Effect of Bi2O3 content on physical and optical properties of 15Li2O-15K2O-xBi2O3-(65−x) B2O3: 5V2O5 glass system

Multi-component bismuth borate glasses doped with vanadium ions 15Li₂O-15K₂O-xBi₂O₃-(65−x) B₂O₃: 5V₂O_5, (x=3, 5, 7, 10, 12 and 15) have been prepared using conventional melt quench technique. Characterization of the prepared glasses has been done using X-ray diffraction, differential scanning calorimetry and density measurements. The effect of Bi₂O₃ content on the optical properties of the present glass system is studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The origin of the Urbach energy is associated with the phonon-assisted indirect transitions. The density and molar volume studies indicate that Bi₂O₃ in these glasses is acting partly as network modifier and partly as network former. The variations in the optical band gap energies, density and molar volume with Bi₂O₃ content have been discussed in terms of changes in the glass structure. Values of the theoretical optical basicity, average crosslink density and the average electronic polarizability are also reported.     

Bi2O3-B2O3-BaO玻璃的制备及其近红外发光性能的研究

采用高温熔融法制备了xBi₂O₃-50B₂O₃-(50-x)BaO玻璃, 测定了样品玻璃的近红外光区的发射谱、荧光寿命以及Raman光谱. 在808 nm波长光的激发下, 50Bi₂O₃-50B₂O₃二元玻璃中未观察到近红外发光; 随体系中BaO的加入, 当x为40, 45以及49时, 玻璃样品中观察到了近红外宽带发光现象; BaO含量进一步增加, 当x=10–30时, 近红外发光现象消失; 而当玻璃中Bi浓度很低时, 在0.5Bi₂O₃-50B₂O₃-50BaO及1Bi₂O₃-50B₂O₃-50BaO玻璃中发现了近红外发光现象, 且存在多个发光峰. 对铋离子近红外发光机理进行了初步的探讨.     

Crystallization kinetics of Li2O-PbO-V2O5 glasses

Lead vanadate glasses of the system 5Li₂O−(45−x) PbO−(50+x) V₂O₅, with x=0, 5, 10, and 15 mol% have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC using continuous-heating techniques. In addition, from dependence of the glass-transition temperature (T_g) on the heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined and the crystallization mechanism was characterized. The results reveal the increase of the activation energy for glass transition which was attributed to the increase in the rigidity, the cross-link density and the packing density of these glasses. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of Li_0.30V₂O₅, Li_0.67O₅V₂, LiV₆O₁₅, Li₄O₄Pb, and O₇Pb₂V₂ in a remaining amorphous matrix.     

Study of PbO-SrO-TiO2-B2O3 glass and glass ceramics

The glasses with composition (50−X)PbO–XSrO-25TiO₂-25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The T_g, T_c, density and CTE of the glass samples were measured. The T_g observed to increase with increasing concentration of SrO, while the T_c first decreased and then increased. The glass samples were converted to glass ceramics by following two stage heat treatment schedule. The glass ceramic samples were characterized by XRD, SEM and dielectric measurements. The XRD results revealed the formation of ferroelectric lead titanate as a major crystalline phase in glass ceramics. Additional phases observed include Sr₂B₂O₅ and PbB₂O₄. The room temperature (RT) dielectric constant of glass and glass ceramics are in the range of 100–120 which is promising for capacitor application.     

On the iron valence states in B2O3-PbO-GeO2 glasses

The Mössbauer effect measurements performed on 20Fe₂O₃ 80 3B₂O₃ (1?x)PbO xGeO₂ glasses show that the ratio between the number of ferrous ions to the total number of iron ions decreases by increasing the GeO₂ content. The Curie constants calculated from the distribution of iron cations obtained by Mössbauer effect data are in agreement with the values determined from magnetic measurements. Finally, we discuss the influence of the glass composition and melting temperature on the iron valence states.     

Effect of Bi2O3 on EPR, optical transmission and DC conductivity of vanadyl doped alkali bismuth borate glasses

Glasses with composition xBi₂O₃·(30−x)M₂O·70B₂O₃ (M=Li, Na) containing 2 mol% V₂O₅ have been prepared over the range 0≤x≤15 (x is in mol%). The electron paramagnetic resonance spectra of VO²⁺ of these glasses have been recorded in the X-band (≈9.3 GHz) at room temperature (RT≈300 K). Spin Hamiltonian parameters, g_∥, g_⊥, A_∥, A_⊥, dipolar hyperfine coupling parameter, P, and Fermi contact interaction parameter, K, have been calculated. The molecular orbital coefficients, α² and γ², have been calculated by recording the optical transmission spectra. In xBi₂O₃·(30−x)Li₂O·70B₂O₃ glasses there is decrease in the tetragonality of the V⁴⁺O₆ complex for x up to 6 mol% whereas for x≥6 mol%, tetragonality increases. In xBi₂O₃·(30−x)Na₂O·70B₂O₃ glasses there is increase in the tetragonality of the V⁴⁺O₆ complex with increasing x. The 3d_xy orbit expands with increase in Bi₂O₃:M₂O ratio. Values of the theoretical optical basicity, Λ_th, have also been reported. The DC conductivity increases with increase in temperature. The order of conductivity is 10⁻⁵ ohm⁻¹ m⁻¹ at low temperature and 10⁻³ ohm⁻¹ m⁻¹ at high temperature. The DC conductivity decreases and the activation energy increases with increase in Bi₂O₃:M₂O ratio.     

Influence of B2O3 to the inhomogeneous broadening and spectroscopic properties of Er/Yb codoped fluorophosphate glasses

In a three-components fluorophosphate glass system, the introduction of H₃BO₃ brings some valuable influence to the spectroscopic and thermal properties of the glasses. With H₃BO₃ increases from 2 to 20 mol%, Ω₆, S_ed4I13/2, FWHM, T_g and fluorescence lifetime change from 3.21×10⁻²⁰ cm², 1.77×10⁻²⁰ cm², 45 nm, 480 °C and 8.8 ms to 4.66×10⁻²⁰ cm², 2.11×10⁻²⁰ cm², 50 nm, 541 °C and 7.4 ms, respectively. σ_abs, σ_emi, FWHM×τ_f×σ_emi has a maximum when H₃BO₃ is 11 mol%. T_g and T_x−T_g increases with H₃BO₃ introduction. Results showed that in fluorophosphate glasses, proper amount of B₂O₃ can be used as a modifier to suppress upconversion and improve spectroscopic properties, broadband property and crystallization stability of the glasses while keeps the fluorescence lifetime relatively high.     

非晶态锂离子导体B2O3-0.7Li2O-0.7LiCl-xAl2O3-0.1V2O5的电学性质和电子自旋共振研究

对两种非晶态B₂O₃-0.7Li₂O-0.7LiCl-xAl₂O₃-0.1V₂O₅(x=0.05和0.15),用差热分析、电导率测量、X射线衍射和电子自旋共振进行研究,发现:1)V₂O₅不仅作非晶网络形成剂,而且改变了晶化过程;2)对B₂O₃-Li_{2关键词：}     

Thermoluminescence of B2O3-Li2O glass system doped with MgO

Lithium borate (LiB) glasses in the system (100−x)B₂O₃-xLi₂O with x=20, 30, 40, 50, 60 and 70 mol% were prepared. The glasses were doped with different concentrations of the order of 10⁻¹, 10⁻², 10⁻³, 10⁻⁴ and 10⁻⁵ of MgO and their thermoluminescent (TL) response was investigated. The irradiations were performed using γ rays from a ⁶⁰Co source in the dose range from 0.1 to 25 kGy. The material displayed good sensitivity for γ-rays and intensity of TL signals is dependent on γ-ray dose and Li₂O content. For each dose level and investigated temperature range (50-350 °C), exactly single isolated glow peak appears in the temperature range of 165-205 °C depending on both Li₂O concentrations and time of exposure. The shape of the glow peak has altered significantly with increase in the gamma ray dose or Li₂O concentrations. The glass composition with x=50 mol% doped with 10⁻³ mol% of MgO presented the best TL response. The results of the present study indicated that the recorded single and isolated high temperature peak is a good candidate for TL dosimetric investigations. This indicates that 50 B₂O₃-50Li₂O-doped with 10⁻³ mol% of MgO is possibly used as materials for radiation dosimetry in the dose range of 0.1-20 kGy.     

Emission analysis of Dy and Pr:Bi2O3-ZnF2-B2O3-Li2O-Na2O glasses

In this paper, we present the spectral results of Dy³⁺ and Pr³⁺ (1.0 mol%) ions doped Bi₂O₃-ZnF₂-B₂O₃-Li₂O-Na₂O glasses. Measurements of X-ray diffraction (XRD), differential scanning calorimetry (DSC) profiles of these rare-earth ions doped glasses have been carried out. From the DSC thermograms, glass transition (T_g), crystallization (T_c) and melting (T_m) temperatures have been evaluated. The direct and indirect optical band gaps have been calculated based on the glasses UV absorption spectra. The emission spectrum of Dy³⁺:glass has shown two emission transitions ⁴F_7/2→⁶H_15/2 (482 nm) and ⁴F_7/2→⁶H_13/2 (576 nm) with an excitation at 390 nm wavelength and Pr³⁺:glass has shown a strong emission transition ¹D₂→³H₄ (610 nm) with an excitation at 445 nm. Upon exposure to UV radiation, Dy³⁺ and Pr³⁺ glasses have shown bright yellow and reddish colors, respectively, from their surfaces.     

Magnetic properties of xCoO.(1−x)[2B2O3.PbO] glasses

The results of magnetic studies on xCoO.(1?x)[2B₂O₃.PbO] glasses with 0?x?50 mol.%, are reported. These results show evidence that the cobalt ions, in this glass system, are in bivalent state and magnetically isolated, having magnetic moments μ=(4.50±0.06)μ_B.     

The structural properties of CdO-Bi2O3 borophosphate glass system containing Fe2O3 and its role in attenuating neutrons and gamma rays

A glass system with chemical formula xBi₂O₃-(30−x)CdO-10B₂O₃-20Fe₂O₃-40P₂O₅ (0≤x≤30) wt% is prepared to be used as radiation shield. The mass attenuation coefficient and half value layer of the glass system to gamma rays have been measured experimentally and compared with those determined from theoretical calculations using the mixture rule of WinXCom program. A database of effective mass removal cross-sections for fast neutrons is also introduced in this work. The obtained results of this study are correlated to the structural properties of these glasses obtained from their IR spectra and the influence of gamma and neutrons irradiation on these structural properties.     

IR and Raman investigation on the structure of (100-x)B2O3-x[0.5 BaO-0.5 ZnO] glasses

Glasses with molar composition of (100-x)B₂O₃-x[0.5 BaO-0.5 ZnO], x=40, 50, 60, 70 were prepared from the melts of ZnO, BaCO₃ and H₃BO₃ mixture. The structure and thermal behavior were characterized by IR and Raman spectroscopy, DSC and Dilatometer. The investigation shows that the transition of the structural unit [BO₄] (B^IV) to [BO₃] (B^III) happens when BaO and ZnO content x increases in the borate glass, resulting in fewer B^III-O-B^IV bonds and more B^III-O-B^III bonds. At the same time, the diborate groups, which are found to be the predominant structural group of the glass with high B₂O₃ content, gradually changes into ring-type metaborate, pyro- and orthoborate groups. With increasing ZnO and BaO content x, the glass transition temperature (T_g) and the softening point (T_f) decreases, while linear expansion coefficient (α) increases, that comes from the weakening of the glass network.     

Magnetic properties of xNiO. (1-x)[2B2O3.PbO] glasses

The results of magnetic studies on xNiO.(1-x)[2B₂O₃.PbO] glasses with 0 ? x ? 40 mol.% are reported. These results evidenced that the nickel ions, in this glass system, are in a divalent state and magnetically isolated. The magnetic moments, μ, decrease from a value 3.31 μ_B for the 5 mol.% NiO to a value 2.90 μ_B for 40 mol.% NiO. These variations can be due to the result of a statistical average of the nickel sites distribution.     

Electrical conductivity of transition metal oxide glasses in the system V2O5B2O3TeO2 at high temperatures

Bulk d.c. conductivities of the electronically conducting transition metal oxide glasses in the system xV₂O₅50B₂O₃(50?x)TeO₂ were measured at different temperatures in the range 310–623 K. The dependence of conductivity on composition is explained on the basis of the role of TeO₂ as a modifier or impurity. The observed kink in the log σ vs 1/T characteristic of the glasses is interpreted as being due to switching over of the conduction mechanism from one type to the other. The activation energies are fitted in a linear relation of the type E_g = A ? BP, where A and B are constants and P, the composition parameter. Comparing the results obtained with those of previous workers in the V₂O₅P₂O₅ and V₂O₅B₂O₃ systems, a physical analysis is presented.     

Magnetic properties of xCuO · (1 - x) [2B2O3 · PbO] glasses

The results of magnetic studies on xCuO · (1 ? x) [2B₂O₃ · PbO] glasses with 0 ? x ? 50 mol.%, are reported. These results evidenced that the copper ions, in this glass system, are in Cu²⁺ and Cu⁺ valence states. From Curie constant is determined the amount of the copper ions in bivalent state. For glasses with x > 5 mol.% CuO, an antiferromagnetic behaviour is evidenced.     

Effect of ZnO/CdO on the structure and electrical conductivity in Li2O·MO·Bi2O3·B2O3 glasses (M=Zn, Cd)

Studies of structural and electrical properties have been carried out on a number of glasses with wide ranging compositions in the glass systems Li₂O·MO·Bi₂O₃·B₂O₃ (where M=Zn or Cd), in order to understand the effect of transition metal (TM) ions on the structure of these glasses. The density and molar volume measurements have also been made to understand the structural changes occurring in these glasses. The dc conductivity measured in the temperature range 423-623 K obeys Arrhenius law. It increases with increase in Li₂O/MO ratio. The results of infrared spectra indicate that TM ions (Zn²⁺ or Cd²⁺) behave as network former in the present system. Boron exists in both tri- and tetra-hedral units in these glasses and no boroxol ring formation takes place in the glass structure. Values of theoretical optical basicity have also been reported.     

Er3+/Yb3+共掺碲硼硅酸盐玻璃的光谱性质和热稳定性研究

制备了系列Er³⁺/Yb³⁺共掺碲硼硅酸盐玻璃样品(85-x)TeO₂-15B₂O₃-xSiO₂ (TBS x=0,5,10,15,20 mol%).测试和分析了样品的吸收光谱、荧光光谱、能级寿命、红外透射光谱及差热特性.并通过对Er³⁺离子⁴I_13/2→⁴I_15/2跃迁发射谱线的高斯拟合，设计了一个简单的四能级结构估算了Er³⁺离子⁴I_13/2和⁴I_15/2能级在碲硼硅酸盐中的Stark分裂情况.研究表明SiO₂的引入能有效地改善玻璃的热稳定性和光谱性能，玻璃析晶温度T_x与玻璃转变温度T_g之差(ΔT=T_x-T_g)可达178℃，说明碲硼硅酸盐是一种适合于光纤拉制的玻璃基质材料.比较了不同基质玻璃中Er³⁺离子的荧光半高宽和受激发射截面，结果表明TBS玻璃系统具有较好的带宽性能，是一种优良的宽带光纤放大器候选基质材料. 关键词： 碲硼硅酸盐 热稳定性 高斯拟合 -基')" href="#">OH^-基     

Optical properties of Er doped GeO2-PbO glass: Effect of doping with Bi2O3

The optical properties of binary and ternary germanate glasses 40.3GeO₂-59.7PbO, 31.3GeO₂-26.8PbO-41.9Bi₂O₃ and 31.5GeO₂-40.4PbO-28.1Bi₂O₃ (wt%) doped with Er³⁺ were investigated. The Judd-Ofelt intensity parameters were calculated and the near-infrared luminescence as well as the upconversion efficiency was analyzed. We observed that the ternary germanate glass containing the highest concentration of Bi₂O₃ presented the largest emission bandwidth for ⁴I_13/2 → ⁴I_15/2 transition and the highest infrared-to-visible upconversion efficiency among the samples studied. These results demonstrate that not only the presence of Bi₂O₃ but also the careful choice of its molecular weight plays a key role in optimizing parameters for using germanate glasses for photonics applications.