Structural and optical properties in gadolinium-aluminum-lead-germanate quaternary glasses

Glasses in the quaternary system 0.05Al₂O₃·0.95[xGd₂O₃·(100-x)(7GeO₂·3PbO)] with 0 ≤ x ≤ 40 mol% have been prepared from melt quenching method. In this paper, we investigated structural and optical properties in gadolinium-alumino-lead-germanate glasses through investigations of FTIR (Fourier-Transform Infrared Spectroscopy) and UV-VIS (Ultra-Violet) spectroscopy.The observations presented in these mechanisms show that by increasing Gd₂O₃ content up to 40 mol%, the glass network modification has taken place mainly in the germanate part, while the excess of oxygen can be accommodated in the host network by the creation of shorter rings of [Ge₂O₇] structural units and the formation of [AlO₄] structural units. The affinity pronounced of the gadolinium cations towards germanate structural units produces the formation of the Gd₂Ge₂O₇ crystalline phase.The UV-VIS spectroscopy data show the charge transfer transitions of Pb^+ 2-O^− 2, Al^+ 3-O^− 2 and Gd^+ 3-O^− 2, respectively. The additional absorption in the range of 300 to 600 nm was attributed to other types of defects such as: non-bridging oxygen ions, change in valency of ions and other color centers.The values of the direct optical band gap of the glasses are determined from the optical absorption spectra. By increasing Gd₂O₃ content in the glass matrix, the optical band gap energy increases indicating changes of the lattice parameters by Gd₂O₃ incorporation.     

Optical and spectroscopic properties of germanotellurite glasses

In this work, new glass compositions in the TeO₂-GeO₂-Nb₂O₅-K₂O system have been prepared and studied. The germanotellurite glasses were prepared by melt-quenching and their density, refractive index and characteristic temperatures have been determined. The structure of these glasses has been studied by infrared and Raman spectroscopies.The progressive replacement of TeO₂ by GeO₂ led to an increase of the glass transition and crystallisation temperatures of the glasses and a simultaneous decrease of their density and refractive index. Typical density and refractive index values of these glasses ranged from 4.98 to 3.85 g cm^− 3 and 2.08 to 1.79, respectively, with increasing GeO₂ content. The infrared spectra are dominated by a band ~ 640 cm^− 1 in the tellurite glass and ~ 800 cm^− 1 in the germanate glass. The Raman spectra of the germanotellurite glasses present an intense boson peak between ~ 34 and 47 cm^− 1, together with high frequency peaks at ~ 670 cm^− 1 and ~ 470 cm^− 1 for high tellurite and high germanate glass compositions, respectively. The vibrational spectra of these germanotellurite glasses indicate that the glass network consists basically of TeO₄ and [TeO₃]/[TeO_3 + 1] units, mixed with GeO₄ and NbO₆ polyhedra.     

UV-visible and infrared absorption spectra of gamma irradiated V2O5-doped in sodium phosphate, lead phosphate, zinc phosphate glasses: A comparative study

Radiation-induced defects generated by successive gamma irradiation have been investigated in V₂O₅-doped phosphate glasses of three basic compositions, namely, sodium metaphosphate, lead metaphosphate and zinc metaphosphate. Glasses were prepared from chemically pure materials. Melting was carried at 900°-1100 °C for 1 h and with several stirrings of the melt to achieve homogeneity. The glassy samples were annealed at 200°-250 °C and left to cool to room temperature at a rate of 20 °C/h. Polished samples from undoped and V-doped samples of equal thickness. ~ 2 mm were measured in a double beam UV-visible spectrophotometer at 200-1000 nm before and after gamma irradiation. Induced defects were analyzed for these three phosphate glass systems. Infrared absorption spectra were measured for the prepared undoped and V-doped samples by the KBr technique before irradiation and after being subjected to a high dose of 7 M Rads (7 × 10⁴ Gy). The cumulative effects of gamma irradiation on the UV-visible spectra are correlated with the intrinsic and extrinsic defects within the various three glasses. Some shielding behavior for the various glasses towards successive gamma irradiation are observed and realized in relation to the different partner anions studied. The effect of gamma irradiation on IR spectra indicates the persistence of the main characteristic bands due to phosphate network and the minor changes are correlated with the possible changes in the bond lengths and/or bond angles of the building units during the irradiation process. The effect of V₂O₅ on the IR spectra is correlated with the depolymerization effect of the glass network.     

A multinuclear NMR study of sodium-borovanadophosphate glasses

xNaVO₃ · yNaPO₃ · (1 − y)NaBO₂ glasses were prepared where x = 0.0, 0.05, 0.5 and 0 ? y ? 1. These glasses have been investigated with multinuclear MAS NMR. ⁵¹V NMR spectra show that two vanadate configurations are possible, assigned as four and five coordinated vanadium. The concentration of the latter group decreases upon addition of sodium-borate. The presence of four and three coordinated boron sites can be deduced from the ¹¹B NMR spectra. The latter boron sites appear only when borate groups are connected to each other. ³¹P NMR spectra of borophosphates and borovanadophosphates show that the ratio of pyro- and metaphosphates is greater in the glasses containing vanadate than in simple borophosphates. These results indicate phosphate to be the most acidic agent and therefore the best chain-terminating group in these glasses.     

On the structure of phosphosilicate glasses

Vibrational spectra of phosphosilicate glasses with P₂O₅ concentrations up to 15 mol% are investigated by the methods of Raman spectroscopy and quantum-chemical modeling. We have found that the Raman band at 1320 cm⁻¹ characteristic for such glasses is not simple and may be decomposed into two components with frequencies at ≈1317 and ≈1330 cm⁻¹ caused in our opinion by single phosphorus centers (OPO₃ tetrahedra surrounded by SiO₄ ones) and by double phosphorus centers (pairs of OPO₃ tetrahedra bonded by a common oxygen atom). In the investigated phosphosilicate glasses manufactured by MCVD and SPCVD methods the ratio of concentrations of single and double centers varies from 1:5 to 1:2. A novel interpretation of the Raman bands distinct from the traditional one is suggested. The approach to the Raman spectra analysis developed in this article can be applied for control and optimization of manufacturing process of phosphosilicate and similar glasses as well as optical fibers.     

Computational and Raman studies of phospho-tellurite glasses as ultrabroad Raman gain media

Molecular orbital calculations of two phospho-tellurite model clusters were performed to clarify the origins of the Raman bands in the Stokes region of over 1000 cm^− 1 in phospho-tellurite glasses. The Raman bands could be attributed to two components of 900-1050 cm^− 1 of symmetrical stretching vibrations of PO₄ units and 1050-1200 cm^− 1 of anti-symmetrical stretching vibrations of PO₄ units. It was also clarified that the top of the valence band of phospho-tellurite glasses consists of the lone pair electrons in a TeO_4 + 1 unit and the bottom of the conduction band of the glass consists of the antibonding hybrids of Te 5p and O 2p orbitals in the equatorial plane of a TeO₄ unit.We have developed new phospho-tellurite glasses which have the Raman gain peak of 30 times as large as silica glass or the Raman gain bandwidth of more than 1200 cm^− 1.     

Structural changes during the crystallization of the Bi4Ge3O12 glasses

Bismuth-germanate glass ceramics with the composition 40% Bi₂O₃-60% GeO₂ (in molar percents) were prepared through controlled crystallization of melt-quenched glass. The Raman and FTIR spectra recorded in the as-made glasses show broad bands at 240, 400, 780 cm^− 1 and 400, 745 cm^− 1 have been assigned Ge-O bonds which appear right after preparation. X-ray diffraction has shown that the as-made glasses are amorphous, but after annealing above the crystallization temperature at 558 °C, BGO nano-crystallites with a size of about 50 nm precipitate in the glass matrix. The Raman and FTIR spectra reveal sharp peaks associated to the “internal” and “external vibrations” of GeO₄ tetrahedral groups inside the BGO nano-crystallites. In the glass ceramic sample the transparency region is shifted at longer wavelengths compared to as-made glass, due to the Rayleigh scattering on the BGO nano-crystallites.     

Short-range order evolution in S-rich Ge-S glasses by X-ray photoelectron spectroscopy

The structure of binary Ge_xS_100 − x chalcogenide glasses (10 < x < 30) is determined by high-resolution X-ray photoelectron spectroscopy (XPS). On the basis of compositional dependence of fitting parameters for Ge and S core level XPS spectra, the ratio between edge- and corner-shared tetrahedra is determined. It is shown that short-range order of these glasses includes fragments of high-temperature crystalline form of GeS₂. When subjected to X-irradiation, the structure of investigated glasses appears to become more homogeneous than that of the as-prepared samples.     

Effect of electron irradiation on Na-K silicate glass investigated using X-ray photoelectron spectroscopy and pattern recognition method

Alkali silicate glasses and melts play an important role in material science. Electron interaction with glasses is important for radioactive waste deposition, where electrons of various energies lead to irreversible changes. These changes are caused mainly by ionization and ballistic interaction of electrons with atoms, introducing structural disorder, changes in atomic composition and chemical state, accompanied by alkali ions diffusion. The Na-K silicate glass (5Na₂O · 10K₂O · 85SiO₂), pristine and electron irradiated (doses from 25 C m⁻² to 20 236 C m⁻²) are investigated using X-ray photoelectron spectroscopy (XPS) and the pattern recognition (PR) and fitting procedures. Changes of composition and chemical state of atoms dependent on electron dose are analyzed. At low doses (100-300 C m⁻²), decrease followed by increase of O and Si concentrations was observed. Surface segregation, probable desorption, and in-bulk diffusion of K and Na ions (doses of about 50 C m⁻² and 2000 C m⁻², respectively) were observed. This was accompanied by changes in the chemical state of K atom, where with an electron dose increasing content of elemental K form accompanied by decreasing potassium peroxide form were observed. No difference in chemical state of Si and O atoms was visible under electron irradiation dose to 20 236 C m⁻², within the sensitivity of the applied method.     

Elastic properties and structural studies on lead-boro-vanadate glasses

This paper describes elastic properties and spectroscopic studies on the xPbO-50B₂O₃-(50 - x)V₂O₅ (where x = 20, 25, 30, 35, 40, 45 and 49 mol%) glass system. Elastic moduli and spectroscopic parameters exhibit compositional dependent trends and the existence of characteristic borovanadate groups in these glasses. The bulk modulus and shear modulus increase with the concentration of [BO_4/2]⁻ and [B₂V₂O₉]²⁻ groups, which increases the dimensionality of the network. The scheme of modification of borate and vanadate groups has been explained by considering the Sanderson’s electronegativity principle. Analysis of infrared(IR) and magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectra suggests the presence of characteristic diborovanadate groups also in these glasses. The results are examined in view of the structural groups formed due to the presence of PbO as a modifier.     

Effect of boron addition on the structure and properties of iron phosphate glasses

Effects of boron addition on the glass forming characteristics, structure and properties of iron phosphate glasses with nominal compositions of xB₂O₃-(40−x)Fe₂O₃-60P₂O₅ (x = 2-20, mol%) and xB₂O₃-(100−x)[Fe₂O₃-60P₂O₅] (x = 2-20, mol%) have been investigated by DTA, XRD, IR and Mössbauer spectroscopy. Although there were some weak local surface crystallizations on especially most of the glasses in group B, all of the compositions formed glass. DTA spectra showed two exothermic peaks corresponding to crystallizations along with an endothermic glass transition peak. T_g increased with increasing B₂O₃ content for the glasses in the first series which indicates that the addition of B₂O₃ increases the thermal stability of glasses in this series while the opposite is observed in the second series. The dissolution rates of boron containing bulk glasses were found to be around 10⁻⁹ gr/cm² min which are comparable to that of the base iron phosphate glass. When the B₂O₃ content was above 14%, new bands related to BO₄ tetrahedral groups have been observed in the IR spectra. The Mössbauer isomer shift values of boron doped glasses were found to be a little lower than that of base glass but both iron ions had distorted octahedral coordination in all glasses. The fraction of Fe²⁺ ions in glasses (Fe²⁺/∑(Fe²⁺ + Fe³⁺)) was found to be 23% for the base glass while it was 10-22% for the boron doped glasses.     

Effect of P2O5 content in two series of soda lime phosphosilicate glasses on structure and properties - Part I: NMR

The effect of the variation in phosphate (P₂O₅) content on the structure of two series of bioactive glasses in the quaternary system SiO₂-Na₂O-CaO-P₂O₅ was studied. The first series (I) was a simple substitution of P₂O₅ for SiO₂ keeping the Na₂O:CaO ratio fixed (1.00:0.87). The second series was designed to ensure charge neutrality in the orthophosphate , therefore as P₂O₅ was added the Na₂O and CaO content was varied to provide sufficient Na⁺ and Ca²⁺ cations to charge balance the orthophosphate present. The glass network connectivity (NC) was calculated for each glass and a modification for the presence of a separate P₂O₅ phase was included (NC′). ³¹P and ²⁹Si magic-angle-spinning nuclear magnetic resonance (MAS-NMR) spectroscopy was performed on glass series I and II to determine the structural units present and their relation to glass properties. ³¹P MAS-NMR spectra of series I resulted in a broad resonance around 9 ppm corresponding to orthophosphate in an amorphous environment. The 9.25 mol% P₂O₅ glass shown to be partially crystalline by X-ray diffraction was heat treated, and the ³¹P MAS-NMR spectrum showed a sharp peak around 3 ppm corresponding to calcium orthophosphate or sodium pyrophosphate and overlapping broader peaks at 8.5, 10.5 and 14 ppm possibly corresponding to two mixed calcium-sodium orthophosphate phases and amorphous sodium orthophosphate respectively. ³¹P MAS-NMR spectra of series II resulted in a broad resonance around 10.5 ppm corresponding to orthophosphate in an amorphous environment. ²⁹Si MAS-NMR spectra of glasses from series I showed a shift in the resonance peak from around −78 to −86 ppm indicating an increase in Q³ species in the glass and a reduction in Q² with phosphate addition confirming the presence of orthophosphate. The heat treated sample showed a sharp ²⁹Si-NMR resonance at −88 ppm, indicating a crystalline Q² six-membered combeite (Na₂O · 2CaO · 3SiO₂) silicate-type phase, which was confirmed by powder X-ray diffraction. ²⁹Si MAS-NMR spectra of glasses from series II showed no shift in the resonance at around −78 ppm across the series, confirming an orthophosphate environment.     

The glass transition temperature and infrared absorption spectra of: (70−x)TeO2 + 15B2O3 + 15P2O5 + xLi2O glasses

Glasses of the system: (70−x) TeO₂ + 15B₂O₃ + 15P₂O₅ + xLi₂O, where x = 5, 10, 15, 20, 25 and 30 mol% were prepared by melt quench technique. Dependencies of their glass transition temperatures (T_g) and infrared (IR) absorption spectra on composition were investigated. It is found that the gradual replacement of oxides, TeO₂ by Li₂O, decreases the glass transition temperature and increases the fragility of the glasses. Also, IR spectra revealed broad weak and strong absorption bands in the investigated range of wave numbers from 4000 to 400 cm⁻¹. These bands were assigned to their corresponding bond modes of vibration with relation to the glass structure.     

Bridging, non-bridging and free (O) oxygen in Na2O-SiO2 glasses: An X-ray Photoelectron Spectroscopic (XPS) and Nuclear Magnetic Resonance (NMR) study

High resolution Na 1s, O 1s and Si 2p core level XPS spectra of six Na₂O-SiO₂ glasses ranging in composition from 100 to 45 mol % SiO₂ have been collected using the Kratos Ultra Axis instrument with its unique charge compensation system. The O 1s spectra for the glasses are well resolved so that bridging oxygen (BO, Si-O-Si) and non-bridging oxygen (NBO, Na-O-Si) signals can be accurately fitted and quantified without resorting to constraints or assumptions. The same samples were analysed by ²⁹Si MAS NMR to obtain Q-species abundances from which BO and NBO proportions were calculated. Similar BO:NBO ratios were obtained by both methods over the entire compositional range studied. They are also consistent with most previous XPS and NMR results for glasses containing more than ~ 65 mol % SiO₂. Our XPS and NMR experimental results, however, differ somewhat from previously published XPS and NMR results for glasses containing less than about 65 mol % SiO₂.Na is mobile in the X-ray beam and mobility causes BO:NBO ratios to increase with time of exposure. Na mobility here has been circumvented to yield reliable BO:NBO ratios of the glasses. The ratios are lower than previously reported in XPS studies and are similar to ratios obtained from our ²⁹Si MAS NMR results on the same glasses. The XPS and ²⁹Si MAS NMR results also indicate the presence of a third oxygen species in sodic glasses. As has been proposed for CaSiO₃ glass and for sodic and potassic glasses containing La, we suggest that O²⁻ is present in sodic glasses at small concentrations. The O²⁻ content correlates with increased soda content and may be associated with, and instrumental in development of, three dimensional percolation channels in the glasses. The XPS O 1s line width of the BO peak is broader than the NBO peak, indicating more than one contribution to the BO peak. As observed in crystalline Na metasilicate and Na disilicate, BO of Na-silicate glasses may be of two types, one arising from BO bridging two Si atoms, and the second BO signal arising from BO bonded not only to two Si atoms but also to Na.     

Structural characterization of ionomer glasses by multinuclear solid state MAS-NMR spectroscopy

In the present study we report the results of ²⁹Si, ²⁷Al, ³¹P and ¹⁹F magic angle spinning nuclear magnetic resonance spectroscopy (MAS-NMR) of 4.5SiO₂-3Al₂O₃-1.5P₂O₅-(5−z)CaO-zCaF₂ glasses with z = 0-3 to elucidate the effect of fluoride content on the glass structure. The ²⁹Si MAS-NMR spectra gave a chemical shift of about −90 ppm corresponding to Q³(3Al) and Q⁴(3Al). The ²⁷Al MAS-NMR showed a large broad central peak around 50 ppm, which is assigned to four-coordinated Al linked via oxygen to P. A shoulder around 30 ppm and a small peak at about 0 to −10 ppm appeared in the ²⁷Al MAS-NMR spectra of the glasses on increasing the fluoride content assigned to five-coordinated and six-coordinated Al species, respectively. The ³¹P MAS-NMR spectra indicated the presence of Al-O-P bonds. The ³¹P chemical shift decreased with increasing fluoride content as a result of calcium being complexed with fluoride. This resulted in a reduction of the number of available cations to charge balance non bridging oxygens in phosphorus and an increase in the number of Al-O-P bonds being formed, instead. The ¹⁹F spectra indicated the presence of Al-F-Ca(n) and F-Ca(n) species in all the glasses containing fluoride as well as an additional Si-F-Ca(n) species in the glasses with higher fluoride content.     

Spectroscopic studies of lead arsenate glasses doped with nickel oxide

Lead arsenate glasses containing different concentrations of NiO ranging from 0 to 1 mol% (in steps of 0.2 mol%) were prepared. The samples were characterized by X-ray diffraction and differential thermal analysis. A number of studies viz., optical absorption, thermoluminescence, magnetic susceptibilities and IR spectra, have been carried out on these glasses. The bands observed in the optical absorption spectra of the glasses have been analyzed using Tanabe-Sugano diagrams for d⁸ ion; the analysis indicates the presence of Ni²⁺ ions in both tetrahedral and octahedral positions. The increase in the concentration of NiO in the glass matrix shows a gradual transformation of nickel ions from tetrahedral positions to octahedral positions in the glass network. The thermoluminescence light output of the X-ray irradiated glasses has exhibited a glow peak at 353 K (with increasing intensity with an increase in the concentration of NiO) in addition to the conventional peak due to the recombination of electron-hole centers; this glow peak is identified due to ³T₂ → ³A₂ emission transition of octahedral Ni²⁺ ions. The value of the magnetic moment evaluated from the measured magnetic susceptibility show a decreasing trend from 3.84 to 3.10 μ_B with the increase in the concentration of NiO. All these studies indicate an increasing presence of octahedral (lasing) Ni²⁺ ions in these glasses with the increase in the concentration of NiO.     

Structural investigation of sodium borate glasses and melts by Raman spectroscopy. III. Relation between the rearrangement of super-structures and the properties of glass

The structure of the intermediate range order (IRO) of sodium borate glasses and melts were quantitatively investigated by the analysis of high-temperature Raman scattering spectra. Raman bands at the middle frequency region of 700-950 cm⁻¹ were normalized using the bands at high frequency spectra and their intensities were compared among the spectra collected from the melts with different composition at various temperature. Bands at 805, 780, 750 and 720 cm⁻¹ were focused and their intensity changes were quantified. The exceeds of temperature over the glass transition temperature did not necessarily cause the decrease of all the band intensities. At Na₂O<15 mol%, 805 cm⁻¹ band was the most sensitive to temperature, while at 15<Na₂O<30, it was switched to 780 cm⁻¹ band and 805 cm⁻¹ band became insensitive. When Na₂O concentration exceeded 30 mol%, 750 and 720 cm⁻¹ bands were decreased with temperature. Accompanying the previous analysis on the structures of short range-order (SRO) of boron atoms [J. Non-Cryst. Solids, in this issue], some models of the structural rearrangement along with temperature were proposed. The combination of the obtained structural informations of IRO and SRO was found to explain the mechanisms causing various characteristic properties of borate glasses and melts, especially immiscibility and boron oxide anomaly of thermal expansion coefficient from the microscopic and dynamic points of view of the vitrification process in melt.     

Theoretical studies of the spin Hamiltonian parameters and the local structures for the tetragonal Cu centers in the LKB glasses

The spin Hamiltonian parameters (g factors g_∥, g_⊥ and the hyperfine structure constants A_∥, A_⊥) for the Cu²⁺ centers in the lithium potassium borate (LKB) glasses xLi₂O·(30 − x)·K₂O·70B₂O₃ (0 ≤ x ≤ 25) were theoretically studied using the high-order perturbation formulas of these parameters for a 3d⁹ ion in a tetragonally elongated octahedron. The [CuO₆]¹⁰⁻ clusters in the LKB glasses are found to suffer the relative elongations of about 3% along the tetragonal axis due to the Jahn-Teller effect. The concentration dependences of the g factors are illustrated by the approximately linear decrease of the cubic field parameter Dq as well as the increases of the covalency factor N and the relative elongation ratio ρ due to the slight expansion of the cell volume or bond lengths with increasing the Li₂O concentration x. Meanwhile, the slow non-linear increases of the hyperfine structure constants are described as the rough exponential increase of the core polarization constant κ with x due to the increase of the tetragonality of the systems. The theoretical spin Hamiltonian parameters and their concentration dependences show good agreement with the experimental data. To evaluate validity and applicability of the present theoretical model and formulas, the EPR results of the Cu²⁺ centers in similar lithium sodium borate (LNB) xLi₂O·(30 − x)·Na₂O·70B₂O₃ (5 ≤ x ≤ 25 mol%) glasses are also analyzed and compared with those in the LKB systems using the uniform model and formulas.     

Determination of sulfur environments in borosilicate waste glasses using X-ray absorption near-edge spectroscopy

Sulfur can be the waste-loading limiting constituent for vitrification of sulfur-bearing radioactive wastes due to low solubility in silicate melts. Methods to improve sulfur loading would benefit from improved understanding of the structural aspects of sulfur incorporation in borosilicate and other glasses. To this end, sulfur XANES spectra were collected for eight crystalline standards and twenty-four glasses, including borosilicate, phosphate, and borate compositions. Spectra for the standards show a systematic energy shift of the sulfur K-edge from 2469 to 2482 eV, as sulfur valence increases from 2− (in sulfides) to 6+ (in sulfates). Most crucible glasses investigated have simple edges near 2482 eV that indicate sulfur in the form of sulfate only. Other glasses, some synthesized under reducing conditions, have complicated edges, indicating sulfate, sulfite, and more reduced species that may include S, S-S doublets, or short polysulfide chains. Sulfide species (S²⁻) were not dominant in any of the samples over the range of redox conditions investigated. These results indicate that sulfur incorporation is considerably more complex than would be suggested by the conventional interpretation of the redox-dependence of sulfur solubility, which considers only sulfate and sulfide species. Raman data indicate that several of the glasses investigated are not homogeneous with regard to all sulfur species.     

Correlation between physical and structural properties of Co doped mixed alkali zinc borate glasses

The physical and structural properties of Co²⁺ doped 20ZnO + xLi₂O + (30 − x)Na₂O + 50B₂O₃ (5 ≤ × ≤ 25) (ZLNB) glasses have been studied and correlated. The physical and structural parameters of all the glasses are evaluated and a non-linear behavior is observed. No sharp peaks are observed in XRD patterns of the glass samples which confirm the amorphous nature. FT-IR spectra of ZLNB glasses reveal diborate units in borate network. The optical absorption spectra suggest the site symmetry of Co²⁺ in the glasses is near octahedral. Crystal field and inter-electronic repulsion parameters are also evaluated. The optical band gap and Urbach energies exhibit the mixed alkali effect. All the samples are found to be strong and stable in structure with low values of Urbach energy which lie between 0.027 eV and 0.039 eV. The correlation between densities and Urbach energies of Co²⁺ doped ZLNB glasses with respect to Li₂O content suggest a changeover conduction mechanism from electronic to ionic, with a diffusivity crossover point at x = 15 mol%.