Journal of Materials Science

, Volume 54, Issue 13, pp 9313–9320 | Cite as

Crystallization mechanism and kinetics of a Fe-diopside (25CaO·25MgO·50SiO2) glass–ceramic

  • Valmor R. MastelaroEmail author
  • Paulo S. Bayer
  • Edgar D. Zanotto


Diopside-based ceramics and glass–ceramics have been studied because of their applications in electronics and biomedicine. However, since diopside glass presents poor internal nucleation ability, sintering combined with surface crystallization of powdered glasses has been reported to obtain diopside glass–ceramics. On the other hand, in this work, we explore the effect of an efficient nucleating agent (Fe2O3) to induce copious internal nucleation in this glass, which enabled the production of single-phase diopside glass–ceramics by the traditional route. The crystallization kinetics of a diopside glass (25CaO·25MgO·50SiO2) containing 8.26 mol% of Fe2O3 was investigated under isothermal conditions by differential thermal analysis (DTA) and was modeled by the Johnson-Mehl-Avrami-Kolmogorov-Erofeev (JMAKE) equation. The crystals formed were iron-diopside—the X-ray diffraction pattern was indexed to the ferric-diopside card (Ca0.991(Mg0.641Fe0.342)(Si1.6Fe0.417)O6). Through a systematic DTA study, we successfully determined the mechanism and kinetics of crystallization of this material, which provided relevant information to guide the development of this novel type of internally crystallized glass–ceramic.



We are thankful to the São Paulo Research Foundation (FAPESP) for funding this research, under the grant number 2013/07793-6 (CEPID). P.S. Bayer would also like to thank the Federal Institute of Science, Technology and Education of Santa Catarina for granting him a leave of absence to complete his doctoral studies.

Compliance with ethical standards

Conflict of interest

All the authors declare that they have no conflict of interest.


  1. 1.
    Redhammer GJ (1998) Mössbauer spectroscopy and rietveld refinement on synthetic ferri-Tschermak’s molecule CaFe3+(Fe3+Si)O6 substituted diopside. Eur J Mineral 10:439–452CrossRefGoogle Scholar
  2. 2.
    Morimoto N (1988) Nomenclature of pyroxenes. Miner Pet 39:55–76CrossRefGoogle Scholar
  3. 3.
    Nonami T, Tsutsumi S (2000) Press-formable CaO-MgO-SiO2-TiO2-Ag2O glass as a biomaterial. J Biomed Mater Res 50:8–15CrossRefGoogle Scholar
  4. 4.
    Goel A, Tulyaganov Du, Pascual MJ et al (2010) Development and performance of diopside based glass-ceramic sealants for solid oxide fuel cells. J Non Cryst Solids 356:1070–1080CrossRefGoogle Scholar
  5. 5.
    Reddy AA, Tulyaganov DU, Mather GC et al (2014) Effect of strontium-to-calcium ratio on the structure, crystallization behavior and functional properties of diopside-based glasses. Int J Hydrog Energy 39:3552–3563CrossRefGoogle Scholar
  6. 6.
    Reddy AA, Tulyaganov DU, Kharton VV, Ferreira JMF (2015) Development of bilayer glass-ceramic SOFC sealants via optimizing the chemical composition of glasses—a review. J Solid State Electrochem 19:2899–2916CrossRefGoogle Scholar
  7. 7.
    Chou CC, Feng KC, Raevski IP et al (2017) Part Ι: effects of two-stage heat treatment on densification, microstructural features and dielectric properties of CaO–MgO–SiO2 glass-ceramics with ZrO2 nucleating agents. Mater Res Bull 96:66–70CrossRefGoogle Scholar
  8. 8.
    Feng KC, Chou CC, Chu LW, Chen H (2012) Zirconia nucleating agent on microstructural and electrical properties of a CaMgSi2O6 diopside glass-ceramic for microwave dielectrics. Mater Res Bull 47:2851–2855CrossRefGoogle Scholar
  9. 9.
    Zanotto ED (2011) A bright future for glass ceramics. Am Ceram Soc Bull 89:609–612Google Scholar
  10. 10.
    Davis MJ, Zanotto ED (2017) Glass-ceramics and realization of the unobtainable: property combinations that push the envelope. MRS Bull 42:195–199CrossRefGoogle Scholar
  11. 11.
    Deubener J, Allix M, Davis MJ et al (2018) Updated the definition of glass-ceramics. J Non Cryst Solids 501:3–10CrossRefGoogle Scholar
  12. 12.
    Colombrini R, Zanotto ED, Craievich AF (1981) Vitrocerâmicos a partir de materias primas naturais. Ceramica 27:213–218Google Scholar
  13. 13.
    Zhang S, Zhang Y, Wu T (2018) Effect of Cr2O3 on the crystallization behavior of synthetic diopside and characterization of Cr-doped diopside glass ceramics. Ceram Int 44:10119–10129CrossRefGoogle Scholar
  14. 14.
    Ray CS, Zhang T, Reis ST, Brow RK (2007) Determining kinetic parameters for isothermal crystallization of glasses. J Am Ceram Soc 90:769–773CrossRefGoogle Scholar
  15. 15.
    Zhang T, Brow RK, Reis ST, Ray CS (2008) Isothermal crystallization of a solid oxide fuel cell sealing glass by differential thermal analysis. J Am Ceram Soc 91:3235–3239CrossRefGoogle Scholar
  16. 16.
    Marotta A, Buri A, Branda F (1981) Nucleation in glass and differential thermal analysis. J Mater Sci 16:341–344CrossRefGoogle Scholar
  17. 17.
    Donald IW (1995) The crystallization kinetics of a glass based on the cordierite composition studied by DTA and DSC. J Mater Sci 30:904–915CrossRefGoogle Scholar
  18. 18.
    Fokin VM, Zanotto ED (1999) Surface and volume nucleation and growth in TiO2-cordierite glasses. J Non Cryst Solids 246:115–127CrossRefGoogle Scholar
  19. 19.
    Fokin VM, Zanotto ED, Yuritsyn NS, Schmelzer JWP (2006) Homogeneous crystal nucleation in silicate glasses: a 40 years perspective. J Non Cryst Solids 352:2681–2714CrossRefGoogle Scholar
  20. 20.
    Prasad NS, Varma KBR (2005) Crystallization kinetics of the LiBO2–Nb2O5 glass using differential thermal analysis. J Am Ceram Soc 88:357–361CrossRefGoogle Scholar
  21. 21.
    Choi HW, Kim YH, Rim YH, Yang YS (2013) Crystallization kinetics of lithium niobate glass: determination of the Johnson-Mehl-Avrami-Kolmogorov parameters. Phys Chem Chem Phys 15:9940–9946CrossRefGoogle Scholar
  22. 22.
    Christian JW (1965) The theory of transformations in metals and alloys: an advanced textbook in physical metallurgy, vol 1, 1st edn. Pergamon Press, OxfordGoogle Scholar
  23. 23.
    Bansal NP, Doremus RH, Bruce AJ, Moynihan CT (1983) Kinetics of crystallization of ZrF4-Ba2-LaF3 glass by differential scanning calorimetry. J Am Ceram Soc 66:233–238CrossRefGoogle Scholar
  24. 24.
    Pietrzak TK, Wasiucionek M, Nowiński JL, Garbarczyk JE (2013) Isothermal nanocrystallization of vanadate-phosphate glasses. Solid State Ionics 251:78–82CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.São Carlos Institute of PhysicsUniversity of São PauloSão CarlosBrazil
  2. 2.Federal Institute of Santa CatarinaJoinvilleBrazil
  3. 3.DEMa – CeRTEV – Federal University of São CarlosSão CarlosBrazil

Personalised recommendations