CN116283452A - Method for preparing explosive/HNS core-shell structure spherical compound based on pickering emulsion method - Google Patents
Method for preparing explosive/HNS core-shell structure spherical compound based on pickering emulsion method Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 24
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- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 claims description 2
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- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
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- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B25/00—Compositions containing a nitrated organic compound
- C06B25/04—Compositions containing a nitrated organic compound the nitrated compound being an aromatic
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Colloid Chemistry (AREA)
Abstract
The invention discloses a method for preparing an explosive/HNS core-shell structure spherical compound based on a pickering emulsion method, which comprises the following steps: carrying out interface modification or modification on the nano HNS, and regulating the HLB value of the nano HNS to obtain modified nano HNS; adding the simple substance explosive into the solvent A, adding the modified nano HNS after dissolving, adding the non-solvent B after stirring, forming emulsion under the auxiliary effect of ultrasonic waves, and drying to obtain the spherical composite with the explosive/HNS core-shell structure. According to the invention, the nano HNS surface is modified and modified, and the HLB value of the nano HNS can be changed, so that the nano HNS is used as a surfactant of a pickering emulsion, and finally the spherical explosive/HNS compound with a shell-core structure is obtained. On one hand, the sensitivity of the explosive is reduced through the spherical structure of the compound, on the other hand, the nano HNS attached to the surface of the compound can better exert the heat-resistant insensitive performance of the nano HNS while repairing the surface defect of the compound, so that the sensitivity of the compound is reduced more effectively, and the stability of the explosive is improved.
Description
Technical Field
The invention belongs to a material composite technology, and particularly relates to a method for preparing an explosive/HNS core-shell structure spherical composite based on a pickering emulsion method.
Background
With the continuous development of science and technology, the requirements of people on the weapon explosive are not only high energy in use, but also green production process, storage stability and the like. The most basic energy unit of the energetic material, namely the energetic compound, is a main factor influencing the strength of the warhead of the weapon, thereby influencing the updating of the weapon equipment. The first synthesis of hexanitrohexaazaisowurtzitane (CL-20) by the American scientist Nielsen) in 1987 attracts the eyes of various scientists, and compared with tetranitrotetraazaisooctane (HMX) which is a second-generation energetic material, the density of CL-20 is improved by 8%, the detonation velocity is improved by 6%, the detonation pressure is improved by 8%, and the energy density is improved by 10%. The CL-20 has high sensitivity to mechanical stimulus, electrostatic stimulus and the like, the crystal form is easy to transform, the thermal stability is low, and the like, and the defects in the aspects greatly limit the use of the CL-20.
Hexanitrostilbene (HNS) is widely applied to the fields of modified additives of aerospace and fusion casting explosive, civil and military heat-resistant equipment and the like due to ideal properties such as stable physicochemical properties, low impact sensitivity, insensitive to static spark, higher thermal stability and the like. The nanometer HNS is subjected to surface modification treatment and is applied to a pickering emulsion containing CL-20, so that the nanometer HNS can be attached to the surface of a spherical compound to form a core-shell structure, the sensitivity of the compound can be effectively reduced, the application range of the CL-20 is enlarged, and the safety of the compound is improved.
Currently, the degaussing technique for CL-20 is mainly focused on both the intra-and the external crystal aspects: the inductance reduction technology in the crystal is mainly CL-20/energetic component dulling eutectic crystal, CL-20/non-energetic component eutectic crystal and the like; the external sense-reducing technology of the crystal mainly comprises the control of the CL-20 crystal form, the ultrafining of the CL-20, the sphericization of the CL-20, the surface coating of the CL-20 and the like. Beam force et al (Beam force, chang Zhipeng, zhang Zhengjin, et al, controlled batch preparation and feel reduction technique for ultra-fine CL-20 [ J ]. Shanghai aerospace (Chinese English), 2020,37 (04): 148-154.) A micron and sub-micron surface smooth, spheroid ultra-fine CL-20 having average particle diameters of 3.43 μm and 320nm was prepared using a type HLG-05 pulverizing apparatus with 0.8mm and 0.3mm zirconia balls as media, and was characterized by analysis to find effective reduction in mechanical and friction sensitivity but reduction in thermal stability and increase in electrostatic spark sensitivity. The electrostatic spraying method is adopted to prepare CL-20/F2604, CL-20/DOS and CL-20/PVB spherical Composites by Yao Jian (Yao J, li B, xie L.preparation and Properties of Spherical CL-20 Composites) [ J ]. ACS omega,2022,7 (42), and the characterization analysis shows that compared with the raw materials CL-20, the mechanical sensitivity is effectively reduced, but the thermal stability is reduced and the explosive energy is greatly reduced. Wang Xinquan et al (Wang Xinquan, bian hong Li, zhang Ximing, et al, preparation of CL-20/NQ composite energetic microspheres and characterization thereof [ J ]. Science and engineering, 2018,18 (01): 234-239.) A spray crystallization process is used to coat Nitroguanidine (NQ) on the surface of refined CL-20 to form a CL-20/NQ composite, and the characterization analysis shows that the impact sensitivity is effectively reduced and the thermal stability is effectively increased, but the experimental process has excessive steps and high requirements on the particle size of CL-20. Hang Guiyun et al (Hang Guiyun, yu Wenli, wang Tao, et al, preparation and Performance test of CL-20/RDX eutectic explosives and Protect [ J ]. Protect, 2021,44 (04): 484-488.) A CL-20/RDX eutectic explosive with a molar ratio of 1:1 was prepared by spray drying, and it was found by characterization analysis that the energy of the explosive was well preserved, and both impact and friction sensitivity were reduced to some extent, but thermal stability was reduced to some extent.
The results show that both the coating and the eutectic can effectively reduce the sensitivity of the explosive, but the single technical means have a certain degree of defects.
Disclosure of Invention
The invention adopts a method for preparing the compound, organically combines various inductance reduction technologies such as coating, eutectic, sphericizing and the like, and is hopeful to obtain the energetic material with high energy and insensitive property. In order to ensure the energy release of the energetic material, all components of the invention are the energetic material, but the realization of uniformly coating the surface of the explosive compound with the nanometer HNS is still a technical problem at present. The invention firstly carries out modification and modification on the surface of nano HNS to change the HLB value of the nano HNS, then uses the nano HNS as a surfactant of a pickering emulsion, and finally obtains the explosive/HNS compound with a core-shell structure.
According to the invention, the spherical composite with the explosive/HNS core-shell structure is prepared by adopting a pickering emulsion method, so that the mechanical sensitivity of the simple substance explosive can be reduced through the spherical structure of the composite, and the crystal surface defect can be reduced through the nano HNS layer on the surface of the composite, the crystal morphology and the surface smoothness can be improved, and the sensitivity can be reduced; on the other hand, the self heat-resistant insensitive performance of the nano HNS can be fully exerted, and the stability of the explosive is improved.
It is an object of the present invention to solve the above-mentioned problems and provide advantages which will be described later.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a method for preparing an explosive/HNS core-shell structured spherical composite based on a pickering emulsion method, comprising the steps of:
step one, carrying out interface modification or modification on nano HNS, and regulating the HLB value of the nano HNS to obtain modified nano HNS;
and step two, adding the simple substance explosive into the solvent A, adding the modified nano HNS after dissolution, adding the non-solvent B after stirring, forming emulsion under the auxiliary effect of ultrasonic waves, and drying to obtain the spherical composite with the explosive/HNS core-shell structure.
Preferably, the method for carrying out interface modification or modification on the nano HNS comprises the following steps: adding nano HNS into 0.01mol/L stearic acid-ethanol, dispersing under the action of ultrasound, stirring at room temperature for 45-60 min, and drying to obtain the modified nano HNS.
Preferably, the mass volume ratio of the nano HNS to the ethanol is 1-2 g:30-60 mL; the mass ratio of the nano HNS to the stearic acid is 8-12 g to 0.3g;
preferably, the stirring speed is 200-300 r/min; the ultrasonic power is 300-1200W, and the frequency is 30-120 KHZ.
Preferably, in the first step, the HLB value is between 10 and 15.
Preferably, the elemental explosive is one or more of hexanitrohexaazaisowurtzitane, hexogen, octogen, ammonium perchlorate, ammonium dinitrate, ammonium nitrate, 5 '-bitetrazole-1, 1' -dioxyhydroxylammonium salt, 3 '-diamino-4, 4' -azofurazan, 3 '-diamino-4, 4' -azofurazan, 1-diamino-2, 2-dinitroethylene, 2,4, 6-trinitrotoluene, picric acid, 1, 3-dinitrobenzene, 1, 2-dinitrobenzene, p-nitrochlorobenzene, p-nitroaniline, p-nitrophenol, 3, 5-dinitroaniline, 3, 5-dinitrotoluene, 2, 4-dinitrophenol, 3, 5-dinitrobenzoic acid, and nitrocellulose.
Preferably, the single-made explosive is a mixture of any two kinds of explosives, and the mass ratio of the mixture of any two kinds of explosives is 0.1-1:1-10.
Preferably, the mass ratio of the modified nano HNS to the explosive is 0.01-1:1; the volume ratio of the solvent A to the non-solvent B is 0.1-1:1-20; the mass volume ratio of the simple substance explosive to the non-solvent B is 1.0-2.5 g:5-45 mL.
Preferably, the ultrasonic treatment time is 10-30 min, the ultrasonic power is 300-1200W, and the frequency is 30-120 kHz.
Preferably, the solvent A and the non-solvent B are one or more of distilled water, methanol, ethanol, acetic acid, ethyl acetate, butyl acetate, isoamyl acetate, acetone, N-butanone, methyl isobutyl ketone, cyclohexane, N-butane, cyclohexanone, toluene cyclohexanone, methyl butanone, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, dimethyl sulfoxide, N-dimethylformamide, diethyl ether, petroleum ether, propylene oxide, glycol ether and acetonitrile; and when solvent a selects a solvent that dissolves the elemental explosive, non-solvent B selects a solvent that does not dissolve the elemental explosive.
The invention at least comprises the following beneficial effects: according to the invention, the nano HNS surface is modified and modified, and the HLB value of the nano HNS can be changed, so that the nano HNS is used as a surfactant of a pickering emulsion, and finally the spherical explosive/HNS compound with a shell-core structure is obtained. On one hand, the sensitivity of the explosive is reduced through the spherical structure of the compound, on the other hand, the nano HNS attached to the surface of the compound can better exert the heat-resistant insensitive performance of the nano HNS while repairing the surface defect of the compound, so that the sensitivity of the compound is reduced more effectively, and the stability of the explosive is improved. In the impact sensitivity test of the spherical compound of the invention and the mechanical mixing of pure CL-20 and CL-20/DNB/HNS (comparative example 1), the H50 of the spherical compound is obviously improved, the exothermic peak is deflected backwards, the exothermic amount is greatly improved, and the invention completely achieves the aim of reducing the sensitivity improvement safety while ensuring the explosive energy to the greatest extent.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the present invention, wherein (a), (b) and (c) are raw material CL-20, raw material DNB and raw material HNS in this order; FIG. (d) is a modified HNS; panel (e) shows a CL-20/DNB/HNS mechanical mixture; FIG. (f) is an enlarged view of a CL-20/DNB/HNS core-shell structure spherical composite;
FIG. 2 is an infrared spectrum (FT-IR) of the modified HNS and the raw materials thereof of the present invention;
FIG. 3 is an X-ray diffraction pattern (XRD) of the present invention, wherein (a) is the four crystalline forms α, β, ε, γ of raw material CL-20; (b) Is a spherical compound with a core-shell structure of the raw materials CL-20, the raw materials DNB, the modified HNS, the CL-20/DNB/HNS mechanical mixture and the CL-20/DNB/HNS mechanical mixture;
FIG. 4 is a DSC of a spherical composite of core-shell structure of the present invention of feedstock CL-20, feedstock DNB, modified HNS, CL-20/DNB/HNS mechanical mixtures and CL-20/DNB/HNS;
FIG. 5 is a graph showing the results of mechanical sensitivity testing of the raw materials CL-20, the raw materials DNB, the CL-20/DNB/HNS mechanical mixture and the CL-20/DNB/HNS spherical composite of the core-shell structure of the present invention.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a method for preparing an explosive/HNS core-shell structure spherical compound based on a pickering emulsion method comprises the following steps:
adding 1g of nano HNS into 30mL of prepared 0.01mol/L stearic acid-ethanol solution, performing ultrasonic dispersion, placing the solution on a magnetic stirrer for stirring for 1h, and then placing the solution in a constant-temperature water bath oven at 35 ℃ for drying to obtain stearic acid modified nano HNS, wherein the HLB value is 14.2; the power of the ultrasonic wave is 300W, and the frequency is 45kHz; the stirring speed is 200r/min;
dissolving 2g of a CL-20/DNB (1, 3-dinitrobenzene) mixture mixed according to a molar ratio of 1:1 in 20mL of ethyl acetate, adding 0.3g of stearic acid-ethanol modified nano HNS, adding 100mL of deionized water after 10min, performing ultrasonic treatment to obtain emulsion, and performing freeze drying to obtain a CL-20/DNB/HNS spherical compound; the ultrasonic time is 15min, the ultrasonic power is 300-1200W, and the frequency is 30-120 kHz.
Comparative example 1:
a method for preparing an explosive/HNS core-shell structure spherical compound based on a pickering emulsion method comprises the following steps:
adding 1g of nano HNS into 30mL of prepared 0.01mol/L stearic acid-ethanol solution, performing ultrasonic dispersion, placing the solution on a magnetic stirrer for stirring for 1h, and then placing the solution in a constant-temperature water bath oven at 35 ℃ for drying to obtain stearic acid modified nano HNS, wherein the HLB value is 14.2; the power of the ultrasonic wave is 300W, and the frequency is 45kHz; the stirring speed is 200r/min;
and step two, mechanically mixing and stirring 2g of the CL-20/DNB mixture mixed according to the molar ratio of 1:1 and 0.3g of the nano HNS modified by stearic acid to obtain the CL-20/DNB/HNS compound.
FIGS. 1 (a), (b), (c), (d), (e) and (f) are pictures of raw material CL-20, raw material DNB, raw material HNS, modified HNS, CL-20/DNB/HNS mechanical mixture, and CL-20/DNB/HNS core-shell structure spherical composite and enlarged view thereof, respectively, obtained by scanning electron microscopy. As can be seen from FIGS. 1 (a), (b), (c) and (d), the particles of raw material CL-20 are mostly octahedral biconical, with a particle size of about 20 to 60 μm; the DNB particles are irregular long rods, and the particle size is about 100-400 mu m; the raw material HNS is mostly spherical crystals with the size of 100nm, contains a small part of irregular crystals and rod-shaped crystals, the rod-shaped crystals disappear after modification, and the crystals are nearly spherical and have uniform sizes; as can be seen from FIG. 1 (e), the particle size of the CL-20/DNB/HNS mechanical mixture is reduced to a certain extent compared with the raw materials due to the grinding effect in the mixing process, but the components are only simply mixed together without specific substantial change in the scanning electron microscope picture; the individual raw material components are not visible in FIG. 1 (f), and several energetic materials form a novel composite, from which it is clear that the regular spherical structure and some core-shell structures with particle size mainly distributed between 1 and 3 μm are observed; the formation reason is that the modified HNS has hydrophilicity and lipophilicity, so that the whole system is changed into an oil-in-water structure, the oil phase of the spherical structure is changed into a sphere with smaller size under the action of ultrasound, after deionized water is added, ethyl acetate in the oil phase is gradually reduced, so that the interaction force among different components of explosive molecules is enhanced and gradually separated out, at the moment, the modified HNS is attached to the surface of a tiny liquid drop to be separated out together, and after drying, due to the reduction of ethyl acetate, the shell strength of some spherical structures is insufficient, and a core-shell structure is formed.
FIG. 2 compares FT-IR spectra of raw HNS and modified HNS. 3097.5cm -1 The peak at which is related to the stretching vibration of-ch=; 1602.9cm -1 The peak at which is related to the stretching vibration of the c=c bond in the benzene ring; 1539.1cm -1 Is at the position of-NO 2 Antisymmetric stretching vibration of the radical 1348.1cm -1 Is at the position of-NO 2 The symmetrical stretching vibration of the groups, the peak in the modified HNS and the raw materials tend to be consistent, which indicates that the chemical property of the HNS is not changed by modification. Is inconsistent with the HNS of the raw material, the modified HNS is 3617.7-3877.2 cm -1 A peak appears at the position, the peak is analyzed to be the stretching vibration peak of the hydroxyl in the stearic acid, and the peak is 1550.7cm -1 The peak appearing at this point is COO - The asymmetric stretching vibration peak of (2) shows that the modification is successful, the stearic acid is successfully modified on HNS, and the HNS is subjected to interface modification, so that the HNS can play a role of a surfactant in the Pickering emulsion, and the stable Pickering emulsion is formed;
the starting materials and products of example 1 and comparative example 1 were characterized by X-ray diffraction (XRD) as shown in fig. 3 (a) (b). In FIG. 3 (b), the material CL-20 exhibits diffraction peaks at 12.0 °, 13.6 °, 20.1 °, 24.9 °, 27.9 °, 28.8℃and the like, which are identical to those of the material CL-20 in FIG. 3 (a), indicating that the crystal form of the material CL-20 is a pure alpha crystal form; the raw material DNB has diffraction peaks at 9.2 degrees, 13.3 degrees, 14.7 degrees, 18.3 degrees, 21.1 degrees, 23.2 degrees and the like; the raw material HNS has diffraction peaks at 2 theta of 8.3 degrees, 14.7 degrees, 18.0 degrees, 20.0 degrees, 23.7 degrees and the like. The diffraction peaks described above are all present in the mechanical mixture (Phys. Mixing), whereas these strong characteristic peaks are not fully present in the CL-20/DNB/HNS core-shell structured spherical composites. In contrast, the spherical compound with the CL-20/DNB/HNS core-shell structure has strong diffraction peaks at 5.4 degrees and 10.5 degrees, which are not shown in the diffraction patterns of the raw material components and the mechanical mixture, and is consistent with the CL-20/DNB eutectic peaks reported in the literature. It was demonstrated that during the preparation of the complex, not a simple mechanical mixing, but a new phase was created, forming the CL-20/DNB/HNS complex.
The thermal decomposition properties of the materials CL-20, DNB, modified HNS, CL-20/DNB/HNS mechanical mixture (Phys. Mixing) and the CL-20/DNB/HNS core-shell structure spherical composite were characterized and analyzed by DSC, and the results are shown in FIG. 4. As can be seen from FIG. 4, the material CL-20 has a crystal transition peak at 178.3℃and a decomposition exothermic peak at 239.8 ℃; the raw DNB has an endothermic peak generated by melting at 91.5 ℃ and an endothermic peak generated by evaporation at 219.8 ℃; raw material HNS has a melting endothermic peak at 321.6 ℃ and an exothermic peak generated by decomposition at 351.2 ℃; from the curves of the CL-20/DNB/HNS mechanical mixture, it can be seen that essentially all peaks of the raw material components can be reflected therein, and that due to the low content of modified HNS, the exothermic peak is not obvious, resulting in only one more obvious exothermic peak at 246.6 ℃, which is delayed by 6.8 ℃ compared to pure CL-20, indicating that the components produce a certain synergy during mechanical mixing; compared with the raw material, the thermal decomposition curve of the CL-20/DNB/HNS core-shell structure spherical compound has larger difference, only one endothermic peak exists at 127.5 ℃, one exothermic peak exists at 247.7 ℃, other peaks except one CL-20 crystal transformation peak in the raw material disappear, the novel and unique thermal decomposition performance is formed, the thermal decomposition exothermic peak of the compound is improved by 7.9 ℃ compared with the raw material, and the thermal decomposition performance is consistent with that of the CL-20/DNB eutectic reported in the literature, so that the novel phase is formed by a plurality of energetic components instead of simple mechanical mixing.
The mechanical sensitivity test is shown in fig. 5. As can be seen from FIG. 5, the characteristic of the raw material CL-20 is high (H 50 ) 13cm, more than 100cm of starting DNB, 21cm of CL-20/DNB/HNS mechanical mixture, 43cm of CL-20/DNB/HNS spherical composite of core-shell structure. H of complex 50 The fact that the CL-20 was mechanically mixed with DNB and HNS was slightly synergistic with the increase of 30cm compared to the increase of 22cm compared to the increase of the mechanical mixture suggests that the CL-20 had limited sensitivity reduction, and the sensitivity was significantly reduced after the preparation of the composite. The reason for this result may be: on one hand, the particle size and the particle morphology of the compound are obviously different from those of a mechanical mixture, the particle size of the compound is smaller, more uniform and more nearly spherical, the compound has larger specific surface area, and meanwhile, the generation of hot spots can be better prevented, and the sensitivity of the compound is reduced; on the other hand, CL-20 and DNB exist in a eutectic form in the compound to form a new phase, and compared with the raw materials, the compound has more stable and better safety; finally, the nano HNS modifies the surface of the CL-20/DNB molecule, so that the defects of the compound are fewer, and the sensitivity is greatly reduced because of the heat-resistant insensitive of HNS.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (10)
1. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method is characterized by comprising the following steps of:
step one, carrying out interface modification or modification on nano HNS, and regulating the HLB value of the nano HNS to obtain modified nano HNS;
and step two, adding the simple substance explosive into the solvent A, adding the modified nano HNS after dissolution, adding the non-solvent B after stirring, forming emulsion under the auxiliary effect of ultrasonic waves, and drying to obtain the spherical composite with the explosive/HNS core-shell structure.
2. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method as set forth in claim 1, wherein the method for carrying out interface modification or modification on the nano HNS is as follows: adding nano HNS into 0.01mol/L stearic acid-ethanol, dispersing under the action of ultrasound, stirring at room temperature for 45-60 min, and drying to obtain the modified nano HNS.
3. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method as claimed in claim 2, wherein the mass volume ratio of the nano HNS to the ethanol is 1-2 g:30-60 mL; the mass ratio of the nano HNS to the stearic acid is 8-12 g/0.3 g.
4. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the Pickering emulsion method as recited in claim 2, wherein the stirring speed is 200-300 r/min; the ultrasonic power is 300-1200W, and the frequency is 30-120 KHZ.
5. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the Pickering emulsion method as recited in claim 1, wherein in the first step, the HLB value is between 10 and 15.
6. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method according to claim 1, wherein the elementary explosive is one or more of hexanitrohexaazaisowurtzitane, hexogen, octogen, ammonium perchlorate, ammonium dinitrate, ammonium nitrate, 5 '-bitetrazole-1, 1' -dioxyhydroxylammonium salt, 3 '-diamino-4, 4' -azofurazan, 3 '-diamino-4, 4' -azofurazan, 1-diamino-2, 2-dinitroethylene, 2,4, 6-trinitrotoluene, picric acid, 1, 3-dinitrobenzene, 1, 2-dinitrobenzene, p-nitrochlorobenzene, p-nitroaniline, p-nitrophenol, 3, 5-dinitroaniline, 3, 5-dinitrotoluene, 2, 4-dinitrophenol, 3, 5-dinitrobenzoic acid and nitrocellulose.
7. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method as recited in claim 6, wherein the single explosive is a mixture of any two explosives, and the mass ratio of the mixture of any two explosives is 0.1-1:1-10.
8. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method as recited in claim 1, wherein the mass ratio of the modified nano HNS to the explosive is 0.01-1:1; the volume ratio of the solvent A to the non-solvent B is 0.1-1:1-20; the mass volume ratio of the simple substance explosive to the non-solvent B is 1.0-2.5 g:5-45 mL.
9. The method for preparing the spherical composite of the explosive/HNS core-shell structure based on the Pickering emulsion method as recited in claim 1, wherein the ultrasonic time is 10-30 min, the ultrasonic power is 300-1200W, and the frequency is 30-120 kHz.
10. The method for preparing the spherical composite with the explosive/HNS core-shell structure based on the pickering emulsion method according to claim 1, wherein the solvent a and the non-solvent B are one or more of distilled water, methanol, ethanol, acetic acid, ethyl acetate, butyl acetate, isoamyl acetate, acetone, N-butanone, methyl isobutyl ketone, cyclohexane, N-butane, cyclohexanone, toluene cyclohexanone, methyl butanone, chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, benzene, toluene, xylene, dimethyl sulfoxide, N dimethylformamide, diethyl ether, petroleum ether, propylene oxide, glycol ether and acetonitrile; and when solvent a selects a solvent that dissolves the elemental explosive, non-solvent B selects a solvent that does not dissolve the elemental explosive.
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