Journal of Thermal Analysis and Calorimetry

, Volume 133, Issue 1, pp 371–377 | Cite as

Structural relaxation of lead and barium-free crystal glasses

  • Mária Chromčíková
  • Eleonóra Gašpáreková
  • Andrea Černá
  • Branislav Hruška
  • Marek Liška


The structural relaxation of Na2O–K2O–CaO–ZrO2–SiO2 (NKCZ), Na2O–K2O–ZnO–ZrO2–SiO2 (NKzZ), Na2O–CaO–ZnO–ZrO2–SiO2 (NCzZ), K2O–CaO–ZnO–ZrO2–SiO2 (KCzZ), and Na2O–K2O–CaO–ZnO–ZrO2–SiO2 (NKCzZ) glasses were studied by thermomechanical analysis. The structural relaxation was described by the Tool–Narayanaswamy–Mazurin model (TNMa). The relaxation function of Kohlrausch, Williams, and Watts (KWW) was used. The parameters of relaxation model were calculated by nonlinear regression analysis of thermodilatometric curves measured under cyclic time–temperature regime by thermomechanical analyzer under the constant load. The values of the exponent b of the KWW equation, modulus K, limit dynamic viscosity η 0 of the Mazurin’s expression for relaxation time, and constant B of the Vogel–Fulcher–Tammann viscosity equation were optimized. It was found that TNMa relaxation model very well describes the experimental data. A more detailed analysis of the obtained results showed that the equimolar substitution of SiO2 by ZrO2 (i.e., the increase of the ZrO2 content in the glass) decreases the parameter b, therefore the continuous distribution of the relaxation times spectrum is widening. A wider spectrum of relaxation times was obtained even in the case of substitution of ZnO for CaO and K2O for Na2O. Substitution of ZrO2 for SiO2 decreases the dynamic viscosity limit η 0 that corresponds to an activation energy increase of temperature dependence of isostructural viscosity. Increased content of ZrO2 in the glass caused the increase of the value of the modulus K.


Glass transition Structural relaxation Thermomechanical analysis 



This work was supported by the Slovak Grant Agency for Science under the grant VEGA 2/0088/16, and by the Slovak Research and Development Agency Project ID: APVV-0487-11.


  1. 1.
    Karell R, Kraxner J, Chromčíková M. Properties of selected zirconia containing silicate glasses. Ceram Silik. 2006;50:78–82.Google Scholar
  2. 2.
    Hofmann AW. Chemical differentiation of the Earth: the relationship between mantle, continental crust, and oceanic crust. Earth Planet Sci Lett. 1988;90:297–314.CrossRefGoogle Scholar
  3. 3.
    Vogel W. Glass chemistry. 2nd ed. Berlin: Springer; 1994.CrossRefGoogle Scholar
  4. 4.
    Proctor BA, Yale B. Glass fibres for cement reinforcement. Philos Trans R Soc Lond. 1980;A294:427–36.CrossRefGoogle Scholar
  5. 5.
    Fisher JG, James PF, Parker JM. Soda lime zirconia silicate glasses as prospective hosts for zirconia-containing radioactive wastes. J Non-Cryst Solids. 2005;351:623–31.CrossRefGoogle Scholar
  6. 6.
    Rada M, Šašek L, Lead-free crystal glass with the refractive index higher than 1,52. WO 1995013993 A1. EU Patent No. 91121730.5; 1991.Google Scholar
  7. 7.
    Šimurka P, Vrábel P, Petrušková V, Liška M, Macho V, Lead, barium and niobium free crystal glass and method of its production. SK Patent No. 285523; 2007.Google Scholar
  8. 8.
    Mazurin OV, Starcev JK, Chodakovskaja RJ. Relaxacionnaja teorija otzhiga stekla i raschet na jej osnove rezhimov otzhiga. Moskva: Moskovskij chimikotechnologicheskij institut; 1986 (in Russian).Google Scholar
  9. 9.
    Rao KJ. Structural chemistry of glasses. Amsterdam: Elsevier; 2002.Google Scholar
  10. 10.
    Scholze H, Kreidl NJ. Technological aspects of viscosity. In: Uhlmann DR, Kreidl NJ, editors. Viscosity and relaxation. Glass: science and technology, vol. 3. New York: Academic Press; 1986. p. 233–73.CrossRefGoogle Scholar
  11. 11.
    Hadac J, Slobodian P, Saha P. Volume and enthalpy relaxation response after combined temperature history in polycarbonate. J Therm Anal Calorim. 2005;80:181–5.CrossRefGoogle Scholar
  12. 12.
    Bari R, Simon SLJ. Determination of the nonlinearity and activation energy marameters in the TNM model of structural recovery. J Therm Anal Calorim. 2017;. doi: 10.1007/s10973-017-6381-6.Google Scholar
  13. 13.
    Pustkova P, Shanelova J, Malek J, Cicmanec P. Relaxation behavior of selenium based glasses. J Therm Anal Calorim. 2005;80:643–7.CrossRefGoogle Scholar
  14. 14.
    Liska M, Chromcikova M. Simultaneous volume and enthalpy relaxation. J Therm Anal Calorim. 2005;81:125–9.CrossRefGoogle Scholar
  15. 15.
    Chromcikova M, Liska M. Simple relaxation model of the reversible part of the StepScan® DSC record of glass transition. J Therm Anal Calorim. 2006;84:703–8.CrossRefGoogle Scholar
  16. 16.
    Liška M, Štubňa I, Antalík J, Perichta P. Structural relaxation with viscous flow followed by thermodilatometry. Ceramics. 1996;40:15–9.Google Scholar
  17. 17.
    Chromčíková M, Dej P. Structural relaxation of NBS711 glass—reliability of the regression estimates of relaxation model. Ceramics. 2006;50:125–59.Google Scholar
  18. 18.
    Williams G, Watts DC, Dev BS, North AN. Further considerations of non-symmetrical dielectric relaxation behavior arising from a simple empirical decay function. Trans Faraday Soc. 1971;67:1323–35.CrossRefGoogle Scholar
  19. 19.
    Kozmidis-Petrovic AF. The impact of the stretching exponent on fragility of glass-forming liquids. J Therm Anal Calorim. 2017;127:1975–81.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2017

Authors and Affiliations

  1. 1.Vitrum Laugaricio, Joint Glass Center of IIC SAS, TnU AD, and FChPT STUTrenčínSlovakia

Personalised recommendations