The Study Of The Photo-sensitive Energetic Complexes Based On3,4-diamino-1,2,4-triazole

Laser initiation technology can be used as a new kind of safe and reliable initiationmethod. Compared with the conventional technique, it shows outstanding advantages,such as avoiding electromagnetic interference, electrostatic discharge and stray current.Photosensitive primary explosives are a kind of special energetic materials, which aresensitive for input laser stimulation and insensitive for environmental stimuli (such asmechanical, thermal, electromagnetic radiation, etc.). We concentrate studies onlaser-sensitive primary explosives, and then apply to laser initiating technology, whichessentially improves the safety and reliability of initiating explosive device. This paperresearches on the synthesis, single crystal cultivation, structure characterization andtesting performance of the energetic complexes with3,4-diamino-1,2,4-triazloe as ligand,seeking the good performance candidates used as photosensitive primary explosives. Themain study contents and the innovative results are as follows:1. Diaminoguanidine hydrochloride is chosen as the raw material to prepare3,4-diamino-1,2,4-triazole ligand. Three series of energetic complexes based on DATrwere synthesized by the reaction of DATr and corresponding to transition metal salts(MX2, M=Mn, Co, Ni, Zn, Cd; X=NO3-, ClO4-, Cl-). The coordination compounds ofperchlorate and chlorine with DATr as ligands were charatcterized by using elementalanalysis and FT-IR.2. Eight single crystal structures obtained by solvent evaporation method werereported for the first time and were determined by X-ray single crystal diffraction method.The crystal data of these complexes [Co3(DATr)6(H2O)6](NO3)6·2H2O,[Ni3(DATr)6(H2O)6](NO3)6·1.5H2O,[Zn3(DATr)6(H2O)6](NO3)6·2H2O,[Co5(DATr)12(H2O)6](ClO4)10,[Ni5(DATr)12(H2O)6](ClO4)10,[Zn5(DATr)14(H2O)2](ClO4)10·2H2O,(DATr)[ZnCl3(DATr)] and [Cd(μ-Cl)2Cl(DATr)]2were described. Several conclusions aredraw by analyzing the coordination structures of the complexes.(1)3,4-diamino-1,2,4-triazole (DATr) has strong coordination ability, in which thecoordination atoms are nitrogen atoms of triazole ring. And DATr can be used as not onlymonodentate ligand, but also bridging bidentate ligand.(2) The multi-nuclear structuresare presented in all the complexes of perchlorate and nitrate with DATr.(3) The singlecrystal structures have no H2O molecules (coordinated water and crystal water) and the anions coordinate with central atoms in the complexes of chlorine with DATr.(4) Lots ofhydrogen bonds including intramolecular and intermolecular exist in all single crystalstructures and make them to develop space network construction, which contributes toimprove the stability of the complexes.3. Thermal decomposition behavior of these complexes was investigated bydifferential scanning calorimetry (DSC), and the rules of their decomposition wereanalyzed. The study results show that the peak temperatures of the first exothermicdecomposition of the complexes are above240°C, which indicates that the complexeshave good thermal stability. Moreover, it is seen that the shape of the exothermic peak areall very sharp, suggesting that these compounds are promising to be used as energeticmaterials. The non-isothermal kinetics Eaand A of thermal decomposition of tencomplexes were calculated by the Kissinger method and Ozawa-Doyle method, and theresults demonstrates that the activation energy data calculated by two method s areconsistent to each other.4. The critical explosive parameters and thermodynamic parameters of theperchlorate and chlorine complexes with DATr were calculated. For different metalcomplexes of DATr, it is seen that the critical explosive temperature of Co complex islowest while that of Cd complex is highest. Heat of combustion of these compounds wasalso studied, and the results show that the heat of combustion of the percholratecomplexes is greater than that of chlorine complexes, which demonstrates thatcomprehensive properties of percholrate complexes are better than that of chlorinecomplexes.5. In order to evaluate their application performance, the friction sensitivities,impact sensitivities and flame sensitivities of the percholrate complexes based on DATrwere tested. The results display that mechanical sensitivity of Co complex is highestwhile that of Zn complex is lowest and all the compounds’ stimulus to flame areinsensitive.6. In order to study the percholrate complexes with DATr being used asphotosensitive primary explosives, laser sensitivity of these complexes was investigated.The experimental results suggest that most of complexes for laser stimulation can beignited or detonated. Compared to BNCP, the cobalt complex and nickel complex ofpercholrate with DATr can be promising laser-sensitive primary explosives. Besides, inorder to further improve their laser sensitivity, the cobalt complex and nickel complex were mixed with5%carbon black. The research tests indicate that doping cansignificantly improve the sensitivity to laser of the complexes.