Abstract
Nitrate ester plasticized polyether (NEPE) propellant has attracted considerable attention as a kind of high-energy propellant. To investigate the evolution of thermal properties of NEPE propellant during storage life, TG-DSC-MS-FTIR was used to determine the thermal behaviors of the propellant samples before and after 5-year natural storage. It was found out that both samples experience five reaction steps and they are attributed by the evaporation and O–NO2 bond breaking of nitrate, crystal transition of HMX and thermal decomposition of plasticizer, HMX and ammonium perchlorate. Decomposition process and temperature ranges of each step maintain consistency, but nitrate ester tends to decompose more than evaporate after storage. In the meantime, the area of DSC peak formed in the third step noticeably increased, which accounts for the lower thermal explosion temperature. To further study the decomposition of plasticizer and HMX, their kinetic triplets were solved. It was found out that the activation energy increases significantly on plasticizer decomposition step because of the enlargement of the nitrate’s particle size. Therefore, it can be drawn that the decline of NEPE propellant’s safety property after storage was contributed by the decomposition step of nitrate ester plasticizer.
Similar content being viewed by others
References
Matečić Mušanić S, Sućeska M, Bakija S. Applicability of dynamic mechanical and thermal methods in investigation of ageing processes of double based rocket propellants. In: Proceedings of 9th Seminar New Trends in Research of Energetic Materials, Pardubice; 2006. p. 214–30.
Matečić Mušanić S, Sućeska M, Rajić Linarić M, Bakija S, Čuljak R. Changes of dynamic mechanic properties of double based rocket propellant during artificial ageing. In: Proceedings of 7th Seminar New Trends in Research of Energetic Materials, Pardubice; 2004. p. 570–83.
Yan QL, Zhu WH, Pang AM, Chi XH, Du XJ, Xiao HM. Theoretical studies on the unimolecular decomposition of nitroglycerin. J Mol Model. 2013;19(4):1617–26.
Suceska M, Musanic SM, Houra IF. Kinetics and enthalpy of nitroglycerin evaporation from double base propellants by isothermal thermogravimetry. Thermochim Acta. 2010;510(1–2):9–16.
Tompa AS. Thermal analysis of liquid and solid propellants. J Hazard Mater. 1980;4(1):95–112.
Sun YL, Li SF. The effect of nitrate esters on the thermal decomposition mechanism of GAP. J Hazard Mater. 2008;154(1–3):112–7.
Menke K, Eisele S. Rocket propellants with reduced smoke and high burning rates. Propellants, Explos, Pyrotech. 1997;22(3):112–9.
Oyumi Y, Inokami K, Yamazaki K, Matsumoto K. Thermal decomposition of BAMO/HMX propellants. Propellants, Explos, Pyrotech. 1993;18(2):62–8.
Qin C, Zhao XB, Li J. Grey relational analysis in influencing factors of NEPE propellant sensitivity. Chin J Energ Mater. 2012;06:762–5.
Jiao QJ, Zhu YL, Xing JC, Ren H, Huang H. Thermal decomposition of RDX/AP by TG-DSC-MS-FTIR. J Therm Anal Calorim. 2014;116(3):1125–31.
Li XY, Liu XL, Cheng Y, Li YC, Mei XL. Thermal decomposition properties of double-base propellant and ammonium perchlorate. J Therm Anal Calorim. 2014;115(1):887–94.
Liu LL, He GQ, Wang YH, Liu PJ. Effect of catocene on the thermal decomposition of ammonium perchlorate and octogen. J Therm Anal Calorim. 2014;117(2):621–8.
House JE Jr, Flentge C, Zack PJ. A study of propellant decomposition by differential scanning calorimetry. Thermochim Acta. 1978;24(1):133–8.
Rodante F. A thermoanalytical study of the decomposition of a double-base propellant. Thermochim Acta. 1986;101:373–80.
Kumari D, Singh H, Patil M, Thiel W, Pant CS, Banerjee S. Synthesis, characterization, thermal and computational studies of novel tetra-azido esters as energetic plasticizers. Thermochim Acta. 2013;562:96–9.
Weese RK, Maienschein JL, Perrino CT. Kinetics of the β → δ solid–solid phase transition of HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine. Thermochim Acta. 2003;401(1):1–7.
Pinheiro GFM, Lourenco VL, Iha K. Influence of the heating rate in the thermal decomposition of HMX. J Therm Anal Calorim. 2002;67(2):445–52.
Lee JS, Hsu CK, Chang CL. A study on the thermal decomposition behaviors of PETN, RDX, HNS and HMX. Thermochim Acta. 2002;392:173–6.
Zhu YL, Huang H, Ren H, Jiao QJ. Kinetics of thermal decomposition of ammonium perchlorate by TG/DSC-MS-FTIR. J Energ Mater. 2014;32(1):16–26.
Wang YH, Liu LL, Xiao LY, Wang ZX. Thermal decomposition of HTPB/AP and HTPB/HMX mixtures with low content of oxidizer. J Therm Anal Calorim. 2015;119(3):1673–8.
Kissinger HE. Reaction kinetics in differential thermal analysis. Anal Chem. 2002;29(11):1702–5.
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38(11):1881–6.
Ozawa T. Kinetic analysis of derivative curves in thermal analysis. J Therm Anal. 1970;2(3):301–24.
Hu RZ, Gao SL, Zhao FQ, Shi QZ, Zhang TL, Zhang JJ. Thermal analysis kinetics. Beijing: Science Press; 2008.
Šatava V, Šesták JJ. Computer calculation of the mechanism and associated kinetic data using a non-isothermal integral method. Therm Anal. 1975;8(3):477–89.
Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data. II. J Polym Sci B. 1964;3:182–5.
Agrawal RK. A new equation for modeling nonisothermal kinetics. J Therm Anal. 1987;34(1):149–56.
Fathollahi M, Pourmortazavi M, Hosseini G. Particle size effects on thermal decomposition of energetic material. J Energ Mater. 2007;26:52–69.
Sovizi MR, Hajimirsadeghi SS, Naderizadeh B. Effect of particle size on thermal decomposition of nitrocellulose. J Hazard Mater. 2009;168(2–3):1134–9.
Zhang TL, Hu RZ, Xie Y, Li FP. The estimation of critical temperatures of thermal explosion for energetic materials using non-isothermal DSC. Thermochim Acta. 1994;244:171–6.
Huang CC, Wu TS. A simple method for estimating the autoignition temperature of solid energetic materials with a single non-isothermal DSC or DTA curve. Thermochim Acta. 1994;239:105–14.
Yi JH, Zhao FQ, Wang BZ, Liu Q, Zhou C, Hu RZ, et al. Thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates of BTATz-CMDB propellant. J Hazard Mater. 2010;181(1–3):432–9.
Semenov N. Theories of combustion processes. Zeitschrift fur Physikalische Chemie. 1928;48:571–82.
Acknowledgements
Funding was provided by National Natural Science Foundation of China (A11172042).
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Sun, Y., Ren, H. & Jiao, Q. Comparison of thermal behaviors and decomposition kinetics of NEPE propellant before and after storage. J Therm Anal Calorim 131, 101–111 (2018). https://doi.org/10.1007/s10973-017-6525-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10973-017-6525-8