Earth-Abundant Metal-Based Catalysts for Composite Solid Propellants
Driss Soubane
This chapter offers a comprehensive review of earth-abundant metal-based (EAM) catalysts in solid propellants, tracing the evolution of combustion laws and rocket propulsion principles, including Tsiolkovsky’s logarithmic equation. We explore the historical development and scientific advancements in solid propellant technologies, with a focus on how metals such as iron, manganese, and copper improve burn rates, enhance combustion efficiency, and lower decomposition temperatures. The chapter also examines catalytic mechanisms, addressing the effects of radiation, exothermic catalytic decomposition, and physical transitions, along with the efficiency and durability of EAMs under extreme conditions. Additionally, we assess the impact of metal-organic frameworks on propellant performance and discuss current technologies and future challenges. The chapter concludes by outlining future research directions, including optimizing catalyst compositions, utilizing nanoscale materials, and developing sustainable, high-performance catalysts for long-duration missions.
Keywords
Solid Propellants, Combustion Efficiency, Burn Rate, Ammonium Perchlorate, Earth-Abundant Metal-Based Catalysts, Sustainability, Future Research Directions
Published online 9/10/2025, 19 pages
Citation: Driss Soubane, Earth-Abundant Metal-Based Catalysts for Composite Solid Propellants, Materials Research Foundations, Vol. 179, pp 1-19, 2025
DOI: https://doi.org/10.21741/9781644903711-1
Part of the book on Applications for Earth-Abundant Transition Metals
References
[1] C. T. Lewis, A Latin dictionary: founded on Andrew’s edition of Freund’s Latin dictionary, Reproduction en fac-Similé. Oxford: Clarendon Press, 1980.
[2] L. C. Lichty, Combustion engine processes, 7th ed. New York: McGraw-Hill, 1967.
[3] D. Soubane, “Renewable energy resources in a nutshell: Present and future,” International Journal of Renewable Energy Resources, vol. 7, no. 2, pp. 37–42, 2017.
[4] D. Soubane, A. Ihlal, and G. Nouet, “The Role Of Cadmium Oxide Within The Thin Films Of The Buffer Cds Aimed At Solar Cells Based Upon CIGS Films Fabrication,” Revue marocaine de la matière condensée, vol. 9, no. Revue marocaine de la matière condensée, Vol. 9 (2007), Mar. 2011, doi: 10.34874/PRSM.MJCM-VOL9ISS0.195.
[5] D. P. Mishra, Fundamentals of rocket propulsion. Boca Raton: CRC Press, Taylor & Francis Group, CRC Press is an imprint of the Taylor & Francis Group, an informa business, 2017.
[6] N. Yadav, P. K. Srivastava, and M. Varma, “Recent advances in catalytic combustion of AP-based composite solid propellants,” Defence Technology, vol. 17, no. 3, pp. 1013–1031, Jun. 2021, doi: 10.1016/j.dt.2020.06.007.
[7] D. Soubane, M. E. Garah, M. Bouhassoune, A. Tirbiyine, A. Ramzi, and S. Laasri, “Hidden Information, Energy Dispersion and Disorder: Does Entropy Really Measure Disorder?,” WJCMP, vol. 08, no. 04, pp. 197–202, 2018, doi: 10.4236/wjcmp.2018.84014.
[8] H. J. Kramer, “Space Stations,” in Observation of the Earth and Its Environment, Berlin, Heidelberg: Springer Berlin Heidelberg, 2002, pp. 983–1004. doi: 10.1007/978-3-642-56294-5_13.
[9] K. J. Laidler, “A glossary of terms used in chemical kinetics, including reaction dynamics (IUPAC Recommendations 1996),” Pure and Applied Chemistry, vol. 68, no. 1, pp. 149–192, Jan. 1996, doi: 10.1351/pac199668010149.
[10] S. T. Thornton and J. B. Marion, Classical dynamics of particles and systems, 5. ed., International student ed., [Nachdr.]. Belmont, Calif.: Thomson, Brooks-Cole, 2008.
[11] O. Darrigol and U. Frisch, “From Newton’s mechanics to Euler’s equations,” Physica D: Nonlinear Phenomena, vol. 237, no. 14–17, pp. 1855–1869, Aug. 2008, doi: 10.1016/j.physd.2007.08.003.
[12] R. W. Johnson, Ed., Handbook of fluid dynamics, Second edition. Boca Raton London New York: CRC Press Taylor & Francis Group, 2016.
[13] G. Ágoston, Guns for the sultan: military power and the weapons industry in the Ottoman Empire. in Cambridge studies in Islamic civilization. New York: Cambridge University Press, 2005.
[14] R. Irons, Hitler’s terror weapons: the price of vengeance. London: Collins, 2003.
[15] K.-H. Wellmann, Ed., Warum ist es nachts dunkel? was wir vom Weltall wirklich wissen; in Zusammenarbeit mit dem neuen Funkkolleg. Stuttgart: Kosmos, 2006.
[16] D. W. Wragg, Ed., A dictionary of aviation. Reading: Osprey, 1973.
[17] E. Bergaust, Wernher von Braun: the authoritative and definitive biographical profile of the father of modern space flight. Washington: National Space Institute, 1976.
[18] J. D. Hunley, “The Enigma of Robert H. Goddard,” Technology and Culture, vol. 36, no. 2, p. 327, Apr. 1995, doi: 10.2307/3106375.
[19] R. Hall, R. D. Hall, and D. J. Shayler, Soyuz: a universal spacecraft. in Springer-Praxis books in astronomy and space sciences. London Berlin Heidelberg: Springer [u.a.], 2003.
[20] M. C. Vilela Salgado, C. M. N. Belderrain, and T. C. Devezas, “Space Propulsion: a Survey Study About Current and Future Technologies,” J.Aerosp. Technol. Manag., vol. 10, Feb. 2018, doi: 10.5028/jatm.v10.829.
[21] M. El Garah, D. Soubane, and F. Sanchette, “Review on mechanical and functional properties of refractory high-entropy alloy films by magnetron sputtering,” emergent mater., vol. 7, no. 1, pp. 77–101, Feb. 2024, doi: 10.1007/s42247-023-00607-8.
[22] A. Okninski, W. Kopacz, D. Kaniewski, and K. Sobczak, “Hybrid rocket propulsion technology for space transportation revisited – propellant solutions and challenges,” FirePhysChem, vol. 1, no. 4, pp. 260–271, Dec. 2021, doi: 10.1016/j.fpc.2021.11.015.
[23] M. W. Beckstead, “Model for double-base propellant combustion,” AIAA Journal, vol. 18, no. 8, pp. 980–985, Aug. 1980, doi: 10.2514/3.7701.
[24] I. E. Smith, “Chemical Rockets and Flame Explosives Technology. Richard T. Holzmann. Marcel Dekker. New York, 1969. Illustrated. 499 pp. £12.25.,” Aeronaut. j., vol. 75, no. 725, pp. 354–354, May 1971, doi: 10.1017/S0001924000045504.
[25] G. T. Healey, “Fundamental Aspects of Solid Propellant Rockets. F. A. Williams, M. Barrere and M. C. Huang. Technivision Services, Slough. 791 pp. Illustrated.,” Aeronaut. j., vol. 74, no. 717, pp. 764–764, Sep. 1970, doi: 10.1017/S0001924000048296.
[26] B. Tan, X. Yang, J. Dou, B. Duan, X. Lu, and N. Liu, “Research progress of EMOFs-based burning rate catalysts for solid propellants,” Front. Chem., vol. 10, p. 1032163, Oct. 2022, doi: 10.3389/fchem.2022.1032163.
[27] L. R. Warren, Z. Wang, C. R. Pulham, and C. A. Morrison, “A Review of the Catalytic Effects of Lead‐Based Ballistic Modifiers on the Combustion Chemistry of Double Base Propellants,” Propellants Explo Pyrotec, vol. 46, no. 1, pp. 13–25, Jan. 2021, doi: 10.1002/prep.202000167.
[28] J. Zhang and J. M. Shreeve, “3D Nitrogen-rich metal–organic frameworks: opportunities for safer energetics,” Dalton Trans., vol. 45, no. 6, pp. 2363–2368, 2016, doi: 10.1039/C5DT04456A.
[29] I. L. Dalinger et al., “Novel energetic CNO oxidizer: Pernitro-substituted pyrazolyl-furazan framework,” FirePhysChem, vol. 1, no. 2, pp. 83–89, Jun. 2021, doi: 10.1016/j.fpc.2021.04.005.
[30] Z. Qin et al., “Effect of spherical Al-Mg-Zr on the combustion characteristics of composite propellants,” FirePhysChem, vol. 2, no. 1, pp. 14–19, Mar. 2022, doi: 10.1016/j.fpc.2022.03.004.
[31] C. Rossi et al., “Solid Propellant Microthrusters on Silicon: Design, Modeling, Fabrication, and Testing,” J. Microelectromech. Syst., vol. 15, no. 6, pp. 1805–1815, Dec. 2006, doi: 10.1109/JMEMS.2006.880232.
[32] Driss Soubane, Tsuneyuki Ozaki, Nathaniel Quitoriano, “Metal-Oxide-Insulator-Semiconductor Memristor based on Low Thermal Budget Approach Silicon Nano-crystals embedded in a silica Matrix,” 40707, 2019
[33] J. Koo, H. Stretz, A. Bray, J. Weispfenning, Z. P. Luo, and R. Blanski, “Nanostructured Materials for Rocket Propulsion System: Recent Progress,” in 44th AIAA/ASME/ASCE/AHS/ASC Structures, Structural Dynamics, and Materials Conference, Norfolk, Virginia: American Institute of Aeronautics and Astronautics, Apr. 2003. doi: 10.2514/6.2003-1769.
[34] D. Soubane and N. J. Quitoriano, “Photoluminescence from low thermal budget silicon nano-crystals in silica,” Nanotechnology, vol. 26, no. 29, p. 295201, Jul. 2015, doi: 10.1088/0957-4484/26/29/295201.
[35] F. Dnaya et al., “A holistic understanding of optical properties in amorphous H-terminated Si-nanostructures: Combining TD-DFT with AIMD,” Results in Optics, vol. 16, p. 100694, Jul. 2024, doi: 10.1016/j.rio.2024.100694.
[36] P. G. Hill and C. R. Peterson, Mechanics and thermodynamics of propulsion, 2nd ed. Reading, Mass: Addison-Wesley, 1992.
[37] G. P. Sutton and O. Biblarz, Rocket propulsion elements, Ninth edition. Hoboken, New Jersey: John Wiley & Sons Inc, 2017.
[38] D. Koks, “The Rocket Equation and that Minus Sign: An Avoidable Pitfall in the Language of Physics,” The Phys. Educat., vol. 04, no. 02, p. 2250009, Jun. 2022, doi: 10.1142/S2661339522500093.
[39] D. Grune, “Studies of the Combustion of Solid Propellants at High Pressures,” Propellants Explo Pyrotec, vol. 1, no. 2, pp. 27–28, Jun. 1976, doi: 10.1002/prep.19760010203.
[40] K. Krowicki and M. Syczewski, “SOLID ROCKET PROPELLANTS”.
[41] M. Summerfield, Ed., Solid Propellant Rocket Research. New York: American Institute of Aeronautics and Astronautics, 1960. doi: 10.2514/4.864766.
[42] J. C. SCHUMACHER, Perchlorates: Their Properties, Manufacture and Uses. in American Chemical Society Monograph, no. no. 146. New York, London: Reinhold Publishing Corp. ; Chapman & Hall, 1960.
[43] R. Fry et al., “Solid propellant burning rate measurement methods used within the NATO propulsion community,” in 37th Joint Propulsion Conference and Exhibit, Salt Lake City,UT,U.S.A.: American Institute of Aeronautics and Astronautics, Jul. 2001. doi: 10.2514/6.2001-3948.
[44] L. Medard, “L’œuvre scientifique de Paul Vieille (1854-1934)/The scientific work of Paul Vieille (1854-1934),” rhs, vol. 47, no. 3, pp. 381–404, 1994, doi: 10.3406/rhs.1994.1211.
[45] M. S. Russell, The chemistry of fireworks, 2nd ed. Cambridge, UK: RSC Pub, 2009.
[46] R. Poreddy, C. Engelbrekt, and A. Riisager, “Copper oxide as efficient catalyst for oxidative dehydrogenation of alcohols with air,” Catal. Sci. Technol., vol. 5, no. 4, pp. 2467–2477, 2015, doi: 10.1039/C4CY01622J.
[47] D. Soubane, A. Tirbiyine, M. Bellioua, S. Laasri, and A. Hajjaji, “Optical Features of Catalyst-Free Zinc Oxide Nanostructures Confined to One Dimension,” Opt. Spectrosc., vol. 127, no. 3, pp. 522–526, Sep. 2019, doi: 10.1134/S0030400X19090261.
[48] A. Bumajdad, S. Al-Ghareeb, M. Madkour, and F. A. Sagheer, “Non-noble, efficient catalyst of unsupported α-Cr2O3 nanoparticles for low temperature CO Oxidation,” Sci Rep, vol. 7, no. 1, p. 14788, Nov. 2017, doi: 10.1038/s41598-017-14779-x.
[49] V. R. Gutman, “Solid Propellent Burning Rate Theory: Recently Advanced Theories, Their Limitations and Possible Areas for Future Investigation,” Aircraft Engineering and Aerospace Technology, vol. 32, no. 9, pp. 255–260, Sep. 1960, doi: 10.1108/eb033297.
[50] K. M. P. Wheelhouse, R. L. Webster, and G. L. Beutner, “Advances and Applications in Catalysis with Earth-Abundant Metals,” Org. Process Res. Dev., vol. 27, no. 7, pp. 1157–1159, Jul. 2023, doi: 10.1021/acs.oprd.3c00207.
[51] G. A. Filonenko, R. Van Putten, E. J. M. Hensen, and E. A. Pidko, “Catalytic (de)hydrogenation promoted by non-precious metals – Co, Fe and Mn: recent advances in an emerging field,” Chem. Soc. Rev., vol. 47, no. 4, pp. 1459–1483, 2018, doi: 10.1039/C7CS00334J.
[52] S. Abelló, E. Bolshak, and D. Montané, “Ni–Fe catalysts derived from hydrotalcite-like precursors for hydrogen production by ethanol steam reforming,” Applied Catalysis A: General, vol. 450, pp. 261–274, Jan. 2013, doi: 10.1016/j.apcata.2012.10.035.
[53] G. Busca, U. Costantino, T. Montanari, G. Ramis, C. Resini, and M. Sisani, “Nickel versus cobalt catalysts for hydrogen production by ethanol steam reforming: Ni–Co–Zn–Al catalysts from hydrotalcite-like precursors,” International Journal of Hydrogen Energy, vol. 35, no. 11, pp. 5356–5366, Jun. 2010, doi: 10.1016/j.ijhydene.2010.02.124.
[54] A. K. Neyestanaki, F. Klingstedt, T. Salmi, and D. Y. Murzin, “Deactivation of postcombustion catalysts, a review,” Fuel, vol. 83, no. 4–5, pp. 395–408, Mar. 2004, doi: 10.1016/j.fuel.2003.09.002.
[55] C.-J. Yang, “An impending platinum crisis and its implications for the future of the automobile,” Energy Policy, vol. 37, no. 5, pp. 1805–1808, May 2009, doi: 10.1016/j.enpol.2009.01.019.
[56] M. L. Firmansyah, F. Kubota, and M. Goto, “Solvent extraction of Pt(IV), Pd(II), and Rh(III) with the ionic liquid trioctyl(dodecyl) phosphonium chloride,” J of Chemical Tech & Biotech, vol. 93, no. 6, pp. 1714–1721, Jun. 2018, doi: 10.1002/jctb.5544.
[57] W. M. Haynes, D. R. Lide, and T. J. Bruno, Eds., CRC Handbook of Chemistry and Physics, 97th ed. CRC Press, 2016. doi: 10.1201/9781315380476.
[58] R. M. Bullock et al., “Using nature’s blueprint to expand catalysis with Earth-abundant metals,” Science, vol. 369, no. 6505, p. eabc3183, Aug. 2020, doi: 10.1126/science.abc3183.
[59] P. Nuss and M. J. Eckelman, “Life Cycle Assessment of Metals: A Scientific Synthesis,” PLoS ONE, vol. 9, no. 7, p. e101298, Jul. 2014, doi: 10.1371/journal.pone.0101298.
[60] K. K. Kuo and R. Acharya, Fundamentals of Turbulent and Multiphase Combustion, 1st ed. Wiley, 2012. doi: 10.1002/9781118107683.
[61] K. Kishore and M. R. Sunitha, “Effect of Transition Metal Oxides on Decomposition and Deflagration of Composite Solid Propellant Systems: A Survey,” AIAA Journal, vol. 17, no. 10, pp. 1118–1125, Oct. 1979, doi: 10.2514/3.61286.
[62] R. A. Yetter, G. A. Risha, and S. F. Son, “Metal particle combustion and nanotechnology,” Proceedings of the Combustion Institute, vol. 32, no. 2, pp. 1819–1838, 2009, doi: 10.1016/j.proci.2008.08.013.
[63] M. B. Padwal and M. Varma, “Thermal decomposition and combustion characteristics of HTPB-coarse AP composite solid propellants catalyzed with Fe 2 O 3,” Combustion Science and Technology, vol. 190, no. 9, pp. 1614–1629, Sep. 2018, doi: 10.1080/00102202.2018.1460599.
[64] S. Singh, M. Chawla, P. F. Siril, and G. Singh, “Manganese oxalate nanorods as ballistic modifier for composite solid propellants,” Thermochimica Acta, vol. 597, pp. 85–92, Dec. 2014, doi: 10.1016/j.tca.2014.10.016.
[65] L. Liu, F. Li, L. Tan, L. Ming, and Y. Yi, “Effects of Nanometer Ni, Cu, Al and NiCu Powders on the Thermal Decomposition of Ammonium Perchlorate,” Propellants Explo Pyrotec, vol. 29, no. 1, pp. 34–38, Feb. 2004, doi: 10.1002/prep.200400026.
[66] L. Liu, F. Li, L. Tan, L. Ming, and Y. Yi, “Effects of Nanometer Ni, Cu, Al and NiCu Powders on the Thermal Decomposition of Ammonium Perchlorate,” Propellants Explo Pyrotec, vol. 29, no. 1, pp. 34–38, Feb. 2004, doi: 10.1002/prep.200400026.
[67] Lalith V. Kakumanu, Narendra Yadav, Srinibas Karmakar, “Composite Solid Propellant, Burn Rate, Combustion Characteristics, Metal Catalysts, Fuel-Binder,” vol. 3, no. 2, pp. 31–36, 2014.
[68] H. Xu, X. Wang, and L. Zhang, “Selective preparation of nanorods and micro-octahedrons of Fe2O3 and their catalytic performances for thermal decomposition of ammonium perchlorate,” Powder Technology, vol. 185, no. 2, pp. 176–180, Jul. 2008, doi: 10.1016/j.powtec.2007.10.011.
[69] K.-T. Lu, T.-M. Yang, J.-S. Li, and T.-F. Yeh, “Study on the Burning Characteristics of AP/Al/HTPB Composite Solid Propellant Containing Nano-Sized Ferric Oxide Powder,” Combustion Science and Technology, vol. 184, no. 12, pp. 2100–2116, Dec. 2012, doi: 10.1080/00102202.2012.703271.
[70] P. R. Patil, V. N. Krishnamurthy, and S. S. Joshi, “Differential Scanning Calorimetric Study of HTPB based Composite Propellants in Presence of Nano Ferric Oxide,” Propellants Explo Pyrotec, vol. 31, no. 6, pp. 442–446, Dec. 2006, doi: 10.1002/prep.200600059.
[71] A. M. Kawamoto, L. C. Pardini, and L. C. Rezende, “Synthesis of copper chromite catalyst,” Aerospace Science and Technology, vol. 8, no. 7, pp. 591–598, Oct. 2004, doi: 10.1016/j.ast.2004.06.010.
[72] D. Kshirsagar et al., “Effect of Nano Cr2O3 in HTPB/AP/Al Based Composite Propellant Formulations,” Def. Sc. Jl., vol. 66, no. 2, p. 100, Mar. 2016, doi: 10.14429/dsj.66.9250.
[73] A. P. Sanoop, R. Rajeev, and B. K. George, “Synthesis and characterization of a novel copper chromite catalyst for the thermal decomposition of ammonium perchlorate,” Thermochimica Acta, vol. 606, pp. 34–40, Apr. 2015, doi: 10.1016/j.tca.2015.03.006.
[74] S. G. Hosseini, R. Abazari, and A. Gavi, “Pure CuCr 2 O 4 nanoparticles: Synthesis, characterization and their morphological and size effects on the catalytic thermal decomposition of ammonium perchlorate,” Solid State Sciences, vol. 37, pp. 72–79, Nov. 2014, doi: 10.1016/j.solidstatesciences.2014.08.014.
[75] Z. Zhou, S. Tian, D. Zeng, G. Tang, and C. Xie, “MOX (M=Zn, Co, Fe)/AP shell–core nanocomposites for self-catalytical decomposition of ammonium perchlorate,” Journal of Alloys and Compounds, vol. 513, pp. 213–219, Feb. 2012, doi: 10.1016/j.jallcom.2011.10.021.
[76] C. Dennis and B. Bojko, “On the combustion of heterogeneous AP/HTPB composite propellants: A review,” Fuel, vol. 254, p. 115646, Oct. 2019, doi: 10.1016/j.fuel.2019.115646.
[77] A. Davenas, Solid rocket propulsion technology, 1st English ed. Oxford New York: Pergamon Press, 1993.
[78] A. Adharsh Unni, R. Kulkarni, C. Singh, V. Singh, V. M. Priya Varshini, and G. Shanmugaraj, “Effects of adding powdered metals with the solid propellants – A review,” J. Phys.: Conf. Ser., vol. 1473, no. 1, p. 012048, Feb. 2020, doi: 10.1088/1742-6596/1473/1/012048.
[79] F. Maggi et al., “Iron oxide as solid propellant catalyst: A detailed characterization,” Acta Astronautica, vol. 158, pp. 416–424, May 2019, doi: 10.1016/j.actaastro.2018.07.037.
