, Volume 26, Issue 17, pp 9021–9033 | Cite as

Interaction and mechanism of nitrocellulose and N-methyl-4-nitroaniline by isothermal decomposition method

  • Liqiong Luo
  • Bo JinEmail author
  • Zuohu Chai
  • Qiong Huang
  • Shijin Chu
  • Rufang PengEmail author
Original Research


The influence of N-methyl-4-nitroaniline (MNA) on the thermal stability of nitrocellulose (NC) was investigated via an isothermal decomposition dynamics research method. The Arrhenius equation and model-fitting were used to calculate the thermal decomposition kinetic parameters of NC and MNA/NC (3 wt%) composite. Results showed that the thermal decomposition activation energy of NC/MNA (3 wt%) was significantly increased compared with that of pure NC, indicating that the thermal stability of NC was increased with stabilizer MNA addition. Subsequently, the storage life of NC and MNA/NC (3 wt%) composite was estimated using Berthelot equation. It was found that if the decomposition extent reaches 0.1% as the end of life criterion, 3 wt% stabilizer MNA addition significantly extended the storage life of NC from 10.57 to 24.9 years at ambient temperature (298.15 K) with the life extension rate reaching 135.6%. Furthermore, the intermediate product produced by MNA and NC action was extracted and characterized via UV–Vis, HPLC, 1H  NMR, FT-IR, and LC–MS, and a possible stabilization mechanism of MNA to NC was proposed.


Nitrocellulose N-methyl-4-nitroaniline Stabilizer Isothermal decomposition Storage life 



We are grateful for financial support by the Science Challenge Project (Project No. TZ2018004), the Natural Science Foundation of China (21875192), Key Projects of the Pre-research Fund of the General Armament Department (Project No. 6140720020101), National Defense Technology Foundation Project (Project No. JSJL2016404B002) and the Institute of Chemical Materials, China Academy of Engineering Physics (Project No. 18zh0079).

Supplementary material

10570_2019_2691_MOESM1_ESM.docx (2.4 mb)
Supplementary file1 (DOCX 2467 kb)


  1. Boers MN (2010) Lifetime prediction of EC, DPA, Akardite II and MNA stabilized triple base propellants, comparison of heat generation rate and stabilizer consumption. Propell Explos Pyrot 30:356–362CrossRefGoogle Scholar
  2. Chai H, Duan QL, Jiang L, Gong L, Chen HD, Sun JH (2019) Theoretical and experimental study on the effect of nitrogen content on the thermal characteristics of nitrocellulose under low heating rates. Cellulose 26:763–776CrossRefGoogle Scholar
  3. Chelouche S, Trache D, Tarchoun AF, Abdelaziz A, Khimeche K, Mezroua A (2019) Organic eutectic mixture as efficient stabilizer for nitrocellulose: kinetic modeling and stability assessment. Thermochim Acta 673:78–91CrossRefGoogle Scholar
  4. Chu SJ (1994) Thermal analysis of explosive. Science press, BeijingGoogle Scholar
  5. Cui G, Yoo JH, Yoo J, Lee SW, Nam H, Cha GS (2001) Differential thick-film amperometric glucose sensor with an enzyme-immobilized nitrocellulose membrane. Electroanalysis 13:224–228CrossRefGoogle Scholar
  6. Frys O, Bajerova P, Eisner A, Skladal J, Ventura K (2011) Utilization of new non-toxic substances as stabilizers for nitrocellulose-based propellants. Propell Explos Pyrot 36:347–355CrossRefGoogle Scholar
  7. Hu RZ, Gao SL, Zhao FQ (2008) Thermal analysis kinetics. Science press, BeijingGoogle Scholar
  8. Krumlinde P, Ek S, Tunestal E, Hafstrand A (2017) Synthesis and characterization of novel stabilizers for nitrocellulose-based propellants. Propell Explos Pyrot 42:78–83CrossRefGoogle Scholar
  9. Lin CP, Li JS, Tseng JM, Mannan MS (2016) Thermal runaway reaction for highly exothermic material in safe storage temperature. J Loss Prevent Proc 40:259–265CrossRefGoogle Scholar
  10. Lindblom T (2002) Reactions in stabilizer and between stabilizer and nitrocellulose in propellants. Propell Explos Pyrot 27:197–208CrossRefGoogle Scholar
  11. Liu R, Zhou ZN, Yin YL, Zhang TL (2012) Dynamic vacuum stability test method and investigation on vacuum thermal decomposition of HMX and CL-20. Thermochim Acta 537:13–19CrossRefGoogle Scholar
  12. Luo LQ, Jin B, Xiao YY, Zhang QC, Chai ZH, Huang Q, Chu SJ, Peng RF (2019a) Study on the isothermal decomposition kinetics and mechanism of nitrocellulose. Polym Test 75:337–343CrossRefGoogle Scholar
  13. Luo LQ, Guo PL, Jin B, Xiao YY, Zhang QC, Chu SJ, Peng RF (2019b) An improved isothermal decomposition dynamics research instrument and its application in HMX/TNT/Al composite explosive. J Therm Anal Calorim. CrossRefGoogle Scholar
  14. Lussier LS, Bergeron E, Gagnon H (2006) Study of the daughter products of Akardite-II. Propell Explos Pyrot 31:253–262CrossRefGoogle Scholar
  15. Shekhar M (2011) Prediction and comparison of shelf life of solid rocket propellants using Arrhenius and Berthelot equations. Propell Explos Pyrot 36:356–359CrossRefGoogle Scholar
  16. Tai C, Zhang SD, Yin YG, Dai ZF, Li YB, Jiang GB, Cai Y, Huang CH, Shi JB (2018) Facile photoinduced generation of hydroxyl radical on a nitrocellulose nembrane surface and its application in the degradation of organic pollutants. ChemSusChem 11:843–847CrossRefGoogle Scholar
  17. Tan HM (2015) The chemistry and technology of solid rocket propellant. Beijing Institute of Technology Press, BeijingGoogle Scholar
  18. Tang QF, Fan XZ, Li JZ, Bi FQ, Fu XL, Zhai LJ (2016) Experimental and theoretical studies on stability of new stabilizers for N-methyl-P-nitroaniline derivative in CMDB propellants. J Hazard Mater 327:187–196CrossRefGoogle Scholar
  19. Trache D, Khimeche K (2013a) Study on the influence of ageing on chemical and mechanical properties of N, N′-dimethyl-N, N′-diphenylcarbamide stabilized propellants. J Therm Anal Calorim 111:305–312CrossRefGoogle Scholar
  20. Trache D, Khimeche K (2013b) Study on the influence of ageing on thermal decomposition of double-base propellants and prediction of their in-use time. Fire Mater 37:328–336CrossRefGoogle Scholar
  21. Trache D, Tarchoun AF (2018a) Analytical methods for stability assessment of nitrate esters-based propellants. Crit Rev Anal Chem. CrossRefGoogle Scholar
  22. Trache D, Tarchoun AF (2018b) Stabilizers for nitrate ester-based energetic materials and their mechanism of action: a state-of-the-art review. J Mater Sci 53:100–123CrossRefGoogle Scholar
  23. Trache D, Khimeche K, Dahmani A (2013a) Solid–liquid phase equilibria for binary mixtures of propellant’s stabilizers. J Therm Anal Calorim 112:215–222CrossRefGoogle Scholar
  24. Trache D, Khimeche K, Dahmani A (2013b) Study of (solid–liquid) phase equilibria for mixtures of energetic; material stabilizers and prediction for their subsequent performance. Int J Thermophys 34:226–239CrossRefGoogle Scholar
  25. Wilker S, Heeb G, Vogelsanger B, Jan P, Jan S (2007) Triphenylamine-a ‘new’ stabilizer for nitrocellulose based propellants-part I: chemical stability studies. Propell Explos Pyrot 32:135–148CrossRefGoogle Scholar
  26. Xiao YY, Bo J, Peng RF, Zhang QC, Liu QQ, Chu SJ, Guo ZC (2016) Thermal decomposition of CL-20 via a self-modified dynamic vacuum stability test. J Therm Anal Calorim 128:1833–1840CrossRefGoogle Scholar
  27. Zayed MA, Hassan MA (2010) Stability of non-isothermally treated double-base propellants containing different stabilizers in comparison with molecular orbital calculations. Propell Explos Pyrot 35:468–476CrossRefGoogle Scholar
  28. Zayed MA, Soliman AA, Hassan MA (2000) Evaluation of malonanilides as new stabilizers for double-base propellants. J Hazard Mater 73:237–244CrossRefGoogle Scholar
  29. Zayed MA, Mohamed AA, Hassan MA (2010) Stability studies of double-base propellants with centralite and malonanilide stabilizers using MO calculations in comparison to thermal studies. J Hazard Mater 179:453–461CrossRefGoogle Scholar
  30. Zayed MA, El-Begawy SEM, Hassan HES (2012) Enhancement of stabilizing properties of double-base propellants using nano-scale inorganic compounds. J Hazard Mater 227–228:274–279CrossRefGoogle Scholar
  31. Zayed MA, El-Begawy SEM, Hassan HES (2013) Mechanism study of stabilization of double-base propellants by using zeolite stabilizers (nano- and micro-clinoptilolite). Arab J Chem 10:573–581CrossRefGoogle Scholar
  32. Zhao X, Rui XT, Wang Y, Zhang RH (2018) A novel method for prediction of propellant shelf-life based on Arrhenius equation. Propell Explos Pyrot 43:348–354CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  1. 1.State Key Laboratory of Environment-friendly Energy MaterialsSouthwest University of Science and TechnologyMianyangChina

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