A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology

Abstract

The application discloses a method for adjusting TKX-50 oxygen balance based on oil-in-oil technology, comprising the following steps: dissolving TKX-50, AP and fluorine rubber into an organic solvent, adding a surfactant and an alkane, stirring and ultrasonicating to obtain an emulsion system; gradually adding ethanol into the emulsion system for extraction, slowly diffusing the organic solvent into ethanol, and gradually separating to form spherical-like compounds when TKX-50, AP and fluorine rubber reach saturation; and filtering, washing and drying to obtain a final sample. The application uniformly composites TKX-50 and AP at a nanometer scale, obtains spherical-like TKX-50 / AP compounds with regular morphology, improves the thermal decomposition performance of TKX-50, and reduces the sensitivity of TKX-50, and the significant advantages include: (1) simple preparation process, high efficiency and low cost; (2) mild experimental conditions and high product quality; (3) small proportion of non-explosive materials used, and no influence on the oxidation effect of the oxidant.

Description

Technical Field

[0001] This invention belongs to the technical fields of regulating the oxygen balance of energetic materials and preparing high-performance energetic materials, specifically a method for regulating the oxygen balance of TKX-50 based on oil-in-oil technology. Background Technology

[0002] With the rapid development of modern weapon systems, high energy and low sensitivity have become important research directions in the field of energetic materials.

[0003] 1,1'-Dihydroxy-5,5'-Bis-tetrazole dihydroxyamine salt (TKX-50), as a novel high-energy explosive, possesses excellent characteristics of high detonation velocity and low sensitivity, showing great promise in the field of explosives. The oxygen balance of energetic materials is a crucial factor determining the content of their components, closely related to the explosive's heat of explosion, specific volume, and toxic gas emissions. However, TKX-50 has an oxygen balance of -27.1%, often resulting in insufficient energy release during its work. Meanwhile, ammonium perchlorate (AP), with an oxygen balance of +34%, is an ideal oxidizer widely used in composite propellants, and micro / nanostructured energetic materials have attracted significant research interest due to their improved energy release and ignition performance. Therefore, it would be highly significant to uniformly composite TKX-50 and AP at the nanoscale to obtain a single-particle zero-oxygen-balance composite with superior performance.

[0004] Li Lan et al. used deionized water as a solvent to dissolve TKX-50 and AP in a zero-oxygen equilibrium ratio. The solution was then injected into a polytetrafluoroethylene container containing sufficient liquid nitrogen. After rapid freezing, high-energy ice containing solid solute was transferred to a freeze dryer and maintained at approximately -100°C and a vacuum of 40 Pa for 72 hours. Finally, a two-component TKX-50 / AP nanocomposite material was obtained through pre-freezing and freeze-drying. This method successfully prepared a nanofibrillated TKX-50 / AP composite material. The size effect, three-dimensional porous structure, and excellent heat and mass transfer properties of the TKX-50 and AP nanoparticles significantly improved the thermal decomposition and laser ignition combustion performance of the composite (Southwest University of Science and Technology, 2022, Master's Thesis).

[0005] Tian Dong et al. first prepared a suspension of a certain amount of TKX-50 with ethyl acetate, then dissolved AP in an appropriate amount of anhydrous ethanol to form a saturated solution. Under stirring at 300 rpm, a peristaltic pump was turned on to pump the saturated solution containing AP at a rate of 0.5 mL / min. -1The compound was added dropwise to a suspension of TKX-50 at a certain rate, and the resulting composite was vacuum filtered, washed, and dried to obtain a core-shell structured TKX-50 / AP composite. This method successfully prepared a core-shell structured TKX-50 / AP composite. Compared to the TKX-50 raw material, the composite exhibited improved thermal stability and thermal safety, and reduced mechanical sensitivity (North China University of Technology, 2023, Master's Thesis).

[0006] Zhai Heng et al. used an emulsion method to dissolve CL-20 and AP in zero oxygen equilibrium ratios in appropriate amounts of ethyl acetate and distilled water, respectively. They added an appropriate amount of the surfactant Tween-80, stirred, and dissolved the mixture. The resulting suspension was sonicated for 10 minutes and then rapidly placed in a -50℃ freezer to solidify quickly. Finally, it was dried in a freeze dryer for 48 hours to obtain a CL-20 / AP composite sample. This method successfully prepared a CL-20 / AP composite sample with irregular crystal morphology, significantly increased heat release, and significantly reduced impact sensitivity (Journal of Explosives and Pyrotechnics, 2018, 41(01): 41-46).

[0007] Currently, there are few reports in the literature, both domestically and internationally, on the preparation of TKX-50 / AP composites, and the techniques reported in these reports all have various shortcomings. As mentioned above, both nanofibrillated and core-shell structured TKX-50 / AP composites exhibit better performance than raw TKX-50 when oxygen balance is zero. Furthermore, other explosives with negative oxygen balances also show improved overall performance when combined with AP. However, their common drawbacks include irregular composite morphology and cumbersome, time-consuming preparation processes, which to some extent limit their application range and large-scale use. Therefore, designing and inventing a simple, efficient process that can uniformly combine TKX-50 and AP at the nanoscale while obtaining composites with more regular morphology, thereby improving the overall performance of TKX-50 and broadening its application range in energetic materials, is an urgent technical problem to be solved in this field. Summary of the Invention

[0008] One object of the present invention is to solve at least the above-mentioned problems and / or defects, and to provide at least the advantages described below.

[0009] To achieve these objectives and other advantages according to the present invention, a method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology is provided, comprising the following steps:

[0010] Step 1: Dissolve TKX-50, AP and fluororubber in an organic solvent, add surfactant and alkane, stir and sonicate to obtain an emulsion system;

[0011] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing the organic solvent to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0012] Preferably, the organic solvent is DMSO; the alkane is one or more of n-pentane, isopentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, and cyclodecane; the added alkane is incompatible with the above organic solvent and acts as a dispersion system in the system.

[0013] Preferably, the surfactant is one or more of gum arabic, shellac, polyvinylpyrrolidone, sodium dodecylbenzene sulfonate, hexadecylpyridine, sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium octadecyl sulfate, sodium dioctane succinate sulfonate, polyvinyl alcohol, polyethylene glycol, dichloromethane, Span 20-80, and Tween 20-80.

[0014] Preferably, the fluororubber is one or more of fluororubber F2311, fluororubber F2312, fluororubber F2313, fluororubber F2314, fluororubber F2601, fluororubber F2602, fluororubber F2603, fluororubber F2604, PVDF, and PTFE, and the fluororubber acts as a binder to enhance the stability of the emulsion system.

[0015] Preferably, in step one, the amount of fluororubber used is 0.01wt% to 50wt% of the total mass of TKX-50 and AP in the emulsion system.

[0016] Preferably, the oxygen balance of the spherical complex is between -27% and +30% (first, the mass ratio of TKX-50 to AP under different oxygen balance values ​​is obtained by using the oxygen balance calculation formula, and then experiments are conducted according to the mass ratio to achieve the oxygen balance of the spherical complex between -27.1% and +30%).

[0017] Preferably, the ultrasound duration in step one is 1–60 min, the ultrasound power is 300–1200 W, and the frequency is 30–120 kHz.

[0018] Preferably, the drying process in step two is any one of room temperature drying, vacuum drying, and freeze drying;

[0019] Preferably, the size of the final sample obtained in step two is 10 nm to 2 mm.

[0020] Preferably, in step one, the ammonium perchlorate is used after pretreatment. The pretreatment process is as follows: ammonium perchlorate and MXene at a mass ratio of 15 to 30:1 are added to a styrene-acrylonitrile copolymer solution and ultrasonically dispersed for 3 to 5 hours to obtain a dispersion. The dispersion is then dripped into cyclohexane under stirring using an electrospray method. After the spraying is completed, the mixture is continuously stirred for 30 to 60 minutes, allowed to stand, filtered, and dried to obtain pretreated ammonium perchlorate.

[0021] Preferably, the styrene-acrylonitrile copolymer solution is prepared by adding the styrene-acrylonitrile copolymer to dimethyl sulfoxide and dimethylformamide in a volume ratio of 2:1 and stirring to dissolve; the concentration of the styrene-acrylonitrile copolymer solution is 5-10 wt%; the mass ratio of ammonium perchlorate to styrene-acrylonitrile copolymer is 3:1; and MXene is any one of Ti3C2, Ti2C, Nb3C4, Nb2C, V3C2, and Mo2C.

[0022] Preferably, the drying process in step two is any one of room temperature drying, vacuum drying, or freeze drying; the size of the spherical TKX-50 / AP composite obtained in step two is 10 nm to 2 mm.

[0023] In this invention, the oxygen balance of the raw material TKX-50 is -27.1%, meaning the oxygen in the explosive cannot completely oxidize combustible elements, resulting in insufficient energy release during its work. Meanwhile, AP has an oxygen balance of +34%, making it an ideal oxidizer widely used in composite propellants. Therefore, combining these two materials can compensate for the incomplete oxidation of combustible elements in TKX-50 while also improving its energy utilization rate.

[0024] This invention is based on oil-in-oil technology. First, the mass ratio of TKX-50 to AP under different oxygen balance values ​​is obtained through oxygen balance calculation formula. Then, it is dissolved in DMSO according to the mass ratio to obtain a DMSO solution in which TKX-50 and AP are uniformly dispersed. At the same time, Tween-80 and F2601 are added to the system as surfactant and binder, respectively. Their contents must be controlled within 5 wt% of the total mass of TKX-50 and AP. This not only increases the stability of the solution system to a certain extent, but also does not affect the oxidation effect of the oxidant. Finally, cyclohexane is selected as another oil phase material because it is immiscible with DMSO and has a similar density, which is more conducive to obtaining a stable emulsion system. The stability of the emulsion is an important factor affecting the morphology of the final sample.

[0025] This invention regulates the oxygen balance of TKX-50 with negative oxygen balance using the oxidant AP. AP and TKX-50 can be uniformly mixed at the nanoscale to form a near-spherical composite of approximately 30 μm. This allows for the regulation of the oxygen balance of TKX-50 over a wide range, thereby enabling the full release of its energy and significantly increasing the heat release of TKX-50. In Example 2, the oxygen balance of the sample was zero, resulting in the greatest increase in heat release, exceeding 35% compared to the raw material. This is expected to significantly improve the energy of the TKX-50 explosive-based warhead.

[0026] The present invention has at least the following beneficial effects:

[0027] This invention uniformly composites TKX-50 and AP at the nanoscale to obtain a morphologically regular spherical TKX-50 / AP composite, which improves the thermal decomposition performance of TKX-50 and reduces the sensitivity of TKX-50. Its significant advantages include: (1) simple preparation process, high efficiency and low cost; (2) mild experimental conditions and high product quality; (3) small proportion of non-energetic materials used, which will not affect the oxidation effect of the oxidant.

[0028] Other advantages, objectives and features of the present invention will become apparent in part from the following description, and in part from those skilled in the art through study and practice of the invention. Attached image description:

[0029] Figure 1 Scanning electron microscope and elemental distribution map of the spherical TKX-50 / AP composite samples prepared in Examples 2, 8 and 6 of this invention;

[0030] Figure 2 The thermal decomposition performance diagram of the mechanically mixed sample of TKX-50 and AP prepared in Example 10 of this invention;

[0031] Figure 3 The thermal decomposition performance diagrams are shown for the near-spherical TKX-50 / AP composite samples prepared in Examples 8, 2, and 6 of this invention.

[0032] Figure 4 This is a schematic diagram showing the impact sensitivity of TKX-50 raw material to zero-oxygen equilibrium samples in Examples 2, 10, 11 and 12.

[0033] Figure 5 This is a schematic diagram showing the friction sensitivity of TKX-50 raw material with zero oxygen balance samples from Examples 2, 10, 11, and 12. Detailed implementation method:

[0034] The present invention will now be described in further detail with reference to the accompanying drawings, so that those skilled in the art can implement it based on the description.

[0035] It should be understood that terms such as “having,” “comprising,” and “including” as used herein do not imply the presence or addition of one or more other elements or combinations thereof.

[0036] Example 1:

[0037] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0038] Step 1: Dissolve 0.112g TKX-50 and 0.088g AP (at this mass ratio, the oxygen balance between TKX-50 and AP is zero) in 10mL DMSO at room temperature to prepare a 2% (w / w) solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion system in which TKX-50 and AP are dissolved and dispersed in cyclohexane.

[0039] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50 and AP reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0040] Example 2:

[0041] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0042] Step 1: Dissolve 0.112g TKX-50, 0.088g AP (at this mass ratio, the oxygen balance between TKX-50 and AP is zero) and 0.01g F2601 (5wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% (w / w) solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0043] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0044] Example 3:

[0045] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0046] Step 1: Dissolve 0.112g TKX-50, 0.088g AP (at this mass ratio, the oxygen balance between TKX-50 and AP is zero) and 0.02g F2601 (10wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% (w / w) solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0047] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0048] Example 4:

[0049] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0050] Step 1: Dissolve 0.112g TKX-50, 0.088g AP (at this mass ratio, the oxygen balance between TKX-50 and AP is zero) and 0.04g F2601 (20wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% mass concentration solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0051] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0052] Example 5:

[0053] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0054] Step 1: Dissolve 0.112g TKX-50, 0.088g AP (at this mass ratio, the oxygen balance between TKX-50 and AP is zero) and 0.1g F2601 (50wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% (w / w) solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0055] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0056] Example 6:

[0057] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0058] Step 1: Dissolve 0.095g TKX-50, 0.106g AP (at this mass ratio, the oxygen balance of TKX-50 and AP is +10%) and 0.01g F2601 (5wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% mass concentration solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0059] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0060] Example 7:

[0061] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0062] Step 1: Dissolve 0.07g TKX-50, 0.135g AP (at this mass ratio, the oxygen balance of TKX-50 and AP is +20%) and 0.01g F2601 (5wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% mass concentration solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0063] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0064] Example 8:

[0065] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0066] Step 1: Dissolve 0.135g TKX-50, 0.07g AP (at this mass ratio, the oxygen balance of TKX-50 and AP is -10%) and 0.01g F2601 (5wt% of the total mass of TKX-50 and AP) in 10mL DMSO at room temperature to prepare a 2% mass concentration solution. Then add 0.01g Tween-80 agent and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50, AP and F2601 dispersed in cyclohexane.

[0067] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0068] Example 9:

[0069] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0070] Step 1: Dissolve 0.2g TKX-50 (without AP, the oxygen balance of the sample is -27%) and 0.01g F2601 (5wt% of TKX-50) in 10mL DMSO at room temperature to prepare a 2% (w / w) solution. Then add 0.01g Tween-80 and 15mL cyclohexane, stir and sonicate for 20min to obtain a DMSO emulsion of TKX-50 and F2601 dispersed in cyclohexane.

[0071] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50 and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0072] Example 10:

[0073] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0074] Step 1: Pre-treat ammonium perchlorate before use. The pre-treatment process is as follows: Add ammonium perchlorate and Ti3C2 at a mass ratio of 20:1 to a 10wt% styrene-acrylonitrile copolymer solution, and ultrasonically disperse for 3 hours to obtain a dispersion. Drop the dispersion into cyclohexane under stirring using an electrospray method. After spraying, continue stirring for 60 minutes, allow to stand, filter, and dry to obtain pre-treated ammonium perchlorate (AP). The styrene-acrylonitrile copolymer solution is prepared by adding the styrene-acrylonitrile copolymer to dimethyl sulfoxide and dimethylformamide at a volume ratio of 2:1, and stirring to dissolve. The mass ratio of ammonium perchlorate to styrene-acrylonitrile copolymer was 3:1. The electro-spraying method was as follows: the dispersion was added to a spray container with a stainless steel nozzle, then a high-voltage power supply was used to apply voltage to the stainless steel nozzle, and a propulsion pump connected to the spray container was used to drip the dispersion in the spray container into cyclohexane under stirring through the stainless steel nozzle; the stirring speed of the cyclohexane was 150 r / min; the spraying conditions used in the electro-spraying method were: ambient temperature of 50℃, output voltage of the high-voltage power supply of 8kV, distance between the receiving device and the stainless steel nozzle of 10cm, and flow rate of 10mL / h.

[0075] 0.112 g TKX-50, 0.088 g pretreated AP and 0.01 g F2601 (5 wt% of the total mass of TKX-50 and AP) were dissolved in 10 mL DMSO at room temperature to prepare a 2% (w / w) solution. Then, 0.01 g Tween-80 and 15 mL cyclohexane were added, and the mixture was stirred and sonicated for 20 min to obtain a DMSO emulsion of TKX-50, pretreated AP and F2601 dispersed in cyclohexane.

[0076] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, pretreated AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0077] Example 11:

[0078] A method for adjusting the oxygen balance of TKX-50 based on oil-in-oil technology includes the following steps:

[0079] Step 1: Pre-treat ammonium perchlorate before use. The pre-treatment process is as follows: Add ammonium perchlorate and Mo2C at a mass ratio of 25:1 to a 10wt% styrene-acrylonitrile copolymer solution, and ultrasonically disperse for 3 hours to obtain a dispersion. Drop the dispersion into cyclohexane under stirring using an electrospray method. After spraying, continue stirring for 60 minutes, allow to stand, filter, and dry to obtain pre-treated ammonium perchlorate (AP). The styrene-acrylonitrile copolymer solution is prepared by adding the styrene-acrylonitrile copolymer to dimethyl sulfoxide and dimethylformamide at a volume ratio of 2:1, and stirring to dissolve. The mass ratio of ammonium perchlorate to styrene-acrylonitrile copolymer is 3:1. The electro-spraying method is as follows: the dispersion is added to a spray container with a stainless steel nozzle, then a high-voltage power supply is used to apply voltage to the stainless steel nozzle, and a propulsion pump connected to the spray container is used to drip the dispersion in the spray container into cyclohexane under stirring through the stainless steel nozzle; the stirring speed of cyclohexane is 150 r / min; the spraying conditions used in the electro-spraying method are: ambient temperature of 50℃, output voltage of high-voltage power supply of 8kV, distance between receiving device and stainless steel nozzle of 10cm, and flow rate of 10mL / h.

[0080] 0.112 g TKX-50, 0.088 g pretreated AP and 0.01 g F2601 (5 wt% of the total mass of TKX-50 and AP) were dissolved in 10 mL DMSO at room temperature to prepare a 2% (w / w) solution. Then, 0.01 g Tween-80 and 15 mL cyclohexane were added, and the mixture was stirred and sonicated for 20 min to obtain a DMSO emulsion of TKX-50, pretreated AP and F2601 dispersed in cyclohexane.

[0081] Step 2: Gradually add ethanol dropwise to the emulsion system for extraction, allowing DMSO to slowly diffuse into the ethanol. When TKX-50, pretreated AP, and fluororubber reach saturation, they gradually precipitate to form a spherical complex. Filter, wash, and dry to obtain the final sample.

[0082] Example 12:

[0083] Weigh out 0.135g of TKX-50 and 0.07g of AP (the oxygen balance of TKX-50 and AP is -10% at this mass ratio), 0.112g of TKX-50 and 0.088g of AP (the oxygen balance of TKX-50 and AP is zero at this mass ratio), and 0.095g of TKX-50 and 0.106g of AP (the oxygen balance of TKX-50 and AP is +10% at this mass ratio), add an appropriate amount of ethanol to each, grind them, and finally dry them to obtain mechanically mixed samples with different oxygen balances.

[0084] Figure 1In the diagram, a) and b) represent the raw materials, c), d), e), f), and g), h) correspond to the SEM images of the samples prepared in Examples 2, 8, and 6, respectively, and i) is the EDS image of the sample from Example 2. Figure 1 In -a and 1-b, it can be observed that the raw material is an irregular polyhedral shape with a size distribution ranging from several micrometers to hundreds of micrometers. Figure 1 -c and 1-d represent TKX-50 / AP composite samples in zero oxygen equilibrium, from... Figure 1 -c reveals that the sample is a spherical complex with a rough surface, resembling spiky spheres, with relatively uniform size and intact spherical shape; from Figure 1 As can be seen from the -d image, the surface of the composite consists of explosive crystals with a nanostructure. Under this structure, AP and TKX-50 are uniformly mixed at the nanoscale, making it easier to fully release energy when performing work. Meanwhile, other electron micrographs also show that samples with -10% oxygen balance (Example 8) and +10% oxygen balance (Example 6) have similar structures, indicating that this preparation technique can prepare composites with different raw material ratios over a wide range, providing technical support for the performance study of nanocomposite materials with different oxygen balance values.

[0085] While using SEM to analyze the microstructure of the samples, EDS was also used to determine the elemental distribution of the composite samples. For example... Figure 1 As shown in -i (sample prepared in Example 2), the elemental mapping diagram shows that N, O, F, and Cl are fully distributed in the composite material. The F and Cl elements come from fluororubber and AP, respectively. This indicates that the fluororubber and oxidant AP added during the preparation process are fully composited with TKX-50.

[0086] Figure 2 The figure shows the DSC curves of the TKX-50 / AP mechanically mixed samples in Example 12 with negative oxygen balance, zero oxygen balance, and positive oxygen balance. The oxygen balance values ​​of the positive and negative oxygen balance samples are +10% and -10%, respectively. It can be seen from the figure that the first thermal decomposition peak of the TKX-50 raw material and the TKX-50 / AP mechanically mixed samples with different proportions are all around 238℃, with little change. However, the temperature of the second thermal decomposition peak is delayed to varying degrees, with the delay being most significant in the zero oxygen balance and negative oxygen balance samples, reaching 270℃. Compared to the heat release of 1623 J / g for the TKX-50 raw material, the heat release of the zero oxygen balance sample reaches 2033 J / g, showing the greatest increase. This is because when the oxygen balance is zero, the oxygen element in the explosive can completely oxidize the combustible elements, resulting in the maximum energy release, optimal work efficiency, and minimal production of harmful gases after the explosion. Meanwhile, the heat release of the negative and positive oxygen balance samples only increases slightly.

[0087] Figure 3 The figures show the DSC curves of the TKX-50 / AP composite samples in Examples 8, 2, and 6, representing negative oxygen balance, zero oxygen balance, and positive oxygen balance, respectively. In all samples, the binder mass was 5 wt% of the total mass of TKX-50 and AP. The oxygen balance values ​​for the positive and negative oxygen balance samples were +10% and -10%, respectively. The figures show that compared to the first thermal decomposition peak of the KX-50 raw material, the first thermal decomposition peak temperature of the three groups of TKX-50 / AP composite samples with different proportions all shifted slightly forward, while the second thermal decomposition peak temperature was delayed by approximately 20°C or more. The heat release of the three groups of samples also increased, with the zero oxygen balance sample showing the largest increase, reaching 2206 J / g, a 35.9% increase compared to the raw material. In summary, the samples prepared using the O / O technology, due to the uniform mixing of the oxidant and the negative oxygen-balanced TKX-50 at the nanoscale, allow for sufficient reaction, ultimately resulting in a significant increase in heat release.

[0088] Figure 4 This is a schematic diagram illustrating the impact sensitivity of TKX-50 raw material to zero-oxygen-equilibrium samples from Examples 2, 10, 11, and 12. Figure 5 This is a schematic diagram illustrating the friction sensitivity of TKX-50 raw material with the zero-oxygen equilibrium samples from Examples 2, 10, 11, and 12. The diagram shows that the characteristic drop height H of the TKX-50 raw material is... 50 The height is 48.4 cm, and the friction sensitivity is 100%; the characteristic drop height H of the mechanically mixed sample in Example 12 is... 50 The drop height is 52.2 cm, and the friction sensitivity is 96%; the characteristic drop height H of the TKX-50 / AP composite explosive in Example 2 is... 50 The value is 63.5 cm, and the friction sensitivity is 76%. The drop height H of the AP composite explosive in Example 10 is... 50 The drop height is 69.5 cm, and the friction sensitivity is 72%. The drop height H of the TKX-50 / AP composite explosive in Example 11 is... 50 The distance is 69.8 cm, and the friction sensitivity is 72%. In comparison, the characteristic drop height of the mechanically mixed sample is H. 50 The change in friction sensitivity is relatively small, while the properties of the composite explosive in Example 2 are significantly improved. 50 The height was increased by 15.1 cm, and the friction sensitivity was reduced by 24%. The composite explosive of Example 10 showed a higher characteristic height H. 50 The height was increased by 21.1 cm, and the friction sensitivity was reduced by 28%; the composite explosive of Example 11 showed a characteristic drop height H. 50The friction sensitivity was increased by 21.4 cm and decreased by 28%, showing a significant change. Furthermore, the pretreated AP achieved better results, indicating that the prepared spherical TKX-50 / AP composite explosive has good safety performance. The above phenomena may be related to the uniform distribution of TKX-50 and AP and the spherical morphology in the composite explosive.

[0089] Although embodiments of the present invention have been disclosed above, they are not limited to the applications listed in the specification and embodiments. They can be applied to various fields suitable for the present invention. For those skilled in the art, other modifications can be easily made. Therefore, without departing from the general concept defined by the claims and their equivalents, the present invention is not limited to the specific details and illustrations shown and described herein.

Claims

1. A method of adjusting TKX-50 oxygen balance based on oil-in-oil technology, characterized by, The method comprises the following steps: Step one, dissolving TKX-50, ammonium perchlorate and fluorine rubber into an organic solvent, adding a surfactant and an alkane, stirring and ultrasonicating to obtain an emulsion system; Step two, gradually adding ethanol to the emulsion system for extraction, allowing the organic solvent to slowly diffuse into the ethanol, and gradually precipitating to form spherical composite when TKX-50, ammonium perchlorate and fluorine rubber reach saturation, and filtering, washing and drying to obtain spherical TKX-50 / AP composite; The surfactant is Tween 80; The fluorine rubber is fluorine rubber F2601; The organic solvent is DMSO, and the alkane is cyclohexane.

2. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 1, wherein, In step one, the amount of fluorine rubber is 0.01wt%-50wt% of the total mass of TKX-50 and AP in the emulsion system.

3. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 1, wherein, The oxygen balance of the spherical TKX-50 / AP composite is between-27% and +30%.

4. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 1, wherein, In step one, the ultrasonicating time is 1-60 min, the ultrasonicating power is 300-1200 W, and the frequency is 30-120 KHZ.

5. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 1 wherein, In step one, the ammonium perchlorate is used after pretreatment, and the pretreatment process is as follows: adding ammonium perchlorate and MXene with a mass ratio of 15-30:1 into a styrene-acrylonitrile copolymer solution, ultrasonicating for 3-5 hours to obtain a dispersion liquid, dropping the dispersion liquid into cyclohexane in a stirring state by electrospraying, continuing to stir for 30-60 min after the spraying is completed, standing, filtering and drying to obtain pretreated ammonium perchlorate.

6. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 5, wherein, The configuration method of the styrene-acrylonitrile copolymer solution is as follows: adding styrene-acrylonitrile copolymer into dimethyl sulfoxide and dimethylformamide with a volume ratio of 2:1, and stirring and dissolving to obtain; the concentration of the styrene-acrylonitrile copolymer solution is 5-10wt%; the mass ratio of ammonium perchlorate to styrene-acrylonitrile copolymer is 3:1; and the MXene is any one of Ti3C2, Ti2C, Nb3C4, Nb2C, V3C2 and Mo2C.

7. The method of TKX-50 oxygen balance adjustment based on oil-in-oil technology of claim 1 wherein, The drying process in step two is any one of normal temperature drying, vacuum drying and freeze drying; and the size of the spherical TKX-50 / AP composite obtained in step two is 10 nm-2 mm.

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