BaO-SiO2-B2O3-TiO2系统玻璃的电子自旋共振研究

采用电子自旋共振(ESR)方法研究了钛在BaO-SiO2-B2O3-TiO2系统玻璃中的价态及Ti3+的结构状态.结果表明:在正常空气气氛下熔制的玻璃中,钛主要以Ti4+形式存在,所产生的顺磁信号归因于玻璃的本征缺陷和熔制时TiO2中氧的逸出而形成的氧空位捕获电子引起,且随温度升高,氧空位浓度减少;在微还原性气氛下,有部分Ti3+形成,出现g┃=1.9954,g┸=1.9823两处顺磁峰,它们对温度有着不同的依从性,即随温度升高:g┃ 峰增强,g┸峰降低;根据Ti3+的g┃ 、g┸)参数的性质,认为Ti3+是处于带四方畸变的八面体配位场中,形成[TiO6];即便在液氮温度下,也难以观察到Ti3+的超精细结构谱线.     

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。     

Li2CO3-B2O3-V2O5掺杂ZnO-TiO2陶瓷低温烧结的研究

以Li2CO3、B2O3和V2O53种常见的低熔点氧化物为烧结助剂,用传统固相法制备了Li2CO3-B2O3-V2O5掺杂的ZnO-TiO2微波介质陶瓷,并利用XRD、SEM等研究了ZnO-TiO2陶瓷的烧结行为、物相组成、显微结构特征及微波介电性能等。结果表明,当掺入3%(质量分数)Li2CO3-B2O3-V2O5时,在840℃烧结2h可制备出体积密度为4.99g/cm3的ZnO-TiO2陶瓷,达到理论密度的96.5%以上,εr、Q.f、τf分别约为24、22900GHz、-4×10-6/℃。     

BaFe12O19/SiO2-B2O3-K2O 微晶玻璃陶瓷的低温合成及其微波性能

采用柠檬酸sol-gel工艺合成了BaFe₁₂O₁₉/SiO₂-B₂O₃-K₂O微晶玻璃陶瓷, 并对其介电常数及其磁导率在100MHz～ 6 GHz 下的变化规律进行了研究。结果表明: BaFe₁₂O₁₉/SiO₂-B₂O₃-K₂O微晶玻璃陶瓷可以在850℃/5 h的条件下烧结而成, 其合成过程与体系中的Ba/Fe 密切相关; 其介电常数基本不随测试频率的变化而变化; 其磁导率实部随测试频率的增加而下降。      

等离子喷涂纳米Al2O3-TiO2复合陶瓷涂层的研究现状

等离子喷涂纳米Al2O3-TiO2复合陶瓷涂层具有耐磨、耐腐蚀、抗热氧化等优良性能,因而成为目前纳米涂层领域的研究热点之一。归纳了纳米结构Al2O3-TiO2喂料的制备方法,介绍了纳米结构涂层的显微结构和力学性能(断裂韧性、显微硬度、结合强度等),分析了纳米结构涂层的抗热氧化性和摩擦学性能,综述了等离子喷涂纳米Al2O3-TiO2复合陶瓷涂层的研究现状,讨论并展望了其未来的发展方向和应用前景。     

Bi2O3-TiO2复合氧化物光催化环己烷选择氧化

环己烷选择性氧化生成的环己醇和环己酮是己内酰胺合成中的重要中间体,在尼龙生产中具有重要作用,但工业路线条件苛刻,效率低。温和条件下环己烷选择性氧化引起极大关注,而光催化在低温环境压力下的饱和 C-H 活化和氧化具有独特优势。本文采用水热法制备了一系列 Bi₂O₃-TiO₂复合催化剂,对其结构、形貌、光学与光电化学性质通过多种方法包括 SEM、XRD、N₂吸脱附、UV-Vis、光致发光光谱、瞬态光电流响应等进行详细表征。在室温、0.1 MPa 氧气为氧化剂、500 W 氙灯模拟太阳光条件下比较了纯 TiO₂、Bi₂O₃ 和 Bi₂O₃-TiO₂ 复合物对环己烷选择性氧化的催化性能,结果表明,复合 Bi₂O₃ 后提高了 TiO₂ 的催化活性,其中 9%Bi₂O₃-T...     

不同Al2O3-TiO2-Cr2O3-SiO2配比等离子喷涂层的耐磨粒磨损性能

为了探讨等离子喷涂制备Al2O3-TiO2-Cr2O3-SiO2层的可行性及其喷涂层的耐磨性,采用等离子喷涂在Q235钢表面分别制备了54%Al2O3-36%TiO2-10%Cr2O3-0.5%SiO2,42%Al2O3-28%TiO2-28.5%Cr2O3-1.5%SiO2和30%Al2O3-20%TiO2-47.5%Cr2O3-2.5%SiO23种陶瓷层,分析了陶瓷涂层的金相显微形貌、显微硬度及耐磨粒磨损性能,并分析了其耐磨粒磨损的机理。结果表明:3种涂层的显微硬度分布均具有梯度分布特性,Al2O3+Cr2O3硬质相含量越高,涂层硬度越大;30%Al2O3-20%TiO2-47.5%Cr2O3-2.5%SiO2喷涂粉制成的涂层的硬度最大,耐磨粒磨损性能最佳。     

添加Bi2O3对ZnO-B2O3-P2O5-SrO体系封接玻璃结构和性能的影响

采用熔融法制备了ZnO-B2O3-P2O5-SrO-Bi2O3系无铅磷酸盐封接玻璃,研究了Bi2O3对该体系玻璃的结构、特征温度、热膨胀系数和化学稳定性的影响。结果表明,随Bi2O3含量的增加,玻璃的密度增大,Tg、Tf先下降后趋于平缓,玻璃的热膨胀系数先上升后趋于平缓;化学稳定性先增强后降低,当Bi2O3为7mol时,达到极小值。     

微弧等离子喷涂碳纳米管/纳米Al2O3-TiO2复合涂层高温性能研究

采用等离子喷涂技术制备了5wt%CNTs/Al2O3-TiO2复合涂层,借助SEM、热红联仪和RAM反射率测试系统对CNTs/Al2O3-TiO2复合涂层的组织结构、高温氧化性能、电磁特性进行了分析.结果表明:CNTs/Al2O3-TiO2复合涂层的组织结构致密、孔隙率低,CNTs分散均匀,碳纳米管与Al2O3-TiO2陶瓷粘结剂之间具有良好的界面相容性.在20～700℃高温氧化过程中,CNTs起始失重温度为471.29℃,CNTs/Al2O3-TiO2复合涂层的高温氧化性能有一定提高,起始失重温度从471.29℃提高到507.8℃,而碳纳米管的失重率从100%下降到33.68%.CNTs/Al2O3-TiO2复合涂层具有较好的高温吸波性能,25℃时复合涂层的反射率峰值为-7.86dB.随温度的升高,CNTs/Al2O3-TiO2复合涂层的反射率峰值不断减小,谐振频率向低频移动,300℃时复合涂层的反射率峰值为-12.88dB,小于-5dB频带宽为4.48GHz.     

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.     

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.     

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.     

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.     

Phase relations in the BaO-B2O3-TiO2 system and the crystal structure of BaTi(BO3)2

In this paper, the subsolidus phase relations in the ternary system BaO-B₂O₃-TiO₂ have been investigated. The phase diagram consists of 15 ternary phase regions. There exist 11 binary compounds and two ternary compounds. The ternary compound, BaTi(BO₃)₂, is isostructural with CaMg(CO₃)₂. It crystallizes in a rhombohedral system with the space group R-3. The lattice parameters are a=5.0205(2) and c=16.3844(1) Å. Final refinement on the diffraction data converge to R_p=9.09, R_wp=12.24, and R_exp=3.75%.     

Preparation, phase formation and photoluminescence properties of ZnO-SiO2-B2O3 glasses with different ZnO/B2O3 ratios

Glasses in ZnO-SiO₂-B₂O₃ ternary system with different ZnO/B₂O₃ ratios were studied as scintillating materials. Differential thermal analysis and X-ray diffraction patterns showed that nucleation of willemite and zinc oxide was considerably facilitated with increasing the ZnO/B₂O₃ ratio. Photoluminescence spectra showed a reduction in intensity over the UV region upon this increment prior to the formation of crystalline phases. Optical basicity as a measure of nonbridging oxygens (NBOs) is elaborated in this study as a major cause of this effect. However, near band edge emission (NBE) after crystallization implied an increase in intensity upon the increment of the ZnO/B₂O₃ ratio which proved the key role of willemite and zinc oxide as UV emission centers.     

An ESR study of the heterogeneous system Cr2O3V2O5

An ESR study of the ‘products’ of the high temperature solid state reaction xCr₂O₃+yV₂O₅ ($\text{0.05≦(}\text{x}\text{y}\text{)≦2.0}$), aided by powder X-ray diffraction and IR spectra, has revealed (i) ‘unfamiliar’ paramagnetic intermediates Cr⁴⁺ and Cr⁵⁺, (ii) provided some clues to the oxidation of Cr³⁺ to Cr⁶⁺, and (iii) demonstrated a variety of exchange interactions involving V⁴⁺ and Cr³⁺.     

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.     

Properties and Structures of Bi2O3-B2O3-TeO2 Glass

Glass formation range of Bi₂O₃—B₂O₃—TeO₂ system has been investigated（B₂O₃ < 40 mol%）.Four glasses with compositions xBi₂O₃—3OB₂O₃—（70—x）TeO₂（x = 40,50,60 and 70 mol%） have been prepared by using melt quenching technique.The effect of Bi₂O₃ content on thermal stability,optical properties and structures of these four Bi₂O₃—B₂O₃—TeO₂ glasses is systematically investigated by inductive coupled plasma emission spectrometer（ICP）,differential scanning calorimetry（DSC）,Raman spectra and X-ray photoelectron spectroscopy（XPS）.It is found that the density,refractive index and optical basicity increase with increasing Bi₂O₃.The Raman spectra and XPS spectra show that the glass network is mainly constituted by the[BiO₆] octahedron,[TeO₄]trigonal bipyramidal,[TeO₃]trigonal pyramid,[BO₃]trigonal pyramid and[BO₄]tetrahedron structural units.With increasing Bi₂O₃,the coordination number around B atom changes from 3 to 4 and [TeO₄]units are converted to[TeO₃]units.Bi⁵⁺ ions may exist in Bi₂O₃—B₂O₃—TeO₂（BBT） system and their amount grows with increasing Bi₂O₃ content.