Graphene Oxide-Intercalated Tetrazole-Based Coordination Polymers: Thermally Stable Hybrid Energetic Crystals with Enhanced Photosensitivity

Abstract

High-energy-density photosensitive pyrotechnics with good thermal stability have been in increasing demand in recent years. In this paper, graphene oxide (GO)-intercalated energetic coordination polymers (ECPs) are prepared with improved thermostability but great photosensitivity by using high nitrogen compounds azotetrazole (AT) and 5,5′-bistetrazole-1,1′diolate dehydrate (BTO) as ligands. The decomposition activation energy (E a ) of Cu-AT has been increased from 135.7 to 151.9 kJ• mol −1 after intercalating 5 wt% GO, and in the meantime, the exothermic peak temperature (T p ) was increased by 12.6 °C. However, the decomposition E a of Cu-BTO decreased under the effect of the same amount of GO with little effect on T p . This confirms that GO has stabilization effects on the Cu-AT crystal, whereas the catalytic effects on Cu-BTO would dominate after dehydration with its crystal lattice collapse. Also, when the content of GO was 3%, the resultant GO 0.03 -Cu-AT exhibits a higher density (2.88 g•cm −3 ) and good thermostability (T p = 293.7 °C). This ECP shows excellent low-energy laser ignition performance, which can be ignited with an energy of less than 1 mJ at a wavelength of 976 nm. Low-energy laser initiation is considered to be a safer but more reliable method than the traditional electrical-based ones.

Structural Control of Energetic Triaminoguanidine Nitrate Polymer Nanostructures for Reduced Thermal Reactivity

“…The Kissinger method only considers the peak data instead of the overall processes, thus, the widely used Freidman isoconversional method has been employed to investigate the relationship between the conversion rate (α) and E a of TAGP samples. As shown in Figure c, the E a of T0.06-1/1-100, T0.02-1/1-100, T0.014-1/1-100, and T0.03-1/1-100 were increased slightly with increasing α.…”

Preparation and Decomposition of Spherical CL-20 Composites with Enhanced Laser Absorbance and Decreased Mechanical Sensitivity

“…Recently, graphene oxide-carbohydrazide-metal (GO-CHZ-M) complexes, a class of photosensitive but mechanically insensitive energetic nanomaterials, have been synthesized and used as an effective burn rate modifier . It has been reported that GO can improve the laser response characteristics of EMs, whereas the metal ions such as Cu 2+ , Co 2+ , and Ni 2+ in these energetic coordination polymers can catalyze the thermal decomposition of EMs . It was shown that the GO-CHZ-Co (3 wt % of GO) complex exhibits an extraordinarily high heat release of 3012 J·g –1 , a short ignition delay time of 214 μs, and a low ignition energy of 0.74 J, with great impact sensitivity (IS) (14.3 J) and friction sensitivity (FS) (over 140 N) .…”

“…12 It has been reported that GO can improve the laser response characteristics of EMs, whereas the metal ions such as Cu 2+ , Co 2+ , and Ni 2+ in these energetic coordination polymers can catalyze the thermal decomposition of EMs. 13 It was shown that the GO-CHZ-Co (3 wt % of GO) complex exhibits an extraordinarily high heat release of 3012 J•g −1 , a short ignition delay time of 214 μs, and a low ignition energy of 0.74 J, with great impact sensitivity (IS) (14.3 J) and friction sensitivity (FS) (over 140 N). 12 It has been demonstrated that GO-CHZ-Co can catalyze the thermal decomposition of AP, where the peak temperature (T p ) of the second exotherm is lowered from 389.7 to 384.3 °C.…”