In order to remove hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX),the main impurity,in process of polymorphic transformation of octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),the solubility ofβ-HMX and RDX in a...In order to remove hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX),the main impurity,in process of polymorphic transformation of octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),the solubility ofβ-HMX and RDX in acetonitrile(ACN)+water in the temperature range of 288.15-333.15 K and in nitric acid(HNO_(3))+water in the temperature range of 298.15-333.15 K were measured by laser dynamic method.The results showed that the solubility of bothβ-HMX and RDX in binary mixed solvents increased monotonously as the temperature increase at a given solvent composition or with increasing of mole fraction of solvent(ACN and nitric acid).Solubility data were well correlated by the modified Apelblat equation,Jouyban-Acree model,Yaws equation and van't Hoff equation,and the Yaws equation achieved the best fitting results according to the relative error and the mean square error root.Furthermore,the solubility ofβ-HMX and RDX in binary mixed solvent was compared,based on the solubility difference and the solvent's own properties,the best separation degree ofβ-HMX and RDX was found when the mole fraction of nitric acid was 0.22 at room temperature,which provided data support for HMX crystallization in mixed solvent.The solubility differences between RDX andβ-HMX in mixed solvents were explained from the formation of intermolecular and intramolecular hydrogen bonds.展开更多
Electrospinning is a simple technique used to fabricate polymeric nano-fibrous membranes.These nano-fibers have found a wide range of valuable applications in the biomedical field.However,it has not been utilized with...Electrospinning is a simple technique used to fabricate polymeric nano-fibrous membranes.These nano-fibers have found a wide range of valuable applications in the biomedical field.However,it has not been utilized with solid high explosives yet.Herein,the electrospinning technique has been used to fabricate polystyrene(PS)/1,3,5-trinitro-1,3,5-triazinane(RDX)composite nanofibers.The governed electrospinning parameters,voltage,distance from the collector,flow rate,mandrel rotating speed,time,and solution concentration,that greatly affect the morphology of the obtained nanofibers were optimized.The fabricated PS/RDX nano-fibers were characterized using scanning electron microscopy(SEM),X-ray diffractometer(XRD),and Fourier Transform Infrared(FTIR)spectroscopy.The impact and friction sensitivities of PS/RDX were also measured.The thermal behavior of the prepared composite and the pure materials were studied by the thermal gravimetric analysis technique(TGA).SEM results proved the fabrication of PS/RDX fibers in the nano-size via electrospinning.FTIR spectroscopy confirmed the existence of the characteristic functional groups of both PS and RDX in the composite nano-fibers.XRD sharp peaks showed the conversion of amorphous PS into crystalline shape via electrospinning and also confirmed the formation of PS/RDX composite.The PS fibers absorbed the heat and increased the onset decomposition of the pure RDX from 181.5 to 200.7℃in the case of PS/RDX fibers.Interestingly,PS/RDX nano-fibers showed the relatively low impact and friction sensitivities of 100 J and 360 N respectively.These results could introduce PS/RDX nanofibrous composite in the field of explosives detection with high levels of safety.展开更多
In order to test the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane(RDX),the linear temperature rise experiment of RDX was carried out by differential scanning calorimeter under different heating rate condit...In order to test the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane(RDX),the linear temperature rise experiment of RDX was carried out by differential scanning calorimeter under different heating rate conditions.The kinetic calculation of RDX thermal decomposition curve was carried out by Kissinger and Ozawa methods,respectively,and the thermal analysis software was used to calculate the parameters such as self-accelerating decomposition temperature.The results show that the initial decomposition temperature range,decomposition peak temperature range,and decomposition completion temperature range of RDX are 208.4-214.2,225.7-239.3 and 234.0-252.4℃,respectively,and the average decomposition enthalpy is 362.9 J·g^-1.Kissinger method was used to calculate the DSC experimental data of RDX,the apparent activation energy obtained is 190.8 kJ·mol^-1,which is coincident with the results calculated by Ozawa method at the end of the reaction,indicating that the apparent activation energy calculated by the two methods is relatively accurate.When the packaging mass values are 1.0,2.0 and 5.0 kg,respectively,the self-accelerating decomposition temperatures are 97.0,93.0 and 87.0℃,respectively,indicating that with the increase of packaging mass,the self-accelerating decomposition temperature gradually decreases,and the risk increases accordingly.展开更多
The thermodynamic properties of the reaction of amide and formaldehyde were calculated via B3LYP method when substituents chosen included CH3,CH2CH3,CH2CH2CH3,CH2CH2CH2CH3,CH（CH3）2,CH2CH（CH3）2,CH（CH3）CH2CH3 and ...The thermodynamic properties of the reaction of amide and formaldehyde were calculated via B3LYP method when substituents chosen included CH3,CH2CH3,CH2CH2CH3,CH2CH2CH2CH3,CH（CH3）2,CH2CH（CH3）2,CH（CH3）CH2CH3 and C（CH3）3.Based on the optimization of the structures for reactants and products,the thermodynamic functions of all the species for an actual state were obtained.The thermodynamic data and the equilibrium constants were investigated within a temperature range of 300―343.15 K.The calculated results show that the reaction is exothermic and spontaneous.The trends of all thermodynamic properties are consistent with the temperature.The preferential order of the substituent effect is CH2CH（CH3）2CH（CH3）CH2CH3CH2CH2CH2CH3 CH2CH2CH3CH2CH3≈CH（CH3）2C（CH3）3≈CH3.展开更多
Simulated wastewater of hexahydro-l,3,5-trinitro-l,3,5-triazine （RDX） and octahydro- 1,3,5,7-tetranitro- 1,3,5,7- tetrazocine （HMX） was treated under anaerobic conditions with co-substrates such as ammonium chlori...Simulated wastewater of hexahydro-l,3,5-trinitro-l,3,5-triazine （RDX） and octahydro- 1,3,5,7-tetranitro- 1,3,5,7- tetrazocine （HMX） was treated under anaerobic conditions with co-substrates such as ammonium chloride, dex- trose, sodium acetic, sodium nitrate and sulfate. The results showed that with nitrogen compounds such as ammonium chloride added as co-substrate, no significant change was observed, indicating that the molar ratio of N/C for RDX and HMX is sufficient for biodegradation. With the addition of dextrose and acetate to the system, biodegradation efficiency was enhanced greatly. For example, with dextrose as the co-substrate, degradation efficiency of 99.1% and 98.5% was achieved for RDX and HMX, respectively, after treatment for 7 days. When so- dium acetic was used as the co-substrate, the enhancement of degradation percentage was similar, but was not as high as that with dextrose, indicating the selectivity of RDX and HMX to co-substrate during anaerobic degrada- tion. With sodium nitrate as the co-substrate, the degradation efficiency of RDX or HMX decreased with the increase of salt concentration. Sodium sulfate has no significant effect on the biodegradation of RDX and HMX. A well-selected co-substrate should be employed in applications for degradation of RDX and HMX wastewaters.展开更多
文摘In order to remove hexahydro-1,3,5-trinitro-1,3,5-triazine(RDX),the main impurity,in process of polymorphic transformation of octrahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX),the solubility ofβ-HMX and RDX in acetonitrile(ACN)+water in the temperature range of 288.15-333.15 K and in nitric acid(HNO_(3))+water in the temperature range of 298.15-333.15 K were measured by laser dynamic method.The results showed that the solubility of bothβ-HMX and RDX in binary mixed solvents increased monotonously as the temperature increase at a given solvent composition or with increasing of mole fraction of solvent(ACN and nitric acid).Solubility data were well correlated by the modified Apelblat equation,Jouyban-Acree model,Yaws equation and van't Hoff equation,and the Yaws equation achieved the best fitting results according to the relative error and the mean square error root.Furthermore,the solubility ofβ-HMX and RDX in binary mixed solvent was compared,based on the solubility difference and the solvent's own properties,the best separation degree ofβ-HMX and RDX was found when the mole fraction of nitric acid was 0.22 at room temperature,which provided data support for HMX crystallization in mixed solvent.The solubility differences between RDX andβ-HMX in mixed solvents were explained from the formation of intermolecular and intramolecular hydrogen bonds.
文摘Electrospinning is a simple technique used to fabricate polymeric nano-fibrous membranes.These nano-fibers have found a wide range of valuable applications in the biomedical field.However,it has not been utilized with solid high explosives yet.Herein,the electrospinning technique has been used to fabricate polystyrene(PS)/1,3,5-trinitro-1,3,5-triazinane(RDX)composite nanofibers.The governed electrospinning parameters,voltage,distance from the collector,flow rate,mandrel rotating speed,time,and solution concentration,that greatly affect the morphology of the obtained nanofibers were optimized.The fabricated PS/RDX nano-fibers were characterized using scanning electron microscopy(SEM),X-ray diffractometer(XRD),and Fourier Transform Infrared(FTIR)spectroscopy.The impact and friction sensitivities of PS/RDX were also measured.The thermal behavior of the prepared composite and the pure materials were studied by the thermal gravimetric analysis technique(TGA).SEM results proved the fabrication of PS/RDX fibers in the nano-size via electrospinning.FTIR spectroscopy confirmed the existence of the characteristic functional groups of both PS and RDX in the composite nano-fibers.XRD sharp peaks showed the conversion of amorphous PS into crystalline shape via electrospinning and also confirmed the formation of PS/RDX composite.The PS fibers absorbed the heat and increased the onset decomposition of the pure RDX from 181.5 to 200.7℃in the case of PS/RDX fibers.Interestingly,PS/RDX nano-fibers showed the relatively low impact and friction sensitivities of 100 J and 360 N respectively.These results could introduce PS/RDX nanofibrous composite in the field of explosives detection with high levels of safety.
文摘In order to test the thermal decomposition of 1,3,5-trinitro-1,3,5-triazinane(RDX),the linear temperature rise experiment of RDX was carried out by differential scanning calorimeter under different heating rate conditions.The kinetic calculation of RDX thermal decomposition curve was carried out by Kissinger and Ozawa methods,respectively,and the thermal analysis software was used to calculate the parameters such as self-accelerating decomposition temperature.The results show that the initial decomposition temperature range,decomposition peak temperature range,and decomposition completion temperature range of RDX are 208.4-214.2,225.7-239.3 and 234.0-252.4℃,respectively,and the average decomposition enthalpy is 362.9 J·g^-1.Kissinger method was used to calculate the DSC experimental data of RDX,the apparent activation energy obtained is 190.8 kJ·mol^-1,which is coincident with the results calculated by Ozawa method at the end of the reaction,indicating that the apparent activation energy calculated by the two methods is relatively accurate.When the packaging mass values are 1.0,2.0 and 5.0 kg,respectively,the self-accelerating decomposition temperatures are 97.0,93.0 and 87.0℃,respectively,indicating that with the increase of packaging mass,the self-accelerating decomposition temperature gradually decreases,and the risk increases accordingly.
基金Supported by the Key Project for Explosives of Commission of Science Technology and Industry for National Defense,China(No.2371000415)
文摘The thermodynamic properties of the reaction of amide and formaldehyde were calculated via B3LYP method when substituents chosen included CH3,CH2CH3,CH2CH2CH3,CH2CH2CH2CH3,CH（CH3）2,CH2CH（CH3）2,CH（CH3）CH2CH3 and C（CH3）3.Based on the optimization of the structures for reactants and products,the thermodynamic functions of all the species for an actual state were obtained.The thermodynamic data and the equilibrium constants were investigated within a temperature range of 300―343.15 K.The calculated results show that the reaction is exothermic and spontaneous.The trends of all thermodynamic properties are consistent with the temperature.The preferential order of the substituent effect is CH2CH（CH3）2CH（CH3）CH2CH3CH2CH2CH2CH3 CH2CH2CH3CH2CH3≈CH（CH3）2C（CH3）3≈CH3.
基金Supported by the National Natural Science Foundation of China(2117619)Major Project of Innovation of Science and Technology of Shaanxi Province(2011KTZB03-03-01)
文摘Simulated wastewater of hexahydro-l,3,5-trinitro-l,3,5-triazine （RDX） and octahydro- 1,3,5,7-tetranitro- 1,3,5,7- tetrazocine （HMX） was treated under anaerobic conditions with co-substrates such as ammonium chloride, dex- trose, sodium acetic, sodium nitrate and sulfate. The results showed that with nitrogen compounds such as ammonium chloride added as co-substrate, no significant change was observed, indicating that the molar ratio of N/C for RDX and HMX is sufficient for biodegradation. With the addition of dextrose and acetate to the system, biodegradation efficiency was enhanced greatly. For example, with dextrose as the co-substrate, degradation efficiency of 99.1% and 98.5% was achieved for RDX and HMX, respectively, after treatment for 7 days. When so- dium acetic was used as the co-substrate, the enhancement of degradation percentage was similar, but was not as high as that with dextrose, indicating the selectivity of RDX and HMX to co-substrate during anaerobic degrada- tion. With sodium nitrate as the co-substrate, the degradation efficiency of RDX or HMX decreased with the increase of salt concentration. Sodium sulfate has no significant effect on the biodegradation of RDX and HMX. A well-selected co-substrate should be employed in applications for degradation of RDX and HMX wastewaters.
