CN115109982A - Deformation CoCrNiAlTi medium-entropy alloy with excellent performance in medium-high temperature range and preparation method thereof - Google Patents
Deformation CoCrNiAlTi medium-entropy alloy with excellent performance in medium-high temperature range and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 93
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- 238000005242 forging Methods 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000265 homogenisation Methods 0.000 claims description 9
- 238000005266 casting Methods 0.000 claims description 8
- 230000007547 defect Effects 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- 238000005728 strengthening Methods 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 230000002159 abnormal effect Effects 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 229910000601 superalloy Inorganic materials 0.000 description 4
- 229910000905 alloy phase Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001325 element alloy Inorganic materials 0.000 description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
- B21J5/00—Methods for forging, hammering, or pressing; Special equipment or accessories therefor
- B21J5/002—Hybrid process, e.g. forging following casting
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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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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Abstract
The invention discloses a deformation CoCrNiAlTi medium entropy alloy with excellent performance in a medium-high temperature range and a preparation method thereof, wherein the alloy comprises the following components in atomic percentage: co: 31-35%, Cr: 28-33%, Ni: 24-28%, Al: 4-7%, Ti: 4-7%, and the deformed CoCrNiAlTi medium-entropy alloy with excellent performance in the medium-high temperature range obtains higher comprehensive mechanical property in the medium-high temperature range, and overcomes the defect of medium-temperature brittleness commonly existing in high-temperature alloys.
Description
Technical Field
The invention belongs to the field of preparation of high-performance high-temperature alloy materials, and particularly relates to a deformed CoCrNiAlTi complex intermediate entropy alloy with excellent comprehensive mechanical properties in a medium-high temperature range and a preparation method thereof.
Background
The high-temperature alloy has higher strength and good comprehensive performance such as high-temperature oxidation corrosion resistance and the like in a high-temperature environment, and is widely applied to important fields such as aerospace, petrochemical industry and the like. Among them, nickel-based and nickel-cobalt-based superalloys are the most widely used high-temperature structural materials at present. Generally, nickel-based and cobalt-based superalloys can be formed by precipitation of L1 2 The structural ordered phase realizes the improvement of high-temperature strength. However, in the case of wrought superalloy, grain boundary strengthening is also required in order to improve high temperature creep resistance and avoid grain boundary sliding because the grain structure is fine. However, for complex composition superalloys, coarse brittle phases (e.g., carbides, Cr-sigma rich phases, Ni) tend to form at grain boundaries by discontinuous nucleation 2 (Al, Ti) -type Heusler phase, Ni 3 Ti-type eta phase and Laves phase) and has low instantaneous tensile plasticity in the medium temperature region (600-800 ℃), which is represented by typical medium temperature brittleness. Therefore, in order to obtain good tensile properties in a medium-high temperature region, it is necessary to precipitate a strengthening phase at grain boundaries of a fine grain structure and to have a good ability to coordinate plastic deformation between the strengthening phase and a matrix.
Disclosure of Invention
In view of the above, the invention provides a CoCrNiAlTi multi-principal element medium entropy alloy with high tensile strength and good tensile plasticity in a medium-high temperature range (600 ℃ -800 ℃) and a preparation method thereof aiming at the common weak point of medium temperature brittleness of nickel-based and nickel-cobalt-based high temperature alloys.
The invention provides a deformation CoCrNiAlTi medium entropy alloy with excellent performance in a medium-high temperature range, which comprises the following components in atomic percentage: co: 31-35%, Cr: 28-33%, Ni: 24-28%, Al: 4-7%, Ti: 4-7 percent.
Preferably, the deformed CoCrNiAlTi medium-entropy alloy with excellent performance in the medium-high temperature range comprises the following components in atomic percentage: co: 32-34%, Cr: 29-31%, Ni: 25-27%, Al: 4.5-5.5%, Ti: 4.5 to 5.5 percent.
The invention also provides a preparation method of the deformation CoCrNiAlTi medium entropy alloy with excellent performance in the medium-high temperature range, which comprises the following steps:
(1) preparing alloy according to the components and the atomic percentage thereof, and casting the alloy into an ingot;
(2) homogenizing the cast ingot to form a homogenized cast ingot;
(3) hot forging the homogenized cast ingot to obtain an alloy hot-forged bar with an FCC single phase;
(4) and carrying out aging heat treatment on the alloy hot forged bar with the FCC single phase to obtain the deformed CoCrNiAlTi medium-entropy alloy bar with excellent performance in a medium-high temperature range.
Preferably, in the step (2), the homogenization treatment is carried out at 1000-1200 ℃ for 18-32h, and the homogenization treatment is carried out with furnace cooling to room temperature after the heat preservation is finished.
Further preferably, in the step (3), the hot forging temperature is 1120-.
More preferably, in the step (3), the hot forging is a multiple-pass forging with a small forging amount.
Further preferably, in the step (4), the temperature of the aging heat treatment is 600-800 ℃, and the time is 2-6 h.
According to the deformed CoCrNiAlTi intermediate entropy alloy with excellent performance in the medium-high temperature range, high-content Cr and gamma '-phase forming elements Al and Ti are added into the Co-rich intermediate entropy alloy, and when a high-volume-fraction gamma' -phase is obtained, recrystallization and the precipitation kinetics of a second phase are regulated and controlled through a thermal mechanical deformation and aging treatment system, so that a CrCo-rich second intermediate entropy alloy phase is precipitated at the grain boundary of a recrystallized structure. When a fine recrystallized grain structure is obtained, a gamma' phase with a high volume fraction of a nanometer level is distributed in the crystal, and a second medium entropy alloy phase with a rich CrCo in a micron-sized block is distributed at the crystal boundary, so that the medium temperature brittleness problem of the alloy is avoided, the comprehensive strengthening and toughening in the medium-high temperature deformation process are realized, and the alloy is endowed with a high strength-plasticity comprehensive performance index in a medium-high temperature range on the basis.
The deformation CoCrNiAlTi intermediate entropy alloy with excellent performance in the medium-high temperature range and the preparation method thereof overcome the defect of medium-temperature brittleness commonly existing in high-temperature alloys by reasonably regulating and controlling the medium-entropy alloy components and the preparation process of the CoCrNiAlTi intermediate entropy alloy, so that the alloy obtains higher comprehensive mechanical performance in the medium-high temperature range. The alloy bar can be processed into products in various forms, and has wide application in the production of aerospace high-temperature parts. The use of conventional elements such as Co, Cr, Ni, Al, Ti and the like ensures that the alloy has moderate price, the material preparation process is relatively simple, and the industrial investment is low.
Drawings
The invention is described in further detail below with reference to the following figures and embodiments:
FIG. 1 is a microstructure diagram of a deformed CoCrNiAlTi medium-entropy alloy with excellent performance in a medium-high temperature range, which is obtained after aging heat treatment;
FIG. 2 is a typical mechanical property curve diagram of the deformed CoCrNiAlTi medium-entropy alloy with excellent performance in the medium-high temperature range in the stretching process.
Detailed Description
The concept of multi-principal-element high-entropy alloy is provided by Yeh equal to 2004, and the alloy has excellent performances such as good thermal stability, high hardness, high strength, high wear resistance, high corrosion resistance and the like which cannot be compared with the traditional alloy. Compared with the traditional high-temperature alloy, the alloy contains L1 2 The strengthening phase high-entropy alloy can realize excellent high-temperature strength performance through the design of a microstructure (gamma + gamma'). However, the medium-temperature brittleness of the multi-principal-element alloy developed at present still generally restricts the practical application of the multi-principal-element alloy. The invention selects the entropy in CoCrNiAlTi (at.%) multi-principal componentGold is used as a research object, and high-volume-fraction L1 is precipitated in crystal grains by adding high-content Cr, Al and Ti elements into a Co-rich multi-principal-element alloy system 2 The strengthening phase precipitates a complex CrCo-rich strengthening phase at the grain boundary, so that comprehensive strengthening and toughening are realized, and in addition, high strength is obtained in a medium-high temperature range, and good plasticity is obtained by overcoming medium-temperature brittleness.
Example 1
(1) Is prepared into Co 33 Cr 31 Ni 26 Al 5 Ti 5 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment on the ingot at 1200 ℃/24h, and cooling the ingot to room temperature along with the furnace to form an ingot with homogenized components;
(3) keeping the temperature of the cast ingot at 1150 ℃ for 4h, selecting a forging method with small forging amount and multiple passes, returning the forge piece after each forging and keeping the temperature for 30min, then forging the forge piece in the next pass, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multiple hot forging;
(4) and carrying out aging heat treatment on the bar after hot forging at the temperature of 700 ℃/4h to obtain the alloy bar.
FIG. 1 is a microstructure diagram of the resulting alloy, showing in FIG. 1, the distribution of bulk CrCo-rich mid-entropy alloy phase at fine recrystallization grain boundaries.
FIG. 2 is a graph of instantaneous tensile properties of the obtained alloy in a medium-high temperature range, and as shown in FIG. 2, the obtained alloy has excellent comprehensive mechanical properties under the conditions of 600 ℃ and 800 ℃. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength is up to 944MPa, the tensile plasticity is 16 percent, and the alloy is superior to most nickel-based and cobalt-based high-temperature alloys.
Example 2
(1) Is prepared into Co 34 Cr 29 Ni 27 Al 5 Ti 5 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment on the ingot at 1200 ℃/18h, and cooling the ingot to room temperature along with the furnace to form an ingot with uniform components;
(3) keeping the temperature of the cast ingot at 1170 ℃ for 4h, selecting a small forging amount and multi-pass forging method, returning the forge piece after each forging and keeping the temperature for 30min, then carrying out next-pass forging, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multi-pass hot forging;
(4) and carrying out aging heat treatment on the bar after hot forging at the temperature of 700 ℃/6h to obtain the alloy bar.
Under the conditions of 600 ℃ and 800 ℃, the obtained alloy has excellent comprehensive mechanical properties. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength is up to 950MPa, the tensile plasticity is 15 percent, and the alloy is superior to most nickel-based and cobalt-based high-temperature alloys.
Example 3
(1) Is prepared into Co 34 Cr 29 Ni 27 Al 6 Ti 4 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment on the ingot at 1000 ℃/32h, and cooling the ingot to room temperature along with the furnace to form an ingot with uniform components;
(3) keeping the temperature of the cast ingot at 1200 ℃ for 5h, selecting a forging method with small forging amount and multiple passes, returning the forge piece after each forging and keeping the temperature for 30min, then forging the forge piece in the next pass, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multiple passes of hot forging;
(4) and carrying out aging heat treatment on the bar after hot forging at the temperature of 800 ℃/2h to obtain the alloy bar.
Under the conditions of 600 ℃ and 800 ℃, the obtained alloy has excellent comprehensive mechanical properties. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength reaches 930MPa, the tensile plasticity is 17 percent, and the alloy is superior to most nickel-based and cobalt-based high-temperature alloys.
Example 4
(1) Is prepared into Co 31 Cr 33 Ni 26 Al 4 Ti 6 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment at 1100 ℃/30h on the cast ingot, and cooling the cast ingot to room temperature along with the furnace to form the cast ingot with uniform components;
(3) keeping the temperature of the cast ingot at 1120 ℃ for 6h, selecting a small forging amount and multi-pass forging method, returning the forge piece after each forging and keeping the temperature for 30min, then forging the forge piece in the next pass, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multi-pass hot forging;
(4) and carrying out aging heat treatment on the hot forged bar at the temperature of 750 ℃/6h to obtain the alloy bar.
Under the conditions of 600 ℃ and 800 ℃, the obtained alloy has excellent comprehensive mechanical properties. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength reaches 960MPa, the tensile plasticity is 14 percent, and the alloy is superior to most nickel-based and cobalt-based high-temperature alloys.
Example 5
(1) Is prepared into Co 32 Cr 33 Ni 26 Al 5.5 Ti 4.5 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment on the cast ingot at 1200 ℃/28h and cooling the cast ingot to room temperature along with the furnace to form a cast ingot with uniform components;
(3) keeping the temperature of the cast ingot at 1190 ℃ for 6h, selecting a forging method with small forging amount and multiple passes, returning the forge piece after each forging and keeping the temperature for 30min, then forging the forge piece in the next pass, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multiple passes of hot forging;
(4) and carrying out aging heat treatment on the bar after hot forging at 650 ℃/6h to obtain the alloy bar.
Under the conditions of 600-800 ℃, the obtained alloy has excellent comprehensive mechanical properties. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength is up to 940MPa, the tensile plasticity is 15 percent, and the alloy is superior to most nickel-based and cobalt-based high-temperature alloys.
Example 6
(1) Is prepared into Co 31 Cr 31 Ni 28 Al 4.5 Ti 5.5 (at.%) alloy, casting 10Kg ingot in vacuum induction furnace;
(2) carrying out homogenization treatment on the cast ingot at 1200 ℃/24h and cooling the cast ingot to room temperature along with the furnace to form a cast ingot with uniform components;
(3) keeping the temperature of the cast ingot at 1200 ℃ for 4h, selecting a forging method with small forging amount and multiple passes, returning the forge piece after each forging and keeping the temperature for 30min, then forging the forge piece in the next pass, and forging the alloy ingot into a thin rod (the surface shrinkage rate is 70-90%) through multiple passes of hot forging;
(4) and carrying out aging heat treatment on the hot forged round bar at the temperature of 600 ℃/2h to obtain the alloy bar.
Under the conditions of 600 ℃ and 800 ℃, the obtained alloy has excellent comprehensive mechanical properties. Wherein, the alloy has abnormal yield under the condition of 700 ℃, the yield strength reaches 935MPa, and the tensile plasticity is 15 percent, which is superior to most nickel-based and cobalt-based high-temperature alloys.
Claims (7)
1. The deformed CoCrNiAlTi medium-entropy alloy with excellent performance in a medium-high temperature range is characterized by comprising the following components in percentage by atom: co: 31-35%, Cr: 28-33%, Ni: 24-28%, Al: 4-7%, Ti: 4-7 percent.
2. The wrought CoCrNiAlTi medium entropy alloy with excellent performance in the medium and high temperature range of claim 1, characterized by comprising, in atomic percent: co: 32-34%, Cr: 29-31%, Ni: 25-27%, Al: 4.5-5.5%, Ti: 4.5 to 5.5 percent.
3. The method for preparing the wrought CoCrNiAlTi medium-entropy alloy with excellent performance in the medium-high temperature range as set forth in claim 1 or 2 is characterized by comprising the following steps:
(1) preparing an alloy according to the components and the atomic percentages thereof as claimed in claim 1 or 2 and casting the alloy into an ingot;
(2) homogenizing the cast ingot to form a homogenized cast ingot;
(3) hot forging the homogenized cast ingot to obtain an alloy hot-forged bar with an FCC single phase;
(4) and carrying out aging heat treatment on the alloy hot forged bar with the FCC single phase to obtain the deformed CoCrNiAlTi medium-entropy alloy bar with excellent performance in a medium-high temperature range.
4. The method for preparing the wrought CoCrNiAlTi medium-entropy alloy with excellent performance in the medium-high temperature range according to claim 3 is characterized in that: in the step (2), the homogenization treatment is carried out at the temperature of 1000-.
5. The method for preparing the wrought CoCrNiAlTi intermediate entropy alloy with excellent performance in the medium and high temperature range according to claim 3 is characterized in that: in the step (3), the hot forging temperature is 1120-1200 ℃.
6. The method for preparing the wrought CoCrNiAlTi intermediate entropy alloy with excellent performance in the medium and high temperature range according to claim 3 is characterized in that: in the step (3), the hot forging is small forging amount and multi-pass forging.
7. The method for preparing the wrought CoCrNiAlTi intermediate entropy alloy with excellent performance in the medium and high temperature range according to claim 3 is characterized in that: in the step (4), the temperature of the aging heat treatment is 600-800 ℃, and the time is 2-6 h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537628A (en) * | 2022-09-19 | 2022-12-30 | 华东理工大学 | Medium-entropy alloy and preparation method and application thereof |
| CN116065077A (en) * | 2022-12-06 | 2023-05-05 | 湘潭大学 | High-temperature antioxidant AlCoCrNiTi high-entropy alloy material and preparation method and application thereof |
| CN116287929A (en) * | 2023-03-21 | 2023-06-23 | 浙江大学 | High-strength high-plasticity CrCoNi-based multi-principal element alloy and preparation method thereof |
| CN116397148A (en) * | 2023-03-21 | 2023-07-07 | 沈阳航空航天大学 | Deformation CoNiCr-based alloy with excellent mechanical properties and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537628A (en) * | 2022-09-19 | 2022-12-30 | 华东理工大学 | Medium-entropy alloy and preparation method and application thereof |
| CN116065077A (en) * | 2022-12-06 | 2023-05-05 | 湘潭大学 | High-temperature antioxidant AlCoCrNiTi high-entropy alloy material and preparation method and application thereof |
| CN116287929A (en) * | 2023-03-21 | 2023-06-23 | 浙江大学 | High-strength high-plasticity CrCoNi-based multi-principal element alloy and preparation method thereof |
| CN116397148A (en) * | 2023-03-21 | 2023-07-07 | 沈阳航空航天大学 | Deformation CoNiCr-based alloy with excellent mechanical properties and preparation method thereof |
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