Influence of the STA boundary conditions on thermal decomposition of thermoplastic polymers

  • David LázaroEmail author
  • Mariano Lázaro
  • Alain Alonso
  • Pedro Lázaro
  • Daniel Alvear


The analysis of polymer chemical decomposition is often highly dependent on the test conditions. In fact, thermal analysis tends to be far more sensitive to instrumental parameters than other branches of chemical analysis. Some of the boundary conditions in thermal analysis have been widely studied in the literature, such as the heating rate or the atmosphere. However, the influence of the sample mass, the gas flow or the use of lid has not been studied enough for thermoplastic polymers. The aim of this paper is to analyse how the experimental boundary conditions of the simultaneous thermal analysis apparatus affect the thermal decomposition of thermoplastic polymers. To do so, a set of 35 experimental tests have been performed including variation of the sample mass, gas flow rate, heating rate, atmosphere and the use of lid in the crucible. Results enable us to analyse the influence in the mass loss and in the energy release or absorbed in the thermal decomposition of thermoplastic polymers, showing the impact of each boundary condition over the thermal decomposition. A comprehensive analysis of the thermal decomposition behaviour of the PVC and LLDPE by considering the influence of all the boundary conditions of the STA is covered. It is especially remarkable the influence of gas flow in the oxidative reactions, and of heating rate in the chemical reactions that thermoplastic polymers undergo in their decomposition. Additionally, sample mass comparison shows only deviation in the oxidative reactions and does not show deviation for the non-oxidative reactions. That seems to show a higher effect on the results because of the energy release in the decomposition reactions than because of the thermal lag due to heat transfer on the sample, as it is usually thought.


TG profiles DSC profiles LLDPE PVC Thermal decomposition 



Authors would like to thank the Consejo de Seguridad Nuclear for the cooperation and co-financing the project “Simulation of fires in nuclear power plants” and CAFESTO Project funded by the Spanish Ministry of Science, Innovation and Universities and the Spanish State Research Agency through Public–Private Partnerships (Retos Colaboración 2017 call, ref RTC-2017-6066-8) co-funded by ERDF under the objective “Strengthening research, technological development and innovation”.


  1. 1.
    Witkowski A, Stec AA, Hull TR. Chapter 7. Thermal decomposition of polymeric materials. In: SFPE, editor. SFPE handbook of fire protection engineering. 5th ed. Berlin: Springer; 2016. p. 1–3493.Google Scholar
  2. 2.
    Sun Y, Gao M, Chai Z, Wang H. Thermal behavior of the flexible polyvinyl chloride including montmorillonite modified with iron oxide as flame retardant. J Therm Anal Calorim. 2018;131(1):65–70.CrossRefGoogle Scholar
  3. 3.
    Alonso A, Puente E, Lázaro P, Lázaro D, Alvear D. Experimental review of oxygen content at mixing layer in cone calorimeter. J Therm Anal Calorim. 2017;129(2):639–54.CrossRefGoogle Scholar
  4. 4.
    ASTM Standard E1131—08 standard test method for compositional analysis by thermogravimetry. West Conshohocken, PA; 2014.Google Scholar
  5. 5.
    EN ISO 11358-1:2015 plastics—thermogravimetry (TG) of polymers-part 1: general principles.Google Scholar
  6. 6.
    UNE-EN ISO 11357-1. Plásticos Calorimetría diferencial de barrido (DSC) Parte 1: Principios generales. (ISO 11357-1:2016).Google Scholar
  7. 7.
    Schindler A, Doedt M, Gezgin Ş, Menzel J, Schmölzer S. Identification of polymers by means of DSC, TG, STA and computer-assisted database search. J Therm Anal Calorim. 2017;129(2):833–42.CrossRefGoogle Scholar
  8. 8.
    Vyazovkin S, Chrissafis K, Di Lorenzo ML, Koga N, Pijolat M, Roduit B, et al. ICTAC Kinetics Committee recommendations for collecting experimental thermal analysis data for kinetic computations. Thermochim Acta. 2014;590:1–23.CrossRefGoogle Scholar
  9. 9.
    Marcilla A, Beltran M. Thermogravimetric kinetic study of poly (vinyl chloride) pyrolysis. Polym Degrad Stab. 1995;3910(95):219–29.CrossRefGoogle Scholar
  10. 10.
    Miranda R, Pakdel H, Roy C, Darmstadt H, Vasile C. Vacuum pyrolysis of PVC I: kinetic study. Polym Degrad Stab. 1999;66(1):107–25.CrossRefGoogle Scholar
  11. 11.
    Morais LC, Maia AAD, Guandique MEG, Rosa AH. Pyrolysis and combustion of sugarcane bagasse. J Therm Anal Calorim. 2017;129(3):1813–22.CrossRefGoogle Scholar
  12. 12.
    Wu J, Wang B, Cheng F. Thermal and kinetic characteristics of combustion of coal sludge. J Therm Anal Calorim. 2017;129(3):1899–909.CrossRefGoogle Scholar
  13. 13.
    Xu W, Li J, Liu F, Jiang Y, Li Z, Li L. Study on the thermal decomposition kinetics and flammability performance of a flame-retardant leather. J Therm Anal Calorim. 2017;128(2):1107–16.CrossRefGoogle Scholar
  14. 14.
    Zong R, Wang Z, Liu N, Hu Y, Liao G. Thermal degradation kinetics of polyethylene and silane-crosslinked polyethylene. J Appl Polym Sci. 2005;98(3):1172–9.CrossRefGoogle Scholar
  15. 15.
    Capote J, Alvear D, Abreu O, Lázaro M, Puente E. Modelling pyrolysis of a medium density polyethylene. Int Rev Chem Eng. 2010;2(7):884–90.Google Scholar
  16. 16.
    Lázaro D, Puente E, Lázaro M, Alvear D. Characterization of polyethylene decomposition reactions using the TG curve. Int Rev Chem Eng. 2014;6(January):77–82.Google Scholar
  17. 17.
    Peterson JD, Vyazovkin S, Wight CA. Kinetics of the thermal and thermo-oxidative degradation of polystyrene, polyethylene and poly(propylene). Macromol Chem Phys. 2001;202(6):775–84.CrossRefGoogle Scholar
  18. 18.
    Jiménez A, Iannoni A, Torre L, Kenny JM. Kinetic modeling of the thermal degradation of stabilized PVC plastisols. J Therm Anal Calorim. 2000;61(2):483–91.CrossRefGoogle Scholar
  19. 19.
    Marquis DM, Guillaume E, Camillo A, Rogaume T, Richard F. Existence and uniqueness of solutions of a differential equation system modeling the thermal decomposition of polymer materials. Combust Flame. 2013;160(4):818–29. Scholar
  20. 20.
    Marquis DM, Pavageau M, Guillaume E, Chivas-Joly C. Modelling decomposition and fire behaviour of small samples of a glass-fibre-reinforced polyester/balsa-cored sandwich material. Fire Mater. 2013;37:413–39.CrossRefGoogle Scholar
  21. 21.
    Abu-Bakar AS, Moinuddin KAM. Effects of variation in heating rate, sample mass and nitrogen flow on chemical kinetics for pyrolysis. 18th Australasian fluid mechanics conference; 2012 December. p. 18–21.Google Scholar
  22. 22.
    Stawski D. The effect of sample weight in thermogravimetric analysis of low viscosity polypropylene in air atmosphere. Polym Test. 2009;28(2):223–5.CrossRefGoogle Scholar
  23. 23.
    Luo J, Li Q, Meng A, Long Y, Zhang Y. Combustion characteristics of typical model components in solid waste on a macro-TGA. J Therm Anal Calorim. 2018;132(1):553–62. Scholar
  24. 24.
    ASTM E1269-11(2018). Standard test method for determining specific heat capacity by differential scanning calorimetry. West Conshohocken: ASTM International; 2018.
  25. 25.
    Wolfinger MG, Rath J, Krammer G, Barontini F, Cozzani V. Influence of the emissivity of the sample on differential scanning calorimetry measurements. Thermochim Acta. 2001;372(1–2):11–8.CrossRefGoogle Scholar
  26. 26.
    Posch W. Polyolefins. In: Applied plastics engineering handbook [Internet]; 2011. p. 23–48.

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.GIDAI Group, University of CantabriaSantanderSpain

Personalised recommendations