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The effect of MgO/TiO2 on structural and crystallization behavior of near invert phosphate-based glasses

Islam, Md Towhidul; Sharmin, Nusrat; Rance, Graham A.; Titman, Jeremy J.; Parsons, Andrew J.; Hossain, Kazi M. Zakir; Ahmed, Ifty


Md Towhidul Islam

Nusrat Sharmin

Kazi M. Zakir Hossain


Varying formulations in the glass system of 40P2O5─(24 − x)MgO─(16 + x)CaO─(20 − y)Na2O─yTiO2 (where 0 ≤ x ≤ 22 and y = 0 or 1) were prepared via melt-quenching. The structure of the glasses was confirmed by X-ray diffraction (XRD), Fourier transform infrared (FTIR), micro Raman and solid-state nuclear magnetic resonance (NMR) spectroscopies. The thermal properties and the activation energy of crystallization (Ec) were measured using thermal analysis and the Kissinger equation, respectively. The glass forming ability of the formulations investigated was seen to decrease with reducing MgO content down to 8 mol% and the glass stability region also decreased from 106 to 90°C with decreasing MgO content. The activation energy of crystallization (Ec) values also decreased from 248 (for 24 mol% MgO glass) to 229 kJ/mol (for the 8 mol% MgO content) with the replacement of MgO by CaO for glasses with no TiO2. The formulations containing less than 8 mol% MgO without TiO2 showed a strong tendency toward crystallization. However, the addition of 1 mol% TiO2 in place of Na2O for these glasses with less than 8 mol% MgO content, inhibited their crystallization tendency. Glasses containing 8 mol% MgO with 1 mol% TiO2 revealed a 12°C higher glass transition temperature, a 14°C increase in glass stability against crystallization and a 38 kJ/mol increase in Ec in comparison to their non TiO2 containing counterpart. NMR spectroscopy revealed that all of the formulations contained almost equal percentages of Q1 and Q2 species. However, FTIR and Raman spectroscopies showed that the local structure of the glasses had been altered with addition of 1 mol% TiO2, which acted as a network modifier, impeding crystallization by increasing the cross-linking between phosphate chains and consequently leading to increased Ec as well as their glass forming ability.


Islam, M. T., Sharmin, N., Rance, G. A., Titman, J. J., Parsons, A. J., Hossain, K. M. Z., & Ahmed, I. (2020). The effect of MgO/TiO2 on structural and crystallization behavior of near invert phosphate-based glasses. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 108(3), 674-686.

Journal Article Type Article
Acceptance Date Dec 1, 2018
Online Publication Date Jun 7, 2019
Publication Date 2020-04
Deposit Date May 14, 2019
Publicly Available Date Jun 8, 2020
Journal Journal of Biomedical Materials Research Part B: Applied Biomaterials
Print ISSN 1552-4973
Electronic ISSN 1552-4981
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 108
Issue 3
Pages 674-686
Keywords Phosphate glass; Crystallisation; Activation energy; Biomaterials
Public URL
Publisher URL
Additional Information This is the peer reviewed version of the following article: Islam, MT, Sharmin, N, Rance, GA, et al. The effect of MgO/TiO2 on structural and crystallization behavior of near invert phosphate‐based glasses. J Biomed Mater Res. 2020; 108B: 674– 686., which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.


Article ID JBMB34421 The Effect Of MgO And TiO2 On Structural And Crystallisation Behaviour Of Near Invert Phosphate-based Glasses (1.5 Mb)

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