Anomalous temperature dependence of the low-frequency vibrational density of states in vitreous B2O3

Inelastic neutron-scattering measurements of v-B₂O₃ reveal an upshift in energy of the first moment of the vibrational density of states for frequencies below ≈ 15 meV as temperature increases from 20 to 300 K. Such a stiffening is at odds with predictions based on some current approaches. Instead, the present result and related anomalies in specific heat and other microscopic and transport properties can be understood in terms of anharmonic motions at low frequencies. The atomic origin of the anharmonicity, and its consequence for the thermodynamical behavior are examined by molecular-dynamics simulations.     

Er3+掺杂的Bi2O3-B2O3-SiO2玻璃的光谱性质

测试了Bi₂O₃-B₂O₃-SiO₂玻璃中的Er³⁺离子的吸收光谱、发射光谱、⁴I_13/2的荧光寿命、拉曼光谱,及OH^-的傅里叶红外吸收光谱。应用Judd-Ofelt理论计算了该玻璃中的Er³⁺离子的J-O参数、振子强度、⁴I_13/2能级的寿命,从而利用测得的⁴I_13/2的荧光寿命得出了⁴I_13/2能级的量子效率(15%)。由于较低量子效率可能与OH^-有关,所以计算了玻璃中的OH^-浓度,发现其浓度较高(1.66×10¹⁹cm^-1,相当于Er³⁺浓度的3倍)。应用McCumber理论和四能级模型计算了Er³⁺离子的受激发射截面和荧光发射光谱的半峰全宽,结果与通过吸收光谱计算所得基本吻合。根据透射率和折射率的关系计算了折射率,发现和测量值相差很大,说明有较大的散射,通过拉曼光谱和显微镜测试,认为是玻璃中的微小气泡造成的。     

Spectroscopic properties of Er3+-doped AlF3-La2O3-Al2O3-SiO2 glasses

Er3+-doped fluoride lanthanum aluminosilicate glasses with compositions of (65- x/2)SiO2 · (25 -and their glass transition temperatures and spectroscopic properties were investigated. The Ω2, Ω4, and Ω6 intensity parameters of glasses were calculated by Judd-Ofelt theory from absorption curves. It was found that glasses transition temperature and melting temperature decreased with the increase of fluoride content in glass, Ω2 decreased gradually with the increase of AlF3 content, but both Ω4 and Ω6 did not increase until AlF3 content increased to 30 mol%. The quantum efficiency of 4I13/2 to 4I15/2 transition of Er3+ ions increases with the increase of AlF3 content in glass. Fluorescent lifetime is longer in glass containing more AlFa content.     

Spectroscopic properties of the Pr3+ ion in TeO2-WO3-PbO-La2O3 and TeO2-WO3-PbO-Lu2O3 glasses

The goal of this work was to investigate the spectroscopic properties of Pr³⁺ ions, embedded in two different tellurite glass matrices, TeO₂-WO₃-PbO-La₂O₃ and TeO₂-WO₃-PbO-Lu₂O₃. The absorption and fluorescence spectra have been recorded and analyzed in terms of the Judd-Ofelt theory along with the luminescence decay of the ³P₀ and ¹D₂ levels of the Pr³⁺ ion. The spectroscopic studies were completed with ellipsometric measurements providing the dispersion relation of the refractive index of the investigated glasses.     

对含Y_2O_3和Gd_2O_3的La_2O_3-B_2O_3-BaO玻璃化学稳定性研究

本文研究了含Ｙ２Ｏ３和Ｇｄ２Ｏ３的Ｌａ２Ｏ３－Ｂ２Ｏ３－ＢａＯ玻璃的耐水性和耐酸性。结果表明，比硅酸盐玻璃化学稳定性差的Ｌａ２Ｏ３－Ｂ２Ｏ３－ＢａＯ玻璃，可以适量的用Ｙ２Ｏ３和Ｇｄ２Ｏ３取代Ｌａ２Ｏ３，可得以改善     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al2O3透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱,发现在Al2O3六配位的八面体结构中,Cr4+的荧光发射也处在1100-1600 nm波段的红外区间,荧光发射峰位于1223 nm附近,类似Cr4+在四面体中的发光行为.同时由于氧化铝晶格常数较小,晶体场强较强,使Cr4+:Al2O3荧光发射峰相对其他Cr4+掺杂的晶体发生蓝移.由于Cr4+:Al2O3中Cr4+是位于八面体配位结构中,其荧光发射峰较窄,半高宽Δλ仅为37 nm.     

B2O3含量对掺铒碲铌酸盐玻璃光谱性质及热稳定性影响

制备了一系列碲铌酸盐玻璃85TeO₂-(15-x)Nb₂O₅-xB₂O₃-1%Er₂O₃(TNBx=0, 3, 6, 9, 12, 15).根据Judd-Ofelt(J-O)和McCumber理论,讨论和分析了B₂O₃含量对掺铒碲铌酸盐玻璃热稳定性及光谱性质影响.研究发现,玻璃开始析晶温度和玻璃转变温度差值ΔT(T_x-T_g),J-O强度参数,FWHM和峰值受激发射截面的乘积在B₂O₃引入摩尔分数为9%时达到最大值.同时,Er³⁺:⁴I_13/2能级寿命也随着B₂O₃含量的增加而单调增加.结果表明,在掺铒碲铌玻璃中,适量的B₂O₃能较好地提高玻璃的热稳定性能和Er³⁺离子的光谱性质.     

Nd3+掺杂B2O3-Nb2O5-BaO-La2O3玻璃光谱性质的研究

 用高温熔融法制备了Nd³⁺(物质的量分数2％）掺杂40B₂O₃-(15-χ)Nb₂O₅-45BaO-χLa₂O₃玻璃，测量了样品的吸收光谱、发射光谱和差热分析（DTA）曲线。根据Nd3+光学跃起矩阵的特点，应用Judd-Ofelt理论，从吸收光谱获得了Nd³⁺光学跃起的强度参数。并计算了Nd³⁺离子的自发辐射跃迁几率、总自发辐射几率、荧光分支比、辐射能级寿命和受激发射截面。结果表明：该体系玻璃中，随着Nb₂O₅ 含量的增加和La₂O₃₂增大，说明材料的对称性降低；而Ω₆减小，说明Nd-O键的共价性和键强增强；受激发射截面减小。DTA实验表明，随着Nb₂O₅含量的增加，材料的热稳定性提高。     

Optical Properties of Yb3+ Doped Bi2O3-3B2O3 Glass

The transmission and fluorescence spectra of Yb3+ doped Bi2O3-3B2O3 glass were measured. The emission cross section have been evaluated using the measured absorption apectra and principle of reciprocity. The measured long lifetime τm(1.0 ms) and large emission cross section σem(1.423 pm2) indicate that Yb3+ doped Bi2O3-3B2O3 glass is a promisiong laser material.     

An anomalous enhancement in the electrical conductivity of Li2O : B2O3 : Al2O3 glasses

The study of electrical conductivity of 27.5 Li₂O : (72.5 − x) B₂O₃ : x Al₂O₃ glass samples has been carried out. It has been observed that the conductivity exhibits Arrhenius behavior for all samples up to glass transition temperature T_g. Beyond T_g, an anomalous enhancement followed by decrease in conductivity has been observed. The results have been explained by dividing the temperature range into two regions. In region-I, it has been observed that the conductivity variation exhibits a maximum at 2.5 mol% Al₂O₃, which has been explained on the basis of Mixed Glass Former Effect (MGFE). An anomalous enhancement in the conductivity observed in region-II has been attributed to the nucleation in the glass. The subsequent decrease in the conductivity has been attributed to the crystallization of the glass samples.     

Er3+单掺及Er3+/Yb3+共掺SiO2-Al2O3-La2O3玻璃光谱性质研究

研究了单掺Er³⁺及Er³⁺/Yb³⁺共掺SiO₂-Al₂O₃-La₂O₃玻璃的光谱性质随稀土离子浓度变化规律,应用McCumber理论计算了玻璃在1.53 μm的发射截面及积分吸收截面.结果表明:在Er³⁺离子掺杂浓度相同时,玻璃在980 nm吸收截面与Yb³⁺掺杂浓度成反比;当样品中Yb³⁺离子掺杂浓度为3.94×10²⁰ cm^-3时,玻璃在1.53 μm的吸收截面和发射截面最大,在1.40～1.60 μm积分吸收截面也最大;Er³⁺/Yb³⁺共掺SiO₂-Al₂O₃-La₂O₃玻璃在1.53 μm的荧光半高宽随Er³⁺掺杂浓度升高而增加,当Er³⁺离子掺杂浓度为2.41×10²⁰ cm^-3时,玻璃的荧光半高宽(FWHM)达到52.5 nm.     

Optical Spectroscopic Study of Al 2 O 3 : Ti 3+ Under Hydrostatic Pressure

This work investigates the effect of hydrostatic pressure on the excitation, emission and lifetime of Ti 3+ - doped Al 2 O 3 in the 0-110 kbar range. The application of pressure induces band shifts that are correlated with the corresponding local structural changes undergone by the TiO 6 complex. The increase of the Stokes-shift and the reduction of the Jahn-Teller (JT) splittings under pressure are analysed in terms of a simple model based on linear electron-phonon couplings to the a_{1_{\rm g}} and the JT e g vibrational modes.     

CaO-SiO_2-Al_2O_3渣系连铸保护渣结构的拉曼光谱研究

在高铝钢连铸过程中,钢水中的Al与CaO-SiO2基连铸保护渣中的SiO2反应导致保护渣中SiO2含量降低而Al2O3含量大幅增加,CaO-SiO2基转变为CaO-SiO2-Al2O3基连铸保护渣而影响高铝钢连铸,所以研究CaO-SiO2基向CaO-SiO2-Al2O3基保护渣转变过程中结构上发生的变化有助于开发出满足高铝钢连铸需求的保护渣。本文利用拉曼光谱研究了CaO-SiO2基和CaO-SiO2-Al2O3基连铸保护渣的结构特点。研究结果表明,CaO-SiO2基保护渣主要由Q0,Q1,Q2和Q3等微结构单元构成的硅酸盐网络结构;当转变为CaO-SiO2-Al2O3基保护渣后,渣样中的网络破坏体优先用于破坏硅酸盐网络结构,当渣中SiO2含量较低时,部分网络破坏体会促进Al 3+形成[AlO4]四面体结构。渣中生成的[AlO4]四面体会进入硅酸盐网络结构形成铝硅酸盐网络结构,以Al-O-Al或Al-O-Si等方式连接,导致渣样结构变得复杂多变。使用Li2O对Na2O和CaO对MgO等摩尔替代研究表明相同价态离子之间的替换能够改变[AlO4]四面体在硅酸盐网络结构上的连接方式,导致CaO-SiO2-Al2O3基保护渣渣样结构易受成分变化而改变;CaF2对CaO等摩尔替代研究发现,当渣中CaF2小于13mol%,CaF2促进渣样网络结构解体,当高于13mol%时,CaF2又会导致渣样聚合度增加。由此可见,在设计CaO-SiO2-Al2O3基保护渣时,既要考虑不同种类离子对渣样结构产生的影响,又要考虑离子含量的影响。     

Cr3+:Al2O3透明多晶陶瓷光谱特性分析

对透光性良好的Cr3+:Al2O3透明多晶陶瓷的光谱性能进行了研究,其吸收光谱中吸收峰与单晶红宝石相一致,按吸收光谱和Tanabe-Sugano能级图,算出其晶场强度参数Dq及Racah参数B分别为1792cm-1,689cm-1,Dq/B=2.6,陶瓷中Cr3+离子所处格位的晶体场强比单晶弱一些,但Cr3+:Al2O3透明陶瓷仍属于强场晶体材料;当Cr3+掺杂浓度到达0.8wt%时,陶瓷的发射谱仍保持较好的R线发射;随Cr3+掺杂浓度的增大,激发峰位发生"红移".在Cr3+:Al2O3透明多晶陶瓷的荧光谱上,发现一个波长为670nm的发射峰,经激发谱确认为Cr3+的发射峰.     

Yb3+掺杂浓度对Er3+/Yb3+共掺SiO2-Al2O3-La2O3玻璃光谱性质的影响

测量了不同Yb3+ 离子掺杂浓度下 ,Er3+ /Yb3+ 共掺SiO2 Al2 O3 La2O3玻璃的吸收光谱、荧光光谱和Yb3+离子2 F5/ 2 的能级寿命 ,应用迈克康伯 (McCumber)理论计算了Er3+ 的受激发射截面σemi,讨论了Yb3+ 离子浓度对其自身吸收性质、Er3+ 离子发光性质 ,以及Yb3+ →Er3+ 能量传递效率 (η)的影响 ,初步探明该基质玻璃中Yb3+ 离子掺杂数浓度的最佳范围为 3 .94× 1 0 2 0 cm- 3至 5 .92× 1 0 2 0 cm- 3,在此掺杂范围内 ,Yb3+ 离子的最大吸收系数为9.8cm- 1 ,Er3+ 的峰值发射截面和Yb3+ →Er3+ 能量传递效率 (η)分别为 0 64× 1 0 - 2 4 m2 和 92 %。     

Mg,Ti共掺Al2O3透明多晶陶瓷光谱性能研究

采用传统无压烧结工艺制备Mg,Ti共掺透明氧化铝陶瓷,测定了其吸收光谱、荧光光谱和激发光谱,结果表明,由于Mg2+的电荷补偿,当Ti掺入量较小时,Ti主要以Ti4+形式存在,(Mg,Ti):Al2O3透明陶瓷只在250nm的紫外波段有吸收峰,为O2-→Ti4+的电荷转移跃迁产生的吸收,并产生Ti4+离子在280-290nm和410-420nm的荧光发射峰;当Ti掺入量较大时,氧化铝透明陶瓷除了存在Ti4+的吸收峰,还表现出Ti3+离子490nm的特征吸收峰,即2T2→2E跃迁产生的宽带吸收,Ti3+离子的发射谱线与Ti:Al2O3单晶的相吻合.     

Magnetic properties of partially devitrified B2O3-MnFe2O4 glass

Crystallization processes of partially devitrifled glass obtained by rapid quenching of 0·17₅ MnO + 0·17₅. Fe₂O₃ + 0·65 B₂O₃ melt were studied by DTA and X-ray analyses and the temperature regions of nucleation, crystallization and decompozition of the spinel phase were established. The magnetization curves measured between 4·2 and 250 K in magnetic fields up to 42 kOe divided the samples into two groups: the original as cast glass and those annealed below the crystallization temperature, as well as above the decomposition temperature showed essentially paramagnetic behaviour, whereas those annealed closely above the crystallization temperature displayed a spontaneous magnetic moment. The former ones could not be classified as superparamagnetic but the temperature dependence of their susceptibility could be explained by interactions of the antiferromagnetic type. The comparison of lattice parameter and Curie temperature of the latter one with crystalline Mn _x Fe_3-x O₄, system indicated pronounced iron enrichment of the spinel phase formed during heat treatment.Based on a paper presented at the Conference of Socialist Countries on Magnetic Oxides and Compounds; Reinhardsbrunn bei Friedrichroda, GDR, October 22nd–27th, 1972.The authors thank Mrs. A.Hadincová for the help with the evaluation of the results.