Study of Chromium-Lead-Phosphate Glasses by XRD, IR, Density and Chemical Durability

Radouan Makhlouk¹, Nadia Beloued¹, Said Aqdim^1,2*

¹Laboratory of Materials Engineering for Environment and Valorization, Faculty of Sciences, Hassan II University Ain Chock, Casablanca, Morocco.
²Mineral Chemistry Laboratory, Department of Chemistry, Faculty of Science, Hassan II University Ain Chock, Casablanca, Morocco.

DOI: 10.4236/ampc.2018.86018                

Abstract

Glasses in the ternary system Cr₂O₃-PbO-P₂O₅ were prepared by direct melting of the mixture with stoichiometric proportions of the reagents Cr₂O₃, PbO and (NH₄)₂HPO₄ at 1080℃. The glasses obtained are transparent in colour and have a non-hygroscopic appearance. The study of the dissolution rate was carried out on ternary glasses xCr₂O₃-(45-x)PbO-55P₂O₅ with (1 ≤ x ≤ 4; mol%), immersed in distilled water at 90℃ for 24 days, indicating a maximum of chemical durability when the level of chromium oxide passed through 2 mol%. Both, IR spectra and X-ray diffraction have indicated the predominance of metaphosphate or cyclic metaphosphate groups with some traces of isolated orthophosphate groups when the Cr₂O₃ content is equal to x = 2. Analysis of the density values also, has showed a maximum density for x = 2 mol%. The covalent radius values of oxygen have indicated that the minimum value rcal (O^2–) is observed for x = 2 mol% and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Cr-O-P) bonds. SEM Micrographs have exhibited two phases, a vitreous phase and a crystalline phase. The radical change in the structure from ultraphosphate Q³ groups to ring metaphosphate Q² and orthophosphate groups Q⁰ seems to be the cause of the formation of crystallites. Beyond 2 mol% of Cr₂O₃, the structure of the glass changed relatively and the orthophosphate phases increased to the detriment of the metaphosphate phases. We observed a decrease in chemical durability. However, it was confirmed that the dissolution rate (D_R) of the S₂ analysed compound is comparable to the values of borosilicate glasses which are used as alternative materials for the immobilisation of nuclear waste substances.

Keywords

Chemical Durability, Phosphate Glasses, Chromium Oxide, IR, XRD, SEM, Nu-clear and Chemical Wastes

1. Introduction

The phosphate-based oxide glasses P₂O₅, compared to their silicate homologous, have important properties due to their low preparation temperatures. These properties, such as a low melting point, high coefficient of thermal expansion and optical properties, make these glasses potential candidates for many technological applications such as: medical field (biomaterials), solid electrolytes, vitrification of nuclear waste, etc. [1] - [10]. The lead iron phosphate glasses used for the disposal of nuclear waste were produced in 1984 [9]. The combination of chromium-doped phosphate glasses with different types of nuclear waste has shown that it is possible to have a waste form with a corrosion rate comparable to that of borosilicate glasses [2] [5] [7]. The previous work performed by our group demonstrated that the substitution of Na₂O with lead oxide by more than 28 mol%, with the presence of 2 mol% of Cr₂O₃ in the vitreous lattice appears to be an unfavourable factor for chemical durability. The phenomenon has been explained by the approach of the boundary zone between the crystal and the glass by the continuous formation of groups of isolated phosphate ${\text{PO}}_4^{3-}$ [5] [6] [7] [11]. Hence, the crystallites exceed a certain limit, and the equilibrium between the glass bath and these crystallites are not longer maintained; we notice, once, a few decrease in the chemical durability. The purpose of this work is to study the evolution of the dissolution rate as a function of the chromium oxide content in distilled water at 90˚C for the studied glasses of the series xCr₂O₃-(45-x)PbO-55P₂O₅ with (1 ≤ x ≤ 4; mol%). The study of the dissolution rate, carried out on these glasses, reveals an important chemical durability for the low contents of chromium oxides (2 mol%).

2. Experimental Section

The synthesis of chromium lead phosphate glasses of composition xCr₂O₃-(45-x)PbO-55P₂O₅ avec (1 ≤ x ≤ 4; mol%) was carried out by the direct fusion of mixtures of (NH₄)₂HPO₄, Pb(NO₃)₂ and Cr₂O₃ in proper proportions. The reagents are finely crushed and then introduced into a porcelain crucible. They are heated to 300˚C for 1 h in the first instance and then to 500˚C for 1 h to complete their decomposition. The reaction mixture is then carried to 1050˚C ± 10˚C for 15 min. The liquid obtained is homogeneous. It is then poured on to an aluminium plate previously heated to 200˚C to avoid thermal shocks. The vitreous state was first evidenced from the shiny and transparency aspect, which was then confirmed from the X-ray diffraction (XRD) patterns. Samples S₁, S₂ and S₄ were respectively annealed at 560˚C and 580˚C, for 72 hours. The chemical durability of these glasses was evaluated by the weight loss of the sample. The samples were polished by glass paper of silica carbon (CSI), cleaned with acetone and immersed in beakers of Pyrex containing 100 ml of distilled water and brought to 90˚C. The surface of the sample must be constantly immersed in the distilled water for 24 days. The density of the glass has been measured at ambient temperature using the Archimedes method. The glass is immersed in a solution of diethyl orthophtalate density, depending on the temperature, is known. The precision is 0.05 g/cm³. The density of the glass is given by the following equation:

$\rho =\frac{m_{\text{glass}}}{\left[m_{\text{glass}}+\left(m_{\text{ortho}}-m_{\text{ortho}+\text{glass}}\right)\right]}{\rho }_{\text{ortho}}$

with:

ρ = Density

m_air = Weight of glass measured in air

m_ortho = Weight of diethyl orthophthalate only

m _ortho+glass = Weight of glass immersed in diethyl orthophthalate

ρ_ortho = 1.11422 g/cm³

The infrared spectra of the phosphate glasses studied have been determined in the region between 1600 and 400 cm⁻¹ with a resolution of 2 cm⁻¹. The samples were finely ground and mixed with KBr (potassium bromide), which is transparent in the infrared, and whose role was to serve as a matrix.

Chemical composition of the departure mixture and some characteristics of the quaternary glasses, are summarized in Table 1.

3. Results and Discussion

3.1. Analysis of Chemical Durability of Series xCr₂O₃-(45-x)PbO-55P₂O₅

The chemical durability (D_R) of the glass is strongly dependent on its composition, in the case of the glass of the xCr₂O₃-(45-x)PbO-55P₂O₅ composition series, the approximate durability analysis is carried out by measuring the dissolution rate (D_R), which is defined as the weight loss of the glasses in g・cm⁻²・min⁻¹. The D_R values shown in Table 1 show a very low dissolution rate for low levels of chromium oxide (2 mol% of Cr₂O₃) introduced into the phosphate network to the detriment of PbO. The substitution of PbO by Cr₂O₃ for more than 2 mol% becomes an unfavourable factor for D_R. Figure 1 shows the variation in the

Table 1. Compositions, density and chemical durability of xCr₂O₃-(45-x)PbO-55P₂O₅ with (1 ≤ x ≤ 4; mol%).

Figure 1. Chemical durability versus Cr₂O₃ for the series of composition xCr₂O₃-(45-x)PbO-55P₂O₅.

dissolution rate of the glasses immersed in distilled water at 900˚C for 24 days [6] [8] [11]. A progressive improvement of D_R from 1.07 × 10⁻⁶ to 5.80 × 10⁻⁸ (g・cm²・min) was noted when the Cr₂O₃ content varied from 1 to 2 mol%, respectively. However, we noted an increase in the dissolution rate (D_R) from 5.80 × 10⁻⁸ to 2 × 10⁻⁷ (g・cm⁻²・min⁻¹) when the Cr₂O₃ content varies from 2 to 4 mol%, respectively.

3.2. Density and Molar Volumes

Density measurements allowed us to follow the evolution of the molar volume depending on the composition of the system xCr₂O₃-(45-x)PbO-55P₂O₅. The density measurements were completed at room temperature. As can be observed from the Figure 2, the variation in density versus Cr₂O₃ content (mol%) indicates a maximum value of x = 2. The molar volume of oxygen (V_OM) and the radius of anions of oxygen r_cal(O²⁻) in the glass have been determined from Equations (1) and (2), respectively

$V_{OM}=M/\rho N_A{N}_0^{\ast }$ (1)

$r_{\text{cal}}\left({\text{O}}^{2-}\right)=\frac{\sqrt[3]{V_{OM}}}{2}$ (2)

With M = molar mass, ρ = density, N_A = Avogadro number; $N_0^{\ast }$ = number of oxygen atoms in the molecular formula. The value of the molar volume and the oxygen radius were calculated from the approximate hypothesis of close packing of oxygen anions O²⁻, having r(O²⁻) recapitulated for each composition in Table 2 [12] [13] [14] [15]. A detailed analysis of the data in Table 2 shows that the molar volume passes through a minimum when the Cr₂O₃ content reaches 2 mol%. However, the covalent radius value of the oxygen atom (O²⁻), calculated by the molar volume using the Equation (2) for each composition, seems to decrease slightly.

Figure 2. Variation of density versus Cr₂O₃ for the series of composition xCr₂O₃-(45-x)PbO-55P₂O₅Cr₂O₃ (mol%).

Table 2. Density and molar volume of system xCr₂O₃-(45-x)PbO-55P₂O₅.

3.3. Structural Approach by Infrared Spectroscopy

The infrared spectra for the xCr₂O₃-(45-x)PbO-55P₂O₅ glasses series (with 1 ≤ x ≤ 4) are shown in Figure 3. As can be seen from this figure, all the phosphate vibration bands of the treated sample are presented in the frequency range between 1600 and 399 cm⁻¹ [16] [17]. The band of approximately 1244 - 1228 cm⁻¹ is attributed to the asymmetric vibration modes uas (PO₂) or the two non-bridging oxygen atoms linked to a phosphorus atom in the phosphate tetrahedron Q² [17]. The vibrations of the bands around 1070 - 1047 cm⁻¹ are characteristic of the stretching vibrations υasy (PO₃) and the terminal groups υs (PO₂) [15] [16] [18]. The band about 912 - 894 cm⁻¹ is attributed to the uasy P-O-P stretching vibrations [16] [17] [18] [19] [20] , while the band at 779 - 771

Figure 3. IR spectra of phosphate glasses of composition xCr₂O₃-(45-x)PbO-55P₂O₅, with (1 ≤ x ≤ 4; mol%).

cm⁻¹ is assigned to the stretching vibration υ_sy P-O-P band of the transition oxygen atoms of phosphorus to a phosphate tetrahedron Q¹ [16] [19] [20] [21]. Bands that appear between 500 and 466 cm⁻¹ are attributed to the P-O-P vibration modes of the skeleton [2] [16] [17] [19]. All characteristics of the phosphate vibrations show that the phosphate glasses of compositions xCr₂O₃-(45-x)PbO-55P₂O₅ (with 1 ≤ x ≤ 4) may have chains or rings of the metaphosphate groups, with some traces of pyrophosphate groups. In fact, when the Cr₂O₃ content (mol%) is equal to x = 2, the vibration bonds υas (PO₂) assigned to metaphosphates groups tend to be the dominant characteristic of the spectrum. As shown in Figure 3, the band becomes more intense.

3.4. X-Ray Diffraction

The XRD pattern shown in the Figure 4 indicates that the local structure of chromium-lead phosphate glasses, evolved from ultraphosptate (O/P = 2.93) to nearby chains (cyclic metaphosphate O/P = 3, isolated orthophosphates O/P = 4) structures Cr(PO₃)₃, Cr₂(PO₃)₆, Pb(PO₃)₂, Pb₂(PO₃)₄, Pb₃(PO₄)₂, Pb₉(PO₄)₆, Pb₃Cr(PO₄)₃ and some trace of Pb₂P₂O₇. When the sample S₁ was thermally treated at 560˚C, the amorphous phase partially disappeared and major Cr (PO₃)₃ [JCDDS FileN˚: 01-077-0672], Pb(PO₃)₂ [JCDDS. File N˚: 00-043-0335], Pb₂(PO₃)₄ [JCDDS File N˚: 01-086-21] Phases occurred in the sample, with minor Pb₃(PO₄)₂ [JCDDS File N˚01-070-1790] and Pb₉(PO₄)₆ [JCDDS file N˚: 00033-0768] Phases. When the Cr₂O₃ content increased in the glass (S₂), the heat treatment caused an increase in crystallization temperature at 580˚C, which

Figure 4. X-ray spectrum of the glasses of compositions S₁, S₂ and S₄ devitrified respectively at 560˚C, 580˚C and 56˚C for 72 hours.

resulted in the disappearance of isolated orthophosphate phase and the formation of CrPO₃)₃, Pb₂(PO₃)₄ and Pb(PO₃)₂. However, the S₄ sample thermally treated at 560˚C, indicate the formation of metaphosphate and/or rings of metaphosphate phase Cr(PO₃)₃, Pb₂(PO₃)₄ with the appearance of isolated orthophosphate phase Pb₉(PO₄)₆ and Pb₃Cr(PO₄)₃ [JCDDS File N˚: 00-047-0830] at the expense of metaphosphate phases [6] [22] [23].

3.5. SEM Micrograph

SEM images in Figure 5 illustrate the morphology of the glasses considered in

(a)(b)

Figure 5. SEM micrograph showing the visual structure of the samples glasses S₂ (a) and S₄ (b).

this work. The glass form of S₂, shown in Figure 5(a), exhibits two phases, a vitreous phase and a crystalline phase. This last one indicates the formation of crystalline agglomerates particle having ring form that indicate, the crystallisation tendency is enhanced and major Cr (PO₃)₃ and Pb₂(PO₃)₄ phases are crystallised in these glasses. The presence of the crystalline phase seems to explain the increase in chemical durability [14] [15] [16]. The SEM micrograph for the sample S₄ indicates a radical change in the structure. There is formation of crystalline phase agglomerates of various sizes, ranging from some microns. This probably explains the structural change towards more short isolated orthophosphate chains as the Cr₂O₃ content increases in the glass network.

4. Discussion

The structure and the chemical durability of the glasses series xCr₂O₃-(45-x)PbO-55P₂O₅ (with 1 ≤ x ≤ 4; mol%) have been investigated using various techniques such as density, X-Ray diffraction and IR. The measured properties indicate that the glasses series chromium-lead-phosphorus-oxygen network become stronger for x = 2. X-ray diffraction indicates that the samples S₁, S₂ and S₄, respectively annealed at 560˚C and 580˚C for 72 h, contain metaphosphates, orthophosphates and certain traces of pyrophosphate phases in all the glasses. When the Cr₂O₃ content is equal to 2 mol%, X ray diffraction and IR spectra, both, confirmed the predominance of metaphosphate groups most probably cyclic. The bands at 1244 - 1228 cm⁻¹, attributed to the asymmetric vibration modes νas (PO₂), become more intense. The predominance of cyclic metaphosphate chains as Cr (PO₃)₃ and Pb₂(PO₃)₄ have led to maximum chemical durability. Analysis of the density values also showed a maximum density for x = 2 mol%. The covalent radius values of oxygen calculated from Equation (2) indicate that the minimum value rcal (O²⁻) is observed for x = 2 mol% and therefore a relatively high reinforcement of the metal-oxygen-phosphorus (Cr-O-P) bond. Additionally, because of the big stability of the energy of field of ligand of d³systems in octahedral symmetry, the ions Cr³⁺ occupy almost exclusively the sites having this symmetry type [23] [24] , while the Pb is estimated to be in the tetrahedral site forming PbO₄ pyramids which are connected in phosphate tetrahedron by covalent links P-O-Pb [25] [26]. Above 2 mol% Cr₂O₃, the glass structure changes relatively, it is found that the DRX spectra intensity of the ring metaphosphate phases decreases, whereas the appearance of the isolated orthophosphate phase becomes important when the Cr₂O₃ content reaches 4 mol%. The substitution of PbO with chromium oxide by more than 2 mol% in the vitreous lattice appears to be an unfavorable factor for chemical durability. The origin of this phenomenon is explained almost probably by the approach of the boundary zone between the crystal and the glass by the continuous formation of groups of isolated phosphate ${\text{PO}}_4^{3-}$ [6] [19]. The decrease of chemical durability observed, can be also explained by the existence of the critical concentrations between the cation ions beyond which each ion seeks, by competition, to have a site that is appropriate to it by moving away from the other. This behavior leads to an increase in the glass volume and a relaxation of the structure [27] [28] and consequently a decrease in density and chemical durability. On the other hand, the PbO oxide have à low melting temperature and can participated with P₂O₅ Oxyde, basis glass matrix, in the extend of the area glass. That explains probably the non evidence of the attributed band of orthophosphate isolated units in the IR spectra beside the X-ray diffraction spectra. Added, the elaboration method of the glasses (melting temperature, tempering speed, etc.) remains a significant factor in the deep understanding of the phenomenon [29].

5. Conclusion

The structure and the chemical durability of chromium lead phosphate glasses of composition xCr₂O₃-(45-x)PbO-55P₂O₅ avec (1 ≤ x ≤ 4; mol%) have been investigated using various techniques such IR, X-ray diffraction, density and SEM micrograph. The study of the dissolution rate carried out on the glasses, immersed in distilled water at 90˚C for 24 days, indicates a maximum chemical durability when the level of chromium oxide passes through 2 mol%. The analysis of the values of the density also showed a maximum density for x = 2 mol%. The covalent radius values of the oxygen indicate that the minimum values are observed for x = 2 mol%, and therefore, a relatively high reinforcement of the metal-oxygen-phosphorus (Cr-O-P) bonds. However, the increase in the Cr₂O₃ content in the vitreous network to the detriment of PbO beyond 2 mol%, is an unfavourable factor for both chemical durability and density. The increase in the Cr + Pb/P ratio leads to an increase in the number of metal-O-P bonds which cause a high tendency for crystallisation and confirms that the dissolution rate (D_R) of the analyzed compounds is comparable to the values of borosilicate glasses and 40 times less than BaBal glasses which are used as alternative materials for the immobilisation of nuclear waste substances.

Acknowledgements

The authors wish to thank National Center for Scientific and Technical Research [Division of Technical Support Unit for Scientific Research (TSUSR) Rabat, Morocco] for their assistance to the realization of this work.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	Velli, L.L., Varsamis, C.P.E., Kamitsos, E.I., Möncke, D. and Ehrt, D. (2005) Structural Investigation of Metaphosphate Glasses. Physics and Chemistry of Glasses-European Journal of Glass Science and Technology Part B, 46, 178-181.
[2]	Aqdim, S. (2007) Investigation des phases vitreuses des systèmes (Li,Na)2O-(Fe,Al)2O3-P2O5 par Spectroscopies Infrarouge et Mössbauer-Structures et Durabilité chimique. These, Faculté des Sciences de Casablanca Ain Chock, Morocco.
[3]	Mbemba, K.M. (2010) Etude de la durabilité chimique des verres alcali-résistants de type cemfil synthétisés à partir des refiom en vue de les valoriser comme renforts dans les matrices cimentaires. These Universite Paris-Est, France.
[4]	El Hadrami, A. (2003) Etude des conditions de confinements du plomb et du cadmium dans des verres à base de méta-phosphates de zinc. Université Cadi Ayyad Marrakech, Maroc.
[5]	Videau, J.J. and Gilles, F. (2010) Les verres phosphates de la spécificité de l’atome de phosphore à la formation, la structure et la durabilité chimique de phosphates vitreux. Institut de Chimie de la Matière Condensée de Bordeaux, CNRS, Université de Bordeaux, France.
[6]	Beloued, N., Chabbou, Z. and Aqdim, S. (2016) Correlation between Chemical Durability Behaviour and Structural Approach of the Vitreous Part of the System 55P2O5-2Cr2O3-(43-x) Na2O-xPbO. Advances in Materials Physics and Chemistry, 6, 149-156. https://doi.org/10.4236/ampc.2016.66016
[7]	Santic, A., Skoko, Z., Gajovic, A., Reis, S.T., Day, D.E. and Mogus-Milankovic, A. (2011) Physical Properties of Lead Iron Phosphate Glasses Containing Cr2O3. Journal of Non-Crystalline Solids, 357, 3578-3584. https://doi.org/10.1016/j.jnoncrysol.2011.07.011
[8]	Makhkhas, Y., Aqdim, S. and Sayouty, E.H. (2013) Study of Sodium-Chromium- Iron-Phosphate Glass by XRD, IR, Chemical Durability and SEM. Journal of Materials Science and Chemical Engineering, 1, 1-6. https://doi.org/10.4236/msce.2013.13001
[9]	Sales, B.C. and Boatner, L.A. (1984) Lead-Iron Phosphate Glass: A Stable Storage Medium for High-Level Nuclear Waste. Sciences, 226, 45-48. https://doi.org/10.1126/science.226.4670.45
[10]	El-Egili, K., Doweidar, H., Moustafa, Y.M. and Abbas, I. (2008) Structure and Some Properties of PbO-P2O5 Glasses. Physica B, 339, 237-245. https://doi.org/10.1016/j.physb.2003.07.005
[11]	Errouissi, Y., Chabbou, Z., Beloued, N. and Aqdim, S. (2017) Chemical Durability and Structural Properties of Al2O3-CaO-Na2O-P2O5 Glasses Studied by IR Spectroscopy, XRD and SEM. Advances in Materials Physics and Chemistry, 7, 353-363. https://doi.org/10.4236/ampc.2017.710028
[12]	Ouchetto, M. (1993) Caractérisation et Approche structural de la région vitreuse du système ternaire Li2O-CdO-P2O5. Diplôme d’étude de 3ème Cycle Sciences Physiques, Faculty of Sciences Rabat, University Mohammed V, Morocco.
[13]	Aqdim, S., Elouadi, B. and Grenech, J.M. (2012) Chemical Durability and Structural Approach of the Glass Series (40-y)Na2O-yFe2O3-5Al2O3-55P2O5—by IR, X-Ray Diffraction and Mössbauer Spectroscopy. Material Sciences and Engineering, 27, Article ID: 012003. https://doi.org/10.1088/1757-899X/28/1/012003
[14]	Chabbou, Z. and Aqdim, S. (2014) Chemical Durability and Structural Proprieties of the Vitreous Part of the System xCaO-(40-x)ZnO-15Na2O-45P2O5. Advances in Materials Physics and Chemistry, 4, 179-180. http://dx.doi.org/10.4236/ampc.2014.410021
[15]	Santic, A., Mogus-Milankovic, A., Furic, K., Bermanec, V., Kim, D.W. and Daye, D.E. (2007) Structural Properties of Cr2O3-Fe2O3-P2O5 Glasses, Part I. Journal of Non-Crystalline Solids, 353, 1070-1077. http://dx.doi.org/10.1016/j.jnoncrysol.2006.12.104
[16]	Aqdim, S. and Albizane, A. (2015) Structural Feature and Chemical Durability of Sodium Aluminium Iron Phosphate Glasses. Journal of Environmental Science, Computer Science and Engineering & Technology, 4, 509-521.
[17]	Aqdim, S. and Ouchetto, M. (2013) Elaboration and Structural Investigation of Iron (III) Phosphate Glasses. Advances in Materials Physics and Chemistry, 3, 332-339. https://doi.org/10.4236/ampc.2013.38046
[18]	Reis, S.T., Faria, D.L.A., Martinelli, J.R., Pontuschka, W.M., Day, D.E. and Partiti, C.S.M. (2002) Structural Features of Lead Iron Phosphate Glasses. Journal of Non-Crystalline Solids, 304, 188-194. https://doi.org/10.1016/S0022-3093(02)01021-9
[19]	Aqdim, S., Errouissi, Y., Cherif, A. and Makhlouk, R. (2017) Elaboration and Characterization of Glasses and Ceramic-Glasses within Theternary Diagram Li2O-Cr2O3-P2O5. Advances in Materials Physics and Chemistry, 7, 123-137. https://doi.org/10.4236/ampc.2017.74011
[20]	Bernardo, E., Varrasso, M., Cadamuro, F. and Hreglich, S. (2006) Vitrification of Wastes and Preparation of Chemically Stable Sintered Glass-Ceramic Products. Journal of Non-Crystalline Solids, 352, 4017-4023. https://doi.org/10.1016/j.jnoncrysol.2006.07.001
[21]	Drabarek, E., McLeod, T.I., Hanna, J.V., Griffith, C.S. and Luca, V. (2009) Tungstate-Based Glass-Ceramics for the Immobilization of Radio Cesium. Journal of Nuclear Materials, 384, 119-129. https://doi.org/10.1016/j.jnucmat.2008.11.018
[22]	Joseph, K., Jolley, K. and Smith, R. (2015) Iron Phosphate Glasses: Structure Determination and Displacement Energy Thresholds, Using a Fixed Charge Potential Model. Journal of Non-Crystalline Solids, 411, 137-144. https://doi.org/10.1016/j.jnoncrysol.2014.12.033
[23]	Santic, A., Kim, C.W., Day, D.E. and Mogus-Milankovic, A. (2010) Electrical Properties of Cr2O3-Fe2O3-P2O5 Glasses. Part II. Journal of Non-Crystalline Solids, 356, 2699-2703. https://doi.org/10.1016/j.jnoncrysol.2010.09.072
[24]	Moss, R.M., Neel, E.A.A., Pickup, D.M., Twyman, H.L., Martin, R.A., Henson, M.D. and Newport, R.J. (2010) The Effect of Zinc and Titanium on the Structure of Calcium-Sodium Phosphate Based Glass. Journal of Non-Crystalline Solids, 356, 1319-1324. https://doi.org/10.1016/j.jnoncrysol.2010.03.006
[25]	El Hadrami, A. (2003) Etude de condition de confinement du plomb et du cadmium dans des verres à base de metaphosphate de Zinc. Université Cadi Ayyad, Marrackech, Maroc, Université Bourdeaux 1.
[26]	Liu, H.S., Chin, T.S. and Yung, S.W. (1997) FTIR and XPS Studies of Low-Melting PbO-ZnO-P2O2 Glasses. Materials Chemistry and Physics, 50, 1-10. https://doi.org/10.1016/S0254-0584(97)80175-7
[27]	Treis, S., Pontuschka, W.M., Partiti, G.S.M. and Faria, D.L.A. (2001) Proprieties and Structural Features of Basal Glasses.
[28]	Mogus-Milankovic, A., Santic, B., Day, D.E. and Ray, C.S. (2001) Electrical Conductivity in Mixed-Alkali Iron Phosphate Glasses. Journal of Non-Crystalline Solids, 283, 119-128. https://doi.org/10.1016/S0022-3093(01)00355-6
[29]	Chanshetti, U.B., Shelke, V.A., Jadhav, S.M., Shankarwar, S.G., Chondhekar, T.K., Shankarwar, A.G. and Jogad, M.S. (2011) Density and Molar Volume Studies of Phosphate Glasses. Facta Universitatis-Series: Physics, Chemistry and Technology, 9, 29-36. https://doi.org/10.2298/FUPCT1101029C