Etude par R.P.E. d'electrolytes vitreux appartenant au systeme B2O3-Li2O-LiCl

An EPR study of fast Li⁺ ion vitreous conductors belonging to the B₂O₃-Li₂O-LiCl system has been carried out. The samples have been subjected to X-ray irradiation at room temperature. Two types of paramagnetic centers have been observed. The first one is the Cl₂^- species (Vk center) present in the part of the vitreous domain which corresponds to low LiCl concentrations, it vanishes when Li⁺ and Cl^- begin to order. The second one is of the B.O.H.C. type often present in alkali borate glasses. Its presence shows the similarity between the boron-oxygen network of the alkali borate glasses and of our samples containing alkali chloride.     

Compositional-dependent lead borate based glasses doped with Eu ions: Synthesis and spectroscopic properties

New multicomponent lead borate based glasses with various PbO/B₂O₃ weight ratio were prepared. The glass samples were analyzed in detail by using Raman and IR absorption spectroscopy. Optical properties of Eu³⁺ ions have been investigated in lead borate based systems, in which PbO/B₂O₃ weight ratios were changed from 1:2 to 8:1 in glass composition. The values of the phonon energy of the host and ⁵D₀ lifetime of Eu³⁺ decrease, whereas absorption and emission intensities, as well as bonding parameter increase with increasing PbO concentration. Additionally, spectral lines are shifted in direction to the lower frequency region. Non-monotonic dependence of the fluorescence intensity ratio R (⁵D₀-⁷F₂/⁵D₀-⁷F₁) upon PbO/B₂O₃ content has been observed in contrast to bonding parameter that is also non-linear but monotonic. Some structural and spectroscopic aspects for Eu-doped lead borate based glasses are presented.     

Fe3+离子在钠-硼玻璃中的顺磁共振

研究了Fe³⁺离子在钠-硼玻璃中的顺磁共振。在表观g=4.27处,有一条尖锐的大致对称的共振线。实验结果表明Fe³⁺离子代替接触二个钠离子的[BO₄]四面体中的硼离子位置。     

Vitrification and transport properties in AgBr-doped chalcogenide systems

Vitrification and transport properties measurements for (AgBr)_x(As₂Se₃)_1−x glasses have been carried out in order to investigate the ion conduction phenomena of these systems. Glass samples were successfully obtained in a composition range of 0 ≤ x ≤ 0.65. The addition of AgBr leads these systems to an exponential increase of electrical conductivity. The ionic component of the electrical conductivity is dominant in highly AgBr-doped glasses. The vitrification brings the fast ion conduction to the present glass systems.     

Composition dependent structural and optical properties of Sm-doped sodium borate and sodium fluoroborate glasses

Sodium borate and fluoroborate glasses doped with trivalent samarium (Sm³⁺) were prepared and their detailed spectroscopic analysis was carried out. The FTIR spectra reveal that, the glasses contain BO₃, BO₄, non-bridging oxygen and strong OH⁻ bonds. From the optical absorption spectra, Judd-Ofelt intensity parameters (Ω_λ, λ=2, 4 and 6) have been evaluated and are in turn used to predict radiative properties such as radiative transition probability (A), stimulated emission cross section () and branching ratios (β_R) for the excited levels of Sm³⁺ ions in sodium borate and sodium fluoroborate glasses. The dependence of the spectral characteristics of Sm³⁺ ions due to compositional changes have been examined and reported. The value is found to decrease with the decrease in the sodium content in the glass. The decay from the ⁴G_5/2 level is found to be non-exponential indicating a cross-relaxation among the Sm³⁺ ions.     

Optical absorption and thermoluminescence studies on LiF-Sb2O3-B2O3 glasses doped with Ni ions

20LiF-(30−x)Sb₂O₃-50B₂O₃:xNiO glasses with the value of x (ranging from 0 to 1.0 mol% in steps of 0.2) were prepared. A number of studies, viz. differential scanning calorimetry, optical absorption, magnetic susceptibility and thermoluminescence, on these glasses were carried out as a function of nickel ion concentration. An anomaly has been observed in all the properties of these glasses when NiO concentration is about 0.6 mol%. The results of these studies were analysed in the light of different environments of nickel ions in the glass network.     

Etude par resonance paramagnetique electronique des verres du systeme B2O3-Na2O-Na3PO4

An EPR study of fast Na⁺ ion vitreous conductors of the system B₂O₃?Na₂O?Na₃PO₄ has been carried out. After X-ray irradiation two types of paramagnetic centers have been observed. The first one is of boron-oxygen hole center (B.O.H.C.) type and similar to that earlier observed for other alkali borate glasses. The second one is of PO₄^2? type. A simulation of its spectrum has been achieved and a defect model discussed.     

Transport processes in heavy metal fluoride glasses

Na self-diffusion, Li self-diffusion, Na⁺–Li⁺ ion exchange, electrical conductivity, and mechanical relaxation have been studied below T_g on glasses of the system ZrF₄–BaF₂–LaF₃–AF (A=Na, Li), with A=10, 20, 30 mol%. Compared to the transport mechanism in alkali-containing silicate glasses, the mechanisms in these non-oxide glasses are anomalous. Thus the self-diffusion coefficient of Na decreases with increasing NaF content, whereas that of Li increases with increasing LiF content. Both the electrical conductivity and the Na⁺–Li⁺ ion exchange reach a minimum at ≈ 20 mol% LiF, and the mechanical relaxation shows one peak for the 20 and 30 mol% LiF-glasses and two peaks for the glass with 10 mol% LiF, evidencing both a contribution of F⁻ and Li⁺ ions to the transport. Moreover, the presence of the three partially interacting mobile species F⁻, Na⁺, Li⁺ obviously leads to an anionic–cationic mixed ion effect. Applying the Nernst–Einstein equation to the Li⁺ transport in LiF-containing glasses shows that its mechanism is dissimilar to that in oxide glasses. Calculated short jump distances possibly can be interpreted as an Li⁺ movement via energetically suitable sites near F⁻ ions. Likewise the Nernst–Planck model, successfully applied to the ionic transport in mixed alkali silicate glasses, obviously does also not hold for the present heavy metal fluoride glasses.     

A determination of the distributions of quadrupole coupling constants in borate glasses using B10 NMR

A method is presented for extracting the distribution of quadrupolar coupling constants (Q_cc) for 3-coordinated boron atoms in glasses containing B₂O₃. Results are presented for vitreous B₂O₃ and seven sodium borate glasses. There is essentially no change in the average coupling constant and the distribution of coupling constants, over the composition region from 0–35 mol.% Na₂O. It is noted that a distribution in asymmetry parameter (η) can also be obtained and that it should be possible to relate the distributions in Q_cc and η to distributions in bond angles and bond lengths in the glasses.     

Ion transport pathways in molecular dynamics simulated alkali silicate glassy electrolytes

The xM₂O-(1 − x)SiO₂ (M = Li, Na, and K, and 0.1 ≤ x ≤ 0.5) glass systems have been studied by constant volume molecular dynamics (MD) simulations. The bond valence (BV) method is applied to the equilibrated configurations to analyse the structural variation in these glass systems with increasing network modifier content, its consequence for M⁺ ion mobility, as well as the distribution of bridging and non-bridging oxygen atoms and the variation of the Q_i values. The contribution of non-bridging oxygen atoms to the BV sums exhibits a transition around x = 1/3 for Li₂O and Na₂O doped glasses. The observed Q_i variation is consistent with a bond order model. Despite slight deviations of the interatomic distances in the MD-simulated glasses, their BV analysis reveals characteristic features of the ion transport pathway. For complex disordered systems with low ion mobilities the bond valence analysis of the pathway characteristics for the mobile ion is thus a viable method to extract ion transport properties even if the mobilities are too low to be directly analysed from the mean square displacements over the simulated period.     

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.     

Magnetoelectric and magnetoelastic interactions in NdFe3(BO3)4 multiferroics

Complex experimental and theoretical investigations of the magnetic, magnetoelectric, and magnetoelastic properties of neodymium iron borate NdFe₃(BO₃)₄ along various crystallographic directions have been carried out in strong pulsed magnetic fields up to 230 kOe in a temperature range of 4.2–50 K. It has been found that neodymium iron borate, as well as gadolinium iron borate, is a multiferroic. It has a much larger (above 300 μC/m²) electric polarization controlled by the magnetic field and giant quadratic magnetoelectric effect. The exchange field between the rare-earth and iron subsystems (～50 kOe) has been determined for the first time from experimental data. The theoretical analysis based on the magnetic symmetry and quantum properties of the Nd ion in the crystal provides an explanation of the unusual behavior of the magnetoelectric and magnetoelastic properties of neodymium iron borate in strong magnetic fields and correlation observed between them.     

Barium borate glass and transparent glass ceramics doped with Pb4Lu2YbF17

Barium borate glasses doped with complex Pb₄Lu₂YbF₁₇ fluoride have been synthesized and investigated. Heat treatment produced glass ceramics containing the crystalline BaF₂:Yb³⁺ phase. The changes in the structural and optical properties of the glass ceramics were revealed by X-ray diffraction, Raman spectroscopy, and luminescence spectroscopy of Yb³⁺ ions in polycrystalline Pb₄Lu₂YbF₁₇, initial glass, and glass ceramics.     

Unique optical traits of Sm3+ -doped magnesium borate glass

A series of Sm³⁺-doped magnesium borate glasses were prepared using the melt quenching and characterized to determine the effects of various Sm³⁺ contents on their optical traits. The absorption and luminescence spectra of the glasses revealed ten and four significant peaks, respectively. In addition, the experimental results on the optical properties were validated using the Judd-Ofelt (J−O) analyses. The obtained J−O intensity parameters (Ω_λ with λ = 2, 4, 6) confirmed the structural changes in the host network due to the Sm³⁺ doping. The value of Ω₂ for the studied glasses indicated the covalent and asymmetric nature of the Sm³⁺− O² linkages. The achieved J−O radiative parameters (quality factor, branching ratio and stimulated emission cross-section) were highest for the glass made with 0.5 mol% of Sm³⁺, demonstrating its lasing potency. The proposed glass compositions may be beneficial for the photonic devices.     

Characterization of Tm doped mixed alkali borate glasses—spectroscopic investigations

The effect of mixed alkalis on the optical absorption spectra of Tm³⁺ in xNa₂O·(30−x)K₂O·70B₂O₃ glasses has been studied. The optical band gap values (E_opt) for both direct and indirect transitions have been obtained using Davis and Mott theory. Spectroscopic parameters like Racah (E¹, E² and E³), spin-orbit (ξ_4f) and Judd-Ofelt intensity parameters (, and ) have been calculated for different x values. Radiative transition probabilities (A_rad), radiative lifetimes (τ_R), branching ratios (β), integrated absorption cross sections (Σ) and multiphonon relaxation rates (W_MPR) are calculated for certain excited states of Tm³⁺ ion. The observed trends in the above parameters as a function of x in these borate glasses have been discussed keeping in view the effect of mixed alkalies in borate glasses. Certain potential lasing transitions have been identified for laser action among the various transitions of Tm³⁺ in these mixed alkali borate glasses.     

Absorption and emission properties of Nd in lithium cesium mixed alkali borate glasses

Lithium cesium mixed alkali borate glasses of the composition 67B₂O₃·xLi₂O·(32−x)Cs₂O (where x=8, 12, 16, 20 and 24) containing 1 mol% Nd₂O₃ were prepared by melt quenching. The absorption spectra of Nd³⁺ were studied from the experimental oscillator strengths and the Judd-Ofelt intensity parameters were obtained. The intensity parameters are used to determine the radiative decay rates (emission probabilities of transitions) (A_T), branching ratios (β) and integrated absorption cross-sections (Σ) of the Nd³⁺ transitions from the excited state J manifolds to the lower lying J′ manifolds. Radiative lifetimes (τ_R) are estimated for certain excited states of Nd³⁺ in these mixed alkali borate glasses. Luminescence spectra were measured and the emission cross-sections (σ_p) were evaluated for the three emission transitions. The variation of luminescence intensity with x was recorded for the three transitions at different excitation power to see the effect of mixed alkalies in these borate glasses.     

The influence of CdSe and ZnSe nanoparticles on the optical properties of Sm<Superscript>3+</Superscript> ions in lead borate glasses

The effect of glass composition and the presence of CdSe/ZnSe nanoparticles (NPs) on the optical absorption and fluorescence of Sm-doped lead borate glasses are studied. Three sets of glass samples xPbO:(99.5-x) B₂O₃:0.5Sm₂O₃, x = 29.5–69.5 mol%, xPbO:(96.5-x) B₂O₃:0.5Sm₂O₃: 3CdSe/ZnSe, x = 36.5, and 56.5 mol% are prepared. NPs are grown by annealing these glasses just below the glass transition temperature. Average size of both types of NPs increases with annealing time; however, CdSe NPs grew to a larger size range (2 to 20 nm) compared to ZnSe NPs (1 to 16 nm). We analyzed the hypersensitive transition, intensity parameters, radiative transition probability, stimulated emission cross section (σ_p), and the area ratio of the electric dipole/magnetic dipole transitions of Sm³⁺. The intensity parameters show a minimum at 11 h annealing for 36.5 mol% and a maximum for the same annealing duration in 56.5 mol% PbO containing CdSe NPs. The σ_p for 56.5 mol% of PbO with CdSe NPs is found to be a maximum when the average NP size is around 14 nm. ZnSe NPs containing glasses also show significant changes in σ_p when the average particle size is ~16 nm, for 36.5 mol% PbO. Our results suggest that the optical properties of Sm³⁺ in lead borate glasses are sensitive to its electronic environment which can be modified by varying the base glass composition and/or incorporating large NPs of CdSe/ZnSe. The large σ_p values that we observe for some of the glass compositions make them attractive materials for photonic devices and photovoltaic applications.

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Graphical abstract

     

Using pressure,temperature and frequency as variables to study the dynamics of mobile ions in materials with disordered structures

Complementary ways for studying the motion of mobile ions in materials with disordered structures are obtained by varying pressure, tempe- rature and frequency. New results are presented based on a combination of experimental work and modelling. Pressure-dependent measurements on alkali borate glasses show there is a remarkable difference between the activation volumes for conduction and diffusion, with ΔV_σ< ΔV_D, implying that the Haven ratio decreases with increasing pressure. We propose a mechanism that is characterised by a directionally positive correlation between successive hops of different ions into a moving vacant site. The effect of increasing pressure is to increase the degree of directional correlation and thus to make the conduction pathways increasingly linear in aspect. In sodium borate glasses with much lower sodium content, a maximum has been observed when ionic conductivity is plotted versus temperature at fixed frequency. This feature is identified as being of the nearly constant loss (NCL) type, caused by localised flip-flop movements of interacting charges in the B₂O₃ network. In crystalline γ-RbAg₄I₅, a related localised effect has also been found, in this case caused by activated hops of silver ions confined within structural “pockets”. Finally, the frequency dependence of the ionic conductivity is reviewed in fragile ionic melts. Fragility is interpreted here as a consequence of the shape of the local ionic potentials, which unlike in glass do not reflect the pre-existence of empty cation sites for successive ions to hop into. This difference in short-range, short-time behaviour leads directly to the emergence of non-Arrhenius dc conductivity and fluidity behaviours in molten salts. We are thus able to establish a common phenomenological and theoretical approach to ion transport in a wide range of systems, largely based on broadband conductivity spectroscopy.     

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.     

Structural investigation of bismuth borate glasses under the influence of γ-irradiation through ultrasonic studies

The ultrasonic velocity and attenuation measurements for different compositions of irradiated heavy metal oxide (HMO) borate glasses xBi₂O₃ (1−x) B₂O₃ (where x=0.25, 0.30, 0.35, 0.40, 0.45) has been investigated at room temperature (303 K) using pulse echo overlap method. The elastic moduli, Debye temperature, Poisson's ratio and other acoustical parameters have been obtained from experimental data. Structural changes after irradiation have been investigated by using FTIR spectroscopy and ultrasonic studies. As the changes are strongly dependent on the internal structure of the absorbing substance, in the present investigation ultrasonic velocities before and after γ-irradiation in bismuth borate glasses are measured as a function of composition, from which the structural changes in the network former B₂O₃ and modifier Bi₂O₃ due to irradiation are obtained.