A study on kinetics of ignition reaction of B4C/KNO3 and B4C/KClO4 pyrotechnic smoke compositions

  • Jingran Xu
  • Chenguang ZhuEmail author
  • Xiao Xie
  • Chenguang Yan
  • Yikai Wang


Presented herein is a study on the ignition reaction kinetics and mechanism of B4C/KNO3 and B4C/KClO4 pyrotechnic smoke compositions using the non-isothermal thermogravimetry and differential scanning calorimetry techniques. The pyrotechnics in oxygen balance of − 10%, − 20% and − 30% were prepared for the experiments. The results of measurements showed that the pyrotechnics in oxygen balance of − 20% had the highest enthalpy. The activation energy (Ea) of ignition reactions was calculated by using Ozawa–Flynn–Wall (OFW) and Kissinger–Akahira–Sunose (KAS) methods. The Ea values of B4C/KNO3 and B4C/KClO4 were 139.5 and 214.6 kJ mol−1 calculated by OFW method, and 129.3 and 210.7 kJ mol−1 by KAS method. The differential and integral reaction mechanism functions of B4C/KNO3 and B4C/KClO4 were determined, respectively, by z(α) master plots method, f1(α) = 2(1 − α)[− ln(1 − α)]1/2, g1(α) = [− ln(1 − α)]1/2, and f2(α) = 3(1 − α)[− ln(1 − α)]2/3, g2(α) = [− ln(1 − α)]1/3. The pre-exponential factors, lnA = 11.6 and 22.3 min−1, were obtained by the intercept of KAS method for ignition reaction of B4C/KNO3 and B4C/KClO4 pyrotechnics. Based on the results, the burning rates, thermal sensitivities and application methods of B4C/KNO3 and B4C/KClO4 were predicted.


Pyrotechnics TG/DSC Ignition reaction Kinetics 



The support for this work was provided by the National Natural Science Foundation of China (Project No. 51676100).


  1. 1.
    Eaton JC, Lopinto RJ, Palmer WG. Health effects of hexachloroethane (HC) smoke; accession number ADA277838; Defense Technical Information Center (DTIC): Fort Belvoir, VA, 1994; pp 1–60.Google Scholar
  2. 2.
    Shaw AP, Poret JC, Gilbert RA, et al. Development and performance of boron carbide-based smoke compositions. Propellants Explos Pyrotech. 2013;38(5):622–8.CrossRefGoogle Scholar
  3. 3.
    Shaw AP, Diviacchi G, Black EL, et al. Versatile boron carbide-based visual obscurant compositions for smoke munitions. ACS Sustain Chem Eng. 2015;3(6):150423154904007.CrossRefGoogle Scholar
  4. 4.
    Thévenot F. Boron carbide—a comprehensive review. J Eur Ceram Soc. 1990;6(4):205–25.CrossRefGoogle Scholar
  5. 5.
    Reddy RG, Wang T, Mantha D. Thermodynamic properties of potassium nitrate–magnesium nitrate compound [2KNO3·Mg(NO3)2]. Thermochim Acta. 2012;531:6–11.CrossRefGoogle Scholar
  6. 6.
    Benenson W, Harris JW, Stocker H et al. Handbook of physics; 2002. ISBN 978-0387952697.Google Scholar
  7. 7.
    Pan GP, Yang S. Pyrotechnic technology. Nanjing: Initiators and Pyrotechnics Technology Committee; 1995.Google Scholar
  8. 8.
    Wendlandt WW. Thermal analysis. 3rd ed. Hoboken: Wiley; 1986.Google Scholar
  9. 9.
    Vyazovkin S, Burnham AK, Criado JM, et al. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520(1–2):1–19.CrossRefGoogle Scholar
  10. 10.
    Pouretedal HR, Loh Mousavi S. Study of the ratio of fuel to oxidant on the kinetic of ignition reaction of Mg/Ba(NO3)2 and Mg/Sr(NO3)2 pyrotechnics by non-isothermal TG/DSC technique. J Therm Anal Calorim. 2018;132:1307–15.CrossRefGoogle Scholar
  11. 11.
    Vyazovkin S. Alternative description of process kinetics. Thermochim Acta. 1992;211(1):181–7.CrossRefGoogle Scholar
  12. 12.
    Flynn JH. The ‘temperature integral’—its use and abuse. Thermochim Acta. 1997;300(1–2):83–92.CrossRefGoogle Scholar
  13. 13.
    Miyata K. Combustion of boron-pyrotechnics. In: Joint propulsion conference and exhibit. 2013.Google Scholar
  14. 14.
    El-Awad AM. Catalytic effect of some chromites on the thermal decomposition of KClO4 mechanistic and non-isothermal kinetic studies. J Therm Anal Calorim. 2000;61(1):197–208.CrossRefGoogle Scholar
  15. 15.
    Liu PJ, Liu LL, He GQ. Effect of solid oxidizers on the thermal oxidation and combustion performance of amorphous boron. J Therm Anal Calorim. 2016;124(3):1587–93.CrossRefGoogle Scholar
  16. 16.
    Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881.CrossRefGoogle Scholar
  17. 17.
    Flynn JH, Wall LA. General treatment of the thermogravimetry of polymers. J Res Natl Bureau Stand Part A. 1966;70:487.CrossRefGoogle Scholar
  18. 18.
    Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 1957;29(11):1702–6.CrossRefGoogle Scholar
  19. 19.
    Akahira T, Sunose T. Method of determining activation deterioration constant of electrical insulating materials. Res Rep (Chiba Inst Technol) Sci Technol. 1971;16:22–31.Google Scholar
  20. 20.
    Malek J. The applicability of Johnson–Mehl–Avrami model in the thermal analysis of the crystallization kinetics of glasses. Thermochim Acta. 1995;267:61–73.CrossRefGoogle Scholar
  21. 21.
    Brown ME. Introduction to thermal analysis. 2nd ed. Dodrecht: Kluwer; 2001.Google Scholar
  22. 22.
    Pouretedal HR, Ebadpour R. Application of Non-isothermal thermogravimetric method to interpret the decomposition kinetics of NaNO3, KNO3, and KClO4. Int J Thermophys. 2014;35(5):942–51.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2019

Authors and Affiliations

  1. 1.School of Chemical EngineeringNanjing University of Science and TechnologyNanjingChina

Personalised recommendations