Tandem metastable quaternary energetic material as well as preparation method and application thereof

Abstract

The invention provides a tandem type metastable-state quaternary energetic material and a preparation method and application thereof, and the preparation method comprises the following steps: preparing a low-ignition high-oxygen-release front grain by using KMnO4 / Al energetic slurry prepared in advance through an additive manufacturing technology, and preparing a high-energy main body reaction grain by using Fe2O3 / PTFE metastable-state polymer slurry prepared in advance; and the low-ignition high-oxygen-release front grain and the high-energy main body reaction grain are spliced in series according to a front-back space sequence to obtain the series-connection type metastable-state KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material. The tandem type metastable-state quaternary energetic material is simple in process and short in production period, individual forming requirements can be met, meanwhile, the combustion speed can be controlled, and the material system has more stable energy release.

Description

Technical Field

[0001] This invention belongs to the field of energetic materials technology, and relates to a series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material based on additive manufacturing technology, its preparation method and application. Background Technology

[0002] Al / PTFE (aluminum / polytetrafluoroethylene) metastable composites, as a special type of energetic material, have attracted widespread attention due to their high reactive energy release, relative stability, and safety. However, existing Al / PTFE systems still suffer from problems such as large amounts of residue after reaction and significant temperature differences between the initial and main reactions. Excessively high reaction thresholds limit their practical applications, resulting in relatively limited use of energetic materials in this system for actual production and manufacturing at present. Furthermore, given the differences in supporting equipment and application spaces, there is still a need for more refined and personalized molding and processing technologies for energetic materials to meet various customized requirements in industrial production. Summary of the Invention

[0003] Therefore, embodiments of the present invention provide a series-structured metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material based on additive manufacturing technology, its preparation method, and its applications. Based on the traditional Al / PTFE system, KMnO4 is introduced as an initiator and strong oxidant in the reaction linkage. Its reaction releases a large amount of heat energy, effectively reducing the overall reaction temperature of the energetic material and minimizing combustion residue. Simultaneously, additive manufacturing technology (also known as 3D printing technology) combined with a special processing and molding process is used to generate a series-structured quaternary energetic material, ensuring further optimization of the combustion performance of the energetic material and meeting personalized customization needs.

[0004] The first aspect of this invention provides a method for preparing a series-connected metastable quaternary energetic material, comprising the following specific steps: S1: mixing potassium permanganate powder and nano-aluminum powder to obtain a mixed powder, dissolving the obtained mixed powder fully with an organic solvent, adding a polymer binder, and mixing thoroughly by heating and stirring to obtain a KMnO4 / Al energetic slurry; S2: blending micron-sized ferric oxide powder and micron-sized polytetrafluoroethylene powder, adding an organic solvent, heating and stirring to obtain a mixed solution, adding a polymer binder for secondary blending to obtain a Fe2O3 / PTFE metastable polymer slurry; S3: separately... 1. The prepared KMnO4 / Al energetic slurry and the Fe2O3 / PTFE metastable polymer slurry prepared in S2 were added to a 3D printer. The 3D printer parameters were adjusted. The KMnO4 / Al energetic slurry was used to prepare a low-ignition, high-oxygen-release pre-particle column, and the Fe2O3 / PTFE metastable polymer slurry was used to prepare a high-energy host reaction column. S4: The low-ignition, high-oxygen-release pre-particle column and the high-energy host reaction column were spliced ​​in series in a front-to-back spatial order. The splicing surface was soaked with a polymer binder. After the structure stabilized, a series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material was obtained.

[0005] Optionally, S1 specifically includes: S11: Mixing 5 parts by weight of potassium permanganate powder and 1 part by weight of nano-aluminum powder by dry powder oscillation in a stirrer to obtain an energetic mixed powder; S12: Dissolving the energetic mixed powder obtained in S11 in acetone at 3 times its own weight to obtain an energetic mixed solution; S13: Using a concentrated solution of fluororubber dissolved in acetone as a polymer binder, adding the energetic mixed solution obtained in S12 to the above polymer binder at 5 times its own weight, heating and stirring at a constant speed until fully mixed to obtain a KMnO4 / Al energetic slurry.

[0006] Optionally, the particle size of the nano-aluminum powder mentioned in S11 is 100nm, and the dry powder is mixed by shaking for 2-3 hours; the heating temperature mentioned in S13 is 40-60℃, the stirring speed is 40r / min, and the mixing time is 3 hours.

[0007] Optionally, S2 specifically includes: S21: mixing micron-sized ferric oxide powder and micron-sized polytetrafluoroethylene powder in a ratio of 1.1-12 using ethyl acetate as an organic solvent, and heating and stirring are performed during the mixing process to obtain an energetic mixed solution; S22: using a concentrated solution obtained by dissolving fluororubber in ethyl acetate as a polymer binder; S23: adding the polymer binder obtained in S22 to the energetic mixed solution obtained in S21 for secondary mixing to obtain Fe2O3 / PTFE metastable polymer slurry.

[0008] Optionally, the particle size of both the micron-sized ferric oxide powder and the micron-sized polytetrafluoroethylene powder in S21 is 50 μm; the heating temperature is 30-50℃, the stirring rate is 40-50 r / min, and the stirring time is 4-5 hours.

[0009] Optionally, in S3, the 3D printer for preparing low-ignition, high-oxygen-release pre-powder and high-energy main reaction powder includes a barrel and a printing module; wherein the barrel is driven by a helical stepper motor and the printing module is driven by a torque converter electrode.

[0010] Optionally, when using KMnO4 / Al energetic slurry to prepare low-ignition, high-oxygen-release pre-particle columns, the feed parameters of the 3D printer barrel are set to 2000-4000 PPS, and the torque parameters of the printing module are set to 3000-5000 PPS. After printing, the printed low-ignition, high-oxygen-release pre-particle column is cooled at 40℃-50℃ for 3-4 hours. When using Fe2O3 / PTFE metastable polymer slurry to prepare high-energy bulk reaction columns, the feed parameters of the 3D printer barrel are set to 1500-2500 PPS, and the torque parameters of the printing module are set to 2000-2800 PPS.

[0011] Optionally, in S4, the polymeric adhesive is a concentrated solution of reactive polyurethane, the solvent used is ethyl acetate, the ratio of ethyl acetate to reactive polyurethane is 3:1, and the soaking time for the splicing surfaces is 12 hours.

[0012] In a second aspect, the present invention provides a tandem metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material prepared according to the preparation method described above.

[0013] A third aspect of the present invention provides an application of the aforementioned series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material in the field of energetic materials.

[0014] The beneficial effects of this invention are as follows: (1) The introduction of KMnO4 and Fe2O3 into the system increases the oxygen content. The excess oxygen can react with the carbon residue after Al / PTFE reaction to generate CO and CO2, which increases the gas production and heat release of the system, reduces the carbon residue after the reaction, effectively improves the defects and deficiencies of Al / PTFE, significantly improves the performance of the entire energetic material system, and improves the detonation level of the system.

[0015] (2) Through structural design, the quaternary structure is divided into two parts: a low-ignition, high-oxygen-release pre-charge and a high-energy main reaction charge. KMnO4 / Al is used as the pre-ignition charge, which has a low initial reaction temperature and is easy to ignite. After the reaction, it transfers heat and energy to the post-charge, causing a second-stage reaction and generating a detonation wave. This design avoids the technical difficulties of high ignition temperature and difficult ignition in traditional metastable systems.

[0016] (3) The use of additive manufacturing technology provides a reasonable and feasible process for the formation of a series structure. By constructing two parts of the drug column separately and then splicing them together with polyurethane adhesive, the two drug columns are processed into a series structure. The preparation process is simple and easy to operate, realizing the possibility of industrial mass production.

[0017] Therefore, the tandem metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic materials based on additive manufacturing technology have potential application prospects in the field of energetic materials.

[0018] Furthermore, additional advantages, objects, and features of the invention will be set forth in part in the description which follows, and will in part become apparent to those skilled in the art upon studying the text, or may be learned by practice of the invention. The objects and other advantages of the invention can be realized and obtained by means of the structures and methods specifically pointed out in the written description, the claims, and the accompanying drawings.

[0019] Those skilled in the art will understand that the objectives and advantages achievable with the present invention are not limited to those specifically described above, and that the above and other objectives achievable with the present invention will become clearer from the following detailed description. Attached Figure Description

[0020] The accompanying drawings, which are provided to further illustrate the invention and form part of this application, are not intended to limit the scope of the invention.

[0021] Figure 1 This is a flowchart illustrating the preparation process of a series-connected metastable quaternary energetic material in an embodiment of the present invention. Figure 2 This is a schematic diagram of the structure of the series-connected metastable quaternary energetic material in an embodiment of the present invention; Figure 3 This is a SEM microstructure test image of the series metastable quaternary energetic material in an embodiment of the present invention; Figure 4 This is a DSC thermodynamic test diagram of a series metastable quaternary energetic material in an embodiment of the present invention; Figure 5 This is a parameter test diagram of a series metastable quaternary energetic material gunpowder in an embodiment of the present invention. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of this invention are used to explain the invention, but are not intended to limit the invention. It should also be noted that, to avoid obscuring the invention with unnecessary details, only structures and / or processes closely related to the solutions according to the invention are shown in the accompanying drawings, while other details not closely related to the invention are omitted.

[0023] It should be emphasized that the term "including / comprises" as used herein refers to the presence of a feature, element, or component, but does not exclude the presence or addition of one or more other features, elements, or components.

[0024] Combination Figure 1 As can be seen, the first aspect of the present invention provides a method for preparing a series metastable quaternary energetic material, comprising the following specific steps: S1: potassium permanganate (KMnO4) powder and nano-aluminum powder (Al) are mixed to obtain a mixed powder. After the mixed powder is fully dissolved in an organic solvent, a polymer binder is added to it. After heating and stirring to fully mix, a KMnO4 / Al energetic slurry is obtained; S2: micron-sized ferric oxide (Fe2O3) powder and micron-sized polytetrafluoroethylene (PTFE) powder are blended. After adding an organic solvent, the mixture is heated and stirred to obtain a mixed solution. A polymer binder is added to it for secondary blending to obtain a Fe2O3 / PTFE metastable material. S3: The KMnO4 / Al energetic slurry prepared in S1 and the Fe2O3 / PTFE metastable polymer slurry prepared in S2 are added to a 3D printer. The 3D printer parameters are adjusted. The KMnO4 / Al energetic slurry is used to prepare a low-ignition, high-oxygen-release pre-particle column, and the Fe2O3 / PTFE metastable polymer slurry is used to prepare a high-energy host reaction column. S4: The low-ignition, high-oxygen-release pre-particle column and the high-energy host reaction column are spliced ​​in series in a front-to-back spatial order. The splicing surface is soaked with a polymer binder. After the structure stabilizes, a series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material is obtained. Figure 2 The figure shown is a schematic diagram of the structure of the series metastable quaternary energetic material prepared in an embodiment of the present invention.

[0025] Optionally, S1 specifically includes: S11: Mixing 5 parts by weight of potassium permanganate powder and 1 part by weight of nano-aluminum powder by dry powder oscillation in a stirrer to obtain an energetic mixed powder; S12: Dissolving the energetic mixed powder obtained in S11 in acetone at 3 times its own weight to obtain an energetic mixed solution; S13: Using a concentrated solution of fluororubber (F2311) dissolved in acetone as a polymer binder, adding the energetic mixed solution obtained in S12 to the above polymer binder at 5 times its own weight, heating and stirring at a constant speed until fully mixed to obtain a KMnO4 / Al energetic slurry.

[0026] Optionally, the nano-aluminum powder in S11 has a particle size of 100 nm, and the dry powder is mixed by shaking for 2-3 hours; the heating temperature in S13 is 40-60℃, the stirring speed is 40 r / min, and the mixing time is 3 hours.

[0027] Optionally, S2 specifically includes: S21: mixing micron-sized ferric oxide powder and micron-sized polytetrafluoroethylene powder in a ratio of 1.1-12 using ethyl acetate as an organic solvent, and heating and stirring are performed during the mixing process to obtain an energetic mixed solution; S22: using a concentrated solution obtained by dissolving fluororubber in ethyl acetate as a polymer binder; S23: adding the polymer binder obtained in S22 to the energetic mixed solution obtained in S21 for secondary mixing to obtain Fe2O3 / PTFE metastable polymer slurry.

[0028] Optionally, the particle size of both the micron-sized ferric oxide powder and the micron-sized polytetrafluoroethylene powder in S21 is 50 μm; the heating temperature is 30-50℃, the stirring rate is 40-50 r / min, and the stirring time is 4-5 hours.

[0029] Optionally, in S3, the 3D printer for preparing low-ignition, high-oxygen-release pre-powder and high-energy main reaction powder includes a barrel and a printing module; wherein the barrel is driven by a helical stepper motor and the printing module is driven by a torque converter electrode.

[0030] Optionally, when using KMnO4 / Al energetic slurry to prepare low-ignition, high-oxygen-release pre-particle columns, the feed parameters of the 3D printer barrel are set to 2000-4000 PPS, and the torque parameters of the printing module are set to 3000-5000 PPS. After printing, the printed low-ignition, high-oxygen-release pre-particle column is cooled at 40℃-50℃ for 3-4 hours. When using Fe2O3 / PTFE metastable polymer slurry to prepare high-energy bulk reaction columns, the feed parameters of the 3D printer barrel are set to 1500-2500 PPS, and the torque parameters of the printing module are set to 2000-2800 PPS.

[0031] Optionally, in S4, the polymeric adhesive is a concentrated solution of reactive polyurethane, the solvent used is ethyl acetate, the ratio of ethyl acetate to reactive polyurethane is 3:1, and the soaking time for the splicing surfaces is 12 hours.

[0032] A second aspect of this invention provides a tandem metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material prepared according to a preparation method. For example... Figure 3 The image shown is a SEM image of the tandem metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material in this embodiment.

[0033] Figure 4 The DSC thermodynamic test charts for different formulations in this embodiment are shown. The tests were conducted in a nitrogen atmosphere at a heating rate of 20℃ / min within the range of 30~1200℃. The reaction trends of the samples with Fe2O3:PTFE ratios of 1:1, 1:1.2, 1:1.4, 1:1.6, and 1:1.8 were basically consistent, with a significant exothermic peak appearing at around 494℃. This is attributed to the fluorination reaction between fluorine and alumina, which significantly increased both the onset temperature and the amount of heat released.

[0034] A third aspect of this invention provides an application of a series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material in the field of energetic materials.

[0035] The present invention will be further described in detail below through specific embodiments. The following embodiments are merely descriptive and not limiting, and should not be used to limit the scope of protection of the present invention.

[0036] Example 1 First, an energetic metal slurry was prepared. Five parts by weight of KMnO4 powder and one part by weight of Al powder with a particle size of 100 nm were mixed. After dry powder mixing with a stirrer for 2 hours, an energetic metal mixed powder was obtained. The obtained energetic metal mixed powder was added to acetone with a mass of three times its own weight. After the mixed powder was fully dissolved, an energetic metal mixed solution was obtained. Then, the prepared energetic metal mixed solution was added to a concentrated solution of fluororubber F2311 dissolved in acetone with a mass of five times its own weight. The heating temperature was adjusted to 40℃, and the mixture was stirred at a speed of 40 r / min for 3 hours. After being fully mixed, an energetic metal slurry was obtained.

[0037] The next step is to prepare a metastable polymer slurry. 50 μm micron-sized ferric oxide (Fe2O3) and micron-sized polytetrafluoroethylene (PTFE) are mixed in a 1:1 ratio with ethyl acetate and heated to 30 °C. The stirring rate is set to 40 r / min. After stirring for 4 hours, a concentrated solution of F2311 is added as a binder. After a second mixing, the metastable polymer slurry is obtained. Next, the preparation of the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column was carried out. The required 3D printer consisted of two modules: a barrel and a printing module, each with its own motor. The barrel module used a helical stepper motor, while the printing module used a torque rheostat motor. To obtain the two types of propellant columns, the 3D printer feed parameters for the low-ignition, high-oxygen-release pre-propellant column were set to 2000 PPS, and the torque parameter to 3000 PPS. After printing, it needed to be cooled at 40°C for 3 hours. For the high-energy main reactive column, the 3D printer feed parameters were set to 1500 PPS, and the torque parameter to 2000 PPS. After molding, the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column were obtained. Finally, the quaternary energetic material was prepared by splicing the low ignition and high oxygen release pre-propellant column and the high-energy main reactive column obtained above in sequence. Then, the joint was soaked with polyurethane polymer adhesive for 12 hours. After the structure stabilized, the metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material based on additive manufacturing technology was obtained.

[0038] Example 2 First, an energetic metal slurry was prepared. Five parts by weight of KMnO4 powder and one part by weight of Al powder with a particle size of 100 nm were mixed. After dry powder mixing with a stirrer for 2.5 h, an energetic metal mixed powder was obtained. The obtained energetic metal mixed powder was added to acetone with a mass of three times its own weight. After the mixed powder was fully dissolved, an energetic metal mixed solution was obtained. Then, the prepared energetic metal mixed solution was added to a concentrated solution of fluororubber F2311 dissolved in acetone with a mass of five times its own weight. The heating temperature was adjusted to 50℃, and the mixture was stirred at a speed of 40 r / min for 3 h. After being fully mixed, an energetic metal slurry was obtained.

[0039] The next step is to prepare a metastable polymer slurry. Ferric oxide (Fe2O3) with a micron-sized particle size of 50 μm and micron-sized polytetrafluoroethylene (PTFE) are mixed with ethyl acetate at a ratio of 1:1.5 and heated to 40°C. The stirring rate is set to 45 r / min, and after stirring for 4.5 hours, a concentrated solution of F2311 is added as a binder. After a second mixing, the metastable polymer slurry is obtained. Next, the preparation of the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column was carried out. The required 3D printer consisted of two modules: a barrel and a printing module, each with its own motor. The barrel module used a helical stepper motor, while the printing module used a torque rheostat motor. To obtain the two types of propellant columns, the 3D printer feed parameters for the low-ignition, high-oxygen-release pre-propellant column were set to 3000 PPS, and the torque parameter to 4000 PPS. After printing, the column needed to be cooled at 45°C for 3.5 hours. For the high-energy main reactive column, the 3D printer feed parameters were set to 2000 PPS, and the torque parameter to 2500 PPS. After molding, the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column were obtained. Finally, the quaternary energetic material was prepared by splicing the low ignition and high oxygen release pre-propellant column and the high-energy main reactive column obtained above in sequence. Then, the joint was soaked with polyurethane polymer adhesive for 12 hours. After the structure stabilized, the metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material based on additive manufacturing technology was obtained.

[0040] Example 3 First, an energetic metal slurry was prepared. Five parts by weight of KMnO4 powder and one part by weight of Al powder with a particle size of 100 nm were mixed. After dry powder mixing with a stirrer for 3 hours, an energetic metal mixed powder was obtained. The obtained energetic metal mixed powder was added to acetone three times its own weight. After the mixed powder was fully dissolved, an energetic metal mixed solution was obtained. Then, the prepared energetic metal mixed solution was added to a concentrated solution of fluororubber F2311 dissolved in acetone five times its own weight. The heating temperature was adjusted to 60℃, and the mixture was stirred at a speed of 40 r / min for 3 hours. After being fully mixed, an energetic metal slurry was obtained.

[0041] The next step is to prepare a metastable polymer slurry. 50 μm micron-sized ferric oxide (Fe2O3) and micron-sized polytetrafluoroethylene (PTFE) are mixed with ethyl acetate in a 1:2 ratio and heated to 50 °C. The stirring rate is set to 50 r / min. After stirring for 5 hours, a concentrated solution of F2311 is added as a binder. After a second mixing, the metastable polymer slurry is obtained. Next, the preparation of the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column was carried out. The required 3D printer consisted of two modules: a barrel and a printing module, each with its own motor. The barrel module used a helical stepper motor, while the printing module used a torque rheostat motor. To obtain the two types of propellant columns, the 3D printer feed parameters for the low-ignition, high-oxygen-release pre-propellant column were set to 3000 PPS, and the torque parameter to 4000 PPS. After printing, the column needed to be cooled at 45°C for 3.5 hours. For the high-energy main reactive column, the 3D printer feed parameters were set to 2000 PPS, and the torque parameter to 2500 PPS. After molding, the low-ignition, high-oxygen-release pre-propellant column and the high-energy main reactive column were obtained. Finally, the quaternary energetic material was prepared by splicing the low ignition and high oxygen release pre-propellant column and the high-energy main reactive column obtained above in sequence. Then, the joint was soaked with polyurethane polymer adhesive for 12 hours. After the structure stabilized, the metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material based on additive manufacturing technology was obtained.

[0042] Comparative Example Al / PTFE binary metastable energetic materials were prepared using a traditional sintering process. The two powders (3:7 by mass) were blended at room temperature, pressed, sintered at approximately 300°C, molded, and cooled to obtain sintered Al / PTFE mixed energetic propellant columns. However, one drawback of this traditional process is the limited shape of the molds, making it impossible to fabricate more precise and complex structures. Furthermore, the processing equipment is large and costly. For example, existing methods cannot easily obtain the size-matched energetic slurry and spatially joined structures between propellant columns as described in the above embodiments.

[0043] Table 1: Performance Comparison of the Series-Type Metastable KMnO4 / Al / Fe2O3 / PTFE Quaternary Energetic Material of the Present Invention As can be seen from Table 1, Example 3 above is a preferred scheme. After introducing KMnO4 and Fe2O3, Al / PTFE improves energy release, reduces reaction residues, and lowers the initial threshold of the reaction. This indicates that the oxygen (O2) generated by the decomposition of KMnO4 can further react with the residues of the original system to improve the energy release of the reaction and maximize the efficient utilization of energy. The addition of Fe2O3 lowers the initial threshold of the chemical reaction, and the pre-ignition reaction can be carried out under lower conditions. Figure 5 The figure shows the test parameters of the tandem metastable quaternary energetic material propellant in this embodiment. It can be clearly seen from the figure that the comparative example uses a traditional Al / PTFE energetic material, while the embodiment uses a tandem metastable KMnO4 / Al / Fe2O4 propellant.3 / The PTFE quaternary energetic material of the present invention shows a significant increase in calorific value and combustion rate compared to the traditional formulation. Calorific value represents the energy contained in the energetic material. It has been verified that the quaternary energetic material of the present invention has an average performance index that is nearly 23% higher than that of the comparative example, showing a significant improvement effect.

[0044] Furthermore, the tandem metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material prepared by this invention meets the requirements of novel active energetic materials, and has the characteristics of low cost, easy production, high energy, and stable performance at room temperature.

[0045] It should be clarified that the present invention is not limited to the specific configurations and processes described above and shown in the figures. For the sake of brevity, detailed descriptions of 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 invention is not limited to the specific steps described and shown. Those skilled in the art can make various changes, modifications, and additions, or change the order of steps, after understanding the spirit of the present invention.

[0046] In this invention, features described and / or illustrated for one embodiment may be used in the same or similar manner in one or more other embodiments, and / or combined with or in place of features of other embodiments.

[0047] The above detailed description further illustrates the purpose, technical solution, and beneficial effects of the invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a series-connected metastable quaternary energetic material, characterized in that, The specific steps include the following: S1: Potassium permanganate powder and nano aluminum powder are mixed to obtain a mixed powder. After the mixed powder is fully dissolved in an organic solvent, a polymer binder is added to it. After heating and stirring to mix thoroughly, KMnO4 / Al energetic slurry is obtained. S2: Micron-sized ferric oxide powder and micron-sized polytetrafluoroethylene powder are mixed together, and after adding an organic solvent, the mixture is heated and stirred to obtain a mixed solution. Then, a polymer binder is added to the mixture for secondary blending to obtain Fe2O3 / PTFE metastable polymer slurry. S3: The KMnO4 / Al energetic slurry prepared in S1 and the Fe2O3 / PTFE metastable polymer slurry prepared in S2 were added to the 3D printer respectively. The 3D printer parameters were adjusted. The KMnO4 / Al energetic slurry was used to prepare a low ignition and high oxygen release pre-powder column, and the Fe2O3 / PTFE metastable polymer slurry was used to prepare a high-energy host reaction column. S4: The S3 low-ignition high-oxygen-release pre-propellant column and the high-energy main reaction column are spliced ​​in series in a front-to-back spatial order, and the splicing surface is soaked with a polymer adhesive. After the structure is stabilized, a series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material is obtained.

2. The preparation method according to claim 1, characterized in that, S1 specifically includes: S11: Mix 5 parts by weight of potassium permanganate powder and 1 part by weight of nano aluminum powder using a stirrer to obtain an energetic mixed powder. S12: Dissolve the energetic mixed powder obtained in S11 in acetone at a volume of 3 times its own mass to obtain an energetic mixed solution; S13: The concentrated solution obtained by dissolving fluororubber in acetone is used as a polymer binder. The energetic mixed solution obtained in S12 is added to the above polymer binder at a mass of 5 times its own. After heating and stirring at a constant speed until the mixture is homogeneous, KMnO4 / Al energetic slurry is obtained.

3. The preparation method according to claim 2, characterized in that: The nano-aluminum powder described in S11 has a particle size of 100nm, and the dry powder is mixed by shaking for 2-3 hours. The heating temperature described in S13 is 40-60℃, the stirring speed is 40r / min, and the mixing time is 3h.

4. The preparation method according to claim 1, characterized in that, S2 specifically includes: S21: Micron-sized ferric oxide powder and micron-sized polytetrafluoroethylene powder are blended in a ratio of 1.1-12 using ethyl acetate as an organic solvent. During the blending process, heating and stirring are performed to obtain an energetic mixed solution. S22: A concentrated solution obtained by dissolving fluororubber in ethyl acetate is used as a polymeric binder; S23: The polymer binder obtained in S22 is added to the energetic mixed solution obtained in S21 for secondary blending to obtain Fe2O3 / PTFE metastable polymer slurry.

5. The preparation method according to claim 4, characterized in that: The particle size of both the micron-sized ferric oxide powder and the micron-sized polytetrafluoroethylene powder in S21 is 50 μm; the heating temperature is 30-50℃, the stirring rate is 40-50 r / min, and the stirring time is 4-5 hours.

6. The preparation method according to claim 1, characterized in that: In S3, the 3D printer for preparing low-ignition, high-oxygen-release pre-propellant columns and high-energy main reaction columns includes a barrel and a printing module; wherein, the barrel is driven by a helical stepper motor, and the printing module is driven by a torque converter electrode.

7. The preparation method according to claim 6, characterized in that: When using KMnO4 / Al energetic slurry to prepare low ignition high oxygen release pre-powder column, set the feeding parameters of the 3D printer barrel to 2000-4000PPS and the torque parameters of the printing module to 3000-5000PPS. After printing, cool the printed low ignition high oxygen release pre-powder column at 40℃-50℃ for 3-4 hours. When using Fe2O3 / PTFE metastable polymer slurry to prepare high-energy bulk reaction columns, the feed parameters of the 3D printer barrel are set to 1500-2500PPS, and the torque parameters of the printing module are set to 2000-2800PPS.

8. The preparation method according to claim 1, characterized in that: In S4, the polymeric adhesive is a concentrated solution of reactive polyurethane, the solvent used is ethyl acetate, the ratio of ethyl acetate to reactive polyurethane is 3:1, and the soaking time for the splicing surfaces is 12 hours.

9. A series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material prepared by the preparation method according to any one of claims 1-8.

10. The application of the series metastable KMnO4 / Al / Fe2O3 / PTFE quaternary energetic material according to claim 9 in the field of energetic materials.

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