Thermal Decomposition Of Ammonium Perchlorate Research Articles

Effects of high‐energy multicore ferrocene‐based catalysts on the thermal decomposition of ammonium perchlorate

AbstractThree high‐energy multicore ferrocene‐based catalysts containing energy bonds (C═N, N–N) (EMFcs), EMFcs‐1, EMFcs‐2, and EMFcs‐3, were designed and synthesized to reduce the high temperature decomposition (HTD) temperature and increase the heat release of ammonium perchlorate (AP) as well as improve anti‐migration performance for the development of composite solid propellants. The theoretical calculation of the highest occupied molecular orbital (EHOMO), the lowest unoccupied molecular orbital (ELUMO), and the electrostatic potential (ESP) were performed to explore the electronic structure of EMFcs (1–3) and predict their catalytic performance on AP. The chemical structures were confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), ultraviolet (UV), and elemental analysis, and the oxidation ability was evaluated by cyclic voltammetry (CV). The catalytic performance of obtained catalysts was verified by differential scanning calorimetry‐thermogravimetry (DSC‐TG), and the results showed that the designed catalysts possessed much higher heat release and catalytic activity on AP thermal decomposition than that of widely used catalyst of catocene in the solid propellant, and EMFcs‐2 with three ferrocene units showed the best catalytic performance due to the highest Fe content in one molecule of EMFcs‐2. The composite of AP containing 5 wt% of EMFcs‐2 can reduce the HTD temperature of AP from 394°C to 285°C and low the activation energy from 185.81 to 103.18 kJ·mol−1 with heat release increasing from 630.60 to 1841.50 J·g−1. Furthermore, the thermal decomposition gaseous products of AP under the catalysis of EMFcs were confirmed by TG‐FTIR to explore the catalytic decomposition mechanism.

Thermodynamics and Catalytic Properties of Two Novel Energetic Complexes Based on 3-Amino-1,2,4-triazole-5-carboxylic Acid.

For energetic materials (EMs), the key point of the present research is to improve the energetic property and reduce sensitivity. In this work, two new energetic complexes, Mn(atzc)2(H2O)2·2H2O (1) and Zn(atzc)2(H2O) (2) (Hatzc = 3-amino-1,2,4-triazole-5-carboxylic acid), were synthesized by solvent evaporation and diffusion methods, respectively. The structural analyses illustrate that 1 and 2 exhibit zero-dimensional structural units, which are linked by hydrogen-bonding interactions to give three-dimensional supramolecular architectures. For complexes 1 and 2, the detonation velocities (D) are 10.4 and 10.2 km·s–1 and detonation pressures (P) are 48.7 and 48.6 GPa, respectively. They are higher than most of the reported EMs, which present prominent detonation characteristics. In addition, two complexes can accelerate the thermal decomposition of ammonium perchlorate and exhibit excellent catalytic activity. Therefore, the two complexes can serve as a new class of promising EMs, which have potential application in the design of new high-efficiency solid catalysts.

Mechanistic Insights into the Thermal Decomposition of Ammonium Perchlorate: The Role of Amino-Functionalized Magnetic Nanoparticles.

This work reports the characterization and application of two promising nanocatalysts for the thermal decomposition of ammonium perchlorate (AP). To obtain these composite materials, magnetite nanoparticles (Fe3O4 NPs) were functionalized with two different amine derivative groups, tertiary amine (Fe3O4 NPs-A1) and quaternary amine. X-ray photoelectron spectroscopy and differential scanning calorimetry provided mechanistic insights into the thermal decomposition of AP. Furthermore, tertiary and quaternary amine groups play a critical role, where the presence of an extra proton could favor an electron-proton transfer as the rate-determining step. Moreover, Fe3O4 NPs-A1 causes a diminution of the high-temperature decomposition of AP positively to 335 °C, increasing the energy release by 278 J g-1 and consequently affording the lowest activation energy (102 kJ mol-1), indicating a low degree of thermal stability, and accelerating the thermal decomposition of AP.

Study on catalytic activity and mechanism of tetrazole-based energetic metal-organic frameworks for thermal decomposition of ammonium perchlorate

ABSTRACT In order to comprehensively improve the energy performance and combustion properties of the propellants, four energetic metal–organic frameworks (EMOFs) constructed from transition-metal ions (Ag+, Cd2+, Pb2+) and tetrazole-based energetic ligands (5-methyl tetrazole (HMtta), N,N-bis(1H-tetrazole-5-yl)-amine (H2bta), 3-(1H-tetrazol-5-yl)-1H-triazole (H2tztr)) were prepared by hydrothermal synthesis. The crystal phase and structure of the as-prepared samples were analyzed by XRD and IR characterization. Their catalytic activity on thermal decomposition of ammonium perchlorate (AP) was evaluated by DSC. The results show that as-prepared EMOFs can significantly reduce the thermal decomposition temperature of AP and increase its heat release. Under the optimal condition that the addition amount is 10 wt%, the high-temperature decomposition peak temperatures of [AgMtta]n/AP, [Cd5(Mtta)9]n/AP, [Pb3(bta)2(O)2(H2O)]n/AP, and [Pb(Htztr)2(H2O)]n/AP are decreased by 107.2°C, 94.2°C, 54.6°C, and 91.1°C compared to the case of pure AP, while the heat releases of them are increased by 1243.9 J∙g−1, 1226.2 J∙g−1, 1332.2 J∙g−1, 1444.4 J∙g−1, respectively. In addition, compared with the reported catalysts such as [Pb(BTF)(H2O)2]n, CuFe2O4, [Cu2(en)2(HBTI)2]2, and [Cu2(en)(HBTI)2]2en, the EMOFs prepared in this study show equal or even higher catalytic activity and heat release. Moreover, the catalytic mechanism of EMOFs on thermal decomposition of AP is also analyzed based on the electron transfer theory. With the excellent energy properties and catalytic performances, the prepared EMOFs may become promising energetic additives for composite solid propellant applications.

Gas-solid two-phase flow method for preparing trimesic acid series MOFs for catalytic thermal decomposition of ammonium perchlorate.

The Zn-BTC, Co-BTC and Zn-Co-BTC series metal-organic frameworks were successfully prepared by a gas-solid two-phase flow (GSF) method with zinc nitrate, cobalt nitrate, and 1,3,5-benzenetricarboxylic acid (H3BTC) as raw materials. Single-crystal structures were obtained by the solvothermal method, and the structure and thermal stability of the target materials were characterized by FT-IR, XRD, SEM, energy-dispersive X-ray spectroscopy and DTA. The three obtained target substances were applied to catalyze the thermal decomposition of ammonium perchlorate (AP), and the performance was longitudinally compared. Testing and calculation results showed that when 10 wt% of the sample was added, monometallic Zn-BTC and Co-BTC lowered the AP pyrolysis temperature by 64.1 °C and 92.3 °C, respectively, and their activation energies decreased from 215.96 kJ mol-1 to 136.27 kJ mol-1 and 125.29 kJ mol-1, respectively. Bimetallic Zn-Co-BTC lowered the AP pyrolysis peak by 103.1 °C and the activation energy to 115.56 kJ mol-1, indicating that the series of samples exhibited good catalytic performance, and the catalytic effect of the bimetallic sample was significantly better than those of the monometallic samples.

Thermal Decomposition of Ammonium Perchlorate Over an Efficient Catalyst Bimetallic Cu-Co-Mof: Catalytic Decomposition Behavior and Applications

Thermal Decomposition of Ammonium Perchlorate Over an Efficient Catalyst Bimetallic Cu-Co-Mof: Catalytic Decomposition Behavior and Applications

Enhanced Anti-Migration Performance of Carbon Nanotubes Confined Ferrocenyl Compounds and Their Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

Enhanced Anti-Migration Performance of Carbon Nanotubes Confined Ferrocenyl Compounds and Their Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

Preparation of different morphology Cu/GO nanocomposites and their catalytic performance for thermal decomposition of ammonium perchlorate.

Cu nanoparticles are more active catalytically than CuO nanoparticles, which have been widely studied as catalysts for organic synthesis, electrochemistry, and optics. However, Cu nanoparticles are easily agglomerated and oxidized in air. In this research, columnar, flower-like, bubble-like and teardrop-shaped Cu/GO nanocomposites were fabricated via a water-solvent thermal method and high temperature calcination technique using deionized water (H2O), methanol (CH3OH), ethanol (CH3CH2OH) and ethylene glycol (EG) as the solvent, respectively. The structures, the morphology and the catalytic performance and catalytic mechanism for thermal decomposition of ammonium perchlorate (AP) of the Cu/GO nanocomposites have been studied by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscopy (SEM), nitrogen adsorption tests (BET), simultaneous thermogravimetry-differential scanning calorimetry (TGA/DSC) and thermogravimetric couplet with Fourier transform infrared spectroscopy (TGA–FTIR), respectively. The experimental results show that the morphology of the Cu/GO nanocomposites has a significant effect on the surface area and the teardrop-shaped Cu/GO nanocomposites have the largest specific surface area and the best catalytic performance among them. When 5 wt% of the Cu/GO nanocomposites was added, the decomposition temperature of AP decreased from 426.3 °C to 345.5 °C and the exothermic heat released from the decomposition of AP increased from 410.4 J g−1 to 4159.4 J g−1. In addition, the four morphological Cu/GO nanocomposites exhibited good stability, their catalytic performance for thermal decomposition of AP remained stable after 1 month in air. Excellent catalytic performance and stability were attributed to the strong catalytic activity of pure metal nanoparticles, and GO can accelerate electron movement and inhibit the agglomeration of nanoparticles, as well as the multiple effects of inhibiting the oxidation of Cu nanoparticles in air. Therefore, it has important application potential in high-energy solid propellant.

Catalytic Effects of Ruthenocene Bimetallic Compounds Derived from Fused Aromatic Ring Ligands on the Main Oxidizing Agent for Solid Rocket Motor

We report the catalytic effect of three ruthenocene bimetallic compounds derived from fused aromatic rings of general formula [{Cp*Ru}2L], with Cp*: pentamethylcyclopentadiene and L = pentalene (1), 2,6-diethyl-4,8-dimethyl-s-indacene (2), and 2,7-diethyl-as-indacene (3), on the thermal decomposition of ammonium perchlorate (AP). The new compound 3 was characterized by a combination of multinuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The differential scanning calorimetry (DSC) analysis of compound 3 shows a decrease in the decomposition temperature of AP to 347 ºC, increases the energy release to 2048 J g-1 and, consequently, leads to the lowest activation energy (42.9 kJ mol−1). These results are comparable to the typically used metallocene (catocene: 347 ºC and 2472 J g-1), suggesting a suitable and competitive alternative to be used as a modifier for composite solid propellants.

Fabrication of Pb₃O₄ and Fe₂O₃ nanoparticles and their application as the catalysts in thermal decomposition of ammonium perchlorate

Nanoparticles (NPs) of lead tetroxide (Pb3O4) with the spherical morphology were manufactured by the reaction of lead nitrate with sodium hydroxide, while the nanoparticles (NPs) of red iron oxide (Fe2O3) with similar morphology were fabricated by hydrothermal route in the presence of ferric chloride hexahydrate as the precursor. Evaluation of the chemical structure, the purity and the morphology of the manufactured Fe2O3 and Pb3O4 NPs was carried out by analysis via X-ray diffraction (XRD) as well as scanning electron microscope (SEM). The outcomes of XRD recognized establishment of the desired oxides, wherever the SEM images clearly exhibited the morphology of the manufactured Pb3O4 and Fe2O3 as the spherical NPs with an average particle sizes of near to 40 and 46 nm, respectively. The catalytic effect of the metallic oxide NPs on the perfection of ammonium perchlorate (AP) thermal decomposing was established by testing their AP nano-composites via differential scanning calorimetric (DSC) together with thermogravimetric analysis (TG). Thermal behavior studies displayed that adding of 5% Fe2O3/Pb3O4 NPs (as the mixture) delivers a concerned catalytic effect during AP thermal decomposition. Additionally, thermal decomposition of AP could be amended by adding of 2% Pb3O4 NPs. Further comparison of the NPs catalytic effects was obtained by computing the values of activation energies (E) and thermodynamic parameters (i.e., ΔS#, ΔH# and ΔG#) for their thermal decomposition by non-isothermal approaches.

Energetic bimetallic complexes as catalysts affect the thermal decomposition of ammonium perchlorate.

Two bimetallic complexes of 4-hydroxy-3,5-dinitropyrazole, [K2Mn(DNPO)2(H2O)4]n·2H2O (BMEP-1) and [K2Zn(DNPO)2(H2O)6]n (BMEP-2), were synthesized and characterized by IR spectroscopy and elemental analysis. The crystal structures of BMEP-1 and BMEP-2 were determined by single-crystal X-ray diffraction. It is noteworthy that these complexes presented different metal-organic frameworks. The thermal behaviors of BMEP-1 and BMEP-2 were investigated by differential scanning calorimetry and thermogravimetric analysis measurements. These bimetallic complexes exhibited high thermal stability (348.0 °C and 331.0 °C) due to their large coordination bonds and three-dimensional interconnected structure. The catalytic performances of BMEP-1 and BMEP-2 on the thermal decomposition of ammonium perchlorate were investigated by TGA-DSC, TGA-FTIR, and non-isothermal kinetic analyses. The results showed that BMEP-1 and BMEP-2 exhibited excellent catalytic performance in the thermal decomposition of ammonium perchlorate. Notably, there was only a single exothermic peak at 302.6 °C and 318.6 °C, and the activation energy values of ammonium perchlorate decreased to 123.88 kJ mol-1 and 128.43 kJ mol-1, respectively. TGA-FTIR results showed that BMEP-1 and BMEP-2, as effective components of catalysis, will promote the production of H2O, N2O, NO2, and HCl in advance, during the thermal decomposition of ammonium perchlorate. BMEP-1 and BMEP-2 are expected to be two candidate additives for the catalytic decomposition of ammonium perchlorate in composite solid propellants.

Copper Oxide/HKUST‐1 Composite Catalyst as Thermal Decomposition Modifier on Ammonium Perchlorate

AbstractMetal‐organic framework and graphitic carbon nitride (g‐C3N4) are structures of high specific surface area. The Cu2+ incorporated classical metal‐organic frameworks (HKUST‐1) synthesized by the solvothermal method was used for the synthesis of ternary composite catalyst. When copper oxide was loaded into HKUST‐1/g‐C3N4, the resulting composite system was found to be highly effective catalysts for the thermal decomposition of ammonium perchlorate (AP). The doped metal oxide in HKUST‐1/g‐C3N4 functioned as a catalyst for the thermal decomposition of ammonium perchlorate. The composite catalyst was characterized by X‐ray diffraction (XRD). The effect of composite catalyst on the thermal decomposition of AP was studied using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results indicated that the composite system showed excellent catalytic activity towards the thermal decomposition of AP. The high‐temperature decomposition of AP decreased by 72 °C on using HKUST‐1 based ternary composite catalyst. The large surface area of HKUST‐1, g‐C3N4, and copper oxide nanoparticles play key roles in reducing the decomposition temperature. This was further confirmed by the kinetic analysis of the sample using the Kissinger‐Akahira‐Sunose method.

Novel powder catalysts of ferrocene-based metal-organic framework and their catalytic performance for thermal decomposition of ammonium perchlorate

It is of great significance to develop a novel and efficient combustion catalyst for thermal decomposition of ammonium perchlorates (AP) to regulate combustion performance of solid propellants. In this work, a series of ferrocene-based transition metals organic frameworks(MOFs) with 1,1′-ferrocenedicarboxylic acid (FcDA) as ligand, namely M-FcDA-MOFs (M = Co(II)、Mn(II)、Cu(II)、Fe(III) and Zn(II)), were successfully fabricated via simple solvothermal method. The samples were characterized by Fourier transform infrared spectroscopy (FT-IR), Field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The specific surface area and thermal stability of the samples were analyzed by N2 absorption/desorption isotherms and thermogravimetry (TG). Catalytic performance of the M-FcDA-MOFs towards the thermal decomposition of AP was investigated with differential scanning calorimetry-thermogravimetry (DSC-TG) techniques. The results show that the ferrocene-based MOFs have large specific surface area and high thermal stability, and can remarkably decrease the high temperature decomposition peak temperature (HTD) and apparent activation energy, enhance the apparent heat release of AP, and their catalytic performance is better than that of commercial combustion catalyst catocene. Among the samples investigated here, the Co-FcDA-MOF exhibited the best catalytic activity, which can decrease the HTD peak temperature and activation energy of AP by 90 °C and 20.4%, respectively, and increase the apparent heat release by 1082 J·g−1.

Additive Manufacturing of a Special-Shaped Energetic Grain and Its Performance.

In order to solve the problems of the complicated forming process, poor adaptability, low safety, and high cost of special-shaped energetic grains, light-curing 3D printing technology was applied to the forming field of energetic grains, and the feasibility of 3D printing (additive manufacturing) complex special-shaped energetic grains was explored. A photocurable resin was developed. A demonstration formula of a 3D printing energetic slurry composed of 41 wt% ultra-fine ammonium perchlorate (AP), 11 wt% modified aluminum (Al), and 48 wt% photocurable resin was fabricated. The special-shaped energetic grains were successfully 3D printed based on light-curing 3D printing technology. The optimal printing parameters were obtained. The microstructure, density, thermal decomposition, combustion performance, and mechanical properties of the printed grain were characterized. The microstructure of the grain shows that the surface of the grain is smooth, the internal structure is dense, and there are no defects. The average density is 1.606 g·cm−3, and the grain has good uniformity and stability. The thermal decomposition of the grain shows that it can be divided into three stages: endothermic, exothermic, and secondary exothermic, and the Al of the grain has a significant catalytic effect on the thermal decomposition of AP. The combustion performance of the grain shows that a uniform flame with a one-way jet is produced, and the average burning rate is 5.11 mm·s−1. The peak pressure of the sample is 45.917 KPa, and the pressurization rate is 94.874 KPa·s−1. The analysis of the mechanical properties shows that the compressive strength is 9.83 MPa and the tensile strength is 8.78 MPa.

Synthesis of ferrocenyl pyrazoline derivatives and their effects on thermal decomposition of ammonium perchlorate

Four ferrocenyl pyrazolines derivatives 3a-3d had been synthesized by the reaction of 1,3-diferrocenyl-2-propen-1-on 1 with hydrazine hydrate, then acylation with corresponding benzoyl chlorides directly. Structures of the target compounds were characterized by IR, MS, 1H NMR, 19F NMR, 13C NMR, HRMS, the crystal structures of 3a and 3b had been confirmed by X-ray single crystal diffraction. The electrochemistry behaviors of 3a-3d had been examined by cyclic voltammetry (CV), relationship between the structure of compounds and the electrochemical behavior of redox were discussed. Thermal decomposition characteristics of ammonium perchlorate (AP) were studied by differential scanning calorimetry (DSC) and thermogravimetric (TG) analysis, the results showed that 3a-3c had obviously accelerative effect on the thermal decomposition of AP.

Kinetics of thermal decomposition of ammonium perchlorate with nanocrystals of NixCo1−x Fe2O4 (x = 0, 0.05, and 1) ferrites

Kinetics of thermal decomposition of ammonium perchlorate with nanocrystals of NixCo1−x Fe2O4 (x = 0, 0.05, and 1) ferrites

When Copper Oxide meets graphene oxide: A core-shell structure via an intermittent spray coating route for a highly efficient ammonium perchlorate thermal decomposition

Ammonium perchlorate (AP) is the primary oxygen source for solid propellants; its thermal decomposition behavior is determinant for the overall performance of the ensuing propellant. In this perspective, a novel Intermittent, Spray Coating, Draying, and Mixing (ISCDM) method is introduced herein to prepare AP@CuO, PA@GO, and AP@CuO@GO core-shell composites. The as-synthesized materials morphological information, crystalline structure, and elemental composition are probed by powder X-ray diffraction, Raman spectroscopy, energy-dispersive X-ray spectroscopy, and scanning electron microscopy. The as-prepared CuO nanospheres were effectively embedded into the AP microparticles surface. AP@CuO microparticles were continuously coated with graphene oxide (GO) nanosheets. Particle size analyzer was used to probe the particle size distribution of core-shell composites. Results show that the application of ISCDM method results in a typical narrow gaussian size distribution with an average diameter of hundred microns ranking from 158.56 µm to 166.22 µm. The thermal decomposition and the catalytic performances were investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). AP@CuO@GO core-shell composite exhibits an excellent thermal decomposition behavior: a low thermal decomposition temperature (LTD) of 337 °C, reduced values of the High thermal decomposition temperature HTD to be overlapped with the LTD step, and a significant energy release of 1543 J g−1 are registered.

Effect of novel graphene-based ferrocene nanocomposites on thermal decomposition of AP

Graphene-based ferrocene nanocomposites play a positive role in improving the comprehensive properties of solid propellants containing ammonium perchlorate (AP). Novel graphene-based ferrocene nanocomposites with different molecular structures were successfully fabricated and characterized systemically using SEM, EDS, FTIR, RAMAN and XPS instruments. Additionally, the catalytic performance of the as-synthesized graphene-based ferrocene nanocomposites on the thermal decomposition and kinetics behavior of AP were studied using DSC and kinetic methods. The result showed the excellent catalytic performance of graphene-based ferrocene nanocomposites, and the molecular structure plays a significant influence on thermal decomposition of AP. Among the nanocomposites considered, the as-synthesized graphene-based ferrocene nanocomposite NG-550-Fe (γ-aminopropyl triethoxy silane as modifier) owns best catalytic activity, and the decomposition peak temperature and activation energy of AP + NG-550-Fe was reduced by 137.7 °C and 151.6 kJ·mol−1 respectively, compared with pristine AP. Combined with the reported studies, the relatively stronger combination of KH-550 and the better dispersion of Fe may be the reason why NG-550-Fe is more effective than other graphene-based ferrocene nanocomposites and traditional supported graphene nanocomposites studied. Results of this study have implications concerning the rational design of graphene-based catalyst, and help to better understand their catalytic performance and mechanism on AP decomposition.

Synthesis and properties of borane‐containing ionic liquids based on biferrocene

AbstractTo develop a new type of energetic ionic liquid (EIL) that has a catalytic effect on the thermal decomposition of ammonium perchlorate (AP) and can be ignited in white fuming nitric acid (WFNA), six borane‐containing ionic liquids based on biferrocene were successfully synthesized, and their structures were determined by x‐ray crystallography. Except for iodized salts, four EILs with high thermal stability burned rapidly in WFNA, one of which, bis[1‐(ferrocenylmethyl)imidazole‐3‐yl] dihydroboronium cyanoborohydride, [Fcmim][BH3CN], produced the shortest ignition delay (ID) time of 5 ms. However, iodized salts demonstrated a better catalytic effect on AP than did BH3CN−‐ or N(CN)2−‐based EILs and bis[1‐(ferrocenylmethyl)benzimidazole‐3‐yl] dihydroboronium iodide, [Fcbemim][I], could advance the final thermal decomposition temperature of AP by 50°C. Anions have a significant effect on the structures and performances of ionic liquids.

Cobalt copper ferrite: burning rate modifier for composite solid propellants and its catalytic activity on the thermal decomposition of ammonium perchlorate

Cobalt copper ferrite: burning rate modifier for composite solid propellants and its catalytic activity on the thermal decomposition of ammonium perchlorate