V2O5-B2O3-TeO2体系低熔点玻璃形成规律及特性

较详细地研究了V2O5-B2O3-TeO2三元体系的熔化温度、冷却熔体的相组成及玻璃形成规律;并测试分析了V2O5-B2O3-TeO2三元体系玻璃的热性能和特征温度。结果表明,V2O5-B2O3-TeO2三元体系具有较低的熔化温度,存在3个不同的结晶区域和一个较广阔的玻璃形成区,其玻璃形成区域为:V2O50%～70%、B2O30%～30%、TeO230%～100%(均为摩尔分数);V2O5-B2O3-TeO2系玻璃具有较低的熔化温度和封接温度,是无铅低温封接玻璃的理想体系之一。     

热处理对Bi2O3-B2O3-SiO2凝胶玻璃粉体结构与性能的影响

采用溶胶-凝胶法制备了一种Bi₂O₃-B₂O₃-SiO₂系玻璃粉体,在200 ℃、400 ℃、600 ℃和800 ℃温度下分别对凝胶玻璃粉体进行热处理,借助SEM、TEM、XRD、FT-IR、Raman、XPS、DSC、热膨胀仪及“纽扣”烧结实验分别测定了经不同温度热处理后玻璃粉体的结构与性能,分析了其结构变化对玻璃粉体转变温度T_g和烧结特性的影响。结果显示,在实验温度范围内,随热处理温度升高,Bi³⁺逐渐进入玻璃网络中,[BiO₆]八面体和[BiO₃]三角体、[BO₄]四面体和[BO₃]三角体分别与[SiO₄]四面体以顶角相连的方式构建玻璃网络结构。O1s和Bi4f的电子结合能逐渐增大,B1s的电子结合能减小,玻璃网络结构稳定性增强,导致玻璃转变温度T_g及玻璃膨胀软化点温度T_d升高、 润湿性降低且热膨胀系数略有降低。经600 ℃热处理后,玻璃粉体具有较优的烧结性能,T_g、T_d分别约为485 ℃及542 ℃,热膨胀系数α约为7.067×10-6/℃。     

Bi2O3纳米晶玻璃三阶非线性光吸收性质的研究

利用溶胶凝胶法结合气氛控制方式合成了含Bi2O3纳米晶钠硼硅玻璃.利用X射线粉末衍射仪(XRD)、X射线光电子能谱(XPS)、透射电子显微镜(TEM)、X射线能量色散谱(EDX)、扫描模式透射电子显微镜(STEM)、高分辨透射电子显微镜(HRTEM)以及选区电子衍射(SAED)对掺杂在钠硼硅玻璃中Bi2O3纳米晶的形貌和微结构进行了表征,同时,利用飞秒开孔Z-scan技术详细地研究了Bi2O3纳米晶玻璃在800 nm处不同激发光强度下的三阶非线性光吸收性质.结果表明,在钠硼硅玻璃中形成了尺寸小于10 nm的Bi2O3单斜晶系纳米晶.随着激发光强度的增强,该玻璃的三阶非线性光吸收性质产生由饱和吸收向反饱和吸收的转变.进一步,计算得到的该玻璃三阶非线性极化率χ(3)的数量级范围在10-19~10-18m2/V2之间.这一结果说明该玻璃具有良好的非线性光学性能,并且在光限幅器等非线性光学领域具有潜在的应用价值.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Sol-gel processing of SiO2-B2O3 glasses

Glasses from the SiO₂-B₂O₃ binary system containing up to 25 mole percent B₂O₃ have been synthesized. These glasses have been characterized by x-ray diffraction, optical transmission measurement, and I.R. absorption spectroscopy. In order to obtain a homogeneous glass, it was determined that a certain degree of hydrolysis of Si(OC₂H₅)₄ was essential before B(OC₂H₅)₃ could be incorporated. Optical transmission data exhibit characteristic absorption bonds related to Si, B, and OH fundamental and combination frequencies. I.R. absorption spectra in the 620 – 1700 cm^?1 range revealed presence of absorption bands related to vibrations of O-Si-O, Si-O-Si, B-O, and Si-O-B bonds.     

填料对铋锌硼低熔封接玻璃膨胀系数的影响及其微结构研究

在匹配封接中,为确保材料和结构在冷热反复循环的稳定性和耐久性,需考察封接材料与基体材料的膨胀系数在工作温度范围内的匹配性,以使封接应力尽可能小。一般来说,低熔点玻璃封接温度越低,膨胀系数越大。为满足低温封接,同时膨胀系数小的实际需求,常常在低温封接玻璃粉中添加低膨胀耐火填料,制成复合型低温焊料。本文对比研究了堇青石、锆英石、β-锂霞石及锂铝硅(LAS)微晶玻璃4种填料对Bi₂O₃-ZnO-B₂O₃低熔封接玻璃膨胀系数的影响,并估算了各自的有效模量。结果表明:在添加量相同的情况下,堇青石填料调节作用最为显著;β-锂霞石、锂铝硅微晶玻璃虽然本身的线膨胀系数为负,但调节效果不理想,与堇青石相比略差;锆英石的有效模量值最大,但因其自身密度大,膨胀系数也大,调节效果不及另外3种填料。     

AuAg/Bi2O3复合材料的光催化降解和还原性能

先用聚丙烯酰胺凝胶法制备出Bi₂O₃颗粒,然后用光还原法将粒径为6~18 nm的AuAg合金纳米颗粒修饰在Bi₂O₃颗粒表面,制备出AuAg/Bi₂O₃复合光催化剂。AuAg合金纳米颗粒的等离子体共振吸收效应(SPR)使AuAg/Bi₂O₃复合物能吸收波长为~577 nm的可见光,拓展了Bi₂O₃的光响应范围,还促进了Bi₂O₃中光生电荷的分离。以甲基橙(MO)、罗丹明(RhB)和铬离子(Cr(VI))作为目标反应物,在模拟太阳光和可见光照射下考察了AuAg/Bi₂O₃的光催化降解和还原活性,发现AuAg合金纳米颗粒修饰提高了Bi₂O₃的光催化性能。用模拟太阳光照射2 h后,RhB和MO的降解率以及Cr(VI)的还原效率分别提高了~34.2%,~38.0%和~56.7%。同时,AuAg/Bi₂O₃还具有良好的光催化和结构稳定性。基于以上结果,提出了AuAg合金纳米颗粒对Bi₂O₃光催化性能的改性机理。     

Superstructures and phase transitions of Bi2O3

Polymorphs of bismuth sesquioxide were studied by TG-DTA and X-ray diffraction methods and by electron microscopy. Phase transitions of the polymorphs are influenced not only by the temperature before cooling and the cooling rate but also by the duration of melting. New commensurate and incommensurate superstructure phases, observed under the electron microscope, are described as the Naxa types, where N is various value between 2 and 2.48. Here a stands for the cell dimension of the δ form, the fluorite-type structure. The superstructures can be derived by a scheme for ordering oxygen vacancies in the defective fluorite-type structure.     

Observation of surface plasmon resonance of silver particles and enhanced third-order optical nonlinearities in AgCl doped Bi2O3-B2O3-SiO2 ternary glasses

Bi₂O₃-B₂O₃-SiO₂ ternary glasses embedded with Ag nanoparticles were prepared by introducing AgCl into the bismuthate glasses using conventional melt quenching method and characterized by several experimental techniques. Scanning electron microscopic studies indicated the formation of Ag contained nanoclusters which crack and become regular with increase of AgCl content in these composites. Optical absorption spectra of the nanocomposites showed the presence of absorption band of surface plasmon resonance (SPR) due to Ag nanoparticles at ∼600 nm. Z-scan measurement with femtosecond laser was used to investigate third-order optical nonlinearities of the nanocomposites. The results show that the nonlinear refraction γ was dramatically increased up to 30 times by the appearance of Ag nanoparticles when excited within its SPR region, while nonlinear absorption due to two-photon absorption exhibited opposite tendency or even saturated behavior. The calculation of figure of merit suggests that the Ag particle embedded Bi₂O₃-B₂O₃-SiO₂ glass composites are promising candidates for optoelectronic devices.     

Bi2O3助熔剂对CaO-B2O3-SiO2/Al2O3玻璃陶瓷复合材料性能的影响

以CaO-B₂O₃-SiO₂(CBS)玻璃粉体和Al₂O₃陶瓷粉体为原料,通过在CBS与Al₂O₃的质量比固定为50:50的玻璃-陶瓷复合材料中添加适量的Bi₂O₃作为烧结助熔剂,探讨了Bi₂O₃助熔剂对CBS/Al₂O₃复合材料的烧结性能、介电性能、抗弯强度和热膨胀系数的影响规律.研究表明:Bi₂O₃助熔剂能通过降低CBS玻璃的转变温度和黏度促进CBS/Al₂O₃复合材料的致密化进程,于880 ℃下烧结即能获得结构较致密、气孔较少的CBS/Al₂O₃复合材料.然而,过量添加Bi₂O₃将使玻璃的黏度过低,从而恶化CBS/Al₂O₃复合材料的烧结性能、介电性能及抗弯强度.当Bi₂O₃的添加量为CBS/Al₂O₃复合材料的1.5wt%时,于880 ℃下烧结即能获得最为致密的CBS/Al₂O₃复合材料,密度为2.82 g·cm^-3,这一材料具有良好的介电性能(介电常数为7.21,介电损耗为1.06×10^-3),抗弯强度为190.34 MPa,0~300 ℃的热膨胀系数为3.52×10^-6 K^-1.     

Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Effect of Bi2Ti2O7 Seeding Layer on Capacitance-voltage Properties of Bi3:54Nd0:46Ti3O12 Films

Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si structure has been fabricated with a preferentially (111)-orientated Bi2Ti2O7 seeding layer as a ferroelectric gate of metal-ferroelectric-insulator ¯eld e®ect transistor. Bi3:54Nd0:46Ti3O12 and Bi3:54Nd0:46Ti3O12/Bi2Ti2O7 ¯lms are both well-crystallized when annealed at 680±C for 40 min, and have smooth, dense and crack-free surfaces. The width of memory window of the ferroelectric gate increases with increasing electric ¯eld applied to the Bi3:54Nd0:46Ti3O12 thin ¯lms. The width of memory window of Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si with seeding layer is relatively wider than that of Au/Bi3:54Nd0:46Ti3O12/Si at the same bias voltage, and the counterclockwise hysteresis curve of Au/Bi3:54Nd0:46Ti3O12/Bi2Ti2O7/Si is referred to as polarization type switching at di®erent voltages. Bi2Ti2O7 seeding layer plays an important role in alleviating the element interdi®usion between Bi3:54Nd0:46Ti3O12 and Si.     

Hydrothermal synthesis and characterization of Bi2O3 nanowires

An alternative two-step method has been proposed for the synthesis of Bi₂O₃ nanowires with a diameter of about 40 nm from common and cost-effective Bi(NO₃)₃·5H₂O, Na₂SO₄, and NaOH. That is, first, Bi₂O(OH)SO₄ nanowires were prepared through the precipitation reaction of Bi(NO₃)₃·5H₂O and Na₂SO₄ in distilled water under the ambient condition and second, monoclinic phase Bi₂O₃ nanowires were prepared via the hydrothermal reaction of Bi₂O(OH)SO₄ and NaOH at 120 °C for 12 h. The resultant products were characterized by X-ray diffraction, field emission scanning electron microscope, and high resolution transmission electron microscopy. In addition, the photocatalytic studies indicated that the as-synthesized Bi₂O₃ nanowires were a kind of promising photocatalyst in remediation of water polluted by some chemically stable azo dyes.     

Structural adaptability in the system Bi2O3  WO3 : Higher members of the homologous series Bi2WnO3n+3

The ultramicrostructure of phases with n = 1, 2 and 3 in the hypothetical series Bi₂W_nO_3n+3 has been investigated by high resolution electron microscopy and energy dispersive X-ray emission spectroscopy. For n = 1 and 2, well ordered phases with the predicted compositions have been obtained, but for n = 3, a severely disordered assemblage containing intergrowths of the two known structures and strips of the n = 3 member is produced. No evidence for ordered structures with n > 2 has yet been obtained.     

Synthesis and structural characterization of (Bi2O3)1?x (Y2O3)x and (Bi2O3)1?x (Gd2O3)x solid solutions

Solid solution series, (Bi₂O₃)_1−x (Y₂O₃)_x and (Bi₂O₃)_1−x (Gd₂O₃)_x, forx = 0.10, 0.20, 0.30 and 0.40 were synthesized by standard ceramic technique. The structural phase characterization was carried out using X-ray powder diffraction technique. It was found that the solid solution containing 20–40 mole% of Y₂O₃ had face-centred cubic structure. All samples of the solid solution series, (Bi₂O₃)_1−x (Gd₂O₃)_x, had rhombohedral single phase in the concentration range 0.10 ≤x ≤ 0.40. Lattice parameters offcc phase of Y₂O₃ doped samples were calculated from the X-ray diffraction data. The lattice constant ‘a’ gradually decreases with increasing content of dopant concentration (x) for the Y₂O₃ doped system and obeys Vegard’s rule. The unit cell parameters for the (Bi₂O₃)_1−x (Gd₂O₃)_x doped samples showing rhombohedral phase were obtained on hexagonal setting.     

CO2 absorption and desorption of Bi2O3-La2O3 powders prepared by mechanical synthesis

In order to obtain CO₂-absorbents to eliminate CO₂ concentration locally, Bi₂O₃-La₂O₃ mixed powders were prepared by mechanical alloying (MA) method using a planetary ball-milling machine. CO₂-absorption and desorption properties were checked by TG-DTA for the obtained powder samples. As a result, the sample shown by (Bi₂O₃)_1−x(La₂O₃)_x [x≤0.50] was found to form α-Bi₂O₃-solid solution with repeated CO₂-adsorption and desorption around 400- 500 °C. Absorbed and desorbed CO₂ contents varied with MA time: the 72 h MA’ed sample had a larger CO₂ content than the 24 h MA’ed sample. The performance depended on the sample composition, and (Bi₂O₃)_0.70(La₂O₃)_0.30 was found to have the highest performance in the present system.     

Preparation and electrical properties of a monophasic ZrO2Y2O3Bi2O3 solid electrolyte

A preparation method is described of monophasic yttria stabilized zirconia doped with Bi₂O₃. This material is prepared from a homogeneous power which, after pressing, is sintered in a Bi₂O₃ atmosphere. The resulting ceramic has a composition of 0.78rO₂-0.206 YO_1.5-0.014BiO_1.5. The grain boundaries are enriched with bismuth. A relative density of 95% of the theoretical one is attained at a considerably lower temperature than the bismuth free sample. The electrical conductivities of the monophasic Bi doped and the Bi-free electrolyte material do not differ significantly.     

Fluorescence and x-ray data of Bi2Al4O9 and Bi2Ga4O9

Green luminescence (peaking at 490 nm) is described for Bi₂Al₄O₉ at 300°K. Bi₂Ga₄O₉ is isomorphous with the Al compound, and the lattice parameters are reported. Its fluorescence is totally quenched at room temperature. The corresponding In compound does not exist.     

网状结构Bi2O3光催化剂的合成及其光催化性能

以Bi(NO3)3·5H2O为原料,天然棉花为模板结合热处理工艺,成功合成了具有网状结构的三斜晶相Bi2O3光催化材料,利用XRD、SEM、TG-DTA和UV-Vis漫反射等技术对样品的晶型结构、形貌及吸光性能等进行了表征。以亚甲基蓝染料分子模拟环境污染物,考察了样品的光催化性能。结果表明,棉花纤维在网状Bi2O3的制备中起到了充分的诱导作用,这种网状结构是由一些直径不一的Bi2O3扁平状网线交错排列、稀疏盘结而形成。TGA分析结果表明,适当的热处理在去除棉花模板的同时可以实现Bi 3+→Bi2O3的转化。在可见光照射下,网状Bi2O3的光催化活性及重复使用性能均优于粉体Bi2O3,反应100min后,对MB的脱色率可达到93%左右,并且重复使用4次后仍可使MB的脱色率保持在85%以上。此外,对网状Bi2O3的形成机理进行了探讨。