Bi_2O_3–ZnO–B_2O_3三元系统玻璃结构与性能

采用X射线吸收精细结构和红外吸收光谱分别对铋锌硼玻璃中铋离子邻近结构和硼氧网络结构进行研究,分析其结构变化对玻璃转变温度Tg和热膨胀系数α的影响。结果表明:1)铋离子以三配位([BiO3])和六配位([BiO6])两种配位状态存在;随Bi2O3含量增加,三配位铋离子的配位数上升,六配位铋离子配位数下降,同时铋离子总配位数上升。2)随Bi2O3含量增加,硼氧网络中硼氧四面体含量下降,硼氧三角体含量上升,硼氧四面体网络解聚形成硼氧三角体网络。3)上述结构因素是造成玻璃转变温度Tg下降和热膨胀系数α上升的主要原因。     

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.     

P2O5对Bi2O3-B2O3-ZnO体系玻璃结构及热性能的影响

采用传统的熔融冷却的方法制备了(40-x)Bi2O3-30B2O3-30ZnO-xP2O5(0≤x≤15mo1％)体系玻璃.使用红外光谱、拉曼光谱、DSC和热膨胀仪研究了封接玻璃的结构和热性能.红外光谱及拉曼光谱结果表明,P2O5作为网络形成体,以[PO4]进入到玻璃的网络结构中,玻璃的网络结构性增强.玻璃结构中[BO3]三角体结构单元相对含量有增多趋势,[BO4]四面体、[BiO3]三角体、[BiO6]八面体结构单元相对含量减少.随着P2 O5含量的增加,玻璃化转变温度和玻璃的初始析晶温度升高;玻璃的密度减小.Bi2O3-B2O3-ZnO-P2O5体系封接玻璃热膨胀系数减小,从8.289×10-6℃-1减小到6.354×10-6℃-1.玻璃的软化点逐渐增大,从416℃升高到524℃.     

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.     

掺Bi的MgO-CaO-Al2O3-SiO2玻璃的吸收和近红外发光特性

研究了4种不同Bi_2O_3掺杂量(0.5%,1%,2%和3%,摩尔分数)的23MgO-11CaO-15Al_2O_3-51SiO_2(摩尔比)玻璃的发光特性。测量了吸收光谱、荧光光谱和荧光寿命。通过电子顺磁共振图谱观察了玻璃受γ辐射前后结构的变化,探讨了玻璃颜色变化和近红外发光的机理。结果表明:在500nm激发下,随着Bi_2O_3掺杂量从1%到3%的逐渐增加,发光波长发生红移,荧光半高宽从312nm增加到352 nm;最优的Bi_2O_3掺杂量为1%,玻璃的受激发射截面和荧光寿命的乘积为3.10×10~(-24)cm~2·s;γ辐射后发光强度的增加和玻璃颜色加深的现象说明Bi掺杂玻璃的近红外发光中心可能是低价态的Bi离子或者Bi团簇。     

Al2O3料浆流变性能的研究

研究了pH值、分散剂柠檬酸铵添加量、固相含量对Al2O3料浆流变性能的影响.结果表明:当pH为9-10时,当分散剂柠檬酸铵添加量为2wt%时,所制备的Al2O3料浆粘度最低,该料浆流动性能最佳.同时,料浆粘度会随料浆固相含量增加而增加.     

氧化铝料浆预浸料结合PIP工艺制备SiC/Al2O3-SiC陶瓷基复合材料及性能研究

连续碳化硅纤维增强碳化硅陶瓷基复合材料（SiC/SiC）具有低密度、耐高温、低氚渗透率和优异的辐照稳定性的优点,在航空、航天、核能等领域具有广泛的应用前景。本文针对PIP工艺制备SiC/SiC复合材料周期长、孔隙率较高及易氧化的问题,通过料浆预浸料工艺在基体中引入氧化铝陶瓷形成SiC/Al2O3-SiC复相基体复合材料,并对复合材料制备工艺过程、微观形貌及力学性能进行系统表征。分析结果表明,SiC/Al2O3-SiC复相基体复合材料制备周期较传统PIP工艺大幅度缩短,且复合材料孔隙率明显降低,从11.6%左右降低至6%,拉伸强度为316.5MPa,提升了12.3%,弯曲强度与SiC/SiC相当,但层间剪切强度较低,仅为16.3MPa,有待进一步提高。     

含ZrO2、Al2O3耐碱玻璃受碱侵蚀的影响因素及机理研究

通过测定耐碱玻璃受碱侵蚀后的总失重量及氧化物SiO2、Al2O3、ZrO2转入碱侵蚀液的量,讨论了影响碱蚀过程的因素(浓度、时间和温度),试验证明:玻璃受碱侵蚀程度随浓度、时间和温度的增大而增强,且温度的影响更大些.在此基础上,提出了其碱蚀机理是溶解-表面富集产生保护膜-保护膜破裂-溶解的循环统一.     

Preparation of transparent Bi2O3-ZnO-B2O3 glass by conventional sintering at low temperatures

Glass components fabricated by the sintering route have wide-ranging applications. However, one issue is that the crystallization tendency of glass powders often leads to residual pore-glass interfaces and crystal-glass interfaces, thereby causing strong light scattering and rendering the sintered glass opaque. This issue is particularly pronounced in glasses with a low glass transition temperature (T_g) due to their weak bonding and thus high crystallization tendency. In the present study, a Bi₂O₃-ZnO-B₂O₃ glass with a low T_g of 364°C was fabricated using the conventional sintering method to explore whether transparent glass materials can be obtained. The temperature range of crystallization of the glass powders was analyzed using differential scanning calorimetry. X-ray diffraction was employed to analyze the crystalline phases formed in the sintered glasses. The microstructure of the sintered glasses was examined using scanning electron microscopy. The optical transmittance of the sintered glasses was measured using ultraviolet-visible spectroscopy. The results show that transparent sintered glasses with the highest transmittance of 54% at the wavelength of 650 nm can be obtained by using a coarser initial particle size, lower forming pressure, and an appropriate sintering temperature/time (430°C/30 min). It is suggested that this combination of processing parameters can suppress glass crystallization while maintaining a low glass viscosity during sintering.     

Degradation mechanism of Cr2O3-Al2O3-ZrO2 refractories in a coal-water slurry gasifier: Role of stress cracks

Durability and corrosion behavior of refractory lining, a core part of a commercial water-coal slurry gasifier, largely determine its gas yield rate and carbon conversion rate. In this work, corrosion behavior of high chromite-containing refractory served for 4200 hours in a water-coal slurry gasifier was studied, and the role of generated stress cracks on its degradation behavior was elucidated. The results demonstrated that the depth of penetration under the assistance of the cracks was up to 2.60 cm, which was much deeper than that in the case free from stress crack. The sub-surface, accompanied by cracking, provided a pathway for slag penetration and resulted in more severe corrosion. Furthermore, the isolation layer of (Cr, Fe, Al)₂O₃ solid solution on the refractory’ surface trapped most of the iron oxides. As a result, a further attack from other main corrosive species was controlled by their diffusion through it.     

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。     

氧化物添加剂对P2O5-ZnO-B2O3系低熔点玻璃物化性能的影响

作为绿色环保材料,无铅低熔点玻璃已经在电子元器件的封装和涂层等领域得到了广泛应用。以P2O5-ZnO-B2O3体系为基础玻璃,通过外加法研究氧化物添加剂(Fe2O3、MnO2、CuO、CeO2和Y2O3)对玻璃密度(ρ)、热膨胀系数(α)、特征温度(Tg和Td)及化学稳定性的影响。实验结果表明:使用适量的添加剂可以增大玻璃密度;除Y2O3外,其它添加剂提高玻璃的热膨胀系数;MnO2、CuO和Y2O3显著降低玻璃的特征温度,但Fe2O3和CeO2的影响较小;加入适量添加剂能显著改善玻璃的化学稳定性,其中加Y2O3的耐酸性最好,加CeO2的耐碱性最好。     

Tailoring the efficient laser-absorption-melting behavior of Bi2O3-B2O3-ZnO-Nd2O3 glass for the OLED encapsulation

The efficient 810 nm laser energy conversion of glass frit had been proven to be the key to the long-term hermetic encapsulation of Organic Light Emitting Display (OLED). A direct laser energy conversion laser-assisted Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ sealing glass material without extra laser absorbent such as carbon black, was designed and systematically investigated. The addition of Nd₂O₃, as glass modifiers with higher cationic field strength, could be conducive to enhancing the polymerization of glass network structure, manifesting that the glass-transition temperature Tg, onset-crystallization temperature Tc and thermal stability ΔT (ΔT = Tc-Tg) increased, while thermal expansion coefficient CTE dropped to 9.72×10⁻⁶/°C and advantageously matched with the glass substrate (8±1×10⁻⁶/°C). More importantly, the absorption rate of BBZ-Nd glass was more than 50 % between 800∼810 nm owing to the 4f-4f electron transition of Nd³⁺ ions, and yet the reflectivity and transmittance of the wavelength at 800–810 nm were lower. As optimal compositions, the addition of 3.0 wt% Nd₂O₃ in Bi₂O₃-B₂O₃-ZnO-Nd₂O₃ glass frit with higher absorption coefficients (80 %) led to instantaneous bonding encapsulation between glass substrates without interfacial cracks or pores with the 808 nm wavelength of the laser at 20 W and 2.4 mm/s.     

Bi_2O_3-B_2O_3-BaO玻璃的结构与热学性能研究

通过调整ω(Bi_2O_3)/ω(BaO)比例关系,研究了Bi_2O_3-B_2O_3-BaO低熔点玻璃体系结构和性能,通过DTA测定了玻璃软化温度和转变温度,热膨胀测试仪测试玻璃膨胀系数,红外光谱仪和X射线衍射仪分别研究玻璃结构和玻璃化程度。结果表明:玻璃的软化温度和转变温度都随着BaO质量分数的增加而增加,两者均处于较低的温度变化区间;玻璃的热膨胀系数随着BaO质量分数的增加而升高,XRD表明,玻璃的玻璃化程度良好,没有析晶。     

An experimental study and WinXCom calculations on X-ray photon characteristics of Bi2O3- and Sb2O3-added waste soda-lime-silica glass

Radiation is used in a variety of different fields, and thus protection from its hazardous effects become a popular subject for researchers. For this purpose, in the present study, waste soda-lime-silica glasses as SiO₂–Na₂O–CaO–Bi₂O₃ and SiO₂–Na₂O–CaO–Sb₂O₃ were investigated for X-rays photon characteristics in the energies of 0.01–0.1 MeV via WinXCom program, and the results were compared with the experimental findings obtained at 0.04 MeV. Waste packaging glass was evaluated by adding varying amounts (0.005, 0.05, and 0.5 percentages) of Bi₂O₃ and Sb₂O₃. Seven different glass batches were prepared by following the procedures of precisely weighing the relevant amounts to obtain 10 g specimen in total, homogeneously mixing the respective contents, and thoroughly melting in an Au–Pt crucible via conventional electrical furnace at 1250 °C for 4 h. The linear attenuation coefficient (LAC) for glass specimens were experienced at 0.04 MeV, and it was found out that increasing contents of both oxides increased the LAC implying that a decrease in X-ray transmission occurred. From the point of WinXCom calculations, the LAC and mass attenuation coefficient (MAC) increased while half value layer (HVL) and mean free path (MFP) thicknesses decreased as the oxide substances increased in the glass specimens. That is, Sb₂O₃ addition provided higher X-rays attenuation characteristics in comparison to Bi₂O₃ additive. Further, the experimental data at 0.04 MeV were compared with WinXCom calculations, and it was figured out that the data were parallel for each other, but the correlation coefficient (R²) was found as 0.15 which means that the values were in loose agreement.     

Effect of Bi2O3 on mechanical features and radiation shielding properties of boro-tellurite glass system

This paper focuses on the effect of Bi₂O₃ content (up to 80 mol%) on mechanical features and radiation shielding characteristics of boro-tellurite glasses within TeO₂–B₂O₃–Bi₂O₃ system. The basic mechanical parameters such as oxygen molar volume, packing density, hardness, and elastic moduli were studied based on Makishima–Mackenzie's theory. The shielding studies of the TeO₂–B₂O₃–Bi₂O₃ glasses included gamma, electron and neutron radiations. The newly developed Phy-X/PSD program and Geant4 simulation were used to calculate the shielding parameters such as mass attenuation coefficient (μ/ρ), tenth value layer (TVL), mean free path (MFP), stopping power (ψ_e)), removal cross section (RCS), CSDA range, effective atomic number (Z_eff), and half value layer (HVL). The concentration of Bi₂O₃ content had a significant effect on the gamma shielding competence of the investigated glasses. Form the results of gamma shielding studies, the highest μ/ρ (99.845 cm²/g) occurred at 0.015 MeV for TBB80 and the lowest μ/ρ (0.039 m²/g) occurred at 4 MeV for TBB40. The maximum values of Z_eff for gamma interaction occurred at 0.02 MeV and they were 77.26, 78.81, 79.94, 80.80, and 81.48 for TBB40, TBB50, TBB50, TBB60, TBB70, and TBB80, respectively. The gamma shielding features of the investigated glasses were compared with those of various ordinary concretes, and Pb-free, Pb-based, and commercial glasses. The Bi₂O₃ content had also a considerable influence on the electron shielding competence of the tested glasses. The maximum values of Z_eff for electron interaction occurred at 14 MeV and they were 44.58, 47.72, 50.41, 52.75, and 53.73 for TBB40, TBB50, TBB50, TBB60, TBB70, and TBB80, respectively. The results revealed that the bismuth boro-tellurite glasses could be useful for the shielding against gamma, electron, and neutron radiations, wherein the Bi₂O₃ content can be balanced according to the type and energy of radiation.