Direct observation of R...R distances in rare-earth (R) phosphate glasses by magnetic difference neutron diffraction

A magnetic difference neutron diffraction study of a rare-earth (Tb) phosphate glass has revealed exclusively the Tb...Tb distances. The difference between data taken with and without an applied magnetic field of 4 T shows Tb...Tb pairwise atomic correlations at 3.9 and 6.4 A, respectively, with relative coordination numbers of 1:14. The first distance arises when two Tb3+ ions share a common oxygen neighbor, and indicates a clustering of rare-earth ions. The second distance arises when two Tb3+ ions are coordinated to different oxygens in the same PO4 group, in a near-linear arrangement.

Structure of rare-earth phosphate glasses by neutron diffraction

Neutron diffraction was used to measure the structure of the phosphate glasses RAl0.30P3.05O9.62, where R denotes Dy or Ho, and RAl0.34P3.20O10.04, where R denotes La or Ce. For each glass, isomorphic structures were assumed and difference function methods were employed to separate, essentially, those correlations involving the rare-earth ion, R3+, from the remainder. The ratio of bridging oxygen, OB, to terminal oxygen, OT, atoms in the PO4 tetrahedra was quantified and in both materials R3+ and Al3+ are found to act as network modifying cations which bind to the OT. The R–OT coordination number is 6.7(1) and 7.5(2) for the Dy/Ho and La/Ce glasses respectively.

Structure of dysprosium and holmium phosphate glasses by the method of isomorphic substitution in neutron diffraction

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction and, by taking the role of Al into explicit account, a self-consistent model of the glass structure was developed. The glass network is found to be made from corner sharing PO4 tetrahedra in which there are, on average, 2.32(9) terminal oxygen atoms, OT, at 1.50(1) Å and 1.68(9) bridging oxygen atoms, OB, at 1.60(1) Å. The network modifying R3+ ions bind to an average of 6.7(1) OT and are distributed such that 7.9(7) R–R nearest neighbours reside at 5.62(6) Å. The Al3+ ion also has a network modifying role in which it helps to strengthen the glass through the formation of OT–Al–OT linkages. The connectivity of the R-centred coordination polyhedra in (M2O3)x(P2O5)1−x glasses, where M3+ denotes a network modifying cation (R3+ or Al3+), is quantified in terms of a parameter fs. Methods for reducing the clustering of rare-earth ions in these materials are then discussed, based on a reduction of fs via the replacement of R3+ by Al3+ at fixed total modifier content or via a change of x to increase the number of OT available per network modifying M3+ cation.

Structure of lanthanum and cerium phosphate glasses by the method of isomorphic substitution in neutron diffraction

Neutron diffraction was used to measure the total structure factors for several rare-earth ion R3+ (La3+ or Ce3+) phosphate glasses with composition close to RAl0.35P3.24O10.12. By assuming isomorphic structures, difference function methods were employed to separate, essentially, those correlations involving R3+ from the remainder. A self-consistent model of the glass structure was thereby developed in which the Al correlations were taken into explicit account. The glass network was found to be made from interlinked PO4 tetrahedra having 2.2(1) terminal oxygen atoms, OT, at 1.51(1) Angstrom, and 1.8(1) bridging oxygen atoms, OB, at 1.60(1) Angstrom. Rare-earth cations bonded to an average of 7.5(2) OT nearest neighbors in a broad and asymmetric distribution. The Al3+ ion acted as a network modifier and formed OT-A1-OT linkages that helped strengthen the glass. The connectivity of the R-centered coordination polyhedra was quantified in terms of a parameter f(s) and used to develop a model for the dependence on composition of the A1-OT coordination number in R-A1-P-O glasses. By using recent 17 A1 nuclear-magnetic-resonance data, it was shown that this connectivity decreases monotonically with increasing Al content. The chemical durability of the glasses appeared to be at a maximum when the connectivity of the R-centered coordination polyhedra was at a minimum. The relation of f(s) to the glass transition temperature, Tg, was discussed.

Identification of the relative distribution of rare-earth ions in phosphate glasses

The relative distribution of rare-earth ions R3+ (Dy3+ or Ho3+) in the phosphate glass RAl0.30P3.05O9.62 was measured by employing the method of isomorphic substitution in neutron diffraction. It is found that 7.9(7) R-R nearest neighbors reside at 5.62(6) Angstrom in a network made from interlinked PO4 tetrahedra. Provided that the role of Al is explicitly considered, a self-consistent account of the local matrix atom correlations can be developed in which there are 1.68(9) bridging and 2.32(9) terminal oxygen atoms per phosphorus.

磷酸盐激光玻璃聚（CH3）2SiO／SiO2防潮膜改性研究

采用溶胶-凝胶方法制备的（CH2）2Si（OC2H5）2预聚体涂膜液中，掺入碱催化的SiO2悬胶体涂膜液，采用旋涂法在掺钕磷酸盐激光玻璃棒端面涂制了改性的防潮膜。当涂膜液中（CH2）2Si（OC2H5）2和SiO2物质的量之比为1：1时。热处理后的膜层耐摩擦性能明显改善；表面粗糙度的均方根值为1．245nm；膜层激光破坏阈值大于15J／cm^2（1053nm，1ns）；在80℃和95％RH的封闭环境中静置336h，膜层的透过率、接触角基本不变。结果证明膜层具有稳定的疏水结构和很好的防潮性能，膜层强度增加，

磷酸盐钕玻璃表面/亚表面损伤特性实验研究

系统地研究了光学研磨过程中,磨料粒径、载荷大小以及机床转速对钕玻璃表面及亚表面损伤的影响。结果表明,机床转速和载荷基本不改变材料表面粗糙度,而较大载荷或较低机床转速产生较大的亚表面缺陷,表面粗糙度和亚表面缺陷缺陷深度基本与最大磨料粒径呈正比,载荷增倍使亚表面缺陷与表面粗糙度的常数比值增加0.05。研究结果为钕玻璃加工工艺改进提供了参考依据。

LD泵浦的镱铒共掺磷酸盐玻璃的光谱性质和激光性质

制备了Er^3＋/Yb^3＋共掺磷酸盐玻璃. 通过分析其吸收光谱, 根据McCumber理论计算得到了Er^3＋离子在波长1533 nm处的峰值发射截面为0.84×10^-20 cm^2, ^4I13/2能级的荧光寿命为8.5 ms. 利用激光二极管作为泵浦源, 成功地实现了Er^3＋/Yb^3＋共掺磷酸盐玻璃激光器的连续运转. 在室温下, 获得最大激光输出功率为80 mW, 斜率效率为16.5%.

铬镱铒共掺磷酸盐玻璃光谱和激光性质研究

测定了Cr14—05铬镱铒共掺磷酸盐玻璃的主要热光参数，并测试了吸收、荧光光谱和激光性能等。结果表明该玻璃具有较好的光谱和热光性质，其激光输出性能可满足人眼安全激光测距光源应用的要求。

掺铒磷酸盐玻璃反应气氛法除水的研究

制备了不同含水量的掺铒磷酸盐玻璃，研究了各种工艺参数对反应气氛法除水效果的影响。结果表明由鼓泡气体带入的除水剂是玻璃除水的主要动力；在通气最初阶段的除水速率最快，并且提高除水温度、增大通气流量均有助于提高除水效率；结合实验从反应热力学角度讨论了除水机理，并指出在玻璃熔体中除水反应受熔体“笼效应”影响，反应速率大小取决于OH与CCl4形成偶遇对概率的大小。

Spectroscopic properties of Er3+ doped TeO2-BaO (Li2O, Na2O)-La2O3 glasses for 1.5-mu m optical amplifiers

This paper reports on the optical spectroscopic properties and thermal stability of Er3+-doped TeO2-BaO (Li2O,NaO)-La2O3 glasses for developing 1.5-mu m fiber amplifiers. Upon excitation at 977 nm laser diode, an intense 1.53-mu m infrared fluorescence has been observed with a broad full width at half maximum (FWHM) of about 60 nm for the Er3+-doped TeO2-BaO (Li2O, Na2O)-La2O3 glass with 10 mol% of BaO. The calculated fluorescence lifetime and the emission cross-sections of the 1.53-mu m transition are 2.91 ms and similar to 9.97 x 10(-21) cm(2), respectively. It is noted that the gain bandwidth, a, x FWHM, of the TeO2-BaO-La2O3Er2O3 glass is about 600, which is significantly higher than that in silicate and phosphate glasses. Meanwhile, it is interesting to note that the TeO2-BaO-La2O3-Er2O3 glass has shown a high glass thermal stability and good infrared transmittance. As a result, TeO2-BaO (Li2O, Na2O)-La2O3 glass with 10 mol% of BaO has been considered to be more useful as a host for broadband optical fiber amplifier. (c) 2005 Elsevier B.V. All rights reserved.

White Light and Multicolor Emission Tuning in Triply Doped Yb3+/Tm3+/Er3+ Novel Fluoro-phosphate Transparent Glass-ceramics

New Yb3+, Er3+ and Tm3+ doped fluoro-phosphate glasses belonging to the system NaPO3–YF3–BaF2–CaF2 and containing up to 10 wt% of rare-earth ion fluorides were prepared and characterized by differential scanning calorimetry, absorption spectroscopy and up-conversion emission spectroscopy under excitation with a 975 nm laser diode. Transparent and homogeneous glass-ceramics have been reproducibly obtained with a view to manage the red, green and blue emission bands and generate white light. X-ray diffraction as well as electron microscopy techniques have confirmed the formation of fluorite-type cubic nanocrystals at the beginning of the crystallization process while complex nanocrystalline phases are formed after a longer heat-treatment. The prepared glass-ceramics exhibit high optical transparency even after 170 h of thermal treatment. An improvement of up-conversion emission intensity – from 10 to 160 times larger – was measured in the glass-ceramics when compared to the parent glass, suggesting an important incorporation of the rare-earth ions into the crystalline phase(s). The involved mechanisms and lifetime were described in detail as a function of heat-treatment time. Finally, a large range of designable color rendering (from orange to turquoise through white) can be observed in these materials by controlling the laser excitation power and the crystallization rate.

Electrical conductivity and dielectric relaxation studies on microwave synthesized Na2SO4 center dot NaPO3 center dot MoO3 glasses

Electrical conductivity and dielectric relaxation studies on SO4 (2-) doped modified molybdo-phosphate glasses have been carried out over a wide range of composition, temperature and frequency. The d.c. conductivities which have been measured by both digital electrometer (four-probe method) and impedance analyser are comparable. The relaxation phenomenon has been rationalized using electrical modulus formalism. The use of modulus representation in dielectric relaxation studies has inherent advantages viz., experimental errors arising from the contributions of electrode-electrolyte interface capacitances are minimized. The relaxation observed in the present study is non-Debye type. The activation energies for relaxation were determined using imaginary parts of electrical modulus peaks which were close to those of the d.c. conductivity implying the involvement of similar energy barriers in both the processes. The enhanced conductivity in these glasses can be attributed to the migration of Na+, in expanded structures due to the introduction of SO4 (2-) ions.