Graphene metal complex-ammonium perchlorate composite, preparation method and application thereof

Abstract

The application provides a graphene metal complex-ammonium perchlorate composite, a preparation method and application thereof, and the preparation method is as follows: graphene-metal complex is ultrasonically dispersed in a solvent to prepare a graphene-metal complex dispersion liquid; ammonium perchlorate is stirred and dissolved in the solvent to prepare an ammonium perchlorate solution; the graphene-metal complex dispersion liquid and the ammonium perchlorate solution are stirred and uniformly mixed, and then spray granulation is performed under a protective atmosphere by using a spray granulator; after the spray granulation is completed, the graphene metal complex-ammonium perchlorate composite is prepared. The graphene metal complex-ammonium perchlorate composite can be used as a combustion catalyst in a solid propellant. The graphene metal complex-ammonium perchlorate composite of the application is not prone to migration in the solid propellant, and can improve the combustion performance of the solid propellant while ensuring the service life of the solid propellant.

Description

Technical Field

[0001] This invention belongs to the field of solid propellant technology, and relates to combustion catalysts for solid propellants, specifically to a graphene metal complex-ammonium perchlorate composite, its preparation method, and its application. Background Technology

[0002] Missiles are crucial weapons in modern warfare, playing a vital role in the tactical operations and strategic deployments of major military powers. Solid propellants are the power source for rocket and missile engines, and their combustion performance is closely related to the combat effectiveness and survivability of missile weapons. Therefore, regulating the combustion performance of solid propellants has become one of the key technologies restricting weapon performance, and using combustion catalysts is one of the most effective and direct means of controlling the burning rate. Ferrocene and its derivatives are commonly used combustion catalysts in hydroxyl-butadiene composite solid propellants, which can effectively improve the combustion performance of solid propellants. However, ferrocene combustion catalysts are prone to migration and volatilization in solid propellants, adversely affecting the service life of solid propellant charges. Summary of the Invention

[0003] To address the shortcomings of existing technologies, the present invention aims to provide a graphene-metal complex-ammonium perchlorate composite, its preparation method, and its application, thereby solving the technical problem of easy migration of combustion catalysts in solid propellants in existing technologies.

[0004] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0005] A method for preparing a graphene-metal complex-ammonium perchlorate composite includes the following steps: ultrasonically dispersing a graphene-metal complex in a solvent to obtain a graphene-metal complex dispersion; dissolving ammonium perchlorate in the solvent by stirring to obtain an ammonium perchlorate solution; mixing the graphene-metal complex dispersion and the ammonium perchlorate solution evenly by stirring, and then spray granulating them under a protective atmosphere using a spray granulator. The spray granulation conditions are: the peristaltic pump speed of the spray granulator is 2-20 rpm, and the temperature of the working chamber of the spray granulator is 120-180℃; after spray granulation, the graphene-metal complex-ammonium perchlorate composite is obtained.

[0006] The present invention also has the following technical features:

[0007] Specifically, the graphene-metal complex is a graphene-ferrocene complex, a graphene-Schiff base iron complex, or a graphene-organic acid iron complex; the graphene-metal complex dispersion is a graphene-ferrocene complex dispersion, a graphene-Schiff base iron complex dispersion, or a graphene-organic acid iron complex dispersion.

[0008] Specifically, the concentration of the graphene-ferrocene complex dispersion is 0.1–2 mg / mL; the concentration of the graphene-Schiff base iron complex dispersion is 0.1–2 mg / mL.

[0009] Specifically, the solvent is selected from acetone, aqueous ethanol solution, aqueous acetone solution, water, ethanol, ethyl acetate, and dimethylformamide.

[0010] Specifically, the volume ratio of water to ethanol in the ethanol-water solution is 1:3; the volume ratio of water to acetone in the acetone-water solution is 1:5.

[0011] Specifically, the protective atmosphere is a nitrogen protective atmosphere with an oxygen concentration of less than 1%.

[0012] Specifically, the mass ratio of the graphene metal complex to ammonium perchlorate is (0.01-0.1):1.

[0013] The present invention also protects the graphene metal complex-ammonium perchlorate complex prepared by the method described above.

[0014] This invention also protects the application of the graphene metal complex-ammonium perchlorate composite as described above as a combustion catalyst in solid propellants. The method of this application includes adding 3-30 wt% of the graphene metal complex-ammonium perchlorate composite to a solid propellant.

[0015] The beneficial technical effects of this invention compared to the prior art are as follows:

[0016] (I) The graphene metal complex-ammonium perchlorate composite of the present invention does not easily migrate in solid propellants, which improves the combustion performance of solid propellants while ensuring the service life of solid propellants.

[0017] (II) The graphene metal complex-ammonium perchlorate composite of the present invention can replace part of the ammonium perchlorate as a functional composite, wherein the introduction of graphene material can improve the mechanical and safety performance of solid propellants. Attached Figure Description

[0018] Figure 1 FTIR spectrum; Figure 1 In the diagram: the green curve A is the FTIR spectrum of the graphene-ferrocene complex, the yellow curve B is the FTIR spectrum of ammonium perchlorate, and the blue curve C is the FTIR spectrum of the graphene-ferrocene complex-ammonium perchlorate complex.

[0019] Figure 2 This is the EDS spectrum of the graphene-ferrocene complex-ammonium perchlorate complex.

[0020] Figure 3 For RAMAN spectra; Figure 3 In the middle: the green curve A is the RAMAN spectrum of the graphene-ferrocene complex, the yellow curve B is the RAMAN spectrum of ammonium perchlorate, and the blue curve C is the RAMAN spectrum of the graphene-ferrocene complex-ammonium perchlorate complex.

[0021] Figure 4 The combustion rate-pressure index curve; Figure 4 In the middle: the yellow curve A is the burning rate-pressure index curve of solid propellants containing graphene-ferrocene complex-ammonium perchlorate complex, and the blue curve B is the burning rate-pressure index curve of solid propellants without graphene-ferrocene complex-ammonium perchlorate complex.

[0022] Figure 5 Macroscopic morphology of solid propellant strip slices after standing for 60 days; Figure 5 In the image: A is a macroscopic morphology image of a solid propellant strip containing a graphene-ferrocene complex after standing for 60 days; B is a macroscopic morphology image of a solid propellant strip containing a graphene-ferrocene complex-ammonium perchlorate complex after standing for 60 days.

[0023] The technical solution of the present invention will be further described below with reference to the embodiments. Detailed Implementation

[0024] It should be noted that, unless otherwise specified, all raw materials used in this invention are those assembled and reported by the inventor's project, for example:

[0025] Graphene-ferrocene complexes are known complexes in the prior art and are described in Chinese patent CN110526945B (i.e., the modified graphene-based iron complex described in that patent).

[0026] Graphene-Schiff base iron complexes are known complexes in the prior art, and are described in the literature Insight intographene-salen metal nanocomposites on combustion performance and mechanism of HMX-CMDB propellant (M.Zhang,FQZhao,H.Li,ZFYuan,S.Dong,Y.Wang,XLChen,YJYang,XDSong,ZFJiang,Chem.Eng.J.429(2022)132175.).

[0027] Following the above technical solutions, specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0028] Example 1:

[0029] This embodiment provides a method for preparing a graphene-ferrocene complex-ammonium perchlorate composite, which specifically includes the following steps: ultrasonically dispersing a graphene-ferrocene complex in acetone to obtain a graphene-ferrocene complex acetone dispersion (1 mg / mL); dissolving ammonium perchlorate in acetone with stirring to obtain an ammonium perchlorate acetone solution; mixing the graphene-ferrocene complex acetone dispersion and the ammonium perchlorate acetone solution evenly with stirring, and then spray granulating under a nitrogen protective atmosphere (oxygen concentration less than 1%) using a spray granulator. The peristaltic pump of the spray granulator rotates at 5 rpm, and the temperature of the working chamber of the spray granulator is 140°C; after spray granulation, the graphene-ferrocene complex-ammonium perchlorate composite is obtained.

[0030] Example 2:

[0031] This embodiment provides a method for preparing a graphene-metal complex-ammonium perchlorate composite, which specifically includes the following steps: A graphene-Schiff base iron complex is ultrasonically dispersed in an ethanol-water solution (the volume ratio of water to ethanol in the ethanol-water solution is 1:3, and the concentration of the graphene-Schiff base iron complex is 0.2–2 mg / mL) to obtain a graphene-Schiff base iron complex water-ethanol dispersion; ammonium perchlorate is dissolved in an ethanol-water solution (the volume ratio of water to ethanol in the ethanol-water solution is 1:3) to obtain an ammonium perchlorate water-ethanol solution; the graphene-Schiff base iron complex water-ethanol dispersion and the ammonium perchlorate water-ethanol solution are stirred and mixed evenly, and then spray-granulated under a nitrogen protective atmosphere (oxygen concentration less than 1%) using a spray granulator. The peristaltic pump speed of the spray granulator is 10 rpm, and the temperature of the working chamber of the spray granulator is 170°C; after spray granulation, the graphene-Schiff base iron complex-ammonium perchlorate composite is obtained.

[0032] Example 3:

[0033] This embodiment provides a method for preparing a graphene-ferrocene complex-ammonium perchlorate composite. The method specifically includes the following steps: ultrasonically dispersing a graphene-ferrocene complex in an acetone aqueous solution (water to acetone volume ratio of 1:5) to obtain a graphene-ferrocene complex water-acetone dispersion (1 mg / mL); dissolving ammonium perchlorate in an acetone aqueous solution (water to acetone volume ratio of 1:5) to obtain an ammonium perchlorate water-acetone solution; mixing the graphene-ferrocene complex water-acetone dispersion and the ammonium perchlorate water-acetone solution evenly, and then spray granulating under a nitrogen protective atmosphere (oxygen concentration less than 1%) using a spray granulator. The peristaltic pump speed of the spray granulator is 8 rpm, and the working chamber temperature of the spray granulator is 150°C. After spray granulation, the graphene-ferrocene complex-ammonium perchlorate composite is obtained.

[0034] Material characterization:

[0035] The infrared spectra of the graphene metal complex-ammonium perchlorate complexes prepared in Examples 1 and 3 are as follows: Figure 1 As shown, the EDS spectrum is as follows Figure 2 As shown, the RAMAN spectrum is as follows Figure 3 As shown.

[0036] Example 4:

[0037] This embodiment describes the application of the graphene ferrocene complex-ammonium perchlorate composite prepared in Examples 1 and 3 as a combustion catalyst in solid propellants. The method of this application includes adding 6 wt% of the graphene ferrocene complex-ammonium perchlorate composite to the solid propellant.

[0038] In this embodiment, the solid propellant is a conventional solid propellant known in the prior art, whose main components are ammonium perchlorate and hydroxyl-terminated polybutadiene.

[0039] Effect verification of Example 4:

[0040] (A) To verify the effect of the graphene-ferrocene complex-ammonium perchlorate composite on the combustion performance of solid propellants, the present invention designed the following experiment: using the above-mentioned solid propellant as a blank control sample, and using a solid propellant containing the graphene-ferrocene complex-ammonium perchlorate composite as an experimental sample, combustion performance tests were conducted. The specific testing procedure referred to the target line method given in the "Ministry Standard of the Ministry of Aerospace Industry of the People's Republic of China" Q915-1985. The test results are as follows: Figure 4 As shown.

[0041] Depend on Figure 4It can be seen that, compared with the blank control sample, the burning rate of the experimental sample was significantly improved in the pressure range of 4–13 MPa, with the burning rate at 13 MPa increasing from 12.18 mm / s to 14.97 mm / s. These results indicate that adding 6 wt% of the graphene-ferrocene complex-ammonium perchlorate composite to the solid propellant can achieve a better combustion catalytic effect.

[0042] (B) To verify the effect of the graphene-ferrocene complex-ammonium perchlorate complex on the migration of solid propellants, the present invention designed the following experiment: A solid propellant containing the graphene-ferrocene complex was used as a control sample, and a solid propellant containing the graphene-ferrocene complex-ammonium perchlorate complex was used as the experimental sample. The propellant strips were left to stand for 60 days, and the macroscopic morphology of the propellant strips was observed. The results are as follows: Figure 5 As shown.

[0043] Depend on Figure 5 It can be seen that, Figure 5 Solid propellant grains containing a graphene-ferrocene complex, as added to component A, exhibited color stratification; the yellow ferrocene showed significant migration within the solid propellant grains. Figure 5 Solid propellant B containing graphene-ferrocene complex-ammonium perchlorate complex has a uniform color and shows no obvious migration.

Claims

1. A method for preparing a graphene-metal complex-ammonium perchlorate composite, characterized in that, The method specifically includes the following steps: ultrasonically dispersing a graphene-metal complex in a solvent to obtain a graphene-metal complex dispersion; dissolving ammonium perchlorate in a solvent by stirring to obtain an ammonium perchlorate solution; mixing the graphene-metal complex dispersion and the ammonium perchlorate solution evenly by stirring, and then spray granulating them using a spray granulator under a protective atmosphere. The spray granulation conditions are: the peristaltic pump speed of the spray granulator is 5-10 rpm, and the temperature of the working chamber of the spray granulator is 140-170°C; after spray granulation, a graphene-metal complex-ammonium perchlorate composite is obtained. The graphene-metal complex is a graphene-ferrocene complex or a graphene-Schiff base iron complex; the graphene-metal complex dispersion is a graphene-ferrocene complex dispersion or a graphene-Schiff base iron complex dispersion.

2. The preparation method of the graphene metal complex-ammonium perchlorate composite as described in claim 1, characterized in that, The concentration of the graphene-ferrocene complex dispersion is 0.1–2 mg / mL; the concentration of the graphene-Schiff base iron complex dispersion is 0.1–2 mg / mL.

3. The preparation method of the graphene metal complex-ammonium perchlorate composite as described in claim 1, characterized in that, The solvent is selected from acetone, aqueous ethanol solution, aqueous acetone solution, water, ethanol, ethyl acetate and dimethylformamide.

4. The preparation method of the graphene metal complex-ammonium perchlorate composite as described in claim 3, characterized in that, The volume ratio of water to ethanol in the ethanol-water solution is 1:3; the volume ratio of water to acetone in the acetone-water solution is 1:

5.

5. The method for preparing the graphene metal complex-ammonium perchlorate composite as described in claim 1, characterized in that, The protective atmosphere is a nitrogen protective atmosphere with an oxygen concentration of less than 1%.

6. The method for preparing the graphene metal complex-ammonium perchlorate composite as described in claim 1, characterized in that, The mass ratio of the graphene metal complex to ammonium perchlorate is (0.01-0.1):

1.

7. A graphene metal complex-ammonium perchlorate complex prepared by the method described in any one of claims 1 to 6.

8. The application of the graphene metal complex-ammonium perchlorate composite as described in claim 7 as a combustion catalyst in solid propellants.

9. The application as described in claim 8, characterized in that, The method of this application includes adding 3 to 30 wt% of a graphene metal complex-ammonium perchlorate complex to a solid propellant.

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