Influence of ligand coordination of cobalt ions on structural properties of ZnO-ZnF2-B2O3 glass system by means of spectroscopic studies

The glasses of the composition 10ZnO-30ZnF₂-60B₂O₃ doped with different concentrations of CoO were prepared. Differential scanning calorimetric (DSC) studies, optical absorption, photoluminescence and infrared spectra of these glasses have been carried out. DSC studies have indicated that the resistance of the glass against devitrification increases with the increase in the concentration of CoO. Optical absorption spectra have exhibited one octahedral band due to ⁴T_1g(F)→²T_1g(H) and two tetrahedral bands due to ⁴A₂(⁴F)→⁴T₁(⁴P) ⁴A₂(⁴F)→⁴T₁(⁴F) transitions of Co²⁺ ions at about 525, 570 and 1400 nm, respectively. As the concentration of CoO is increased the tetrahedral bands are observed to grow at the expense of octahedral band. The luminescence spectra have exhibited two emission bands in the spectral regions of 600-700 nm and 800-900 nm due to ⁴T₁(⁴P)→⁴A₂(⁴F) and ⁴T₁(⁴P)→⁴T₂(⁴F) tetrahedral transitions of Co²⁺ ions, respectively. With the increasing content of cobalt ions in the glass matrix, the half width and intensity of these bands are observed to increase. The analysis of the results of these two spectra coupled with IR spectra has indicated that as the concentration of CoO is increased in the glass matrix, the tetrahedral occupancy of cobalt ions dominates over the octahedral occupancy and increase the rigidity of the glass network.     

Structure of Na2O·MO·SiO2·CaF2 (M=Mg,Ca) oxyfluoride glasses

(9−x)CaO·xMgO·15Na₂O·60SiO₂·16CaF₂(x=0, 2, 4, 6, and 9) oxyfluoride glasses were prepared. Utilizing the Raman scattering technique together with ²⁹Si and ¹⁹F MAS NMR, the effect of alkaline metal oxides on the Q species of glass was characterized. Raman results show that as magnesia is added at the expense of calcium oxide, the disproportional reaction Q³→Q⁴+Q² (Qⁿ is a SiO₄ tetrahedron with n bridging oxygens) prompted due to the high ionic field strength of magnesia, magnesium oxide entered into the silicate network as tetrahedral MgO₄, and removed other modifying ions for charge compensation. This reaction was confirmed by ²⁹Si MAS NMR. ¹⁹F MAS NMR results show that fluorine exists in the form of mixed calcium sodium fluoride species in all glasses and no Si–F bonds were formed. As CaO is gradually replaced by MgO (x=6, 9), a proportion of the magnesium ions combines with fluorine to form the MgF⁺ species. Meanwhile, some part of Na⁺ ions complex F⁻ in the form of F–Na(6).     

Yb3+/Ho3+/Tm3+共掺碲酸盐玻璃的上转换白光发射及其机理研究

采用高温熔融法分别制备了Yb3+/Ho3+,Yb3+/Tm3+和Yb3+/Ho3+/Tm3+共掺的碲酸盐玻璃。在980nm红外激光激发下,Yb3+/Ho3+/Tm3+共掺的玻璃样品显示了强的蓝光、绿光和红光发射,分别对应于Tm3+的1 G4→3 H6跃迁、Ho3+的5 F4(5 S2)→5I 8跃迁以及Ho3+的5 F5→5I 8和Tm3+的1 G4→3 F4跃迁。通过对比发现,Yb3+/Ho3+/Tm3+共掺样品中的红、绿光积分发射强度比值(3.95)明显大于Yb3+/Ho3+共掺样品(1.69),这是由于Ho3+和Tm3+间存在交叉弛豫过程3 H4(Tm3+)+5I 6(Ho3+)→3 F4(Tm3+)+5 F5(Ho3+)和3 F4(Tm3+)+5I 8(Ho3+)→3 H6(Tm3+)+5I 7(Ho3+)所致。在激发功率密度为8.2 W.cm-2时,Yb3+/Ho3+/Tm3+共掺样品的上转换发光色坐标值为x=0.345,y=0.338,非常接近于等能白光(x=0.333,y=0.333)。     

偏硼酸锶系列发光材料的制备及其发光性能研究

利用液相共沉淀法制备了SrB2O4 4H2O和SrB2O4 4H2O∶Eu3+,利用高温焙烧前驱体法制备了SrB2O4和SrB2O4∶Eu3+发光材料,通过X射线粉晶衍射(XRD)、X射线能谱分析(EDS)和扫描电子显微镜(SEM)等手段对产物进行了表征.通过荧光光谱研究了其发光性质,并考察了反应时间及Eu3+掺杂浓度对发光强度的影响.结果表明,基质SrB2O4 4H2O和SrB2O4在紫外区具有较强的发光性能,SrB2O4 4H2O∶Eu3+和SrB2O4∶Eu3+均在613 nm有最强发射峰.通过调整反应时间和提高掺杂量,可以克服结构水的猝灭作用的影响,大大提高SrB2O4 4H2O∶Eu3+发光性能,且具有更高的红橙比,是一种良好的新型发光基质.     

邻苯二甲酸二甲酯系材料中α-弛豫的降温介电谱测量与分析

对邻苯二甲酸二甲酯(dimethyl phthalate)、邻苯二甲酸二乙酯(diethyl phthalate)、邻苯二甲酸二丁酯(dibutyl phthalate)和邻苯二甲酸二异辛酯 (dioctyl phthalate)系列材料中, α-弛豫的降温介电谱进行了测量, 得出了相应材料α-弛豫的平均弛豫时间τ_α^a 随温度T的变化关系. 通过τ_α^a 的实验结果与经验的Vogel-Fulcher-Tammann)定律τ_α^a = τ_α⁰ exp (A/(T-T₀))的拟合, 获得了上述系列材料的τ_α⁰, A和T₀. 分析发现, 随邻苯二甲酸二甲酯系列分子侧链中碳原子数目n的变化, 材料的τ_α⁰, A, T₀ 和T_g 表现出一定的规律性, 具体为随n的增加, 即分子内部自由度的增多, A和T_g 都表现出近乎相同的先减后再增的趋势, 而1/τ_α⁰ 和T₀ 则表现出基本相同的先快速减小, 然后保持基本上不变的趋势. 关键词： 玻璃化转变 介电谱 α-弛豫')" href="#">α-弛豫 邻苯二甲酸二甲酯系列材料     

空间微小碎片累积撞击损伤效应加速模拟研究

利用等离子体驱动微小碎片加速器对太阳同步轨道上太阳电池在轨10年遭遇微小碎片超高速撞击的累积损伤效应进行了加速模拟, 获得了电池性能参数的损伤结果, 并与所建立的损伤评估模型的预测结果进行了分析比较, 二者基本一致.     

以最大原子密度定义合金相中的第一近邻团簇

本文提出利用不同壳层所包含的径向原子密度, 即单位体积内的原子个数随着径向的分布, 来方便而精确地定义团簇, 即具有最大径向原子密度的且表面呈现三角密堆结构的完整壳层为第一近邻团簇. 最后以Al-Ni-Zr合金相为例说明了该方法的合理性与适用性, 及此方法所定义的团簇与非晶形成的关系.     

冲击加载下Zr51Ti5Ni10Cu25Al9金属玻璃的塑性行为

进行了10—27 GPa应力范围内Zr₅₁Ti₅Ni₁₀Cu₂₅Al₉金属玻璃的平面冲击实验以研究其高压-高应变率加载下的塑性行为.由样品自由面粒子速度剖面的分析获得了冲击加载过程的轴向应力,并通过轴向应力与静水压线的比较获得剪应力.实验结果表明,尽管存在明显的松弛效应,但Zr基金属玻璃的Hugoniot弹性极限随着冲击应力的增加而增加.然而,塑性波阵面上的剪应力则显示先硬化而后软化现象,而且软化的幅度随冲击应力的增加而增加.冲击加载下Zr基金属玻璃的上述剪应力变化特征与分子动力学模拟结果比较一致,但与压剪实验结果和一维应力冲击实验结果明显不同.     

用于可见照明的超宽带黄色荧光玻璃

报道了一种新的可用蓝光发光二极管（LED）有效激发的黄色发光玻璃.这种超宽带黄色荧光玻璃样品是在低硅钙铝酸盐玻璃基质中掺杂Ce³⁺,并采用熔融法制备的.通过对吸收光谱、激发光谱、荧光光谱以及不同激发源下荧光强度和峰值波长的测试,分析了样品的发光特性.并利用蓝光LED来激发样品,获得白光发射.从色坐标的计算和玻璃本身的优势来看,这一发光体系在照明和显示等方面具有很大的潜在应用价值.     

阳离子对Er3+掺杂硼酸盐玻璃结构和发光特性的影响

针对Si/Al掺杂量增大使BaO-(1-x)SiO₂-xAl₂O₃-B₂O₃-0.005Er³⁺(x=0,0.5,1,摩尔分数)玻璃样品的1 540 nm红外发光和540 nm上转换发光强度呈现相反的变化趋势,讨论了阳离子掺杂对稀土离子周边对称性和电负性变化与荧光行为的内在关系。红外傅里叶透射光谱显示,不同掺杂浓度下样品的最大声子能量没有明显变化,说明光谱随掺杂浓度的变化与玻璃体系的最大声子能量无关。根据Judd-Ofelt理论计算了⁴I_13/2和⁴S_3/2能级的光学参数,通过比较两能级的跃迁几率(A)、寿命(τ)、荧光分支比(β)和受激发射截面(σ)等光学参数,发现⁴I_13/2能级和⁴S_3/2能级的相关参数呈现相反的趋势。最后测试了样品⁴I_13/2能级下1 540 nm的寿命,进一步从电负性角度考虑了样品的发光效率。理论计算和实验结果相符。