Thermal Reactivity of High-Density Hybrid Hexahydro-1,3,5-trinitro-1,3,5-triazine Crystals Prepared by a Microfluidic Crystallization Method.

In this paper, the two-dimensional (2D) high nitrogen triaminoguanidine-glyoxal polymer (TAGP) has been used to dope hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) crystals using a microfluidic crystallization method. A series of constraint TAGP-doped RDX crystals using a microfluidic mixer (so-called controlled qy-RDX) with higher bulk density and better thermal stability have been obtained as a result of the granulometric gradation. The crystal structure and thermal reactivity properties of qy-RDX are largely affected by the mixing speed of the solvent and antisolvent. In particular, the bulk density of qy-RDX could be slightly changed in the range from 1.78 to 1.85 g cm-3 as a result of varied mixing states. The obtained qy-RDX crystals have better thermal stability than pristine RDX, showing a higher exothermic peak temperature and an endothermic peak temperature with a higher heat release. Ea for thermal decomposition of controlled qy-RDX is 105.3 kJ mol-1, which is 20 kJ mol-1 lower than that of pure RDX. The controlled qy-RDX samples with lower Ea followed the random 2D nucleation and nucleus growth (A2) model, whereas controlled qy-RDX with higher Ea (122.8 and 122.7 kJ mol-1) following some complex model between A2 and the random chain scission (L2) model.

Hybrid RDX crystals assembled under constraint of 2D materials with largely reduced sensitivity and improved energy density.

In this paper, the widely used energetic material RDX had been modified with 2D high nitrogen polymer (TAGP). Various hybrid RDX crystals (qy-RDX) with higher detonation velocity and better thermostability had been obtained as a result of strong intermolecular interactions between TAGP and RDX molecules. The performance of the qy-RDX had been characterized to clarify the inherent mechanisms. It shows that the⊿Hf of qy-RDX could be largely changed in the range of 23.4 kJ kg-1 to 1343.6 kJ kg-1, whereas the density varies only from 1.81 g cm-3 to 1.86 g cm-3. The resulted detonation velocities are in the range of 8725.5 m·s-1 to 9251.8 m·s-1, depending on the content and state of the TAGP dopant. The sensitivity of the resulted qy-RDX is much better than pristine RDX due to improved crystal quality as well as higher concentration of hydrogen bonds. The impact energy is improved from 8.5 J (RDX) to 22 J (qy-RDX-1), whereas the friction sensitivity improves form 130 N to over 360 N for the same case. The Ea for thermal decomposition of qy-RDX-1has reduced from 147.8 kJ mol-1 (RDX) to (124.5 kJ mol-1), since TAGP dopant could be considered as active catalytic sites after melting of RDX.