Investigation of vanadium–sodium silicate glasses using XANES spectroscopy

X-ray absorption near edge structure spectroscopy has been used to investigate the electronic and atomic structure of (V₂O₅)_x(Na₂O)_0.30(SiO₂)_0.70−x (x < 0.1) glasses obtained by melt-quench technique. The results show no sign of metallic clustering of V atoms, but mixed oxidation states (+4 and +5) of V and strong V3d–O2p hybridization in the glasses. Detailed analysis has revealed that the glass samples contain about 15% V⁴⁺ and 85% V⁵⁺ and the ligand-field splitting is about 1.6 eV.     

Conductivity and spectroscopic studies of Li<Subscript>2</Subscript>O-V<Subscript>2</Subscript>O<Subscript>5</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

Lithium vanadium-borate glasses with the composition of 0.3Li₂O–(0.7-x)B₂O₃–xV₂O₅ (x?=?0.3, 0.325, 0.35, 0.375, 0.4, 0.425, 0.45, and 0.475) were prepared by melt-quenching method. According to differential scanning calorimetry data, vanadium oxide acts as both glass former and glass modifier, since the thermal stability of glasses decreases with an increase in V₂O₅ concentration. Fourier transform infrared spectroscopy data show that the vibrations of [VO₄] structural units occur at V₂O₅ concentration of 45 mol%. It is established that the concentration of V⁴⁺ ions increases exponentially with the growth of vanadium oxide concentration. Direct and alternative current measurements are carried out to estimate the contribution both electronic and ionic conductivities to the value of total conductivity. It is shown that the electronic conductivity is predominant in the total one. The glass having the composition of 0.3Li₂O-0.275B₂O₃-0.475V₂O₅ shows the highest electrical conductivity that has the value of 7.4?×?10^?5 S cm^?1 at room temperature.     

EPR and magnetic susceptibility studies of the interaction between Cu2+ and Mn2+ ions in x(CuO·MnO)(1−x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility experiments have been performed on x(CuO·MnO)(1?x)[2B₂O₃·K₂O] glasses with x varying in the range 0?x?50 mol.%. For x?3 mol.% both Cu²⁺ and Mn²⁺ ions are present mostly as the isolated species. The increase of the g-tensor values and bonding parameters (α², β², δ²) for Cu²⁺ ions together with the increase of TM ions concentration in the 0.2–1 mol.% range was noticed. In the case of 5 ? x ? 30 mol.% the dipole-dipole and superexchange interactions occur between transition metal ions, the first type of interactions prevailing in this range of concentration. For x30 mol.% the superexchange interaction prevail. The strong interaction between Cu²⁺ and Mn²⁺ gives rise to the exchange coupled Cu²⁺Mn²⁺ pairs in the studied glasses with x 3 mol.%.     

Mössbauer spectra and electrical conductivity ofxFe2O3−(40-x)V2O5−60P2O5 glasses

Mössbauer spectra and electrical conductivities were measured for the purpose of studying on the conduction mechanism of xFe₂O₃?(40-x)V₂O₅?60P₂O₅ glasses. The ratios Fe²⁺/Fe²⁺+Fe³⁺ in xFe₂O₃?(40-x)V₂O₅?60P₂O₅ glasses were determined by Mössbauer spectroscopy. On the composition dependence of D. C. conductivities in these glasses, the minimum of log σ at each temperature was obtained at 25Fe₂O₃?15V₂O₅?60P₂O₅. The conductivities of ternary glassses in Fe rich region could be explained only by the changes of carrler (Fe²⁺) concentration and the hopping conduction between Fe²⁺ ions and Fe³⁺ ions in binary glasses. In V rich region, the saturation tendency of D. C. conductivities are observed. It was suggested to be explained by increasing of V⁴⁺ ions due to the influence of Fe ions.     

Effect of Li2O on the structure,electrical and dielectric properties of xLi2O·(20−x)CaO·30P2O5·30V2O5·20Fe2O3 glasses

Glasses of the general formula xLi₂O·(20?x)CaO·30P₂O₅·30V₂O₅·20Fe₂O₃ with x=0, 5, 10, 15 and 20 mol% were prepared; IR, density, electrical and dielectric properties have been investigated. Lithia-containing glasses revealed more (P₂O₇)^4?, FeO₆, V–O^? and PO^? groups and mostly have lower densities than those of lithia-free ones. The electrical properties showed random behavior by replacing Li₂O for CaO, which has been assigned to the change of the glass structure. The results of activation energy and frequency-dependent conductivity indicate that the conduction proceeds via electronic and ionic mechanisms, the former being dominant. The mechanism responsible for the electronic conduction is mostly thermally activated hopping of electrons from Fe(II) ions to neighboring Fe(III) sites and/or from V⁴⁺ to V⁵⁺. The dielectric constant (ε′) showed values that depend on the structure of glass according to its content of Li₂O. The (ε′) values are ranging between 3 and 41 at room temperature for 1 kHz, yet at high temperatures, glass with 20 mol Li₂O exhibits values of 110 and 3600 when measurement was carried out in the range 0.1–1 kHz, and at 5 MHz, respectively.     

Conversion of covalent to ionic character of V2O5–CeO2–PbO–B2O3 glasses for solid state ionic devices

xV₂O₅–xCeO₂–(30−x)PbO–(70−x) B₂O₃ glasses are synthesized by using the melt quench technique. The number of studies such as XRD, density, molar volume, optical band gap, refractive index and FTIR spectroscopy are employed to characterize the glasses. The band gap decreases from 2.20 to 1.78 eV and density increases from 3.49 to 4.25 g/cm³. FTIR spectroscopy reveals that incorporation of V₂O₅ in glass network helps to convert the structural units of [BO₃] into [BO₄]. At higher concentration of vanadium, VO vibration of [VO₅] structural units and V–O–V vibration are present. The bond ionicity of glasses increases with incorporation of V₂O₅ contents.     

Photoluminescence and decay behavior of Tb3+ ions in sodium fluoro-borate glasses for display devices

We report the optical absorption, photoluminescence and fluorescence decay properties of Tb³⁺-doped sodium fluoro-borate (SFB) glasses. Different concentrations of Tb³⁺-doped SFB glasses were prepared by conventional melt quenching technique using a chemical composition (in mol%) 25Na₂O–5LaF₃–10CaF₂–10AlF₃–(50?x) B₂O₃?x TbF₃ (0.01≤x≥4). The Judd-Ofelt model has been adopted to determine the radiative parameters of the ⁵D₄→⁷F_6–3 emission transitions. The effect of Tb³⁺ ion concentration on the emission from the ⁵D_3,4 excited levels is discussed in detail. The analysis of optimization of Tb³⁺ ion concentration for efficient green color display devises is reported. The resonance energy transfer mechanism responsible for non-radiative decay rates is clearly explored.     

The valence states of manganese ion in potassium-borate oxide glasses

EPR and magnetic susceptibility measurements have been performed on xMnO·(1-x) [2B₂O₃·K₂O] with 0?x?50 mol %. The X-ray diffraction analysis showed that in this glass system homogeneous glasses are formed up to x = 70 mol %.EPR and magnetic susceptibility data have shown that in the glasses with x ? 5 mol % only Mn²⁺ ions are present as magnetically isolated species. EPR spectra are modified with the increasing of manganese ions content. In the concentration range 0.5 ? x ? 5 mol %, the spectra are characterized by appearance of three resonance absorptions at g ? 4.3 and g ? 3.3 without hyperfine structure, and at g ? 2.0 with hyperfine structure. For the glasses with x >62; 5 mol %, the resonance spectra are characterized by the appearance of the broad line at g ? 2, characteristic for clustered ions. The magnetic susceptibility data suggest the appearance of superexchange interactions for x >62; 5 mol %. From Curie constant values and qualitative chemical analysis we have established that in the glasses with x ? 10 mol % both, Mn²⁺ and Mn³⁺ ions are present.     

EPR study of the impurity paramagnetic centres in (CaO−Ga2O3−GeO2) glasses

The X-band EPR spectra of Cr³⁺, Mn²⁺, and Fe³⁺ impurity ions in glasses of (CaO?Ga₂O₃?GeO₂) system are investigated in the 77÷300 K temperature range. The experimental data analysis yields the following results: (i) Impurity chromium ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glasses network in Cr³⁺ (3d³,⁴F_3/2) paramagnetic valence state only and occupy the strong distorted oxygen coordinated octahedral sites. (ii) For all activated and non-activated (CaO?Ga₂O₃?GeO₂) glasses the iron impurity is present at concentration roughly 0.01 wt.%. Isotropic EPR signals atg _eff=4.29 andg _eff=2.00 are assigned to Fe³⁺ (3d⁵,⁶S_5/2) ions in the sites with strong rhombic distortion and in the sites with nearly cubic symmetry respectively. (iii) The manganese EPR spectrum in (CaO?Ga₂O₃?GeO₂) glasses is weakly dependent on temperature, doping procedure as well as manganese concentration. EPR spectra of impurity manganese ions in glasses with Ca₃Ga₂Ge₃O₁₂ and Ca₃Ga₂Ge₄O₁₄ compositions are virtually identical and belong to Mn²⁺ (3d⁵,⁶S_5/2) ions. Impurity manganese ions are incorporated into the (CaO?Ga₂O₃?GeO₂) glass network as isolated Mn²⁺ centres and clusters of Mn²⁺ ions.     

Effects of vitrification suppression on structure morphology, conductivity and dielectric properties of vanadium phosphate glasses

Vitrification suppression in the (V₂O₅)_1−x (P₂O₅)_x glasses where x=0.10, 0.15, 0.20, and 0.25 was controlled by changing the rate of quenching glasses. The structure variations occurring in the glasses were detected by differential thermal analysis and optical microscope. The results implied the separation and growth of V₂O₅ orthorhombic microcrystal in the samples with x=0.10 and 0.15 whereas other samples did not illustrate remarkable changes in their microstructure. However, in temperature range between 300 and 473 K a semiconducting behavior for all samples appears during the study of electrical conductivity-temperature dependence. A decrease in conductivity values accompanied with some variations in activation energies by reducing quenching rate was observed. The conductivity results suggested that the conduction occurs by the phonon assisted hopping of a small polaron between V⁴⁺ and V⁵⁺ states at relatively higher temperature range above θ_D/2. Whereas at relatively low temperatures the conduction may occur by electron jumping between filled and empty states at Fermi level in the disordered matrix besides polaronic conduction. Reasonable values for the density of localized states, carrier concentration and carrier mobility were estimated and discussed. Also, dielectric constant and dielectric loss were studied as a function of frequency at different temperatures confirming the structure variations in the glass system.     

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.     

Optical,physical and structural studies of vanadium doped P2O5–BaO–Li2O glasses

Glasses in the compositions (Li₂O)₂₅–(BaO)₂₅–(P₂O₅)_50−x–(V₂O₅)_x (with x=0.5,1.0,1.5,2.0,2.5, and 3.0 mol%) have been prepared by the conventional melt quenching technique. X-ray powder diffractrogram show broad peaks which conforms glassy nature of the sample. Differential scanning calorimetry (DSC) thermograms show characteristic glass transition temperature (T_g) and it increases with increasing substitution of V₂O₅ for P₂O₅. The measured physical parameters like density, refractive index, ionic concentration and electronic polarizability are found to vary linearly with increasing x. Infrared spectra exhibits few bands, which are attributed to (P=O)_AS, (P=O)_S, (V=O), (P–O–P)_AS,P–O–V, (P–O–P)_AS and O–P–O vibrations. The optical absorption spectra of VO²⁺ ions in these glasses show three bands and are assigned to the ²B₂→ ²E,²B₂→ ²B₁ and ²B₂→ ²A₁ transitions. Electron paramagnetic resonance spectra of all the glass samples exhibit resonance signals characteristic of VO²⁺ ions. The values of Spin-Hamiltonian parameters indicate that the VO²⁺ ions are present in octahedral sites with tetragonal compression and belong to C_4V symmetry.     

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.     

Stabilizing the triclinic structure of Mn2V2O7 via isovalent cationic substitution

The thermal expansion of Mn₂V₂O₇ in the temperature range of ?190 to 1030°C is studied. The volumetric thermal expansion coefficients for triclinic (α) and monoclinic (β) modifications are 2.57 × 10^?5 and 3.86 × 10^?5 1/deg, respectively. It is shown that as the Ni²⁺ concentration in Mn_2?2x Ni_2x V₂O₇ rises, the point of the α → β phase transition point moves from room temperature for Mn₂V₂O₇ to 155 ° 5°C for Mn_1.46Ni_0.54V₂O₇ (27 mol % Ni₂V₂O₇).     

EPR and magnetic susceptibility studies of iron ions in ZnO-Fe2O3-SiO2-CaO-P2O5-Na2O glasses

Room temperature electron paramagnetic resonance (EPR) spectra and temperature dependent magnetic susceptibility data have been obtained on bulk x(ZnO,Fe₂O₃)(65−x)SiO₂20(CaO, P₂O₅)15Na₂O (6≤x≤21 mole%) glasses prepared by melt quenching method. EPR spectra of the glasses revealed absorptions centered at g≈2.1 and 4.3. The variations of the intensity and line width of these absorption lines with composition have been interpreted in terms of the variation in the concentration of the Fe²⁺ and Fe³⁺ ions in the glass and the interaction between the iron ions. EPR and magnetic susceptibility data of the glasses reveal that both Fe²⁺ and Fe³⁺ ions are present in the glasses, with their relative concentration being dependent on the glass composition. The studies reveal superexchange type interactions in these glasses, which are strongly dependent on their iron content.     

Asymptotic inverse spectral problem for anharmonic oscillators

We study perturbationsL=A+B of the harmonic oscillatorA=1/2(??²+x ²?1) on ?, when potentialB(x) has a prescribed asymptotics at ∞,B(x)～|x|^?α V(x) with a trigonometric even functionV(x)=Σa _mcosω _m x. The eigenvalues ofL are shown to be λ _k =k+μ _k with small μ _k =O(k ^?γ), γ=1/2+1/4. The main result of the paper is an asymptotic formula for spectral fluctuations {μ _k }, $$\mu _k \sim k^{ - \gamma } \tilde V(\sqrt {2k} ) + c/\sqrt {2k} ask \to \infty ,$$ whose leading term \(\tilde V\) represents the so-called “Radon transform” ofV, $$\tilde V(x) = const\sum {\frac{{a_m }}{{\sqrt {\omega _m } }}\cos (\omega _m x - \pi /4)} .$$ as a consequence we are able to solve explicitly the inverse spectral problem, i.e., recover asymptotic part |x ^?α|V(x) ofB from asymptotics of {µ _k }. ₁ ^∞      

Coordination of Mg2+ in oxide glasses determined by x-Ray emission spectroscopy

Chemical shifts of K_{α 1.2} of Mg²⁺ having octahedral or tetrahedral coordination in several oxide crystals were systematically measured using a high resolution spectrometer of the 2-crystal type. The shift between the emissions from 6- and 4-coordinated Mg²⁺ was small (≈0.25eV), but large enough to be measured, with the peak energy for 6-coordinated Mg²⁺ being higher. The fact is in accordance with the well established relation for Al³⁺. A nearly linear relation was obtained between the shift and Lewis basicity of the oxides. The relation was applied to the determination of the coordination number of Mg²⁺ in borate and silicate glasses. Magnesium in xK₂O·yMgO·(100?x?y)B₂O₃ glasses (x + y?40 mol%) was found to be in 6-coordination, while in the glass 25K₂O·25MgO·50SiO₂ it was found to be in 4-coordination. These results agreed well with expectations from the chemical shift-basicity relationship.     

Electron paramagnetic resonance, optical and electrical properties of vanadyl doped alkali germanoborate glasses

Glasses with composition xGeO₂.(0.30−x)M₂O.0.70B₂O₃ (M=Li, K) containing 2.0 mol% of V₂O₅ have been prepared in the range 0.00≤x≤0.15 by normal melt quenching method. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHPs) of VO²⁺ ions, dipolar hyperfine coupling parameter, P, Fermi contact interaction parameter, K and molecular orbital coefficients (α² and γ²) have been calculated. In GeO₂·Li₂O·B₂O₃ glasses there is no change in the tetragonality of the V⁴⁺O₆ complex and the size of 3d_xy orbit also remains unchanged with increase in GeO₂ content. In GeO₂·K₂O·B₂O₃ glasses, there is an increase in the tetragonality of the V⁴⁺O₆ complex and the 3d_xy orbit expands with increase in GeO₂ content. Values of the theoretical optical basicity, Λ_th, have also been reported. Optical band gap decreases with increase in GeO₂ content. The dc conductivity of these glasses decreases and the activation energy increases with increase in GeO₂:M₂O ratio.     

Activation energy and conductivity of glasses in the P2O5–V2O5–Li2O system

The conductivity of glasses in the 50\textP_\text2 \textO_\text5 - x\textV_\text2 \textO_\text5 - ( 50 - x )\textLi_\text2 \textO50{\text{P}}_{\text{2}} {\text{O}}_{\text{5}} - x{\text{V}}_{\text{2}} {\text{O}}_{\text{5}} - \left( {50 - x} \right){\text{Li}}_{\text{2}} {\text{O}} system was studied as a function of temperature and composition. For all compositions, the conductivity variation as a function of temperature followed an Arrhenius type relationship. Isothermal variation of conductivity as a function of composition showed a minimum for a molar ratio x near 20. Probable mechanisms for decrease of conductivity with decrease of vanadium oxide concentration were explained. The minimum in room temperature was attributed to increase of V⁴⁺/V⁵⁺ with decrease of vanadium oxide in specific concentrations of vanadium oxide. Activation energy increased with decrease of V₂O₅ content. This behavior was attributed to increase of average spacing between vanadium ions.     

Silver phosphovanadte vitreous electrolytes

Glass formation and electrical conductivity studies on the AgI-Ag₂O-[xV₂O₅ + (1-x)P₂O₅], O ⩽ x ⩽ 1, have been carried out. Glass forming region is found to be within 40 and 66.7 m/o AgI. For similar mole fraction of AgI, quaternary glasses show higher conductivities than the individual ternary systems. Glass transition temperature is found to be almost independent of the V₂O₅/P₂O₅ ratio.