Special materials in pyrotechnics VII: Pyrotechnics used in thermal batteries

Thermal batteries are unique direct current (DC) electrical power sources with long shelf live, high reliability and higher power density than classical alkaline batteries. This paper gives a brief overview into the working principle of thermal batteries and reviews the properties of zirconium/barium chromate (Zr/BaCrO₄) pyrolant previously used as first fire and iron/potassium perchlorate (Fe/KClO₄) pyrolant (Heat), commonly applied as heating pellet in thermal batteries and its hazard properties. The review gives 64 references to the public domain. CAS-Nos. Zr: [7440-67-7], BaCrO₄: [10294-40-3], Fe: [7439-89-6], KClO₄: [7778-74-7], Viton: [9011-17-0].CAS-Nos. Zr: [7440-67-7], BaCrO₄: [10294-40-3], Fe: [7439-89-6], KClO₄: [7778-74-7], Viton: [9011-17-0].     

Burning rate and other characteristics of strontium titanate (SrTiO3) supplemented AP/HTPB/Al composite propellants

In a quest of search for a new burning rate modifier for composite propellant, strontium titanate (SrTiO₃), a perovskite oxide has been chosen for evaluation in a composite propellant formulation based on its other catalytic applications. Initially, SrTiO₃ was characterized for particle size, morphology and material/phase identification (using XRD). By varying SrTiO₃ content in a standard composite propellant, different compositions were prepared and their performance and processing parameters like the end of mix (EOM) viscosity, mechanical properties, density, burning rate, pressure exponent (n-value), etc. were measured. The results reveal that 2% SrTiO₃ causes more than 12% enhancement in propellant burning rate (at 70 ksc pressure) in comparison to the standard propellant composition. The pressure exponent also increases to 0.46, whereas the standard composition was having its value as 0.35.     

Thermal decomposition of ammonium perchlorate catalyzed with CuO nanoparticles

Ammonium perchlorate (APC) is the most common oxidizer in use for solid rocket propulsion systems. However its initial thermal decomposition is an endothermic process that requires 102.5 J·g⁻¹. This manner involves high activation energy and could render high burning rate regime. This study reports on the sustainable fabrication of CuO nanoparticles as a novel catalyzing agent for APC oxidizer. Colloidal CuO nanoparticles with consistent product quality were fabricated by using hydrothermal processing. TEM micrographs demonstrated mono-dispersed particles of 15 nm particle size. XRD diffractogram demonstrated highly crystalline material. The synthesized colloidal CuO particles were effectively coated with APC particles via co-precipitation by using fast-crash solvent–antisolvent technique. The impact of copper oxide particles on APC thermal behavior has been investigated using DSC and TGA techniques. APC demonstrated an initial endothermic decomposition stage at 242 °C with subsequent two exothermic decomposition stages at 297.8 °C and 452.8 °C respectively. At 1 wt%, copper oxide offered decrease in initial endothermic decomposition stage by 30%. The main outcome of this study is that the two main exothermic decomposition peaks were merged into one single peak with an increase in total heat release by 53%. These novel features can inherit copper oxide particles unique catalyzing ability for advanced highly energetic systems.     

Surface modification of ammonium nitrate by coating with surfactant materials to reduce hygroscopicity

Ammonium nitrate (AN) is promising oxidizer in green propellants. In this work, the physical coating method was improved to modify the surface of ammonium nitrate particles with different surfactant materials to reduce hygroscopicity. Cetylalcohol, stearic acid, stearyl alcohol, palmic acid, lauric acid, stearsmide, tetradecylamine, dodecylamine, and tetradecanol were used as coating surfactant agents. The hygroscopicity was tested for ammonium nitrate with and without coating. Fourier transform infrared (FTIR) and scanning electron microscopy (SEM) were used to characterize the surface of coated and uncoated ammonium nitrate. The mass ratio of coating layer and decline of absorption rate of ammonium nitrate coated by cetylalcohol were 1.00%, and 28.40%, respectively. The results indicate that coating with cetylalcohol surfactant have advantages over the other surfactants in term of low mass ratio of coating layer, and high decline of moisture absorption rate. Thus, cetylalcohol would be a promising coating surfactant material for ammonium nitrate. The idea and approach presented in this study have potential to made hydrophobic layer on the surface of particles to reduce hygroscopicity of AN, and also help the researcher to improving anti-hygroscopicity of ammonium salts.     

Recent progress on transition metal oxides and carbon-supported transition metal oxides as catalysts for thermal decomposition of ammonium perchlorate

As a main oxidizer in solid composite propellants, ammonium perchlorate (AP) plays an important role because its thermal decomposition behavior has a direct influence on the characteristic of solid com-posite propellants. To improve the performance of solid composite propellant, it is necessary to take measures to modify the thermal decomposition behavior of AP. In recent years, transition metal oxides and carbon-supported transition metal oxides have drawn considerable attention due to their extraor-dinary catalytic activity. In this review, we highlight strategies to enhance the thermal decomposition of AP by tuning morphology, varying the types of metal ion, and coupling with carbon analogue. The enhanced catalytic performance can be ascribed to synergistic effect, increased surface area, more exposed active sites, and accelerated electron transportation and so on. The mechanism of AP decom-position mixed with catalyst has also been briefly summarized. Finally, a conclusive outlook and possible research directions are suggested to address challenges such as lacking practical application in actual formulation of solid composite propellant and batch manufacturing.     

Preparation of ammonium nitrate-based solid composite propellants supplemented with polyurethane/nitrocellulose blends binder and their thermal decomposition behavior

To improve the performance of solid composite propellants (SCPs) supplemented with ammonium nitrate (AN) as an oxidizer, the incorporation of energetic ingredients such as explosives, energetic binders or catalysts is a common effective approach. For this purpose, polyurethane (PU), a typical inert binder, was mixed with nitrocellulose (NC) as an energetic polymer. Numerous composite solid propellant compositions based on AN and NC-modified polyurethane binder with different NC ratios were prepared. The prepared formulations were characterized using Fourier transform infrared spectroscopy (FTIR), RAMAN spectroscopy, X-ray diffraction (XRD), electron densimetry, thermogravimetric (TG) analysis, and differential scanning calorimetry (DSC). A kinetic study was then performed using the iterative Kissinger-Akahira-Sunose (It-KAS), Flynn-Wall-Ozawa (It-FWO), and non-linear Vyazovkin integral with compensation effect (VYA/CE) methods. The theoretical performances, such as theoretical specific impulse, adiabatic flame temperature, and ideal exhaust gaseous species, were also determined using the NASA Lewis Code, Chemical Equilibrium with Application (CEA). Spectroscopic examinations revealed the existence of NC and full polymerization of PU in the prepared propellants. According to density tests, the density of the propellant increases as the nitrocellulose component increases. According to the thermal analysis and kinetics study, the increase in NC content catalyzed the thermal decomposition of the AN-based composite solid propellants. Based on the theoretical study, increasing the amount of NC in the propellant increased the specific impulse and, as a result, the overall performance.     

Theoretical calculation and experimental study on the interaction mechanism between TKX-50 and AP

The combination of 5,5′-bistetrazole-1,1′-diolate (TKX-50) and ammonium perchlorate (AP) can make greater use of the chemical energy of TKX-50 based energetic materials. The research on the interaction mechanism between TKX-50 and AP is very important for designing TKX-50-AP compounds and judging the formation feasibility of composite particles, which can lay a theoretical foundation for the preparation of TKX-50-AP mixed crystals and the application of TKX-50 in propellant, propellant and explosive. Herein, in order to research the interaction mechanism between TKX-50 and AP, density-functional theory calculation was applied to optimize three configurations of TKX-50-AP compounds. The geometry structure, electrostatic potential and binding energy of the compounds were predicted, and the electronic density topological analysis was also carried out. Then TKX-50-AP mixed crystals structures were constructed, and the radial distribution function of H–O and H–N in mixed crystals was calculated. Finally, solvent/non-solvent method was applied to prepare TKX-50-AP composites, and the infrared spectroscopy and the non-isothermal decomposition performance of the composites were characterized. Results show that the superposition of positive charges in TKX-50 molecule and negative charges in AP makes the electrostatic potential distributions of TKX-50-AP compounds different from that of TKX-50 and AP. The interaction energies of TKX-50-AP 1, TKX-50-AP 2 and TKX-50-AP 3 are 39.743 kJ/mol, 61.206 kJ/mol and 27.702 kJ/mol, respectively. The interaction between TKX-50 molecules and AP molecules in TKX-50-AP mixed crystals both depends on hydrogen bonds and van der Waals force, and the number and strength of hydrogen bonds are significantly greater than that of van der Waals force. The composition of AP and TKX-50 makes the absorption peak of the five-membered rings and NH₃OH⁺ of TKX-50 shift to low wavenumber in the infrared spectroscopy. In general, TKX-50 interacts with AP via hydrogen bonds and van der Waals force, and the calculated results are in good agreement with the experimental results. The composition of TKX-50 and AP can also prolong the decomposition process.