Applied Chemistry Today

Applied Chemistry Today

Catalytic effect of catocene on the thermal decomposition kinetic of NTO and NTO/TNT explosives

Document Type : Original Article

Authors
Hadi Panahi
Hamid Reza Pouretedal
Sajjad Damiri
Department of Applied Chemistry, Maleke-ashtar University of Technology, Shahin-shahr, Esfahan, I. R. Iran
10.22075/chem.2025.36249.2325
Abstract
The catalytic effect of catocene was studied on the kinetic of thermal decomposition of NTO (3-Nitro-1, 2, 4-triazol-5-one) and NTO/TNT (Trinitrotoluene) explosives. NTO is an insensitive explosive and can use as an alternative of many nitramine explosives and thus composite explosive of NTO/TNT shows the properties of an insensitive explosive. FT-IR spectra show the minor changes in molecular bonds of NTO and TNT with addition of catocene. SEM-EDS (Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy) analysis indicates the morphology of prepared samples and presence of catalyst in the matrix of samples. TG/DSC (Thermal Gravimetry/Differential Scanning Calorimetery) method is used to study the thermal behaviour of NTO and NTO/TNT in absence and presence of 3% wt. of catocene. A decrease 5 oC in exothermic peak temperature of DSC curves and a decrease 50 kJ/mol in activation energy (Ea) of thermal decomposition reactions of NTO and NTO/TNT are seen in presence of catocene. The activation energies are calculated by model-free methods of Ozawa–Flynn–Wall (OFW), and Kissinger–Akahira–Sunose (KAS). Tests of sensitivity to impact, friction, and electric discharge show the stability of NTO and NTO/TNT against external stimuli in the presence of catalyst.
Keywords
Catocene
catalyst
NTO explosive
TNT explosive
thermal
kinetic
Subjects
[1] Beardall, D. J., Botcher, T. R., & Wight, C. A. (1995). Explosive thermal decomposition mechanism of NTO. MRS Online Proceedings Library, 418, 379-384.
[2] Usman, M., Wang, L., Yu, H., Haq, F., Haroon, M., Ullah, R. S., Khan, A., Fahad, S., Nazir, A., & Elshaarani, T. (2018). Recent progress on ferrocene-based burning rate catalysts for propellant applications. Journal of Organometallic Chemistry, 872, 40-53.
[3] Liu, L.-I., He, G.-Q., Wang, Y.-H., & Liu, P.-J. (2014). Effect of catocene on the thermal decomposition of ammonium perchlorate and octogen. Journal of Thermal Analysis and Calorimetry, 117, 621-628.
[4] Pouretedal, H. R., Damiri, S., Ravanbod, M., Haghdost, M., & Masoudi, S. (2017). The kinetic of thermal decomposition of PETN, Pentastite and Pentolite by TG/DTA non-isothermal methods. Journal of Thermal Analysis and Calorimetry, 129, 521-529.
[5] Vyazovkin, S., Burnham, A. K., Criado, J. M., Pérez-Maqueda, L. A., Popescu, C., & Sbirrazzuoli, N. (2011). ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochimica acta, 520 (1-2), 1-19.
[6] Zhang, X. (2020). Applications of kinetic methods in thermal analysis: a review. Engineered Science, 14 (2), 1-13.
[7] Damiri, S., Pouretedal, H. R., & Ghane, A. (2017). Thermal decomposition kinetic study and mass loss prediction of desensitized RDX energetic material using DTA/TGA thermal analysis and accelerated ageing technique. Applied Chemistry Today, 12 (44), 33 - 54.
[8] Lynch, J. C., Brannon, J. M., & Delfino, J. J. (2002). Dissolution rates of three high explosive compounds: TNT, RDX, and HMX. Chemosphere, 47 (7), 725-734.
[9] Oxley, J. C., Smith, J. L., Zhou, Z., & McKenney, R. L. (1995). Thermal decomposition studies on NTO and NTO/TNT. The Journal of Physical Chemistry, 99 (25), 10383-10391.
[10] Yang, G., Nie, F., Li, J.,Guo, Q., & Qiao, Z. (2007). Preparation and characterization of nano-NTO explosive. Journal of Energetic Materials, 25 (1), 35-47.
[11] Nie, P.-S., Jin, S.-H., Li, L.-J., Chen, K., Chen, Y., & Yu, R. (2022). Shock initiation performance of NTO-based polymer bonded explosive. Defence Technology, 18 (9), 1538-1545.
[12] Pouretedal, H. R., Damiri, S., & Panahi, H. (2022). Thermal Stability, Kinetic Triplet Study and Sensitivity Evaluation of Composite Explosive of 1, 3, 5, 7-Tetranitro-1, 3, 5, 7-tetrazocane (HMX) and Nitro-1, 2, 4-triazol-5-one (NTO). Russian Journal of Applied Chemistry, 95 (10), 1641-1651.
[13] Chaturvedi, S., Dave, & P. N. (2013). A review on the use of nanometals as catalysts for the thermal decomposition of ammonium perchlorate. Journal of Saudi Chemical Society, 17 (2), 135-149.
[14] Safari, J., & Zarnegar, Z. (2012). Magnetic Fe3O4 nanoparticles as a highly efficient catalyst for the synthesis of imidazoles under ultrasound irradiation. Iranian Journal of Catalysis, 2 (3), 121-128.
[15] Damiri, S., Pouretedal, H. R., & Mahmoudi, M. (2022). Sensitive electrocatalytic assay of cyclotetramethylene tetranitramine (HMX) explosive on carbon nanotube/Ag nanocomposite electrode. Iranian Journal of Catalysis, 12 (1), 69-76.
[16] Damiri, S., Samiei, Z., & Pouretedal, H. R. (2024). Electrochemical characteristics and supercapacitance of the self-assembled Catocene complex on carbon microfiber electrode. Applied Chemistry Today, 19 (73), 11 - 26.
[17] Ravanbod, M., & Pouretedal, H. R. (2016). Catalytic effect of Fe2O3, Mn2O3, and TiO2 nanoparticles on thermal decomposition of potassium nitrate. Journal of Thermal Analysis and Calorimetry, 124, 1091-1098.
[18] Jiang, B.,Zhang, W.,Yang, J.,Yu, Y.,Bao, T..,Zhou, X. (2015). Low‐Temperature Oxidation of Catocene and Its Influence on the Mechanical Sensitivities of a Fine‐AP/Catocene Mixture. Propellants, Explosives, Pyrotechnics, 40 (6), 854-859.
[19] Shen, S.-M.,Wang, S.-W.,Chiu, Y.-S.,Chen, S.-I.,Chang, F.-M..,Huang, C.-C. (1993). Thermal decomposition of cured GAP-AP propellants containing catocene. Thermochimica acta, 216, 255-266.
[20] Zecheru, T., Rotariu, T., Matache, L.-C., Sava, A.-C., Lungu, R.-M.,Voicu, A., & Cosereanu, L. (2014). Synthesis and Applications of 3-nitro-1, 2, 4-triazol-5-one based Hybrid Energetic Compositions. Revista de Chimie, 65, 1186-1189.
[21] Hanafi, S., Trache, D., Abdous, S., Bensalem, Z., & Mezroua, A. (2019). 5-Nitro-1, 2, 4-triazole-3-one: A review of recent advances. Chinese Journal of Energetic Materials, 27 (4), 326-347.
[22] Stewart, J.,Bosco, S..,Carper, W. (1986). Vibrational spectra of 2, 4, 6-trinitrotoluene and its isotopically substituted analogues. Spectrochimica Acta Part A: Molecular Spectroscopy, 42 (1), 13-21.
[23] Wang, M., He, X., Xiong, Q., Jing, R., Zhang, Y., Wen, Z., Kuang, Q., Pu, X., Li, M., & Xu, T. (2016). A facile strategy applied to simultaneous qualitative-detection on multiple components of mixture samples: a joint study of infrared spectroscopy and multi-label algorithms on PBX explosives. RSC Advances, 6 (6), 4713-4722.
[24] Lippincott, E. R., & Nelson, R. D. (1958). The vibrational spectra and structure of ferrocene and ruthenocene. Spectrochimica Acta, 10 (3), 307-329.
[25] Wang, L., Yu, H., Saleem, M., Akram, M., Abbasi, N. M., Khalid, H., Sun, R., & Chen, Y. (2016). Ferrocene-based polyethyleneimines for burning rate catalysts. New Journal of Chemistry, 40 (4), 3155-3163.
[26] Sinditskii, V. P., Smirnov, S. P., & Egorshev, V. Y. (2007). Thermal decomposition of NTO: an explanation of the high activation energy. Propellants, Explosives, Pyrotechnic, 32 (4), 277-287.
[27] Li, J. S., Chen, J. J., Hwang, C. C., Lu, K. T., & Yeh, T. F. (2019). Study on thermal characteristics of TNT based melt‐cast explosives. Propellants, Explosives, Pyrotechnics, 44 (10), 1270-1281.
[28] Ravi, P., Badgujar, D. M., Gore, G. M., Tewari, S. P., & Sikder, A. K. (2011). Review on melt cast explosives. Propellants, Explosives, Pyrotechnics, 36 (5), 393-403.
[29] Sarangapani, R., Ramavat, V., Reddy, S., Subramanian, P., & Sikder, A. (2015). Rheology studies of NTO–TNT based melt-cast dispersions and influence of particle–dispersant interactions. Powder Technology, 273, 118-124.
[30] Kondrikov, B. N., Smirnov, S., Minakin, A., & Doherty, R. M. (2004). Chemical kinetics of the thermal decomposition of NTO. Propellants, Explosives, Pyrotechnics, 29 (1), 27-33.
[31] Paziewska, P., Gańczyk-Specjalska, K., Lewczuk, R., & Bogusz, R. (2022). The influence of catocene on properties of heterogeneous solid rocket propellants with reduced quantity of HCl in combustion products. New Trends in Research of Energetic Materials, Czech Republi, 24th Seminar, 483-492.
[32] Dave, P. N., Sirach, R., & Chaturvedi, S. (2022). Kinetics of the thermolysis of 3-nitro-2,4-dihydro-3H-1,2,4-triazol-5-one (NTO) and nanosize NTO the presence of nickel-zinc-cobalt ferrite. International Journal of Chemical Kinetics, 54 (11), 659-668.
[33] Dave, P. N., Sirach, R., Thakkar, R., & Chaturvedi, S. (2023). Thermal Decomposition of 3-Nitro-1, 2, 4-Triazole-5-One (NTO) and Nanosize NTO Catalyzed by NiFe2O4. Arabian Journal for Science and Engineering, 48 (1), 467-474.
[34] Atghaei, M., Shafaatian, B., & Rezvani, S. A.  (2024). Investigation of interaction of CT-DNA with new nickel and palladium complexes containing Ferrocene group with N and S donor atoms. Applied Chemistry Today, 19 (72), 189 - 204.
[35] Pouretedal, H. R., Damiri, S., & Bighamian, Z. (2020). The non-isothermal gravimetric method for study the thermal decomposition kinetic of HNBB and HNS explosives. Defence Technology, 16 (1), 251-256.
[36] Vyazovkin, S., & Wight, C. A. (1998). Isothermal and non-isothermal kinetics of thermally stimulated reactions of solids. International Reviews in Physical Chemistry, 17 (3), 407-433.
[37] Kumar, P., Joshi, P. C., Kumar, R., & Biswas, S. (2018). Catalytic effects of Cu-Co* on the thermal decomposition of AN and AN/KDN based green oxidizer and propellant samples. Defence Technology, 14 (3), 250-260.
[38] Edri, I., Feldgun, V., Karinski, Y., & Yankelevsky, D. (2013). Afterburning aspects in an internal TNT explosion. International Journal of Protective Structures, 4 (1), 97-116.
[39] Licht, H. H. (2000). Performance and sensitivity of explosives. Propellants, Explosives, Pyrotechnics, 25 (3), 126-132.
[40] Busby, T., Smith, J., Sheehan, P., & Oxley, J. (2023). Modifying explosive behavior with additives. Propellants, Explosives, Pyrotechnics, 48 (8), e202200324.
Applied Chemistry Today
Volume 20, Issue 77
Autumn 2025
Pages 23-34