Nanocrystalline Transition Metal Oxides as Catalysts in the Thermal Decomposition of Ammonium Perchlorate

Nanocrystalline transition metal oxides (NTMOs) have been successfully prepared by three different methods: novel quick precipitation method (Cr₂O₃ and Fe₂O₃); surfactant mediated method (CuO), and reduction of metal complexes with hydrazine as reducing agent (Mn₂O₃). The nano particles have been characterized by X‐ray diffraction (XRD) which shows an average particle diameter of 35–54 nm. Their catalytic activity was measured in the thermal decomposition of ammonium perchlorate (AP). AP decomposition undergoes a two step process where the addition of metal oxide nanocrystals led to a shifting of the high temperature decomposition peak toward lower temperature. The kinetics of the thermal decomposition of AP and catalyzed AP has also been evaluated using model fitting and isoconversional method.     

Effect of Zn Powders on the Thermal Decomposition of Ammonium Perchlorate

In this paper, the catalytic effect of Zn nanopowders on thermal decomposition of ammonium perchlorate (AP) as well as those of Zn micropowders has been investigated using differential thermal analysis (DTA). The results show that both nanometer and micrometer Zn powders show similar excellent catalytic effect on the decomposition of AP, while the total heat releases of AP added by Zn nanopowders are generally higher than those of AP added by Zn micropowders. In addition, an attempt has been made to explain the observed results with the help of theoretical considerations and data generated during this work.     

Experimental Investigation on the Heterogeneous Kinetic Process of the Low Thermal Decomposition of Ammonium Perchlorate Particles

The thermal decomposition of ammonium perchlorate has been extensively studied in the past. Nevertheless, the various results published illustrate, on the one hand, significant differences regarding the influence of different parameters on the decomposition and on the other hand, a lack of useful quantitative laws to predict the thermal behaviour of this crystal under a range of conditions (temperature, duration of exposure, presence of confinement).     

Effects of Nanometer Ni,Cu, Al and NiCu Powders on the Thermal Decomposition of Ammonium Perchlorate

A study of the decomposition behaviour for Ammonium Perchlorate(AP) was carried out by differential thermal analysis and the two decomposition peaks were observed. The high temperature peak was found to shift to lower temperatures, but the corresponding shift in the low temperature peak was smaller due to the effect of nanometer metal powders. Results shows that Cu and NiCu nanopowders decreased both the high and low decomposition temperature, while Ni and Al nanopowders just decreased the high decomposition temperature and increased the low decomposition temperature. Metal micron‐sized powders show catalytic effects on the thermal decomposition of AP, but their effects are less than that of nanometer metal powders. With the increase in content, nanometer metal powders enhanced their catalytic effect on the high temperature decomposition of AP, however their effect was weakened on the low temperature decomposition.     

Kinetics of Thermal Decomposition of Ammonium Perchlorate with Nanocrystals of Binary Transition Metal Ferrites

This article was published in Early View with DOI 10.1002/prep.200800017 – what is wrong. It has appeared with the correct DOI 10.1002/prep.200900017 – in Propellants, Explosives, Pyrotechnics 2009 (34) issue 1/2009 on pp 78‐83.     

Preparation of Nano‐Sized Copper β‐Resorcylate (β‐Cu) and its Excellent Catalytic Activity for the Thermal Decomposition of Ammonium Perchlorate

Copper β‐resorcylate (cupric 2,4‐dihydroxy‐benzoate, β‐Cu) nanoparticles were prepared at a large‐scale via a facile wet mechanical grinding method and vacuum freeze‐drying process. The as‐prepared β‐Cu nanoparticles were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and Fourier‐transform infrared spectroscopy (FT‐IR). The results revealed that the nano‐sized β‐Cu is of semi‐spherical shape and of homogeneous distribution, with a fairly uniform size of 100 nm. The formation mechanism of β‐Cu nanoparticles in the whole process was discussed in detail. Furthermore, the catalytic properties of as‐obtained β‐Cu were investigated. The TG/DSC study showed that nano‐sized β‐Cu could be a promising additive for accelerating the thermal decomposition of ammonium perchlorate (AP).     

Preparation of Magnesium‐based Hydrogen Storage Materials and Their Effect on the Thermal Decomposition of Ammonium Perchlorate

Magnesium‐based hydrogen storage materials (MgH₂, Mg₂NiH₄, and Mg₂Cu‐H) were prepared and their structures were determined by XRD and ICP investigations. Mg₂NiH₄ has a monoclinic crystal structure and Mg₂Cu‐H is a mixture of MgCu₂ and MgH₂. The effects of magnesium‐based hydrogen storage materials on the thermal decomposition of ammonium perchlorate (AP) were studied by thermal analysis (DSC). It was found that magnesium‐based hydrogen storage materials show obvious boosting effects on the thermal decomposition of AP. The thermal decomposition peak temperature of AP was decreased, while the heat release of the decomposition of AP was increased. It was revealed that the effects of magnesium‐based hydrogen storage materials on the decomposition of AP become stronger with increasing content. The influence mechanism on the thermal decomposition of AP is suggested as follows: hydrogen released from magnesium‐based hydrogen storage materials and Mg, Ni, or Cu react with the decomposed products of AP.     

纳米CuCr_2O_4的制备及其对AP热分解性能的影响

采用HLG-5型纳米化粉碎机制备了粒径约为60nm的纳米CuCr2O4,用X射线衍射仪(XRD)、透射电子显微镜(TEM)表征了样品的结构及形貌,分析了纳米CuCr2O4的形成机理,用差示扫描量热仪(DSC)研究了原料CuCr2O4和纳米CuCr2O4对AP热分解性能的影响。结果表明,与原料CuCr2O4相比,质量分数2%的纳米CuCr2O4对AP具有更好的催化性能,可使AP的低温分解峰减弱,高温分解峰温降低67℃,反应速率常数提高数倍,使AP的表观分解热从821J/g提高到1 393J/g,增长率为69.7%。     

Preparation of Cu/CNT Composite Particles and Catalytic Performance on Thermal Decomposition of Ammonium Perchlorate

Composite particles of carbon nanotubes (CNTs) and Cu were prepared by a chemical reduction method. Characterization of Cu/CNT composite particles was performed by TEM, SEM, FT‐IR, XRD, XPS, AAS, DTA and EDS. The results show that the surface of CNTs is covered by Cu particles, and that the diameter of Cu/CNT composite particles gets larger than that of CNTs. Furthermore, in the presence of Cu/CNT composite particles, the peak temperature of the high‐temperature decomposition of ammonium perchlorate (AP) decreased by 126.3 °C, and the peak of the low‐temperature decomposition disappeared. Compared with a sample of simply mixed Cu and CNTs, the peak temperature of the high‐temperature decomposition of AP‐Cu/CNTs composite particles decreased by 11.4 °C. Compared with Cu, the peak temperature of the high‐temperature decomposition of AP‐Cu/CNT composite particles decreased by 20.9 °C. This work shows that the catalytic performance of Cu on the thermal decomposition of AP can be improved by compounding with CNTs.     

On the Thermal Stability of Partially Decomposed Ammonium Perchlorate

The response of propellants and explosives to thermal stimuli is an important aspect of their behavior, especially for their safe storage and handling. In the case of ammonium perchlorate (AP), the principal oxidizer used in solid composite propellants, exposure to elevated temperatures causes various levels of decomposition and morphological changes. These changes occur in both neat AP particles and AP based propellants. The hazards associated with thermally damaged, or partially decomposed AP are investigated. It is found that AP is more thermally stable after partial low temperature decomposition. Also, it is found that the extent of decomposition of the AP particles is strongly influenced by prior thermal damage. This dependency is attributed to the exhaustion of nucleation sites on certain crystal planes. Specific surface area measurements of the thermally damaged particles show that the particles recrystallize before they can decompose to a further extent in low temperature decomposition. The behavior of partially decomposed AP in the presence of a propellant binder is also examined.     

高氯酸铵比表面积对推进剂热稳定性的影响

研究了高氯酸铵（ＡＰ）比表面积对推进剂热稳定性的影响。ＡＰ比表面积的增大会导致推进剂初始分解温度、高低温热分解峰温和高低温下分解反应活化能的降低，但分解反应速度常数随ＡＰ比表面积的增大而增大。键合剂可以改善推进剂的热稳定性。     

Thermal Decomposition of Energetic Materials 86. Cryogel Synthesis of Nanocrystalline CL‐20 Coated with Cured Nitrocellulose

An unusual energetic composite, in which spherical nano‐dimensional particles of CL‐20 were uniformly coated with HDI‐cross‐linked nitrocellulose, was synthesized by the sol‐gel to cryogel method. Up to 90% solid loading was achieved. The particle size of CL‐20 was determined to be in the range of 20–200 nm by transmission electron microscopy, atomic force microscopy, and X‐ray powder diffraction. The decomposition characteristics of the composite were investigated by DSC and T‐jump/FTIR spectroscopy. The decomposition properties were controlled mostly by nitrocellulose until the percentage of CL‐20 was well above 50%. The drop weight impact sensitivity of the cryogels was essentially independent of the composition.     

Chemical and Textural Characterization of Iron Oxide Nanoparticles and Their Effect on the Thermal Decomposition of Ammonium Perchlorate

Metal oxide nanoparticles have been used as burning rate catalysts for ammonium perchlorate (AP) decomposition in composite solid propellants. Though most papers point to the efficiency of different sizes, shapes and compositions, the texture of the agglomerated particles plays an important role in the catalytic efficiency, but this aspect is not always discussed. In this paper, iron oxide and composite iron oxide/silica powders were synthesized in microemulsion systems and their effect on the decomposition of AP was investigated. X‐ray diffraction (XRD) analysis and Fourier transformed infrared spectroscopy (FT‐IR) showed that the synthesized powders have an amorphous to nanocrystalline pattern, with Fe₂O₃ composition. The use of different FT‐IR spectroscopic techniques – transmission, diffuse reflectance (DRIFT) and universal attenuated total reflectance (UATR) – allied to electron microscopy analysis allowed the characterization of the samples’ surface, indicating that silicon oxide forms a thick matrix that covers the iron oxide nanoparticles. Adsorption of N₂, light scattering and electron microscopy pointed that all samples are formed by mesoporous agglomerated nanoparticles containing micropores indicating that silicon oxide forms a thick matrix that covers the iron oxide nanoparticles. Adsorption of N₂, pointed that all samples show different microstructures and light scattering indicated results refer to agglomerated particles. Finally, the catalytic effect of the samples on the decomposition of AP was evaluated by thermogravimetric analysis coupled to differential thermal analysis (TG/DTA), showing that only the high temperature decomposition step of AP was affected by the catalyst, shifting to lower temperatures the higher the surface area of the synthesized iron oxide sample, regardless of the presence of the silica matrix.     

A Thermal Decomposition Model of Aminoguanidium 5,5′‐Azobis‐1H‐Tetrazolate and the Effect of Pressure and Particle Size on the Rate of Decomposition

The temperature histories of aminoguanidinium 5,5′‐azobis‐1H‐tetrazolate (C₄H₁₄N₁₈, AGAT) were measured in order to construct a thermal decomposition model of the compound. The effects of chamber pressure and AGAT particle size were also examined. The results of the study suggest that the thermal decomposition of AGAT occurs in three phases: solid phase, condensed phase, and residue. It was found that the condensed phase consists of decomposition zone I where dramatic temperature rise occurs, decomposition zone II where gradual temperature rise occurs, and the cooling zone where decomposition and temperature stop rising. It was also suggested that the temperature of the decomposition surface which is the interface of the solid phase and the condensed phase was ∼500 K, and that N₂ and NH₃ were suggested to occur in the vicinity of the decomposition surface of decomposition zone I. In addition, it was suggested that the thickness of the decomposition zones I and II decreases and that the maximum‐temperature‐reached increases with an increase in atmospheric pressure. The rate of decomposition of AGAT was found to follow Vieille's equation and the rate of decomposition increases with an increase in pressure. The rate of decomposition increased slightly with an increase in particle size.     

An Investigation on Thermal Decomposition of DNTF‐CMDB Propellants

The thermal decomposition of DNTF‐CMDB propellants was investigated by pressure differential scanning calorimetry (PDSC) and thermogravimetry (TG). The results show that there is only one decomposition peak on DSC curves, because the decomposition peak of DNTF cannot be separated from that of the NC/NG binder. The decomposition of DNTF can be obviously accelerated by the decomposition products of the NC/NG binder. The kinetic parameters of thermal decompositions for four DNTF‐CMDB propellants at 6 MPa were obtained by the Kissinger method. It is found that the reaction rate decreases with increasing content of DNTF.     

Preparation,Crystal Structure and Explosive Properties of Copper(II) Perchlorate Complex with 4‐Amino‐1,2,4‐Triazole and Water

A complex from copper(II) perchlorate with 4‐amino‐1,2,4‐triazole (4‐AT, C₂H₄N₄) was synthesized, and elemental composition, molecular structure, and explosive properties were determined. To this end, elemental and X‐ray analyses were carried out, sensitivity to mechanical and thermal stimuli was measured, mechanism of thermal decomposition was investigated, and kinetic parameters of decomposition were determined. In the next step measurements of heat of combustion and detonation velocity were performed. Detonation parameters were also calculated. It was stated that the complex has slightly distorted square bipyramidal (4+2) coordination. The four basal bonds are formed by nitrogen atoms of four 4‐AT molecules. The coordination of the metal is completed by two axial oxygen atoms, one of the perchlorate ion, and one of the water molecule. With respect to explosive properties, tetrakis(4‐AT)copper(II) perchlorate monohydrate belongs to the group of sensitive secondary explosives.     

New High‐Nitrogen Materials Based on Nitroguanyl‐Tetrazines: Explosive Properties,Thermal Decomposition and Combustion Studies

This paper describes the explosive sensitivity and performance properties of two novel high‐nitrogen materials, 3,6‐bis‐nitroguanyl‐1,2,4,5‐tetrazine ( 1 , (NQ₂Tz)) and its corresponding bis‐triaminoguanidinium salt ( 2 , (TAG)₂(NQ)₂Tz)). These materials exhibit very low pressure dependence in burning rate. Flash pyrolysis/FTIR spectroscopy was performed, and insight into this interesting burning behavior was obtained. Our studies indicate that 1 and 2 exhibit highly promising energetic materials properties.     

Combustion Characteristics of Ammonium Nitrate and Carbon Mixtures Based on a Thermal Decomposition Mechanism

In order to obtain a better understanding of the combustion characteristics of ammonium nitrate (AN) and carbon (C) mixtures (AN/C), burning tests and differential scanning calorimetry (DSC) were performed. AN mixed with carbon that is oxidized by nitric acid (HNO₃), such as activated carbon (AC), burned at 1 MPa. However, AN mixed with carbon that is not oxidized by HNO₃, such as graphite, did not burn under 7 MPa. Compositions with more than stoichiometric amounts of activated carbon had higher burning rates. Heat characteristic examinations found a similar trend. The burning rate of AN/AC mixed with CuO as a combustion catalyst deteriorated faster than an additive‐free one. From the DSC result, AN/AC/CuO had a higher onset temperature and a lower heat of reaction than AN/AC. These results suggested that, in the combustion wave of AN/C, a thermal decomposition zone is formed on the burning surface, and combustion performance was affected by the thermal decomposition of AN/C.     

Differential Scanning Calorimetric Study of HTPB based Composite Propellants in Presence of Nano Ferric Oxide

A comparative study of the thermal decomposition of ammonium perchlorate (AP)/hydroxy terminated polybutadiene (HTPB) based composite propellants has been carried out in presence and absence of nano iron oxide at different heating rates in a dynamic nitrogen atmosphere using differential scanning calorimetry. The pronounced effect was a lowering of the high temperature decomposition by 49 °C. A higher heat release up to 40% was observed in presence of nano ferric oxide (3.5 nm). The kinetic parameters were evaluated using the Kissinger method. The increase of the rate constant in the catalyzed propellant confirmed the enhancement of the catalytic activity of ammonium perchlorate. The scanning electron micrographs of nano Fe₂O₃ incorporated in HTPB revealed a well‐separated characteristic necklace‐like structure of α‐Fe₂O₃ particles at high magnification.