As-cast eutectic high-entropy alloy material with strong plasticity and preparation method thereof
By preparing CrFeNiMoNbM high-entropy alloys with non-equiatomic ratios and employing tungsten inert gas melting and suction casting methods, the room temperature brittleness problem of as-cast eutectic high-entropy alloys was solved, achieving high strength and high plasticity.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- HEILONGJIANG UNIVERSITY OF SCIENCE AND TECHNOLOGY
- Filing Date
- 2026-05-28
- Publication Date
- 2026-06-26
AI Technical Summary
The brittleness problem of cast eutectic high-entropy alloys containing the Laves phase at room temperature has not been effectively solved in the existing technology, which seriously limits their application. In addition, traditional hot working methods increase cost and process complexity, and there are no reports on improving tensile plasticity.
Using CrFeNiMoNbM high-entropy alloy materials with non-equiatomic ratios, as-cast eutectic high-entropy alloys are prepared by tungsten inert gas melting and suction casting methods. The specific steps include repeated melting under argon atmosphere protection and pouring the melt into a copper mold to form a as-cast eutectic high-entropy alloy with strong plasticity.
The prepared as-cast eutectic high-entropy alloy material exhibits high strength and high plasticity, with tensile strength of 711 MPa~1013 MPa and strain of 1.85%~5.2%, solving the problem of room temperature brittleness. The process is simple and the quality is good.
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Figure CN122279358A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of high-entropy alloy materials, specifically relating to a cast eutectic high-entropy alloy material with strong plasticity and its preparation method. Background Technology
[0002] High entropy alloys (HEAs) achieve unique microstructures and macroscopic properties by introducing five or more principal elements with equal or near-equal atomic ratios, creating a "high entropy effect." HEAs with a predominantly FCC structure exhibit good plasticity but relatively insufficient strength, while HEAs with a predominantly BCC structure possess high strength but low plasticity. To address the inherent strength-plasticity contradiction in HEAs, the properties of eutectic alloys are introduced into the HEA system, leading to the development of eutectic high entropy alloys (EHEAs).
[0003] Some EHEAs exhibit poor plasticity due to the presence of a large amount of hard and brittle Laves phase, severely limiting their use as engineering materials. Although grain refinement can effectively improve the strength-plasticity of traditional binary alloys containing intermetallic compounds, improving the strength-plasticity of multi-principal EHEAs containing brittle Laves phases remains a serious challenge.
[0004] To address the room-temperature brittleness of as-cast eutectic high-entropy alloys containing the Laves phase, hot working methods (such as homogenization annealing and hot rolling) are commonly used to improve the compressive plasticity of these alloys. However, hot working increases costs and process complexity. There are no reports on improving the tensile plasticity of as-cast eutectic high-entropy alloys containing the Laves phase, which severely restricts their widespread application. Summary of the Invention
[0005] The purpose of this invention is to solve the problem of room temperature brittleness in existing cast eutectic high-entropy alloys containing the Laves phase, and to provide a cast eutectic high-entropy alloy material with strong plasticity and its preparation method.
[0006] A cast eutectic high-entropy alloy material with strong plasticity is a non-equiatomic CrFeNiMoNbM high-entropy alloy; the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M in the CrFeNiMoNbM high-entropy alloy is (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2), wherein M is Gd, Er or Y.
[0007] A method for preparing a cast eutectic high-entropy alloy material with strong plasticity is specifically carried out according to the following steps:
[0008] 1. Weigh out Cr, Fe, Ni, Mo, Nb and M respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M as (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2) to obtain raw materials;
[0009] 2. Place the raw materials into the copper crucible of the tungsten inert arc furnace, and repeatedly purge the furnace with high-purity argon gas 4-6 times to purge the air from the furnace. Each time, maintain the gas pressure inside the furnace at 5 × 10⁻⁶. -3 ~6×10 -3 Pa, then under argon atmosphere protection and current of 250~300A, repeatedly melt 4~6 times, each melting time is 2.5~3min, to obtain melt. Finally, in the melting copper crucible, the melt is poured into the copper mold by suction casting method to prepare a cast eutectic high entropy alloy material with strong plasticity and a diameter of not less than 10mm.
[0010] Advantages of this invention:
[0011] I. The cast eutectic high-entropy alloy material with strong plasticity prepared by this invention has excellent mechanical properties such as high strength and high plasticity. The method of preparing the cast eutectic high-entropy alloy material with strong plasticity by this invention adopts the casting method, which is simple and produces good quality, and solves the problem of room temperature brittleness of eutectic high-entropy alloys containing Laves phase.
[0012] II. The tensile strength (σ) of the cast eutectic high-entropy alloy material with strong plasticity prepared by this invention is 711MPa~1013MPa, and the strain (ε) is 1.85%~5.2%. Attached Figure Description
[0013] Figure 1 Comparison of the microstructure morphology of the alloys prepared in Examples 1, 2, and 3, with magnified images embedded, where (a) is Example 1, (b) is Example 2, and (c) is Example 3;
[0014] Figure 2 Comparison images of the microstructure morphology of the alloys prepared in Examples 4, 5, 6, 7, and 8 are shown, with magnified images embedded. Among them, (a) is Example 4, (b) is Example 5, (c) is Example 6, (d) is Example 7, and (e) is Example 8. Detailed Implementation
[0015] Specific Implementation Method 1: This implementation method is a cast eutectic high-entropy alloy material with strong plasticity, which is a non-equiatomic ratio CrFeNiMoNbM high-entropy alloy; the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M in the CrFeNiMoNbM high-entropy alloy is (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2), wherein M is Gd, Er or Y.
[0016] Specific Implementation Method Two: This implementation method differs from Specific Implementation Method One in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.98:1.96:1.96:0.3:0.5:0.02; and M is Gd. Other steps are the same as in Specific Implementation Method One.
[0017] Specific Implementation Method Three: The difference between this implementation method and Specific Implementation Method One or Two is that the atomic ratio of each element Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.94:1.88:1.88:0.3:0.5:0.06; and M is Gd. Other steps are the same as in Specific Implementation Method One or Two.
[0018] Specific Implementation Method Four: The difference between this implementation method and Specific Implementation Methods One to Three is that the atomic ratio of each element Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.97:1.94:1.94:0.3:0.5:0.03; and M is Y. Other steps are the same as in Specific Implementation Methods One to Three.
[0019] Specific Implementation Method Five: This implementation method differs from Specific Implementation Methods One to Four in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.98:1.96:1.96:0.3:0.5:0.02; and M is Er. Other steps are the same as in Specific Implementation Methods One to Four.
[0020] Specific Implementation Method Six: This implementation method differs from Specific Implementation Methods One to Five in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.94:1.88:1.88:0.3:0.5:0.06; and M is Er. Other steps are the same as in Specific Implementation Methods One to Five.
[0021] Specific Implementation Method Seven: This implementation method differs from Specific Implementation Methods One to Six in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.91:1.82:1.82:0.3:0.5:0.09; and M is Er. Other steps are the same as in Specific Implementation Methods One to Six.
[0022] Specific Implementation Method Eight: This implementation method differs from Specific Implementation Methods One to Seven in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.88:1.76:1.76:0.3:0.5:0.12; and M is Er. Other steps are the same as in Specific Implementation Methods One to Seven.
[0023] Specific Implementation Method Nine: This implementation method differs from Specific Implementation Methods One to Eight in that the atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.84:1.68:1.68:0.3:0.5:0.16; and M is Er. Other steps are the same as in Specific Implementation Methods One to Eight.
[0024] Specific Implementation Method Ten: This implementation method differs from Specific Implementation Methods One through Nine in that it involves a method for preparing a cast eutectic high-entropy alloy material with strong plasticity, specifically completed according to the following steps:
[0025] 1. Weigh out Cr, Fe, Ni, Mo, Nb and M respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M as (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2) to obtain raw materials;
[0026] 2. Place the raw materials into the copper crucible of the tungsten inert arc furnace, and repeatedly purge the furnace with high-purity argon gas 4-6 times to purge the air from the furnace. Each time, maintain the gas pressure inside the furnace at 5 × 10⁻⁶. -3 ~6×10 -3 Pa, then under argon atmosphere protection and current of 250~300A, repeatedly melt 4~6 times, each melting time is 2.5~3min, to obtain melt. Finally, in the melting copper crucible, the melt is poured into the copper mold by suction casting method to prepare a cast eutectic high entropy alloy material with strong plasticity and a diameter of not less than 10mm.
[0027] The beneficial effects of the present invention are verified using the following embodiments:
[0028] Example 1: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0029] 1. Weigh out Cr, Fe, Ni, Mo, Nb, and Gd according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb, and Gd as 0.98:1.96:1.96:0.3:0.5:0.02 to obtain the raw materials;
[0030] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.98 Fe 1.96 Ni 1.96 Mo 0.3 Nb 0.5 Gd 0.02 ).
[0031] Example 2: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0032] I. Weigh out Cr, Fe, Ni, Mo, Nb, and Gd according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb, and Gd of 0.94:1.88:1.88:0.3:0.5:0.06 to obtain the raw materials;
[0033] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.94 Fe 1.88 Ni 1.88 Mo 0.3 Nb 0.5 Gd 0.06 ).
[0034] Example 3: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0035] 1. Weigh out Cr, Fe, Ni, Mo, Nb and Y respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Y of 0.97:1.94:1.94:0.3:0.5:0.03 to obtain raw materials;
[0036] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.97 Fe 1.94 Ni 1.94 Mo 0.3 Nb 0.5 Y 0.03 ).
[0037] Example 4: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0038] 1. Weigh out Cr, Fe, Ni, Mo, Nb and Er respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Er of 0.98:1.96:1.96:0.3:0.5:0.02 to obtain raw materials;
[0039] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.98 Fe 1.96 Ni 1.96 Mo 0.3 Nb 0.5 Er 0.02 ).
[0040] Example 5: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0041] I. Weigh out Cr, Fe, Ni, Mo, Nb and Er respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Er of 0.94:1.88:1.88:0.3:0.5:0.06 to obtain the raw materials;
[0042] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.94 Fe 1.88 Ni 1.88 Mo 0.3 Nb 0.5 Er 0.06 ).
[0043] Example 6: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0044] 1. Weigh out Cr, Fe, Ni, Mo, Nb and Er respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Er of 0.91:1.82:1.82:0.3:0.5:0.09 to obtain the raw materials;
[0045] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.91 Fe 1.82 Ni 1.82 Mo 0.3 Nb 0.5 Er 0.09 ).
[0046] Example 7: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically completed according to the following steps:
[0047] 1. Weigh out Cr, Fe, Ni, Mo, Nb and Er respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Er in the CrFeNiMoNbM high entropy alloy as 0.88:1.76:1.76:0.3:0.5:0.12 to obtain raw materials;
[0048] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.88 Fe 1.76 Ni 1.76 Mo 0.3 Nb 0.5 Er 0.12 ).
[0049] Example 8: A method for preparing a cast eutectic high-entropy alloy material with strong plasticity, characterized in that the preparation method is specifically carried out according to the following steps:
[0050] 1. Weigh out Cr, Fe, Ni, Mo, Nb and Er respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and Er in the CrFeNiMoNbM high-entropy alloy as 0.84:1.68:1.68:0.3:0.5:0.16 to obtain the raw materials;
[0051] 2. Place the raw materials into the copper crucible of the tungsten inert gas (TIG) furnace, and repeatedly purge the furnace with high-purity argon gas five times to purge the air from the furnace. Each time, maintain the furnace pressure at 5 × 10⁻⁶. -3 Pa, then repeatedly melted 5 times under argon atmosphere and 300A current, each melting time being 3 minutes, to obtain a melt. Finally, in a copper crucible, the melt was poured into a copper mold using a suction casting method to prepare a cast eutectic high-entropy alloy material (Cr) with a diameter of 10mm and possessing strong plasticity. 0.84 Fe 1.68 Ni 1.68 Mo 0.3 Nb 0.5 Er 0.16 ).
[0052] The tensile strength (σ) and strain (ε) of the cast eutectic high-entropy alloy materials with strong plasticity prepared in Examples 1-8 are shown in Table 1;
[0053] Table 1
[0054]
[0055] As shown in Table 1, the cast eutectic high-entropy alloy material with strong plasticity prepared by the present invention has excellent mechanical properties such as high strength and high plasticity, as well as significant work hardening ability. The method of preparing the cast eutectic high-entropy alloy material with strong plasticity by the present invention adopts the casting method, which is simple and produces good quality, and solves the problem of room temperature brittleness of eutectic high-entropy alloys containing Laves phase.
[0056] Figure 1 Comparison of the microstructure morphology of the alloys prepared in Examples 1, 2, and 3, with magnified images embedded, where (a) is Example 1, (b) is Example 2, and (c) is Example 3;
[0057] Figure 2 Comparison images of the microstructure morphology of the alloys prepared in Examples 4, 5, 6, 7, and 8 are shown, with magnified images embedded. Among them, (a) is Example 4, (b) is Example 5, (c) is Example 6, (d) is Example 7, and (e) is Example 8.
[0058] from Figure 1 and Figure 2 The microscopic images show that the improvement in strength and plasticity of the alloy prepared by this invention is partly due to the formation of the primary FCC phase and partly due to the interaction between the FCC phase and the lamellar eutectic; the ratio of the improvement in strength and plasticity is related to the ratio of the FCC phase to the Laves phase.
Claims
1. A cast eutectic high-entropy alloy material with strong plasticity, characterized in that... The cast eutectic high-entropy alloy material with strong plasticity is a non-equiatomic high-entropy alloy of CrFeNiMoNbM; the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M in the CrFeNiMoNbM high-entropy alloy is (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2), wherein M is Gd, Er or Y.
2. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.98:1.96:1.96:0.3:0.5:0.02; and M is Gd.
3. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.94:1.88:1.88:0.3:0.5:0.06; M is Gd.
4. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.97:1.94:1.94:0.3:0.5:0.03; and M is Y.
5. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of each element Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.98:1.96:1.96:0.3:0.5:0.02; and M is Er.
6. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.94:1.88:1.88:0.3:0.5:0.06; M is Er.
7. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.91:1.82:1.82:0.3:0.5:0.09; M is Er.
8. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.88:1.76:1.76:0.3:0.5:0.12; M is Er.
9. The cast eutectic high-entropy alloy material with strong plasticity according to claim 1, characterized in that... The atomic ratio of Cr, Fe, Ni, Mo, Nb, and M in the CrFeNiMoNbM high-entropy alloy is 0.84:1.68:1.68:0.3:0.5:0.16; M is Er.
10. The method for preparing a cast eutectic high-entropy alloy material with strong plasticity as described in claim 1, characterized in that... The preparation method described herein is specifically carried out according to the following steps:
1. Weigh out Cr, Fe, Ni, Mo, Nb and M respectively according to the atomic ratio of each element Cr, Fe, Ni, Mo, Nb and M as (0.8~1):(1.5~2):(1.5~2):(0.1~0.4):(0.3~0.7):(0.01~0.2) to obtain raw materials; 2. Place the raw materials into the copper crucible of the tungsten inert arc furnace, and repeatedly purge the furnace with high-purity argon gas 4-6 times to purge the air from the furnace. Each time, maintain the gas pressure inside the furnace at 5 × 10⁻⁶. -3 ~6×10 -3 Pa, then under argon atmosphere protection and current of 250~300A, repeatedly melt 4~6 times, each melting time is 2.5~3min, to obtain melt. Finally, in the melting copper crucible, the melt is poured into the copper mold by suction casting method to prepare a cast eutectic high entropy alloy material with strong plasticity and a diameter of not less than 10mm.