Sulfur-free nitrogen-free metastable quaternary energetic material based on additive manufacturing technology as well as preparation method and application of sulfur-free nitrogen-free metastable quaternary energetic material

Abstract

The invention provides a sulfur-free nitrogen-free metastable-state quaternary energetic material based on an additive manufacturing technology as well as a preparation method and application thereof. The preparation method comprises the following steps: S1, preparing Fe2O3 / PTFE oxide slurry; s2, Al / Mg / PTFE metastable state composite slurry with the adjusted viscosity is prepared and obtained; s3, blending the Fe2O3 / PTFE oxide slurry obtained in the step S1 and the Al / Mg / PTFE metastable composite slurry obtained in the step S2 according to a certain proportion, and stirring to obtain Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry; and S4, adding the Al / Mg / PTFE / Fe2O3 metastable-state quaternary energetic slurry obtained in S3 into a 3D printer charging barrel, adjusting equipment parameters, and processing to obtain the Al / Mg / PTFE / Fe2O3 sulfur-free nitrogen-free metastable-state quaternary energetic material based on the additive manufacturing technology. According to the quaternary energetic material, the ignition temperature of an existing Al / PTFE composite system material can be reduced, meanwhile, carbon residues formed after combustion are further reduced, elements such as nitrogen and sulfur are not used, environmental protection is focused, meanwhile, the processing technology is simple, and the personalized forming requirement can be met.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of energetic materials, and relates to Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic materials based on an additive manufacturing technology and a preparation method and application thereof. BACKGROUND

[0002] With the development of the technical field of energetic materials, Al / PTFE (aluminum / polytetrafluoroethylene) metastable composite energetic materials have attracted industry attention due to their high reaction energy release and relatively stable reaction characteristics. On the one hand, the existing technology often introduces oxidants (such as AP, ammonium perchlorate, etc.) into the composite material system to solve the problems of multiple reaction residues and high reaction threshold value, but this means introduces nitrogen elements into the composite material system, which inevitably produces environmentally unfriendly gases such as NO2 and NO after the reaction ends. On the other hand, traditional single-base and double-base energetic materials also inevitably contain elements such as S and N, which also require special attention to environmental protection during production and use, resulting in restrictions on the development of batch preparation processes. In addition, there is still a lack of flexible and personalized means to meet the growing demand for customized preparation processes in the industry. SUMMARY

[0003] In view of this, the embodiments of the application provide Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free quaternary energetic materials based on an additive manufacturing technology and a preparation method and application thereof. On the basis of the traditional Al / PTFE system, Mg and Fe2O3 are introduced. The ignition temperature of Mg is lower, and it is added to the system to reduce the overall reaction temperature of the energetic material and reduce the remaining combustion residues. The addition of Fe2O3 introduces oxygen elements into the system, reduces carbon residues, and improves energy utilization and gas production. The entire system focuses on green environmental protection, and compared with traditional nitrogen-based energetic materials, the gases and residues produced by the system are more environmentally friendly. At the same time, the additive manufacturing technology (also known as 3D printing technology) is used in combination with a special processing and molding process to generate sulfur-free and nitrogen-free quaternary energetic materials to ensure further optimization of the combustion performance of the energetic materials and personalized customization requirements.

[0004] In a first aspect, the application provides a preparation method of a metastable quaternary energetic material without sulfur and nitrogen, comprising the following specific steps: S1: preparing a concentrated solution of metal oxide and a PTFE polymer solution in advance, adding the concentrated solution of iron metal oxide into the PTFE polymer solution in batches, and obtaining Fe2O3 / PTFE oxide slurry through heating and stirring; S2: blending nano-aluminum powder, nano-magnesium powder and PTFE powder, and then adding the high molecular binder prepared in advance into a sufficient amount of organic solvent after ultrasonic treatment, fully dissolving, stirring and heating and evaporating to obtain Al / Mg / PTFE metastable composite slurry with adjusted viscosity; S3: blending the Fe2O3 / PTFE oxide slurry obtained in S1 and the Al / Mg / PTFE metastable composite slurry obtained in S2 according to a certain proportion, and stirring to obtain Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry; and S4: adding the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry obtained in S3 into a 3D printer cartridge, adjusting the equipment parameters, and processing to obtain an Al / Mg / PTFE / Fe2O3 metastable quaternary energetic material based on additive manufacturing technology.

[0005] Optionally, S1 specifically comprises: S11: dissolving micron-sized Fe2O3 powder in a sufficient amount of ethyl acetate, heating and stirring until fully dissolved, and then cooling to room temperature to obtain a concentrated solution of metal oxide; S12: dissolving PTFE powder in a sufficient amount of ethyl acetate, and fully stirring to obtain a polymer solution; and S13: adding the concentrated solution of iron metal oxide prepared in S11 into the polymer solution prepared in S12 in batches, gradually volatilizing the solvent through heating and stirring to control the overall viscosity of the mixed solution, and obtaining Fe2O3 / PTFE oxide slurry.

[0006] Optionally, in S11, the particle size of the micron-sized Fe2O3 is 100 μm, the heating temperature is 40-50℃, and the stirring rate is 30-45 r / min; and in S13, the heating is to raise the temperature from room temperature to 40℃ at a speed of 1.6℃ / min, and the stirring rate is 40 r / min.

[0007] Optionally, S21: fully dissolving fluoro rubber in ethyl acetate with a mass of 5 times that of the fluoro rubber to obtain a high molecular binder; S22: blending nano-aluminum powder, nano-magnesium powder and PTFE powder, and then obtaining metastable mixed powder through ultrasonic treatment; and S23: adding the metastable mixed powder obtained in S22 and the high molecular binder obtained in S21 into a sufficient amount of organic solvent, fully dissolving, stirring and heating and evaporating to obtain Al / Mg / PTFE metastable composite slurry with adjusted viscosity.

[0008] Optionally, in S22, the particle size of the nano-aluminum powder and the nano-magnesium powder is 50 nm, and the ultrasonic treatment time is 3-5 h.

[0009] Optionally, in S23, the organic solvent is ethyl acetate, the stirring is mechanical stirring, the stirring rate is 40-60 r / min, and the cut-off temperature of the heating evaporation is 60-80 DEG C.

[0010] Optionally, in S3, the mixing ratio of the Fe2O3 / PTFE oxide slurry and the Al / Mg / PTFE metastable composite slurry is 2:1, and the stirring rate is 25 r / min.

[0011] Optionally, in S4, the adjusting the equipment parameters comprises setting the feeding speed of the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry to 15-30 mm / s and the extrusion speed to 9-18 mm / s.

[0012] In a second aspect, the application provides an Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material prepared by the method.

[0013] In a third aspect, the application provides an application of the metastable Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material in the field of energetic materials.

[0014] The application has the following advantages: (1) The application establishes an Al / Mg / PTFE / Fe2O3 quaternary system, which is sulfur-free and nitrogen-free, and does not produce environmentally unfriendly gases after combustion, and is more focused on production cost and ecological impact while taking into account sample performance.

[0015] (2) Fe2O3 can introduce oxygen into the system during the reaction, and can react with the carbon residue of Al / PTFE to generate CO, CO2 and other products, and by adding nano-Mg powder to the original system, the reaction temperature and reaction heat of the system are reduced, effectively improving the defects and deficiencies of Al / PTFE, and significantly improving the performance of the entire energetic material system.

[0016] (3) The use of additive manufacturing technology provides a reasonable and feasible process for sample structure formation, and the preparation process is simple and easy to operate, and industrialized mass production is possible.

[0017] Therefore, the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic material based on additive manufacturing technology has potential application prospects in the field of energetic materials.

[0018] In addition, additional advantages, objects, and features of the present application 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 can be learned from practice of the present application. The objectives and other advantages of the present application can be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.

[0019] It will be understood by those within the art that the objects and advantages of the present application can be met by the specific embodiments described below, and that the present application can be achieved with the following detailed description. BRIEF DESCRIPTION OF DRAWINGS

[0020] The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description, serve to explain the principles of the application.

[0021] Figure 1 Preparation flow chart of the metastable quaternary energetic material without sulfur and nitrogen in the embodiment of the present application; Figure 2 TG-DSC curve of the metastable quaternary energetic material without sulfur and nitrogen in the embodiment of the present application; Figure 3 TG-DSC curves of the quaternary energetic material under different Al / Mg ratios in the embodiment of the present application; Figure 4 Thermogravimetric curve, differential-thermogravimetric curve and Gram-Schmidt curve of the metastable quaternary energetic material without sulfur and nitrogen in the embodiment of the present application. DETAILED DESCRIPTION

[0022] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the embodiments and drawings. The schematic embodiments of the present application and the descriptions thereof are used to explain the present application, but are not used as limitations of the present application. It should be noted that, in order to avoid the present application being obscured by unnecessary details, only the structures and / or processes closely related to the solutions according to the present application are shown in the drawings, and other details not closely related to the present application are omitted.

[0023] It should be emphasized that the term "comprises / comprising" when used in this specification is taken to specify the presence of stated features, elements, or components, but does not preclude the presence or addition of one or more other features, elements, or components.

[0024] Combination Figure 1It can be known that the first aspect of the embodiment of the present application provides a preparation method of a non-sulfur and non-nitrogen metastable quaternary energetic material, comprising the following specific steps: S1: preparing a metal oxide concentrated solution and a PTFE polymer solution in advance, adding the iron metal oxide concentrated solution into the PTFE polymer solution in batches, and obtaining Fe2O3 / PTFE oxide slurry through heating and stirring; S2: blending nano-aluminum powder, nano-magnesium powder and PTFE powder, and after ultrasonic treatment, adding the high molecular binder prepared in advance into a sufficient amount of organic solvent to be fully dissolved, and then stirring and heating and evaporating to obtain Al / Mg / PTFE metastable composite slurry after adjusting the viscosity; S3: blending the Fe2O3 / PTFE oxide slurry obtained in S1 and the Al / Mg / PTFE metastable composite slurry obtained in S2 according to a certain proportion, and stirring to obtain Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry; S4: adding the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry obtained in S3 into a 3D printer barrel, adjusting the equipment parameters, and processing to obtain an Al / Mg / PTFE / Fe2O3 non-sulfur and non-nitrogen metastable quaternary energetic material based on additive manufacturing technology.

[0025] Optionally, S1 specifically comprises: S11: dissolving micron-grade Fe2O3 powder in a sufficient amount of ethyl acetate, cooling to room temperature after heating and stirring to be fully dissolved to obtain a metal oxide concentrated solution; S12: dissolving PTFE powder in a sufficient amount of ethyl acetate, and fully stirring to obtain a polymer solution; S13: adding the iron metal oxide concentrated solution prepared in S11 into the polymer solution prepared in S12 in batches, gradually volatilizing the solvent through heating and stirring to control the overall viscosity of the mixed solution, and obtaining Fe2O3 / PTFE oxide slurry.

[0026] Optionally, in S11, the particle size of micron-grade Fe2O3 is 100 μm, the heating temperature is 40-50℃, and the stirring rate is 30-45 r / min; in S13, the heating is to raise the temperature from room temperature to 40℃ at a speed of 1.6℃ / min, and the stirring rate is 40 r / min.

[0027] Optionally, S21: fully dissolving fluoro rubber in ethyl acetate with a mass of 5 times that of the fluoro rubber to obtain a high molecular adhesive; S22: blending nano-aluminum powder, nano-magnesium powder and PTFE powder, and obtaining metastable mixed powder after ultrasonic treatment; S23: adding the metastable mixed powder obtained in S22 and the high molecular adhesive obtained in S21 into a sufficient amount of organic solvent to be fully dissolved, and then stirring and heating and evaporating to obtain Al / Mg / PTFE metastable composite slurry after adjusting the viscosity.

[0028] Optionally, in S22: the particle size of nano-aluminum powder and nano-magnesium powder is 50 nm, and the ultrasonic treatment time is 3-5 h.

[0029] Optionally, in S23: the organic solvent is ethyl acetate, the stirring is mechanical stirring, the stirring rate is 40-60 r / min, and the cut-off temperature of the heating evaporation is 60-80℃.

[0030] Optionally, in S3: the mixing ratio of the Fe2O3 / PTFE oxide slurry and the Al / Mg / PTFE metastable composite slurry is 2:1, and the stirring rate is 25 r / min.

[0031] Optionally, in S4: the adjusting the equipment parameters comprises setting the feeding speed of the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry to 15-30 mm / s and the extrusion speed to 9-18 mm / s.

[0032] In a second aspect of the embodiment, an Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material prepared according to the preparation method is provided. Figure 2 、 3 Fig. 2 shows the TG-DSC curves of the Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material and the TG-DSC curves of the Al / Mg / PTFE / Fe2O3 quaternary energetic material with different Al / Mg ratios in the embodiment. Specifically, Figure 3 Fig. 2 shows the TG-DSC curves of the Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material and the TG-DSC curves of the Al / Mg / PTFE / Fe2O3 quaternary energetic material with different Al / Mg ratios in the embodiment. Specifically,

[0033] In a third aspect of the embodiment, the Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material is applied in the field of energetic materials.

[0034] The application will be further described in detail below through specific implementation examples. The following examples are only descriptive and not limiting, and cannot limit the protection scope of the application.

[0035] Example 1 First, Fe2O3 / PTFE oxide slurry was prepared. Fe2O3 powder with a particle size of 100 μm was dissolved in sufficient ethyl acetate, heated at 40℃, and stirred at a speed of 30 r / min until completely dissolved, and then cooled to room temperature to obtain a concentrated solution of iron metal oxide; PTFE powder was dissolved in sufficient solvent and stirred to obtain a polymer solution; the prepared concentrated solution of iron metal oxide was added to the prepared polymer solution in batches, heated to 40℃ at a heating rate of 1.6℃ / min, and stirred at a speed of 40 r / min to gradually evaporate the solvent to control the overall viscosity of the mixed solution, to obtain Fe2O3 / PTFE oxide slurry.

[0036] Then, Al / Mg / PTFE metastable composite slurry was prepared. Fluoro rubber F2311 was dissolved in five times its mass of ethyl acetate to obtain a high molecular adhesive; nano-aluminum powder and nano-magnesium powder with a particle size of 50 nm were blended with PTFE powder, and after ultrasonic treatment for 3 hours, metastable mixed powder was obtained; the prepared high molecular adhesive and metastable mixed powder were added to sufficient ethyl acetate and dissolved, and mechanically stirred at a speed of 40 r / min and heated to 60℃ to evaporate continuously, to obtain Al / Mg / PTFE metastable composite slurry with adjusted viscosity.

[0037] Then, the prepared Fe2O3 / PTFE oxide slurry and the prepared Al / Mg / PTFE metastable composite slurry were blended at a ratio of 2:1, and stirred to obtain a quaternary energetic slurry; Finally, the prepared quaternary energetic slurry was added to the 3D printer cartridge, and the 3D printer equipment parameters were adjusted to a feeding speed of 15 mm / s and an extrusion speed of 9 mm / s, and a quaternary energetic material based on additive manufacturing technology was processed, which was sulfur-free and nitrogen-free Al / Mg / PTFE / Fe2O3.

[0038] Example 2 Firstly, Fe2O3 / PTFE oxide slurry. Fe2O3 powder with a particle size of 100 μm is dissolved in sufficient ethyl acetate, heated at 45℃, stirred at a speed of 40 r / min until fully dissolved, and then cooled to room temperature to obtain a concentrated iron metal oxide solution; PTFE powder is dissolved in sufficient solvent, and the mixture is stirred to obtain a polymer solution; the prepared concentrated iron metal oxide solution is added to the prepared polymer solution in batches, heated at a heating rate of 1.6℃ / min to 40℃, and stirred at a speed of 40 r / min to gradually evaporate the solvent to control the overall viscosity of the mixed solution, thereby obtaining Fe2O3 / PTFE oxide slurry.

[0039] Then, Al / Mg / PTFE metastable composite slurry is prepared. Fluoro rubber F2311 is fully dissolved in ethyl acetate with a mass of five times that of the fluoro rubber F2311 to obtain a high polymer adhesive; nano-aluminum powder and nano-magnesium powder with a particle size of 50 nm are blended with PTFE powder, and the mixture is subjected to ultrasonic treatment for 4 hours to obtain a metastable mixed powder; the prepared high polymer adhesive and the prepared metastable mixed powder are added to sufficient ethyl acetate and fully dissolved, and then mechanically stirred at a speed of 50 r / min and heated to 70℃ to evaporate, thereby obtaining Al / Mg / PTFE metastable composite slurry with adjusted viscosity.

[0040] After that, the prepared Fe2O3 / PTFE oxide slurry and the prepared Al / Mg / PTFE metastable composite slurry are blended at a ratio of 2:1, and a quaternary energetic slurry is obtained by stirring; Finally, the prepared quaternary energetic slurry is added to a 3D printer cartridge, and the device parameters of the 3D printer are adjusted to a feeding speed of 25 mm / s and an extrusion speed of 12 mm / s, and a quaternary energetic material based on additive manufacturing technology is obtained.

[0041] Example 3 Firstly, Fe2O3 / PTFE oxide slurry is prepared. Fe2O3 powder with a particle size of 100 μm is dissolved in sufficient ethyl acetate, heated at 45℃, stirred at a speed of 40 r / min until fully dissolved, and then cooled to room temperature to obtain a concentrated iron metal oxide solution; PTFE powder is dissolved in sufficient solvent, and the mixture is stirred to obtain a polymer solution; the prepared concentrated iron metal oxide solution is added to the prepared polymer solution in batches, heated at a heating rate of 1.6℃ / min to 40℃, and stirred at a speed of 40 r / min to gradually evaporate the solvent to control the overall viscosity of the mixed solution, thereby obtaining Fe2O3 / PTFE oxide slurry.

[0042] Then, the Al / Mg / PTFE metastable composite slurry is prepared. Fluorine rubber F2311 is fully dissolved in ethyl acetate with a mass of five times itself to obtain a polymer adhesive; nano-aluminum powder and nano-magnesium powder with a particle size of 50 nm are blended with PTFE powder, and a metastable mixed powder is obtained after ultrasonic treatment for 4 hours; the polymer adhesive prepared above and the metastable mixed powder prepared above are added to a sufficient amount of ethyl acetate and fully dissolved, and then mechanically stirred at a speed of 60 r / min and evaporated by heating to 80°C, to obtain the Al / Mg / PTFE metastable composite slurry after adjusting the viscosity.

[0043] Then, the Fe2O3 / PTFE oxide slurry prepared above and the Al / Mg / PTFE metastable composite slurry prepared above are blended at a ratio of 2:1, and a quaternary energetic slurry is obtained by stirring; Finally, the prepared quaternary energetic slurry is added to the 3D printer barrel, and the 3D printer equipment parameters are adjusted to a feeding speed of 30 mm / s and an extrusion speed of 18 mm / s, and a quaternary energetic material based on additive manufacturing technology is obtained.

[0044] Comparative Example The Al / PTFE binary energetic material is prepared by using a traditional sintering process. Seven parts of nano-aluminum powder and three parts of PTFE powder are blended at room temperature to obtain a composite powder, and the obtained composite powder is pressed to obtain a pressed state energetic grain column. Then, the pressed state energetic grain column is placed in an environment at about 300°C for sintering and molded, and a sintered Al / PTFE mixed energetic grain column is formed after cooling.

[0045] Table 1: Comparison table of performance test of sulfur-free and nitrogen-free quaternary Al / Mg / PTFE / Fe2O3 energetic material As can be seen from Table 1, the above Example 3 is a preferred scheme. After introducing Fe2O3 and Mg powder into the Al / PTFE system, the pre-ignition reaction temperature is reduced, and the gas production and explosion pressure of the system are improved, which shows that the addition of Mg powder effectively reduces the initial threshold of the reaction, Fe2O3 introduces oxygen elements, and can react with the carbon residue in the original system for secondary energy release, further improving the combustion performance of the system. Figure 4The thermal gravimetric curve, the differential-thermal gravimetric curve and the Gram-Schmidt curve of the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic material prepared in the embodiment of the present application are shown in the figure. It can be obviously seen that the thermal gravimetric starting temperature is 533 DEG C, at this time, the absolute value of the differential thermal gravimetric value increases obviously, the FTFE starts to decompose, and the GS curve also shows an obvious turning point. The PTFE starts to decompose, and it can be seen from the thermal gravimetric-infrared three-dimensional spectrogram test result that an obvious absorption peak appears at 533 DEG C, and the gas generation amount reaches the maximum at 620 DEG C.

[0046] In addition, the metastable Al / Mg / PTFE / Fe2O3 quaternary energetic material prepared in the present application meets the requirements of stable combustion performance, high gas production and high efficient energy release, and has certain application value and prospect.

[0047] It should be noted that the present application is not limited to the specific configurations and processes described above and shown in the figures. For the sake of brevity, detailed descriptions of well-known methods are omitted here. In the above embodiments, several specific steps are described and shown as examples. However, the method process of the present application is not limited to the specific steps described and shown, and those skilled in the art can make various changes, modifications and additions, or change the order of the steps, after understanding the spirit of the present application.

[0048] In the present application, the features described and / or exemplified for one embodiment can be used in the same way or in a similar way in one or more other embodiments, and / or in combination with or instead of the features of other embodiments.

[0049] The above specific description further details the purpose, technical solution and beneficial effects of the present application. It should be understood that the above description is only for specific embodiments of the present application and is not used to limit the protection scope of the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims

1. A method for preparing a sulfur-free and nitrogen-free metastable quaternary energetic material based on additive manufacturing technology, characterized in that, The specific steps include the following: S1: Prepare a concentrated solution of metal oxide and a PTFE polymer solution in advance. Add the concentrated solution of iron metal oxide to the PTFE polymer solution in batches. After heating and stirring, obtain Fe2O3 / PTFE oxide slurry. S2: Nano aluminum powder, nano magnesium powder and PTFE powder are blended together, ultrasonically treated, and then added together with the pre-prepared polymer binder into a sufficient amount of organic solvent to fully dissolve. After stirring and heating to evaporate, Al / Mg / PTFE metastable composite slurry with adjusted viscosity is obtained. S3: The Fe2O3 / PTFE oxide slurry obtained in S1 and the Al / Mg / PTFE metastable composite slurry obtained in S2 are mixed in a certain proportion and stirred to obtain Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry; S4: Add the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry obtained in S3 into the barrel of the 3D printer, adjust the equipment parameters, and process it to obtain the Al / Mg / PTFE / Fe2O3 sulfur-free and nitrogen-free metastable quaternary energetic material based on additive manufacturing technology.

2. The preparation method according to claim 1, characterized in that, S1 specifically includes: S11: Dissolve micron-sized Fe2O3 powder in sufficient ethyl acetate, heat and stir until fully dissolved, then cool to room temperature to obtain a concentrated solution of metal oxide; S12: Dissolve PTFE powder in sufficient ethyl acetate and stir thoroughly to obtain a polymer solution; S13: The concentrated iron metal oxide solution prepared in S11 is added in batches to the polymer solution prepared in S12. The solvent is gradually evaporated by heating and stirring to control the overall viscosity of the mixed solution, thus obtaining Fe2O3 / PTFE oxide slurry.

3. The preparation method according to claim 2, characterized in that: The micron-sized Fe2O3 in S11 has a particle size of 100 μm, the heating temperature is 40-50℃, and the stirring rate is 30-45 r / min; The heating described in S13 is to raise the temperature from room temperature to 40°C at a rate of 1.6°C / min, and the stirring rate is 40 r / min.

4. The preparation method according to claim 1, characterized in that, S2 specifically includes: S21: Dissolve fluororubber fully in 5 times its own weight of ethyl acetate to obtain a polymer adhesive; S22: Nano-aluminum powder, nano-magnesium powder and PTFE powder are blended together and ultrasonically treated to obtain metastable mixed powder; S23: The metastable mixed powder obtained in S22 and the polymer binder obtained in S21 are added together to a sufficient amount of organic solvent and fully dissolved. After stirring and heating to evaporate, the viscosity-adjusted Al / Mg / PTFE metastable composite slurry is obtained.

5. The preparation method according to claim 4, characterized in that, In S22: The nano-aluminum powder and nano-magnesium powder have a particle size of 50 nm, and the ultrasonic treatment time is 3-5 hours.

6. The preparation method according to claim 5, characterized in that, In S23: The organic solvent is ethyl acetate, the stirring is mechanical stirring at a rate of 40-60 r / min, and the evaporation cutoff temperature is 60-80℃.

7. The preparation method according to claim 1, characterized in that, In S3: The Fe2O3 / PTFE oxide slurry and the Al / Mg / PTFE metastable composite slurry are mixed in a ratio of 2:1, and the stirring speed is 25 r / min.

8. The preparation method according to claim 1, characterized in that, In S4: The adjustment of equipment parameters includes setting the feeding rate of the Al / Mg / PTFE / Fe2O3 metastable quaternary energetic slurry to 15-30 mm / s and the extrusion speed to 9-18 mm / s.

9. A sulfur- and nitrogen-free metastable quaternary energetic material of Al / Mg / PTFE / Fe2O3 based on additive manufacturing technology, prepared by the preparation method according to any one of claims 1-8.

10. The application of the sulfur- and nitrogen-free metastable quaternary energetic material Al / Mg / PTFE / Fe2O3 based on additive manufacturing technology according to claim 9 in the field of energetic materials.

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