The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the ...The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge.In this work,HMX-PEI/rGO/g-C_(3)N_(4)(HPrGC)composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C_(3)N_(4).The g-C_(3)N_(4) used for desensitization has a richπ-conjugated system and shows outstanding ability in reducing friction sensitivity.The hierarchical structure of HPrGC formed by electrostatic self-assembly andπ-πstacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution,thus exhibiting a prominent synergistic desensitization effect on HMX.The results show that rGO/gC_(3)N_(4) coating has no effect on the crystal structure and chemical structure of HMX.More importantly,the perfect combination of g-C_(3)N_(4) and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity(IS:21 J,FS:216 N).Obviously,the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings.展开更多
The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricat...The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues.The coordination complexes which consist of natural polyphenol tannic acid(TA) and Fe~Ⅲ were chosen to construct the inner shell,while the graphene sheets were used to build the outer shell.The resulting CL-20/TA-Fe~Ⅲ/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content,which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell.The phase transition(ε to γ) temperature increased from 173.70 ℃ of pure CL-20 to 191.87℃ of CL-20/TA-Fe~Ⅲ/graphene composites.Meanwhile,the characteristic drop height(H_(50)) dramatically increased from 14.7 cm of pure CL-20 to112.8 cm of CL-20/TA-Fe~Ⅲ/graphene composites,indicating much superior safety performance after the construction of the double-shell structure.In general,this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.展开更多
Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a c...Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a catalytic center point.The carbon aerogel(C(CS)/g-C_(3)N_(4)/Co)with a three-dimensional network-like structure was prepared by assembling the three materials through experimental operations such as freeze-drying and high-temperature carbonization.It was demonstrated by scanning and transmission characterization that the CS in the carbon aerogel could provide more active sites for the cobalt nanoparticles,and the doping of graphite-phase carbon nitride as a template dispersed the cobalt nanoparticles and changed the conductivity of the CS.To investigate the catalytic effect of carbon aerogel on ammonium perchlorate(AP),it was investigated by differential thermal analyzer and TG thermal analysis.This carbon aerogel was very effective in catalyzing AP,and the 10 wt% content of the catalyst reduced the AP pyrolysis peak from 703.9 to 595.5 K.And to further investigate the synergistic effect of the three materials,further carbon aerogels such as C(CS)/Co,g-C_(3)N_(4)/Co were prepared and applied to catalyze AP,and the same ratio reduced the AP pyrolysis peak by 98.1℃ and 97.7℃.This result indicates a synergistic effect of the assembly of the three materials.展开更多
Boron is a very promising and highly attractive fuel because of high calorific value. However, the practical applications in explosives and propellants of boron have been limited by long ignition delay time and low co...Boron is a very promising and highly attractive fuel because of high calorific value. However, the practical applications in explosives and propellants of boron have been limited by long ignition delay time and low combustion efficiency. Herein, nano-Al and graphene fluoride(GF) as surface activated materials are employed to coat boron(B) particles to improve ignition and combustion performance. The reaction heat of nano-Al coated B/KNO_(3)and GF coated B/KNO_(3)are 1116.83 J/g and 862.69 J/g, respectively, which are higher than that of pure B/KNO_(3)(823.39 J/g). The ignition delay time of B/KNO_(3)could be reduced through nano-Al coating. The shortest ignition delay time is only 75 ms for B coated with nano-Al of 8 wt%, which is much shorter than that of pure B/KNO_(3)(109 ms). However, the ignition delay time of B/KNOcoated with GF has been increased from 109 to 187 ms. B coated with GF and nano-Al shown significantly influence on the pressure output and flame structure of B/KNO_(3). Furthermore, the effects of B/O ratios on the pressure output and ignition delay time have been further fully studied. For B/KNO_(3)coated with nano-Al and GF, the highest pressures are 88 KPa and 59 KPa for B/O ratio of 4:6, and the minimum ignition delay time are 94 ms and 148 ms for B/O ratio of 7:3. Based on the above results, the reaction process of boron coated with GF and nano-Al has been proposed to understand combustion mechanism.展开更多
The performance of the chemical fuel determines the altitude,range and longevity of spacecraft in air and space exploration.Promising alternatives(e.g.,hypergolic ionic liquids or high-energy composites)with high-ener...The performance of the chemical fuel determines the altitude,range and longevity of spacecraft in air and space exploration.Promising alternatives(e.g.,hypergolic ionic liquids or high-energy composites)with high-energy density,heat of formation and fast initial rate are considered as potential chemical fuels.As the high-energy density material,hexanitrohexaazaisowurtzitane(CL-20)often serves as secondary explosive with poor self-propagating combustion behaviors.Herein,90%loading CL-20 microspheres with uniform particle sizes are precisely prepared by microfluid method,which exhibit unique hierarchical structure.The morphology,thermal behaviors,as well as combustion performance were further investigated.The results demonstrated that as-prepared spherical particles exhibit prominent thermal compatibility,and the enhanced self-sustaining combustion performance.This work provides an efficient method achieving the uniform high-energy density particles with excellent self-sustaining combustion performance.展开更多
To improve the safety of HMX,HMX/NH_(2)-GO composite was prepared with aqueous ammonia functionalized graphene oxide(NH_(2)-GO).The composite was characterized by SEM,Zeta potential,XPS,Raman spectrum,XRD,HPLC,DSC and...To improve the safety of HMX,HMX/NH_(2)-GO composite was prepared with aqueous ammonia functionalized graphene oxide(NH_(2)-GO).The composite was characterized by SEM,Zeta potential,XPS,Raman spectrum,XRD,HPLC,DSC and BAM sensitivity test.The results indicated that the functionalization with aqueous ammonia can enhance the interaction between GO and HMX,and more efficiently desensitize the explosive.The optimal impact sensitivity of the HMX/NH_(2)-GO composite can be not less than 40 J,which is also the most insensitivity compared to the previous reports prepared by coating desensitization with non-energetic desensitized material.Moreover,the potential reason for the different impact and friction sensitivity was also discussed,which may bring a novel perspective to achieve the desensitization of energetic material.展开更多
To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose(NC)/nitroglycerine(NG),we synthesized N-(...To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose(NC)/nitroglycerine(NG),we synthesized N-(4-methoxy)phenylpyrrolidine-C_(60) and four different of bis(N-(4-methoxy)phenylpyrrolidine)-C_(60) compounds through Prato reaction.Their structures were characterized by UVevis,^(1)H NMR,^(13)C NMR,high-resolution mass spectroscopy,and single-crystal X-ray diffraction.Their stabilization effect to NC/NG were investigated using differential scanning calorimetry,methyl violet,vacuum stabilization effect,weight loss,and accelerating rate calorimeter tests.The results indicated these compounds had excellent stabilization effect to NC/NG.The stabilization effect of the fulleropyrrolidine bisadducts to NC/NG is significantly better than that of fulleropyrrolidine monoadduct and C_(60).Moreover,the position where pyrrolidine binds to fullerene in fulleropyrrolidine bisadducts is different,and its stabilization effect to NC is also different.The stabilization effect order of different bisadduct isomers to nitrocellulose is as follows:e-edge>trans-2>cis-2>trans-3.Electron paramagnetic resonance(EPR)and FT-IR were used to study the stabilization mechanism of fulleropyrrolidine derivatives to NC/NG.The EPR results also show that fulleropyrrolidine bisadducts with different addition sites have different abilities to absorb nitroxide,and their ability is better than that of the monoadduct and C_(60),which is consistent with the results of stabilization effect performance test.展开更多
3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-...3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-rich compounds containing N-H.The thermal stabilities of DNTF and its hybrid systems were investigated using differential thermal analysis/thermogravimetry(TG),vacuum stability test,and accelerating rate calorimetry under isothermal,non-isothermal,and adiabatic conditions,respectively.Results showed that the thermal stability and thermal safety of DNTF significantly decreased after combining with nitrogen-rich compounds containing N-H.Calculation results showed that the activation energy of the DNTF hybrid systems was significantly lower than that of DNTF.The TGIR was used to monitor the generation of fugitive gases during the thermal decomposition of the DNTF/5-aminotetrazole(5-ATZ)hybrid.Moreover,the nitrogen-rich molecules containing N-H interacted extensively with DNTF,and this interaction accelerated the thermal degradation of DNTF.展开更多
A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose...A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose(NC)-based propellants.Single-crystal X-ray diffraction,nuclear magnetic resonance,highresolution mass spectrometry,Fourier transform infrared(FT-IR)spectroscopy,and UV-Vis spectroscopy were used to characterize the structures of the synthesized fullerene anisole derivative stabilizers.Methyl violet,differential scanning calorimetry test,isothermal weight loss,vacuum stability test,and adiabatic accelerated test were used to study their compatibility with NC and their ability to stabilize NC.The results show that the designed and synthesized novel fullerene anisole derivative stabilizer has good compatibility with NC,and their overall stabilizing effects on NC are better than those of the traditional stabilizers,diphenylamine(DPA),and N,N’-dimethyl-N,N’-diphenylurea(C2).The stabilizing effects was ranked as:3b>2d>2a>2c>C2>2b>DPA>NC.In addition,FT-IR analysis and electron spin resonance spectroscopy were applied to explore the stability mechanism of fullerene-based stabilizers to NC.The results reveal that the new fullerene stabilizer can adsorb and effectively eliminate the nitrogen oxide free radicals generated by NC degradation;therefore,it can forbid the autocatalytic degradation of NC and stabilize NC.展开更多
基金the financial support from the National Natural Science Foundation of China (Grant No.51972278)the Open Project of the State Key Laboratory of Environment-friendly Energy Materials (Southwest University of Science and Technology,Grant No.20fksy16)。
文摘The interfacial interaction between HMX molecules and coating materials is the key to the safety performance of explosives and has received extensive attention.However,screening suitable coating agents to enhance the interfacial effect to obtain high-energy and low-sensitivity explosives has long been a major challenge.In this work,HMX-PEI/rGO/g-C_(3)N_(4)(HPrGC)composites were innovatively prepared by a multi-level coating strategy of two-dimensional graphite rGO and g-C_(3)N_(4).The g-C_(3)N_(4) used for desensitization has a richπ-conjugated system and shows outstanding ability in reducing friction sensitivity.The hierarchical structure of HPrGC formed by electrostatic self-assembly andπ-πstacking can effectively dissipate energy accumulation under heat and mechanical stimulation through structural evolution,thus exhibiting a prominent synergistic desensitization effect on HMX.The results show that rGO/gC_(3)N_(4) coating has no effect on the crystal structure and chemical structure of HMX.More importantly,the perfect combination of g-C_(3)N_(4) and rGO endows HPrGC with enhanced thermal stability and ideal mechanical sensitivity(IS:21 J,FS:216 N).Obviously,the new fabrication of HPrGC enriches the variety of desensitizer materials and helps to deepen the understanding of the interaction between explosives and coatings.
基金financially supported by the National Natural Science Foundation of China (Grant No. 22275173)the Open Project of State Key Laboratory of Environment-friendly Energy Materials (Grant No. 22kfhg10)。
文摘The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues.The coordination complexes which consist of natural polyphenol tannic acid(TA) and Fe~Ⅲ were chosen to construct the inner shell,while the graphene sheets were used to build the outer shell.The resulting CL-20/TA-Fe~Ⅲ/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content,which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell.The phase transition(ε to γ) temperature increased from 173.70 ℃ of pure CL-20 to 191.87℃ of CL-20/TA-Fe~Ⅲ/graphene composites.Meanwhile,the characteristic drop height(H_(50)) dramatically increased from 14.7 cm of pure CL-20 to112.8 cm of CL-20/TA-Fe~Ⅲ/graphene composites,indicating much superior safety performance after the construction of the double-shell structure.In general,this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.
基金the financial support received from the Natural Science Foundation of China(21875192)Outstanding Youth Science and Technology Talents Program of Sichuan(no.19JCQN0085)Open Project of State Key Laboratory of Environment-friendly Energy Materials(Southwest University of Science and Technology,No.22fksy18)。
文摘Biomass chitosan(CS)was used as a template,graphitic phase carbon nitride(g-C_(3)N_(4))with high nitrogen content and certain catalytic activity was used as a dopant,and nano-transition metal cobalt(Co)was used as a catalytic center point.The carbon aerogel(C(CS)/g-C_(3)N_(4)/Co)with a three-dimensional network-like structure was prepared by assembling the three materials through experimental operations such as freeze-drying and high-temperature carbonization.It was demonstrated by scanning and transmission characterization that the CS in the carbon aerogel could provide more active sites for the cobalt nanoparticles,and the doping of graphite-phase carbon nitride as a template dispersed the cobalt nanoparticles and changed the conductivity of the CS.To investigate the catalytic effect of carbon aerogel on ammonium perchlorate(AP),it was investigated by differential thermal analyzer and TG thermal analysis.This carbon aerogel was very effective in catalyzing AP,and the 10 wt% content of the catalyst reduced the AP pyrolysis peak from 703.9 to 595.5 K.And to further investigate the synergistic effect of the three materials,further carbon aerogels such as C(CS)/Co,g-C_(3)N_(4)/Co were prepared and applied to catalyze AP,and the same ratio reduced the AP pyrolysis peak by 98.1℃ and 97.7℃.This result indicates a synergistic effect of the assembly of the three materials.
基金supported by the National Natural Science Foundation of China (11872341 and 22075261)。
文摘Boron is a very promising and highly attractive fuel because of high calorific value. However, the practical applications in explosives and propellants of boron have been limited by long ignition delay time and low combustion efficiency. Herein, nano-Al and graphene fluoride(GF) as surface activated materials are employed to coat boron(B) particles to improve ignition and combustion performance. The reaction heat of nano-Al coated B/KNO_(3)and GF coated B/KNO_(3)are 1116.83 J/g and 862.69 J/g, respectively, which are higher than that of pure B/KNO_(3)(823.39 J/g). The ignition delay time of B/KNO_(3)could be reduced through nano-Al coating. The shortest ignition delay time is only 75 ms for B coated with nano-Al of 8 wt%, which is much shorter than that of pure B/KNO_(3)(109 ms). However, the ignition delay time of B/KNOcoated with GF has been increased from 109 to 187 ms. B coated with GF and nano-Al shown significantly influence on the pressure output and flame structure of B/KNO_(3). Furthermore, the effects of B/O ratios on the pressure output and ignition delay time have been further fully studied. For B/KNO_(3)coated with nano-Al and GF, the highest pressures are 88 KPa and 59 KPa for B/O ratio of 4:6, and the minimum ignition delay time are 94 ms and 148 ms for B/O ratio of 7:3. Based on the above results, the reaction process of boron coated with GF and nano-Al has been proposed to understand combustion mechanism.
基金supported by the Project of State Key Laboratory of Environment-friendly Energy Materials,Southwest University of Science and Technology(No.20fksy18)。
文摘The performance of the chemical fuel determines the altitude,range and longevity of spacecraft in air and space exploration.Promising alternatives(e.g.,hypergolic ionic liquids or high-energy composites)with high-energy density,heat of formation and fast initial rate are considered as potential chemical fuels.As the high-energy density material,hexanitrohexaazaisowurtzitane(CL-20)often serves as secondary explosive with poor self-propagating combustion behaviors.Herein,90%loading CL-20 microspheres with uniform particle sizes are precisely prepared by microfluid method,which exhibit unique hierarchical structure.The morphology,thermal behaviors,as well as combustion performance were further investigated.The results demonstrated that as-prepared spherical particles exhibit prominent thermal compatibility,and the enhanced self-sustaining combustion performance.This work provides an efficient method achieving the uniform high-energy density particles with excellent self-sustaining combustion performance.
基金the National Natural Science Foundation of China(No.51972278)the Natural Science Foundation of Southwest University of Science and Technology(No.18zx7138)the Project of State Key Laboratory of Environment-friendly Energy Materials,Southwest University of Science and Technology(project no.20fksy16).
文摘To improve the safety of HMX,HMX/NH_(2)-GO composite was prepared with aqueous ammonia functionalized graphene oxide(NH_(2)-GO).The composite was characterized by SEM,Zeta potential,XPS,Raman spectrum,XRD,HPLC,DSC and BAM sensitivity test.The results indicated that the functionalization with aqueous ammonia can enhance the interaction between GO and HMX,and more efficiently desensitize the explosive.The optimal impact sensitivity of the HMX/NH_(2)-GO composite can be not less than 40 J,which is also the most insensitivity compared to the previous reports prepared by coating desensitization with non-energetic desensitized material.Moreover,the potential reason for the different impact and friction sensitivity was also discussed,which may bring a novel perspective to achieve the desensitization of energetic material.
基金This work was supported by National Natural Science Foundation of China(51972278)Outstanding Youth Science and Technology Talents Program of Sichuan(no.19JCQN0085)Open Project of State Key Laboratory of Environment-friendly Energy Materials,Southwest University of Science and Technology(No.19fksy04).
文摘To explore the effect of different positions and number of pyrrolidine bound to the carbon cage on the stabilization effect of fulleropyrrolidine derivatives to nitrocellulose(NC)/nitroglycerine(NG),we synthesized N-(4-methoxy)phenylpyrrolidine-C_(60) and four different of bis(N-(4-methoxy)phenylpyrrolidine)-C_(60) compounds through Prato reaction.Their structures were characterized by UVevis,^(1)H NMR,^(13)C NMR,high-resolution mass spectroscopy,and single-crystal X-ray diffraction.Their stabilization effect to NC/NG were investigated using differential scanning calorimetry,methyl violet,vacuum stabilization effect,weight loss,and accelerating rate calorimeter tests.The results indicated these compounds had excellent stabilization effect to NC/NG.The stabilization effect of the fulleropyrrolidine bisadducts to NC/NG is significantly better than that of fulleropyrrolidine monoadduct and C_(60).Moreover,the position where pyrrolidine binds to fullerene in fulleropyrrolidine bisadducts is different,and its stabilization effect to NC is also different.The stabilization effect order of different bisadduct isomers to nitrocellulose is as follows:e-edge>trans-2>cis-2>trans-3.Electron paramagnetic resonance(EPR)and FT-IR were used to study the stabilization mechanism of fulleropyrrolidine derivatives to NC/NG.The EPR results also show that fulleropyrrolidine bisadducts with different addition sites have different abilities to absorb nitroxide,and their ability is better than that of the monoadduct and C_(60),which is consistent with the results of stabilization effect performance test.
基金the financially sponsor of the Natural Science Foundation of China(Grant No.51972278)the Outstanding Youth Science and Technology Talents Program of Sichuan(Grant No.19JCQN0085)the Open Project of State Key Laboratory of Environment-friendly Energy Materials(Southwest University of Science and Technology,Grant No.21fksy19)。
文摘3,4-Dinitrofurazanfuroxan(DNTF),as a high-energy-density material,features good thermal stability and wide applications.This study aimed to elucidate the thermal decomposition mechanism of DNTF combined with nitrogen-rich compounds containing N-H.The thermal stabilities of DNTF and its hybrid systems were investigated using differential thermal analysis/thermogravimetry(TG),vacuum stability test,and accelerating rate calorimetry under isothermal,non-isothermal,and adiabatic conditions,respectively.Results showed that the thermal stability and thermal safety of DNTF significantly decreased after combining with nitrogen-rich compounds containing N-H.Calculation results showed that the activation energy of the DNTF hybrid systems was significantly lower than that of DNTF.The TGIR was used to monitor the generation of fugitive gases during the thermal decomposition of the DNTF/5-aminotetrazole(5-ATZ)hybrid.Moreover,the nitrogen-rich molecules containing N-H interacted extensively with DNTF,and this interaction accelerated the thermal degradation of DNTF.
基金financial support received from the Natural Science Foundation of China(Grant No.51972278)Outstanding Youth Science and Technology Talents Program of Sichuan(Grant No.19JCQN0085)Open Project of State Key Laboratory of Environment-friendly Energy Materials(Southwest University of Science and Technology,Grant No.20fksy16)。
文摘A series of fullerene anisole derivative stabilizers was synthesized by nucleophilic substitution reaction using hexachlorofullerene and benzyl alcohol as raw materials to extend the service duration of nitrocellulose(NC)-based propellants.Single-crystal X-ray diffraction,nuclear magnetic resonance,highresolution mass spectrometry,Fourier transform infrared(FT-IR)spectroscopy,and UV-Vis spectroscopy were used to characterize the structures of the synthesized fullerene anisole derivative stabilizers.Methyl violet,differential scanning calorimetry test,isothermal weight loss,vacuum stability test,and adiabatic accelerated test were used to study their compatibility with NC and their ability to stabilize NC.The results show that the designed and synthesized novel fullerene anisole derivative stabilizer has good compatibility with NC,and their overall stabilizing effects on NC are better than those of the traditional stabilizers,diphenylamine(DPA),and N,N’-dimethyl-N,N’-diphenylurea(C2).The stabilizing effects was ranked as:3b>2d>2a>2c>C2>2b>DPA>NC.In addition,FT-IR analysis and electron spin resonance spectroscopy were applied to explore the stability mechanism of fullerene-based stabilizers to NC.The results reveal that the new fullerene stabilizer can adsorb and effectively eliminate the nitrogen oxide free radicals generated by NC degradation;therefore,it can forbid the autocatalytic degradation of NC and stabilize NC.
