Dielectric Relaxation in CaO–Bi2O3–B2O3 Glasses

Glasses in the system CaO–Bi₂O₃–B₂O₃ (in molar ratio) have been prepared using melt-quenching route. Ion transport characteristics were investigated for this glass using electric modulus, ac conductivity and impedance measurements. The ac conductivity was rationalized using Almond–West power law. Dielectric relaxation has been analyzed based on the behavior of electric modulus behavior. The activation energy associated with the electrical relaxation determined from the electric modulus spectra was found to be 1.76 eV, close to that the activation energy for dc conductivity (1.71 eV) indicating that the same species took part in both the processes. The stretched exponent β (0.5–0.6) is invariant with temperature for the present glasses.     

Na0.5Bi0.5TiO3 phase relations: Thermodynamics and phase equilibria in the systems Bi2O3 – TiO2, Na2O – TiO2, and Na2O – Bi2O3 – TiO2

The lead-free piezoelectric material sodium bismuth titanate (NBT, Na_0.5Bi_0.5TiO₃) has attracted considerable attention owing to its promising dielectric, piezoelectric, and electrical properties. However, the literature on the binary subsystems is contradictory and there are only limited data for the ternary system. The present work surveys all of the reports of the binary subsystems Bi₂O₃ – TiO₂ and Na₂O – TiO₂ and synthesizes these data into inclusive revised versions. The compatibilities for the ternary system Na₂O – Bi₂O₃ – TiO₂ were determined experimentally, thus enabling the construction of a complete isothermal section at 800 °C. The compatibilities associated with the problematic binary subsystem Na₂O – Bi₂O₃, which experiences extreme volatilisation, were determined through the generation of the absent standard-state thermodynamic functions for the relevant binary and ternary phases, thus providing a full suite of thermodynamic data for this system. The thermodynamic stability diagrams for Na₂O, Bi₂O₃, and TiO₂ thus were calculated. The isothermal section also addresses the contradictions in the literature concerning the formation of solid solutions of Bi₁₂TiO_20-x / Bi_12-xTi_1+xO_20+0.5x, pyrochlore (Bi₂Ti₂O₇ / Na_wBi_2-xTi_2-yO_7-z), BTO (Bi₄Ti₃O₁₂ / Na_xBi₄Ti₃O_12+0.5x), and NBT (Na_0.5Bi_0.5TiO₃ / Bi_1±xNa_xTiO_3.5±x). Further, it was observed that the congruent melting point of NBT, which was determined to be 1225 °C, was preceded by the onset of gradual structural destabilization at 940 °C. Also, the NBT rhombohedral → tetragonal phase transformation was observed at an onset temperature of ∼250 °C. The present work thus provides platform data for the fabrication and reactivities of materials in the ternary system Na₂O – Bi₂O₃· TiO₂ and its binary subsystems.     

Near Constant Loss Dielectric Response in 2Bi2O3–B2O3 Glasses

Electrical conduction and relaxation phenomena in bismuth borate glasses in the composition 2Bi₂O₃–B₂O₃ (Bi₄B₂O₉) were investigated. Dielectric studies carried out on these glasses revealed near constant loss response in the 1 kHz–1 MHz frequency range at moderately high temperatures (300–450 K) associated with relatively low loss (tan δ = 0.006) and high dielectric constant (ε_r′ = 37) at 1 kHz, 300 K. The variation in AC conductivity with temperature at different frequencies showed a cross over from near constant loss response characterized by local ion vibration within the potential well to universal Jonscher's power law dependence triggered by ion hopping between potential wells or cages. Thermal activation energy for single potential well was found to be 0.48 ± 0.05 eV from cross over points. Ionic conduction and relaxation processes were rationalized by modulus formalism. The promising dielectric properties (relatively high ε_r′ and low tan δ) of the present glasses were attributed to high density (93% of its crystalline counterpart), high polarizability, and low mobility associated with heavy metal cations, Bi³⁺.     

Bi2O3-B2O3-SiO2玻璃的热性质

研究了Bi2O3-B2O3-SiO2系玻璃的成玻性能、转变温度(Tg)和热膨胀系数(CTE)，确定了该系统易熔封接玻璃的玻化范围以及玻璃的转变温度和玻璃的热膨胀系数与玻璃组成的关系。     

The formation mechanism of pores and unbonding in the Al2O3/Al2O3 joints brazed by 50Bi2O3–35B2O3–15ZnO glass

50Bi₂O₃–35B₂O₃–15ZnO (mol. %) glass referred to as Bi50 glass, was used to braze Al₂O₃ ceramics. The phase transformations and wettability of the Bi50 glass on Al₂O₃ substrates at different temperatures were investigated. The results showed that the chemical compatibility of Bi50 glass and Al₂O₃ substrates at 650 °C was excellent. However, Al₂O₃/Al₂O₃ joints having a considerable volume fraction of pores and unbonding were obtained when the joining procedures were carried out by a one-step brazing method. Based on the experiments and simulation results, the prime determinants responsible for the presence of the pores and unbonding within the brazing joints can be divided into two aspects: (i) the intrinsic causes leading to the formation of closed pores (ii) the external factors causing the failure of pores and glass separation. Ultimately, an advanced joining procedure named two-step brazing was proposed, and joints nearly free of defects were acquired.     

The morphological evolution of the Bi2Mo3O12(010) surface in air–H2O atmospheres

Atomic force microscopy (AFM) has been used to examine the morphological evolution of the Bi₂Mo₃O₁₂(010) surface at 400–600 °C in dry air and air–2.3% H₂O. The (010) cleavage surface is characterized by atomically flat terraces separated by straight steps that are integer multiples of b/2 (5.75 Å) in height. During treatments at or above 500 °C, the surface is etched due to the volatilization of Mo. In dry air, etching affects both steps and flat terraces and results in step recession, the development of half-unit-cell (b/2) step loops (pits and islands), and the accumulation of Bi-rich surface deposits. In air–2.3% H₂O, steps are etched with preference to terraces, and this leads to step recession as well as the formation of Bi-rich deposits. Mo volatilization proceeds at an enhanced rate in air–2.3% H₂O and culminates in the nucleation and growth of Bi₂MoO₆ and Bi₂Mo₂O₉ precipitates at 500 and 600 °C, respectively.     

Influence of Bi2O3 flux in the structural and photoluminescence properties of SrAl2O4:Eu2+ phosphors

SrAl₂O₄:Eu²⁺ phosphors with various content of Bi₂O₃ flux were synthesized and analyzed. It was observed that the crystallinity and the particle size of the phosphors were increased with the addition of Bi₂O₃ flux. These phenomena are considered to be caused via the melting of the Bi₂O₃ flux particles during the synthesis of the phosphors. The melted Bi₂O₃ flux increased the mobility and homogeneity of solid reactants, thereby enhancing the photoluminescence intensity of the phosphors. SrAl₂O₄:Eu²⁺ phosphors with Bi₂O₃ as the flux exhibited a broad green emission with a peak at 520 nm. The highest photoluminescence emission intensity was observed when 5 mol% Bi₂O₃ flux was added into the phosphors. The emission is due to 4f⁶5d→4f⁷ (⁸S_7/2) transitions of the Eu²⁺ ions. Moreover, Bi₂O₃ flux extended the application of the ultraviolet excited phosphors toward the blue-light excited phosphors. Nevertheless, the influence of Bi₂O₃ on the afterglow and the emission color of SrAl₂O₄:Eu²⁺ phosphors were not significant. This research indicated that Bi₂O₃ flux is effective flux for synthesizing SrAl₂O₄:Eu²⁺ phosphors.     

Bi2O3-B2O3-Ga2O3玻璃的光学折射率和带隙研究

采用传统熔融淬冷法制备了5组高Bi2O3含量的Bi2O3-B2O3-Ga2O3系统玻璃样品.测试了玻璃样品的密度,折射率和吸收光谱.利用经典的Tauc方程计算了样品的间接允许光学带隙Eopgi,直接允许光学带隙Eopgd和Urbach能量ΔE.根据Duffy等人提出的经验推导公式计算了样品的能量带隙Eg.研究了Ga2O3含量对玻璃样品的密度、折射率、摩尔折射度Rm、金属标准值Mm、光学带隙、能量带隙和Urbach能量的影响,并分析了它们之间的关系.结果表明:随着Ga2O3含量的增加,玻璃样品的密度和折射率逐渐增大,但Ga3+对玻璃折射率的影响要小于B3+;玻璃样品的紫外吸收增强,光学带隙和能量带隙逐渐减小,光学带隙和能量带隙的比值约为1:1.1;Urbach能量逐渐减小,即玻璃中带裂变和缺陷形成的趋势越小.     

Phase equilibria in the La2O3-Y2O3-Nd2O3 system at 1500 °C

The phase equilibria in the ternary La₂O₃-Y₂O₃-Nd₂O₃ system at 1500 °C were studied by X-ray diffraction, petrography, and electron microscopy in the overall concentration range. The samples of different compositions have been prepared from nitrate acid solutions by evaporation, drying, and calcination at 1100 and 1500 °C. The solid solutions based on various polymorphous forms of source components and ordered phase of LaYO₃ were revealed in the system. The isothermal section of the phase diagram for the La₂O₃-Y₂O₃-Nd₂O₃ system has been developed. It was established that in the ternary La₂O₃-Y₂O₃-Nd₂O₃ system there exist fields of solid solutions based on hexagonal (A) and monoclinic (B) modifications of La₂O₃ and Nd₂O₃, cubic (C) modification of Y₂O₃, as well as perovskite-type structure of LaYO₃ (R) with rhombic distortions. The systematic study that covered the whole composition range excluded the formation of new phases. The refined lattice parameter of the unit cell and the boundaries of the homogeneity fields for solid solutions were determined.     

Bi2O3-SiO2系统高温熔体研究进展

Bi2O3-SiO2系统是一类重要的无机硅酸盐系统,其晶体材料具有光学、光电、电导、声光、压电等性能.本文综述了目前对于Bi2O3-SiO2系统高温熔体的认识,分析了Bi2O3-SiO2系统高温熔体的粘度突变、液相状态及熔体结构,最后阐明了该领域研究热点、可能的应用以及需要进一步研究开发的课题.     

Bi2O3-CaO-ZnO-Nb2O5系陶瓷介电性能研究

借助XRD,SEM,HP4140B微电流计和HP4274A阻抗分析仪等测试手段,研究实验制备的BCZN[(Bi1.5Ca0.5)(Zn0.5Nb1.5)O7]陶瓷试样介电性能,并第一次提出了介电常数临界温度和介质损耗临界温度的概念。结果表明:BCZN陶瓷是高频稳定形陶瓷,具有面心立方焦绿石结构,且在最佳烧结温度和保温时间下,为均一的α相单相结构;在很宽的频率范围内,介电常数较高(εr≈81)且很稳定,介质损耗很小(tanδ≈-1.0×10-4);它的介电常数在温度低于介电常数临界温度时,与温度呈线性关系,在温度高于介电常数临界温度时,发生高温突变;介质损耗在温度低于介质损耗临界温度时几乎不变,在温度高于介质损耗临界温度时,发生高温突变;介电常数临界温度和介质损耗临界温度都随频率的升高而升高。     

Stability in the system CaO–Al2O3–H2O

The solubility of AH₃, CAH₁₀, C₂AH_7.5, and C₃AH₆ was determined experimentally at 7 to 40 °C and up to 570 days. During the reaction of CA, at 20 °C and above initially C₂AH_7.5 formed which was unstable in the long-term. The solubility products calculated indicate that the solubilities of CAH₁₀, C₂AH_7.5 and C₄AH₁₉ increase with temperature while the solubility of C₃AH₆ decreases. Thus at temperatures above 20 °C, C₃AH₆ is stable, while at lower temperature also CAH₁₀ and C₄AH₁₉ are stable, depending on the C/A ratio.At early hydration times, CAH₁₀ can be stable initially at 30 °C and above, as the formation of amorphous AH₃ stabilises CAH₁₀ with respect to C₃AH₆ + 2AH₃. With time, as the solubility AH₃ decreases due to the formation of microcrystalline AH₃, CAH₁₀ becomes unstable at 20 °C and above.     

Large third-order optical nonlinearity of ZnO–Bi2O3–B2O3 glass–ceramic containing Bi2ZnB2O7 nanocrystals

Homogeneous transparent optical glass–ceramics precipitated with unique nonlinear crystals are promising materials for photonic applications. We have utilized heat treatment method to prepare transparent ZnO–Bi₂O₃–B₂O₃ glass–ceramic containing Bi₂ZnB₂O₇ nonlinear nanocrystals. A large third-order nonlinear susceptibility χ⁽³⁾ of glass–ceramic is measured by Z-scan technique, which mainly attributed to unique [BiO₆] and [B₂O₅] units in Bi₂ZnB₂O₇ crystal structure and the quantum size effect of nanoparticles. The discovery is of great potential in the application of nonlinear optical integrated devices.     

Erbium doped Bi2O3-B2O3 glass-ceramics containing Bi3B5O12 and CaF2 nanocrystallites for 1.53 μm fiber lasers

Trivalent erbium ions doped Bi₂O₃-B₂O₃ transparent glass ceramics containing CaF₂ were prepared and characterized through X -ray diffraction, scanning electron microscopy, Fourier transform infrared absorption, optical absorption, and near infrared emission for 1.53 μm fiber lasers. The glass ceramics obtained by applying thermal treatment at 575 °C for 5 h and 575 °C for 10 h contain Bi₃B₅O₁₂ and CaF₂ crystallites. The Judd-Ofelt theory was applied to evaluate various spectroscopic and laser characteristic properties. The NIR emission corresponding to the ⁴I_13/2 → ⁴I_15/2 (∼1.53 μm) transition was studied by exciting the samples at 514.5 nm laser radiation. The stimulated emission cross-sections of ∼1.53 μm luminescence were also obtained applying the Mc Cumber theory. The experimental results confirm that the transparent glass ceramic obtained at a thermal treatment of 575 °C for 10 h is more suitable to design fiber lasers for diverse applications in the fields of industry, medicine and scientific research.     

La3+取代Bi3+的 Bi2O3-ZnO-Nb2O5基陶瓷的结构与介电性能

研究了Ｌａ２Ｏ３取代的Ｂｉ２Ｏ３－ＺｎＯ－Ｎｂ２Ｏ５（ＢＺＮ）基陶瓷Ｂｉ１．５－ｘＬａｘＺｎ０．５（Ｚｎ０．５Ｎｂ１．５）Ｏ７的结构和介电性能。采用固相反应法制备陶瓷样品,用Ｘ射线衍射技术分析样品的相结构,未用Ｌａ２Ｏ３取代的纯ＢＺＮ陶瓷的晶体结构为立方焦绿石单相;当Ｌａ２Ｏ３取代量较少时,样品的结构仍然保持立方焦绿石单相结构,但出现了超晶格衍射线（２１１）;当Ｌａ２Ｏ３取代量继续增加。样品的晶体     

Synthesis,structural and electrical properties of novel pyrochlores in the Bi2O3–CuO–Ta2O5 ternary system

A series of non-stoichiometric cubic pyrochlores with general formula, Bi_3?xCu_1.8Ta_3+xO_13.8+x (BCT) was successfully prepared by solid state reaction at the firing temperature of 950 °C over 2 days. The solid solution mechanism is proposed as one-to-one replacement of Bi³⁺ for Ta⁵⁺, together with a variation in oxygen content in order to achieve electroneutrality. The solid solution limit is confirmed by X-ray diffraction technique (XRD) for which linear variation of lattice constants is observed at 0 ≤ x ≤ 0.6. The refined lattice constants are found to be in the range of 10.4838 (8) Å–10.5184 (4) Å and the grain sizes of these samples determined by scanning electron microscopy (SEM) fall between 1 and 40 μm. Meanwhile, thermal analyses show no physical or chemical change for the prepared pyrochlores. The relative densities of the densified pellets for AC impedance measurements are above 85% and the measured relative permittivity, ?′ and dielectric loss, tan δ for composition, x = 0.2 at ambient temperature are ～60 and 0.07 at 1 MHz, respectively. The calculated activation energies are 0.32–0.40 eV and the conductivity values, Y′ are in the order of 10^?3 at 400 °C. The conduction mechanisms of BCT pyrochlores are probably attributed to the oxygen non-stoichiometry and mixed valency of copper within the structure.     

Bi2O3-ZnO-B2O3低熔点封接玻璃的烧结特性

利用X射线衍射、扫描电子显微镜对Bi2O3-ZnO-B2O3系统低熔点玻璃的烧结性能、结晶特性以及烧结后玻璃试样的结构进行了研究.结果表明:随着B2O3含量的增加,玻璃的转变温度与软化温度都随之提高,影响了玻璃的烧结.Bi2O3-ZnO-B2O3系统低熔点玻璃粉末的烧结有黏性液相参与,使得玻璃试样的致密化更加有效,效率更高.当B2O3含量为5.24%(以质量计)时,玻璃的析晶倾向增大,试样中析出了Bi2482O39晶相.当温度继续升高时,试样的烧结收缩出现了"滞缓",有大量的液相出现,且在表面张力的作用F出现了流散.     

Flame-spraying synthesis of aluminate glasses in the Al2O3–La2O3 system

The paper deals with the synthesis and characterisation of binary aluminate glasses in the La₂O₃–Al₂O₃ system with Al₂O₃ contents changing between 74.6 and 86.9 mol% (48–65 wt.%), and of ternary glasses with 75.7 mol% Al₂O₃ doped with 1 mol% of Nd₂O₃ or Er₂O₃. Six binary and two ternary compositions were prepared. Flame synthesis facilitated the preparation of X-ray amorphous microspheres in the systems with 58 wt.% Al₂O₃, and with eutectic composition in the pseudobinary LaAlO₃–LaAl₁₁O₁₈ system doped with Er. Other systems contained low fractions of crystalline LaAlO₃ perovskite, regardless of the composition. The diameter of prepared microspheres ranged between 2 and 10 μm. They were transparent for visible light, as well as in the IR wavenumber range from 1300 to 4000 cm^?1.