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。     

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.     

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.     

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.     

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。     

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.     

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⁺.     

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.     

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     

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.     

Bi2O3-SiO2系统固相反应研究

利用XRD、DSC研究了Bi2O3-SiO2系统的固相反应.按物质的量比1∶1将Bi2O3与SiO2混合物在一定温度下处理一定时间获得生成产物并探讨了不同反应条件下产物生成规律.结果表明:亚稳化合物Bi2SiO5在固相反应时产生,并随温度及保温时间按一定规律变化.750 ℃保温不同时间所获试样的XRD谱表明随着固相反应时间的延长,反应物Bi2O3的衍射峰减弱,生成物Bi12SiO20衍射峰增强,反应越完全.在固相反应过程中生成的亚稳相Bi2SiO5随着反应时间延长衍射峰减弱.固相反应温度由700 ℃升高至900 ℃过程中,Bi12SiO20逐渐转变为Bi4Si3O12.     

Experimental determination of the liquidus line in the high Bi2O3 region in the TiO2–Bi2O3 system

Liquidus line in the high-Bi₂O₃-containing region of the TiO₂–Bi₂O₃ system was determined experimentally. The equilibrating and quenching technique with subsequent electron probe microanalyser (SEM-EDS) microanalysis were employed. Based on the data, liquidus line was constructed between 60 and 92 mol% Bi₂O₃. The current results showed a higher solubility of Bi₂O₃ in the liquid phase in equilibrium with the Bi₄Ti₃O₁₂ compound compared with the existing phase diagram. In addition, differential scanning calorimetry (DSC) was used to estimate the transformations covering the composition range from 60 to 95 mol% Bi₂O₃. Further, the phase diagram of the TiO₂–Bi₂O₃ system was calculated using a quasichemical model for the liquid phase. The thermodynamic properties of the intermediate compounds were estimated from the data of TiO₂ and Bi₂O₃ pure solids.     

Bi2O3-B2O3-ZnO系玻璃着色的光谱吸收特性研究

以Bi2 O3-B2 O3-ZnO为基础玻璃,分别采用不同金属氧化物对其着色,研究着色剂种类、着色剂引入量以及玻璃粉粒径对玻璃粉热辐射吸收光谱性能的影响.结果表明:Co2 O3在600～690 nm和大于1120 nm波长范围的玻璃粉具有最高的吸收率;CuO和MnO分别在690～1120 nm和480～590 nm区间的吸收率高于其它着色剂,对氧化钴该波长的低吸收率具有互补性;采用复合着色剂玻璃的光谱吸收率不具有质量加和特性;玻璃粉的光谱吸收率随玻璃粉粒径的增大而明显增大.研究旨在为热辐射加热封接工艺封接玻璃的开发提供依据.     

Bi2O3-B2O3-BaO系玻璃的光学折射率与带隙

研究了Bi2O3-B2O3-BaO三元系统的玻璃形成区,给出了该三元系统玻璃形成范围.采用熔融淬冷法制备了60Bi2O3-(40-x)B2O3-xBaO(x=5,10,15,20)和65Bi2O3-25B2O3-10BaO(以摩尔计)的5组高Bi2O3含量的Bi2O3-B2O3-BaO玻璃样品.测试了玻璃样品的折射率和吸收光谱,根据经典的Tauc方程计算了间接允许光学带隙和直接允许光学带隙,计算了样品的能量带隙,并估算了它们之间的关系.研究结果表明;随着BaO含量的增加,玻璃样品折射率逐渐增大,但Ba2 对玻璃折射率的影响要远小于Bi3 ;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1:1.2.     

含Bi2O3的MgO-Al2O3-SiO2玻璃核化与晶化动力学研究

使用差热分析(DTA)的方法研究了含Bi2O3的MgO-Al2O3-SiO2玻璃粉末(粒度≤0．054mm)的核化与晶化动力学。由此方法确定了样品最大成核速度温度，同时计算出晶体生长的活化能和动力学参数。结果表明，含Bi2O3玻璃的晶化指数(n)和晶体生长维数(m)都为1．15(约等于1)，这说明该玻璃的晶化机制是表面晶化。由Kissinger和Augis—Bennett方程计算出的活化能较为接近，平均值为401kJ／mol。     

Bi0/Bi2O2CO3/N-TiO2复合材料的制备及其光催化性能

利用TiO2纳米带作为基底,乙二胺作为还原剂及氮源,采用溶剂热法合成光催化复合材料Bi0/Bi2O2CO3/N-TiO2。通过XRD、SEM、TEM等对催化剂的结构进行表征,结果显示,直径为1.2~2.1 nm的单质铋（Bi0）和碳酸氧铋（Bi2O2CO3）的复合量子点均匀生长在一维TiO2纳米带（TiO2 NBs）表面。在可见光照射下,相比于TiO2（降解率30.95％）,Bi0/Bi2O2CO3/N-TiO2在3 h内实现了对有机污染物罗丹明B的高效降解（降解率95.02％）。最后进行活性物质捕获实验,证实h+和•OH是材料参与光催化降解罗丹明B的主要活性物质。     

Bi0/Bi2O2CO3/N-TiO2复合材料的制备及其光催化性能

利用TiO2纳米带作为基底,乙二胺作为还原剂及氮源,采用溶剂热法合成光催化复合材料Bi0/Bi2O2CO3/N-TiO2.通过XRD、SEM、TEM等对催化剂的结构进行了表征.结果显示,直径为1.2～2.1 nm的单质铋(Bi0)和碳酸氧铋(Bi2O2CO3)的复合量子点均匀生长在一维TiO2纳米带(TiO2 NBs)表面.在可见光照射下,相比于TiO2 NBs(降解率30.95％),Bi0/Bi2O2CO3/N-TiO2在3 h内实现了对有机污染物罗丹明B的高效降解(降解率95.02％).活性物质捕获实验证实,h+和?OH是材料参与光催化降解罗丹明B的主要活性物质.     

Sm2O3掺杂的Bi2O3-ZnO-Nb2O5基陶瓷的烧结特性与介电性能

用传统的固相法合成了Sm2O3掺杂的Bi2O3-ZnO-Nb2O5(BZN)基陶瓷(Bi1.5-xSmxZn0.5)(Zn0.5Nb1.5)O7(0≤x≤0.6,BSZN),通过XRD、AV2782阻抗分析仪等测试手段对其烧结行为、相结构及介电性能进行了系统研究.结果表明纯BZN陶瓷的结构为立方焦绿石单相;当Sm2O3掺杂量较少(0＜x≤0.5)时,样品的相结构仍然保持立方焦绿石单相;随着Sm2O3掺杂量的进一步增加(x≥0.6),样品出现其它相.同时,试样的介电性能随结构的变化而呈现有规律的变化.