锂铝硅酸盐玻璃结构与紫外透过性能的研究

采用红外光谱和X射线光电子能谱方法研究了锂铝硅酸盐玻璃结构与紫外透过性能的关系.结果表明:紫外透过性能是桥氧键与非桥氧键共同作用决定的.在锂铝硅酸盐玻璃中随着Li2O含量的增加,产生断网结构,非桥氧数量上升,导致紫外透过性能降低.而Al2O3中的Al3+进入玻璃网络形成了Si-O-Al反对称桥氧,减缓透过率的下降趋势.     

在硅酸盐矿物,玻璃和熔体中Si和Al的配位与局部结构：K—边 …

本文采用步辐射的ＳｉＫ－边Ｘ－射线吸收近边结构（ＸＡＮＥＳ）谱研究了Ｓｉ在ＳｉＯ２－Ｐ２Ｏ５和Ｎａ２Ｏ－ＳｉＯ２－Ｐ２Ｏ５的低压磷硅酸盐玻璃中结构与配位,以及Ｓｉ的配位几何随玻璃中Ｐ２Ｏ５含量而变化：同步辐射的Ａｌ Ｋ－边ＸＡＮＥＳ谱研究了Ａｌ在铝硅酸盐成分为ＮａＡｌＳｉ２Ｏ６－ＮａＡｌＳｉ３Ｏ８的玻璃和熔体中的配位和局部结构,并提供了直接的实验证据该成分的玻璃体系中由于压力的变化所诱导Ａｌ配位的     

亚碲酸铅玻璃微结构的Raman光谱研究

测定了亚碲酸铅玻璃的常温及高温Raman光谱。实验表明随着PbO浓度增大,亚碲酸盐玻璃中的四配位与三配位结构单元之间存在转化关系,体系总体非桥氧数增加。当加入的PbO摩尔浓度增大至50%后,四配位结构单元密度相对较少,这时玻璃结构中主要以三配位结构单元形式存在。同时还测定了40PbO·60TeO2玻璃的升温Raman光谱,观察到四配位结构单元桥氧、四配位结构单元非桥氧以及三配位结构单元非桥氧对称伸缩振动的谱峰由于温度升高引起的结晶化过程导致向高频移动,谱峰变得尖锐,强度增大。熔点后,Raman光谱出现展宽效应,强度降低。在玻璃处于熔化状态下,四配位中的微结构单元会进一步向三配位转化,熔体内部微结构单元含量会相对平衡。     

二元碱金属硅酸盐玻璃团簇结构的拉曼散射活性及其阳离子效应

提出一种拉曼光谱校正方法.通过计算二元碱会属硅酸盐团簇基元的拉曼光谱,对实验光谱高频区的非桥氧(Onb)对称伸缩振动的强度进行了校正,从而建立谱峰强度和团簇实际浓度的直观相关关系,同时,分析研究了二元碱金属硅酸盐玻璃阳离子对谱峰强度的影响.校正后的拉曼光谱可以真实地显示同化学成分的二元碱金属硅酸盐玻璃表观实验拉曼谱峰强...     

Raman spectra of soda-lime-silicate glass doped with rare earth

Soda-lime-silicate glasses doped with different rare earth oxides (La₂O₃, CeO₂, Nd₂O₃, Gd₂O₃ and Y₂O₃) of 1 mol% content were prepared by the traditional melting-quenching methods. In order to reveal the effects of rare earth elements on the behavior of soda-lime-silicate glass the structures of soda-lime-silicate glasses doped with different rare earth oxides were determined using an INVIA confocal microRaman spectrometer equipped with a CCD detector, and viscosities of glass melts were measured using a rotating crucible viscometer; the melting temperature of the studied glasses was derived on the basis of the Arrhenius equation. Three expressions of the fraction of non-bridging oxygen (NBO/NBO+BO), average number of non-bridging oxygen (NBO) per tetrahedron (NBO/tetrahedron) and average number of bridging corners per tetrahedron (bridges/tetrahedron) for investigated soda-lime-silicate glasses were given, and the effect of rare earth dopants on the structure of soda-lime-silicate was characterized by the Raman shift, variation of the [SiO₄] tetrahedron structural unit Qⁿ (n=1,2,3,4), fraction of non-bridging oxygen and the average number of bridging corners per tetrahedron. The effect of doping rare earth oxides into glass on the viscosity and melting temperature was interpreted by changes in structure of soda-lime-silicate glasses doped with rare earth oxides.     

Sputter-deposited network glasses

Thin films of lithium borate, sodium borate, rubidium borate, and lithium silicate glasses are prepared by ion beam sputter deposition in a thickness range between 70 and 1,400 nm. The chemical, structural, and electrical properties of the films are determined by transmission electron microscopy and impedance spectroscopy. A comparison between the thin glass layers and the corresponding bulk glasses, prepared from the melt, shows that both have similar chemical compositions and atomic short range orders. In contrast, the ionic conductivities of the borate glass films are found to be significantly increased compared to the corresponding bulk materials, while the increase depends on the chemical composition of the glasses and is not observed in the case of the silicate system. We propose a modified network structure of the sputter-deposited glass layers, namely, an increased nonbridging oxygen concentration, to be responsible for the elevated ionic conductivity.     

硅酸盐熔体团粒结构类声子振动的高温拉曼光谱研究

硅酸盐熔体是典型的近程有序,远程无序的准稳定态分数维体系,文章采用X射线小角散射(SAXS)、低波数拉曼光谱(LWRS)及高温拉曼光谱(HTRS)实时、原位分析等技术,对高温熔融法和溶胶凝胶法合成的CaO-Al₂O₃-SiO₂和Na₂O-Al₂O₃-SiO₂系列低维非晶硅酸盐试样进行了团粒结构粒度及其类声子振动频率的定量测定,获得了低温硅酸盐凝胶、高温硅酸盐熔体及其淬火玻璃相均具有纳米级(几个纳米至几十纳米)自相似团粒结构和类声子振动模的重要结论,进而建立了测定高温熔体介观团粒结构粒度的HTRS测定法,结果表明硅酸盐熔体的团粒结构粒度在高温下均会比其室温玻璃相的团粒尺度小,且高温熔体的网络结构基元也向桥氧数减少之基元转变。这些结论为探索自然界岩浆的地球化学特征、岩浆的结晶和演化以及低维硅酸盐材料结构性能的改进提供重要理论依据及信息。     

碲酸盐玻璃的拉曼光谱研究

本文测试了TeO2-ZnO和TeO2-BaO两种二元系统不同金属氧化物浓度下玻璃的拉曼光谱,通过比较这两种碲酸盐玻璃系统拉曼光谱的异同,表明碲酸盐玻璃系统中随着金属氧化物浓度的增加,使玻璃网络中的TeO4双三角锥向TeO3三角棱锥转化,并且在TeO2-BaO二元玻璃中出现了非桥氧键。同时初步研究了TeO2-ZnO-Na2O三元玻璃的拉曼光谱,发现当TeO2-ZnO二元玻璃中加入5mol%的Na2O时,其结构并没有发生显著的变化。     

阳离子对硅酸盐玻璃激光拉曼光谱影响的研究

运用拉曼光谱技术研究了Na2O(K2O)—CaO(MgO)—SiO2,Na2O(K2O)—Al2O3—SiO2,Na2O(K2O)—B2O3—SiO2,Na2O(K2O)—PbO—SiO2和PbO—BaO—SiO2五个系统的玻璃。结果表明,阳离子对玻璃近程结构的改造会引起拉曼特征的变化。部分样品是根据古玻璃平均成分在实验室烧制的,这项研究对于运用激光拉曼光谱区分不同系统的古代硅酸盐玻璃有重要意义。     

Influence of MgO on structure and optical properties of alumino-lithium-phosphate glasses

MgO doped lithium alumino phosphate glasses (PLA: P₂O₅+Li₂O+Al₂O₃+MgO) were prepared by melt quenching technique. Raman spectra display three significant peaks at 698, 1164 and 1383 cm⁻¹ attributed to: symmetric stretching vibrations of the bridging oxygen (BO) in the P–O–P chains, symmetric stretching vibrations of the PO₂ groups, and the asymmetric vibrations vas(PO₂) of the non-bridging oxygen (NBO) atoms, respectively. Also, the density, molar volumes and ion concentration have been discussed and correlated with the structural changes within the glassy matrix. Some optical constants such as refractive index and dispersion parameters (E_o: single-oscillator energy and E_d: dispersive energy) of the glasses were determined. Finally, the values of the optical band gap for direct and indirect allowed transitions have been determined from the absorption edge studies. It is deduced that the values of E_opt increase with increasing MgO content. It was assigned to structural changes induced from the formation of non-bridging oxygen. The Urbach energy (ΔE) was found to decrease from 0.578 to 0.339 eV with increasing MgO content from 0.5 to 2 mol.     

Vibrational modes of sodium–tellurite glasses: Local structure and Boson peak changes

Raman spectra of xNa₂O−(1−x)TeO₂ glasses were measured and analyzed over a broad composition range. The network structure of the glass consists of a mixture of TeO₄ trigonal bipyramids and TeO₃ trigonal pyramidal units. Increase of alkali content results in conversion of the TeO₄ units into TeO₃ units with a varying number of non-bridging oxygen atoms. This local structure transformation becomes more evident at x=0.2, where rigidity percolation theory predicts a threshold for the rigid-to-floppy transition. However, other spectral features such as the composition dependence of the energy of the Boson peak do not support the occurrence of the stiffness transition. The controversial dependence of dynamical parameters such as the fragility index as a function of Na₂O concentration is also discussed.     

Synthesis and characterization of Ce doped silica (SiO2) nanoparticles

A series of silica doped with different mol percentages of Ce³⁺ concentration was synthesized using a sol-gel method to determine the dependence of photoluminescence wavelengths and intensity on the concentrations of the dopants. Sol-gel glasses are porous networks that have been densified through chemical processing and heat treatment. Rare-earths (REs) are insoluble in silica; due to this insolubility RE ions in silicate glasses enter as network modifiers and compete for non-bridging oxygen in order to complete their coordination. The morphological, structural, thermal and optical properties of the phosphors were characterized by X-ray diffraction, scanning electron microscopy, UV-vis absorption, photoluminescence, thermogravimetric analyses and differential scanning calorimeter. Silica (SiO₂) gel containing Ce³⁺ ions was sputter coated with Au (gold) in order to monitor surface morphology of the samples. The highest emission intensity was found for the sample with a composition of 0.5 mol% Ce³⁺. Cerium doped silica glasses had broad blue emission corresponding to the ²D_3/2-²F_J transition at 448 nm but exhibited apparent concentration quenching above concentrations of 0.5 mol% Ce³⁺.     

Density and structural changes of silicate glasses under high pressure

ABSTRACT

Density and structural changes of matter in their liquid or amorphous form, such as silicates melts, molecular fluids, or glasses, are of extreme importance to model the interior of planetary bodies. However, measuring the evolution of amorphous materials under extreme conditions of pressure and temperature remains challenging mainly because of the sample dimensions and the weak interaction with X-ray probes. This contribution highlights recent developments to measure the density of amorphous material, mainly silicate glasses made of light elements, to high pressure conditions. In particular, the X-ray absorption method at synchrotron sources is discussed as a new opportunity for high pressure experiments on glasses, fluids, and melts. Recent achievements using X-ray Raman scattering spectroscopy to obtain data on the local electronic environment of the main constituents of silicate glasses at high pressure are also presented. Finally, perspectives of these recent developments are discussed as well as their potential for high pressure research in the next years.     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd     

A temperature-dependent Raman study of the xLiCl–(1–x)TeO2 glasses and melts

Raman scattering has been employed to study the temperature and composition dependence of the vibrational modes for the glass-forming oxyhalide mixtures xLiCl–(1–x)TeO₂ (x=0, 0.2, 0.3, 0.35, 0.5 and 0.67) in the glassy, supercooled and liquid state up to 600 °C. The analysis has shown that the network structure of the glass/melt is formed by mixing trigonal bipyramid and trigonal pyramid units. The change of LiCl content and/or temperature results to conversion of the trigonal bipyramid to trigonal pyramid units with a varying number of non-bridging chlorine and oxygen atoms. The fraction of the terminal oxygen atoms doubly bonded to tellurium versus temperature has been directly estimated from the Raman spectroscopic results with the aid of a structural model concerning the tellurite network systems. A well-resolved Boson peak (BP) dominates the low-frequency Raman spectra. The temperature dependence of the maximum of the BP has also been determined and discussed in the framework of its microscopic origin.     

A high-resolution 19F NMR spectroscopic study of barium fluorozirconate glasses and related crystals

Fluorozirconate glasses have attracted considerable attention not only for their transparency in the infrared, but also due to their high fluorine ion conductivities and extreme fragility in the viscosity-temperature relationship. We report on structural studies of binary BaF2-ZrF4 glasses with 58-78 mol% ZrF4 using high-resolution magic-angle-spinning 19F NMR. High-speed 19F MAS NMR allows us to resolve at least three unique fluorine environments in these binary glasses. These fluorine environments are attributed to one type of bridging fluorine, between corner-sharing Zr-F coordination polyhedra, and two types of non-bridging fluorine (NBF), one of which is bonded to one Zr and one Ba atom while the other is bonded to one Zr and two Ba atoms. The concentration of the first type of NBF increases with decreasing ZrF4 concentration, while that of the second type is essentially independent of glass composition. These assignments have been made on the basis of detailed 19F NMR studies of a wide variety of crystalline fluorozirconates with known crystal structures. A comparison between the glass and crystal 19F NMR spectra rules out any significant concentration of edge-shared Zr-F polyhedra in these binary glasses. The Zr atoms in all glasses are found to be coordinated to approximately 7.8+/-0.2F atoms.     

Paramagnetic defects in gamma-irradiated Na/K-silicate glasses

Gamma-irradiated alkali silicate glasses of the variable composition 22xNa₂O · 22(1 ? x)K₂O · 3CaO · 75SiO₂ have been studied using the electron paramagnetic resonance (EPR) method. It has been established that, upon the successive replacement Na ?? K in the two-alkali silicate glass, the EPR spectrum of hole centers on nonbridging oxygen atoms can be represented as a superposition of signals from the oxygen centers HC ₁(Na), HC ₂(Na), HC ₁(K), and HC ₂(K), which are characteristic of single-alkali silicate systems. The concentration dependences of hole and electron paramagnetic centers do not exhibit specific features that can be interpreted as a manifestation of the ??mixed-alkali effect.?? The results obtained have been discussed taking into account the extended model of centers on nonbridging oxygen atoms.     

Synthesis,Structural and Optical Studies of Barium Strontium Titanate Borosilicate Glasses Doped with Ferric Oxide

Various barium strontium titanate borosilicate glasses were prepared by a rapid melt-quench technique. Spectroscopic studies have been carried out on investigated glasses for their structural information. Infrared and Raman spectroscopic studies showed that these glasses are formed by glass-forming network of borate and silicate as well as network modifiers in the form of cations of alkaline earth atoms. The borate and silicate networks are modified by barium, strontium, titanium, and iron cations in glass matrix. The network of triborate unit is modified in tetraborate unit by adding ferric oxide in a glassy matrix. The optical studies are performed by ultraviolet-visible spectroscopy and it confirms that the band gap decreases with increase in the concentration of ferric oxide.     

Li2O-B2O3-SiO2系统玻璃的Raman光谱研究

在Li₂O≥30mol％的Li₂O-B₂O₃-SiO₂系统玻璃中,以Li₂O代B₂O₃或SiO₂都导致玻璃网络中带非桥氧的硼酸盐和硅酸盐基团的量的增加;以B₂O₃代SiO₂则使玻璃网络中带和不带非桥氧的硼酸盐基团以及带非桥氧的硅酸盐基团的量都增加。 关键词：     

Correlations between Raman parameters and elemental composition in lead and lead alkali silicate glasses

This article examines the influence of the composition on the Raman spectra of lead silicate glass. Modern and historic lead alkali glasses and high‐lead glazed ceramics were analysed complementarily by Raman spectrometry and elemental techniques, either electron microprobe, proton induced X‐ray emission (PIXE) or scanning electron microscope with energy dispersive spectrometry (SEM‐EDS). The results showed that lead alkali silicate and high‐lead silicate glasses can be easily distinguished from their Raman spectra profile. In lead alkali silicate glasses, continuous variations were observed in the spectra with the compositional change. In particular, the position of the intense peak around 1070 cm⁻¹ was linearly correlated to the lead content in the glass. A unique decomposition model was developed for the spectra of lead alkali silicate glasses. From the combination of the Raman and elemental analyses, correlations were established between the spectral components and the composition. These correlations permitted to interpret the spectra and access additional compositional information, such as the lead content from area ratio A₉₉₀/A_900–1150, the total alkali + alkaline‐earth content from the area ratio A₁₁₀₀/A_900–1150 or the silica content from the area ratio A₁₁₅₀/A_900–1150. In lead silicate glass containing over 25 mol% PbO, the compositional variation induced no variation in the SiO₄ network region of the Raman spectra [150–1350 cm⁻¹], therefore no correlations and compositional information could be gained from the glass spectra in this range of composition. This new development of Raman spectroscopy for the analyses of glass will be very valuable for museums to not only access compositional information non‐destructively but also to understand the structural changes involved with their alteration. Copyright © 2008 John Wiley & Sons, Ltd.