Enhancing the combustion of nAl with AlF3 coating: gas-solid reaction mechanism for reducing combustion agglomeration of Al powder.

The combustion agglomeration of nano-aluminum (nAl) powder leads to incomplete combustion, which seriously hinders its application as metal fuel. In this work, nAl@AlF3 composites were produced by coating nAl with AlF3via a facile chemical deposition method. TEM and SEM analyses indicated that the AlF3 layer was evenly coated on the surface of nAl with a thickness of 4.6-9.1 nm, thereby varying the quantity of AlF3 applied. Experimental results from combustion indicated that the prepared nAl@AlF3 composites exhibit superior combustion efficiency, a higher combustion rate, and reduced combustion agglomeration as compared to raw nAl. Contrary to the widely accepted explanation that volatilization of AlF3 hinders Al combustion agglomeration, we proved that the gas-solid reaction between nAl and AlF3 plays an important role in inhibiting the sintering of nAl particles produced. The gaseous intermediate (i.e., AlOF and HF) released from the hydrolysis of AlF3 could reduce the diffusion barrier of Al2O3 to facilitate the reaction of Al core, which enhances the combustion reaction kinetics. More importantly, these gaseous products actively participate in the reaction cycle to continuously exert their catalytic effects.

Facile Recrystallization Process for Tuning the Crystal Morphology and Thermal Safety of Industrial Grade PYX.

In this study, the crystal appearance of industrial grade 2,6-diamino-3,5-dinitropyridine (PYX) was mostly needle-shaped or rod-shaped with an average aspect ratio of 3.47 and roundness of 0.47. According to national military standards, the explosion percentage of impact sensitivity s about 40% and friction sensitivity is about 60%. To improve loading density and pressing safety, the solvent-antisolvent method was used to optimize the crystal morphology, i.e., to reduce the aspect ratio and increase the roundness value. Firstly, the solubility of PYX in DMSO, DMF, and NMP was measured by the static differential weight method, and the solubility model was established. The results showed that the Apelblat equation and Van't Hoff equation could be used to clarify the temperature dependence of PYX solubility in a single solvent. Scanning electron microscopy (SEM) was used to characterize the morphology of the recrystallized samples. After recrystallization, the aspect ratio of the samples decreased from 3.47 to 1.19, and roundness increased from 0.47 to 0.86. The morphology was greatly improved, and the particle size decreased. The structures before and after recrystallization were characterized by infrared spectroscopy (IR). The results showed that no chemical structure changes occurred during recrystallization, and the chemical purity was improved by 0.7%. According to the GJB-772A-97 explosion probability method, the mechanical sensitivity of explosives was characterized. After recrystallization, the impact sensitivity of explosives was significantly reduced from 40% to 12%. A differential scanning calorimeter (DSC) was used to study the thermal decomposition. The thermal decomposition temperature peak of the sample after recrystallization was 5 °C higher than that of the raw PYX. The thermal decomposition kinetic parameters of the samples were calculated by AKTS software, and the thermal decomposition process under isothermal conditions was predicted. The results showed that the activation energy (E) of the samples after recrystallization was higher by 37.9~527.6 kJ/mol than raw PYX, so the thermal stability and safety of the recrystallized samples were improved.

Comparative Study on Thermal Response Mechanism of Two Binders during Slow Cook-Off.

The HTPE (hydroxyl-terminated polyether) propellant had a lower ignition temperature (150 °C vs. 240 °C) than the HTPB (hydroxy-terminated polybutadiene) propellant in the slow cook-off test. The reactions of the two propellants were combustion and explosion, respectively. A series of experiments including the changes of colors and the intensity of infrared characteristic peaks were designed to characterize the differences in the thermal response mechanisms of the HTPB and HTPE binder systems. As a solid phase filler to accidental ignition, the weight loss and microscopic morphology of AP (30~230 °C) were observed by TG and SEM. The defects of the propellant caused by the cook-off were quantitatively analyzed by the box counting method. Above 120 °C, the HTPE propellant began to melt and disperse in the holes, filling the cracks, which generated during the decomposition of AP at a low temperature. Melting products were called the "high-temperature self-repair body". A series of analyses proved that the different thermal responses of the two binders were the main cause of the slow cook-off results, which were likewise verified in the propellant mechanical properties and gel fraction test. From the microscopic point of view, the mechanism of HTPE's slow cook-off performance superior to HTPB was revealed in this article.

Probing the Reaction Mechanisms of 3,5-Difluoro-2,4,6-Trinitroanisole (DFTNAN) through a Comparative Study with Trinitroanisole (TNAN).

To probe the thermal decomposition mechanisms of a novel fluorinated low-melting-point explosive 3,5-difluoro-2,4,6-trinitroanisole (DFTNAN), a comparative study with trinitroanisole (TNAN) was performed under different heating conditions. The thermal decomposition processes and initial reactions were monitored by DSC-TG-FTIR-MS and T-jump-PyGC-MS coupling analyses, respectively. The results show that fluorine decreased the thermal stability of the molecular structure, and the trigger bond was transferred from the ortho-nitro group of the ether to the para-nitro group. The possible reaction pathway of DFTNAN after the initial bond breakage is the rupture of the dissociative nitro group with massive heat release, which induces the ring opening of benzene. Major side reactions include the generation of polycyclic compounds and fluorine atom migration. Fluorine affects the thermal stability and changes the reaction pathway, and fluorinated products appear in the form of fluorocarbons due to the high stability of the C-F bond.

Influence of Fluorinated Polyurethane Binder on the Agglomeration Behaviors of Aluminized Propellants.

In this study, fluorinated polyurethane (FPU) was prepared from dialcohol-terminated perfluoropolyether as a soft segment; isophorone diisocyanate (IPDI) as a curing agent; 1,2,4-butanetriol (BT) as a crosslinker; and 1,4-butanediol (BDO) as a chain extender. Fourier transform infrared spectroscopy (FTIR) and 1H NMR were used to characterize the structure of the FPU. The mechanical properties of the FPUs with different BDO and BT contents were also measured. The tensile strength and breaking elongation of the optimized FPU formula were 3.7 MPa and 412%, respectively. To find out the action mechanism of FPU on Al, FPU/Al was prepared by adding Al directly to FPU. The thermal decomposition of the FPU and FPU/Al was studied and compared by simultaneous differential scanning calorimetry-thermogravimetry-mass spectrometry (DSC-TG-MS). It was found that FPU can enhance the oxidation of Al by altering the oxide-shell properties. The combustion performance of the FPU propellant, compared with the corresponding hydroxyl-terminated polyether (HTPE)-based polyurethane (HPU) propellant, was recorded by a high-speed video camera. The FPU propellants were found to produce smaller agglomerates due to the generation of AlF3 in the combustion process. These findings show that FPU may be a useful binder for tuning the agglomeration and reducing two-phase flow losses of aluminized propellants.

Synergetic Effect of Potassium Oxysalts on Combustion and Ignition of Al/CuO Composites.

In this study, we studied the synergetic effect of potassium oxysalts on combustion and ignition of nano aluminum (Al) and nano copper oxide (CuO) composites. Potassium periodate (KIO4) and potassium perchlorate (KClO4) are good oxidizers with high oxygen content and strong oxidizability. Different contents of KIO4 and KClO4 were added to nano Al/CuO and the composites were assembled by sonication. When the peak pressure of nano Al/CuO was increased ~5-13 times, the pressurization rate was improved by ~1-3 orders of magnitude, the ignition delay time was shortened by ~0.08 ms-0.52 ms and the reaction completeness was adjustable when 30-70% KIO4 and KClO4 were added into the composites. The reaction of Al/KIO4 and Al/KClO4 at a lower temperature was helpful to ignite the ternary composite. Meanwhile, CuO significantly reduced the peak temperature of oxygen released from the decomposition of KIO4 and KClO4. The synergetic effect of binary oxidizers made the combustion performance of the ternary composites better than that of the binary composites. The present work indicates that KIO4 and KClO4 are promising additives for nano Al/CuO to tune and promote the combustion performance. The ternary composites have potential application in energy devices and combustion apparatus.

Synthesis of nitrogen-doped porous hollow carbon nanospheres with a high nitrogen content: A sustainable synthetic strategy using energetic precursors.

Improving the recovery and utilization efficiency of obsolete energetic materials (EMs) is essential for addressing environmental pollution. In this sense, a sustainable one-step high-temperature carbonization strategy using 2,2',4,4',6,6'-hexanitrostilbene-based (HNS-based) energetic hollow nanospheres as energetic precursors was used to fabricate nitrogen-doped (N-doped) porous hollow carbon nanospheres with a high N content. The experimental results suggested carbon-based materials with a hollow spherical framework nanostructure can be obtained by the high-temperature carbonization of energetic precursors. The obtained samples possessed N-doped contents of 19.54 wt% at the carbonization temperature of 600 °C and even 6.10 wt% at 900 °C. In addition, hollow carbon nanospheres with a large number of hierarchical pores and a high surface area (503.5 m2/g) were produced at 900 °C. This strategy prevented unnecessary safety risks and improved recovery and utilization efficiency in a more sustainable and economic manner than conventional disposal methods of EMs. Therefore, this work provides a proof-of-principle concept for the fabrication of carbon-based fundamental functional materials from obsolete EMs.

Dual-mode response behavior of a graphene oxide implanted energetic system under different thermal stimuli.

GO, produced by the Hummers' method and characterized by scanning electron microscopy (SEM), elemental analysis (EA), Fourier-transform infrared spectroscopy (FT-IR), Fourier-transform infrared nanospectroscopy (nano FT-IR), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and simultaneous thermal analysis combined with mass spectrometry (TG-DSC-MS), was appended to boron/potassium nitrate (B/KNO3) in different proportions, to regulate the response of B/KNO3 to thermal stimuli. The addition of GO delayed the onset temperature of the reaction between B and KNO3, and brought the second reaction stage forward, however, it did not change the reaction mechanism. The integral model functions, which were in good agreement with the values calculated using the Kissinger and Ozawa method, took the form of Jander equations for three-dimensional diffusion processes. Results showing the sensitivity to flame testing demonstrated that the higher the GO content, the more insensitive the system was to temperature, which was consistent with the conclusion of the previous thermal analysis on the onset temperature of the reaction between B and KNO3. In a closed-vessel test, as the GO content increased, the pressure peak and maximum slopes of pressure-time curves increased. Under a thermal stimulus, GO was reduced to RGO, and when the stimulation was small and slow, this helped with heat dissipation and improved safety. If the stimulation was enough to ignite the energetic materials, GO contributed to the rapid attainment of the reaction temperature and sped up the reaction process.

Carbon-free energetic materials: computational study on nitro-substituted BN-cage molecules with high heat of detonation and stability.

A new series of high-energy density materials (HEDMs) B6N6H6-n (NO2) n (n = 1-6) are studied at the M06-2X/6-311++G**, ωB97XD/6-311++G** and B3LYP/6-311++G** levels. Analysis of the structural changes caused by substituting the NO2 and the electronic structures, such as electron localization function (ELF), Wiberg bond index (WBI), charge transfer and bond dissociation energies (BDE), provide important insights into the essence of the chemical characteristics and stability. Moreover, the Born-Oppenheimer molecular dynamic (BOMD) simulation is performed to verify their stability, which suggests that only the BN-cage derivatives with one and two nitro groups bonding with boron atoms (NO2-1-1 and NO2-2-1) can remain stable under ambient conditions. To predict the detonation performance and sensitivity of these two stable BN-cage energetic molecules accurately, the density, gas phase enthalpy of formation, enthalpy of sublimation, detonation performance, impact sensitivity and BDE are calculated systematically. The calculation results show that both NO2-1-1 and NO2-2-1 have a higher heat of detonation, higher value of h 50, and larger BDE of trigger bonds than CL-20.