CN112898103A - Preparation method of g-C3N 4-based composite energetic material - Google Patents
Preparation method of g-C3N 4-based composite energetic material Download PDFInfo
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Abstract
The invention discloses a g-C3N4The preparation method of the base composite energetic material adopts simple physical grinding, in-situ reduction and electrostatic self-assembly methods respectively to prepare the g-C3N4Physically grinding the mixture and explosive according to a certain mass ratio to obtain a composite material 1, and carrying out in-situ reduction on the ultrasonically treated g-C3N4Coating GO on the surface of the explosive crystal to obtain a composite material 2, modifying the surface of the ammonium nitrate explosive by utilizing the high cationic property of polyethyleneimine, and further obtaining a composite material 3 by an electrostatic self-assembly method. In the invention, g-C3N4The crystal of the ammonium nitrate explosive is combined with GO to reduce the sensitivity to obtain the ammonium nitrate explosive composite material with the sensitivity reducing function and the high energy performance, and g-C is utilized3N4High stability with GO, high thermal conductivity and lubricity, thus passivating the mechanical sensitivity of the energetic material.
Description
Technical Field
The invention belongs to the technical field of energetic material compounding, and particularly relates to g-C3N4A preparation method of a base composite energetic material.
Background
In order to meet the military requirement of high performance of modern weaponry under the modern war environment, the weaponry system puts higher requirements on the comprehensive performance of simple substance energetic materials. The development of energetic materials with low sensitivity and high safety is urgently needed, and the influence of mechanical sensitivity, electric spark sensitivity and the like of the energetic materials on the safety of the energetic materials is concerned, and the energy property of the energetic materials is also considered to ensure the high energy property of the energetic materials. Therefore, how to prepare the high-energy low-sensitivity energy-containing composite material is one of the most concerned subjects in the field of single-substance explosive modification research at present.
The common modification method of the high-sensitivity single-substance material mainly comprises eutectic and coating, compared with the problem of crystal form transformation which is easily caused in eutectic modification, the effective coating of the surface of the sensitive explosive is a more preferable mode for reducing the mechanical sensitivity of the sensitive explosive, and the traditional coating technology generally has the defects of uneven explosive surface, weak bonding force of the coating material and the single-substance explosive, energy loss and the like. Based on the method, the energetic composite material with high energy performance and high safety is developed and prepared, so that the energetic composite material can be better applied to military systems, and the method has great significance for the practical application development of the energetic material.
The carbon material has excellent electrical, magnetic, mechanical and optical properties due to the abundant size structure and unique micro-morphology. The graphene oxide shows outstanding thermal conductivity and lubricity due to rich oxygen-containing functional groups and conjugated structures, is suitable for surface coating modification of high-sensitivity single-substance explosive materials, and has attracted close attention and research of many scholars for decades. Although the surface-coated graphene material is proved to be capable of effectively improving the safety performance of the energetic material, the graphene material has high carbon content, so that the defects of explosive energy loss, low coating rate and the like after coating are easily caused, and therefore, a new desensitizer is urgently sought, and not only has a desensitizing effect, but also can make up the energy performance of the energetic material. Thus, preparation of g-C is employed3N4The base composite energetic material has important significance for improving the comprehensive performance of the high sensitive explosive.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides g-C3N4The preparation method of the base composite energetic material aims to solve the problems of poor stability, low mechanical sensitivity and energy loss of a coated explosive sample of the ammonium nitrate explosive. The technical scheme of the invention is as follows:
g-C3N4The preparation method of the base composite energetic material comprises the steps of respectively adopting physical grinding, in-situ reduction and electrostatic self-assembly methods to prepare the g-C3N4Physically grinding the mixture and explosive according to a certain mass ratio to obtain a composite material 1, and carrying out in-situ reduction on the ultrasonically treated g-C3N4Coating GO on the surface of an explosive crystal to obtain a composite material 2, modifying the surface of the ammonium nitrate explosive by utilizing the high cationic property of polyethyleneimine, and further obtaining a composite material 3 by an electrostatic self-assembly method; g-C is prepared by the above method3N4The crystal of the ammonium nitrate explosive is combined with GO to reduce the sensitivity to obtain the ammonium nitrate explosive composite material with the sensitivity reducing function and the high energy performance, and g-C is utilized3N4High stability with GO, high thermal conductivity and lubricity, thus passivating the mechanical sensitivity of the energetic material.
The method comprises the following specific steps:
the method comprises the following steps: the crucible is placed in a muffle furnace by taking urea as a raw material, and light yellow powder g-C is obtained after high-temperature calcination at 550 DEG C3N4；
Step two: mixing explosive raw material and g-C of step one3N4The materials are mixed according to the mass ratio of 99/1, 98/2 and 97/3, and are put into a mortar for even grinding to obtain a physically ground composite material 1;
step three: mixing graphene oxide GO with g-C obtained in the first step3N4Dispersing the material in deionized water, and obtaining GO and g-C after uniform ultrasonic dispersion3N4The suspension of (a);
step four: according to the ammonium nitrate explosive: g-C3N4: adding a proper amount of ammonium nitrate explosive into the suspension liquid obtained in the third step according to different mass ratios of GO, and performing ultrasonic dispersion treatment to obtain the mixture containing ammonium nitrate explosive and g-C3N4And GO suspension, wherein the mixed solution contains ammonium nitrate explosive and g-C3N4And GO in a mass ratio of 97/3/0, 97/0/3, 97/2/1;
step five: adding hydrazine hydrate into the mixed solution obtained in the fourth step, wherein the mass fraction of the hydrazine hydrate is 80%, stirring for 2 hours at the rotating speed of 400r/min at the temperature of 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room-temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain the product with the g-C ratio3N4And an ammonium nitrate explosive compound energetic material 2 with GO as a desensitizer;
step six: mixing ammonium nitrate explosive and g-C3N4Ultrasonically dispersing in deionized water, dropwise adding a polyethyleneimine water solution, stirring at the rotation speed of 400r/min at room temperature for 2h to obtain the explosive containing ammonium nitrate and g-C3N4And PEI;
step seven: dripping GO dispersion liquid into the mixed liquid obtained in the step six, stirring and reacting for 2 hours at room temperature at the rotating speed of 400r/min to obtain the mixture containing ammonium nitrate explosive and g-C3N4A mixed solution of PEI and GO, the mixed solution containing ammonium nitrate explosive and g-C3N4And GO in a mass ratio of 97/3/0, 97/0/3, 97/2/1;
step eight: adding 80% of hydrazine hydrate into the mixed solution obtained in the step seven, reacting for 2 hours at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room-temperature deionized water for multiple times, putting into a vacuum drying oven, and drying to obtain the explosive surface modifier PEI, g-C3N4And an ammonium nitrate explosive compound energetic material 3 with GO as a desensitizer.
Such ammonium nitrate explosives include, but are not limited to: cyclotetramethylene tetranitramine HMX, bicyclic octogen BCHMX, cyclotrimethylene trinitroamine RDX or hexanitrohexaazaisowurtzitane CL-20.
The polyethyleneimine includes but is not limited to: 600. 1800 or 10000 molecular weight polyethyleneimine.
The concentration of the graphene oxide material suspension is 0.5 mg/ml.
The concentration of the polyethyleneimine suspension is 0.5 mg/ml.
And thirdly, carrying out ultrasonic treatment for 50-55 min.
And fourthly, carrying out ultrasonic treatment for 60-65 min.
And sixthly, carrying out ultrasonic treatment for 90-100 min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention discloses a method for preparing a high-performance gas by adding GO and g-C3N4After the composite desensitizer is used, the thermal stability and safety of the energetic material can be enhanced, and the energy loss of the coated energetic material can be effectively compensated, so that the comprehensive performance of the energetic material is improved.
2. According to the invention, after a certain amount of polyethyleneimine is added into the energetic material, the interaction between the energetic material and the desensitizer can be enhanced, the crystal transition temperature is increased, and the sense reduction effect of the energetic material is effectively improved.
3. The preparation method of the invention takes water as a reaction solvent, has mild reaction, does not introduce organic reagents, and is environment-friendly.
4. The preparation method is suitable for energetic material particles which are insoluble in water, and has stronger universality and good practical application prospect.
Drawings
FIG. 1 post-sonication g-C3N4SEM photograph of
FIG. 2 post-sonication HMX/g-C3N4(97/3) SEM photograph of composite Material
FIG. 3 post-sonication HMX/g-C3N4SEM photograph of/rGO (97/1/2) composite material
FIG. 4 HMX/g-C3N4DSC curves of/rGO (97/1/2) composite and HMX as starting material
FIG. 5 post-sonication HMX/g-C3N4SEM photograph of/rGO (97/2/1) composite material
FIG. 6HMX/g-C3N4DSC curves of/rGO (97/2/1) composite and HMX as starting material
FIG. 7 post-sonication HMX-PEI/g-C3N4SEM photograph of/rGO (97/1/2) composite material
FIG. 8 HMX-PEI/g-C3N4DSC curves of/rGO (97/1/2) composite and HMX as starting material
FIG. 9 post-sonication HMX-PEI/g-C3N4SEM photograph of/rGO (97/1.5/1.5) composite material
FIG. 10 HMX-PEI/g-C3N4DSC curves of/rGO (97/1.5/1.5) composite and raw HMX
FIG. 11 HMX-PEI/g-C3N4XRD patterns of/rGO (97/2/1) composite material and HMX (high molecular weight X) raw material
FIG. 12HMX, rGO, g-C3N4And HMX-PEI/g-C3N4XPS-N1s fitting map of/rGO (97/2/1) composite material
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
g-C3N4the preparation method of the base composite energetic material comprises the following steps:
s1, putting a crucible into a muffle furnace by taking urea as a raw material, and calcining at 550 ℃ to obtain light yellow powder g-C3N4；
S2 ammonium nitrate explosive (described by taking HMX as an example) and g-C3N4The materials are mixed according to a certain mass ratio, and are put into a mortar to be uniformly ground to obtain a physically ground HMX composite material 1;
s3, carrying out GO and g-C on graphene oxide3N4Dispersing the material in deionized water, and performing ultrasonic dispersion for 50min to obtain GO and g-C3N4The suspension of (a);
s4, according to the proportion of the ammonium nitrate explosive: g-C3N4: adding proper ammonium nitrate explosive into GO and g-C according to different mass ratios of GO3N4The suspension is subjected to ultrasonic dispersion for 60min to obtain the suspension containing HMX and g-C3N4And a mixture of GO suspension;
s5, adding 80% hydrazine hydrate into the mixed solution obtained in the step S4, stirring the mixed solution for 2 hours at the rotating speed of 400r/min at the temperature of 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room-temperature deionized water for multiple times, and drying the washed solution in a vacuum drying oven to obtain the product with g-C3N4And a HMX composite energetic material 2 with GO as a desensitizer;
s6, mixingHMX and g-C3N4Ultrasonically dispersing in deionized water, ultrasonically adding a polyethyleneimine aqueous solution dropwise after 90min, and stirring at the rotating speed of 400r/min at room temperature for reacting for 2h to obtain the product containing HMX and g-C3N4And PEI;
s7, adding the GO dispersion liquid into the mixed liquid of S6, stirring and reacting for 2 hours at room temperature at the rotating speed of 400r/min to obtain the product containing HMX and g-C3N4A mixed solution of PEI and GO;
s8, adding 80% hydrazine hydrate into the mixed solution of S7, reacting for 2h at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, filtering, washing with room temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain the explosive g-C modified explosive using PEI as the surface modifier3N4And a HMX composite energetic material 3 with GO as a desensitizer;
embodiments 1 to 6 are embodiments of enhancing graphene-insensitive nitroamine-based energetic material by using polyethyleneimine, and specifically include the following steps:
example 1:
g-C3N4the preparation method of the base HMX composite energetic material comprises the following process steps:
g-C3N4preparation of powder:
grinding 20 g of urea raw material uniformly, placing the urea raw material in a crucible, heating the raw material to 500 ℃ at a heating rate of 2K/min, keeping the temperature for 4h, cooling to room temperature, taking out the urea raw material, and grinding uniformly to obtain g-C3N4And (3) powder.
According to HMX: g-C3N4The mass ratio of the mixture is 97/3, and 30mg of the mixture is mixed with C3N4And 970mgHMX, grinding to obtain HMX/g-C3N4(97/3) composite material having an impact sensitivity of 5.0J (raw material HMX of 3.6J) and a friction sensitivity of 128N (raw material HMX of 96N).
g-C prepared in example 13N4Powder and HMX/g-C3N4(97/3) the crystal morphology of the composite material was as shown in FIGS. 1 and 2 by SEM analysis, g-C prepared in example 13N4The powder has a few layered structures,the size is small and uniform. HMX/g-C3N4(97/3) g-C in the Crystal of the composite Material3N4The stack of lamellae is distributed over the HMX surface.
Example 2:
g-C3N4and formulation of GO suspension:
20mg g-C were weighed respectively3N4Adding 10mgGO into 60mL deionized water, and performing ultrasonic dispersion for 50min to obtain g-C3N4And GO suspension (configured concentration 0.5 mg/mL);
mixing the components in a ratio of HMX: g-C3N4: the GO is doped according to the mass ratio of 97/2/1, and 970mgHMX explosive is added into the g-C3N4Mixing with GO suspension, and processing with ultrasound for 60min to obtain suspension containing HMX, g-C3N4Adding 64 mu L of hydrazine hydrate (the mass fraction is 80%) into the mixed solution of GO suspension, stirring for 2h at the rotating speed of 400r/min at the temperature of 100 ℃ in an oil bath, cooling to room temperature, carrying out suction filtration, washing with room-temperature deionized water for multiple times, putting into a vacuum drying oven, and drying to obtain the product with g-C3N4And GO is a desensitizer HMX/g-C3N4the/rGO (97/1/2) composite material has an impact sensitivity of 12J (raw material HMX of 3.6J) and a friction sensitivity of 128N (raw material HMX of 96N).
HMX/g-C prepared in example 23N4The crystal morphology of the/rGO (97/1/2) composite material is shown in figure 3 by scanning electron microscope analysis, and HMX/g-C prepared in example 23N4the/rGO (97/1/2) composite surface exhibits more of the convoluted rGO with a smaller amount of lamellar structured g-C3N4This may be due to g-C3N4And difference in rGO addition.
HMX/g-C prepared in example 23N4Thermal analysis was performed on/rGO (97/1/2) composite and feedstock HMX, the results of which are shown in fig. 4: compared with the raw material HMX, HMX/g-C3N4The crystal transition endothermic peak temperature and the decomposition exothermic peak temperature of the/rGO (97/1/2) composite material are both slightly improved, the decomposition exothermic peak temperature is 557.60K, which is improved by about 1K compared with pure HMX (556.96K), and the difference of the decomposition peak temperatures is lower than 2K, which shows that the cladding materialThe explosive material and the explosive raw material have good compatibility, and the thermal stability of the explosive composite material can be improved through in-situ reduction coating.
Example 3:
g-C3N4and formulation of GO suspension:
10mg g-C were weighed respectively3N4Adding 20mgGO into 60mL deionized water, and performing ultrasonic dispersion for 50min to obtain g-C3N4And GO suspension (configured concentration 0.5 mg/mL);
mixing the components in a ratio of HMX: g-C3N4: the GO is doped according to the mass ratio of 97/2/1, and 970mgHMX explosive is added into the g-C3N4Mixing with GO suspension, and processing with ultrasound for 60min to obtain suspension containing HMX, g-C3N4Adding 64 mu L of hydrazine hydrate (the mass fraction is 80%) into the mixed solution of GO suspension, stirring for 2h at the rotating speed of 400r/min at the temperature of 100 ℃ in an oil bath, cooling to room temperature, carrying out suction filtration, washing with room-temperature deionized water for multiple times, putting into a vacuum drying oven, and drying to obtain the product with g-C3N4And GO is a desensitizer HMX/g-C3N4the/rGO (97/2/1) composite material has an impact sensitivity of 18J (raw material HMX of 3.6J) and a friction sensitivity of 144N (raw material HMX of 96N).
HMX/g-C prepared in example 33N4The crystal morphology of the/rGO (97/2/1) composite material is shown in figure 5 by scanning electron microscope analysis, and HMX/g-C prepared in example 33N4g-C with layered structure on surface of/rGO composite material3N4And a wrinkled rGO, which can completely coat HMX crystals due to the larger specific surface area of GO and intuitively exhibit g-C3N4And coating of the HMX explosive crystals with rGO.
HMX/g-C prepared in example 33N4Thermal analysis of the/rGO (97/2/1) composite and feedstock HMX, the results of the analysis are shown in fig. 6: compared with the raw material HMX, HMX/g-C3N4The decomposition exothermic peak temperature of the/rGO (97/2/1) composite material is slightly improved, the decomposition exothermic peak temperature is 557.73K, the decomposition exothermic peak temperature is improved by about 1K compared with that of pure HMX (556.96K), and the difference of the decomposition peak temperatures is lower than 2K, which indicates that the cladding material and the explosive are coatedThe raw materials have good compatibility and pass through g-C3N4And surface coating of rGO, the thermal stability of HMX can be improved.
Example 4:
preparing a graphene oxide suspension: weighing 20mg of graphene oxide, adding the graphene oxide into 40mL of water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide suspension (the preparation concentration is 0.5 mg/mL);
g-C3N4and formulation of GO suspension: 970mg of HMX and 10mg of g-C were weighed separately3N4Adding into 30mL deionized water, ultrasonically dispersing for 90min, adding dropwise 5mL polyethyleneimine water solution (with configuration concentration of 0.5mg/mL), stirring at room temperature at a rotation speed of 400r/min for reaction for 2h to obtain the final product containing HMX and g-C3N4And PEI;
slowly dripping the prepared 40mLGO suspension into the mixed solution while stirring, adding 96 mu L of hydrazine hydrate, reacting for 2h at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain g-C (g-C) explosive surface modifier PEI (PEI)3N4HMX-PEI/g-C with GO as a desensitizer3N4the/rGO (97/1/2) composite material has an impact sensitivity of 18J (raw material HMX of 3.6J) and a friction sensitivity of 144N (raw material HMX of 96N).
HMX-PEI/g-C prepared in example 43N4The crystal morphology of the/rGO (97/1/2) composite material is shown in figure 7 by scanning electron microscope analysis, and HMX/g-C prepared in example 43N4The surface of the/rGO composite material shows a wrinkled rGO and is accompanied by g-C with a layered structure3N4Description of g-C3N4And rGO can successfully coat HMX to form a composite.
HMX-PEI/g-C prepared in example 43N4Thermal analysis of the/rGO (97/1/2) composite and feedstock HMX, the results of the analysis are shown in fig. 8: compared with the raw material HMX, HMX-PEI/g-C3N4The decomposition exothermic peak temperature of the/rGO (97/1/2) composite material is slightly improved, the decomposition exothermic peak temperature is 557.90K, and is improved compared with that of pure HMX (556.96K)About 1K, indicating that PEI is used as an explosive surface modifier, g-C3N4HMX-PEI/g-C with GO as a desensitizer3N4The thermal stability of the/rGO (97/1/2) composite can be improved.
Example 5:
preparing a graphene oxide suspension: weighing 15mg of graphene oxide, adding the graphene oxide into 30mL of water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide suspension (the preparation concentration is 0.5 mg/mL);
g-C3N4and formulation of GO suspension: 970mg HMX and 15mg g-C were weighed separately3N4Adding into 30mL deionized water, ultrasonically dispersing for 90min, adding dropwise 5mL polyethyleneimine water solution (with configuration concentration of 0.5mg/mL), stirring at room temperature at a rotation speed of 400r/min for reaction for 2h to obtain the final product containing HMX and g-C3N4And PEI;
slowly dripping the prepared 30mLGO suspension into the mixed solution while stirring, adding 96 mu L of hydrazine hydrate, reacting for 2h at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain the g-C explosive surface modifier PEI3N4HMX-PEI/g-C with GO as a desensitizer3N4the/rGO (97/1.5/1.5) composite material has an impact sensitivity of 26J (raw material HMX of 3.6J) and a friction sensitivity of 160N (raw material HMX of 96N).
HMX-PEI/g-C prepared in example 53N4The crystal morphology of the/rGO (97/1.5/1.5) composite material is shown in figure 9 by scanning electron microscope analysis, and HMX/g-C prepared in example 53N4The surface of the/rGO composite material shows a wrinkled rGO and is accompanied by g-C with a layered structure3N4The overall coating effect is more prominent, probably because the addition of PEI enhances the interfacial bonding of the explosive crystal and the coating material.
HMX-PEI/g-C prepared in example 53N4Thermal analysis was performed on the/rGO (97/1.5/1.5) composite and the feedstock HMX, the results of which are shown in FIG. 10: the decomposition peak temperature of the raw material HMX is 556.96K, compared with that of the raw material HMX, HMX-PEI/g-C3N4The exothermic peak temperature of decomposition of the/rGO (97/2/1) composite material is increased by 1.31K, which shows that HMX-PEI/g-C3N4The thermal stability of the/rGO (97/1.5/1.5) composite material is improved.
Example 6:
preparing a graphene oxide suspension: weighing 10mg of graphene oxide, adding the graphene oxide into 20mL of water, and performing ultrasonic dispersion for 60min to obtain a graphene oxide suspension (the preparation concentration is 0.5 mg/mL);
g-C3N4and formulation of GO suspension: 970mg HMX and 20mg g-C were weighed separately3N4Adding into 40mL deionized water, ultrasonically dispersing for 90min, adding dropwise 5mL polyethyleneimine water solution (with configuration concentration of 0.5mg/mL), stirring at room temperature at a rotation speed of 400r/min for reaction for 2h to obtain the final product containing HMX, g-C3N4And PEI;
slowly dripping the prepared 20mLGO suspension into the mixed solution while stirring, adding 64 mu L of hydrazine hydrate, reacting for 2h at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain the g-C explosive surface modifier PEI3N4HMX-PEI/g-C with GO as a desensitizer3N4The impact sensitivity of the/rGO (97/2/1) composite material is 40J (raw material HMX is 3.6J) and the friction sensitivity is 192N (raw material HMX is 96N).
HMX-PEI/g-C prepared in example 63N4XRD crystal form analysis is carried out on the/rGO (97/2/1) composite material and the raw material HMX, the analysis result is shown in figure 11, and HMX-PEI/g-C3N4The diffraction peaks of the/rGO (97/2/1) composite material are well matched with the XRD spectrum of theoretical beta-HMX (JCPDS NO. 45-0893), and are represented by three groups of characteristic peaks of the beta-HMX at 15.9 degrees, 20.4 degrees and 31.8 degrees, which respectively correspond to (-111), (-102) and (1-32) lattice planes. Furthermore, the composite material shows a relatively weak characteristic absorption peak compared to the starting material HMX, which also reflects g-C3N4And coating of rGO on HMX surface.
HMX-PEI/g-C prepared in example 63N4XPS chemical bond analysis was performed on/rGO (97/2/1) composite and feedstock HMX, and the results are shown in FIG. 12: g-C was obtained by high resolution C1s spectroscopy3N4HMX, rGO and HMX-PEI/g-C3N4The atomic structural environment of the/rGO (97/2/1) composite. At C3N4In (3), the carbon atom can be divided into three characteristic peaks at 284.4, 285.7 and 288.0 eV, respectively from the C-C, C = N and C-N groups. The C1 region of HMX has two peaks corresponding to C-C (284.9 eV) and N-C-N (287.7 eV), respectively. For rGO, the C1s component consists of four peaks, C = C, C-O, C = O and O-C = O, respectively. HMX-PEI/g-C compared to the starting HMX3N4The basic C1s distribution at 284.9 eV (C-C/C = C species) in the/rGO (97/2/1) composite is significantly reduced. At the same time, in rGO and C3N4Two new peaks appear in the product, which are respectively assigned to rGO and g-C3N4The C-O/C = N (285.4 eV) and O-C = O/C-N (288.2 eV) groups indicate the presence of each cladding material in the composite.
Claims (9)
1. g-C3N4The preparation method of the base composite energetic material is characterized in that the g-C is prepared by respectively adopting physical grinding, in-situ reduction and electrostatic self-assembly methods3N4Physically grinding the mixture and explosive according to a certain mass ratio to obtain a composite material 1, and carrying out in-situ reduction on the ultrasonically treated g-C3N4Coating GO on the surface of an explosive crystal to obtain a composite material 2, modifying the surface of the ammonium nitrate explosive by utilizing the high cationic property of polyethyleneimine, and further obtaining a composite material 3 by an electrostatic self-assembly method;
g-C is prepared by the above method3N4The crystal of the ammonium nitrate explosive is combined with GO to reduce the sensitivity to obtain the ammonium nitrate explosive composite material with the sensitivity reducing function and the high energy performance, and g-C is utilized3N4High stability with GO, high thermal conductivity and lubricity, thus passivating the mechanical sensitivity of the energetic material.
2. g-C as claimed in claim 13N4Base composite energy-containing materialThe preparation method of the material is characterized by comprising the following specific steps:
the method comprises the following steps: the crucible is placed in a muffle furnace by taking urea as a raw material, and light yellow powder g-C is obtained after high-temperature calcination at 550 DEG C3N4；
Step two: mixing explosive raw material and g-C of step one3N4The materials are mixed according to the mass ratio of 99/1, 98/2 and 97/3, and are put into a mortar for even grinding to obtain a physically ground composite material 1;
step three: mixing graphene oxide GO with g-C obtained in the first step3N4Dispersing the material in deionized water, and obtaining GO and g-C after uniform ultrasonic dispersion3N4The suspension of (a);
step four: according to the ammonium nitrate explosive: g-C3N4: adding a proper amount of ammonium nitrate explosive into the suspension liquid obtained in the third step according to different mass ratios of GO, and performing ultrasonic dispersion treatment to obtain the mixture containing ammonium nitrate explosive and g-C3N4And GO suspension, wherein the mixed solution contains ammonium nitrate explosive and g-C3N4And GO in a mass ratio of 97/3/0, 97/0/3, 97/2/1;
step five: adding hydrazine hydrate into the mixed solution obtained in the fourth step, wherein the mass fraction of the hydrazine hydrate is 80%, stirring for 2 hours at the rotating speed of 400r/min at the temperature of 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room-temperature deionized water for multiple times, and drying in a vacuum drying oven to obtain the product with the g-C ratio3N4And an ammonium nitrate explosive compound energetic material 2 with GO as a desensitizer;
step six: mixing ammonium nitrate explosive and g-C3N4Ultrasonically dispersing in deionized water, dropwise adding a polyethyleneimine water solution, stirring at the rotation speed of 400r/min at room temperature for 2h to obtain the explosive containing ammonium nitrate and g-C3N4And PEI;
step seven: dripping GO dispersion liquid into the mixed liquid obtained in the step six, stirring and reacting for 2 hours at room temperature at the rotating speed of 400r/min to obtain the mixture containing ammonium nitrate explosive and g-C3N4A mixed solution of PEI and GO, the mixed solution containing ammonium nitrate explosive and g-C3N4And GO in a mass ratio of 97/3/0, 97/0/3, 97/2/1;
step eight: adding 80% of hydrazine hydrate into the mixed solution obtained in the step seven, reacting for 2 hours at 400r/min at 100 ℃ in an oil bath, cooling to room temperature, performing suction filtration, washing with room-temperature deionized water for multiple times, putting into a vacuum drying oven, and drying to obtain the explosive surface modifier PEI, g-C3N4And an ammonium nitrate explosive compound energetic material 3 with GO as a desensitizer.
3. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: such ammonium nitrate explosives include, but are not limited to: cyclotetramethylene tetranitramine HMX, bicyclic octogen BCHMX, cyclotrimethylene trinitroamine RDX or hexanitrohexaazaisowurtzitane CL-20.
4. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: the polyethyleneimine includes but is not limited to: 600. 1800 or 10000 molecular weight polyethyleneimine.
5. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: the concentration of the graphene oxide material suspension is 0.5 mg/ml.
6. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: the concentration of the polyethyleneimine suspension was 0.5 mg/ml.
7. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: and thirdly, carrying out ultrasonic treatment for 50-55 min.
8. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: and fourthly, carrying out ultrasonic treatment for 60-65 min.
9. g-C as claimed in claim 23N4The preparation method of the base composite energetic material is characterized by comprising the following steps: and sixthly, carrying out ultrasonic treatment for 90-100 min.
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