Hydrothermal synthesis of Ba5Nb4O15 ultrafine powders

Ba₅Nb₄O₁₅ ultrafine powders were prepared by hydrothermal method using Ba(NO₃)₂ and Nb₂O₅ precursors. The synthesis characteristics were influenced by the chemical form of precursors, reaction temperature, mole ratio of Ba/Nb and pH value. The chemical form of the precursors has a strong influence on the products of Ba₅Nb₄O₁₅. There was no requisite compound in the final product when Nb₂O₅ powder was used as Nb-precursor. In addition, the reaction completeness was also dependent on the synthesis temperature. The best single phase Ba₅Nb₄O₁₅ ultrafine powders were obtained at a temperature of 230 °C. The most appreciate Ba/Nb molar ratio was 3/2. The reactions were only carried out in a solution with pH value between 12 and 14. When pH was equal or larger than 14, there was no product of Ba₅Nb₄O₁₅ powder in the reactor.     

De-sintering of Ba5Nb4O15 ceramic and its influence on microwave characteristics

The sintering behaviour of a cation-deficient perovskite, Ba₅Nb₄O₁₅, is investigated in the present study. The highest density can be achieved through pressureless sintering at 1250 °C is only 93%. A further increase in sintering temperature results in a decrease in density; for example, the density is only 82% after sintering at 1435 °C. The density decrease, de-sintering, can be related to the formation of abnormal grains ( > 1250 °C) and the reduction of niobium ions ( > 1400 °C). The permittivity of sintered Ba₅Nb₄O₁₅ specimen shows strong dependence on density; however, the quality factor (Qxf) increases to 45,000 with the increase of sintering temperature. The increase in quality factor is attributed to the ordering of cations in the perovskite structure.     

Low-temperature sintering and microwave dielectric properties of Ba5Nb4O15 with ZnB2O4 glass

The Influence of ZnB₂O₄ glass addition on the sintering temperature and microwave dielectric properties of Ba₅Nb₄O₁₅ has been investigated using dilatometry, X-ray diffraction, scanning electron microscopy and network analyzer. It was found that a small amount of glass addition to Ba₅Nb₄O₁₅ lowered the sintering temperature from 1400 to 900 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases such as Ba₃B₂O₆. The Ba₅Nb₄O₁₅ ceramics with ZnB₂O₄ glass, sintered at a low temperature, exhibited good microwave dielectric characteristics, i.e., a quality factor (Q × f) = 12,100 GHz, a relative dielectric constant (ɛ_r) = 40, a temperature coefficient of resonant frequency (τ_f) = 48 ppm/°C. The dielectric properties were discussed in terms of the densification of specimens and the influence of glassy phases such as Ba₃B₂O₆ and ZnB₂O₄.     

Nb5+掺杂改性CaBi4Ti4O15压电陶瓷的研究

采用传统固相烧结法,制备了CaBi4Ti(1-x)NbxO1(5x=0.00-0.05,CBT-N)系铋层状结构无铅压电陶瓷。研究了Nb5+掺杂对CBT压电陶瓷压电与介电性能的影响。研究结果表明:添加Nb5+离子,改善了CBT陶瓷的烧结特性,提高了瓷体的致密度。Nb2O5的引入降低了CBT系列陶瓷的介质损耗,改善了陶瓷的压电与介电性能。当掺入量x=0.04(CaBi4Ti0.96Nb0.04O15)时制备的CBT基铋层状压电陶瓷具有优异的压电性能:d33=14pC/N,Qm=3086,εr=212,tanδ=0.0041,kt/kp=1.681。     

掺杂玻璃助剂的Ba5Nb4O15陶瓷烧结特性及介电性能

引入玻璃烧结助剂,采用液相烧结手段制备了低温烧结Ba5Nb4O15微波介质陶瓷.采用X射线衍射和扫描电子显微技术分析了陶瓷的物相组成和微观形貌.研究表明:陶瓷主晶相为Ba5Nb4O15,铋硅酸盐玻璃在陶瓷中以液相形式存在,促使陶瓷烧结温度从1300℃降至1100℃.添加4wt.％铋硅酸盐玻璃的Ba5Nb4O15陶瓷在1100℃烧结,具有良好的微波性能:相对介电常数εr=39.01,品质因子Q × f=12214GHz.     

Impedance Spectroscopy,Broadband, and Microwave Dielectric Properties of Mechanically Alloyed Ba5Nb4O15 Ceramics

Ba₅Nb₄O₁₅ (BNO) ceramics were synthesized by the mechanical alloying method. The transmission electron microscope images of BNO powders revealed rod‐shaped grains. Mechanically alloyed BNO exhibited maximum density of 97.3% and is explained on the basis of Herring's scaling law. Both the dielectric constant and loss tangent show a stable response up to 0.2 GHz. Further, the dielectric response of BNO ceramics measured above 350°C shows relaxation behavior and is explained using Havriliak–Negami equation. The obtained stable dielectric response of BNO is suitable for type I capacitor and dielectric resonator applications.     

Microwave dielectric properties of low temperature fired Ba5Nb4O15 ‐ BaWO4 ceramics supplemented with their own nanoparticles for LTCC applications

Polycrystalline Ba₅Nb₄O₁₅ (BNO) ‐ BaWO₄ (BWO) composite ceramics are prepared by adding their own nanoparticles as a sintering aid. The prepared samples exhibited the maximum relative density of 98.2% at 900°C. The complex dielectric response of these composite ceramics are analysed by Havriliak ‐ Negami (HN) equation. The BNO ‐ BWO composite added with x=3 wt% of their nanoparticles, fired at 900oC displayed the best microwave dielectric properties; εr=39 and Q×f0=59.8 THz at 9.44 GHz. The obtained results of BNO ‐ BWO composite makes this material as a potential candidate for LTCC applications.     

Ba(Ti 1 - 5/4 x Nb x )O 3 Relaxor Ferroelectrics

Compositional modifications of ferroelectric BaTiO 3 were systematically investigated for Nb +5 substituents ( x ). Relaxor ferroelectric behavior was induced for x ≥4 at%.     

Effect of milling on the anisotropic grain growth in a sintered Ba5Nb4O15 specimen and its effect on microwave dielectric properties

In this study, relationships between the processing, microstructure, and properties of barium niobate (Ba₅Nb₄O₁₅) are investigated. The milling of a Ba₅Nb₄O₁₅ powder in water is effective with respect to size reduction. However, after milling in water, BaCO₃ is formed within the slurry. With the increase in the amount of BaCO₃ formed, the aspect ratio of the elongated Ba₅Nb₄O₁₅ grains increases. The formation of the elongated Ba₅Nb₄O₁₅ grains prohibits the densification. Hence, the microwave dielectric properties, including permittivity and quality factor, are poor because of the low density. In addition, milling in ethanol is carried out for comparison: A lower amount of BaCO₃ is formed after milling in ethanol; the extent of anisotropic grain growth is thus reduced.     

Photogalvanic current in the incommensurate phase in Ba2NaNb5O15

The linear photogalvanic effect in the phase transition (commensurate tetragonal-to-in-commensurate) region has been studied in Ba₂NaNb₅O₁₅ crystal. The results show a strong correlation between the photogalvanic current and the modulation period of the incommensurate phase.     

Preparation and morphology of anisometric KSr2Nb5O15 particles

Anisometric KSr₂Nb₅O₁₅ (KSN) particles were synthesized by conventional mixed-oxide (CMO) method and molten salt synthesis (MSS) method, respectively. In MSS method, preparation of KSN was carried out in both SrCO₃–Nb₂O₅–K₂CO₃–KCl system (system I) and SrNb₂O₆–Nb₂O₅–KCl system (system II). The results revealed that the single-phase KSN obtained by CMO method was clumped and without obvious acicular morphology, making it difficult to use in texturing processes. In system I, though acicular KSN particles were synthesized by controlling the amount of KCl salt, they were easily contaminated by the presence of blade-like Sr₂Nb₂O₇. In contrast, pure KSN particles with high aspect ratio and uniform size were successfully synthesized by controlling the ratio of SrNb₂O₆/Nb₂O₅ in the new system (system II). The obtained KSN particles which are 5–30 μm in length and 2–4 μm in diameter are ideal templates for fabricating textured ceramics with tungsten bronze structure. Growth mechanisms in MSS method were also proposed in this work.     

Large piezoelectric coefficient with enhanced thermal stability in Nb5+-doped Ba0.85Ca0.15Zr0.1Ti0.9O3 ceramics

Chemical doping is an indispensable tool to tailor the properties of the commercial piezoelectric materials. However, a high piezoelectric coefficient with enhanced thermal stability is rarely achieved by one dopant in some high-performance ferroelectrics, e.g., the recently discovered eco-friendly (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ (BCZT) ceramics. In order to optimize the piezoelectric property in BCZT system by a simple way, we investigated the doping effect of Fe³⁺, Nb⁵⁺ and Bi³⁺ cations in BCZT ceramics respectively. The results indicate that only Nb⁵⁺-doped BCZT ceramics display a combination of large piezoelectric coefficient and enhanced thermal stability, compared with others. Moreover, the established phase diagrams and in-situ transmission electron microscope (TEM) observations reveal that such optimized piezoelectric properties after Nb⁵⁺ doping originates from (i) the low polarization anisotropy near the ambient tetragonal (T)-orthorhombic (O) phase transition and (ii) the easy domain wall motion of persistent miniaturized ferroelectric domains upon heating.     

Structure,Microwave Dielectric Properties and Thermally Stimulated Depolarization Currents of (1 − x)Ba0.6Sr0.4La4Ti4O15–xBa5Nb4O15 Solid Solutions

(1 ? x)Ba_0.6Sr_0.4La₄Ti₄O₁₅–xBa₅Nb₄O₁₅ (x = 0.05, 0.1, 0.15 and 0.2, BSLT–BN) ceramic samples were prepared by co‐firing the mixtures of Ba_0.6Sr_0.4La₄Ti₄O₁₅ and Ba₅Nb₄O₁₅ powders. Crystal structure, microwave dielectric properties and thermally stimulated depolarization currents (TSDC) of the BSLT–BN series ceramics were investigated. X‐ray diffraction patterns reveal that all the samples exhibit a hexagonal perovskite structure, which implies that the BSLT–BN mixtures form solid solutions. With increasing Ba₅Nb₄O₁₅ content, the diffraction peaks shift to low angles and the sintering temperature of BSLT–BN decreases. Raman spectra analysis reveals the shifting and splitting of the vibration modes. The microwave dielectric properties of the well‐sintered (1 ? x)BSLT–xBN ceramics vary with Ba₅Nb₄O₁₅ content. The dielectric permittivity of the ceramics exhibits a slight decreasing trend. The quality factor varies in the range of 45 000–11 200 GHz, whereas near‐zero temperature coefficients of the resonant frequency may be achieved by changing the Ba₅Nb₄O₁₅ content. TSDC was utilized to explore the extrinsic loss mechanism associated with defects. TSDC relaxation peaks are mainly generated by oxygen vacancies, and the Ba₅Nb₄O₁₅ content has a significant influence on the TSDC spectra.     

X-ray induced change of birefrigenge in Ba2NaNb5O15 crystals

In Ba₂NaNb₅O₁₅: Fe, Mo crystals X-ray induced change of birefringence was observed. The effect is connected with the formation of some X-ray-induced centers which are responsible for the coloration of the crystal as well.     

Photochromic effect of transparent lead-free ferroelectric KSr2Nb5O15 ceramics

Transparent KSr₂Nb₅O₁₅ (KSN) lead-free ferroelectric ceramics have been synthesized via modified pressureless sintering method. A significant photochromic effect was observed for the transparent KSN ceramics prepared without rare-earth dopant modification. The piezoelectric properties depend on the grain orientations were investigated. The optical transmittance of the KSN ceramics is greater than 40% in the wavelength range of 530–800 nm. After NUV irradiation, the absorbance was enhanced by more than 40% in a broad visible range (more than 79%). The absorbance returned to the initial value after a thermal bleaching process. The results of the cycling tests and response experiments showed the stability and saturation of the photochromic effect. In addition, the possible photochromic mechanism of the KSN ceramics is discussed and the photochromic centers are identified. This transparent KSN ceramics exhibits an obvious photochromic effect and is a potential candidate materials for optical data storage and information recording applications.     

铋层状化合物Sr0.3Ba0.7Bi4-xLaxTi4O15陶瓷材料的介电性能

采用固相烧结工艺制备了铋层状化合物Sr0．3Ba0.7Bi4-xLaxTi4O15铁电陶瓷。X射线衍射证实：La含量很大的范围内(x=0～1)均形成了层状钙钛矿结构固熔体。Sr0.3Ba0.7Bi3.25La0.75Ti4O15粉料在低温下难以烧结,随着烧结温度的提高,Sr0．3Ba0.7Bi4-xLaxTi4O15陶瓷密度增加的同时,产生焦绿石相,但La的加入在一定程度上抑制焦绿石相的形成．Sr0．3Ba0.7Bi4-xLaxTi4O15陶瓷的介电常数峰在10kHz时较宽,在100Hz时,介电常数峰被随温度升高而逐渐增大的介电常数所“屏蔽”,材料损耗角正切随温度升高而增大,在低频下增加得更快。     

Low-frequency acoustic study of ferroelastic phase transitions in Ba2NaNb5O15

The peculiarities of low-frequency internal friction near the first order low-temperature (110 K) and second order high-temperature (573 K) phase transitions in improper Ba₂NaNb₅O₁₅ ferroelastic were studied. A large and wide internal friction peak and diffused step-like change in the temperature dependence of shear modulus were also observed within an incommensurate phase between these two phase transitions.     

Low temperature sintering and microwave dielectric properties of Ba3Ti5Nb6O28 with ZnO–B2O3 glass additions for LTCC applications

The effects of ZnB₂O₄ glass additions on the sintering temperature and microwave dielectric properties of Ba₃Ti₅Nb₆O₂₈ have been investigated using dilatometer, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and a network analyzer. The pure Ba₃Ti₅Nb₆O₂₈ system showed a high sintering temperature (1250 °C) and had the good microwave dielectric properties: Q × f of 10,600 GHz, ɛ_r of 37.0, τ_f of −12 ppm/°C. It was found that the addition of ZnB₂O₄ glass to Ba₃Ti₅Nb₆O₂₈ lowered the sintering temperature from 1250 to 925 °C. The reduced sintering temperature was attributed to the formation of ZnB₂O₄ liquid phase and B₂O₃-rich liquid phases. Also the addition of ZnB₂O₄ glass enhanced the microwave dielectric properties: Q × f of 19,100 GHz, ɛ_r of 36.6, τ_f of 5 ppm/°C. From XPS and XRD studies, these phenomena were explained in terms of the reduction of oxygen vacancies and the formation of secondary phases having the good microwave dielectric properties.     

Grain-orientation-engineered multilayer NaSr2Nb5O15 ferroelectric ceramics via templated grain growth

It is difficult to take both texture degree and density into account by the conventional method, especially when one-dimensional particles are used as templates to prepare textured ferroelectric ceramics. Here, we proposed a strategy to improve the texture degree and density of ceramics simultaneously by a grain-orientation-engineered technique. To solve the problem of directional arrangement of template particles, template layers without mixed matrix were prepared by the brushing technique. Dense textured NaSr₂Nb₅O₁₅ ceramics with grain size gradient distribution were designed by the lamination of template and matrix layers. An evaluation method of texture degree was developed. Ferroelastic and ferroelectric domains were observed simultaneously in the oriented grains, which was further confirmed that the ferroelectric-ferroelastic phase transition occurred for the NaSr₂Nb₅O₁₅ ceramics at the low temperature. The obtained textured NaSr₂Nb₅O₁₅ ceramics exhibited the high piezoelectric constant (d₃₃ =134 pC/N). The present research offers a route for designing grain-oriented ferroelectric ceramics.