Abstract
A modified peak-deconvolution procedure for complex crystallization processes was introduced. The method is based on the constrained curve-fitting technique using the Fraser–Suzuki (FS) function, where the FS asymmetry parameter a 3 correlates with the value of the Johnson–Mehl–Avrami (JMA) kinetic parameter m. The correlation was verified for an extensive number of theoretically simulated JMA curves; in addition, the dependencies of the a 3 parameter on other kinetic variables (E, A, q +) were quantified. The suggested deconvolution procedure was tested on two glassy systems with different overlay degree of the involved overlapping surface and bulk crystallization processes. In both cases, the kinetic analysis of deconvoluted data provided reasonable, consistent and accurate results. However, certain level of knowledge and experience was needed in order to correctly recognize and consequently account for all deviations from the theoretical behavior caused by thermal gradients or imperfections of the data acquisition process. As the input data for the fitting procedure can be in any form equivalent to the dα/dT temperature dependence, the method seems to be highly universal and may be applied to data obtained by various TA techniques.
Similar content being viewed by others
References
Málek J. Kinetic analysis of crystallization processes in amorphous materials. Thermochim Acta. 2000;355:239–53.
Málek J. The kinetic analysis of non-isothermal data. Thermochim Acta. 1992;200:257–69.
Gotor FJ, Criado JM, Malek J, Koga N. Kinetic analysis of solid-state reactions: the universality of master plots for analyzing isothermal and nonisothermal experiments. J Phys Chem A. 2000;104:10777–82.
Sempere J, Nomen R, Serra R, Soravilla J. The NPK method—an innovative approach for kinetic analysis of data from thermal analysis and calorimetry. Thermochim Acta. 2002;388:407–14.
Sempere J, Nomen R, Serra R. Progress in non-parametric kinetics. J Therm Anal Calorim. 1999;56:843–9.
Sanchez-Jimenez PE, Perez-Maqueda LA, Perejon A, Criado JM. Combined kinetic analysis of thermal degradation of polymeric materials under any thermal pathway. Polym Degrad Stab. 2009;94:2079–85.
Perez-Maqueda LA, Criado JM, Malek J. Combined kinetic analysis for crystallization kinetics of non-crystalline solids. J Non Cryst Solids. 2003;320:84–91.
Lesnikovich AI, Levchik SV. A method of finding invariant values of kinetic parameters. J Therm Anal. 1983;27:89–94.
Lesnikovich AI, Levchik SV. Isoparametric kinetic relations for chemical transformations in condensed substances (analytical survey)—reactions involving participation of solid substances. J Therm Anal. 1985;30:677–702.
Perejón A, Sánchéz-Jiménez PE, Criado JM, Pérez-Maqueda LA. Kinetic analysis of complex solid-state reactions. A new deconvolution procedure. J Phys Chem B. 2011;115:1780–91.
Fraser RDB, Suzuki E. Resolution of overlapping absorption bands by least squares procedures. Anal Chem. 1966;38:1770–3.
Fraser RDB, Suzuki E. Resolution of overlapping bands—functions for simulating band shapes. Anal Chem. 1969;61:37–9.
Johnson WA, Mehl KF. Reaction kinetics in processes of nucleation and growth. Trans AIME. 1939;135:416–42.
Avrami M. Kinetics of phase change I—general theory. J Chem Phys. 1939;7:1103–12.
Avrami M. Kinetics of phase change. II—transformation-time relations for random distribution of nuclei. J Chem Phys. 1940;7:212–24.
Avrami M. Granulation, phase change, and microstructure—kinetics of phase change III. J Chem Phys. 1941;7:177–84.
Šesták J. Thermophysical properties of solids. Their measurements and theoretical analysis. Amsterdam: Elsevier; 1984.
Svoboda R, Málek J. Extended study of crystallization kinetics for Se–Te glasses. J Therm Anal Calorim. 2012. doi:10.1007/s10973-012-2347-x.
Šesták J. Science of heat and thermophysical studies: a generalized approach to thermal analysis. Amsterdam: Elsevier; 2005.
Runge C. Über empirische Funktionen und die Interpolation zwischen äquidistanten Ordinaten. Zeitschrift für Mathematik und Physik. 1901;46:224–43.
Svoboda R, Málek J. Interpretation of crystallization kinetics results provided by DSC. Thermochim Acta. 2011;526:237–51.
Barták J, Svoboda R, Málek J. Electrical properties and crystallization kinetics of Se–Te chalcogenide glasses. J Appl Phys (accepted).
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29:1702–6.
Friedman HL. Kinetics of thermal degradation of char-forming plastics from thermogravimetry. Application to a phenolic plastic. New York: Wiley; 1964.
Svoboda R, Málek J. Particle size influence on crystallization behavior of Ge2Sb2Se5 glass. J Non-Cryst Solid. 2012;358:276–84.
Acknowledgements
This work has been supported by the Czech Science Foundation under Project No. P106/11/1152.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Svoboda, R., Málek, J. Applicability of Fraser–Suzuki function in kinetic analysis of complex crystallization processes. J Therm Anal Calorim 111, 1045–1056 (2013). https://doi.org/10.1007/s10973-012-2445-9
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-012-2445-9