Three composition-dependent features of the mixed-modifier effect in ternary ZnO–Na2O–B2O3 glasses
DOI:
https://doi.org/10.1007/s10854-026-16947-0الملخص
This article delves into the complex relationship between zinc oxide (ZnO) and sodium oxide (Na2O) in ternary borate glasses, uncovering how their interaction reshapes the glass network and influences ionic conductivity. The study systematically examines three series of glasses with varying compositions—x ZnO.(30−x)Na2O.70B2O3, x ZnO.(40−x)Na2O.60B2O3, and x ZnO.(50−x)Na2O.50B2O3—using a combination of FTIR spectroscopy, electrical conductivity measurements, and molecular dynamics (MD) simulations. The findings reveal that ZnO’s role is not static but evolves with the glass composition, shifting from a primary modifier in boron-rich glasses to a partial network former in glasses with lower boron content. This dual behavior directly impacts the balance between BO3 and BO4 units, as well as the formation of non-bridging oxygens (NBOs), which in turn governs the glass’s structural connectivity and ionic transport properties. A key discovery is the identification of a mixed-modifier effect, where the interplay between Na2O and ZnO produces non-linear variations in activation energy, conductivity, and ion mobility. The study demonstrates that these variations are closely tied to the relative concentrations of Na+ and Zn2+ ions, as well as their local coordination environments. For instance, the activation energy for ionic conduction exhibits a pronounced maximum at specific Na+/Zn2+ ratios, highlighting the sensitivity of transport properties to compositional changes. The MD simulations provide atomic-scale insights into these trends, showing how Zn2+ ions transition from occupying modifier sites to forming ZnO4 tetrahedra, which further stabilizes the glass network. The research also explores how the separation distance between Na+ ions influences conductivity and activation energy, offering a new perspective on the factors controlling ion migration in these glasses. By integrating experimental and computational approaches, the article provides a holistic understanding of the mixed-modifier effect in ZnO–Na2O–B2O3 glasses, challenging conventional assumptions about the roles of modifiers in glass networks. The results not only advance fundamental knowledge of glass structure but also offer practical implications for designing glasses with tailored electrical properties for applications in electronics, energy storage, and optical devices.المراجع
V. Dua, S.K. Arya, K. Singh, Review on transition metals containing lithium borate glasses: properties, applications and perspectives. J. Mater. Sci. 58(21), 8678–8699 (2023)
A.A. Abul-Magd, A.S. Abu-Khadra, A.M. Abdel-Ghany, Influence of La2O3 on the structural, mechanical and optical features of cobalt doped heavy metal borate glasses. Ceram. Int. 47(14), 19886–19894 (2021)
M.T. Sebastian, H. Wang, H. Jantunen, Low temperature co-fired ceramics with ultra-low sintering temperature: a review. Curr. Opin. Solid State Mater. Sci. 20(3), 151–170 (2016)
P. Naresh, G.N. Raju, M.S. Reddy, T.V. Rao, I.V. Kityk, N. Veeraiah, Dielectric and spectroscopic features of ZnO–ZnF2–B2O3: MoO3 glass ceramic—a possible material for plasma display panels. J. Mater. Sci. Mater. Electron. 25(11), 4902–4915 (2014)
H. Doweidar, G. El-Damrawi, M. Al-Zaibani, Distribution of species in Na2O-CaO-B2O3 glasses as probed by FTIR. Vib. Spectrosc. 68, 91–95 (2013)
S.B. Kolavekar, N.H. Ayachit, Structural analysis on the basis of effect of molybdenum on the Pr2O3 doped lead borate glasses series-II. J. Phys. Conf. Ser. 2070(1), 012031 (2021)
T.N. Ashoka, S.B. Kolavekar, K.N. Sathish, S. Shashidhar, K. Keshavamurthy, A.H. Almuqrin, D.A. Aloraini, M.I. Sayyed, R. Rajaramakrishna, A.G. Pramod, S.V. Rao, Effect of silver nanoparticles size on the ultrafast optical nonlinear and optical limiting properties of Nd3+ doped antimony borate glasses. Infrared Phys. Technol. 138, 105268 (2024)
S.B. Kolavekar, N.H. Ayachit, Comparative studies on the role of Pr2O3 in the structural analysis (theoretical) of the molybdenum borate glasses. Mater. Today Proc. 92, 1061–1063 (2023)
K. Hanamar et al., Physical, structural, and photoluminescence characteristics of Sm2O3 doped lithium zinc borate glasses bearing large concentrations of modifier. J. Inorg. Organomet. Polym. Mater. 33(6), 1612–1620 (2023)
P.F. James, Glass ceramics: new compositions and uses. J. Non-Cryst. Solids 181(1–2), 1–15 (1995)
W. Vogel, Classical theories of glass structure, in Glass Chemistry. (Springer, 1994), pp.41–56
D.G. Minser, B. Walden, W.B. White, Structure of alkali–zinc silicate glasses by Raman spectroscopy. J. Am. Ceram. Soc. 67(3), C–47 (1984)
T. Dumas, J. Petiau, EXAFS study of titanium and zinc environments during nucleation in a cordierite glass. J. Non-Cryst. Solids 81(1–2), 201–220 (1986)
E. Matsubara et al., Structural study of binary phosphate glasses with MgO, ZnO, and CaO by X-ray diffraction. J. Non-Cryst. Solids 103(1), 117–124 (1988)
G. Ennas, A.N. Musinu, G. Piccaluga, A. Montenero, G. Gnappi, Structure and chemical durability of zinc-containing glasses. J. Non-Cryst. Solids 125(1–2), 181–185 (1990)
A.B. Rosenthal, S.H. Garofalini, The structure of amorphous Na2O:ZnO:3 SiO2. J. Non-Cryst. Solids 92(2–3), 354–362 (1987)
L.H. Kieu, J.M. Delaye, L. Cormier, C. Stolz, Development of empirical potentials for sodium borosilicate glass systems. J. Non-Cryst. Solids 357(18), 3313–3321 (2011)
W.J. Dell, P.J. Bray, S.Z. Xiao, 11B NMR studies and structural modeling of Na2O-B2O3–SiO2 glasses of high soda content. J. Non-Cryst. Solids 58(1), 1–16 (1983)
M. Fortino et al., Assessment of interatomic parameters for the reproduction of borosilicate glass structures via DFT-GIPAW calculations. J. Am. Ceram. Soc. 102(12), 7225–7243 (2019)
L. Deng, J. Du, Development of effective empirical potentials for molecular dynamics simulations of the structures and properties of boroaluminosilicate glasses. J. Non-Cryst. Solids 453, 177–194 (2016)
V.V. Gowda, R. Anavekar, Elastic properties and spectroscopic studies of Na2O-ZnO–B2O3 glass system. Bull. Mater. Sci. 27, 199–205 (2004)
L. Balu, R. Amaravel, R. Ezhil Pavai, Effect of ZnO on physical, structural and mechanical properties of B2O3–Na2O–ZnO glasses. J. Appl. Phys. 8, 140–146 (2016)
B. Parameswarlu, B. Rajam, A. Vijaykanth, Synthesis and characterization of ZnO–Na2O–Bi2O3–B2O3 glass system. Int. Res. J. Eng. Technol. 9(3), 683 (2022)
Y. Yang, B. Chen, C. Wang, H. Zhong, L. Cheng, J. Sun, Y. Peng, X. Zhang, Investigation on structure and optical properties of Er3+, Eu3+ single-doped Na2O–ZnO–B2O3–Te O2 glasses. Opt. Mater. 31(2), 445–450 (2008)
H.A. Alghasham, Y.A. Ismail, D.A. Aloraini, K.S. Shaaban, Elucidating the influences of MoO3 in Na2O–ZnO–B2O3–SiO2: fabrication, optical, and γ-ray protection properties for novel high-density glasses. Mater. Today Commun. 38, 107840 (2024)
M. Marzouk, I. Ali, H. ElBatal, Optical, FT infrared and photoluminescence spectra of CeO2-doped Na2O–ZnO–B2O3 host glass and effects of gamma irradiation. J. Non-Cryst. Solids 485, 14–23 (2018)
A.M. Babeer, H.Y. Amin, M.I. Sayyed, A.E.R. Mahmoud, M.S. Sadeq, Composition influence of La2O3 on the structural and radiation shielding features of CoO–Na2O–ZnO–B2O3 glass matrix. Opt. Mater. 149, 115131 (2024)
R.V. Anavekar, N. Devaraj, G. Parthasarathy, E.R. Gopal, J. Ramakrishna, Temperature and pressure dependence of direct current electrical resistivity in the Na2O–ZnO–B2O3 glass system. Phys. Chem. Glasses 30(5), 172–179 (1989)
M. AL-Zaibani, R.A. Althobiti, E.F. El Agammy, E. Alzahrani, G. El-Damrawi, H. Doweidar, A.A. Al-Muntaser, Electrical conduction in ternary Na2O–ZnO–B2O3 glasses: a unique dependence on the mobility of Na+ ions as main charge carriers. J. Non-Cryst. Solids 650, 123367 (2025)
S.B. Kolavekar, N.H. Ayachit, Ionic conductivity and dielectric relaxations in Li+ ions doped zinc borate glass system. ECS J. Solid State Sci. Technol. 11(10), 103009 (2022)
H. Doweidar, Y.M. Moustafa, G. El-Damrawi, R.M. Ramadan, Electrical conduction in alkali borate glasses: a unique dependence on the concentration of modifier ions. J. Phys. Condens. Matter 20(3), 035107 (2007)
H. Doweidar, A simple approach to the mixed alkali effect. Phys. Chem. Glasses 40(6), 345–349 (1999)
M. Neyret, M. Lenoir, A. Grandjean, N. Massoni, B. Penelon, M. Malki, Ionic transport of alkali in borosilicate glass: role of alkali nature on glass structure and on ionic conductivity at the glassy state. J. Non-Cryst. Solids 410, 74–81 (2015)
S. Plimpton, Fast parallel algorithms for short-range molecular dynamics. J. Comput. Phys. 117(1), 1–19 (1995)
A. Shahboub, Effect of ZrO2 on structural, mechanical, and durability of nuclear waste glasses: insights from MD, DFT, and experimental studies. Ceram. Int. 51(13), 18178-18190 (2025).
G. Lusvardi, G. Malavasi, L. Menabue, M.C. Menziani, Synthesis, characterization, and molecular dynamics simulation of Na2O–CaO–SiO2–ZnO glasses. J. Phys. Chem. B 106(38), 9753–9760 (2002)
H. Doweidar, K. El-Egili, R. Ramadan, M. Al-Zaibani, Structural investigation and properties of Sb2O3–PbO–B2O3 glasses. J. Non-Cryst. Solids 497, 93–101 (2018)
H. Doweidar, K. El-Egili, R. Ramadan, M. Al-Zaibani, Structural units distribution, phase separation and properties of PbO–TiO2–B2O3 glasses. J. Non-Cryst. Solids 466, 37–44 (2017)
E.I. Kamitsos, M.A. Karakassides, G.D. Chryssikos, Vibrational spectra of magnesium-sodium-borate glasses. 2. Raman and mid-infrared investigation of the network structure. J. Phys. Chem. 91(5), 1073–1079 (1987)
E.I. Kamitsos, M.A. Karakassides, G.D. Chryssikos, A vibrational study of lithium borate glasses with high Li2O content. Phys. Chem. Glasses 28(5), 203–209 (1987)
E.I. Kamitsos, A.P. Patsis, M.A. Karakassides, G.D. Chryssikos, Infrared reflectance spectra of lithium borate glasses. J. Non-Cryst. Solids 126(1–2), 52–67 (1990)
B.N. Meera, B.N. Meera, A.K. Sood, N. Chandrabhas, J. Ramakrishna, Raman study of lead borate glasses. J. Non-Cryst. Solids 126(3), 224–230 (1990)
M.S. Gaafar, N.S. Abd El-Aal, O.W. Gerges, G. El-Amir, Elastic properties and structural studies on some zinc-borate glasses derived from ultrasonic, FT-IR and X-ray techniques. J. Alloys Compd. 475(1–2), 535–542 (2009)
R.E. Youngman, NMR spectroscopy in glass science: a review of the elements. Materials 11(4), 476 (2018)
M.A. Azooz, H.A. ElBatal, Preparation and characterization of invert ZnO–B₂O₃ glasses and their shielding behavior towards gamma irradiation. Mater. Chem. Phys. 240, 122129 (2020)
O.L.G. Alderman, N.S. Tagiara, I.T. Slagle, R. Gabrielsson, P. Boggs, M. Wagner, A. Rossini, S.W. Martin, S. John, L. Rocha, R.M. Wilson, A review of the fraction of four-coordinated boron in binary borate glasses. Rep. Prog. Phys. 88, 076501 (2025)
C.S.P. Kumar, S. Pratap, C.S. Sumuka, N.S. Reddy, Review on the structure of borate glasses by Raman spectroscopic technique. Ceram. Int. (2025). (Please add volume/pages if available.)
E. Zakaria, I. Ali, H. Aly, Kinetic study of the isotopic exchange of Na⁺ and Zn²⁺ ions on iron and chromium titanates. J. Radioanal. Nucl. Chem. 260, 389–397 (2004)
L. Heuser, M. Nofz, Alkali and alkaline earth zinc and lead borate glasses: structure and properties. J. Non-Cryst. Solids: X 15, 100109 (2022)
التنزيلات
منشور
الرخصة
الحقوق الفكرية (c) 2026 "This Open Access article is distributed under the Creative Commons Attribution 4.0 International License (CC BY 4.0), permitting unrestricted use, distribution, and adaptation provided the original author and source are properly credited."
هذا العمل مرخص بموجب Creative Commons Attribution 4.0 International License.
