Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous...Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous explosive reactions when subjected to external stimuli such as electrical discharge.Therefore,developing a reliable model for predicting their electrostatic discharge sensitivity(ESD)becomes imperative.This study proposes a novel and straightforward model based on the presence of specific groups(-NH_(2) or-NH-,-N=N^(+)-O^(-)and-NNO_(2),-ONO_(2) or-NO_(2))under certain conditions to assess the ESD of NRHECs and their salts,employing interpretable structural parameters.Utilizing a comprehensive dataset comprising 54 ESD measurements of NRHECs and their salts,divided into 49/5 training/test sets,the model achieves promising results.The Root Mean Square Error(RMSE),Mean Absolute Error(MAE),and Maximum Error for the training set are reported as 0.16 J,0.12 J,and 0.5 J,respectively.Notably,the ratios RMSE(training)/RMSE(test),MAE(training)/MAE(test),and Max Error(training)/Max Error(test)are all greater than 1.0,indicating the robust predictive capabilities of the model.The presented model demonstrates its efficacy in providing a reliable assessment of ESD for the targeted NRHECs and their salts,without the need for intricate computer codes or expert involvement.展开更多
Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal ...Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal structures were determined by single-crystal X-ray diffraction.The results reveal that the compounds have similar molecular structures and the crystals belong to the triclinic system,space group P with a = 11.491（3）,b = 13.564（3）,c = 15.496（3） ,V = 2180.4（8） 3,C17H28 Zn2N36O19,Mr = 1203.02 g·mol-1,Dc = 1.832 g·cm-3,μ（MoKα） = 1.221 mm-1,F（000） = 1223,Z = 2,R = 0.0596 and wR = 0.1514 for 11289 observed reflections（I 〉 2σ（I）） for Zn2（DAT）5（H2O）3（TNR）2 and a = 11.5291（13）,b = 13.4894（15）,c = 15.4852（17） ,V = 2164.8（4） 3,C17H28Co2N36O19,Mr = 1190.14 g·mol-1,Dc = 1.826 g·cm-3,μ（MoKα） = 0.888 mm-1,F（000） = 1211,Z = 2,R = 0.0576 and wR = 0.1431 for 11218 observed reflections（I 〉 2σ（I）） for Co2（DAT）5（H2O）3（TNR）2,respectively.The thermal decomposition characteristics of the com-pounds were investigated using differential scanning calorimetry and thermal gravimetry-diffediffer-rential thermal gravimetry.The results of thermal decomposition processes were similar for the two compounds.Both undergo four-step decomposition after the loss of coordinated H2O molecules.The final solid residues for the two DAT complexes were the corresponding metal oxides.The kinetic parameter of the first exothermic process of the compounds was studied by applying the Kissinger and Ozawa-Doyle methods.The thermodynamic parameters of the activation could be calculated.Sensitivity tests revealed that Co2（DAT）5（H2O）3（TNR）2 was more sensitive than Zn2（DAT）5（H2O）3（TNR）2.展开更多
Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and non...Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and noncontact atomic force microscopy(nc-AFM),we investigated the adsorption structure of DOATF molecules on Au(111)surface,which shows the four furanzan rings in the STM images and a bright protrusion off the center of the molecule in the nc-AFM images.Combined with density functional theory(DFT)calculations,we confirmed that the bright feature in the nc-AFM images is an N-O coordinate bond pointing upwards in one of the two azoxy groups;while the other N-O bond pointing towards the Au(111)surface.Our work contributes for a deeper understanding of the adsorption structure of macrocyclic compounds,which would promote the designing of DOATF-metal frameworks.展开更多
In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts...In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts, have been presented focusing on the most recent investigations. These classes of compounds, known as high nitrogen compounds, are generally high energy density materials. Therefore, if available some of their ballistic properties were included.展开更多
Primary explosives are utilized as a reliable initiator for secondary explosives in an extensive range of military and civilian operations. Heavy-metal-based primary explosives are moderate performing, more sensitive,...Primary explosives are utilized as a reliable initiator for secondary explosives in an extensive range of military and civilian operations. Heavy-metal-based primary explosives are moderate performing, more sensitive, and environmentally hazardous, posing a direct and indirect threat to health and safety.Therefore, heavy-metal-based primaries have been replaced by environment-friendly metal-based primary explosives, such as potassium complexes. This review presents not only a summary of the current progress of new-generation potassium-based primary explosives and their methods of preparation, energetic properties, and applications, but also a further comparison with traditional primary explosives. In addition, this work discusses the necessity of heavy metal-free primary explosives and the major challenges faced in replacing traditional primary explosives.展开更多
In this work,NH_(2)-substituted oxazoles and NO_(2)/NF_(2)/NHNO_(2)-substituted ethylenes/acetylenes were designed and used as dienes and dienophiles,respectively,in order to develop new bridge-ring insensitive high e...In this work,NH_(2)-substituted oxazoles and NO_(2)/NF_(2)/NHNO_(2)-substituted ethylenes/acetylenes were designed and used as dienes and dienophiles,respectively,in order to develop new bridge-ring insensitive high energy compounds through the Diels-Alder reaction between them.The reaction type,reaction feasibility and performance of reaction products were investigated in detail theoretically.The results showed that dienes most possibly react with dienophiles through the HOMO-diene controlled normal Diels-Alder reaction at relatively low energy barrier.Tetranitroethylene could react with the designed dienes much more easily than other dienophiles,and was employed to further design 29 new bridge-ring energetic compounds.Due to high heat of formation,density and oxygen balance,all designed bridge-ring energetic compounds have outstanding detonation performance,16 of them have higher energy than HMX(1,3,5,7-tetranitro-1,3,5,7-tetrazocine)and 2 others even possess comparative energy with the representative of high energy compounds CL-20(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane).The predicted average h50 value of these bridge-ring energetic compounds is 83 cm,showing their low impact sensitivity.The NH2 groups could obviously impel the proceeding of Diels-Alder reactions,but would slightly decrease the energy and sensitivity performance.In all,the new designed bridge-ring compounds have both high energy and low sensitivity,and may be produced through Diels-Alder reactions at relatively low energy barrier.This paper may be helpful for the theoretical design and experiment synthesis of new advanced insensitive high energy compounds.展开更多
文摘Nitrogen-rich heterocyclic energetic compounds(NRHECs)and their salts have witnessed widespread synthesis in recent years.The substantial energy-density content within these compounds can lead to potentially dangerous explosive reactions when subjected to external stimuli such as electrical discharge.Therefore,developing a reliable model for predicting their electrostatic discharge sensitivity(ESD)becomes imperative.This study proposes a novel and straightforward model based on the presence of specific groups(-NH_(2) or-NH-,-N=N^(+)-O^(-)and-NNO_(2),-ONO_(2) or-NO_(2))under certain conditions to assess the ESD of NRHECs and their salts,employing interpretable structural parameters.Utilizing a comprehensive dataset comprising 54 ESD measurements of NRHECs and their salts,divided into 49/5 training/test sets,the model achieves promising results.The Root Mean Square Error(RMSE),Mean Absolute Error(MAE),and Maximum Error for the training set are reported as 0.16 J,0.12 J,and 0.5 J,respectively.Notably,the ratios RMSE(training)/RMSE(test),MAE(training)/MAE(test),and Max Error(training)/Max Error(test)are all greater than 1.0,indicating the robust predictive capabilities of the model.The presented model demonstrates its efficacy in providing a reliable assessment of ESD for the targeted NRHECs and their salts,without the need for intricate computer codes or expert involvement.
基金supported by the National Natural Science Foundation of China (NSAF: 10776002)the project of State Key Laboratory of Science and Technology (No. QNKT11-06, YBKY10-03)the Program for New Century Excellent Talents in University (NCET-09-0051)
文摘Two novel energetic coordination compounds Zn2（DAT）5（H2O）3（TNR）2 and Co2（DAT）5（H2O）3（TNR）2 were synthesized and their structures were characterized by elemental analysis and FT-IR spectroscopy.The crystal structures were determined by single-crystal X-ray diffraction.The results reveal that the compounds have similar molecular structures and the crystals belong to the triclinic system,space group P with a = 11.491（3）,b = 13.564（3）,c = 15.496（3） ,V = 2180.4（8） 3,C17H28 Zn2N36O19,Mr = 1203.02 g·mol-1,Dc = 1.832 g·cm-3,μ（MoKα） = 1.221 mm-1,F（000） = 1223,Z = 2,R = 0.0596 and wR = 0.1514 for 11289 observed reflections（I 〉 2σ（I）） for Zn2（DAT）5（H2O）3（TNR）2 and a = 11.5291（13）,b = 13.4894（15）,c = 15.4852（17） ,V = 2164.8（4） 3,C17H28Co2N36O19,Mr = 1190.14 g·mol-1,Dc = 1.826 g·cm-3,μ（MoKα） = 0.888 mm-1,F（000） = 1211,Z = 2,R = 0.0576 and wR = 0.1431 for 11218 observed reflections（I 〉 2σ（I）） for Co2（DAT）5（H2O）3（TNR）2,respectively.The thermal decomposition characteristics of the com-pounds were investigated using differential scanning calorimetry and thermal gravimetry-diffediffer-rential thermal gravimetry.The results of thermal decomposition processes were similar for the two compounds.Both undergo four-step decomposition after the loss of coordinated H2O molecules.The final solid residues for the two DAT complexes were the corresponding metal oxides.The kinetic parameter of the first exothermic process of the compounds was studied by applying the Kissinger and Ozawa-Doyle methods.The thermodynamic parameters of the activation could be calculated.Sensitivity tests revealed that Co2（DAT）5（H2O）3（TNR）2 was more sensitive than Zn2（DAT）5（H2O）3（TNR）2.
基金the National Key Research and Development Projects of China(Grant No.2019YFA0308500)the National Natural Science Foundation of China(Grant No.61888102)the Funds from the Chinese Academy of Sciences(Grant Nos.XDB30000000 and YSBR-003)。
文摘Furazan macrocyclic compound 3,4:7,8:11,12:15,16-tetrafurazan-1,9-dioxazo-5,13-diazocyclohexadecane(DOATF)is an ideal energetic material with high heat of formation.Here,using scanning tunneling microscopy(STM)and noncontact atomic force microscopy(nc-AFM),we investigated the adsorption structure of DOATF molecules on Au(111)surface,which shows the four furanzan rings in the STM images and a bright protrusion off the center of the molecule in the nc-AFM images.Combined with density functional theory(DFT)calculations,we confirmed that the bright feature in the nc-AFM images is an N-O coordinate bond pointing upwards in one of the two azoxy groups;while the other N-O bond pointing towards the Au(111)surface.Our work contributes for a deeper understanding of the adsorption structure of macrocyclic compounds,which would promote the designing of DOATF-metal frameworks.
文摘In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts, have been presented focusing on the most recent investigations. These classes of compounds, known as high nitrogen compounds, are generally high energy density materials. Therefore, if available some of their ballistic properties were included.
基金the NSAF (U1830134)NSFC (22175025), for their generous financial supportsupported by a project of State Key Laboratory of Explosion Science and Technology (Beijing Institute of Technology). The project number is YBKT21-02
文摘Primary explosives are utilized as a reliable initiator for secondary explosives in an extensive range of military and civilian operations. Heavy-metal-based primary explosives are moderate performing, more sensitive, and environmentally hazardous, posing a direct and indirect threat to health and safety.Therefore, heavy-metal-based primaries have been replaced by environment-friendly metal-based primary explosives, such as potassium complexes. This review presents not only a summary of the current progress of new-generation potassium-based primary explosives and their methods of preparation, energetic properties, and applications, but also a further comparison with traditional primary explosives. In addition, this work discusses the necessity of heavy metal-free primary explosives and the major challenges faced in replacing traditional primary explosives.
基金the Natural Science Foundation of Jiangsu(BK20170761)Natural Science Foundation of Nanjing Institute of Technology(JCYJ201806)+1 种基金Science Innovation Project for Undergraduates of Nanjing Institute of Technology(TB202002005)Outstanding Scientific and Technological Innovation Team in Colleges and Universities of Jiangsu Province,and Jiangsu Overseas Visiting Scholar Program for University Prominent Young&Middle-aged Teachers and Presidents.
文摘In this work,NH_(2)-substituted oxazoles and NO_(2)/NF_(2)/NHNO_(2)-substituted ethylenes/acetylenes were designed and used as dienes and dienophiles,respectively,in order to develop new bridge-ring insensitive high energy compounds through the Diels-Alder reaction between them.The reaction type,reaction feasibility and performance of reaction products were investigated in detail theoretically.The results showed that dienes most possibly react with dienophiles through the HOMO-diene controlled normal Diels-Alder reaction at relatively low energy barrier.Tetranitroethylene could react with the designed dienes much more easily than other dienophiles,and was employed to further design 29 new bridge-ring energetic compounds.Due to high heat of formation,density and oxygen balance,all designed bridge-ring energetic compounds have outstanding detonation performance,16 of them have higher energy than HMX(1,3,5,7-tetranitro-1,3,5,7-tetrazocine)and 2 others even possess comparative energy with the representative of high energy compounds CL-20(2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane).The predicted average h50 value of these bridge-ring energetic compounds is 83 cm,showing their low impact sensitivity.The NH2 groups could obviously impel the proceeding of Diels-Alder reactions,but would slightly decrease the energy and sensitivity performance.In all,the new designed bridge-ring compounds have both high energy and low sensitivity,and may be produced through Diels-Alder reactions at relatively low energy barrier.This paper may be helpful for the theoretical design and experiment synthesis of new advanced insensitive high energy compounds.
