CN110983101A - High-yield high-ductility medium-high-entropy alloy and preparation method thereof - Google Patents
High-yield high-ductility medium-high-entropy alloy and preparation method thereof Download PDFInfo
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- CN110983101A CN110983101A CN201911101011.8A CN201911101011A CN110983101A CN 110983101 A CN110983101 A CN 110983101A CN 201911101011 A CN201911101011 A CN 201911101011A CN 110983101 A CN110983101 A CN 110983101A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/05—Alloys based on copper with manganese as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D17/00—Pressure die casting or injection die casting, i.e. casting in which the metal is forced into a mould under high pressure
- B22D17/14—Machines with evacuated die cavity
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
Abstract
The invention discloses a medium-high entropy alloy with high yield and high elongation, which consists of the following elements in percentage by weight: 22-30 wt% of Mn, 4-10 wt% of Al, 5-20 wt% of Ni, 0.5-2 wt% of Ce and the balance of Cu, and vacuum die-casting molding is adopted, so that the medium-high entropy alloy has high strength and high plasticity.
Description
Technical Field
The invention relates to the technical field of material science, in particular to a high-yield high-elongation medium-high-entropy alloy and a preparation method thereof.
Background
With the development of modern economy, science and technology and military, people put higher requirements on the performance of materials. The requirements for material properties are also different for different use environments. For electronic products and automobile parts, materials having high strength and high plasticity are required. The conventional aluminum alloy and magnesium alloy are mature in technology and low in cost, but the mechanical strength of the conventional aluminum alloy and magnesium alloy is low, so that the further application of the conventional aluminum alloy and magnesium alloy is limited. Copper alloys have excellent castability and good plasticity, but their strength is low.
High entropy alloys are a recently emerging alloy design concept with excellent properties. Compared with the traditional alloy, the high-entropy alloy has high yield strength and ductility, good microstructure stability, good fatigue performance and good corrosion resistance. However, the high-entropy alloy material in the prior art has low strength, cannot simultaneously ensure high strength and high plasticity, and even if the high-entropy alloy material can simultaneously achieve high strength and high plasticity, the manufacturing process steps are relatively complex.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide the medium-high entropy alloy with high yield and high ductility and the preparation method thereof, which can simultaneously give consideration to high strength and high plasticity, have simple element composition and simple process steps, and are suitable for industrialized large-scale production.
The purpose of the invention is realized by adopting the following technical scheme:
a high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: mn22-30 wt%, Al 4-10 wt%, Ni 5-20 wt%, Ce 0.5-2 wt% and Cu for the rest.
According to
Wherein n is a number of elements; c. CiIs the atomic percentage of the ith component; r is a gas constant. The mass percent of the metal elements is converted into the atomic percent, the atomic percent is substituted into the formula, and the entropy value of the alloy is calculated to be larger than 1.2R, and the alloy belongs to the medium-entropy alloy.
The metal raw material is added in the invention for the following functions:
cu: copper has excellent ductility and corrosion resistance, while copper has good castability.
Mn: the manganese and the copper can be dissolved in each other infinitely, and the solid solution strengthening effect is achieved. Manganese can be used as a deoxidizer in the smelting process to reduce the oxygen content of the alloy; can also improve the fluidity of the solution and improve the molding capacity. In the alloy, Mn and Ni can form Mn/Ni compound to play the role of precipitation strengthening.
Ni: nickel is the main alloying element of cupronickel. Copper and nickel can be dissolved in each other infinitely to form a solid solution, and the solid solution strengthening effect is achieved. The nickel can enter a corrosion product cuprous oxide lattice structure in the copper alloy in an ion form, so that the corrosion resistance of the alloy is improved.
Al: aluminum is a common additive element for bronzes. The potential of the aluminum standard cone electrode is-1.66V, ions are more easily formed, and a compact oxide film is formed by combining oxygen, so that the corrosion resistance of the alloy is further improved. Meanwhile, the aluminum and the nickel can form NiAl compounds, so that the effect of precipitation strengthening is achieved, the strength of the alloy is improved, and the plasticity of the alloy is reduced.
Ce: the addition of cerium can play a role in purifying melt, degassing and impurity removal and improving microstructure. Experiments prove that the yield strength and the elongation can be obviously improved by adding cerium.
The medium-high entropy alloy with high yield and high ductility only consists of five metal elements, and the used raw materials are all industrial common raw materials.
Specifically, the medium-high entropy alloy with high yield and high ductility consists of the following elements in percentage by weight: mn27 wt%, Al 5%, Ni 12%, Ce 0.65% and Cu in balance.
The preparation method of the medium-high entropy alloy with high yield and high elongation comprises the following steps:
1) pretreatment: carrying out ultrasonic cleaning and drying on the raw materials;
2) smelting: vacuumizing, smelting, refining and cooling. Wherein, the refining after smelting is to ensure that all components are uniformly mixed, simultaneously remove gas and impurities in the melt, purify the melt and improve the ingot casting quality;
3) die-casting and forming: the mold temperature is 260-280 ℃, and the melt temperature is 990-1030 ℃.
Further, in the step 1), the water temperature is 60 ℃, and the cleaning time is 360 s; the drying temperature is 110 ℃, and the drying time is 1200 s.
Further, in the step 2), the vacuum degree is 1 Pa; the smelting power is 150kW, and the smelting time is 25-30 min; the refining power is 110kW, and the refining time is 7-10 min; the cooling time is 10-15 min.
Further, in the step 3), die casting is carried out in a vacuum die casting machine, and the vacuum degree is 50 Pa. Compared with the common die casting method, the vacuum die casting method has the following characteristics: (1) the porosity is greatly reduced; (2) the vacuum die-cast casting has high hardness and fine microstructure.
Compared with the prior art, the invention has the beneficial effects that:
(1) the raw materials used in the invention are low in price and stable and easily available, the yield strength and the elongation can be obviously improved by adding cerium, and the high yield is ensured and the high plasticity is realized.
(2) The preparation method provided by the invention is simple in steps and suitable for industrial production.
Drawings
FIG. 1 is a schematic metallographic view of an entropy alloy without the addition of cerium;
FIG. 2 is a schematic metallographic view of the cerium-doped cerium alloy of the present invention.
Detailed Description
The present invention is further described below with reference to specific embodiments, and it should be noted that, without conflict, any combination between the embodiments or technical features described below may form a new embodiment.
Example 1
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: mn25 wt%, Al4 wt%, Ni 15 wt%, Ce 0.5 wt% and Cu balance.
The preparation method of the medium-high entropy alloy with high yield and high elongation comprises the following steps:
1) pretreatment: carrying out ultrasonic cleaning and drying on the raw materials; wherein the water temperature is 60 ℃, and the cleaning time is 360 s; the drying temperature is 110 ℃, and the drying time is 1200 s.
2) Smelting: vacuumizing, smelting, refining and cooling; wherein the vacuum degree is 1 Pa; the smelting power is 150kW, and the smelting time is 25 min; the refining power is 110kW, and the refining time is 7 min; the cooling time was 10 min.
3) Die-casting and forming: die casting in a vacuum die casting machine, wherein the vacuum degree is 50Pa, the die temperature is 260 ℃, and the melt temperature is 990 ℃.
Example 2
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 27 wt% of Mn, 5 wt% of Al, 12 wt% of Ni, 0.65 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high elongation comprises the following steps:
1) pretreatment: carrying out ultrasonic cleaning and drying on the raw materials; wherein the water temperature is 60 ℃, and the cleaning time is 360 s; the drying temperature is 110 ℃, and the drying time is 1200 s.
2) Smelting: vacuumizing, smelting, refining and cooling; wherein the vacuum degree is 1 Pa; the smelting power is 150kW, and the smelting time is 26 min; the refining power is 110kW, and the refining time is 8 min; the cooling time was 11 min.
3) Die-casting and forming: die casting in a vacuum die casting machine, wherein the vacuum degree is 50Pa, the die temperature is 270 ℃, and the melt temperature is 1000 ℃.
Example 3
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 26 wt% of Mn, 6 wt% of Al, 10 wt% of Ni, 0.8 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high elongation comprises the following steps:
1) pretreatment: carrying out ultrasonic cleaning and drying on the raw materials; wherein the water temperature is 60 ℃, and the cleaning time is 360 s; the drying temperature is 110 ℃, and the drying time is 1200 s.
2) Smelting: vacuumizing, smelting, refining and cooling; wherein the vacuum degree is 1 Pa; the smelting power is 150kW, and the smelting time is 30 min; the refining power is 110kW, and the refining time is 10 min; the cooling time was 15 min.
3) Die-casting and forming: die casting in a vacuum die casting machine, wherein the vacuum degree is 50Pa, the die temperature is 280 ℃, and the melt temperature is 1030 ℃.
Example 4
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 29 wt% of Mn, 7 wt% of Al, 10 wt% of Ni, 1.2 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high elongation is the same as that of the embodiment 1.
Example 5
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 27 wt% of Mn, 5 wt% of Al, 12 wt% of Ni, 1.8 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high ductility is the same as that of the embodiment 2.
Example 6
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 30 wt% of Mn, 3 wt% of Al, 15 wt% of Ni, 2 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high ductility is the same as that of the embodiment 3.
Example 7
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 22 wt% of Mn, 8 wt% of Al, 10 wt% of Ni, 2 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high elongation is the same as that of the embodiment 1.
Example 8
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 30 wt% of Mn, 8 wt% of Al, 15 wt% of Ni, 2 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high ductility is the same as that of the embodiment 3.
Control group 1
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: 27 wt% of Mn, 5 wt% of Al, 13 wt% of Ni, 0 wt% of Ce and the balance of Cu.
The preparation method of the medium-high entropy alloy with high yield and high elongation is the same as that of the embodiment 1.
A high-yield high-ductility medium-high entropy alloy is composed of the following elements in percentage by weight: mn28 wt%, Al5 wt%, Ni 12 wt%, Ce 3 wt% and Cu balance.
The preparation method of the medium-high entropy alloy with high yield and high elongation is the same as that of the embodiment 1.
Performance testing
Tensile strength, yield strength and elongation were measured for examples 1-8 and the control, using the international GB/T228.1-2010 test standard. The metallographic test was then carried out on example 1 and the control.
TABLE 1 Performance test data for examples 1-6 and control
| Tensile strength (Mpa) | Yield strength (Mpa) | Elongation (%) | |
| Example 1 | 989 | 832 | 6.0 |
| Example 2 | 999 | 850 | 5.5 |
| Example 3 | 986 | 865 | 4.0 |
| Example 4 | 953 | 824 | 4.0 |
| Example 5 | 998 | 867 | 2.5 |
| Example 6 | 948 | 820 | 2.5 |
| Example 7 | 995 | 858 | 2.0 |
| Example 8 | 980 | 847 | 2.0 |
| Control group 1 | 956 | 843 | 1.5 |
| |
942 | 814 | 1.5 |
As can be seen from Table 1, the comparative group 1, which does not contain cerium, has lower tensile strength, yield strength and elongation than those of examples 1-8, so the cerium content has a significant effect on the properties of the alloy; the contents of manganese, nickel and aluminum do not greatly affect the properties within the scope of the invention. Cerium can improve the strength of the alloy and obviously improve the plasticity of the alloy. The elongation of the alloy increases and then decreases with increasing cerium content. The Ce content of control 2 was 3 wt% which is greater than the maximum Ce content defined in the present invention, but the tensile strength, yield strength and elongation of control 2 were all lower than those of examples 1-8, and as described above, it was shown that the Ce content defined in the present invention is in the range of 0.5-2 wt% as the optimum range. Wherein example 2 gave the best overall properties with tensile strength, yield strength and elongation of 999Mpa, 850Mpa and 5.5% respectively.
As shown in fig. 1 and 2, the microstructure of the alloy greatly differs before and after the addition of cerium. After the cerium element is added, the fine second phase distributed in the alloy matrix is more uniform, and the strength and the plasticity of the alloy can be comprehensively improved. Meanwhile, a small amount of petal-shaped tissues below 20 microns appear in the matrix, and the proper amount of the tissues can comprehensively improve the performance of the alloy.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (6)
1. The medium-high entropy alloy with high yield and high ductility is characterized by comprising the following elements in percentage by weight: mn22-30 wt%, Al 4-10 wt%, Ni 5-20 wt%, Ce 0.5-2 wt% and Cu for the rest.
2. The high-yield high-ductility medium-high entropy alloy as claimed in claim 1, characterized by consisting of the following elements in percentage by weight: 27 wt% of Mn, 5 wt% of Al, 55.35 wt% of Cu, 12 wt% of Ni and 0.65 wt% of Ce.
3. The method for preparing the high-yield high-elongation medium-high entropy alloy as claimed in any one of claims 1 to 2, characterized by comprising the following steps:
1) pretreatment: carrying out ultrasonic cleaning and drying on the raw materials;
2) smelting: vacuumizing, smelting, refining and cooling;
3) die-casting and forming: the mold temperature is 260-280 ℃, and the melt temperature is 990-1030 ℃.
4. The method for preparing the high-yield high-ductility medium-high entropy alloy as claimed in claim 3, wherein in the step 1), the water temperature is 60 ℃, and the cleaning time is 360 s; the drying temperature is 110 ℃, and the drying time is 1200 s.
5. The method for preparing the high-yield high-ductility medium-high entropy alloy as claimed in claim 3, wherein in the step 2), the vacuum degree is 1 Pa; the smelting power is 150kW, and the smelting time is 25-30 min; the refining power is 110kW, and the refining time is 7-10 min; the cooling time is 10-15 min.
6. The method for preparing the high-yield high-ductility medium-high entropy alloy as claimed in claim 3, wherein in the step 3), the die casting is carried out in a vacuum die casting machine, and the vacuum degree is 50 Pa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322396A (en) * | 2021-05-26 | 2021-08-31 | 沈阳航空航天大学 | Copper-nickel-based medium-entropy alloy with excellent comprehensive mechanical properties and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS594946A (en) * | 1982-06-30 | 1984-01-11 | Hitachi Metals Ltd | Production of cu-al-mn magnetic alloy |
| CN105525134A (en) * | 2015-02-05 | 2016-04-27 | 比亚迪股份有限公司 | High-strength alloy and preparation method thereof |
| CN107641732A (en) * | 2017-09-19 | 2018-01-30 | 西南交通大学 | A kind of preparation method of high-damping two-phase Mn Cu alloys |
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- 2019-11-12 CN CN201911101011.8A patent/CN110983101A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS594946A (en) * | 1982-06-30 | 1984-01-11 | Hitachi Metals Ltd | Production of cu-al-mn magnetic alloy |
| CN105525134A (en) * | 2015-02-05 | 2016-04-27 | 比亚迪股份有限公司 | High-strength alloy and preparation method thereof |
| CN107641732A (en) * | 2017-09-19 | 2018-01-30 | 西南交通大学 | A kind of preparation method of high-damping two-phase Mn Cu alloys |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113322396A (en) * | 2021-05-26 | 2021-08-31 | 沈阳航空航天大学 | Copper-nickel-based medium-entropy alloy with excellent comprehensive mechanical properties and preparation method thereof |
| CN113322396B (en) * | 2021-05-26 | 2021-12-17 | 沈阳航空航天大学 | Copper-nickel-based medium-entropy alloy with excellent comprehensive mechanical properties and preparation method thereof |
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Application publication date: 20200410 |