Medium-range order in cesium borate glasses probed by double-resonance NMR

Rotational-echo double-resonance NMR is used to probe the proximity of Cs+ network modifiers to network-forming boron in binary cesium borate glasses. Low- and high-alkali glasses show distinctly different dephasing curves, which indicate preferential association of Cs+ with four-co-ordinate boron ([4]degrees )B) at low-alkali contents only. Different [4]B sites within a given glass appear to be subject to the same 133Cs dipolar field, thus placing constraints on the possible assignments of multiple tetrahedral boron peaks to different types of medium-range order and guiding future structural modeling studies.     

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.     

掺镱硼酸盐激光玻璃的光谱性质

测试了掺镱硼酸盐玻璃的吸收光谱和荧光光谱;计算了掺镱硼酸盐玻璃光谱参数;计论了网络修饰体种类、Ｂ２Ｏ３含量和高价离子Ｌａ＾３＋、Ｔｉ＾４＋、Ｎｂ＾５＋、Ｔａ＾５＋氧化物的引入对掺镱硼酸盐玻璃光谱性质的影响,通过两种不同的方法对其受激发射截面进行计算,对结果进行了比较和分析。     

What are the structural features of the active site that define binuclear copper proteins function?

The structural basis that define the physiological functions of binuclear copper enzymes is discussed in the frame of the data generated by a broad spectroscopic approach, spanning from paramagnetic NMR and pulsed EPR to x-ray absorption spectroscopies. The structural features discussed for the different oxidation and ligation states accessible to a binuclear copper sites are the coordination geometry for the first and second shell, the metal-metal distance and the role of the bridging exogenous ligand(s). A structural model will be presented to rationalize both the differentiation in function within the protein families and the reaction mechanism of those proteins that are enzymatically active.     

Inelastic light scattering in strontium borate glasses in the systemxSrO.(1−x)B2O3 and (SrCl2) y .[xSrO.(1−y−x)B2O3]1−y

Raman spectra of strontium borate binary glasses in the systemxSrO.(1-x)B₂O₃ forx=0.20, 0.25, 0.30, 0.35, 0.40, and 0.50 and ternary glasses in the system (SrCl₂) _y .[xSrO.(1−y−x)B₂O₃]_1−y fory=0.10, 0.20, 0.30 and 0.40 andx=0.20 and 0.35, are reported. Raman spectra of the glasses show experimental evidence of glass network modifying nature of SrO in borate matrix. SrO causes a change of boron atom coordination number from 3 to 4 resulting in the complex structural groupings comprising of BO₄ and BO₃ units. Strontium cations are not easily accommodated in the glass structure and tend to break up the network at high concentration (x) of SrO, causing non-bridging oxygens. The effect of temperature variation of binary glasses has also been studied. The introduction of SrCl₂ to the binary stronium borate glass causes a large change in intensity of low frequency Raman scattering whereas there is no change in the vibrational dynamics in the high frequency region. The temperature reduced Raman spectra represents true vibrational density of states. Martin-Brenig model developed for the low frequency region has been discussed to obtain the structural correlation range in the glass.     

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.     

Photoemission study of Nb-Ni glasses

The photoemission spectra for two Nb-Ni glasses are compared with those for the pure elements Nb and Ni. A decrease in the density of states at the Fermi level is found for glasses as compared with that of either pure element. The significance of this result as related to the formation of the glass is discussed.     

非晶中结构遗传性及描述

非晶态物质广泛存在于人们的日常生活和工业生产活动中,但人们对其原子结构及其结构与性能关系的认识还远不如对晶体材料那样充分.非晶态物质的原子结构不具备空间平移对称性,这使得传统针对晶体材料的实验技术和手段无法直接有效地应用到非晶态物质的结构分析中.用常规的衍射实验数据分析方法并不能直接地观察到非晶态物质的本征结构特征,但这些实验衍射数据往往隐含有极其重要的微观结构信息.本文简要综述了这些衍射数据背后所隐含的与金属玻璃中程序相关的结构信息.研究发现,非晶态物质中的一类隐含序与晶体结构中的球周期序紧密相关,意味着非晶态物质与晶体材料之间在原子结构上存在着非凡的同源性.进一步的研究结果还表明,不同隐含拓扑序之间纠缠的强弱与体系本身的玻璃形成能力存在明显的对应关系,这为衡量金属合金玻璃形成能力强弱的经验规律——混乱原理提供了微观结构上的理解,同时为进一步深入认识和理解非晶态材料衍射数据所隐含的微观结构信息提供了新的分析思路和方法.     

硅酸盐玻璃中的Na,Mg K-边XANES谱研究

本文利用同步辐射的NaK 边X 射线近边结构 (XANES)谱研究了含Na玻璃 (Na2 O SiO2 P2 O5和Na2 O SiO2 )的NaK 边的特征 ,同时建立了含磷 (P)的钠玻璃中NaK 边的能量 ,其能量位置随着P的含量增加 ,而增大其能量位置。CaMgSi2 O6(Di) NaAlSi3 O8(Ab)玻璃中MgK 边XANES的能量和Mg—O的键长有关系。在Di Ab玻璃中的Mg—O键距是 2± 0 0 4 。表明本方法可以作为研究含Mg玻璃的配位与局部结构新方法     

Stabilization of elements in unusual oxidation states and temperature-reversible dynamics of electron pairs in oxide glasses. EPR-investigation

Binary, three-component and multi-component borate, phosphate, germanate and silicate glasses, as well as barium-aluminophosphate glasses containing oxide of metals of (I–V) B groups, metals of the first transition series from titanium to nickel, niobium, tantalum, molybdenum and tungsten are investigated by EPR and optical spectroscopy at 77 and 300 K. The formation of metal ions in unusual oxidation states, such as Ag⁰, Zn¹⁺, Cd¹⁺, Hg¹⁺, Ga²⁺, Tl²⁺, Ge³⁺, Sn³⁺, Pb³⁺, Sb⁴⁺, Bi⁴⁺, Nb⁴⁺, Ti³⁺, Ni¹⁺, Mo⁵⁺, Cr³⁺, and Cr⁵⁺ was established. They were stabilized in the aforementioned glasses at specific compositions of components for an unlimited time at 300 K. It is shown that the reversible low temperature effect of disproportionation on atoms such as Nb, Ti, V, Mo, and W proves that in glass under ionizing gamma-radiation and temperature the reactions of disproportionation occur together with the reconstruction of conformation, the electron density transfer, the atomic displacement and the change (reversible or not) of a local structure of glass. It is shown that the formation of metal clusters in glass is connected with reaction of disproportionation.     

Er3+单掺和Er3+/Yb3+双掺铋硼酸盐玻璃的研究

用高温熔融法制备了Er^3 单掺和Er^3 /Yb^3 双掺铋硼酸盐玻璃样品，测量了上述玻璃样品的吸收光谱，荧光光谱，荧光寿命以及红外透过率。对高浓度掺杂Er^3 的铋硼酸盐玻璃中的浓度猝灭现象作出了解释。分析了Er^3 ／Yb^3 双掺铋硼酸盐玻璃样品中Yb^3 离子对Er^3 离子的敏化过程。研究发现Er^3 ／Yb^3 双掺铋硼酸盐玻璃在1．5～1．6μm波段有宽达81nm的荧光半峰全宽。实验还发现在熔制过程中通入氧气对其荧光寿命和红外透过率都有明显的提高。由于该玻璃材料表现出较好的物化性能。因此该材料可望成为宽带光纤放大器的适宜的基质材料。     

Site connectivities in silver borophosphate glasses: new results from 11B{31P} and 31P{11B} rotational echo double resonance NMR spectroscopy

Local and medium range order in the glass system 50Ag2O-50[(B2O3)x-(P2O5)(1-x)] (x=0, 0.1, 0.2, 0.3, 0.4, 0.5, and 0.6) have been investigated by high-resolution solid state nuclear magnetic resonance (NMR) techniques. The detailed local site distribution has been derived from deconvolution analysis of the 11B and 31P magic-angle spinning (MAS) NMR signals. Quantitative information regarding the extent of boron-oxygen-phosphorus connectivity has been obtained on the basis of 11B[31P} and 31P{11B} rotational echo double resonance experiments. Incorporation of borate into silver metaphosphate glasses produces four-coordinate BO4/2- sites, which crosslink the metaphosphate chains, resulting in a significant increase in the glass transition temperature. Furthermore, the presence of borate favors the disproportionation of P(2) chain-like units into P(1) and P(3) sites, an effect not observed in binary alkali phosphate glasses. Finally, borate incorporation beyond x=0.3 results in the formation of neutral BO3/2 units, indicating some net charge transfer from the borate to the phosphate network former species. This latter result corresponds to the general metal ion scavenging effect observed for phosphate species in other mixed network former glass systems. In the present system, the effect is relatively moderate, however, suggesting that anionic BO4/2- groups are stabilized by the interaction with the phosphate groups.     

Two-mode nature of the Raman spectrum of lithium niobate crystals

The ordering of the host and impurity cations in nominally pure (with different values of Li/Nbratio) and doped lithium niobate crystals is studied using Raman spectroscopy. It is shown that depending on the composition-controlled ordering of structural units of the cationic sublattice the crystal may exhibit, in the region of bridge stretching vibrations of the oxygen ions, either single-mode or two-mode behavior. The nominally pure lithium niobate crystals show, within the homogeneity region, single-mode behavior, while the crystals doped with divalent or trivalent cations show single-mode behavior at low concentrations of the dopant and two-mode behavior at higher concentrations.     

Strength,plasticity and brittleness of bulk metallic glasses under compression: statistical and geometric effects

To investigate the flaw sensitivity and reliability of bulk metallic glasses (BMGs), compressive testing was performed on a statistically significant number of specimens. Despite the fact that BMGs exhibit little or no macroscopic plasticity before failure (similar to other brittle materials), we observe surprisingly high uniformity in compressive strength. Weibull analysis was employed to study the statistical dispersion in strength, giving very high Weibull moduli of about 25 for an intrinsically brittle glass, and near 75 for an intrinsically malleable one. This high uniformity is encouraging for the use of BMGs in structural applications. Furthermore, we illustrate that subtle imperfections in the test geometry (i.e. miscut or deviations from orthogonality) dramatically affect the compression response. In brittle glasses these act as failure-critical flaws, whereas in malleable glasses they constrain shear bands, lead to tilting and bending during testing, and give rise to misleading macroscopic measurements of plastic deformation.     

Non-bridging oxygens in borate glasses: characterization by 11B and 17O MAS and 3QMAS NMR

The concentrations of non-bridging oxygens (NBO) in oxide glasses has major effects on their properties and on those of their precursor glass melts. In borate and borosilicate glasses, the presence of NBO bonded to boron has generally been inferred from 11B NMR spectra and mass balance considerations. Here we report the direct observation of such NBO using 17O MAS and 3QMAS techniques, and compare estimates of their populations with those derived from high-resolution 11B MAS spectra. For the latter, two independent methods are used, based on the ratios of trigonal to tetrahedral boron and on the concentrations of trigonal boron sites with large quadrupolar asymmetry parameters. We include data on crystalline sodium pyroborate (Na4B2O5) and sodium metaborate (NaBO2), and several sodium and barium borate glasses. 17O chemical shifts and quadrupolar coupling constants for NBO bonded to boron vary considerably depending on their coordination environment. In borosilicates, peaks for this species may be hidden by overlap with B-O-Si or Si-O-Si resonances.     

Shear viscosity of the Pd<Subscript>40</Subscript>Cu<Subscript>40</Subscript>P<Subscript>20</Subscript> metallic glass under conditions of isochronous heating below the glass transition temperature

The shear viscosity is measured under conditions of isochronous (linear) heating below the glass transition temperature of the Pd₄₀Cu₄₀P₂₀ metallic glass, which is characterized by the polymorphic crystallization into the Pd₂Cu₂P tetragonal phase with a lower density than the initial glass. It is shown that the rate dependence of the shear viscosity can be interpreted as a result of the irreversible structural relaxation by analogy with the case of the previously studied metallic glasses despite the unusual ratio of the densities of the material in noncrystalline and crystalline states.     

Composition-dependent photosensitivity in As-S glasses induced by bandgap light: structural origin by Raman scattering

Massive photoinduced short- and medium-range structural changes (photopolymerization) in As-S glasses are induced by near-bandgap light and studied by Raman scattering. Structural changes involve bond restructuring in sulfur-rich nanodomains of these nanoscale-phase-separated glasses. The spectral dependence of the photopolymerization effect demonstrates that various wavelengths can be used to optically change the structure of As-S glasses. The immense structural changes are relevant to recent findings about the role of bandgap light illumination for fabricating channel waveguides in noncrystalline arsenic sulfides.     

Structure-conductivity relations in ion conducting glasses

The bond valence method has been applied to reverse Monte Carlo (RMC) produced structural models of a wide range of ion conducting glasses in order to elucidate the relation between the microscopic structure and the ionic conductivity. Our approach allows us to predict the ionic conductivity of the glasses directly from the “pathway volume” of the structural models and to investigate the nature of these low-dimensional conduction pathways. The pathways are defined to be the regions in the structural models where the valence mismatch for each mobile ions remains below a given threshold value. The results for the metal-halide doped glasses show the importance of including M⁺ sites with a high oxide coordination for the long range mobility, responsible for the dc conductivity. Thus, there are no long range migration pathways for M⁺ sites in an entire halide environment. Rather, the mobile ions are generally moving between sites with a local environment of both oxygens and halide ions, in contrast to earlier proposed “cluster models” where it has been assumed that cations associated with salt clusters are responsible for the high ionic conductivity. Finally, our bond valence approach provides a direct explanation for why the conductivity is favoured by highly polarizable anions and cations, since the pathway volume is related to the softness of the M⁺-X bond. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Structural studies and mechanical properties of some borate glasses doped with different alkali and cobalt oxides

Mixed alkali borate glasses doped with CoO, have been prepared by the melt quenching technique. Elastic properties and FT-IR spectroscopic studies have been employed to study the role of CoO and the mixed alkali effect on the structure of the investigated glass system. Elastic properties and Debye temperature have been investigated using sound wave velocity measurements at 4 MHz at room temperature. The density, molar volume and glass transition temperatures were employed to investigate the structure of these glasses. Infrared spectra of these glasses revealed that the borate network is affected by the increase in the concentration of CoO content and the mixed alkali oxides. These results are interpreted in terms of the change in the topology of these glass structures. The elastic moduli are observed to increase with the increase of CoO content due to the increased average bond connectivity.     

Multiphonon relaxation of rare earth ions in borate,phosphate, germanate and tellurite glasses

Non-radiative multiphonon relaxation rates were obtained for excited electronic states in borate, phosphate, germanate and tellurite glasses. The rates were calculated from the intensities of fluorescence in the visible range of the spectrum, the measured radiative transitions and the decay times of fluorescence. A functional dependence was found between the relaxation rates and the energy gaps of the rare earth ion. It was shown that by changing the glass host from the borate to tellurite matrix, an increase in visible fluorescence was achieved. This was especially notable in Er³⁺, where the increase of fluorescence from germanate to tellurite was by a factor of 15.