Composite reactive structural material and its preparation method and application

Abstract

The present application relates to the technical field of composite reaction structure material, and particularly relates to a composite reaction structure material, a preparation method and application thereof, comprising the following steps: S1. Topology optimization model construction, a topology optimization model of a component is constructed in laser additive manufacturing modeling software, and is imported into a selective laser melting (SLM) operating system; S2. High-entropy alloy reaction structure material powder preparation, and high-entropy alloy reaction structure material powder after drying treatment is put into a powder bin of the SLM operating system; S3. High-entropy alloy reaction structure material skeleton forming, high-entropy alloy reaction structure material powder is layer by layer melted and accumulated on a substrate by using the SLM process, and a high-entropy alloy reaction structure material skeleton with a topology optimization model structure is prepared; S4. An (Al, Ti) / PTFE / organic solvent mixture is filled into the high-entropy alloy reaction structure material skeleton with the topology optimization model structure, and after the solvent is volatilized, a high-strength and high-activity composite reaction structure material component is obtained.

Description

Technical Field

[0001] This invention relates to the field of composite reactive structural material design and laser additive manufacturing, specifically to a composite reactive structural material, its preparation method, and its applications. Background Technology

[0002] Polyfluoride / (Al,Ti) is a typical reactive structural material, usually prepared into damage elements using powder metallurgy techniques primarily involving pressing and sintering. However, with the advancement of target armor protection technology, the strength of existing (Al,Ti) / PTFE material damage elements cannot meet the mechanical performance requirements of the penetration process. Therefore, it is necessary to develop a reactive structural material damage element with both high strength and high energy release, along with its preparation method.

[0003] High-entropy alloys possess excellent comprehensive properties, including high strength and toughness, high hardness, and excellent corrosion resistance, making them highly promising for applications and commercial value. High-entropy alloy reactive materials (HEAs-RMS), composed of high-oxidation-energy-releasing elements such as Al, Ti, Zr, and Ta, are a class of materials that meet the mechanical strength requirements for structural components. Furthermore, they can react with oxygen in the air and rapidly release a large amount of energy under impact and breakage conditions, exhibiting both high oxidation energy release and structural strength. They can be used simultaneously as structural components and energetic damage elements. However, traditional casting and powder metallurgy methods are insufficient for manufacturing high-performance, complex components. In addition, HEAs-RMS are highly dependent on oxygen in the environment, thus limiting their practical applications. Summary of the Invention

[0004] The purpose of this invention is to provide a composite reactive structural material, its preparation method, and its application, thereby solving the technical problem in the prior art that it is impossible to improve the damage effect of HEAs-RMS components without significantly reducing or even reducing their mechanical service performance.

[0005] This invention discloses a method for preparing composite reactive structural materials, comprising the following steps:

[0006] S1. Topology optimization model construction: Construct a topology optimization model of the component in the laser additive manufacturing modeling software and import it into the Selective Laser Melting (SLM) operating system;

[0007] S2. Preparation of high-entropy alloy reactive structural material powder: Place the dried high-entropy alloy reactive structural material powder into the powder hopper of the SLM operating system.

[0008] S3. Forming of high-entropy alloy reactive structural material skeleton: The high-entropy alloy reactive structural material powder is melted and deposited layer by layer on the substrate using the SLM process to prepare a high-entropy alloy reactive structural material skeleton with a topology optimization model structure.

[0009] S4. Preparation of composite reactive structural material components: An Al / PTFE / organic solvent mixture is filled into a high-entropy alloy reactive structural material framework with a topology-optimized model structure. After the solvent is evaporated, a high-strength and high-activity composite reactive structural material component is obtained.

[0010] Furthermore, the high-entropy alloy reactive structural material powder includes Al, Ti, Zr, Co, Cr, Fe, and Ni elements.

[0011] Furthermore, the purity of each element in the high-entropy alloy reactive structural material powder is ≥90%.

[0012] Furthermore, the elemental composition of the high-entropy alloy reactive structural material powder is as follows: 2 at.% ≤ Al ≤ 20 at.%, 10 at.% ≤ Ti ≤ 50 at.%, 10 at.% ≤ Zr ≤ 20 at.%, 10 at.% ≤ Co ≤ 20 at.%, 10 at.% ≤ Cr ≤ 20 at.%, 10 at.% ≤ Fe ≤ 20 at.%, 20 at.% ≤ Ni ≤ 30 at.%.

[0013] Furthermore, after the elemental components of the high-entropy alloy reactive structural material powder are mixed, they undergo plasma spheroidization treatment, followed by sieving. Powder smaller than the sieve aperture of the metal powder is placed in a vacuum drying oven, heated to 90-150°C in a vacuum environment, kept at that temperature for 1-5 hours, and then cooled with the oven for later use.

[0014] Furthermore, all elements in the high-entropy alloy reactive structural material powder are spherical powders with a sphericity ≥80%.

[0015] Furthermore, the substrate is a stainless steel plate or a zirconium alloy substrate.

[0016] Furthermore, the substrate undergoes surface cleaning before use, specifically including the following steps: First, the substrate surface is machined to remove the oxide layer and ensure that the substrate surface is flat and clean; then, it is immersed in acetone for ultrasonic cleaning and wiped clean with anhydrous ethanol; finally, it is fixed on the worktable of the selective laser melting system.

[0017] Furthermore, the 3D modeling software is used for mathematical modeling and structural optimization using ANSYS finite element analysis software.

[0018] A robust and tough skeleton model was designed by performing topology optimization on HEAs-RMS using ANSYS finite element analysis software.

[0019] Furthermore, the laser melting process parameters in the SLM manufacturing are as follows: laser power of 50-500W, scanning speed of 200-1400mm / min, spot diameter of 30-100μm, single-layer powder thickness of 10-120μm, and overlap rate of 10%-90%.

[0020] Furthermore, the SLM is used to print in a working chamber filled with inert gas.

[0021] Furthermore, the inert gas is argon.

[0022] Furthermore, the (Al, Ti) / PTFE / organic solvent mixture is obtained by mixing Al powder or Ti powder and PTFE micro powder with an organic solvent using electromagnetic stirring.

[0023] Furthermore, the particle size of both the Al powder or Ti powder and the PTFE micro powder is 10 micrometers; the mass ratio of Al powder or Ti powder to PTFE micro powder is 1:1; and the organic solvent is ethanol, dichloromethane, n-hexane, or acetone.

[0024] A composite reactive structural material was prepared using the method described above.

[0025] An application of a composite reactive structural material for use as a reactive structural material damage element.

[0026] Compared with the prior art, the beneficial effects of the present invention are:

[0027] 1. The technical solution of this invention can produce high-performance, structurally complex HEAs-RMS components by optimizing topology and setting different laser scanning path programs according to requirements. Based on specific laser process parameters and high-entropy alloy element ratios, HEAs-RMS components with uniform microstructure, stable structure, excellent performance, and complex structure can be prepared. This invention features high automation, good controllability, high product quality, customizable production, and high commercial value.

[0028] 2. In order to meet the urgent need for promoting the practical application of reactive structural materials, this patent proposes a solution for a composite reactive structural material with a high entropy alloy reactive structural material skeleton strengthened by polyfluoride / Al, based on the interdisciplinary integration of materials and manufacturing disciplines. This solution can make up for the problem of HEAs-RMS' dependence on oxygen and low energy release efficiency, and can also solve the problem of insufficient penetration performance caused by the poor mechanical properties of Al / PTFE system.

[0029] 3. This patent utilizes topology optimization technology to design and optimize an oxidation-release energy high-entropy alloy skeleton, and then uses SLM laser additive manufacturing technology to form the topology-optimized high-entropy alloy skeleton. Therefore, the development of SLM laser additive manufacturing technology provides a new technical solution for the homogenized fabrication of strong and tough HEAs-RMS skeletons.

[0030] 4. Al / PTFE, which achieves fluorination energy release through pressure infiltration, is filled into a high-entropy alloy skeleton to obtain a composite reactive structural material that combines oxidation and fluorination energy release. This composite material can not only serve as a load-bearing component and fragmentation damage element of the warhead structure, but also as a provider of damage energy. Attached Figure Description

[0031] To more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation on the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 This is a structural model diagram of Embodiment 1 of the present invention. The left side is a cubic porous structure, and the right side is a fluorite-like porous structure.

[0033] Figure 2 This is a physical diagram of the component in Embodiment 1 of the present invention.

[0034] Figure 3 This is the compressive stress-strain curve of the component in Example 1 of the present invention.

[0035] Figure 4 This is a structural model diagram of Embodiment 2 of the present invention.

[0036] Figure 5 This is a physical diagram of the component in Embodiment 2 of the present invention.

[0037] Figure 6 This is the compressive stress-strain curve of the component in Embodiment 2 of the present invention. Detailed Implementation

[0038] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0039] Example 1

[0040] The composite reactive structure material preparation method of the above-mentioned device used in this embodiment, S1, the reactive structure high entropy alloy element composition is Al, Co, Cr, Fe and Ni; the purity of each element is ≥99.5%;

[0041] S2. The five elemental substances from step S1 are subjected to gas atomization powdering in a certain ratio. The specific ratio of the five elements is as follows: Al atomic content is 16.39 at.%, Co atomic content is 16.39 at.%, Cr atomic content is 16.39 at.%, Fe atomic content is 16.39 at.%, and Ni atomic content is 34.44 at.%.

[0042] S3. The alloy powder after the alloying treatment by gas atomization in step S2 is sieved. The metal powder sieve mesh sizes are 600 mesh and 325 mesh, respectively. Alloy powders with particle sizes smaller than 325 mesh and larger than 600 mesh are collected and placed in a vacuum drying oven for drying. Specifically, the powder is heated to 120°C in a vacuum environment, kept at that temperature for 2 hours, and then cooled with the oven for later use.

[0043] S4. The substrate is made of 316L stainless steel. The substrate surface cleaning includes the following steps: First, the substrate surface is polished with an angle grinder; then, it is immersed in acetone, and then the substrate is placed in anhydrous ethanol for ultrasonic cleaning. After cleaning, the above polishing, immersion and cleaning steps are repeated once. The cleaned substrate is dried. Finally, the surface-treated substrate is fixed in the working chamber of the SLM system.

[0044] S5. Use 3D modeling software to construct structural models, namely a body-centered porous structure and a fluorite-like structure. The structural model diagrams are attached. Figure 1 As shown;

[0045] S6. Set the laser process parameters and laser scanning path in the SLM system; the laser process parameters are: laser power of 60W, scanning speed of 300mm / s, powder layer thickness of 50μm, overlap rate of 70%, and spot diameter of 60μm.

[0046] First, under the protection of an inert gas atmosphere, the dried powder from step S3 is placed into the powder hopper of the SLM system chamber. Then, the SLM system is started, and according to the set laser process parameters and scanning path, the powder is deposited layer by layer onto a 316L stainless steel substrate under the protection of an inert gas atmosphere to fabricate a HEAs-RMS component. The model diagram is shown below. Figure 1 As shown in the attached image, the actual product is also shown. Figure 2 As shown.

[0047] Using the method described in this example, HEAs-RMS components with different structures were manufactured, and compression tests were conducted on the HEAs-RMS components.

[0048] Appendix Figure 3 The compressive stress-strain curve of the component is shown. The tensile sample conforms to the standard GB / T7314-2017 "Metallic Materials - Compression Test at Room Temperature". It can be seen that within the process parameters of this embodiment, the processing quality and related mechanical properties of the HEAs-RMS component samples prepared by this method can reach the level required for industrial applications.

[0049] S7. Al powder and PTFE micro powder are mixed by electromagnetic stirring using an organic solvent. The viscosity and flowability of the Al / PTFE / organic solvent mixture are adjusted by controlling the amount of solvent.

[0050] S8. The Al / PTFE / organic solvent mixture prepared in step S8 is loaded into the HEAs-RMS component with a 3D framework structure prepared in step S6 using vacuum filtration. The component is then dried for 1 hour to evaporate the solvent and encapsulated. Finally, a high-strength, high-activity composite reactive structural material component is obtained.

[0051] Example 2

[0052] This embodiment, as a preferred embodiment of the present invention, discloses a method for preparing a composite reactive structural material, comprising the following steps:

[0053] S1, the high-entropy alloy of the reaction structure is composed of Al, Ti, Zr, Ta and Nb elements; the purity of each element is ≥99.5%;

[0054] S2. The five elemental substances from step S1 are subjected to plasma spheroidization powdering treatment according to a certain ratio. The specific ratio of the five elements is as follows: Al element atomic content is 3.12 at.%, Ti element atomic content is 46.87 at.%, Zr element atomic content is 12.5 at.%, Ta element atomic content is 12.5 at.%, and Nb element atomic content is 25 at.%.

[0055] S3. The alloy powder after plasma spheroidization alloying treatment in step S2 is sieved. The metal powder sieve mesh sizes are 600 mesh and 325 mesh, respectively. Alloy powders with particle sizes smaller than 325 mesh and larger than 600 mesh are collected and placed in a vacuum drying oven for drying. Specifically, the powder is heated to 120°C in a vacuum environment, kept at that temperature for 2 hours, and then cooled with the oven for later use.

[0056] S4. The substrate is made of 316L stainless steel. The substrate surface cleaning includes the following steps: First, the substrate surface is polished with an angle grinder; then, it is immersed in acetone, and then the substrate is placed in anhydrous ethanol for ultrasonic cleaning. After cleaning, the above polishing, immersion and cleaning steps are repeated once. The cleaned substrate is dried. Finally, the surface-treated substrate is fixed in the working chamber of the SLM system.

[0057] S5. Use 3D modeling software to construct a structural model, which is a fluorite-like structure. The structural model diagram is attached. Figure 4 As shown;

[0058] S6. Set the laser process parameters and laser scanning path in the SLM system; the laser process parameters are: laser power of 80W, scanning speed of 200mm / s, powder layer thickness of 50μm, overlap rate of 70%, and spot diameter of 60μm.

[0059] S6. First, under the protection of an inert gas, the dried powder from step S3 is placed into the powder hopper of the SLM system chamber. Then, the SLM system is started, and according to the set laser process parameters and scanning path, the powder is deposited layer by layer onto a 316L stainless steel substrate under the protection of an inert gas to fabricate a HEAs-RMS component. The model diagram is shown below. Figure 4 As shown in the attached image, the actual product is also shown. Figure 5 As shown.

[0060] Using the method described in this example, HEAs-RMS components of different sizes were manufactured, and compression tests were conducted on the HEAs-RMS components.

[0061] Appendix Figure 6 The compressive stress-strain curve of the component is shown. The tensile sample conforms to the standard GB / T7314-2017 "Metallic Materials - Compression Test at Room Temperature". It can be seen that within the process parameters of this embodiment, the processing quality and related mechanical properties of the HEAs-RMS component samples prepared by this method can reach the level required for industrial applications.

[0062] S7. Al powder and PTFE micro powder are mixed by electromagnetic stirring using an organic solvent. The viscosity and flowability of the Al / PTFE / organic solvent mixture are adjusted by controlling the amount of solvent.

[0063] S8. The Al / PTFE / organic solvent mixture prepared in step S7 is filled and loaded into the HEAs-RMS component with a 3D framework structure prepared in step S6 using a pressure filling method. The component is then dried for 1 hour to evaporate the solvent and encapsulated. Finally, a high-strength, high-activity composite reactive structural material component is obtained.

[0064] The above are the embodiments listed in this example. However, this example is not limited to the optional embodiments described above. Those skilled in the art can arbitrarily combine the above methods to obtain other various embodiments. Anyone can derive other various forms of embodiments based on the inspiration of this example. The above specific embodiments should not be construed as limiting the scope of protection of this example. The scope of protection of this example should be determined by the claims, and the specification can be used to interpret the claims.

Claims

1. A method for preparing a composite reactive structural material, characterized in that: Includes the following steps: S1. Topology optimization model construction: Construct the topology optimization model of the component in the laser additive manufacturing modeling software and import it into the SLM operating system; S2. Preparation of high-entropy alloy reactive structural material powder: Place the dried high-entropy alloy reactive structural material powder into the powder hopper of the SLM operating system; S3. Forming of high-entropy alloy reactive structural material skeleton: The high-entropy alloy reactive structural material powder is melted and deposited layer by layer on the substrate using the SLM process to prepare a high-entropy alloy reactive structural material skeleton with a topology optimization model structure. S4. Preparation of composite reactive structural material components: An Al / PTFE / organic solvent mixture is filled into a high-entropy alloy reactive structural material framework with a topology-optimized model structure. After the solvent is evaporated, a high-strength and high-activity composite reactive structural material component is obtained. The high-entropy alloy reactive structural material powder includes Al, Ti, Zr, Co, Cr, Fe, and Ni elements; The elemental composition of the high-entropy alloy reactive structural material powder is as follows: 2 at.% ≤ Al ≤ 20 at.%, 10 at.% ≤ Ti ≤ 50 at.%, 10 at.% ≤ Zr ≤ 20 at.%, 10 at.% ≤ Co ≤ 20 at.%, 10 at.% ≤ Cr ≤ 20 at.%, 10 at.% ≤ Fe ≤ 20 at.%, 20 at.% ≤ Ni ≤ 30 at.%; The high-entropy alloy reactive structural material powder is mixed with elemental components, then subjected to plasma spheroidization treatment, and then sieved. Powder smaller than the sieve aperture of the metal powder is placed in a vacuum drying oven, heated to 90-150°C in a vacuum environment, kept at that temperature for 1-5 hours, and then cooled with the oven for later use.

2. The method for preparing a composite reactive structural material according to claim 1, characterized in that: The purity of each element in the high-entropy alloy reactive structural material powder is ≥90%.

3. The method for preparing a composite reactive structural material according to claim 1, characterized in that: All elements in the high-entropy alloy reactive structural material powder are spherical powders with a sphericity ≥80%.

4. The method for preparing a composite reactive structural material according to claim 1, characterized in that: The laser additive manufacturing modeling software was used to first perform mathematical modeling and structural optimization using ANSYS finite element analysis software.

5. The method for preparing a composite reactive structural material according to claim 1, characterized in that: The laser melting process parameters in the laser additive manufacturing are as follows: laser power of 50-500 W, scanning speed of 200-1400 mm / min, spot diameter of 30-100 μm, single-layer powder thickness of 10-120 μm, and overlap rate of 10%-90%.

6. A composite reactive structural material, characterized in that: It is prepared using the method for preparing a composite reactive structural material according to any one of claims 1-5.

7. The application of the composite reactive structural material according to claim 6, characterized in that: Used to react with structural materials that cause damage.

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