Metal sphere filled energetic rotational cast body and forming method and applications

Abstract

The application provides a metal ball filled energetic rotary casting body and a forming method and application thereof. The preparation raw material of the metal ball filled energetic rotary casting body comprises metal balls, epoxy resin, energetic particles and a curing agent. The energetic particles comprise aluminum powder, a polytetrafluoroethylene layer coated on the surface of the aluminum powder and optionally a fluororubber layer coated on the surface of the polytetrafluoroethylene layer. The curing agent comprises a structural curing agent and an energetic curing agent. The structural curing agent comprises at least one of an alicyclic amine and an aromatic amine. The energetic curing agent comprises a polyether amine. The rotary casting body of the application has the advantages that the internal spherical fillers are uniformly and closely distributed, the resin curing shrinkage is low, the surface of the casting body is smooth, the internal porosity defects are few, the compressive strength is significantly improved, the types of the energetic materials are variable, the content of the energetic materials in the cylinder can be controlled and the rotary casting cylinder of the energetic materials has good mechanical properties.

Description

Technical Field

[0001] This invention belongs to the field of composite material structural and functional integrated component preparation, and particularly relates to an energetic rotary casting body filled with metal spheres, its molding method and application. Background Technology

[0002] In the field of modern equipment, structural materials are required to meet comprehensive performance requirements, including lightweight, high strength, and multifunctional integration. Cylindrical rotating bodies, as typical configurations of key components, directly impact the reliability and service effectiveness of the system. To endow such structures with special functions, introducing functional components into structural materials to achieve "structure-function" integration has become an important direction for technological development.

[0003] However, existing technologies still face many challenges in the preparation of energetic rotating cylinders. Traditional metal cylinders are mostly manufactured using "subtractive manufacturing" processes such as spinning, forging, and milling. The composition of the raw materials is fixed before processing, making it difficult to introduce reactive energetic materials during the forming process. Moreover, the high temperature and high pressure processing environment can easily induce the energetic components to release energy unexpectedly, posing serious safety hazards and making it difficult to achieve safe and controllable energeticization. In recent years, although some studies have attempted to introduce energetic materials into polymer-based composite systems, such as by alternately layering energetic thin layers with fiber prepregs, or by directly mixing energetic particles into the resin matrix and then molding them by winding or vacuum introduction, these methods still have significant drawbacks: on the one hand, the cohesive strength of the energetic layer itself is low, and it is prone to cracking or interlayer delamination under external load, resulting in a decrease in overall mechanical properties; on the other hand, since the density of energetic metal particles (such as aluminum, boron, etc.) is much higher than that of the resin matrix (usually 2–10 times), they are very prone to settling during casting and curing, resulting in uneven distribution of energetic components inside the cylinder. This not only weakens the uniformity and controllability of energy release, but also causes stress concentration due to local enrichment, further reducing the load-bearing capacity. In addition, high filler content can significantly change the rheological properties of the resin, causing air bubbles to be trapped during the casting process and forming internal pore defects. At the same time, the curing shrinkage rate of traditional epoxy systems is relatively high, which can easily cause problems such as surface depressions and microcracks. This makes the amount of energetic materials added strictly limited (usually the volume fraction is difficult to exceed 40%), which seriously restricts the energy release performance of the rotary cylinder.

[0004] Therefore, the rotary cylinders produced by existing technologies generally suffer from key problems such as uneven distribution of energetic components in the cylinder, limited addition amount, numerous internal pore defects, large curing shrinkage, poor surface quality, and insufficient cylinder compressive strength, making it difficult to meet the urgent needs of high-end equipment for high-performance integrated energetic structures. Summary of the Invention

[0005] The main objective of this invention is to provide an energetic rotary casting filled with metal spheres, a molding method therefor, and its application, aiming to solve the technical problems of uneven distribution of metal spheres due to sedimentation and low cohesive strength of energetic components in the preparation of energetic rotary cylinders in the prior art.

[0006] To achieve the above objectives, the present invention provides an energetic rotary casting body filled with metal spheres, wherein the raw materials for preparing the energetic rotary casting body filled with metal spheres include metal spheres, epoxy resin, energetic particles and curing agent;

[0007] The energetic particles include: aluminum powder, a polytetrafluoroethylene layer covering the surface of the aluminum powder, and a fluororubber layer covering the surface of the polytetrafluoroethylene layer.

[0008] The epoxy resin includes: structural epoxy resin and energetic epoxy resin;

[0009] The curing agent includes: structural curing agent and energetic curing agent;

[0010] The structural curing agent includes at least one of alicyclic amines and aromatic amines;

[0011] The energetic curing agent includes polyetheramine.

[0012] According to the first aspect of the present invention, at least the following beneficial effects are achieved:

[0013] This invention effectively solves key technical problems in existing energetic rotary casting bodies, such as low cohesive strength, uneven filler distribution, and limited energetic material addition, through the synergistic design of metal spheres, modified epoxy resin system, multilayer coated energetic particles, and composite curing agent. The epoxy resin combined with the structural curing agent significantly reduces resin curing shrinkage and minimizes microcracks and porosity defects while ensuring high crosslinking density and mechanical strength. Furthermore, the energetic particles employ a fluororubber layer coated on the surface of the polytetrafluoroethylene layer, which not only enhances energy output but also improves compatibility with the resin matrix through the fluororubber. The resulting energetic rotary casting body has a smooth surface, no visible internal defects, and a compressive strength of 81–83 MPa, achieving an integrated high-performance rotary casting cylinder with adjustable energetic material types, controllable content, and excellent mechanical properties.

[0014] In some embodiments, the epoxy resin includes: structural epoxy resin and energetic epoxy resin;

[0015] The structural epoxy resin includes alicyclic glycidyl ester type epoxy resin;

[0016] The energetic epoxy resin includes linear glycidyl ether type epoxy resin.

[0017] In some embodiments, the alicyclic amine includes IPDA.

[0018] In some embodiments, the aromatic amine includes at least one of DDM and DDS.

[0019] In some embodiments, the energetic curing agent includes at least one of D400, D2000, and T3000.

[0020] In some embodiments, the alicyclic glycidyl ester type epoxy resin includes at least one of E51 and TDE85.

[0021] In some embodiments, the linear glycidyl ether epoxy resin includes at least one of DER736 and DER732.

[0022] In some embodiments, the molar ratio of the energetic curing agent to the structural curing agent is 1:4 to 9.

[0023] In some embodiments, the molar ratio of the energetic curing agent to the structural curing agent is 1:4 to 7.

[0024] In some embodiments, the ratio of epoxy equivalent of the epoxy resin to active hydrogen equivalent of the curing agent is 0.95 to 1.05:1, and the number of carbon atoms derived from alicyclic or aromatic ring structures in the epoxy resin accounts for 10% to 20% of the total number of carbon atoms in the epoxy resin.

[0025] In some embodiments, the molar ratio of the structural resin to the energetic resin is 4 to 9:1.

[0026] In some embodiments, the molar ratio of the structural curing agent to the epoxy resin is 0.8 to 0.9:2.

[0027] In some embodiments, the molar ratio of the energetic curing agent to the epoxy resin is 0.2 to 0.1:2.

[0028] A structural resin component, wherein the main molecular chain of the structural resin component contains rigid structural units selected from six-membered alicyclic rings and / or benzene rings.

[0029] In some embodiments, the molecular backbone of the energetic resin contains ether bond structural units, and the oxygen element of the ether bond structure in the energetic resin component accounts for 8 to 11% of the molar proportion in the monomer.

[0030] In some embodiments, the oxygen element with an ether bond structure in the energetic curing agent component accounts for 7% to 12% of the molar percentage in the monomer.

[0031] In some embodiments, the ether-containing energetic binder further includes an additive, wherein the additive comprises a content greater than 0 and ≤5 wt%.

[0032] The additives include at least one of curing accelerators, anti-aging agents, and energetic diluents.

[0033] In some embodiments, the curing accelerator is selected from at least one of imidazole accelerators, phenolic accelerators, and substituted urea accelerators.

[0034] In some embodiments, the anti-aging agent is selected from at least one of antioxidants, ultraviolet absorbers, and light stabilizers.

[0035] In some embodiments, the energetic diluent is selected from at least one of azides, nitrates, and glycidyl ethers.

[0036] Furthermore, the ether-containing energetic binder also includes energetic particles, the content of which is greater than 0 and ≤20 wt%; the energetic particles include aluminum powder, a polytetrafluoroethylene layer coated on the surface of the aluminum powder, and a fluororubber layer coated on the surface of the polytetrafluoroethylene layer.

[0037] In some embodiments, the aluminum powder has a diameter of 100 nm to 10 μm, the PTFE particles have a diameter of 1 μm to 10 μm, and the fluororubber includes synthetic rubber produced by copolymerization of fluorinated olefin monomers;

[0038] The fluorinated olefin monomers include at least one of vinylidene fluoride, vinylidene fluoride, and trifluorochloroethylene.

[0039] In some embodiments, the mass percentage of fluororubber in the energetic particles is greater than 0 and ≤ 5 wt%.

[0040] In some implementations, the mass percentage of PTFE in the energetic particles is 1 to 10%.

[0041] The present invention also provides a method for forming an energetic rotary casting filled with metal spheres, comprising the following steps:

[0042] S1. After filling the cavity of the molding die with metal balls, vacuum the mold after filling.

[0043] S2. The structural epoxy resin, the energetic epoxy resin, the energetic particles and the energetic curing agent are mixed and pre-cured to obtain a mixed adhesive solution, which is then mixed with the structural curing agent to obtain a casting adhesive solution;

[0044] S3. After the casting adhesive is injected from the lower end cover of the mold, it is first preheated at 0.7 to 0.9 times the initial curing temperature for 30 to 90 minutes, then kept at the peak curing temperature until the degree of curing is ≥98%, and finally cured at the termination curing temperature for 60 to 90 minutes.

[0045] S4. After curing, cool and demold to obtain the energetic rotary casting filled with the metal spheres;

[0046] The structure of the molding die includes: an outer mold, a core column, an upper end cap, a lower end cap, and a limiting ring;

[0047] The outer mold is a cylindrical structure, and the core column is a cylinder coaxially arranged with the outer mold. A cavity is formed between the core column and the inner wall of the outer mold, and the cavity is used to fill metal balls.

[0048] The upper and lower end faces of the core column are respectively provided with circular protrusions for positioning; the upper and lower end faces of the core column are also respectively provided with 4 semi-circular groove diversion channels evenly distributed along the circumference, and the diversion channels of the upper end face and the lower end face are staggered by 40°~50° along the circumference.

[0049] The limiting ring is a ring-shaped component, coaxially nested between the core column and the outer mold. The lower end face of the limiting ring contacts the metal ball, and the upper end face of the limiting ring contacts the upper end cover. The inner side of the limiting ring forms an inner flow gap with the core column, and the outer side forms an outer flow gap with the outer mold.

[0050] The upper end cover has an overflow port at its center, and the lower end cover has an adhesive inlet at its center. The adhesive for pouring is injected from the adhesive inlet of the lower end cover, guided by the flow channel and the buffer tank, and synchronously fills the annular cavity from the outer flow gap before overflowing from the upper end cover.

[0051] The upper and lower end faces of the core column are respectively provided with circular protrusions for positioning; the upper and lower end faces of the core column are also respectively provided with 4 semi-circular groove diversion channels evenly distributed along the circumference, and the diversion channels of the upper end face and the lower end face are staggered by 45° along the circumference.

[0052] In this invention, the molding die solves the problems of filling uniformity, density, and structural integrity faced in the preparation of high-energy rotary castings by precisely controlling the flow through a limiting ring and guiding the flow through staggered channels. Specifically: 1. By precisely matching the area of ​​the limiting ring and the outer flow gap, the resin slurry is synchronously and uniformly filled in the annular cavity, thereby ensuring the stability and density of the metal ball arrangement; in traditional casting processes, when high-viscosity energetic slurry is injected into the annular cavity, it is easy to cause it to rise rapidly along one side due to the difference in flow resistance, resulting in the metal balls being washed away and displaced, locally accumulated, or voided, which seriously damages the structural uniformity. In this invention, a plastic limiting ring is set at the top between the core and the outer mold, and its inner side forms an inner flow gap with the core and its outer side forms an outer flow gap with the outer mold, respectively. This design ensures that the slurry is synchronously propelled upwards from both the inner and outer sides at almost the same flow rate, eliminating radial velocity differences and avoiding turbulence, air resistance, or flow deviation. This allows the metal balls to maintain a pre-set dense packing state throughout the injection process, significantly improving the spatial distribution uniformity and structural compactness of the filler, laying the foundation for high mechanical properties. 2. Through the synergistic flow channel system of the 45° staggered flow channel on the core column end face and the circumferential buffer groove, the slurry is guided to spirally impregnate, eliminating dead zones and reducing internal porosity defects. Even if synchronous ascent is achieved, if the slurry flows only along a single path, it is still difficult to fully impregnate the area near the core column axis or top, easily forming a "flow dead zone" and entraining gas. This invention features four circumferentially distributed semi-circular channel channels on the upper and lower end faces of the core column, with the channels on the upper and lower end faces staggered circumferentially by 45°. This allows the slurry to be propelled in a spiral motion within the annular cavity, extending the flow path and enhancing its penetration into the gaps between the metal balls. Simultaneously, each end face integrates an circumferential rectangular buffer groove, directly connected to the channel channels, serving to stabilize pressure, buffer, and homogenize the flow rate, effectively suppressing air bubble entrapment caused by injection impact. Furthermore, a central circular groove and radial semi-circular groove are added to the top of the core column, specifically for collecting and discharging residual gas and excess adhesive, ensuring a dense and defect-free top area. This multi-stage flow channel system works synergistically to significantly reduce internal porosity and improve the overall density and surface finish of the casting. 3. The micro-tapered core column and positioning boss design ensure smooth demolding and consistent wall thickness, indirectly improving the mechanical reliability of the product. In high-filling, high-crosslinking systems, difficulty in demolding can easily lead to surface tearing or internal micro-cracks, affecting compressive strength. This invention designs the core pillar with a slightly tapered structure (minimum 0.005mm) that is smaller at the top and larger at the bottom, and sets circular positioning bosses on the upper and lower end faces. This ensures that the core pillar and the outer mold are precisely coaxial during mold assembly, ensuring uniform wall thickness of the annular cavity, and facilitates ejection and demolding after curing, avoiding stress concentration or structural damage caused by forced disassembly. Although this detail is not a core flow control method, it plays an important supporting role in the dimensional accuracy and mechanical integrity of the final product.

[0053] In some embodiments, the area ratio of the outer flow gap to the area of ​​the inner flow gap is 0.5 to 1:1.

[0054] Under the above conditions, the flow imbalance problem caused by the asymmetry of the flow cross-section when filling high-viscosity energetic resin slurry in the cavity of the molding die is solved. When the gap area ratio is too high or too low, the slurry will preferentially pass through the side with less flow resistance (i.e., larger gap) quickly, causing the other side to be filled with lag or even have cavities, which in turn leads to defects such as metal ball distribution displacement, local dry areas or bubble retention. When the area of ​​the inner flow gap is larger than that of the outer flow gap, and the ratio of the area of ​​the outer flow gap to the area of ​​the inner flow gap is 0.5 to 1:1, it can be ensured that the slurry advances synchronously upward on both sides of the outer wall of the core column and the inner wall of the outer mold at basically the same flow rate, eliminating radial flow velocity gradients and avoiding turbulence, short-circuit flow or pressure accumulation, thereby achieving stable and uniform wetting of the metal ball bed. This structure not only ensures that the orderly and dense arrangement of metal balls in three-dimensional space is not disturbed, but also significantly improves the filling density of the resin between particles, reduces internal pores and interface defects, and ultimately enables the casting to obtain higher structural uniformity, surface smoothness and compressive strength.

[0055] In some embodiments, the diameter of the flow channel is 70% to 85% of the diameter of the metal ball.

[0056] In traditional processes, when a high-density metal ball filling is achieved within an annular cavity, the high-viscosity energetic slurry often struggles to fully penetrate the interparticle gaps, tending to flow along localized low-resistance paths. This results in insufficient filling in certain areas or uneven distribution of energetic particles, thus limiting the effective loading capacity of the energetic resin system. To address this, this invention precisely controls the diameter of the distribution channel to 70%–85% of the metal ball diameter. On one hand, because the distribution channel diameter is smaller than the metal ball diameter, leakage of the metal balls from the channel during filling or injection is effectively prevented, ensuring their stable arrangement within the cavity. On the other hand, this size still retains a sufficient flow cross-section, allowing the high-viscosity energetic slurry to smoothly penetrate the metal ball stack, achieving full and uniform wetting of the entire annular space. This not only avoids flow dead zones but also significantly increases the actual upper limit of the energetic particle-resin composite system, achieving synergistic optimization of higher energy density and mechanical properties while ensuring structural density.

[0057] In some embodiments, the upper and lower end faces of the core column are respectively provided with circumferential rectangular buffer grooves, the circumferential rectangular buffer grooves are connected to the semi-circular groove diversion channels on the corresponding end faces, and the groove depth and groove width of the circumferential rectangular buffer grooves are the same.

[0058] This design effectively solves the problems of impact, air entrapment, and uneven filling caused by sudden changes in flow rate or pressure concentration during the injection of high-viscosity energetic resin slurries. Specifically, when the slurry enters the lower end face area from the inlet, it first flows into a circumferential rectangular buffer tank. This tank acts as a temporary "pressure stabilizing chamber," buffering the initial injection impact, balancing the circumferential pressure, and smoothly distributing the slurry into four evenly distributed semi-circular channel channels, preventing excessively high local flow rates that could cause disturbance to the metal ball or air bubble entrainment. At the upper end face, the slurry flows spirally and then converges again into the buffer tank before being discharged through the overflow port. This helps release residual gas and accommodate excess adhesive, preventing air accumulation or bulging at the top. Since the buffer tank and the channel channels are completely consistent in depth and width, they form a seamless continuous flow channel system, ensuring consistent flow resistance and avoiding eddies or stagnation caused by sudden changes in cross-section. As a result, this structure significantly improves the filling stability and venting efficiency of the slurry in the annular cavity, effectively reduces internal porosity defects, and ensures the density and surface smoothness of the top and circumferential areas of the casting, providing key structural support for achieving highly uniform and high-strength energetic rotary castings.

[0059] In some embodiments, the core post is an integral cylinder tapered along the axial direction, with the smaller diameter end located at the upper end and the larger diameter end located at the lower end; the demolding taper of the core post satisfies the following range: 0.05° ≤ demolding taper ≤ ( ;

[0060] Where d is the diameter of the metal sphere and L is the axial length of the casting.

[0061] Under the above conditions, surface scratches, microcracks, and even structural damage to the product can be avoided due to excessive frictional resistance during demolding. Furthermore, the maximum taper ensures minimal axial gap variation in the annular filling cavity, maintaining uniform density and wall thickness of the metal spheres along the entire length, preventing localized accumulation or voids caused by excessive taper, which could affect the uniformity of energetic material distribution and mechanical properties. In addition, the tapered structure, wider at the bottom and narrower at the top, combined with positioning bosses on the upper and lower end faces, automatically guides the core pillar to center during mold assembly, further ensuring coaxiality. Therefore, this limited demolding taper not only significantly improves the demolding success rate in high-filling, high-bonding systems but also effectively maintains the accuracy of the rotary gating geometry and the symmetry of the internal structure, providing crucial structural assurance for obtaining energetic products with intact surfaces, high compressive strength, and stable performance.

[0062] In some embodiments, the inner wall of the outer mold is tapered axially, with the larger diameter end of the inner wall corresponding to the glue inlet end and the smaller diameter end corresponding to the glue outlet end. The taper angle is 0.05° ≤ demolding taper ≤ ( The taper of the outer mold is the same as the taper of the core column.

[0063] Under the above conditions, on the one hand, the inner wall of the outer mold has a micro-conical structure that is smaller at the top and larger at the bottom. This structure works in conjunction with the demolding taper of the core pillar to gradually narrow the cross-section of the annular cavity along the flow direction. This helps to maintain the stable advancement of the slurry front during the injection process and avoids "stuck cavities" at the top or excessive accumulation at the bottom due to the uniform diameter of the cavity. At the same time, this micro-conical structure can compensate for the volume shrinkage effect during the resin curing process, reducing defects such as internal stress concentration, interface debonding, or surface depression caused by uneven shrinkage. On the other hand, it ensures that the metal balls maintain a highly ordered and densely packed arrangement during filling and injection (avoiding ball slippage or local loosening due to excessive taper) and ensures that the wall thickness deviation of the final casting along the axial direction is minimal, meeting the requirements of geometric accuracy and uniform mass distribution for rotating bodies.

[0064] The present invention also provides the application of energetic rotary castings filled with metal spheres in industrial materials. Attached Figure Description

[0065] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0066] Figure 1 This is a schematic diagram of the rotary casting mold in the embodiment. Figure 1 (a) is a schematic cross-sectional view of the overall structure of the rotary casting mold; Figure 1 (b) is a schematic diagram of a rotary casting mold.

[0067] Figure 2 This is a schematic diagram of the core column of the rotary casting mold in the embodiment.

[0068] Figure 3 This is a schematic diagram showing the position of the limiting ring of the rotary casting mold in the embodiment. Figure 3 (a) is a schematic diagram of the end face structure of the molding die. Figure 3 (b) is a schematic diagram of the limiting ring structure.

[0069] Figure 4 This is a schematic diagram of the rotary casting body before and after grinding in Example 1. Figure 4 (a) is the rotary casting body before polishing. Figure 4 (b) is the polished rotary gating body.

[0070] Figure 5 This is a schematic diagram of the rotary casting body in Comparative Example 1.

[0071] Figure 6 This is a schematic diagram of the rotary casting body in Comparative Example 2.

[0072] Figure 7 This example illustrates the selection of the curing characteristic temperature on the variable-temperature DSC curve.

[0073] Figure 8 This is an example of a study on curing time in the embodiments.

[0074] Figure 9 The viscosity-time curve is an example from the embodiment.

[0075] Reference numerals: 01. Large-diameter interface; 02. Upper end cap; 03. Limiting ring; 04. Sample; 05. Core column; 06. Outer mold; 07. Lower end cap; 08. Small-diameter interface; 09. Sealing ring; 010. Fixing screw; 011. Upper guide tube; 012. Lower guide tube; 013. Throttling valve; 014. Positioning pin; 015. Semi-circular flow channel on the upper end face of the core column; 016. Semi-circular flow channel on the lower end face of the core column; 017. Top circular groove; 018. Core circumferential rectangular resin buffer tank; 019. Radial semi-circular flow channel; 20. Outer flow gap; 21. Inner flow gap;

[0076] The realization of the objective, functional characteristics and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0077] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0078] Furthermore, the technical solutions of the various embodiments of the present invention can be combined with each other, but only if they are based on the ability of those skilled in the art to implement them. When the combination of technical solutions is contradictory or cannot be implemented, it should be considered that such combination of technical solutions does not exist and is not within the scope of protection claimed by the present invention.

[0079] To further illustrate the present invention, the following examples are provided:

[0080] Example 1

[0081] This embodiment provides an energetic rotary casting filled with metal spheres and a molding method thereof, wherein a schematic diagram of the rotary casting mold in Embodiment 1 is shown below. Figure 1As shown, the components include: large-diameter interface 01, upper end cap 02, limiting ring 03, sample 04, core column 05, outer mold 06, lower end cap 07, small-diameter interface 08, sealing ring 09, fixing screw 010, upper guide pipe 011, lower guide pipe 012, and throttle valve 013. The inner diameter of the small end of the cast rotary cylinder is 23.4 mm, the outer diameter is 34.1 mm, the inner diameter of the large end is 25.1 mm, the outer diameter is 35.8 mm, the axial length of the cylinder is 88.0 mm, and the diameter of the metal ball is 2.5 mm. Therefore, the mold release angle is set to 1° (release taper ≤ 1°). ),in, Figure 1 (a) is a schematic cross-sectional view of the overall structure of the rotary casting mold; Figure 1 (b) is a schematic diagram of a rotary casting mold. The specific molding steps are as follows:

[0082] Mold preparation:

[0083] S1.1. Assemble all parts except the limiting ring and the upper end cap. Fill the gap between the core and the outer mold (the cavity of the molding die) with metal balls. A schematic diagram of the core of the rotary casting mold is shown below. Figure 2 In the core column, the upper and lower end faces are respectively provided with circular bosses for positioning. The upper and lower end faces of the core column are also respectively provided with four circumferentially distributed semi-circular channel channels, and the channel channels on the upper and lower end faces are staggered by 45° circumferentially. The semi-circular channel 015 on the upper end face of the core column, the semi-circular channel 016 on the lower end face of the core column, the top circular groove 017, the circumferential rectangular resin buffer groove 018, and the radial semi-circular channel 019 are also provided. A schematic diagram of the position of the limiting ring of the rotary casting mold in the embodiment is shown below. Figure 3 As shown, the components include a limiting ring 03, a core post 05, an outer mold 06, an outer flow gap 20, and an inner flow gap 21. Figure 3 (a) is a schematic diagram of the end face structure of the molding die. Figure 3 (b) is a schematic diagram of the limiting ring structure;

[0084] S1.2. When filling with metal balls, use a funnel slightly larger than the diameter of the metal balls to pour the balls evenly into the gap. The spatial arrangement of the metal ball filling material is a densely packed form of equal spheres. During the pouring process, use a tool to strike the outer mold in a circumferential and stable manner to provide a vibration frequency.

[0085] S1.3. When the spherical filling reaches the target height, assemble the limiting ring and the upper end cap. Then, assemble the small-diameter interface on the lower end cap of the mold and the large-diameter interface on the upper end cap, and adapt them to the guide pipes respectively. Before starting the pouring, seal the guide pipe connected to the bottom of the mold and connect the guide pipe connected to the top to the vacuum pump to extract the gas inside the mold and reduce the internal air pressure. Then, evacuate the forming mold and check the vacuum degree. If the vacuum degree is stable at -0.095MPa, turn off the vacuum pump. If the air pressure is still less than -0.095~0.1MPa after holding the pressure for 30 minutes, the mold is considered to have good airtightness and the subsequent pouring work can proceed. The diameter of the filling metal ball is 2.5mm, the diameter of the runner is 2mm, and the diameter of the runner is 80% of the diameter of the metal ball. The ratio of the area of ​​the outer flow gap to the area of ​​the inner flow gap is modified to 0.5:1. Figure 3 As shown;

[0086] S2.1. At room temperature, add the resins sequentially into the reactor in the order of energetic epoxy resin and structural epoxy resin, mix, and then apply vacuum until the absolute vacuum reaches 10. 2 Below Pa, mixed adhesive solution A is obtained, and mixed adhesive solution A is heated to 40~50℃ at a heating rate of less than 5℃ / min;

[0087] S2.2. Mix the mixed adhesive A with an energetic curing agent at a molar ratio of 40 to 7:1 at a temperature of 40 to 50°C, and add energetic particles. The mass ratio of energetic particles to mixed adhesive A is 1:4 to 19 to obtain mixed adhesive B.

[0088] S2.3. Pre-curing treatment is performed on mixed adhesive B to obtain mixed adhesive C. The pre-curing treatment conditions are: temperature of 80~200℃, time of 1~3h, the degree of curing of mixed adhesive C after the pre-curing treatment is required to be 5~30%, and after the pre-curing is completed, the mixed adhesive C is cooled to room temperature at a cooling rate of 2~5℃ / min.

[0089] S2.4. Before casting begins, mix the mixed adhesive C with the structural curing agent at room temperature, and obtain mixed adhesive D (adhesive for casting) after mixing.

[0090] S2.5. Perform differential scanning calorimetry (DSC) on the mixed adhesive solution D to measure the curing temperature and curing time. The curing temperature test procedure is as follows: 1) Use a differential scanning calorimeter to test the non-isothermal heat flow curves of the adhesive solution at different heating rates. The heating rates are set to 2 ℃ / min, 3 ℃ / min, 5 ℃ / min, 7 ℃ / min, and 10 ℃ / min, respectively. Sequentially obtain the initial curing temperature Ton, peak curing temperature Tpn, and final curing temperature Ten from each curve. The selection of the three curing characteristic temperatures on the heat flow curve refers to the test standard HB 7614-1998. An example curve is shown below. Figure 7 As shown, scatter plots of three characteristic curing temperatures corresponding to different heating rates were established. Then, extrapolation was used to perform linear fitting on the three characteristic curing temperature points at different heating rates to obtain the intercept values ​​on the y-axis, as shown below. Figure 8 As shown, these three intercept values ​​are recorded as the initial curing temperature To (60-110℃), peak curing temperature Tp (100-160℃), and final curing temperature Te (130-180℃) of the system; 2) The curing time test method is as follows: using the peak curing temperature of the mixed adhesive system as the ambient temperature, an isothermal DSC test is performed to obtain the time x (in min) when the adhesive reaches 98% curing degree; 3) The curing regime design scheme is as follows: using 0.7-0.9To as the preheating temperature, the temperature is maintained at the preheating temperature for 30-90 min; using Tp as the peak curing temperature, the temperature is maintained at the peak curing temperature for x-x+30 min; using Te as the post-curing temperature, the temperature is maintained at the post-curing temperature for 60-90 min;

[0091] S2.6. Take another mixed adhesive solution D and use a rheometer to measure the viscosity-time curve of the mixed adhesive solution at a preheating temperature (0.7-0.9 To) according to the Chinese chemical industry standard HG / T 6261-2023. An example curve is shown below. Figure 9 As shown, the time length (t1-t2) when the viscosity is below 800 mPa·s is taken as the reference value for the pouring time, and the actual pouring time should not exceed this time length;

[0092] S3.1. The mixed adhesive solution D (hereinafter referred to as energetic resin) after mixing treatment is injected into the mold through the guide tube. The flow rate of the energetic resin during casting is controlled by a throttle valve, and the flow rate is 45~60mm. 3 / s, the resin enters from the small-diameter interface of the lower end cap of the mold and pours into the entire internal molding space of the mold at a uniform flow rate, and then flows out from the large-diameter interface of the upper end cap. When the resin flows to the height of the guide tube of 50~80mm, the pouring ends, the throttle valve of the lower guide tube is closed, and the upper guide tube is connected to the atmospheric environment. Let it stand for 1~2 minutes to allow the air bubbles in the glue to be discharged.

[0093] S3.2. The oven is preheated to 0.9T1 before casting begins. After casting is completed, the mold containing the casting is placed in the oven and cured with energetic resin. The curing conditions include: preheating temperature set to 0.9T1 for 320 min; main curing temperature set to T2 for x min; post-curing temperature set to T3 for 60 min. After curing, the cured material is cooled to 70°C at a cooling rate of 10°C / min.

[0094] S4.1. Use an ejector tool to demold the product. The ejector tool mainly consists of a fixed block, an ejector shim, and an ejector sleeve. When demolding, first connect the fixed block to the end face of the outer mold, place the ejector shim on the top of the core, and use the ejector screw in the fixed block to eject downwards to the core. After the core is ejected, replace the ejector shim with the ejector sleeve, and use the ejector screw in the fixed block to eject downwards to the product.

[0095] S4.2. Grind the cast body after demolding. Use sandpaper with a grit ranging from 400 to 1500 grit, gradually increasing the grit until the cast body reaches the required dimensions. Compare the dimensions before and after grinding. Figure 4 (a) and Figure 4 As shown in (b).

[0096] Example 2

[0097] This embodiment provides an energetic rotary casting body filled with metal spheres and a molding method thereof. The inner diameter of the small end of the cast rotary cylinder is 23.4 mm, the outer diameter is 34.1 mm, the inner diameter is 25.1 mm, the outer diameter is 35.8 mm, the axial length of the cylinder is 88.0 mm, and the diameter of the metal spheres is 2.5 mm. Therefore, the mold release angle is set to 1°. The specific steps are as follows:

[0098] S1.1. Before assembling the molding die, apply release agent evenly to each component three times. Allow each layer to air dry naturally at room temperature (25℃) for 20 minutes. Finally, heat the mold to 120℃ in an oven at 3℃ / min and keep it at that temperature for 1 hour. After that, allow it to cool naturally to room temperature. First, assemble the lower end cap, core, and outer mold. After the metal ball filler is filled, assemble the limiting ring and then assemble the upper end cap to complete the assembly of all components of the molding die. Fill the gap between the core and the outer mold (the cavity of the molding die) with metal balls.

[0099] S1.2. When filling with metal balls, use a funnel slightly larger than the diameter of the metal balls to pour the balls evenly into the gap. The spatial arrangement of the metal ball filling material is a densely packed form of equal spheres. During the pouring process, use a tool to strike the outer mold in a circumferential and stable manner to provide a vibration frequency.

[0100] S1.3. When the metal spheres are filled to the target value, assemble the limiting ring and the upper end cap; then assemble the small-diameter interface on the lower end cap of the mold, and install the large-diameter interface on the upper end cap to adapt to the guide tubes respectively; connect the other end of the guide tube at the upper end cap to the vacuum pump, and use a throttle valve to lock and throttle the guide tube at the lower end cap. Then evacuate the molding mold and check the vacuum degree. The vacuum degree is considered to be good if it is stable between -0.095MPa and -0.1MPa, which meets the experimental requirements. Then proceed with the casting of the mixed adhesive D energetic resin.

[0101] S2.1. At room temperature, the energetic epoxy resin (polyethylene glycol diglycidyl ether DER736, whose monomers are shown in Formula I, 3≤n1<5) and the structural epoxy resin (E51, whose monomers are shown in Formula II) are added sequentially to the reactor. The molar ratio of the energetic epoxy resin to the structural epoxy resin is 1:1. After mixing, the mixture is evacuated until the absolute vacuum reaches 10. 2 Below Pa, mixed adhesive solution A is obtained, at which point the molar percentage of alicyclic (or benzene ring) carbon atoms in the mixed adhesive solution is 8.29%, and mixed adhesive solution A is heated to 40°C at a heating rate of less than 5°C / min;

[0102]

[0103] Formula I;

[0104]

[0105] Formula II;

[0106] S2.2. At a temperature of 40°C, the mixed adhesive A and the energetic curing agent (D400, whose molecular monomers are as shown in Formula III, 5≤n3≤7) are mixed at a molar ratio of 10:1. Then, energetic particles are added, with a mass ratio of energetic particles to mixed adhesive A of 1:9. After mixing, mixed adhesive B is obtained; and after mixing, vacuum treatment is performed until the absolute vacuum degree reaches below 102 Pa to obtain mixed adhesive B.

[0107]

[0108] Formula III;

[0109] S2.3. Pre-curing treatment is performed on mixed adhesive B to obtain mixed adhesive C. The pre-curing treatment conditions are: temperature of 100℃, time of 2h, the degree of curing of mixed adhesive C after the pre-curing treatment is required to be within the range of 20%, and after the pre-curing is completed, the mixed adhesive C is cooled to room temperature at a cooling rate of 10℃ / min so that the viscosity of mixed adhesive C is around 2800 mPa·s.

[0110] S2.4. Before casting begins, mix the mixed adhesive C with the structural curing agent (IPDA) at room temperature. The molar ratio of the structural curing agent to the mixed adhesive A is 4:10. After mixing, perform vacuum treatment until the absolute vacuum degree reaches below 102 Pa to obtain mixed adhesive D (adhesive for casting).

[0111] Steps S2.5 to S2.6 are the same as in Example 1;

[0112] S3.1. Casting the mixed adhesive D: The energetic resin containing metal particles, after being mixed and treated, is poured through a guide tube. The flow rate of the poured resin is controlled by a throttle valve and kept at 48 mm³ / s. The mixed adhesive D enters from the small-diameter (6 mm inner diameter) interface of the lower end cap of the mold and is poured into the entire internal molding space of the mold at a uniform flow rate. Then it flows out from the large-diameter (10 mm inner diameter) interface of the upper end cap. When the liquid level of the outflowing mixed adhesive D in the guide tube is 70 mm below the interface outlet, the casting is stopped. At the same time, the upper guide tube is connected to the atmosphere. Then, the lower guide tube is blocked by a throttle valve to complete the casting process and allow it to cure.

[0113] S3.2. Use an oven, preheat to 80℃, place the molding mold in the oven, and set the temperature and time to 80℃ / 30min-120℃ / 1h 30min-135℃ / 1h. After curing, perform oven cooling, cooling the cured material to 60℃ at a cooling rate of 10℃ / min.

[0114] S4.1. The product is demolded using an ejector fixture, which mainly consists of a fixed block, an ejector shim, and an ejector sleeve. The fixed block has two connecting screw holes and one ejector screw hole. First, the fixed block is connected to the end face of the outer mold. The ejector shim is placed on the top of the core pillar. Using the ejector screw in the fixed block, the core pillar is ejected downwards. After the core pillar is ejected, the ejector shim is replaced in the ejector sleeve, and the core pillar is ejected downwards to the finished product using the ejector screw in the fixed block.

[0115] S4.2. Grind the cast body after demolding. Use sandpaper with a grit of 400 to 1500 grit, gradually increasing the grit until the cast body reaches the qualified dimensions.

[0116] Comparative Example 1

[0117] This comparative example provides an energetic rotary casting filled with metal spheres and a molding method thereof. The difference between this comparative example and Example 1 is that: no top limiting ring is added, resulting in uneven distribution of the metal spheres within the rotary cylinder (e.g., Figure 5 As shown), specifically:

[0118] S1.1. Before assembling the molding die, apply release agent evenly to each component three times. Allow each layer to air dry naturally at room temperature (25℃) for 20 minutes. Finally, heat the mold to 120℃ in an oven at 3℃ / min and keep it at that temperature for 1 hour. After that, allow it to cool naturally to room temperature. First, assemble the lower end cap with the core and the outer mold. The upper end cap should be assembled after the metal ball filler is filled to complete the assembly of all components of the molding die. Fill the gap between the core and the outer mold (the cavity of the molding die) with metal balls.

[0119] S1.2. When filling with metal balls, use a funnel slightly larger than the diameter of the metal balls to pour the balls evenly into the gap. The spatial arrangement of the metal ball filling material is a densely packed form of equal spheres. During the pouring process, use a tool to strike the outer mold in a circumferential and stable manner to provide a vibration frequency.

[0120] S1.3. When the metal spheres are filled to the target value, assemble a small-diameter interface on the lower end cap of the mold and a large-diameter interface on the upper end cap to adapt to the guide tubes respectively; connect the other end of the guide tube on the upper end cap to a vacuum pump, and use a throttle valve to lock and throttle the guide tube on the lower end cap. Then evacuate the molding mold and check the vacuum degree. If the vacuum degree is stable between -0.095MPa and -0.1MPa, it is considered good and meets the experimental requirements. Then proceed with the casting of the mixed adhesive D energetic resin.

[0121] S2.1. At room temperature, add the energetic epoxy resin (polyethylene glycol diglycidyl ether DER736) and the structural epoxy resin (E51) sequentially into the reactor. The molar ratio of the energetic epoxy resin to the structural epoxy resin is 1:1. After mixing, apply vacuum until the absolute vacuum reaches 10. 2 Below Pa, mixed adhesive solution A is obtained, at which point the molar percentage of alicyclic (or benzene ring) carbon atoms in the mixed adhesive solution is 8.29%, and mixed adhesive solution A is heated to 40°C at a heating rate of less than 5°C / min;

[0122] S2.2. At a temperature of 40°C, the mixed adhesive A and the energetic curing agent (D400) are mixed at a molar ratio of 10:1, followed by the addition of energetic particles at a mass ratio of 1:9 to mixed adhesive A. After mixing, mixed adhesive B is obtained; and after mixing, a vacuum treatment is performed until the absolute vacuum degree reaches 10. 2 Below Pa, mixed adhesive solution B is obtained;

[0123] S2.3. Pre-curing treatment is performed on mixed adhesive B to obtain mixed adhesive C. The pre-curing treatment conditions are: temperature of 100℃, time of 2h, the degree of curing of mixed adhesive C after the pre-curing treatment is required to be within the range of 20%, and after the pre-curing is completed, the mixed adhesive C is cooled to room temperature at a cooling rate of 10℃ / min so that the viscosity of mixed adhesive C is around 2800 mPa·s.

[0124] S2.4. Before pouring begins, mix adhesive C with structural curing agent (IPDA) at room temperature. The molar ratio of IPDA to adhesive A is 4:10. After mixing, perform vacuum treatment until the absolute vacuum reaches 10. 2 When Pa is below, mixed adhesive solution D (adhesive solution for casting) is obtained.

[0125] S2.5. Perform differential scanning calorimetry (DSC) on the mixed adhesive solution D to measure the curing temperature and curing time. The curing temperature test procedure is as follows: 1) Use a differential scanning calorimeter to test the non-isothermal heat flow curves of the adhesive solution at different heating rates. The heating rates are set to 2 ℃ / min, 3 ℃ / min, 5 ℃ / min, 7 ℃ / min, and 10 ℃ / min, respectively. Sequentially obtain the initial curing temperature Ton, peak curing temperature Tpn, and final curing temperature Ten from each curve. The selection of the three curing characteristic temperatures on the heat flow curve refers to the test standard HB 7614-1998. An example curve is shown below. Figure 7 As shown, scatter plots of three characteristic curing temperatures corresponding to different heating rates were established. Then, extrapolation was used to perform linear fitting on the three characteristic curing temperature points at different heating rates to obtain the intercept values ​​on the y-axis, as shown below. Figure 8 As shown, these three intercept values ​​are denoted as the initial curing temperature To (60-110℃), peak curing temperature Tp (100-160℃), and final curing temperature Te (130-180℃) of the system. 2) The curing time is tested by using the peak curing temperature of the mixed adhesive system as the ambient temperature for isothermal DSC testing, and obtaining the time x (in minutes) when the adhesive reaches 98% curing degree. 3) The curing regime design is as follows: using 0.7-0.9To as the preheating temperature, holding at the preheating temperature for 30-90 minutes; using Tp as the peak curing temperature, holding at the peak curing temperature for x-x+30 minutes; using Te as the post-curing temperature, holding at the post-curing temperature for 60-90 minutes.

[0126] S2.6. Take another mixed adhesive solution D and use a rheometer to measure the viscosity-time curve of the mixed adhesive solution at a preheating temperature (0.7-0.9 To) according to the Chinese chemical industry standard HG / T 6261-2023. An example curve is shown below. Figure 9As shown, the time length (t1-t2) when the viscosity is below 800 mPa·s is taken as the reference value for the pouring time, and the actual pouring time should not exceed this time length;

[0127] S3.1. Casting of mixed adhesive D: The energetic resin containing metal particles, after mixing treatment, is poured through a guide pipe with a throttle valve controlling the resin flow rate at 48 mm. 3 / s, the mixed adhesive D enters from the small-diameter (6mm inner diameter) interface of the lower end cap of the mold and pours into the entire internal molding space of the mold at a uniform flow rate. Then it flows out from the large-diameter (10mm inner diameter) interface of the upper end cap. When the liquid level of the flowing mixed adhesive D in the guide tube is 70mm away from the interface outlet, the pouring ends. At the same time, the upper guide tube is connected to the atmospheric environment, and then the lower guide tube is blocked by the throttle valve to complete the pouring work and wait for curing.

[0128] S3.2. Use an oven, preheat to 80℃, place the molding mold in the oven, and set the temperature and time to 80℃ / 30min-120℃ / 1h 30min-135℃ / 1h. After curing, perform oven cooling, cooling the cured material to 60℃ at a cooling rate of 10℃ / min.

[0129] S4.1. The product is demolded using an ejector fixture, which mainly consists of a fixed block, an ejector shim, and an ejector sleeve. The fixed block has two connecting screw holes and one ejector screw hole. First, the fixed block is connected to the end face of the outer mold. The ejector shim is placed on the top of the core pillar. Using the ejector screw in the fixed block, the core pillar is ejected downwards. After the core pillar is ejected, the ejector shim is replaced in the ejector sleeve, and the core pillar is ejected downwards to the finished product using the ejector screw in the fixed block.

[0130] S4.2. Grind the cast body after demolding. Use sandpaper with a grit of 400 to 1500 grit, gradually increasing the grit until the cast body reaches the qualified dimensions.

[0131] Comparative Example 2

[0132] This comparative example provides an energetic rotary casting filled with metal spheres and a molding method thereon. The difference between this comparative example and Example 2 is that the curing conditions in step S3.2 are changed. After the casting is cured, small air bubbles appear on the surface of the casting, both inside and out. Figure 6 As shown, the surface resin shrinks simultaneously, forming irregular raised and recessed textures. When the casting is not filled with metal spherical fillers, the appearance morphology reflects the differences caused by the curing process. Specifically, in step S3.2, the oven was not preheated beforehand. The molding die was directly placed in the oven and heated from room temperature to 80℃ at 10℃ / min, then kept at that temperature for 30 minutes, and then heated to 120℃ at 10℃ / min and kept at that temperature for 2 hours for curing.

[0133] Test case

[0134] This test example tested the compressive strength of samples prepared under different formulations and processing conditions according to GB / T1041-2008 / ISO604:2002. The test results are shown in Table 1.

[0135] Table 1. Compression Performance Test

[0136]

[0137] The compressive strength test data shown in the table clearly demonstrate that the metal ball-filled energetic rotary casting prepared using the structural design and molding process described in this invention has significantly better mechanical properties than the comparative example. Moreover, during the compression process, the rotary cylinders of the embodiment and the comparative example exhibited different fracture patterns in the compression test: when the filler (metal ball) is evenly distributed in the rotary body, there are few defects inside the rotary body, and after exceeding the compression limit, the entire rotary cylinder will only show a large number of cracks and will not break apart; however, when the filler is unevenly distributed in the rotary cylinder, larger defects will appear inside the cylinder, and a large stress concentration phenomenon will occur during the compression process. After exceeding the compressive strength limit, the entire cylinder will collapse and the fragments will scatter.

[0138] This invention optimizes the core column distribution channel layout and sets a limiting ring to form a balanced flow channel with an inner / outer flow gap ratio of approximately 1:0.5. Combined with a specific epoxy resin / curing agent system and a highly filled metal ball structure, it effectively suppresses the sedimentation and agglomeration of metal balls during the casting process, achieving uniform distribution of filler and full wetting of resin. This significantly reduces internal porosity and interface defects, improving the overall density and load-bearing capacity of the material. In contrast, the comparative example lacks the above-mentioned synergistic design, resulting in uneven filling or flow dead zones, and relatively lower mechanical properties.

[0139] In the metal filler uniformity test, Embodiment 1 of the present invention simulated and analyzed the ideal filling state of metal balls in the mold cavity using a simulation model. The simulation results show that, after deducting the space occupied by the limiting ring, the maximum number of metal balls that the mold cavity can accommodate is approximately 2700. Under the above conditions, it is considered the theoretically optimal distribution form for achieving uniform and dense packing of metal balls.

[0140] In the actual implementation (Example 1), after casting and curing, non-destructive testing and analysis were performed on the resulting rotary casting body. It was found that the number of metal spheres inside was close to 2700, and the metal spheres exhibited a uniform and orderly spatial distribution within the annular cavity. This indicates that the molding die structure provided by this invention (especially the synchronous filling mechanism through the external flow gap formed by the limiting ring, the staggered flow channel layout, and the circumferential buffer groove design) effectively guides the resin liquid to rise uniformly, preventing the metal spheres from shifting, accumulating, or forming voids during casting, thereby achieving a uniform distribution of the filler in three-dimensional space.

[0141] Furthermore, compression tests further verified the direct correlation between filling uniformity and mechanical behavior. The casting prepared in this embodiment exhibited a typical cracking deformation failure mode in the compression test—that is, when the load exceeded the limit, numerous fine cracks appeared on the surface of the casting, but the overall structure remained intact without collapse. This failure mode indicates that the casting has few internal defects, uniform stress distribution, and high load-bearing capacity. In contrast, the comparative example, due to the lack of key designs such as limiting rings, resulted in uneven distribution of metal spheres, leading to significant stress concentration during compression, ultimately causing cracking and fragmentation failure, with scattered fragments and a significant decrease in mechanical properties.

[0142] In summary, by optimizing the mold flow channel and filling control structure, this invention ensures a highly uniform distribution of metal spheres within the casting body. This is not only verified through simulation and actual measurement, but also intuitively demonstrated through failure modes in compression tests, highlighting the significant advantages of this invention in improving the uniformity, density, and load-bearing capacity of energetic rotary casting bodies.

[0143] In summary, the above-described technical solutions of the present invention are merely preferred embodiments of the present invention and do not limit the patent scope of the present invention. All equivalent structural transformations made using the contents of the present invention's specification and drawings under the technical concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. An energetic rotary casting filled with metal spheres, characterized in that, The raw materials for preparing the energetic rotary casting filled with metal spheres include metal spheres, epoxy resin, energetic particles, and curing agent; The energetic particles include: aluminum powder, a polytetrafluoroethylene layer covering the surface of the aluminum powder, and a fluororubber layer covering the surface of the polytetrafluoroethylene layer. The epoxy resin includes: structural epoxy resin and energetic epoxy resin; The curing agent includes: structural curing agent and energetic curing agent; The structural curing agent includes at least one of alicyclic amines and aromatic amines; The energetic curing agent includes polyetheramine.

2. The energetic rotary casting body filled with metal spheres according to claim 1, characterized in that, The structural epoxy resin includes alicyclic glycidyl ester type epoxy resin; The energetic epoxy resin includes linear glycidyl ether type epoxy resin.

3. The energetic rotary casting body filled with metal spheres according to claim 1, characterized in that, The molar ratio of the energetic curing agent to the structural curing agent is 1:4~9.

4. A method for forming an energetic rotary casting body filled with metal spheres as described in any one of claims 1 to 3, characterized in that, Includes the following steps: S1. After filling the cavity of the molding die with metal balls, vacuum the mold after filling. S2. The structural epoxy resin, the energetic epoxy resin, the energetic particles and the energetic curing agent are mixed and pre-cured to obtain a mixed adhesive solution, which is then mixed with the structural curing agent to obtain a casting adhesive solution; S3. After the casting adhesive is injected from the lower end cover of the mold, it is first preheated at 0.7 to 0.9 times the initial curing temperature for 30 to 90 minutes, then kept at the peak curing temperature until the degree of curing is ≥98%, and finally cured at the final curing temperature for 60 to 90 minutes. S4. After curing, cool and demold to obtain the energetic rotary casting filled with the metal spheres; The structure of the molding die includes: an outer mold, a core column, an upper end cap, a lower end cap, and a limiting ring; The outer mold is a cylindrical structure, and the core column is a cylinder coaxially arranged with the outer mold. A cavity is formed between the core column and the inner wall of the outer mold, and the cavity is used to fill metal balls. The upper and lower end faces of the core column are respectively provided with circular protrusions for positioning; the upper and lower end faces of the core column are also respectively provided with 4 semi-circular groove diversion channels evenly distributed along the circumference, and the diversion channels of the upper end face and the lower end face are staggered by 40°~50° along the circumference. The limiting ring is a ring-shaped component, coaxially nested between the core column and the outer mold. The lower end face of the limiting ring contacts the metal ball, and the upper end face of the limiting ring contacts the upper end cover. The inner side of the limiting ring forms an inner flow gap with the core column, and the outer side forms an outer flow gap with the outer mold. The upper end cover has an overflow port at its center, and the lower end cover has an adhesive inlet at its center. The adhesive for pouring is injected from the adhesive inlet of the lower end cover, guided by the flow channel and the buffer tank, and synchronously fills the annular cavity from the outer flow gap before overflowing from the upper end cover.

5. The molding method of an energetic rotary casting body filled with metal spheres according to claim 4, characterized in that, The ratio of the area of ​​the outer flow gap to the area of ​​the inner flow gap is 0.5 to 1:

1.

6. The molding method of an energetic rotary casting body filled with metal spheres according to claim 4, characterized in that, The diameter of the flow channel is 70% to 85% of the diameter of the metal ball.

7. The molding method of an energetic rotary casting body filled with metal spheres according to claim 4, characterized in that, The upper and lower end faces of the core column are respectively provided with circumferential rectangular buffer slots. The circumferential rectangular buffer slots are connected to the semi-circular slot distribution channels on the corresponding end faces. The depth and width of the circumferential rectangular buffer slots are the same.

8. The molding method of an energetic rotary casting body filled with metal spheres according to claim 4, characterized in that, The core is a one-piece cylinder that is tapered along the axial direction, with the smaller diameter end located at the upper end and the larger diameter end located at the lower end; the demolding taper of the core satisfies: 0.05° ≤ demolding taper ≤ ; Where d is the diameter of the metal sphere and L is the axial length of the casting.

9. The molding method of an energetic rotary casting body filled with metal spheres according to claim 4, characterized in that, The inner wall of the outer mold is tapered along the axial direction. The tapered angle of the outer mold is the same as that of the core column. The large diameter end of the inner wall corresponds to the glue inlet end, and the small diameter end of the inner wall corresponds to the glue outlet end.

10. The application of an energetic rotary casting filled with metal spheres as described in any one of claims 1 to 3 in industrial materials.

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