Assembling preparation method of aluminum-based composite energetic material

Abstract

The invention provides an assembly preparation method of an aluminum-based composite energetic material, which comprises the following steps: step 1, under a stirring condition, controlling the mixing reaction temperature, adding an ammonium perchlorate-triethylene diamine aqueous solution into a nano-aluminum-graphene oxide assembly dispersion liquid, stirring for reaction, and obtaining a precursor assembly dispersion liquid after the reaction; 2, under the mixing reaction temperature and stirring condition, perchloric acid is dropwise added into the precursor assembly dispersion liquid prepared in the step 1, and a reaction is conducted after dropwise adding is completed; and after the reaction is completed, carrying out post-treatment to obtain the aluminum-based composite energetic material. According to the method, the energetic material DAP-4 synthesis mother liquor is used as an in-situ synthesis system, compounding of energetic components and fuel components can be achieved, meanwhile, core-shell coating and embedding of nano Al by DAP-4 are achieved through the self-assembly and induction effects of graphene oxide, interface contact between reaction components can be increased, and the reaction efficiency is improved. And nano Al can be effectively isolated from contact with space oxygen and water molecules, and activity reduction caused by further oxidation is prevented.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, and relates to aluminum-based composite energetic materials, specifically to an assembly and preparation method for aluminum-based composite energetic materials. Background Technology

[0002] Nano-aluminum metal fuels have become a core component for improving the energy density and combustion efficiency of solid propellants due to their advantages such as good combustion performance, high calorific value, high energy density, and ease of control. Studies have shown that when the size of aluminum particles is reduced to the nanoscale, their specific surface area increases significantly, which can significantly promote the interfacial reaction kinetics with oxidizers, achieving a burning rate increase of more than 50%.

[0003] However, the high surface activity of nano-aluminum particles makes them highly susceptible to oxidation in air, forming a dense Al₂O₃ passivation layer (2–5 nm thick). This passivation layer not only reduces the reactivity of nano-Al but also decreases the content of active Al, severely limiting its energy release efficiency. Numerous researchers have developed various aluminum-based composite energetic materials to enhance the energy release of nano-Al through surface modification, physical assembly, and core-shell structure design. For example, various nanocomposite energetic materials have been prepared by coating nano-Al with PTFE core-shell technology. However, due to drawbacks such as high organic material content, uneven coating leading to reduced system energy density, difficulty in in-situ assembly, and complex preparation processes hindering mass production, aluminum-based composite energetic materials remain somewhat distant from practical application. Therefore, based on the aforementioned problems and shortcomings, there is an urgent need to develop novel aluminum-based composite materials with in-situ assembly capabilities to overcome the technical bottlenecks in energy performance and preparation. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide an assembly and preparation method for aluminum-based composite energetic materials, thereby solving the technical problem that existing preparation methods are difficult to achieve in-situ assembly.

[0005] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0006] A method for assembling and preparing an aluminum-based composite energetic material, the method comprising the following steps:

[0007] Step 1, Preparation of precursor assembly dispersion:

[0008] First, graphene oxide powder is added to an organic solvent and ultrasonically dispersed to form a graphene oxide dispersion.

[0009] Secondly, nano-aluminum powder was added to the graphene oxide dispersion and ultrasonically dispersed, followed by stirring to obtain a nano-aluminum-graphene oxide assembled dispersion.

[0010] Next, water was used as a solvent, and ammonium perchlorate and triethylenediamine were added and stirred until dissolved to form an ammonium perchlorate-triethylenediamine aqueous solution.

[0011] Then, under stirring conditions and by controlling the mixing reaction temperature, ammonium perchlorate-triethylenediamine aqueous solution was added to the nano-aluminum-graphene oxide assembly dispersion, and the reaction was stirred to obtain the precursor assembly dispersion.

[0012] Step 2, Assembly and preparation of composite energetic materials:

[0013] Under mixed reaction temperature and stirring conditions, perchloric acid was added dropwise to the precursor assembly dispersion prepared in step one. After the addition was complete, the reaction was carried out. After the reaction was completed, the mixture was stirred and cooled to room temperature. Finally, after separation, washing and drying, the aluminum-based composite energetic material could be collected.

[0014] The present invention also has the following technical features:

[0015] In steps one and two, the mixing reaction temperature is 30℃~60℃.

[0016] In step one, the organic solvent is any one or a combination of anhydrous methanol, anhydrous ethanol, and N,N-dimethylformamide.

[0017] In step one, the dispersion concentration of the graphene oxide dispersion is 0.05 mg / mL to 2.0 mg / mL.

[0018] In step one, the dispersion concentration of the nano-aluminum is 1.0 mg / mL to 20 mg / mL.

[0019] In step one, the volume ratio of the organic solvent to water is (1-3):1.

[0020] In step one, the amount of ammonium perchlorate and triethylenediamine added in the ammonium perchlorate-triethylenediamine aqueous solution is in the range of 0.05 g / mL to 0.2 g / mL, and the mass ratio of ammonium perchlorate to triethylenediamine is in the range of 0.9 to 1.2.

[0021] In step one, after adding nano-aluminum powder and ultrasonically dispersing for 15 minutes, continue stirring for 60 minutes; the stirring reaction time is 30 minutes.

[0022] In step two, the dropping rate is in the range of 1 mL / min to 5 mL / min; the reaction time is 30 min after dropping.

[0023] Preferably, in steps one and two, the mixing reaction temperature is 60°C.

[0024] Preferably, in step one, the organic solvent is anhydrous ethanol; the dispersion concentration of the graphene oxide dispersion is 0.3 mg / mL; the dispersion concentration of the nano-aluminum is 20 mg / mL; the volume ratio of the organic solvent to water in step one is 1:1; the amount of ammonium perchlorate added in the ammonium perchlorate-triethylenediamine aqueous solution is 0.2002 g / mL; the amount of triethylenediamine added in the ammonium perchlorate-triethylenediamine aqueous solution is 0.1928 g / mL; after adding the nano-aluminum powder, ultrasonic dispersion is carried out for 15 min, and stirring is continued for 60 min; the stirring reaction time is 30 min.

[0025] Preferably, in step two, the dropping rate is 5 mL / min; the reaction time is 30 min after the dropping is complete.

[0026] Compared with the prior art, the present invention has the following technical effects:

[0027] (I) The method of the present invention uses the DAP-4 synthesis mother liquor as the in-situ synthesis system, which can realize the composite of energetic components and fuel components. At the same time, the self-assembly and induction of graphene oxide can realize the core-shell coating and embedding of nano-Al by DAP-4. This can not only increase the interfacial contact between the reaction components, but also effectively isolate the nano-Al from the contact between space oxygen and water molecules, preventing further oxidation and reduction of activity.

[0028] (II) More importantly, in the combustion decomposition reaction process, the method of the present invention produces Cl from the decomposition of DAP-4. - ClO4 - It can also promote the reaction of the inert oxide layer of nano-Al, thereby increasing the energy density of the reaction system. The graphene oxide embedded in the composite system can also produce carbon and oxygen gas products during combustion, enhancing the pressure output of the composite system in the formulation.

[0029] (III) The method of the present invention directly uses the synthesis system as the raw liquid for integrated functional compounding, which is simpler to operate, safer to control the process, and can be prepared in batches. It has the advantages of sustainability and is conducive to promoting the practical application of composite energetic materials.

[0030] (IV) The method of the present invention has the technical advantages of simple operation, safety and efficiency, and sustainable batch production. Attached Figure Description

[0031] Figure 1 This is a schematic diagram of the preparation process of aluminum-based composite energetic materials.

[0032] Figure 2 An optical photograph of the prepared aluminum-based composite energetic material.

[0033] Figure 3The image shows the XRD pattern of the prepared aluminum-based composite energetic material.

[0034] Figure 4 The image shows a SEM image of the prepared aluminum-based composite energetic material.

[0035] Figure 5 The image shows the DSC diagram of the prepared aluminum-based composite energetic material.

[0036] The specific content of the present invention will be further explained and described in detail below with reference to the embodiments. Detailed Implementation

[0037] It should be noted that, unless otherwise specified, all materials and devices used in this invention are those known in the art. For example, DAP-4 and graphene oxide are both commonly used DAP-4 and graphene oxide known in the art.

[0038] In this invention, the aluminum-based composite energetic material is Al@GO@DAP-4. DAP-4 has the molecular formula (C6H2O) 14 Known compounds of N2)[NH4(ClO4)3].

[0039] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0040] Example 1:

[0041] This embodiment provides a method for assembling and preparing an aluminum-based composite energetic material. The method includes the following steps: 2.5 mg of graphene oxide powder is weighed and added to 50 mL of anhydrous ethanol, then ultrasonically dispersed to form a graphene oxide dispersion. Next, 50 mg of nano-aluminum powder is weighed and added to the graphene oxide dispersion, ultrasonically dispersed for 15 min, and then stirred for 60 min to obtain a nano-aluminum-graphene oxide assembly dispersion. Then, 50 mL of deionized water is used as a solvent to dissolve 3.0 g of ammonium perchlorate and 2.9 g of triethylenediamine, and stirred until homogeneous to form an ammonium perchlorate-triethylenediamine aqueous solution. Under stirring conditions, the mixing reaction temperature is controlled at 40°C. The ammonium perchlorate-triethylenediamine aqueous solution is slowly added to the nano-aluminum-graphene oxide dispersion, and the reaction is stirred for 30 min to obtain a gray-black precursor assembly dispersion. Additionally, 7.5 g of perchloric acid is weighed and added dropwise to the above dispersion at a rate of 1 mL / min under stirring conditions at 40°C, and the reaction is carried out for 30 min, followed by stirring and cooling to room temperature. Finally, after separation, washing, and drying, a grayish-black solid product was collected, which is the aluminum-based composite energetic material Al@GO@DAP-4.

[0042] Example 2:

[0043] This embodiment provides a method for assembling and preparing an aluminum-based composite energetic material. The method includes the following steps: 400 mg of graphene oxide powder is weighed and added to 200 mL of N,N-dimethylformamide, then ultrasonically dispersed to form a graphene oxide dispersion. Next, 4.0 g of nano-aluminum powder is weighed and added to the graphene oxide dispersion, ultrasonically dispersed for 15 min, and then stirred for 60 min to obtain a nano-aluminum-graphene oxide assembly dispersion. Then, 70 mL of deionized water is used as a solvent to dissolve 13.5 g of ammonium perchlorate and 15.0 g of triethylenediamine, and stirred until homogeneous to form an ammonium perchlorate-triethylenediamine aqueous solution. Under stirring conditions, the mixing reaction temperature is controlled at 60°C. The ammonium perchlorate-triethylenediamine aqueous solution is slowly added to the nano-aluminum-graphene oxide dispersion, and the reaction is stirred for 30 min to obtain a gray-black precursor assembly dispersion. Additionally, 36.5 g of perchloric acid is weighed and added dropwise to the above dispersion at a rate of 5 mL / min under stirring conditions at 60°C, and the reaction is carried out for 30 min, followed by stirring and cooling to room temperature. Finally, after separation, washing, and drying, a grayish-black solid product was collected, which is the aluminum-based composite energetic material Al@GO@DAP-4.

[0044] Example 3:

[0045] This embodiment provides a method for assembling and preparing an aluminum-based composite energetic material. The method includes the following steps: 100 mg of graphene oxide powder is weighed and added to 100 mL of anhydrous methanol, and ultrasonically dispersed to form a graphene oxide dispersion. Then, 1.0 g of nano-aluminum powder is weighed and added to the graphene oxide dispersion, ultrasonically dispersed for 15 min, and stirred for 60 min to obtain a nano-aluminum-graphene oxide assembly dispersion. Next, 5.0 g of ammonium perchlorate and 4.8 g of triethylenediamine are dissolved in 50 mL of deionized water as a solvent, and stirred until homogeneous to form an ammonium perchlorate-triethylenediamine aqueous solution. Under stirring conditions, the mixing reaction temperature is controlled at 30 °C, and the ammonium perchlorate-triethylenediamine aqueous solution is slowly added to the nano-aluminum-graphene oxide dispersion. After stirring for 30 min, a gray-black precursor assembly dispersion is obtained. In addition, 12.5 g of perchloric acid is weighed and added dropwise to the above dispersion at a rate of 2 mL / min under stirring conditions at 30 °C, and reacted for 30 min. The mixture is then stirred and cooled to room temperature. Finally, after separation, washing, and drying, a grayish-black solid product was collected, which is the aluminum-based composite energetic material Al@GO@DAP-4.

[0046] Example 4:

[0047] This embodiment provides a method for assembling and preparing an aluminum-based composite energetic material. The method includes the following steps: 150 mg of graphene oxide powder is weighed and added to 500 mL of anhydrous ethanol, and ultrasonically dispersed to form a graphene oxide dispersion. Then, 10 g of nano-aluminum powder is weighed and added to the graphene oxide dispersion, ultrasonically dispersed for 15 min, and stirred for 60 min to obtain a nano-aluminum-graphene oxide assembly dispersion. Next, 100.1 g of ammonium perchlorate and 96.4 g of triethylenediamine are dissolved in 500 mL of deionized water as a solvent, and stirred until homogeneous to form an ammonium perchlorate-triethylenediamine aqueous solution. Under stirring conditions, the mixing reaction temperature is controlled at 60 °C, and the ammonium perchlorate-triethylenediamine aqueous solution is slowly added to the nano-aluminum-graphene oxide dispersion. After stirring for 30 min, a gray-black precursor assembly dispersion is obtained. In addition, 250.2 g of perchloric acid is weighed and added dropwise to the above dispersion at a rate of 5 mL / min under stirring conditions at 60 °C, and reacted for 30 min. The mixture is then stirred and cooled to room temperature. Finally, after separation, washing, and drying, a grayish-black solid product was collected, which is the aluminum-based composite energetic material Al@GO@DAP-4.

[0048] In this embodiment, Figure 1 This diagram illustrates the preparation principle of aluminum-based composite energetic materials using this method. Figure 2 Optical photographs of aluminum-based composite energetic materials prepared using the method of this invention. Figure 3 The XRD pattern of the aluminum-based composite energetic material prepared by the method of the present invention shows that the sample mainly contains two components, Al and DAP-4, indicating that the prepared aluminum-based composite energetic material has good purity. Figure 4 The SEM image of the aluminum-based composite energetic material prepared by the method of the present invention is shown. It can be seen that micro-nano aluminum powder and DAP-4 form a composite assembly with the assistance of graphene oxide. Figure 5 The DSC curves of DAP-4 and the aluminum-based composite energetic material prepared by the method of this invention were compared. It can be seen from the figure that after assembly and composite, the presence of aluminum powder and graphene oxide caused the decomposition peak temperature of DAP-4 to advance, indicating that the two had a significant catalytic effect on DAP-4.

[0049] Example 5:

[0050] This embodiment provides a method for assembling and preparing an aluminum-based composite energetic material. The method includes the following steps: 50 mg of graphene oxide powder is weighed and added to 100 mL of N,N-dimethylformamide, and ultrasonically dispersed to form a graphene oxide dispersion. Then, 1.5 g of nano-aluminum powder is weighed and added to the graphene oxide dispersion, ultrasonically dispersed for 15 min, and stirred for 60 min to obtain a nano-aluminum-graphene oxide assembly dispersion. Next, 70 mL of deionized water is used as a solvent to dissolve 14.0 g of ammonium perchlorate and 13.5 g of triethylenediamine, and stirred until homogeneous to form an ammonium perchlorate-triethylenediamine aqueous solution. Under stirring conditions, the mixing reaction temperature is controlled at 36°C. The ammonium perchlorate-triethylenediamine aqueous solution is slowly added to the nano-aluminum-graphene oxide dispersion, and the reaction is stirred for 30 min to obtain a gray-black precursor assembly dispersion. Additionally, 35 g of perchloric acid is weighed and added dropwise to the above dispersion at a rate of 4 mL / min under stirring conditions at 36°C, and the reaction is carried out for 30 min, followed by stirring and cooling to room temperature. Finally, after separation, washing, and drying, a grayish-black solid product was collected, which is the aluminum-based composite energetic material Al@GO@DAP-4.

Claims

1. A method for assembling and preparing an aluminum-based composite energetic material, characterized in that, The method includes the following steps: Step 1, Preparation of precursor assembly dispersion: First, graphene oxide powder is added to an organic solvent and ultrasonically dispersed to form a graphene oxide dispersion. Secondly, nano-aluminum powder was added to the graphene oxide dispersion and ultrasonically dispersed, and then stirred to obtain a nano-aluminum-graphene oxide assembly dispersion. Next, using water as a solvent, ammonium perchlorate and triethylenediamine were added and stirred until dissolved to form an ammonium perchlorate-triethylenediamine aqueous solution; Then, under stirring conditions and by controlling the mixing reaction temperature, ammonium perchlorate-triethylenediamine aqueous solution was added to the nano-aluminum-graphene oxide assembly dispersion, and the reaction was stirred. After the reaction, the precursor assembly dispersion was obtained. Step 2, Assembly and preparation of composite energetic materials: Under mixed reaction temperature and stirring conditions, perchloric acid was added dropwise to the precursor assembly dispersion prepared in step one. After the addition was complete, the reaction was carried out. After the reaction was completed, the mixture was stirred and cooled to room temperature. Finally, after separation, washing and drying, the aluminum-based composite energetic material could be collected.

2. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In steps one and two, the mixing reaction temperature is 30℃~60℃.

3. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, the organic solvent is any one or a combination of anhydrous methanol, anhydrous ethanol, and N,N-dimethylformamide.

4. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, the dispersion concentration of the graphene oxide dispersion is 0.05 mg / mL to 2.0 mg / mL.

5. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, the dispersion concentration of the nano-aluminum is 1.0 mg / mL to 20 mg / mL.

6. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, the volume ratio of the organic solvent to water is (1-3):

1.

7. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, the amount of ammonium perchlorate and triethylenediamine added in the ammonium perchlorate-triethylenediamine aqueous solution is in the range of 0.05 g / mL to 0.2 g / mL, and the mass ratio of ammonium perchlorate to triethylenediamine is in the range of 0.9 to 1.

2.

8. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step one, after adding nano-aluminum powder and ultrasonically dispersing for 15 minutes, continue stirring for 60 minutes; the stirring reaction time is 30 minutes.

9. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In step two, the dropping rate is in the range of 1 mL / min to 5 mL / min; the reaction time is 30 min after dropping.

10. The assembly and preparation method of the aluminum-based composite energetic material as described in claim 1, characterized in that, In steps one and two, the mixing reaction temperature is 60°C; In step one, the organic solvent is anhydrous ethanol; the dispersion concentration of the graphene oxide dispersion is 0.3 mg / mL; the dispersion concentration of the nano-aluminum is 20 mg / mL; the volume ratio of the organic solvent to water in step one is 1:1; the amount of ammonium perchlorate added in the ammonium perchlorate-triethylenediamine aqueous solution is 0.2002 g / mL; the amount of triethylenediamine added in the ammonium perchlorate-triethylenediamine aqueous solution is 0.1928 g / mL; after adding the nano-aluminum powder, ultrasonic dispersion is carried out for 15 min, and stirring is continued for 60 min; the stirring reaction time is 30 min. In step two, the dropping rate is 5 mL / min; the reaction time is 30 min after the dropping is complete.

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