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.     

Raman and Infrared Spectroscopic Characterization of the Silicate Mineral Lamprophyllite

The mineral lamprophyllite is fundamentally a silicate based upon tetrahedral siloxane units with extensive substitution in the formula. Lamprophyllite is a complex group of sorosilicates with general chemical formula given as A₂B₄C₂Si₂O₇(X)₄, where the site A can be occupied by strontium, barium, sodium, and potassium; the B site is occupied by sodium, titanium, iron, manganese, magnesium, and calcium. The site C is mainly occupied by titanium or ferric iron and X includes the anions fluoride, hydroxyl, and oxide. Chemical composition shows a homogeneous phase, composed of Si, Na, Ti, and Fe. This complexity of formula is reflected in the complexity of both the Raman and infrared spectra. The Raman spectrum is characterized by intense bands at 918 and 940 cm^?1. Other intense Raman bands are found at 576, 671, and 707 cm^?1. These bands are assigned to the stretching and bending modes of the tetrahedral siloxane units.     

Modifier cation (Ba,Ca, La,Y) field strength effects on aluminum and boron coordination in aluminoborosilicate glasses: the roles of fictive temperature and boron content

The field strength of modifier cations has long been known to have important effects on oxide glass properties, but effects on network structure can be complex. For two series of barium, calcium, lanthanum and yttrium aluminoborosilicates with two different B/Si ratios, we report systematic variations in boron and aluminum coordination determined by NMR, and glass transition and heat capacities from differential scanning calorimetry. Data on glasses with different fictive temperatures allow B and Al speciation to be compared on an isothermal basis, rather than as conventionally done for as-quenched structures. Temperature and compositional effects can thus be isolated. These data and comparison to previous studies on glasses with lower B/Si ratios clearly show that higher modifier cation field strength increases the fraction of five- and six-coordinated Al in all compositions. In contrast, the previously documented trend towards more three-coordinated boron (and hence more non-bridging oxygens, NBO) in low B/Si glasses with higher field strength cations reverses in high B/Si and in high NBO compositions. Al and B coordination numbers both decrease with higher fictive temperature in the glasses studied here, suggesting a simple mechanism of coupled structural change.     

Investigation of the boron-oxygen network in borate glasses by infrared spectroscopy

Lithium borate glasses are fast ionic conductors in which the lithium ions conductivity is all the more important as the content in lithium oxide and in lithium salt is higher. In the perspective of their use as electrolytes in solid state micro-batteries, we have studied the conformation of the boron-oxygen network of lithium halides “doped” glasses by MIR spectroscopy. The modifying properties of the lithium oxide on the binary system B₂O₃-Li₂O are investigated by the same technique and the results are used to understand the modifications of the boron-oxygen network induced by the “doping salt”. The observed results depend on the type of salt anions: fluoride anions participate directly to the O/B network while chloride and bromide anions are in interstitial position in the glass matrix.     

Self- and foreign alkaline-earth diffusion in mixed cation silicate glasses

Self-diffusion of alkaline-earth ions in various mixed cation silicate glasses of the composition A₂O·2MO·4SiO₂ was investigated by radiotracer diffusion measurements below the respective glass transition temperatures. Including previous measurements, we have analyzed the diffusivity of divalent ions in mixed cation systems with A = Li, Na, K, Cs and M = Ca, Sr, Ba. The activation enthalpy depends strongly on the type of cations, revealing an increasing diffusivity for glasses with cations of similar size. The behavior is consistent with mechanical loss spectroscopy measurements performed on the same glasses. In addition foreign atom diffusion of calcium and barium in strontium containing glasses were performed. In the case the ionic radius of the alkali ions exceeds that of the alkaline-earth ions the diffusion activation enthalpy of the foreign ion equals the activation enthalpy of self-diffusion. The results can be described on the basis of a theoretical model proposed by Kirchheim [R. Kirchheim, J. Non-Cryst. Solids 328 (2003) 157] that relates the activation enthalpy to electrostatic and elastic contributions.     

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.     

Nanocrystals formation on Ho doped strontium barium niobate glass

The study of two different methods to obtain strontium barium niobate nanocrystals immersed in a glass matrix has been carried out. Ho₂O₃-doped SrO-BaO-Nb₂O₅-B₂O₃ glasses were fabricated using the melt quenching method. Glass ceramic samples were obtained from the precursor glass by thermal treatment in a furnace and by laser irradiation. These glass ceramic samples are formed by a glassy phase and a crystalline phase of strontium barium niobate nanocrystals. This structure was confirmed by X-ray diffraction and Atomic Force Microscope images. The incorporation of Ho³⁺ ions in the strontium barium niobate nanocrystals were corroborated by optical measurements, which produced an increment in the luminescence intensity compared to the precursor glass.     

Preparation and fluorescence properties of novel red-emitting Eu-activated amorphous alkaline earth silicate phosphors

This study reports the synthesis of novel red-emitting Eu³⁺-activated amorphous alkaline earth silicate phosphors with high emission intensities. Eu³⁺-activated barium (strontium) silicate hydrate phosphors were synthesized using a liquid phase reaction and then heated at 850 °C for 0.5 h to form amorphous barium (strontium) silicate phosphors. These amorphous phosphors emitted in the red region following near-UV (395 nm) irradiation. The internal quantum efficiencies of the Eu³⁺-activated amorphous barium silicate phosphor and strontium silicate phosphor were 56% and 60%, respectively, even though these phosphors were in the amorphous state.     

Luminescence characteristics of Dy3+ in different host matrices

Luminescence characteristics of Dy³⁺ have been studied in barium borate, calibo glasses, lanthanum chloride, acetic acid and dimethyl sulphoxide. Typical spectra and decay times obtained in various hosts have been reported. Emission is efficient in a glassy matrix.     

Redox reactions and inward cationic diffusion in glasses caused by CO and H2 gases

We find that inward diffusion of network-modifying cations can occur in an iron-containing silicate glass when it is heat-treated in CO/CO₂ (98/2 v/v) or H₂/N₂ (1/99 v/v) gases at temperatures around the glass transition temperature. The inward diffusion is caused by the reduction of ferric to ferrous ions and this diffusion leads to formation of a silica-rich surface layer with a thickness of 200–600 nm. The diffusion coefficients of the network-modifying divalent cations are calculated and they are different for the glasses treated in the CO and H₂ gases. At the applied partial pressures of CO and H₂, the H₂-bearing gas creates the silica-rich layer more effectively than the CO-bearing gas. The layer increases the hardness and chemical durability of the glass due to the silica network structure in the surface layer.     

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.     

Direct correlation between nonrandom ion hopping and network structure in ion-conducting borophosphate glasses

We present temperature-dependent conductivity spectra of sodium borophosphate glasses with a varying borate/phosphate ratio but a constant sodium oxide content which can be mapped into time-dependent mean square displacements. For the first time, we show that characteristic lengths of ion transport derived thereof are directly linked to features of network structure, viz., the number of boron oxide tetrahedra. Our results also shed light on the mixed network former effect.     

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。     

Effect of alkali content on AC conductivity of borate glasses containing two transition metals

Sodium borate glasses containing iron and molybdenum ions with the total concentration of transition ions constant and gradual substitution of sodium oxide (network modifier) by borate oxide (network former) was prepared. Densities, molar volume, DC and AC conductivities are measured. The trends of these properties are attributed to changes in the glass network structure. Their DC and AC conductivity increased with increasing NaO concentration. The increase of AC conductivity of sodium borate glasses is attributed to the chemical composition and the hopping mechanism of conduction. Measurements of the dielectric constant (ε) and dielectric loss (tan δ) as a function of frequency (50 Hz–100 kHz) and temperature (RT—600 K) indicate that the increase in dielectric constant and loss (ε and tan δ) values with increasing sodium ion content could be attributed to the assumption that Fe and Mo ions tend to assume network-forming position in the glass compositions studied.The variation of the value of frequency exponent s for all glass samples as the function of temperature at a definite frequency indicates that the value of s decreases with increasing the temperature which agrees with the correlated barrier-hopping (CBH) model.     

不同玻璃组分对β-NaYF4:Yb3+,Er3+/Tm3+粉体的侵蚀性研究及对发光性能的影响

选用硅酸盐、硼酸盐以及磷酸盐3种常用的玻璃体系,与β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体均匀混合压片后在不同的温度(400～700 ℃)下进行热处理。采用X射线衍射技术和荧光光谱技术等测试手段研究不同玻璃形成体以及碱金属离子对β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体的侵蚀情况以及对发光性能的影响。研究结果表明,在硼酸盐玻璃体系与β-NaYF₄:Yb³⁺,Er³⁺/Tm³⁺粉体复合热处理过程中,Li⁺和K⁺离子会取代β-NaYF₄晶体中Na原子的位置。 在相同热处理温度下,不同玻璃体系与β-NaYF₄晶体反应剧烈程度:磷酸盐>硼酸盐>硅酸盐。     

Bismuth silicate glass containing heavy metal oxide as a promising radiation shielding material

Optical and FTIR spectroscopic measurements and electron paramagnetic resonance (EPR) properties have been utilized to investigate and characterize the given compositions of binary bismuth silicate glasses. In this work, it is aimed to study the possibility of using the prepared bismuth silicate glasses as a good shielding material for γ-rays in which adding bismuth oxide to silicate glasses causes distinguish increase in its density by an order of magnitude ranging from one to two more than mono divalent oxides. The good thermal stability and high density of the bismuth-based silicate glass encourage many studies to be undertaken to understand its radiation shielding efficiency. For this purpose a glass containing 20% bismuth oxide and 80% SiO₂ was prepared using the melting–annealing technique. In addition the effects of adding some alkali heavy metal oxides to this glass, such as PbO, BaO or SrO, were also studied. EPR measurements show that the prepared glasses have good stability when exposed to γ-irradiation. The changes in the FTIR spectra due to the presence of metal oxides were referred to the different housing positions and physical properties of the respective divalent Sr²⁺, Ba²⁺ and Pb²⁺ ions. Calculations of optical band gap energies were presented for some selected glasses from the UV data to support the probability of using these glasses as a gamma radiation shielding material. The results showed stability of both optical and magnetic spectra of the studied glasses toward gamma irradiation, which validates their irradiation shielding behavior and suitability as the radiation shielding candidate materials.     

Europium doped strontium borate glasses and their optical properties

Optical absorption and luminescence spectra of europium doped strontium borate glasses prepared in different conditions are studied. It is found that the percentage of Eu³⁺ ions varies from 100 to 30% being controlled by the conditions of preparation. The mechanism, favoring reduction of europium to Eu²⁺ state in polycrystalline strontium tetraborate, is much weaker in glasses of the same composition. In samples containing mixed valence europium at densities of 8×10²⁰ cm⁻³, the efficient transfer of optical excitation from Eu³⁺ to Eu²⁺, suppressing the Eu³⁺ luminescence, has been found. The most reliable way of monitoring the percentage of europium ions in different valences for strontium borate glasses is the measuring of absorption at f-f transition ⁷F₀→⁵D₂ of Eu³⁺.     

偏硼酸钡低温相的晶体结构

本文报道了新型信频材料——偏硼酸钡[Ba₃(B₃O₆)₂]低温相的晶体结构。晶体属三方晶系,空间群为C₃⁴-R3,取六方坐标系,晶胞参数为a=b=12.532?,c=12.717?,z=6。在PhilipsPW-1100四圆衍射仪上收集到独立衍射693个。采用重原子法通过三维帕特逊和三维傅里叶合成测定结构,并用对角矩阵最小二乘法修正至R=0.046。该晶体是一个由Ba²⁺和(B₃O₆)^3-环交错组成的层状阶梯式结构。其阴离子(B₃O₆)^3-环基本上是平面状的。基团平面垂直于三次轴;Ba²⁺近邻有7个氧原子。将此结构与偏硼酸钡高温相比较表明,由于钡阳离子的非中心对称分布改变了阴离子硼氧环共轭基团的电子云密度,这一结构上的变化对该晶体的倍频效应做了主要贡献。 关键词：