Thermal decomposition and kinetic evaluation of composite propellant material catalyzed with nano magnesium oxide


  • Zaheer-ud-Din Babar School of Chemical and Materials Engineering (NUST)
  • Abdul Qadeer Malik School of Chemical and Materials Engineering (NUST)



Magnesium oxide nano particles have been used to catalyze the composite propellant material based on hydroxy terminated polybutadiene (HTPB) and ammonium perchlorate (AP). Thermal decomposition and the kinetic parameters of catalyzed and non-catalyzed version of the composite solid propellant have been investigated in the present work.  X-ray diffraction (XRD) technique and scanning electron microscope (SEM) were used to characterize the MgO nano particles before they were added to the propellant material. The average size of the particles was found to be approximately 20-30 nm. The Arrhenius kinetic parameters of both versions of the propellant were evaluated using Kissinger method. Moreover, three isoconversional methods also have been used for the kinetic analysis of both versions of propellant. These methods include Friedman method, Flynn–Wall–Ozawa method and Kissinger-Akahira-Sunose Method. The comparative analysis of the kinetic parameters as well as the thermal behavior of pure and catalyzed composite solid propellant (CSP) has been done under identical set of reaction conditions. The results indicate that MgO nano particles have an obvious catalytic effect on the thermal decomposition of the composite propellant and consequently, the kinetic parameters also change significantly. The decomposition peak temperature of the propellant decreased nearly 22oC due to the addition of two percent of MgO as a catalyst. The activation energy of the catalyzed propellant however, increased by 28 kJmol-1 from 127.1 kJmol-1 to 155.4 kJmol-1. Both the frequency factor and the rate constant increased in the catalyzed version of the propellant material and confirmed that a noticeable catalytic activity has taken place. 


G.Singh, I.P.S.Kapoor, R.Dubey and P.Srivastava, "Preparation characterization and catalytic behavior of CdFe2O4 and Cd nanocrystals on AP, HTPB and composite solid propellants", Thermochimica Acta, Vol. 511, No.1, 2010, pp. 112-118.

R.F.B. Gongalves, J.A.F.F.Rocco and K.Iha, "Thermal decomposition kinetics of aged solid propellant based on ammonium perchlorate–AP/HTPB binder", 44th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit, July 2008.

S.Ramamurthy and P. Shrotri, "Catalytic decomposition of ammonium perchlorate a survey. Journal of Energetic Materials, Vol.14,No.2, 1996, pp.97-126.

K.Ishitha and P. Ramakrishna, "Studies on the role of iron oxide and copper chromite in solid propellant combustion", Combustion and Flame, 2014.

P.R.Patil, V.e.N. Krishnamurthy, and S.S. Joshi, "Effect of Nano‐Copper Oxide and Copper Chromite on the Thermal Decomposition of Ammonium Perchlorate". Propellants, Explosives, Pyrotechnics, Vol.33, No.4, 2008, pp. 266-270.

K.Kishore, V.P. Verneker and M. Sunitha, "Effect of catalyst concentration on burning rate of composite solid propellants", AIAA Journal, Vol. 15, No.11, 1977,pp. 1649-1651.

X.Sun et al., "ZnO twin-cones: synthesis, photoluminescence, and catalytic decomposition of ammonium perchlorate". Inorganic chemistry, Vol.47, No.10,2008, pp. 4146-4152.

P.R.Patil, V.e.N. Krishnamurthy and S.S. Joshi, "Differential scanning calorimetric study of HTPB based composite propellants in presence of nano ferric oxide". Propellants, Explosives, Pyrotechnics, Vol.31, No.6, 2006,pp. 442-446.

G.Duan et al., "The catalytic effect of nanosized MgO on the decomposition of ammonium perchlorate". Powder technology, Vol.172,No.1,2007,pp. 27-29.

Klerk, W.P.C., W. Colpa, and P.V.Ekeren, "Ageing studies of magnesium–sodium nitrate pyrotechnic compositions".Journal of thermal analysis and calorimetry, Vol.85,No.1,2006,pp.203-207.

J.A. Conkling, C. Mocella, "Chemistry of pyrotechnics: basic principles and theory", 2010, CRC press.

M.E. Brown, "Introduction to thermal analysis: techniques and applications". Vol. 1, 2001, Springer.

I.Fiamengo,M. Sućeska, and S. Matečić Mušanić, "Determination of Nitroglycerine Content in Double Base Propellants by Isothermal Thermogravimetry", Central European Journal of Energetic Materials, Vol.7, No.1, 2010,pp. 3-19.

K.Krishnan et al., "Kinetics of decomposition of nitramine propellant by differential scanning calorimetry", Defence Science Journal, Vol.42, No.3, 2013,pp. 135-139.

S.G Hosseini, and A. Eslami, "Thermoanalytical investigation of relative reactivity of some nitrate oxidants in tin-fueled pyrotechnic systems". Journal of thermal analysis and calorimetry, Vol.101,No.3, 2010,pp.1111-1119.

H.E.Kissinger, "Reaction kinetics in differential thermal analysis", Analytical chemistry,Vol.29,No.11, 1957,pp.1702-1706.

B.Lehmann and J. Karger-Kocsis, "Isothermal and non-isothermal crystallisation kinetics of pCBT and PBT", Journal of Thermal Analysis and Calorimetry,Vol.95,No.1, 2009,pp. 221-227.

T.Hatakeyama, and F. Quinn, "Fundamentals and Applications to Polymer Science, Thermal Analysis", 1994.

S.Vyazovkin and C.A. Wight, "Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data", Thermochimica acta,Vol 340, 1999,pp. 53-68.

M.Sunitha et al., "Kinetics of Alder-ene reaction of Tris (2-allylphenoxy) triphenoxycyclotriphosphazene and bismaleimides—a DSC study". Thermochimica acta,Vol.374,No.2, 2001,pp. 159-169.

T.Vlase et al., "Comparative results of kinetic data obtained with different methods for complex decomposition steps". Journal of thermal analysis and calorimetry,Vol.88,No.3, 2007, pp. 631-635.

M.Venkatesh, P. Ravi, and S.P. Tewari, "Isoconversional Kinetic Analysis of Decomposition of Nitroimidazoles: Friedman method vs Flynn–Wall–Ozawa Method, The Journal of Physical Chemistry A, Vol.117,No.40, 2013,pp.10162-10169.

B. Janković, "Kinetic analysis of the nonisothermal decomposition of potassium metabisulfite using the model-fitting and isoconversional (model-free) methods". Chemical Engineering Journal, Vol. 139, No.1,2008,pp.128-135.

A.Said and R. Al-Qasmi, "The role of copper cobaltite spinel, CuxCo3xO4 during the thermal decomposition of ammonium perchlorate". Thermochimica acta, Vol.275,No.1, 1996, pp. 83-91.

A.Eslami, S. Hosseini and S. Pourmortazavi, "Thermoanalytical investigation on some boron–fuelled binary pyrotechnic systems". Fuel, Vol.87, No.15,2008, pp. 3339-3343.

S.Pourmortazaviet al., "Effect of nitrate content on thermal decomposition of nitrocellulose". Journal of hazardous materials,Vol.162,No.2, 2009,pp.1141-1144.

Z.Babar and A.Q. Malik, "Thermal and kinetic comparison of various oxidizers used in propellant/pyrotechnic compositions", Caspian Journal of Applied Sciences Research, Vol.2, No 7, 2013,pp.63-69.

S.Vyazovkin et al., "ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data",Thermochimica Acta, Vol.520,No.1, 2011,pp.1-19.

J.Rocco et al., "Thermal degradation of a composite solid propellant examined by DSC", Journal of thermal analysis and calorimetry, Vol.75,No.2,2004,pp.551-557.

Dubey, B., et al., The catalytic behaviour of NiFe2-xCrxO4 (0.0<= x<= 2.0) during the thermal decomposition of ammonium perchlorate, polystyrene and their composite propellants. Indian J Chem, 2001. 40: p. 841-847.

K.Kishore, V.R.P.Verneker and M.R. Sunitha, "Effect of manganese dioxide on the thermal decomposition of ammonium perchlorate", Journal of Applied Chemistry and Biotechnology, Vol.27, No.2, 1977,pp.415-422.

E. Alizadeh-Gheshlaghi et al., "Investigation of the catalytic activity of nano-sized CuO, Co3O4 and CuCo2O4 powders on thermal decomposition of ammonium perchlorate". Powder technology, Vol.217, 2012,pp.330-339.






Engineering Sciences