homogeneous microstructure for x < 0.75 but there was evidence of a core‐shell cation distribution for x = 0.75 which could be suppressed in part through quenching from the sintering temperature. X‐ray diffraction (XRD) suggested a gradual structural transition from pseudocubic to rhombohedral for 0.63 < x < 0.70, characterized by the coexistence of phases. The temperature dependence of relative permittivity, polarization‐electric field hysteresis loops, bipolar strain‐electric field curves revealed that BBFT transformed from relaxor‐like to ferroelectric behavior with an increase in x, consistent with changes in the phase assemblage and domain structure. The largest strain was 0.41% for x = 0.63 at 10 kV/mm. The largest effective piezoelectric coefficient (d₃₃^*) was 544 pm/V for x = 0.63 at 5 kV/mm but the largest Berlincourt d₃₃ (148 pC/N) was obtained for x = 0.70. We propose that d₃₃^* is optimized at the point of crossover from relaxor to ferroelectric which facilitates a macroscopic field induced transition to a ferroelectric state but that d₃₃ is optimized in the ferroelectric, rhombohedral phase. Unipolar strain was measured as a function of temperature for x = 0.63 with strains of 0.30% achieved at 175°C, accompanied by a significant decrease in hysteresis with respect to room temperature measurements. The potential for BBFT compositions to be used as high strain actuators is demonstrated by the fabrication of a prototype multilayer which achieved 3 μm displacement at 150°C.     

(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.     

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.