A high-plasticity high-activity single-phase energetic high-entropy alloy and a preparation method thereof

Abstract

The application discloses a high-plasticity high-activity single-phase energetic high-entropy alloy, which is composed of A-type high-plasticity solid solution matrix elements and B-type high-reactivity components and is expressed as A x B y The A-type high-plasticity solid solution matrix elements are two or more of Co, Cr, Fe and Mn, the B-type high-reactivity components are two or more of Ni, Al, Ti, Zr, AlMg, AlCe and AlY, and the following conditions are met: 40<=x<=75, 25<=y<=60 and x+y=100. The high-plasticity high-activity single-phase energetic high-entropy alloy is composed of the high-plasticity solid solution matrix elements and the high-reactivity components, the high-plasticity solid solution matrix elements ensure plasticity and subsequent machinability, the high-reactivity components ensure high reactivity and energetic characteristics, the high-plasticity high-activity single-phase energetic high-entropy alloy forms a single solid solution, the element performance of the high-reactivity components is reserved, and thus the characteristics of high activity and energy are realized.

Description

Technical Field

[0001] This invention belongs to the field of design and preparation technology of high-entropy alloy materials, specifically relating to a highly ductile, highly active single-phase energetic high-entropy alloy and its preparation method. Background Technology

[0002] Traditional energetic materials are mainly based on metal powders such as aluminum, nickel, and magnesium, which are mixed with fluorinated polytetrafluoroethylene (PTFE) and other oxidizing agents to prepare them. They have the characteristics of high energy density and good energy release characteristics. The preparation process mainly involves molding and sintering. As energetic structural materials, they have poor overall plasticity and almost no processing performance. In addition, the composite material has low density and low kinetic energy, which greatly reduces their destructive effectiveness.

[0003] With the development and emergence of numerous new protective structures and materials, traditional energetic materials are no longer sufficient to meet damage requirements. To further improve the processing performance, density, and plasticity of energetic structural materials, energetic structural materials based on the design concept of high-entropy alloys have emerged. Unlike traditional alloy materials, high-entropy alloys are a new type of metallic material containing multiple main elements, each with a content greater than 5%. Therefore, high-entropy alloys can achieve solid solution treatment with other high-density, high-plasticity metallic matrices while introducing energetic materials based on metals such as aluminum, nickel, magnesium, and zirconium. This ensures both reactivity and improved material density and plasticity, achieving an organic combination of multiple performance requirements and realizing highly efficient damage.

[0004] Therefore, there is a need for a highly ductile, highly active single-phase energetic high-entropy alloy and its preparation method. Summary of the Invention

[0005] The technical problem to be solved by this invention is to address the shortcomings of the prior art by providing a highly ductile, highly reactive single-phase energetic high-entropy alloy. This highly ductile, highly reactive single-phase energetic high-entropy alloy is composed of a type A highly ductile solid solution matrix element and a type B highly reactive component. The highly ductile solid solution matrix element ensures the material's plasticity and subsequent processability, while the highly reactive component guarantees the material's high reactivity and energetic characteristics. This allows the highly ductile, highly reactive single-phase energetic high-entropy alloy to form a single solid solution without generating a large number of intermetallic compounds. Furthermore, the elemental properties of the type B highly reactive component are retained, thereby achieving the characteristics of high activity and energy.

[0006] To solve the above-mentioned technical problems, the technical solution adopted by the present invention is: a high-plasticity, high-activity single-phase energetic high-entropy alloy, characterized in that the high-entropy alloy is composed of type A high-plasticity solid solution matrix elements and type B high-reactivity components, with the molecular formula denoted as A. x B yThe matrix elements of the type A high-plasticity solid solution are two or more of Co, Cr, Fe, and Mn, and the high-reactivity components of type B are two or more of Ni, Al, Ti, Zr, AlMg, AlCe, and AlY, and satisfy 40≤x≤75, 25≤y≤60, and x+y=100. This invention utilizes a high-plasticity, high-activity single-phase energetic high-entropy alloy composed of a type A high-plasticity solid solution matrix element and a type B high-reactivity component. The high-plasticity solid solution matrix element ensures the material's plasticity and subsequent processability, while the high-reactivity component guarantees its high reactivity and energetic characteristics. This results in a single-phase energetic high-entropy alloy forming a single solid solution without the formation of large amounts of intermetallic compounds. Furthermore, the elemental properties of the type B high-reactivity component are retained, thus achieving high activity and energetic characteristics. The alloy composition of the high-plasticity solid solution matrix element and the high-reactivity component, with types A and B, is designed to be 40≤x≤75 and 25≤y≤60, ensuring a high-entropy effect in the material's thermodynamics. Through high mixing entropy stabilization, a solid solution alloy is formed, achieving multi-principal element functionalization and an organic combination of high strength, high toughness, and high reactivity.

[0007] In this invention, A x B y The ratio of the total mass of the matrix elements of type A high-plasticity solid solution to the total mass of type B high-reactivity components is x:y.

[0008] The above-mentioned high-plasticity, high-activity single-phase energetic high-entropy alloy is characterized in that the high-entropy alloy satisfies 45≤x≤70, 30≤y≤55, and x+y=100.

[0009] In addition, the present invention provides a method for preparing a highly ductile, highly active single-phase energetic high-entropy alloy, characterized in that the method includes the following steps:

[0010] Step 1: Remove the oxide scale from the metal raw material to obtain clean metal raw material. Then, classify the clean metal raw material according to its volatility, melting point less than 1000℃ and melting point greater than or equal to 1000℃ to obtain volatile clean metal raw material, clean metal raw material with melting point less than 1000℃ and clean metal raw material with melting point greater than or equal to 1000℃.

[0011] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, then place the volatile clean metal raw material obtained in Step 1 at the bottom of the crucible, and then put in the clean metal raw material with a melting point greater than or equal to 1000℃ to obtain the first melting raw material.

[0012] Step 3: The raw material obtained in Step 2 is smelted under argon protection. The smelting current is 700A~1600A, the smelting power is 300kW~800kW, and the smelting time is 2min~7min. Then the furnace is cooled to obtain a first ingot.

[0013] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0014] Step 5: Flip the secondary ingot obtained in Step 4 and add the clean metal raw material with a melting point of less than 1000℃ obtained in Step 1. Then repeat Step 3 and Step 4 to obtain the vacuum magnetic levitation melting ingot.

[0015] Step 6: Perform vacuum consumable melting on the vacuum magnetic levitation melting ingot obtained in Step 5, and then cut off the riser to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0016] This invention classifies clean metal raw materials into categories based on volatility, melting point less than 1000℃, and melting point greater than or equal to 1000℃. On the one hand, melting raw materials with similar melting points ensures thorough mixing, achieves uniform chemical composition, reduces melting difficulty, saves overall costs, and improves quality and efficiency. On the other hand, it avoids the volatilization of low-melting-point metals caused by directly melting low-melting-point and high-melting-point metals, ensuring the accuracy of the alloy composition. Volatility mainly refers to Al metal raw materials. The purpose of this invention is to use a vacuum magnetic levitation method to melt four times to avoid alloy segregation and ensure the uniformity of chemical composition. The subsequent electric arc melting is to remove internal defects such as pores and inclusions, thereby improving the utilization rate of the alloy. Furthermore, the melting current and melting power are controlled based on the melting point of the alloy, taking into account both high efficiency and energy saving. The melting time is controlled based on the fluidity and volatility of the alloy to ensure uniform mixing of all components of the material.

[0017] The method described above is characterized in that the purity of the metal raw material in step one is not less than 99.9%. This invention ensures the purity and performance of the prepared high-plasticity, high-activity single-phase energetic high-entropy alloy by controlling the purity of the metal raw material.

[0018] The above method is characterized in that the argon protection conditions in step three are obtained by the following method: first, the vacuum magnetic levitation melting furnace is evacuated to 2×10⁻⁶ ppm. -2 The pressure is below 5000 Pa, then argon gas is introduced and controlled at 5000 Pa to 6000 Pa. This invention isolates air by drawing a vacuum and introducing argon gas, thus preventing air from affecting the smelting process.

[0019] The above method is characterized in that the vacuum degree in the vacuum self-consumable melting process in step six is ​​not greater than 2 × 10⁻⁶. -2Pa, the arc-starting material is made of titanium fine rods or sponge titanium shavings. During melting, the arc-starting voltage is 20V~50V, and the arc-starting current is 2500A~5500A. After the molten pool stabilizes, the melting current is controlled at 3000A~15000A according to the melting point of the metal raw material. In this invention, the arc-starting voltage and arc-starting current are matched. According to the melting point of the metal raw material, the corresponding arc-starting voltage and arc-starting current are set to achieve the purpose of quickly forming a molten pool in the crucible. Taking into account efficiency and energy saving, the arc-starting voltage is set to 20V~50V and the arc-starting current is set to 2500A~5500A during melting. After the molten pool stabilizes, the melting current is controlled at 3000A~15000A according to the melting point of the metal raw material. This improves the melting rate of the alloy material and the overall melting efficiency. The larger melting current can maintain the volume of the molten pool. Combined with magnetic stirring, it further ensures the uniformity of the composition. However, the smelting current should not be too high, as it is not conducive to the removal of non-metallic inclusions and other impurities by flotation.

[0020] The above method is characterized by employing a feeding process in step six of the vacuum consumable melting process. The melting current is gradually reduced in a gradient manner. Depending on the fluidity and melting point of the metal raw material, the feeding process is divided into three stages: in the first stage, the melting current is reduced by 10%~20% and held for 2~5 minutes; in the second stage, the melting current is further reduced by 15%~25% and held for 2~5 minutes; in the third stage, the melting current is reduced by 10%~20% and held for 5~15 minutes. Subsequently, the melting current is gradually reduced to 0 at a rate of 200A / min~500A / min. This invention employs a three-stage feeding process, which has the advantages of minimizing riser defects, increasing ingot usability, and allowing for slow solidification of the molten pool, enabling non-metallic inclusions to float and ensuring material purity.

[0021] The above method is characterized in that the high-plasticity, high-activity single-phase energetic high-entropy alloy described in step six has a single-phase structure and a density of not less than 7 g / cm³. 3 The plasticity under quasi-static conditions is not less than 20%.

[0022] Compared with the prior art, the present invention has the following advantages:

[0023] 1. This invention uses a type A high-plasticity solid solution matrix element and a type B high-reactivity component to form a high-plasticity, high-activity single-phase energetic high-entropy alloy. The high-plasticity solid solution matrix element ensures the plasticity and subsequent processability of the material, while the high-reactivity component ensures the high reactivity and energetic characteristics of the material. This results in a high-plasticity, high-activity single-phase energetic high-entropy alloy forming a single solid solution without generating a large number of intermetallic compounds. On this basis, the elemental properties of the type B high-reactivity component are retained, thereby achieving the characteristics of high activity and energy.

[0024] 2. This invention designs the high-plasticity solid solution matrix elements and high-reactivity components, and the alloy composition of type A and type B is 40≤x≤75, 25≤y≤60, to ensure that the material generates a high entropy effect in thermodynamics. Through the high mixing entropy, a solid solution alloy is stably formed, realizing the multi-principal element functionalization and achieving an organic combination of high strength, high toughness and reactivity.

[0025] 3. This invention classifies clean metal raw materials into those that are volatile, have a melting point less than 1000℃, and have a melting point greater than or equal to 1000℃. On the one hand, melting raw materials with similar melting points together ensures thorough mixing, achieves uniform chemical composition, reduces melting difficulty, saves overall costs, and improves quality and efficiency. On the other hand, it avoids the volatilization of low-melting-point metals caused by directly melting low-melting-point and high-melting-point metals, thus ensuring the accuracy of the alloy composition.

[0026] 4. The purpose of the four-stage vacuum magnetic levitation melting method in this invention is to avoid alloy segregation and ensure the uniformity of chemical composition. The subsequent electric arc melting is to remove internal defects such as pores and inclusions, thereby improving the utilization rate of the alloy. Furthermore, the melting current and melting power are controlled based on the melting point of the alloy, taking into account both high efficiency and energy saving. The melting time is controlled based on the fluidity and volatility of the alloy to ensure uniform mixing of the various components of the material.

[0027] 5. The present invention has a clear design concept, simple operation, stable alloy material performance, safety and reliability, and is economical and efficient. Furthermore, the high-entropy alloy designed and prepared can improve plasticity while ensuring good reactivity, which can effectively meet the needs proposed in the background art.

[0028] The technical solution of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description

[0029] Figure 1 This is a microstructure diagram of the highly ductile, highly active single-phase energetic high-entropy alloy prepared in Example 1 of the present invention.

[0030] Figure 2 The diagram shows the quasi-static compressive properties of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in Example 1 of this invention.

[0031] Figure 3 The tensile properties of the highly ductile, highly active single-phase energetic high-entropy alloy prepared in Example 1 of this invention are shown in the diagram.

[0032] Figure 4 The diagram shows the dynamic compression performance of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in Example 1 of this invention.

[0033] Figure 5 The X-ray diffraction pattern is shown for the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in Example 1 of this invention. Detailed Implementation

[0034] Example 1

[0035] This implementation includes the following steps:

[0036] Step 1: Press Co 20 Cr 10 Fe 15 Ni 46 Weigh out Al7Ti2 metal raw materials with a purity of not less than 99.9%, remove the oxide scale from the metal raw materials to obtain clean metal raw materials;

[0037] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, and then put the clean metal raw materials of Cr, Ti, Fe, Co and Ni obtained in Step 1 into it in sequence to obtain the raw materials for the first melting.

[0038] Step 3: Place the raw materials obtained in Step 2 into the vacuum magnetic levitation melting furnace. First, evacuate the vacuum magnetic levitation melting furnace to a vacuum level of 2×10. -2 The pressure is below Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000Pa~6000Pa. The melting current is controlled at 1300A, the melting power at 450kW, and the melting time at 5min. The furnace is then cooled to obtain a first ingot.

[0039] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0040] Step 5: Flip the secondary ingot obtained in Step 4 and add the clean Al metal raw material obtained in Step 1. Then repeat Step 3 and Step 4 to obtain a vacuum magnetic levitation melting ingot.

[0041] Step Six: The vacuum magnetic levitation melting and casting ingot obtained in Step Five is then melted and cast at a vacuum level not exceeding 2 × 10⁻⁶. -2 Pa, the arc-starting material is a thin titanium rod. The arc-starting voltage during melting is 30V and the arc-starting current is 3000A. After the molten pool stabilizes, the melting current is controlled at 8000A according to the melting point of the metal raw material. In vacuum magnetic levitation melting, the melting current is slowly reduced in a gradient manner. According to the different fluidity and melting point of the metal raw material, the feeding is divided into 3 stages. In the first stage, the melting current is controlled to decrease by 15% and held for 3 minutes. In the second stage, the melting current is controlled to decrease by 20% and held for 5 minutes. In the third stage, the melting current is controlled to decrease by 15% and held for 10 minutes. Then the melting current is gradually reduced to 0 at a rate of 450A / min for feeding. Then the riser is removed to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0042] Testing revealed that the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment exhibited high purity, no casting defects, formed a single solid solution, and did not produce a large amount of intermetallic compounds. It possessed a single-phase structure with a density of 7.815 g / cm³. 3 It exhibits a quasi-static plasticity of 25%, a compression ratio exceeding 50%, a compressive yield strength of approximately 500 MPa, and a tensile yield strength of approximately 450 MPa. It possesses excellent compressive and tensile properties, good ductility, and significant work hardening. It can be processed into various energetic structural materials and exhibits a significant positive strain rate effect. Through high-speed impact penetration experiments, it has been verified that under high-speed impact, the high-plasticity, highly active single-phase energetic high-entropy alloy undergoes deflagration. It can be used to manufacture various damage elements, including shaped charge shields and pre-fragmented components.

[0043] Figure 1 This is a microstructure image of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment. Figure 1 As can be seen from the above, the high plasticity and high activity single-phase energetic high-entropy alloy prepared in this embodiment exhibits equiaxed grain characteristics with random grain orientation, with an average grain size of 87 μm, and some twins can be observed inside the grains.

[0044] Figure 2 This is a quasi-static compressive properties diagram of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment. Figure 2 As can be seen, the three curves correspond to different tensile strain rates, with tensile rates of 1×10⁻⁶ and 1×10⁻⁶ respectively. -3 s -1 5×10 -3 s -1 1×10 -2 s -1 The high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment has good compressibility under different quasi-static compressive strain rates, with a compression amount exceeding 50% and a compressive yield strength of about 500 MPa.

[0045] Figure 3 The tensile property diagram shows the high plasticity, high activity, single-phase energetic high-entropy alloy prepared in this embodiment. Figure 3 As can be seen, the three curves correspond to different tensile strain rates, with tensile rates of 1×10⁻⁶ and 1×10⁻⁶ respectively. -3 s -1 5×10 -3 s -1 1×10 -2 s -1The high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment has good tensile properties, good ductility, obvious work hardening phenomenon, tensile yield strength of about 450 MPa, moderate strength, and good processing performance, and can be processed into various energetic structural materials.

[0046] Figure 4 This is a dynamic compressive performance diagram of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment. Figure 4 As can be seen, the four curves correspond to different dynamic strain rates, with strain rates of 1380 s⁻¹. -1 2170s -1 2836s -1 and 3640s -1 The high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment has a significant positive strain rate effect. That is, as the strain rate increases, the yield strength and plasticity of the alloy are significantly improved simultaneously. It can be used to make various damage elements, including shaped charge shields and pre-fragmented materials.

[0047] Figure 5 The X-ray diffraction pattern of the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in Example 1 of this invention is shown below. Figure 5 As can be seen from the data, the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment only has a face-centered cubic (FCC) structure and no other obvious impurity peaks are observed, indicating that the alloy does not have any other second precipitated phase and belongs to a single-phase structure material.

[0048] Example 2

[0049] This implementation includes the following steps:

[0050] Step 1: Press Co 20 Cr 20 Fe 20 Mn 10 Ni 26 Weigh out metal raw materials with a purity of not less than 99.9% and remove the oxide scale from the metal raw materials to obtain clean metal raw materials;

[0051] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, then place the Mn obtained in Step 1 at the bottom of the water-cooled copper crucible, and then put in the clean metal raw materials Cr, Fe, Co and Ni in sequence to obtain the first melting raw material;

[0052] Step 3: Place the raw materials obtained in Step 2 into the vacuum magnetic levitation melting furnace. First, evacuate the vacuum magnetic levitation melting furnace to a vacuum level of 2×10. -2The pressure is below Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000Pa~6000Pa. The melting current is controlled at 1000A, the melting power at 400kW, and the melting time at 2min. The furnace is then cooled to obtain a first ingot.

[0053] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0054] Step 5: Flip the secondary ingot obtained in Step 4 and add the AlMg clean metal raw material obtained in Step 1. Then repeat Step 3 and Step 4 to obtain the vacuum magnetic levitation melting ingot.

[0055] Step Six: The vacuum magnetic levitation melting and casting ingot obtained in Step Five is then melted and cast at a vacuum level not exceeding 2 × 10⁻⁶. -2 Pa, the arc-starting material is a thin titanium rod. The arc-starting voltage during melting is 20V and the arc-starting current is 2500A. After the molten pool stabilizes, the melting current is controlled at 3000A according to the melting point of the metal raw material. In vacuum magnetic levitation melting, the melting current is slowly reduced in a gradient manner. According to the different fluidity and melting point of the metal raw material, the feeding is divided into 3 stages. In the first stage, the melting current is controlled to decrease by 10% and held for 2 minutes. In the second stage, the melting current is controlled to decrease by 15% and held for 2 minutes. In the third stage, the melting current is controlled to decrease by 10% and held for 5 minutes. Then the melting current is gradually reduced to 0 at a rate of 200A / min for feeding. Then the riser is removed to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0056] Testing revealed that the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment exhibited high purity, no casting defects, formed a single solid solution, and did not produce a large amount of intermetallic compounds. It possessed a single-phase structure with a density of 7.732 g / cm³. 3 It exhibits a quasi-static plasticity of 25%, a compression ratio exceeding 50%, a compressive yield strength of approximately 500 MPa, and a tensile yield strength of approximately 450 MPa. It possesses excellent compressive and tensile properties, good ductility, and significant work hardening. It can be processed into various energetic structural materials and exhibits a significant positive strain rate effect. Through high-speed impact penetration experiments, it has been verified that under high-speed impact, the high-plasticity, highly active single-phase energetic high-entropy alloy undergoes deflagration. It can be used to manufacture various damage elements, including shaped charge shields and pre-fragmented components.

[0057] Example 3

[0058] This implementation includes the following steps:

[0059] Step 1: Press Co 45 Cr 15 Fe 15 Ni15 Weigh out Zr6Al2Ti2 metal raw materials with a purity of not less than 99.9%, remove the oxide scale from the metal raw materials to obtain clean metal raw materials;

[0060] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, and then put the clean metal raw materials of Cr, Zr, Ti, Fe, Co and Ni obtained in Step 1 into it in sequence to obtain the raw materials for the first melting.

[0061] Step 3: Place the raw materials obtained in Step 2 into the vacuum magnetic levitation melting furnace. First, evacuate the vacuum magnetic levitation melting furnace to a vacuum level of 2×10. -2 The pressure is below Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000Pa~6000Pa. The melting current is controlled at 1600A, the melting power at 600kW, and the melting time at 7min. The furnace is then cooled to obtain a first ingot.

[0062] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0063] Step 5: Flip the secondary ingot obtained in Step 4 and add the clean Al metal raw material obtained in Step 1. Then repeat Step 3 and Step 4 to obtain a vacuum magnetic levitation melting ingot.

[0064] Step Six: The vacuum magnetic levitation melting and casting ingot obtained in Step Five is then melted and cast at a vacuum level not exceeding 2 × 10⁻⁶. -2 Pa, the arc-starting material is sponge titanium shavings. The arc-starting voltage during melting is 50V and the arc-starting current is 4500A. After the molten pool stabilizes, the melting current is controlled at 15000A according to the melting point of the metal raw material. In vacuum magnetic levitation melting, the melting current is slowly reduced in a gradient manner. According to the different fluidity and melting point of the metal raw material, the feeding is divided into 3 stages. In the first stage, the melting current is controlled to decrease by 20% and held for 5 minutes. In the second stage, the melting current is controlled to decrease by 25% and held for 5 minutes. In the third stage, the melting current is controlled to decrease by 20% and held for 15 minutes. Then the melting current is gradually reduced to 0 at a rate of 500A / min for feeding. Then the riser is removed to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0065] Testing revealed that the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment exhibited high purity, no casting defects, formed a single solid solution, and did not produce a large amount of intermetallic compounds, exhibiting a single-phase structure with a density of 7.911 g / cm³. 3It exhibits a quasi-static plasticity of 30%, a compression of over 50%, a compressive yield strength of approximately 500 MPa, and a tensile yield strength of approximately 450 MPa. It possesses excellent compressive and tensile properties, good ductility, and significant work hardening. It can be processed into various energetic structural materials and exhibits a significant positive strain rate effect. Through high-speed impact penetration experiments, it has been verified that under high-speed impact, the high-plasticity, highly active single-phase energetic high-entropy alloy undergoes deflagration. It can be used to manufacture various damage elements, including shaped charge shields and pre-fragmented components.

[0066] Example 4

[0067] This implementation includes the following steps:

[0068] Step 1: Press Co 25 Fe 15 Ni 30 Zr 15 Al 10 Weigh out Ti5 metal raw materials with a purity of not less than 99.9%, remove the oxide scale from the metal raw materials to obtain clean metal raw materials;

[0069] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, and then put the clean metal raw materials Zr, Ti, Fe, Co and Ni obtained in Step 1 into it in sequence to obtain the first melting raw materials;

[0070] Step 3: Place the raw materials obtained in Step 2 into the vacuum magnetic levitation melting furnace. First, evacuate the vacuum magnetic levitation melting furnace to a vacuum level of 2×10. -2 The pressure is below Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000Pa~6000Pa. The melting current is controlled at 700A, the melting power at 800kW, and the melting time at 5min. The furnace is then cooled to obtain a first ingot.

[0071] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0072] Step 5: Flip the secondary ingot obtained in Step 4 and add the clean Al metal raw material obtained in Step 1. Then repeat Step 3 and Step 4 to obtain a vacuum magnetic levitation melting ingot.

[0073] Step Six: The vacuum magnetic levitation melting and casting ingot obtained in Step Five is then melted and cast at a vacuum level not exceeding 2 × 10⁻⁶. -2Pa, the arc-starting material is a thin titanium rod. The arc-starting voltage during melting is 35V and the arc-starting current is 3500A. After the molten pool stabilizes, the melting current is controlled at 10000A according to the melting point of the metal raw material. In vacuum magnetic levitation melting, the melting current is slowly reduced in a gradient manner. According to the different fluidity and melting point of the metal raw material, the feeding is divided into 3 stages. In the first stage, the melting current is controlled to decrease by 10% and held for 5 minutes. In the second stage, the melting current is controlled to decrease by 20% and held for 4 minutes. In the third stage, the melting current is controlled to decrease by 10% and held for 15 minutes. Then the melting current is gradually reduced to 0 at a rate of 300A / min for feeding. Then the riser is removed to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0074] Testing revealed that the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment exhibited high purity, no casting defects, formed a single solid solution, and did not produce a large amount of intermetallic compounds, exhibiting a single-phase structure with a density of 7.128 g / cm³. 3 It exhibits a quasi-static plasticity of 24%, a compression ratio exceeding 50%, a compressive yield strength of approximately 500 MPa, and a tensile yield strength of approximately 450 MPa. It possesses excellent compressive and tensile properties, good ductility, and significant work hardening. It can be processed into various energetic structural materials and exhibits a significant positive strain rate effect. Through high-speed impact penetration experiments, it has been verified that under high-speed impact, the high-plasticity, highly active single-phase energetic high-entropy alloy undergoes deflagration. It can be used to manufacture various damage elements, including shaped charge shields and pre-fragmented components.

[0075] Example 5

[0076] This implementation includes the following steps:

[0077] Step 1: Press Co 20 Fe 20 Ni 29 Cr 15 Weigh out metal raw materials with a purity of not less than 99.9% and remove the oxide scale from the metal raw materials to obtain clean metal raw materials;

[0078] Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, and then put the clean metal raw materials of Cr, Fe, Co and Ni obtained in Step 1 into it in sequence to obtain the raw materials for the first melting.

[0079] Step 3: Place the raw materials obtained in Step 2 into the vacuum magnetic levitation melting furnace. First, evacuate the vacuum magnetic levitation melting furnace to a vacuum level of 2×10. -2The pressure is below Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000Pa~6000Pa. The melting current is controlled at 800A, the melting power at 300kW, and the melting time at 5min. The furnace is then cooled to obtain a first ingot.

[0080] Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot.

[0081] Step 5: Flip the secondary ingot obtained in Step 4 and add the clean metal raw materials AlY and AlCe obtained in Step 1. Then repeat Step 3 and Step 4 to obtain the vacuum magnetic levitation melting ingot.

[0082] Step Six: The vacuum magnetic levitation melting and casting ingot obtained in Step Five is then melted and cast at a vacuum level not exceeding 2 × 10⁻⁶. -2 Pa, the arc-starting material is sponge titanium shavings. The arc-starting voltage during melting is 30V and the arc-starting current is 5500A. After the molten pool stabilizes, the melting current is controlled at 8000A according to the melting point of the metal raw material. In vacuum magnetic levitation melting, the melting current is slowly reduced in a gradient manner. According to the different fluidity and melting point of the metal raw material, the feeding is divided into 3 stages. In the first stage, the melting current is controlled to decrease by 10% and held for 5 minutes. In the second stage, the melting current is controlled to decrease by 20% and held for 4 minutes. In the third stage, the melting current is controlled to decrease by 10% and held for 15 minutes. Then the melting current is gradually reduced to 0 at a rate of 300A / min for feeding. Then the riser is removed to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy.

[0083] Testing revealed that the high-plasticity, high-activity single-phase energetic high-entropy alloy prepared in this embodiment exhibited high purity, no casting defects, formed a single solid solution, and did not produce a large amount of intermetallic compounds. It possessed a single-phase structure with a density of 7.232 g / cm³. 3 It exhibits a quasi-static plasticity of 22%, a compression ratio exceeding 50%, a compressive yield strength of approximately 500 MPa, and a tensile yield strength of approximately 450 MPa. It possesses excellent compressive and tensile properties, good ductility, and significant work hardening. It can be processed into various energetic structural materials and exhibits a significant positive strain rate effect. Through high-speed impact penetration experiments, it has been verified that under high-speed impact, the high-plasticity, highly active single-phase energetic high-entropy alloy undergoes deflagration. It can be used to manufacture various damage elements, including shaped charge shields and pre-fragmented components.

[0084] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention in any way. Any simple modifications, alterations, and equivalent changes made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A highly ductile, highly active single-phase energetic high-entropy alloy, characterized in that, The molecular formula of this high-entropy alloy is Co. 20 Cr 10 Fe 15 Ni 46 Al7Ti2, Co 20 Cr 20 Fe 20 Mn 10 Ni 26 Al2Mg2, Co 45 Cr 15 Fe 15 Ni 15 Zr6Al2Ti2, Co 25 Fe 15 Ni 30 Zr 15 Al 10 Ti5 or Co 20 Fe 20 Ni 29 Cr 15 Al8Ce4Y4; The method for preparing the highly ductile, highly active single-phase energetic high-entropy alloy includes the following steps: Step 1: Remove the oxide scale from the metal raw material to obtain clean metal raw material. Then, classify the clean metal raw material according to its volatility, melting point less than 1000℃ and melting point greater than or equal to 1000℃ to obtain volatile clean metal raw material, clean metal raw material with melting point less than 1000℃ and clean metal raw material with melting point greater than or equal to 1000℃. Step 2: Clean the water-cooled copper crucible in the vacuum magnetic levitation melting furnace, then place the volatile clean metal raw material obtained in Step 1 at the bottom of the crucible, and then put in the clean metal raw material with a melting point greater than or equal to 1000℃ to obtain the first melting raw material. Step 3: The raw material obtained in Step 2 is smelted under argon protection. The smelting current is 700A~1600A, the smelting power is 300kW~800kW, and the smelting time is 2min~7min. Then the furnace is cooled to obtain a first ingot. Step 4: After flipping the primary ingot obtained in Step 3, repeat Step 3 to smelt it and obtain a secondary ingot. Step 5: Flip the secondary ingot obtained in Step 4 and add the clean metal raw material with a melting point of less than 1000℃ obtained in Step 1. Then repeat Step 3 and Step 4 to obtain the vacuum magnetic levitation melting ingot. Step Six: Perform vacuum consumable melting on the vacuum magnetic levitation melting ingot obtained in Step Five, then remove the riser to obtain a high-plasticity, high-activity single-phase energetic high-entropy alloy; the high-plasticity, high-activity single-phase energetic high-entropy alloy has a single-phase structure and a density of not less than 7 g / cm³. 3 The plasticity under quasi-static conditions is not less than 20%.

2. The high-plasticity, high-activity single-phase energetic high-entropy alloy according to claim 1, characterized in that, The purity of the metal raw material mentioned in step one shall not be less than 99.9%.

3. The high-plasticity, high-activity single-phase energetic high-entropy alloy according to claim 1, characterized in that, The argon protection conditions described in step three are obtained by the following method: first, the vacuum magnetic levitation melting furnace is evacuated to a vacuum level of 2×10⁻⁶. -2 The pressure is below 5000 Pa, then argon gas is introduced and the argon gas pressure is controlled at 5000 Pa to 6000 Pa.

4. The high-plasticity, high-activity single-phase energetic high-entropy alloy according to claim 1, characterized in that, In step six, the vacuum degree during vacuum consumable melting shall not exceed 2 × 10⁻⁶. -2 Pa, the arc-starting material is titanium fine rod or sponge titanium shavings. The arc-starting voltage during melting is 20V~50V, and the arc-starting current is 2500A~5500A. After the molten pool stabilizes, the melting current is controlled at 3000A~15000A according to the melting point of the metal raw material.

5. The high-plasticity, high-activity single-phase energetic high-entropy alloy according to claim 1, characterized in that, In step six, the vacuum self-consuming melting process employs a feeding process, gradually reducing the melting current in a gradient manner. Depending on the fluidity and melting point of the metal raw material, the feeding process is divided into three stages. In the first stage, the melting current is controlled to decrease by 10% to 20% and then held for 2 to 5 minutes. In the second stage, the melting current is further controlled to decrease by 15% to 25% and then held for 2 to 5 minutes. In the third stage, the melting current is controlled to decrease by 10% to 20% and then held for 5 to 15 minutes. Subsequently, the melting current is gradually reduced to 0 at a rate of 200 A / min to 500 A / min.

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