Structure–property correlations in the SiO<Subscript>2</Subscript>–PbO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

SiO₂–PbO–Bi₂O₃ glasses having the composition of 35SiO₂–xPbO–(65−x)Bi₂O₃ (where x = 5, 10, 15, 20, 25, 35, 45; in mol%) have been prepared using the conventional melting and annealing method. Density, molar volume and Vickers microhardness of the prepared glasses were measured. Infrared (IR) and UV–visible spectroscopic techniques were used for structural studies of these glasses. Density as well as the microhardness increase systematically and, conversely, the molar volume decreases with increasing the lead oxide content. This behavior can be explained by the correlation with the glass structure. Increasing the lead oxide content (≥20 mol%) increases the network former PbO₄ groups which can play an important role in increasing the connectivity and compactness of the glass matrix via increasing the cross-linking with the other constituent silicate and bismuthate structural units. The increased compactness may explain, in turn, the increase of the density and microhardness. IR spectra reinforce the idea that bismuth participates in the glassy network predominantly as BiO₆ octahedral structural units. UV–VIS optical absorption spectra revealed UV-charge transfer absorption bands related to the contribution of Pb²⁺ ions in the region 350–385 nm; in addition to the extrinsic absorption of trace iron impurities in the range 220–290 nm. In the visible region, three optical bands in the ranges 415–435, 605–650 and 880–890 nm were correlated with the contribution of electronic transitions in Bi³⁺ ions. Calculation of the optical mobility gap and the width of the energy tail of glass from the UV–VIS absorption indicated a slight increase followed by a decrease in their values. The behavior change occurred at the glass in which PbO content is 20 mol% where lead oxide starts to participate into the glassy matrix as a network former. The combination of analytical FTIR and UV–visible spectroscopy provided a consistent picture of structure–property relations in this glass system.     

Compositional dependence of the structural and dielectric properties of Li<Subscript>2</Subscript>O–GeO<Subscript>2</Subscript>–ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

(10Li₂O–20GeO₂–30ZnO–(40-x)Bi₂O₃–xFe₂O₃ where x = 0.0, 3, 6, and 9 mol%) glasses were prepared. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, DC and AC conductivities, and dielectric properties (constant ε′, loss tan δ, AC conductivity, σ _ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of iron ion concentration. The analysis of the results indicate that, the density and molar volume decrease with an increasing of iron content indicates structural changes of the glass matrix. The glass transition temperature T _g and onset of crystallization temperature T _x increase with the variation of concentration of Fe₂O₃ referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter ΔT decrease with increase Fe₂O₃ content, indicates an increasing concentration of iron ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BiO₃, BiO₆, ZnO₄, GeO₄, and GeO₆. The structural changes observed by varying the Fe₂O₃ content in these glasses and evidenced by FTIR investigation suggest that the iron ions play a network modifier role in these glasses while Bi₂O₃, GeO₂, and ZnO play the role of network formers. The temperature dependence of DC and AC conductivities at different frequencies was analyzed using Mott’s small polaron hopping model and, the high temperature activation energies have been estimated and discussed. The dielectric constant and dielectric loss increased with increase in temperature and Fe₂O₃ content.     

Structural and dielectric properties of Li2O–ZnO–BaO–B2O3–CuO glasses

Glass samples of the system (15Li₂O–30ZnO–10BaO–(45 − x)B₂O₃–xCuO where x = 0, 5, 10 and 15 mol%) were prepared by using the melt quenching technique. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, a.c. conductivity and dielectric properties (constant εφ, loss tan δ, a.c. conductivity, σ_ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of copper ion concentration. The analysis of the results indicate that the density increases while molar volume decreases with increasing of copper content indicates structural changes of the glass matrix. The glass transition temperature, T _g, and crystallization temperature, T _c, increase with the variation of concentration of CuO referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter (T _c − T _g) decreases with increasing CuO content, indicates an increasing concentration of copper ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BO₃, BO₄, and ZnO₄. The structural changes observed by varying the CuO content in these glasses and evidenced by FTIR investigation suggest that the CuO plays a network modifier role in these glasses while ZnO plays the role of network formers. The dielectric constant decreased with increase in temperature and CuO content. The variation of a.c. conductivity with the concentration of CuO passes through a maximum at 5 mol%. In the high temperature region, the a.c. conduction seems to be connected with the mixed conduction viz., electronic conduction and ionic conduction.     

Degradation study on ternary zinc magnesium phosphate glasses

Glasses with composition (ZnO)₃₀(MgO) _x (P₂O₅)_70−x (x = 5, 8, 10, 13, 15, 18, and 20 mol.%) have been successfully prepared by the melt-quenching technique. Degradation study has been carried out by means of measuring their chemical durability against buffer solutions with initial pH values of 4.01, 7.00, and 10.01 at an ambient temperature for up to 30 days. The dissolution rate (D _R) was obtained by calculating the measured weight loss of the glasses per unit surface area per unit immersion time. The results show that the glasses have better corrosion resistance in basic solution. It was also found that the weight loss is related to the MgO concentration with lower P₂O₅ concentration exhibiting greater corrosion resistance irrespective of acidic, neutral, or basic solutions as immersion liquid. All the sample surfaces and edges were corroded and the solutions experienced a decrease in pH values during the duration of the corrosion test.     

Electrical and magnetic properties of copper tellurite glasses

The glasses of composition (100 − x)TeO₂–xCuO (x = 10, 20, 30, 40, 50 mol%) were prepared by melt quenching method. Differential Scanning Calorimetry (DSC), DC conductivity, Electron Spin Resonance (ESR), and magnetization measurements were undertaken on the glass samples. The glass-transition temperature, T _g, decreases and the thermal stability (ΔT = T _o − T _g) increases with the increase in CuO content. The electrical conduction in these glasses is due to polaron hopping mechanism in the adiabatic regime. The ESR spectra of the x = 10 glass consists of a broad symmetrical line characteristic of Cu²⁺ clusters. The ESR signal linewidth increases and intensity decreases drastically with increase in CuO content from 10 to 20 mol%. No ESR signal could be observed for the glass samples with x ≥ 40. The absence of EPR signal is ascribed to antiferromagnetic interactions between the Cu²⁺ clusters. The magnetization measurements indicate all the samples to be in paramagnetic state. The M–H plots show a small hysteresis loop in the low-field region. These studies indicate the coexistence of antiferromagnetic (AFM) as well as ferromagnetic (FM) interactions between Cu ²⁺ ions in these glasses. The significant change in the properties of the glass at x = 20 is ascribed to the structural changes caused by CuO in the glass matrix.     

Structural investigations of some bismuth–borate–vanadate glasses doped with gadolinium ions

X-ray diffraction (XRD), Fourier transform infrared (FTIR) and electron paramagnetic resonance (EPR) spectroscopies have been employed to investigate the xGd₂O₃ · (95 − x)[2Bi₂O₃ · B₂O₃] · 5V₂O₅ glass system, with 0 ≤ x ≤ 25 mol%. The glass samples have been prepared by melting at 1,100 °C for 10 min followed by rapid cooling at room temperature. The structure of samples was analyzed by means of XRD. The pattern obtained did not reveal any crystalline phase in the samples up to 25 mol%. FTIR spectroscopy data suggest that the gadolinium ions play the network modifier role in the studied glasses. These data show that the glass network consists of BiO₃, BiO₆, BO₃, BO₄, and VO₄ structural units. The FTIR data show that a conversion among these units takes place and this process mainly depends on the Gd₂O₃ content. The EPR spectra of the studied glasses exhibit three important features with effective g-values of ≈5.9, 2.85, 2.0 and a weaker feature at g _eff ≈ 4.8. For low Gd₂O₃ contents (x ≤ 10 mol%), the EPR spectra have the typical ‘‘U’’-type shape. For higher contents of Gd₂O₃ (x > 10 mol%), the spectral features are broadened and finally are dominated by a single broad absorption line located at g _eff ≈ 2.0. This broad EPR line is associated to the Gd³⁺ ions present predominantly as clustered species.     

Structure,electrical, and optical properties of ZnO-substituted PbO for the Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> co-doped Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–GeO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O glass system

Glasses of the 0.5Er³⁺/2.5Yb³⁺ co-doped (40Bi₂O₃–20GeO₂–(30 − x)PbO–xZnO–10Na₂O system where x = 0.0, 5, 10, 15, 20, 25, and 30 mol%) have been characterized by FT-IR spectroscopy measurements to obtain information about the influence of ZnO-substituted PbO on the local structure of the glass matrix. The density and the molar volume have been determined. The influences of the ZnO-substituted PbO on the structure of glasses have been discussed. The dc conductivity measured in the temperature range 475–700 K obeys Arrhenius law. The conductivity decreases while the activation energy for conduction increases with increase ZnO content. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range 400–1100 nm. The values of the optical band gap E _opt for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of dielectric constant have been determined.     

Er- and Nd-doped yttrium aluminosilicate glasses: Preparation and characterization

The undoped, and Nd-, Er-doped low silica high alumina yttrium aluminosilicate (YAS) glasses were prepared by flame synthesis in the form of transparent glass microbeads with diameters ranging from a few to several tens of micrometers. The silica content ranged between 5 and 20 mol.%. The prepared glass microbeads were characterized by optical microscopy, SEM XRD, FT-IR and UV–VIS–NIR spectroscopy. The glass forming ability of glasses, expressed in terms of the difference between the glass transition temperature, T_g, and the onset of crystallization, T_x, improved with increasing silica content. Doping of YAS15 glass with neodymium or erbium at the level of 1–5 mol.% leads to decrease of both the T_g and T_x. However, the glass forming ability was not affected. The UV–VIS–NIR reflectance spectra in the spectral range from 300 to 1800 nm shows characteristic absorptions, due to the optically active Nd³⁺ and Er³⁺ ions in the host glass.     

Gadolinium doping of vanadate-tellurate glasses and glass ceramics

In order to further elucidate the local structure of ternary xGd₂O₃(100 − x)[0.7TeO₂ · 0.3V₂O₅] glasses with x = 0, 5, 10, 15, 20 mol%, FTIR spectroscopy, XRD diffraction and density measurement were performed. FTIR and density data show that by increasing the gadolinium ions content of the samples the excess of oxygen may be accommodated by the inter-conversion of some [VO₄] into [VO₅] structural units and of [TeO₃] into [TeO₄] units. The composition of the heat-treated glasses was found to consist mainly of the Te₂V₂O₉ crystalline phase. Varying x between 15 and 20 mol% Gd₂O₃ produces structural modification having as result an increase of the glass network polymerization degree. Accordingly, the gadolinium ions play a particular role related to the improvement of the homogeneity of the glasses and in accommodating the glass network with the excess of oxygen.     

Surface degradation behaviour of sodium borophosphate glass in aqueous media: Some studies

The degradation behaviour of phosphate glass with nominal composition, 40Na₂O-10BaO-xB₂O₃-(50-x)P₂O₅, where 0 ≤ x ≤ 20 mol%, was studied in water, HCl and NaOH solutions at room temperature to 60°C for different periods extending up to 300 h. These glasses were synthesized by conventional melt-quench technique. Dissolution rates were found to increase with B₂O₃ content in the glass. The dissolution rates for the glass having 10 mol% B₂O₃ were found to be 0·002 g/cm² and 0·015 g/cm² in distilled water and 5% NaOH solution, respectively, at room temperature after 225 h of total immersion period, whereas it increased considerably to 0·32 g/cm² in 5% NaOH at 60°C after 225 h. However, glass samples with x = 15 and 20 mol% B₂O₃ were dissolved in 5% HCl solution after 5 h immersion. The degradation behaviour has been correlated with the structural features present in the glass. The optical microscopy of the corroded surface revealed that the corrosion mechanism were different in acid and alkali media.     

The presence of fivefold germanium as a possible transitional phase in the iron–lead–germanate glass system

Glasses in the system xFe₂O₃·(100 − x)[7GeO₂·3PbO] with 0 ≤ x ≤ 60 mol% have been prepared from melt quenching method. In this article, we investigated changes in germanium coordination number in iron–lead–germanate glasses through molar volume analysis, measurements of densities, investigations of FTIR, and UV–VIS spectroscopy. The observations present in these mechanisms show that the lead ions have an affinity pronounced toward [GeO₅] and [FeO₄] structural units with non-bridging oxygens. The excess of oxygen can be supported into the glass network by the formation of [FeO₆] structural units and the apparition of the germanate anomaly. At higher content of iron (III) oxide, the anomaly behavior of the germanium is due to the formations of [FeO₆] structural units. Our results show that the presence of fivefold germanium as a possible transitional phase from four to sixfold germanium it is necessary for the formation of the [FeO₆] structural units and the apparition of the Fe₂O₃ crystalline phase. Pb⁺² ions with 6s² configuration show strong absorption in the ultraviolet due to parity allowed s²-sp transition.     

The improvement of the amorphous environment of the germanate–tellurate glasses in the presence of the gadolinium ions

Glasses in the system xGd₂O₃·(100 − x)[TeO₂·GeO₂] with 0 ≤ x ≤ 50 mol% have been prepared from melt quenching method. In this paper, we investigated changes of the coordination numbers of germanium, tellurium, and gadolinium ions by investigations of FTIR, EPR, and UV–VIS spectroscopy. By analyzing the structural changes resulted from the IR spectra we found that the bending modes of [GeO₄] structural units and the deformed modes of the Te–O–Te linkages produce intercalation of the [GdO _n ] entities in the germanate–tellurate chain network and densification of the glasses by increasing the number of [GeO₆] structural units. EPR spectra of the studied samples reveal that the gadolinium ions play a role of network former. The UV–VIS spectra show broad UV absorption bands located in the 250–350 nm region. Their intensity increase with the increasing of Gd₂O₃ content showing that these stronger transitions can be due to the presence of the O=Ge bonds (n–π* excitations) of [GeO₅] structural units. The [GeO₅] structural units are more stable thermodynamically than their analogues and the [GeO₆] structural units produce the improvement of the amorphous character of these glasses.     

Structural investigation of xFe2O3 · (100 − x)[P2O5 · TeO2] glass system by FT-IR study and EPR spectroscopy

Glasses from xFe₂O₃ · (100 − x)[P₂O₅ · TeO₂] system, with 0 ≤ x ≤ 50 mol%, were investigated by X-ray diffraction, FT-IR and EPR spectroscopies. The XRD patterns show a vitreous state of studied samples for x ≤ 35 mol% Fe₂O₃. The FT-IR spectrum of the P₂O₅ · TeO₂ glass matrix reveals a structure formed from PO₄, TeO₄ and TeO₃ units. The addition and the increasing of Fe₂O₃ content modify progressively the structure of the glass matrix. The local structure in the investigated glasses was revealed by means of EPR using Fe³⁺ (3d⁵; ⁶S_5/2) ions as paramagnetic probes. The EPR spectra present two resonance absorption lines characteristic to Fe³⁺ ions centred at g_eff ≈ 2.0, for 0.5 ≤ x ≤ 35 mol% and g_eff ≈ 4.3, for 0.5 ≤ x ≤ 5 mol%. The variation of the EPR parameters, the intensity and line-width of these absorption lines, with iron ions composition has been followed.     

Raman spectroscopic investigation of sodium borosilicate glass structure

Raman spectra of sodium borosilicate glasses with a wide range of Na₂O/B₂O₃ ratios were systematically measured. Variations of the spectra with glass composition were studied to interpret the implied distribution of Na⁺ ions between silicate and borate units. When Na₂O/B₂O₃ is less than 1, all Na⁺ ions are associated with borate units as indicated by the absence of the 1100 cm⁻¹ band of Si-O⁻ non-bridging bond stretching. For the (1−x)Na₂O · SiO₂ ·xB₂O₃ glass withx≦0.4 the peak-height ratio of the 950 cm⁻¹ band to the 1080 cm⁻¹ band was used to analyse semiquantitatively the distribution of the Na⁺ ions between silicate and borate units. Sodium ions are divided between silicate and borate units approximately in proportion to the amount of SiO₂ and B₂O₃ present in these glasses. Some of the high sodium content glasses were crystallized and their spectra were compared with the bulk glass spectra. The distribution of Na⁺ ions in the glass was quite different from their distribution after crystallization. Spectra of high silica glasses that had been heat-treated for phase separation indicated exclusion of borate units from the silica network and the formation of borate groups. For high boron content glasses, no change was observed on heat treatment. Raman bands due to borate groups seem to be little affected by their environments. Also affiliated with the Department of Geosciences.     

Preparation and studies of some thermal,mechanical and optical properties of<Emphasis Type="Italic">x</Emphasis>Al<Subscript>2</Subscript>O<Subscript>3</Subscript>(1 −<Emphasis Type="Italic">x</Emphasis>)NaPO<Subscript>3</Subscript> glass system

Sodium aluminophosphate glasses having compositions of xAl₂O₃(1-x)NaPO3 (x = 0.05-0.2) were prepared using conventional melt-quench technique. Density, glass transition temperature, microhardness (MH), thermal expansion coefficient (TEC) and transmission characteristics were measured as a function of alumina content for different samples. They were found to depend on O/P ratio with pronounced changes taking place for O/P ratio ≥3.5. Density, glass transition temperature and microhardness were found to increase up to 15 mol% of alumina and then they showed a decreasing trend. Thermal expansion coefficient decreased continuously with alumina content. Optical gaps for different glass samples as measured from transmission characteristics were found to be in the range 3.13–3.51 eV. It initially decreased with alumina content up to 15 mol% and then increased. The behaviour was explained on the basis of change in the average aluminum coordination number from six Al(6) to four Al(4) (i.e. Al(OP)₆/Al(OP)₄ ratio) along with the changes in polyhedra linkages in the glass network due to change in O/P ratio.     

Glasses formation,characterization, and crystal-structure determination in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–TeO<Subscript>2</Subscript> system prepared in an air

A glass-forming domain is found and studied within Bi₂O₃–Sb₂O₃–TeO₂ system. The glasses composition were obtained in pseudo-binary xSbO_1.5, (1−x)TeO₂ for 0.05 ≤ x ≤ 0.20. The constitution of glasses in the system Sb₂O₃–TeO₂ was investigated by DSC, Raman, and Infrared spectroscopy. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated based Infrared and Raman studies and showed the transition of TeO₄, TeO₃₊₁, and TeO₃ units with increasing Sb₂O₃ content. XRD results reveal the presence of three crystalline: γ-TeO₂, α-TeO₂, and SbTe₃O₈ phases during the crystallization process. The density of glasses has been measured. The investigation in the ternary system by the solid state reaction using XRD reveals the existence of a solid solution Bi_1−x Sb_1−x Te_2x O₄ isotopic to BiSbO₄ with 0 ≤ x ≤ 0.1.     

Structural transformations in amorphous As x Se1−x (0 ≤ x ≤ 0.20) films

Structural transformations are examined by the employment of Raman scattering measurements for amorphous Se-rich As _x Se_1−x (0 ≤ x ≤ 0.2) alloys. It is found that the molecular structure of amorphous Se (a-Se) on the scale of medium-range order differs from the structure of most inorganic glasses and may be placed between 3-dimensional network glasses and polymeric ones. Further experiments show the existence of successive phases in laser-induced glass—crystalline transition with pronounced threshold behavior. By comparing peak width, peak location and Raman intensity in the range of bond modes it is derived that the changes occur not monotonically with increasing As content. The composition-induced changes of the spectra are explained by cross-linking of Se chains. Under laser irradiation, the changes in the optical transmission, holographic recording properties and Raman spectra of amorphous As _x Se_1−x films with 0 < x ≤ 0.2 have been examined. The dependence of the transmissivity and diffraction efficiency on the irradiation energy density shows two qualitatively different regions. Below the energy density threshold, E _th, only small changes in the local structure of the system can be detected. In the low-energy region, transient changes in transmissivity are observed. Qualitative explanation of this behavior may be based on associating such with alternating of deep defect states. Above E _th, the changes were attributed to crystallization transformation. The corresponding Raman spectra reveal transformation of the system from amorphous into the crystalline phase under laser irradiation. Although several articles and texts have provided reviews on various properties and applications of chalcogenide glasses, there is no thorough study of local atomic structure and its modification for Se-rich amorphous As _x Se_1−x . The present paper is concerned with this problem.     

Structural and electrical properties of fritless Ni(1?x)CuxMn2O4 (0?≤?x?≤?1) thick film NTC ceramic

Spinel structured NTC thermistor Ni_(1−x)Cu _x Mn₂O₄ (0 ≤ x ≤ 1) ceramics was prepared by oxalic precursor method and fritless thick films screen printed on alumina. The composition dependent structural and electrical properties are reported in this paper. The results show that with increasing copper ion substitution both Cu²⁺ and Mn⁴⁺ predominantly occupy the octahedral site. The concentration of Cu²⁺ ions in octahedral site increases while that of Ni²⁺ ions decreases linearly. The thick film Ni_(1−x)Cu _x Mn₂O₄ ceramic comply with Arrhenius equation. A thermistor constant of ~1,200 K has been obtained for fritless thick film NTC ceramics using inorganic binders in the RT/90 thermal range.     

Novel structural properties of the lead–vanadate–tellurate glass ceramics

In this paper, we have examined and analyzed the effects of systematic intercalation of the lead ions on vanadate–tellurate glass ceramics with interesting results. The structural properties of the lead–vanadate–tellurate glass ceramics of compositions xPbO·(100 − x)[6TeO₂·4V₂O₅], x = 0 − 100 mol%, are reported for the first time. It has been shown by X-ray diffraction that single-phase homogeneous glasses with a random network structure can be obtained in this system. Among these unconventional lead–vanadate–tellurate glass ceramics, we found that network formers are good host material for lead ions and are capable to intercalate a variety of species such as Te₂V₂ ⁵⁺O₉, Pb₃(V⁵⁺O₄)₂, Pb₂V₂ ⁵⁺O₇, and V₂O₅-rich amorphous phase. On the other hand, these glass ceramics contain V⁴⁺ and V⁵⁺ ions necessary for the electrical conduction. Based on these experimental results, we propose that the V⁴⁺=O bonds are created by two different mechanisms: the first of reduction of V⁵⁺ ions to V⁴⁺ ions and thus of creation of V⁴⁺=O bonds.     

Study of lithium–zinc borophosphate glasses

Mixed lithium–zinc borophosphate glasses were prepared and studied in three compositional series xLi₂O–(50−x)ZnO–50P₂O₅, xLi₂O–(50−x)ZnO–10B₂O₃–40P₂O₅ and xLi₂O–(50−x)ZnO–20B₂O₃–30P₂O₅ with x = 0, 10, 20, 30, 40 and 50 mol% Li₂O. The obtained glasses were characterized by the measurements of the density (ρ), molar volume (V _M), glass transition temperature (T _g) and thermal expansion coefficient (α). For the investigation of structural changes ¹¹B and ³¹P MAS NMR and Raman spectroscopy were applied. The replacement of zinc by lithium in borophosphate glasses slightly decreases V _M and T _g, while α increases. In Li–Zn metaphosphate glasses the compositional dependence of T _g reveals a minimum, while at the borophosphate series T _g decreases monotonously with increasing Li₂O content. Chemical stability of Li–Zn borophosphate glasses is very good for glasses with x = 0–30 mol% Li₂O. Spectral studies showed in the glass series with 10 mol% B₂O₃ only the presence of BO₄ sites. In the glasses with 20 mol% B₂O₃ the presence of BO₃ and two BO₄ sites was revealed in ZnO-rich glasses and only one BO₄ site in Li₂O-rich glasses; the number of BO₃ groups decreases with increasing Li₂O content which is ascribed to the formation of P–O–Zn covalent bonds in ZnO-rich glasses.