Thermal Decomposition Temperature Of Ammonium Perchlorate Research Articles

Facile Grinding Method for Preparing Nano-Cu-Cr-Fe Composite Metal Oxides with Enhanced Catalytic Activity for Thermal Decomposition of Ammonium Perchlorate

ABSTRACT Ammonium perchlorate (AP) is a commonly used oxidant for solid propellants, and improving the thermal decomposition performance of AP has been the focus of research, as its thermal decomposition performance directly affects the performance of the propellant. Among a variety of catalysts, nanocomposite metal oxides have demonstrated a significant role in facilitating the thermal decomposition of AP. In this study, Cu-Cr-Fe ternary metal oxides with different molar ratios (5:2:8, 5:4:6, 5:6:4, 5:8:2) were prepared by a facile mechanical grinding method to investigate their catalytic effect on the thermal decomposition properties of AP. The structure and morphology of Cu-Cr-Fe ternary metal oxides were investigated using X-ray diffractometer (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and the catalytic effect of different ternary catalysts on the thermal decomposition performance of AP was also investigated using thermal weight (TG) and differential scanning calorimetry (DSC) techniques. The results show that Cu-Cr-Fe ternary nanocomposite metal oxides with a molar ratio of 5:2:8 prepared by mechanical grinding exhibit excellent catalytic effect on the thermal decomposition of AP, as well as nanometallic oxides (Cu-Cr-Fe = 5:2:8) prepared using the co-precipitation and physical mixing methods. Furthermore, the ternary Cu-Cr-Fe (molar ratio of 5:2:8) composite metal oxide prepared by mechanical grinding resulted in a significant decrease in the thermal decomposition temperature of AP, which decreased from 441.3°C to 352.5°C, the heat of decomposition increased from 941 J/g to 1680 J/g, and the Gibbs free energy of AP decreased from 199.8 kJ/mol to 173.2 kJ/mol. This demonstrates the good synergistic catalytic effect between CuO, Cr2O3 and Fe2O3 nanoparticles, which is expected to facilitate the application of ternary nanocomposite metal oxides in the field of solid propellants.

Influence of BaZnCuO3 and BaZnCuO3/rGO on the thermal decomposition of ammonium perchlorate and 3‐nitro‐3H‐1,2,4‐triazol‐5‐one (NTO)

AbstractBaZnCuO3 (BZC) was synthesized using the sol–gel method. The BZC was incorporated in reduced graphene oxide (rGO) to produce BZC/rGO composite. The synthesized catalysts were characterized using Raman, scanning electron microscopy (SEM), powder X‐ray diffraction (XRD), and ultraviolet–visible (UV–Vis) analysis. The comparative effect of BZC and BZC/rGO composite was studied on the thermal decomposition of 3‐nitro‐3H‐1,2,4‐triazol‐5‐one (NTO) and ammonium perchlorate (AP) using the simultaneous thermogravimetric technique (TG‐DTA). Thermal investigations suggest that BZC was a better catalyst for decreasing the thermal decomposition temperature and the thermokinetic parameters of both AP and NTO compared to BZC/rGO composite. BZC can reduce the thermal decomposition temperature of AP and NTO by 121 and 46°C, respectively. The findings support BZC as a possible catalyst in the thermolysis of both NTO and 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.

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.

Synthesis of nanorods assembled V‐doped WO3 microspheres and the catalytic performance in thermal decomposition of ammonium perchlorate

AbstractV‐doped WO3 microspheres composed of nanorods radially grown from the center were fabricated via a simple hydrothermal method. The as‐obtained products were characterized by several techniques such as X‐ray powder diffraction (XRD), energy dispersive spectrometer (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), Raman spectrum, and Brunauer–Emmett–Teller (BET). It was found that V atoms were incorporated inside the hexagonal WO3 lattice. On the basis of time‐dependent experiments, the formation mechanism for the as‐prepared V‐doped WO3 micro‐nanostructures was discussed. In addition, the catalytic properties of the synthesized material on the thermal decomposition of ammonium perchlorate (AP) were evaluated by thermal gravimetric and differential thermal analysis (TG/DTA), which showed the thermal decomposition temperatures of AP in the presence of 1, 2, and 4 wt% of V‐doped WO3 micro‐nanostructures were reduced to 399, 393, and 380°C, respectively.

In situ synthesis of copper stearate/ammonium perchlorate shell–core composite for self-catalytic thermal decomposition

In this study, copper stearate (CS) was investigated as a potential catalyst for the thermal decomposition of ammonium perchlorate (AP). Copper stearate/ammonium perchlorate (CS/AP) shell–core composite was prepared by in situ synthesis and characterized to sample by SEM and EDS, it shows that CS is evenly dispersed on the surface of AP and forms a shell–core structure. Through using DSC and analyzing the thermal decomposition performance of CS/AP composite,the results show that the thermal decomposition temperature of AP decreased with the increase of catalyst content,when catalyst content is 4%, the thermal decomposition temperature of AP goes down 78.4 °C, and its catalytic effect is best. CS/AP shell–core composite provides a fresh idea for the thermal decomposition of AP.

Constructing Sheet-On-Sheet Structured Graphitic Carbon Nitride/Reduced Graphene Oxide/Layered MnO₂ Ternary Nanocomposite with Outstanding Catalytic Properties on Thermal Decomposition of Ammonium Perchlorate.

We unprecedentedly report that layered MnO2 nanosheets were in situ formed onto the surface of covalently bonded graphitic carbon nitride/reduced graphene oxide nanocomposite (g-C3N4/rGO), forming sheet-on-sheet structured two dimension (2D) graphitic carbon nitride/reduced graphene oxide/layered MnO2 ternary nanocomposite (g-C3N4/rGO/MnO2) with outstanding catalytic properties on thermal decomposition of ammonium perchlorate (AP). The covalently bonded g-C3N4/rGO was firstly prepared by the calcination of graphene oxide-guanidine hydrochloride precursor (GO-GndCl), following by its dispersion into the KMnO4 aqueous solution to construct the g-C3N4/rGO/MnO2 ternary nanocomposite. FT-IR, XRD, Raman as well as the XPS results clearly demonstrated the chemical interaction between g-C3N4, rGO and MnO2. TEM and element mapping indicated that layered g-C3N4/rGO was covered with thin MnO2 nanosheets. Furthermore, the obtained g-C3N4/rGO/MnO2 nanocomposite exhibited promising catalytic capacity on thermal decomposition of AP. Upon addition of 2 wt % g-C3N4/rGO/MnO2 ternary nanocomposite as catalyst, the thermal decomposition temperature of AP was largely decreased up by 142.5 °C, which was higher than that of pure g-C3N4, g-C3N4/rGO and MnO2, respectively, demonstrating the synergistic catalysis of the as-prepared nanocomposite.

Synthesis of ferrocene‐modified poly(glycidyl methacrylate) and its burning rate catalytic property

A series of ferrocene‐modified poly(glycidyl methacrylate) (PGMA‐Fc) compounds were synthesized and applied as burning rate catalysts in simulative solid propellant to overcome migration problems. 1H NMR and Fourier transform infrared spectroscopies and gel permeation chromatography were used to characterize the synthesized polymers. Their electrochemical behavior was evaluated using cyclic voltammetry. Their catalytic performance for the decomposition of ammonium perchlorate (AP) was investigated using thermogravimetric analysis. Anti‐migration studies were conducted in migration tubes under 50°C. The results show that PGMA‐Fc has a good catalytic effect on lowering the thermal decomposition temperature of AP. Anti‐migration studies show that PGMA‐Fc has better anti‐migration performance than ferrocene and catocene.

Synthesis and catalytic performance of ferrocene‐based compounds as burning rate catalysts

To overcome migration problems of ferrocene‐based burning rate catalysts and to enhance burning rate of ammonium perchlorate (AP)‐based propellants, eleven ferrocene‐based compounds (1–11) were synthesized by the condensation reaction of ferrocenecarbonyl chloride with corresponding amines and alcohols. The synthesis of 1–11 was confirmed using 1H NMR, Fourier transform infrared and UV–visible spectroscopy. Their electrochemical properties were analyzed using cyclic voltammetry. The compounds showed redox behavior due to the presence of ferrocene. Their catalytic behavior in the thermal decomposition of AP was investigated using thermogravimetry (TG) and differential TG (DTG). In the presence of 5 wt% 1–11, the thermal decomposition temperature of AP was significantly decreased. TG and DTG analyses showed that 1–11 had a good catalytic effect in the thermal decomposition of AP. Anti‐migration studies showed that migration of 1–11 was slower than that of 2,2‐bis(ethylferrocenyl)propane (catocene) and ferrocene. The effect of the presence of polar elements like oxygen and nitrogen on anti‐migration behavior of small ferrocene‐based compounds was also investigated. Oxygen‐containing compounds showed better anti‐migration behavior than nitrogen‐containing compounds.

Facile fabrication of Fe3O4 and Co3O4 microspheres and their influence on the thermal decomposition of ammonium perchlorate

Fe3O4 and Co3O4 microspheres were successfully synthesized by the hydrothermal decomposition of iron oxalate and cobalt oxalate solution. The composition and morphology of synthesized powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The catalytic properties of the as-obtained Fe3O4 and Co3O4 microspheres on the thermal decomposition of ammonium perchlorate (AP) were evaluated by thermo-gravimetric analysis and differential thermal analysis (TGA/DTA) methods. The thermal decomposition temperatures of AP in the presence of 1, 2, 4 and 8 wt% of Fe3O4 microspheres were respectively decreased by 58, 80, 102 and 129 °C (lowered to 398, 376, 354 and 327 °C). And the thermal decomposition temperatures of AP in the presence of 1, 2, 4 and 8 wt% of Co3O4 microspheres were respectively decreased by 55, 74, 112 and 131 °C (lowered to 401, 382, 344 and 325 °C). The analysis of the thermal gravimetric analyzer couplet with infrared spectroscopy (TG-IR) test reveal that the additives can accelerate the thermal decomposition of AP via the high-temperature decomposition. All the results suggest the as-prepared Fe3O4 and Co3O4 microspheres have highly catalytic properties on the thermal decomposition of AP, which can be used as the promising additives in the future.

The influence of VO2(B) nanobelts on thermal decomposition of ammonium perchlorate

Abstract The influence of vanadium dioxide VO2(B) on thermal decomposition of ammonium perchlorate (AP) has not been reported before. In this contribution, the effect of VO2(B) nanobelts on the thermal decomposition of AP was investigated by the Thermo- Gravimetric Analysis and Differential Thermal Analysis (TG/DTA). VO2(B) nanobelts were hydrothermally prepared using peroxovanadium (V) complexes, ethanol and water as starting materials. The thermal decomposition temperatures of AP in the presence of I wt.%, 3 wt.% and 6 wt.% of as-obtained VO2<B) nanobelts were reduced by 39 °C. 62 °C and 74 °C, respectively. The results indicated that VO2(B) nanobelts had a great influence on the thermal decomposition temperature of AP Furthermore, the influence of the corresponding V2Os, which was obtained by thermal treatment of VO2(B) nanobelts, on the thermal decomposition of AP was also investigated. The resufs showed that VO2(B) nanobelts had a greater influence on the thermal decomposition temperature of AP than that of V2Os.

Fabrication and catalytic activity of ultra-long V2O5 nanowires on the thermal decomposition of ammonium perchlorate

Ultra-long V2O5 nanowires were successfully synthesized using peroxovanadium (V) complexes solution by a template-free hydrothermal method without the addition of organic surfactant or inorganic ions. The as-obtained products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). It was found that the peroxovanadium (V) complexes can be easily transformed to V2O5 nanowires by this hydrothermal route. Furthermore, the catalytic properties of the as-prepared V2O5 nanowires on the thermal decomposition of ammonium perchlorate (AP) were evaluated by Thermo-Gravimetric Analysis and Differential Thermal Analysis (TGA/DTA), which showed the thermal decomposition temperatures of AP in the presence of 1, 3, 5 and 10wt% of V2O5 nanowires were reduced to 414, 390, 383 and 368°C (decreased by 42, 66, 73 and 88°C), respectively.

Synthesis, complexation of 1,2,3-(NH)-triazolylferrocene derivatives and their catalytic effect on thermal decomposition of ammonium perchlorate

Ferrocenyl 1,2,3-triazoles 3a–3f and their Cu(II) or Zn(II) complexes have been synthesized and characterized. Compound 3d was structurally determined by X-ray crystallography. The DTA and TG measurements confirm the obvious catalytic effect of the representative compounds 3a and 3b on the decreasing of the decomposition temperature of ammonium perchlorate (AP) (by 32.3 and 36.2 °C respectively), whereas the Cu or Zn complexes of 3a lowers the thermal decomposition temperature of AP more dramatically, by 60.6 and 61.9 °C respectively. So ferrocenyl 1,2,3-triazoles 3a–3f and their Cu(II) or Zn(II) complexes are a kind of potentially high-burning-rate catalyst.

Synthesis of porous sheet-like Co3O4 microstructure by precipitation method and its potential applications in the thermal decomposition of ammonium perchlorate

Porous sheet-like cobalt oxide (Co3O4) were successfully synthesized by precipitation method combined with calcination of cobalt hydroxide precursors. The structure, morphology and porosity properties of the products were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and nitrogen adsorption–desorption measurement. The as-prepared sheet-like microstructures were approximately 2–3μm in average diameter, and the morphology of the cobalt hydroxide precursors was retained after the calcination process. However, it appeared a large number of uniform pores in the sheets after calcination. In order to calculate the potential catalytic activity, the thermal decomposition of ammonium perchlorate (AP) has been analyzed, in which cobalt oxide played a role of an additive and the porous sheet-like Co3O4 microstructures exhibited high catalytic performance and considerable decrease in the thermal decomposition temperature of AP. Moreover, a formation mechanism for the sheet-like microstructures has been discussed.

Facile synthesis of V2O3/C composite and the effect of V2O3 and V2O3/C on decomposition of ammonium perchlorate

A V2O3/carbon core–shell structured composite (V2O3/C) was successfully synthesised using V2O5 and glucose as the starting materials by a facile hydrothermal route and subsequent calcinations at 700°C for 2 h under Ar atmosphere. The as-obtained products were characterised by X-ray powder diffraction, energy-dispersive X-ray spectrometer, elemental analysis, Fourier transform infrared spectroscopy, Raman spectrum, scanning electron microscopy and transmission electron microscopy. Furthermore, V2O3 and V2O3/C were explored as the additives to the thermal decomposition of ammonium perchlorate (AP), the key component of composite solid propellants. The thermal decomposition temperatures of AP in the presence of V2O3 and V2O3/C were reduced by 49 and 73°C, respectively, which indicates that V2O3/C has higher activity than that of V2O3.

Ultrafine α-Fe<sub>2</sub>O<sub>3</sub> Nanoparticles: Facile Synthesis, Characterization and their Catalytic Activity on Ammonium Perchlorate

Ultrafine α-Fe2O3nanoparticles have been synthesized by a facile hydrothermal method. The products were characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM). The diameter of the as-obtained α-Fe2O3nanoparticles is about 6.8 nm on average. The solvent have great effect on the morphology of the final products. Furthermore, the effect of ultrafine α-Fe2O3nanoparticles on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermal gravimetric analyzer (TG) and differential thermal analysis (DTA). The thermal decomposition temperature of AP in the presence of α-Fe2O3nanoparticles was reduced by 99 °C.

Improve the catalytic activity of α-Fe 2O 3 particles in decomposition of ammonium perchlorate by coating amorphous carbon on their surface

Sphere- and pod-like α-Fe 2O 3 particles have been selectively synthesized using NH 3·H 2O and NaOH solution to adjust the pH value of the designed synthetic system, respectively. The sphere-like α-Fe 2O 3 particles with diameter about 25 nm on average were encapsulated into carbon shells to fabricate a novel core–shell composite (α-Fe 2O 3@C) through the coating experiments. The catalytic performance of the products on the thermal decomposition of ammonium perchlorate (AP) was investigated by thermal gravimetric analyzer (TG) and differential thermal analysis (DTA). The thermal decomposition temperatures of AP in the presence of pod-like α-Fe 2O 3, sphere-like α-Fe 2O 3 and α-Fe 2O 3@C are reduced by 72, 81 and 109 °C, respectively, which show that α-Fe 2O 3@C core–shell composites have higher catalytic activity than that of α-Fe 2O 3.

Synthesis and characterization of KNd 2Ti 3O 9.5 nanocrystal and its catalytic effect on decomposition of ammonium perchlorate

A novel kind of perovskite type oxide KNd 2Ti 3O 9.5 nanocrystals with an average size of 12 nm were successfully fabricated by a stearic acid sol–gel method (SAM) using Ti(OBu) 4, KOH, Nd 2O 3 and stearic acid as the raw materials. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used to characterize the products. The catalytic effect of the KNd 2Ti 3O 9.5 nanoparticles on thermal decomposition of ammonium perchlorate (AP) was investigated by differential thermal analysis (DTA) and thermal gravimetry (TG) experiments. Results indicated that the obtained KNd 2Ti 3O 9.5 nanocrystals took on cubic structure and presented both good dispersibility and uniform crystallite size. Also, they have an intense catalytic effect on the thermal decomposition of AP. Adding 2% of KNd 2Ti 3O 9.5 nanoparticles to AP can obviously decrease the thermal decomposition temperature of AP by 50 °C, increase the heat of decomposition from 590 J g −1 to 1659 J g −1 and obviously quicken the decomposition reaction rate.

Mixed oxides derived from Cu–Co layered double hydroxide nanorods: Preparation, characterization and their catalytic activities

In the present work, a series of Cu–Co layered double hydroxide (LDH) nanorods were prepared using a co-precipitation reaction with hydrothermal treatment for the first time. Mixed oxides obtained by calcination of Cu–Co LDHs (Cu–Co CLDHs) were used as new catalysts for promoting thermal decomposition of ammonium perchlorate (AP). The catalytic activities were investigated by differential thermal analysis (DTA). Thermal decomposition temperature of AP was considerably decreased in the presence of Cu–Co CLDHs. Cu–Co CLDHs exhibit higher catalytic activity than the mechanical mixture of CuO and Co 2O 3. The catalytic mechanism was also briefly discussed.

The effect of specific surface area of TiO2 on the thermal decomposition of ammonium perchlorate

The thermal decomposition of ammonium perchlorate (AP) is considered to be the first step in the combustion of AP-based composite propellants. In this report, the effect of the specific surface area of titanium oxide (TiO2) catalysts on the thermal decomposition characteristics of AP was examined with a series of thermal analysis experiments. It was clear that the thermal decomposition temperature of AP decreased when the specific surface area of TiO2 increased. It was also possible that TiO2 influences the frequency factor of AP decomposition because there was no observable effect on the activation energy.