Thermal Decomposition Of Ammonium Perchlorate Research Articles

Synthesis of poly(2-(methacryloyloxy) ethyl ferrocene carboxylate-co-glycidyl methacrylic acid)s and their anti-migration and burning rate catalytic properties

Ferrocene (Fc)-based polymers have promising application in burning rate catalysts (BRCs) for solid composite propellants, and some of them have already been practically used. However, they have some drawbacks such as high migration during a long-time storage. Copolymers of poly(2-(methacryloyloxy) ethyl ferrocene carboxylate-co-glycidyl methacrylic acid)s (P(FHEMA-co-GMA)s) were synthesized to overcome the migration problem of Fc-based BRCs as well as to boost the burning rate (BR) of ammonium perchlorate (AP)-based propellants. The structures of the obtained P(FHEMA-co-GMA)s were confirmed by proton nuclear magnetic resonance (1H NMR) and Fourier transform infrared (FT-IR) spectroscopy. Cyclic voltammetry (CV) method was used to study their electrochemical behavior, and the P(FHEMA-co-GMA)s showed redox behavior for the existence of the Fc units. Because of the formation of integrated network structures, the P(FHEMA-co-GMA)s have good anti-migration performances. The BR catalytic property of P(FHEMA-co-GMA)s were investigated by thermogravimetry (TG) and differential thermogravimetry (DTG). They showed competent catalytic effects on the thermal decomposition of AP.

Morphology-dependent catalytic activity of Fe2O3 and its graphene-based nanocomposites on the thermal decomposition of AP

The spherical, hollow and tubular Fe2O3 (s, h and t) and their graphene-based nanocomposites rGO-Fe2O3 (s, h and t) were fabricated using the facile solvothermal methods. The morphologies and compositions of the as-synthesized Fe2O3 (s, h and t) and rGO-Fe2O3 (s, h and t) nanocomposites were systematically characterized by SEM, TEM, XRD, FTIR and XPS methods. Then, the effect of the catalytic performance of Fe2O3 (s, h and t) and rGO-Fe2O3 (s, h and t) nanocomposites on the thermal decomposition of ammonium perchlorate (AP) were studied by DSC method. The DSC results showed that all of the Fe2O3 (s, h and t) and rGO-Fe2O3 (s, h and t) nanocomposites can effectively promote the thermal decomposition of AP. Besides, rGO-Fe2O3(s) nanocomposite has the best catalytic performance, and the high-temperature decomposition exothermic peak of AP was significantly reduced after its mixing with rGO-Fe2O3 (s) nanocomposite. It can be seen that the effects of Fe2O3 on AP decomposition is mainly reflected in the high temperature process, while the effects of rGO-Fe2O3 (s) on AP decomposition is reflected in both high and low temperature stages, and the effect on the high temperature stage is more significant. The excellent catalytic performance of rGO-Fe2O3 (s) nanocomposite can be attributed to the in-situ growth of Fe2O3 on the surface of rGO, which contributes to the low temperature decomposition process of AP.

Superb catalytic activity of as-green synthesized copper ferrite's thermal decomposition of ammonium perchlorate

A simple one step method is employed for the synthesis of CuFe2O4 nanoparticles (NPs) aided by utilizing egg albumin (EA) and aloe vera (AV) as solvents. The samples were characterized using X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), Thermo Gravimetric/Differential Thermal Anaysis (TG/DTA), Vibration Sample Magnetometer (VSM) and X-ray Photolectron Spectroscopy (XPS). XRD analysis of the samples sowed the presence of CuFe2O4 and CuO in the samples. The ambient VSM study proved the ferrimagnetism behavior of the CuFe2O4. TG/DTA was used to study the catalytic activity of the CuFe2O4 nanoparticles, the results revealed that a 78 °C reduction in the decomposition temperature of Ammonium Perchlorate (AP) was achieved while using 6% CuFe2O4 prepared using a mixed EA-AV and calcinated at 700 °C. Hence, CuFe2O4 can be potent catalytic agent in several environmental applications as an efficient catalyst.

Preparation of g‐C3N4 Nanosheets/CuO with Enhanced Catalytic Activity on the Thermal Decomposition of Ammonium Perchlorate

AbstractThe thermal oxidation etching assisted g‐C3N4 nanosheets/CuO was prepared through a facile co‐precipitation strategy. In this work, the structure, morphology, and composition of g‐C3N4 (UCN, prepared by urea), g‐C3N4 nanosheets (TCN, prepared by thermal oxidation etching of UCN), g‐C3N4/CuO (UCN/CuO), g‐C3N4 nanosheets/CuO (TCN/CuO) were characterized via X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR), X‐ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Furthermore, the catalytic effect of the obtained samples on the thermal decomposition of ammonium perchlorate (AP) was examined by thermal gravimetric analysis (TGA). As a result, in the case of 5 wt% TCN/CuO, the high decomposition temperature of AP decreased by 120.6 °C, which is much lower than that of UCN, TCN, CuO and UCN/CuO. In addition, the exothermic heat released from the decomposition of AP increased from 430.64 J g−1 to 2856.08 J g−1. This evident catalytic activity may be related to the synergistic effect of CuO and TCN. This work provides a novel strategy for the construction of composite catalyst for the thermal decomposition of AP, which is supposed to possess significant potential in the solid propellant field.

Thermal Decomposition of Ammonium Perchlorate in the Presence of Copper Tungsten Oxide (CuWO4)

AbstractThe catalytic effect of copper tungsten oxide (CuWO4) was investigated on the thermal decomposition of ammonium perchlorate (AP) using differential scanning calorimetry. A lowering of the high‐temperature decomposition peak temperature of AP was observed due to catalytic effect of copper tungsten oxide particles, now referred to as CTO in this paper henceforth. The kinetic parameters were evaluated using the Kissinger method. The decrease in the activation energy confirmed the catalytic activity of CTO. Further, CTO was evaluated in a standard composite propellant formulation having 86 % solid loading. Propellant performance and processing parameters such as the end of mix (EOM) viscosity, density, burning rate, pressure exponent (n‐value), etc. were measured for standard as well as a composition containing 1 % CTO. The results revealed that at 1 % level CTO causes more than 36 % increase in propellant burning rate compared to the standard propellant composition at 6.86 MPa pressure. The pressure exponent also increased to 0.48, whereas the standard composition was having its value of 0.41.

Exploring the Roles of ZIF-67 as an Energetic Additive in the Thermal Decomposition of Ammonium Perchlorate

Energetic additives can effectively increase the heat release of ammonium perchlorate (AP) decomposition to prevent nonenergetic additives from decreasing the energy density of composite solid prop...

Mesoporous cauliflower-like CuO/Cu(OH)2 hierarchical structures as an excellent catalyst for ammonium perchlorate thermal decomposition

Nanostructured CuO-based materials are promising catalysts in the thermal decomposition of ammonium perchlorate (AP). Here, a facile ammonia-evaporation-induced fabrication of novel mesoporous nanoparticles-aggregated cauliflower-like CuO/Cu(OH)2 structures is reported. The influence of the as-prepared material on AP decomposition was analyzed by TG and DSC and the results revealed its excellent catalytic performance. Adding 3 wt% CuO/Cu(OH)2 to AP decreases the decomposition temperature by 96 °C, reduces the activation energy from 86 ± 4 kJ mol−1 to 65.2 ± 0.6 kJ mol−1 and increases the total heat release by 38.6%. Such catalytic activity approaches or exceeds those of the best performing CuO-based catalysts, making CuO/Cu(OH)2 a strong candidate for use in catalyzed thermal decomposition of AP.

Cu-MOF derived Cu/Cu2O/C nanocomposites for the efficient thermal decomposition of ammonium perchlorate

C-dispersed Cu/Cu2O/C nanocomposites were prepared using a simple one-step calcination of Cu-MOF. The morphology and the structure of the Cu/Cu2O/C nanocomposites were characterized using X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy. The thermal decomposition catalytic effect of the obtained nanocomposites on ammonium perchlorate (AP) was investigated using the differential thermal analysis (DTA), and the catalytic mechanism was analyzed. The results showed that Cu-MOF increased the pyrolysis peak temperature of AP to 382.51 ​°C. Cu/Cu2O/C calcined at different temperatures had better catalytic effect on AP than Cu-MOF, and Cu/Cu2O/C-350 had the best catalytic effect on AP, decreasing the decomposition peak temperature and activation energy of AP by 87.55 ​°C and 86.51 ​kJ ​mol−1, respectively. Results showed that the prepared Cu/Cu2O/C-350 nanocomposites were a promising catalyst for AP.

A novel metal-organic framework precursor strategy to fabricate sub-micron CuO microspheres for catalytic thermal decomposition of ammonium perchlorate

A novel metal-organic framework (MOF) precursor strategy to fabricate CuO microspheres via air-flow impacting (AFI) synthetic method was reprted in the work. The MOF precursor HKUST-1 and its derived CuO microspheres were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, the catalytic activity of CuO microspheres on the thermal decomposition of ammonium perchlorate (AP) was investigated by differential thermal analysis (DTA). The results of DTA indicated that the addition of CuO microspheres to AP observably reduces the decomposition temperature due to its high contact area and much catalytic active sites. The HKUST-1 derived CuO microspheres are expected to remarkably improve the catalytic performance in AP-based composite solid rocket propellants.

3D Hierarchically ordered porous carbon entrapped Ni nanoparticles as a highly active catalyst for the thermal decomposition of ammonium perchlorate

The thermal decomposition behavior of ammonium perchlorate (AP) directly influences the combustion performance of the composite solid propellants (CSPs). To enhance the effective thermal decomposition of AP, a highly active catalyst was prepared by entrapping Ni nanoparticles (NPs) inside three-dimensional hierarchically ordered porous carbon (3D HOPC). The obtained HOPC/Ni nanohybrid possessed interconnected porous structures, a high specific surface area (996 m2 g-1), large pore volume (1.43 cm3 g-1), and highly dispersed Ni NPs. To investigate the catalytic activity of the HOPC/Ni nanohybrid for AP thermal decomposition, an AP/HOPC/Ni nanocomposite was synthesized by homogeneously confining AP nanocrystals into the HOPC/Ni nanohybrid to form a high contact area. Because of the synergistic effect between the 3D HOPC and Ni NPs as well as the size effect of the AP nanocrystals, the HOPC/Ni nanohybrid decreased the high-temperature decomposition (HTD) peak temperature of AP by 136.1 °C and increased the heat release from 371 to 2681 J g-1, demonstrating better catalytic activity than the individual 3D HOPC and Ni NPs components. It can be foreseen that the HOPC/Ni nanohybrid may be a promising, highly active catalyst that meets the development needs of AP-based CSPs.

Rare-earth, nitrogen-rich, oxygen heterocyclic supramolecular compounds (Nd, Sm, and Eu): Synthesis, structure, and catalysis for ammonium perchlorate

Three novel rare-earth, nitrogen-rich and oxygen heterocyclic supramolecular complexes, namely [Nd (BTF)2(H2O)5]n, [Sm(BTF)2(H2O)5]n, and [Eu(BTF)2(H2O)5]n, were synthesized. A single crystal was obtained by the solvent evaporation method, and the structure and coordination mode of metal complexes were determined by single crystal X-ray diffraction. Results show that the supramolecular complexes contain many hydrogen bonds and thus have good thermal stability (Tdec > 540 K). The thermal decomposition of ammonium perchlorate (AP) catalyzed by the complexes was investigated by differential thermal analysis, which reveals a pre-eminent catalytic effect on AP. The high temperature decomposition peak of AP can be advanced by nearly 90 K at the amount of added complexes of 10 wt%, and the activation energy of AP descent range is from 70 to 150 kJ/mol. The other properties were fully characterized through elemental analysis and Fourier transform infrared spectroscopy.

Heterobimetallic Catalysts for the Thermal Decomposition of Ammonium Perchlorate: Efficient Burning Rate Catalysts for Solid Rocket Motors and Missiles

We show the synthesis and characterization of four heterobimetallic compounds derived from s-indacene of general formula [{(CO)3Mn}-s-Ic-{MCp*}]q with M = Fe, Co, Ni, and Ru; q = 0, 1+. The complexes reported here were characterized by 1H and 13C NMR, elemental analysis and FT-IR. Additionally, the X-ray crystal structure of [(CO)3Mn-s-Ic-FeCp*] (1) and Mössbauer spectra are reported. The heterobimetallic compounds exhibit higher quasireversible redox potentials compared with ferrocene and catocene under the same reaction conditions. The complexes were tested as catalysts on the thermal decomposition of ammonium perchlorate examined by a differential scanning calorimetry technique to study their catalytic behavior. Compound (1) causes a decrease of ammonium perchlorate's decomposition temperature to 315 °C, consequently increasing the heat release by 138 J·g-1. Conversely, [{(CO)3Mn}-s-Ic'-{CoCp*}] (2) presents a higher heat release (2462 J·g-1), comparable to catocene.

Catalytic Thermal Decomposition of Ammonium Perchlorate by a Series of Energetic Complexes

Catalytic Thermal Decomposition of Ammonium Perchlorate by a Series of Energetic Complexes

Farrow-derived layered porous carbon aerogel for AP catalytic thermal decomposition

We extract natural fibers from waste palm bamboo leaves to prepare a composite carbon aerogel. This is a new type of environmentally friendly catalyst that shows excellent catalytic performance for the thermal decomposition of ammonium perchlorate.

Synthesis and Anti-migration Studies of Ferrocene-Based Amides as Burning Rate Catalysts

To overcome the migration problems of burning rate catalysts (BRCs), ferrocene-based amide compounds (AM-Fcs) were synthesized. The successful synthesis of AM-Fcs were confirmed by proton nuclear magnetic resonance, and Fourier transform infrared spectroscopy. The electrochemistry behaviors of AM-Fcs were examined by cyclic voltammetry (CV). The CV experimental results indicated that these AM-Fcs showed good electrochemical performances, which were contributable to their burning rate (BR) catalytic activity in composite solid propellants. The anti-migration test of AM-Fcs verified significantly slower migration than ferrocene and the most commonly used BRCs catocene. Thermal stability and BR catalytic impact of AM-Fcs on the thermal decomposition of ammonium perchlorate (AP) were studied by thermogravimetry and differential thermogravimetry. These AM-Fcs revealed good catalytic behaviors on the thermal degradation of AP.

In situ synthesis of oxidized MXene-based metal cobalt spinel nanocomposites for an excellent promotion in thermal decomposition of ammonium perchlorate

Oxidized MXene-supported MCo2O4 (oxidized MXene/MCo2O4, M = Mn, Zn, Cu and Co) nanocomposites with an excellent catalytic performance for AP decomposition were successfully synthesized through a facile hydrothermal assisted calcination method.

Catalytic effect of solvothermally prepared Cu2(bdc)2(bpy) metal-organic framework on thermal decomposition of ammonium perchlorate

Cu2(bdc)2 (bpy) metal-organic framework (MOF) was prepared by solvothermal method and the structure was characterized by powder X-ray diffraction (PXRD), scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FT-IR). The specific surface area and the pore size distributions was estimated by Brunauer–Emmett–Teller (BET) method and micropore (MP) plot. This metal-organic framework was used as catalyst to improve the thermal decomposition of ammonium perchlorate (AP) and thermal behaviors of the mixed samples containing the catalyst and ammonium perchlorate were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetric (DSC) experiments. The results showed that in the catalyzed samples, the heat released from thermal decomposition of ammonium perchlorate is much higher (more than 3 times in sample containing 4% by weight of the metal-organic framework as catalyst) and thermal decomposition temperature was significantly lower than that of pure AP (about 110 ​°C decrease in sample containing 2% by weight of catalyst). Thermal decomposition temperature range of AP was reduced from 178 ​°C to 105 ​°C and 61 ​°C in the samples containing 4% and 2% by weight of catalyst respectively. The results of kinetic calculations obtained from Kissinger method showed effective catalytic performance of this metal-organic framework by increasing the thermal decomposition rate constant of AP more than 1.8 times at a much lower temperature.

CuO/PbO Nanocomposite: Preparation and Catalysis for Ammonium Perchlorate Thermal Decomposition.

In this present article, we reported a facile and efficient milling method to prepare a series of CuO/PbO nanocomposite metal oxides (CuO/PbO NMOs), with CuO/PbO molar ratios of 1:2, 1:1, 1:0.5, and 1:0.25 as a potential catalyst to catalyze the thermal decomposition of ammonium perchlorate (AP). The obtained CuO/PbO NMOs were systematically characterized. X-ray diffraction (XRD), X-ray energy-dispersive spectrometry (EDS) and X-ray photoelectron spectroscopy (XPS) analyses showed that the characteristic peaks of CuO/PbO NMOs were almost the superposition of nano CuO and nano PbO, while few new weak peaks were observed resulting from the lattice defects and new structural arrangements and chemical bonds between nano CuO and nano PbO during a high-energy grinding process. Scanning electron microscopy (SEM) and transition electron microscopy (TEM) observations exhibited that the particle sizes of the CuO/PbO NMOs were distributed in the range of 10–20 nm. Thermogravimetric (TG) analysis coupled with differential scanning calorimetric (DSC) techniques verified that CuO/PbO NMOs with a CuO/PbO molar ratio of 1:1 presented the best catalytic effect for AP thermal decomposition among the other CuO/PbO NMOs, as well as the single nano CuO and nano PbO. The outstanding catalytic performance is mainly reflected as follows: shifting the peak temperature of AP in high-temperature decomposition stages from 441.3 to 347.6 °C, increasing the decomposition heat of AP from 941 to 1711 J/g, and decreasing the Gibbs free energy of AP from 199.8 to 172.1 kJ/mol, supporting the existence of a synergistic catalytic effect between nano CuO and nano PbO.

The effect of LaFeO3@MnO2 on the thermal behavior of energetic compounds: An efficient catalyst with core-shell structure

Large particle size and low specific surface area are two major factors of restricting metal oxides as combustion catalyst with high performance. The construction of three-dimensional (3D) heterojunction materials with synergistic effect is conducive to enhancing the catalytic activity. In this work, LaFeO3 were prepared by a facile solvo-thermal method and post-heat treament. However, the LaFeO3 with a large particle size shows poor specific surface area, resulting in a low catalytic activity. In order to improve its catalytic activity, a 3D core/shell heterostructured LaFeO3@MnO2 composite was constructed by coupling LaFeO3 with MnO2. The core-shell structured LaFeO3@MnO2 provides a larger specific surface area and high catalytic effect on the thermal decomposition of ammonium perchlorate (AP) with a reduced decomposition temperature from 403.73 °C to 281.38 °C, an enhanced energy release from 649.6 J·g−1 to 966.5 J·g−1, and a decreased apparent activation energy from 139.05 kJ·mol−1 to 110.88 kJ·mol−1. Additionally, LaFeO3@MnO2 also shows efficient catalytic effects on the thermal decomposition of hexanitrohexaazaisowurzitane (CL-20) and cyclotetramethylenetetranitramine (HMX).

Highly active catalysts based on 3D hierarchically ordered porous carbon with entrapped Fe2O3 nanoparticles for the thermal decomposition of ammonium perchlorate

Highly active catalyst with excellent ability to reduce the high-temperature decomposition (HTD) temperature and increase the apparent specific heat releases of ammonium perchlorate (AP) is an urgent requirement for the development of composite solid propellants. To this end, three-dimensional hierarchically ordered porous carbon (3D HOPC)/Fe2O3 composite scaffolds with high BET surface area (964–1697 m2/g) and large pore volume (1.40–2.36 cm3/g) are synthesized for higher catalytic activity. The entrapment of Fe2O3 nanoparticles (3.8–10.6 nm) inside 3D HOPC ensures their high dispersion and stability during the catalysis, and their size and content are readily tunable by adjusting the iron source concentration. The catalytic activity of HOPC/Fe2O3 composite scaffolds is investigated through synthesizing AP/HOPC/Fe2O3 nanocomposites, in which AP nanocrystals are homogeneously confined. Owing to the synergistic effect between 3D HOPC and Fe2O3 nanoparticles, HOPC/Fe2O3 composite scaffolds exhibit outstanding catalytic activity for AP thermal decomposition in decreasing the HTD peak temperature from 440.9 to 280.5 °C, lowering the activation energy from 176.4 to 132.2 kJ/mol, and increasing the heat release from 371 to 2114 J/g. This work constructs a highly active catalyst configuration by entrapping nano transition metal oxides inside carbon scaffolds, which has broad application prospects in AP-based composite solid propellants.