CN117418150A - L1 2 CoFeNi-based medium entropy alloy with reinforced nano particles and dislocation simultaneously and preparation method thereof - Google Patents
L1 2 CoFeNi-based medium entropy alloy with reinforced nano particles and dislocation simultaneously and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 115
- 239000000956 alloy Substances 0.000 title claims abstract description 115
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229910019233 CoFeNi Inorganic materials 0.000 title abstract 5
- 239000002994 raw material Substances 0.000 claims abstract description 42
- 238000005097 cold rolling Methods 0.000 claims abstract description 41
- 238000000137 annealing Methods 0.000 claims abstract description 34
- 238000005728 strengthening Methods 0.000 claims abstract description 33
- 230000032683 aging Effects 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000006104 solid solution Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims description 27
- 238000002844 melting Methods 0.000 claims description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 18
- 229910052802 copper Inorganic materials 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 239000011159 matrix material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000861 blow drying Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 abstract description 11
- 238000003723 Smelting Methods 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 238000010586 diagram Methods 0.000 description 10
- 238000005096 rolling process Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 230000035882 stress Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910000601 superalloy Inorganic materials 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
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- 238000001887 electron backscatter diffraction Methods 0.000 description 3
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- 230000007547 defect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
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- 238000010899 nucleation Methods 0.000 description 1
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- 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 L1 2 CoFeNi-based medium entropy alloy with simultaneous strengthening of nano particles and dislocation, the composition being (CoFeNi) 100‑x‑y‑ z Ti x Al y V z Wherein x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0; the invention also discloses a preparation method of the CoFeNi-based medium entropy alloy, which comprises the following steps: arc smelting the raw materials, and sequentially carrying out solid solution treatment, primary cold rolling, annealing, secondary cold rolling and aging ordering treatment on the obtained intermediate alloy cast ingot. The microstructure of the high-strength CoFeNi-based medium-entropy alloy prepared by the method consists of a small quantity of recrystallized regions and a large quantity of unrecrystallized regions, and the two regions have high-density L1 2 Nanoparticles which can act as precipitation strengthening and have no recrystallized regionContains high-density dislocation and can play the role of dislocation reinforcement.
Description
Technical Field
The invention belongs to medium entropyThe technical field of alloy preparation, in particular to L1 2 The nano-particle and dislocation simultaneous strengthening CoFeNi-based intermediate entropy alloy and the preparation method thereof are also related.
Background
The high-entropy alloy and the medium-entropy alloy are novel metal materials composed of a plurality of main elements, and have been widely concerned with the excellent performances of the metal materials, and particularly the high-entropy alloy and the medium-entropy alloy with face-centered cubic structure (fcc) attract more researchers' attention due to the excellent elongation, better corrosion resistance, radiation resistance and other performances of the metal materials. However, fcc-structured high-or medium-entropy alloys (CoCrFeNiMn, coCrFeNi, coFeNi, etc.) are generally low in strength and yield strength is generally lower than 400MPa, thus limiting their industrial application.
In order to increase the yield strength thereof, researchers have employed various methods such as solid solution strengthening, fine grain strengthening, complex phase strengthening, precipitation strengthening, dislocation strengthening, and the like. Among them, the precipitation strengthening effect is most excellent, especially L1 2 Precipitation strengthening of nanoparticles, e.g. adding L1 to entropy alloys in CoFeNi 2 Phase forming elements Ti and Al ((CoFeNi) 86 Al 7 Ti 7 ) Its yield strength increases from 200MPa to 1050MPa (T.Yang, Y.Zhao, Y.Tong, Z.Jiao, J.Wei, J.Cai, X.Han, D.Chen, A.Hu, J.Kai, science 362 (2018) 933-937); addition of L1 to CoCrFeNi medium entropy alloy 2 Phase forming elements Ti and Al ((FeCoNiCr) 94 Ti 2 Al 4 ) Its yield strength increases from 165MPa to 1005MPa (T.Yang, Y.Zhao, Y.Tong, Z.Jiao, J.Wei, J.Cai, X.Han, D.Chen, A.Hu, J.Kai, science 362 (2018) 933-937). Such L1 2 Although the precipitation strengthening effect of the nanoparticles is good, the yield strength is still not high enough, and how to further increase the yield strength to excavate the maximum potential of the alloy is the main problem encountered at present.
Disclosure of Invention
The invention aims to provide L1 2 The nano particles and dislocation simultaneously strengthen the CoFeNi-based medium entropy alloy, and solves the problem of low yield strength of the medium entropy alloy in the prior art.
The technical proposal adopted by the invention is that，L1 2 The nano particles and dislocation are reinforced simultaneously, and the alloy component of the intermediate entropy alloy is (CoFeNi) 100-x-y-z Ti x Al y V z Wherein x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe and Ni are formed according to the equal atomic percentage; the medium entropy alloy has fcc matrix and L1 2 And (3) phase (C).
The invention adopts another technical proposal that L1 2 The preparation method of the CoFeNi-based medium entropy alloy with the nano particles and the dislocation reinforced simultaneously is implemented according to the following steps:
step 1, polishing, cleaning and blow-drying Co, fe, ni, ti, al, V raw materials;
step 2, according to (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe and Ni are composed according to equal atomic percentage, x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe, ni, ti, al, V elemental metal raw materials are weighed;
step 3, arc melting the raw materials to obtain (CoFeNi) 100-x-y-z Ti x Al y V z A medium entropy alloy ingot;
and step 4, sequentially carrying out solid solution treatment, primary cold rolling, annealing, secondary cold rolling and aging ordering treatment on the intermediate entropy alloy cast ingot to obtain the CoFeNi-based intermediate entropy alloy.
The present invention is also characterized in that,
the step 3 specifically comprises the following steps:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 425-475A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 5-6 min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.3, turning the primary ingot in a water-cooled copper crucible, and repeating the arc melting of the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform structure components 100-x-y-z Ti x Al y V z And (3) casting a medium-entropy alloy ingot.
In the step 4, the treatment temperature is 1150-1200 ℃ and the heat preservation time is 12-48 h during the solution treatment.
In the step 4, the thinning rate of the primary cold rolling is 60-80 percent.
In the step 4, the annealing temperature is 900-1050 ℃ and the annealing time is 3-60 min; the thinning rate of the secondary cold rolling is 0-15%.
If the temperature is higher than 980 ℃ during annealing, dislocation is provided for high-temperature annealing by secondary cold rolling; if the temperature is lower than 980 ℃ during annealing, the thinning rate of the secondary cold rolling is 0, namely the secondary cold rolling is not needed.
In the step 4, in the aging ordering treatment process: the aging temperature is 600-800 ℃, and the aging time is 0.5-24 h.
The beneficial effects of the invention are as follows: l1 prepared by the invention 2 High strength CoFeNi-based medium entropy alloy with simultaneous strengthening of nano-particles and dislocations, whose microstructure is composed of a small amount of recrystallized regions and a large amount of unrecrystallized regions (i.e., deformed regions, volume fraction of which is 80% or more to ensure high density of dislocations), both of which have a high density of L1 2 The nano particles can play a role of precipitation strengthening (Ti, al and V belong to L1) 2 A phase forming element, contributing to L1 2 Phase formation, cold rolling induced lattice defects promote L1 during post aging 2 The precipitation of nano particles), and the non-recrystallized region (i.e. the deformation region) contains high-density dislocation, which can play a role in strengthening the dislocation, thereby improving the yield strength of the medium-entropy alloy.
Drawings
FIG. 1 is a graph of the present invention calculated using JMatPro software (CoFeNi) 82 Ti 5 Al 5 V 8 A solidification path diagram of the medium-entropy alloy;
FIG. 2a shows the results of the invention in example 1, example 2 and comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 XRD pattern of the medium entropy alloy;
FIG. 2b is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 Peak fitting map of diffraction peak of (311) crystal face of the medium entropy alloy;
FIG. 2c is a diagram of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 Peak fitting map of diffraction peak of (311) crystal face of the medium entropy alloy;
FIG. 2d is a diagram of example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 Peak fitting map of diffraction peak of (311) crystal face of the medium entropy alloy;
FIG. 3a is a schematic diagram of example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 OM plot of medium entropy alloy;
FIG. 3b is a diagram of example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of medium entropy alloy (one);
FIG. 3c is a sample of the composition of example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of medium entropy alloy (ii);
FIG. 4a is a diagram of example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM plot of medium entropy alloy;
FIG. 4b is a diagram of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM plot of medium entropy alloy;
FIG. 4c is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM plot of medium entropy alloy;
FIG. 4d is a diagram of example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM value of the medium entropy alloy;
FIG. 4e is a sample of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM value of the medium entropy alloy;
FIG. 4f is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 KAM value of the medium entropy alloy;
FIG. 5 shows the results of the three conditions of inventive example 1, example 2 and comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 A tensile stress strain curve of the medium entropy alloy;
FIG. 6a is a diagram of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 OM plot of medium entropy alloy;
FIG. 6b is a diagram of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of medium entropy alloy (one);
FIG. 6c is a sample of example 2 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of medium entropy alloy (ii);
FIG. 7a is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 OM plot of medium entropy alloy;
FIG. 7b is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of medium entropy alloy (one);
FIG. 7c is a comparative example 1 of the present invention (CoFeNi) 82 Ti 5 Al 5 V 8 SEM image of the medium entropy alloy (two).
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
Inventive L1 2 Nano-particle and dislocation simultaneous strengthening CoFeNi base intermediate entropy alloy, specifically adding L1 into CoFeNi intermediate entropy alloy 2 Phase forming elements Ti, al, V, designed with fcc matrix +L1 using JMatPro software 2 Of the phase (CoFeNi) 100-x-y-z Ti x Al y V z A medium entropy alloy;
the alloy composition of the medium entropy alloy is (CoFeNi) 100-x-y-z Ti x Al y V z Wherein x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe and Ni are formed according to the equal atomic percentage;
inventive L1 2 The preparation method of the CoFeNi-based medium entropy alloy with the nano particles and the dislocation reinforced simultaneously is implemented according to the following steps:
step 1, polishing, cleaning and blow-drying a Co, fe, ni, ti, al, V simple substance metal raw material;
step 2, according to JMatPro software design (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe and Ni are composed according to equal atomic percentage, x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe, ni, ti, al, V elemental metal raw materials are weighed according to atomic percentage;
the specific process of adopting the JMatPro software design is as follows: the material module of Nicke Based Superalloy is selected and then is according to (CoFeNi) 100-x-y-z Ti x Al y V z Inputting components, wherein Co, fe and Ni are composed according to equal atomic percentages, x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and then 'Step Temperature' in a 'Thermodynamic Properties' module is selected for calculation.
Step 3, arc melting the raw materials weighed in the step 2 to obtain (CoFeNi) 100-x-y-z Ti x Al y V z A medium entropy alloy ingot; the method specifically comprises the following steps:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 425-475A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 5-6 min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.3, turning the primary ingot in a water-cooled copper crucible, and repeating the arc melting of the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform structure components 100-x-y-z Ti x Al y V z A medium entropy alloy ingot;
step 4, pair (CoFeNi) 100-x-y-z Ti x Al y V z Sequentially carrying out solid solution treatment, primary cold rolling, annealing, secondary cold rolling and aging ordering treatment on the intermediate entropy alloy cast ingot to obtain L1 2 A CoFeNi-based medium entropy alloy with simultaneous strengthening of nano particles and dislocations;
when in solution treatment, the treatment temperature is 1150-1200 ℃, and the heat preservation time is 12-48 h.
The thinning rate of the primary cold rolling is 60-80 percent;
the annealing temperature is 900-1050 ℃ and the annealing time is 3-60 min; the thinning rate of the secondary cold rolling is 0-15%;
if the temperature is higher than 980 ℃ during annealing, the annealing is performed at high temperature, at this time, the structure is completely recrystallized, the dislocation density is reduced, the dislocation is provided by secondary cold rolling, and then L appears during aging 12 The nano particles play a role in strengthening simultaneously.
If the temperature is lower than 980 ℃ during annealing and the non-recrystallized region contains a large number of dislocation, the thinning rate of secondary cold rolling is 0, namely secondary cold rolling is not needed, and the dislocation density is kept high;
in the aging ordering treatment process: the aging temperature is 600-800 ℃, and the aging time is 0.5-24 h.
The invention can keep high dislocation density during low-temperature annealing after primary cold rolling, and can obtain high-density L1 through later aging treatment 2 Nanoparticles, can realize L1 2 The simultaneous strengthening of the nanoparticles and dislocations. In order to further increase the strength, secondary rolling may be used. The primary rolling in the method is mainly used for eliminating defects in the casting process, and dislocation is introduced to provide crystallization nucleation sites for the later-stage high-temperature annealing recrystallization. The secondary rolling mainly provides dislocation, and L1 with high density can be obtained in the later aging process (low-temperature aging does not obviously eliminate dislocation) 2 Nanoparticles, thus L1 can be realized 2 The simultaneous strengthening of the nanoparticles and dislocations.
Example 1
L1 2 The preparation method of the high-strength CoFeNi-based medium entropy alloy with the simultaneous strengthening of nano particles and dislocation comprises the following steps:
step 1, polishing, clearing and drying a Co, fe, ni, ti, al, V simple substance metal raw material;
step 2, according to JMatPro software design (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe, ni are composed in equal atomic percentages, x=5.0, y=5.0, z=8.0, i.e. (CoFeNi) 82 Ti 5 Al 5 V 8 Weighing Co according to atomic percent,Fe. Ni, ti, al, V elemental metal stock;
the specific process of adopting the JMatPro software design in the step 2 is as follows: the material module of Nicke Based Superalloy is selected and then is according to (CoFeNi) 100-x-y-z Ti x Al y V z The input components, wherein Co, fe and Ni are composed according to equal atomic percentages, x=5.0, y=5.0 and z=8.0, and then the Step Temperature in the Thermodynamic Properties module is selected for calculation.
Step 3, arc melting the raw materials weighed in the step 2 to obtain (CoFeNi) 82 Ti 5 Al 5 V 8 A medium entropy alloy ingot; the method specifically comprises the following steps:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 450A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 6min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.3, turning the primary ingot in a water-cooled copper crucible, and repeating the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform tissue components 82 Ti 5 Al 5 V 8 And casting an ingot of the medium-entropy alloy.
Step 4, pair (CoFeNi) 82 Ti 5 Al 5 V 8 The intermediate-entropy alloy ingot is sequentially subjected to solid solution, primary cold rolling, low-temperature/high-temperature annealing, secondary cold rolling (if the previous step is the low-temperature annealing, the cold rolling is not performed), and aging ordering treatment to obtain L1 2 The nano particles and dislocation are reinforced simultaneously.
In the solution treatment process in the step 4: the treatment temperature is 1150 ℃ and the heat preservation time is 24 hours.
The reduction rate of the primary cold rolling process in the step 4 is 65%.
And 4, a high-temperature annealing process in the step: the temperature was 1000℃and the treatment time was 3min.
The reduction rate of the secondary cold rolling in step 4 is 15%, and since the former step is high temperature annealing, the dislocation density is reduced, and thus the secondary rolling is required to maintain a high dislocation density.
And (4) an aging ordering treatment process in the step (4): the aging temperature is 700 ℃, and the aging time is 1h.
In example 1 of the present invention, the design and calculation were performed using JMatPro software (CoFeNi) 82 Ti 5 Al 5 V 8 The solidification path of the medium entropy alloy, as shown in FIG. 1, shows that the alloy structure will be composed of fcc matrix and L1 2 Phase composition. In example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 XRD results of the medium entropy alloy are shown in FIG. 2a, indicating matrices fcc and L1 of the alloy 2 The diffraction peaks of the nanoparticles almost coincide and the fcc matrix at the (311) plane was analyzed by XRD with L1 2 Fitting patterns of nanoparticles (as shown in fig. 2 d) indicate that the lattice constants are very close and the two phases are highly coherent. In example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The OM and SEM results of the medium entropy alloy show that the microstructure consists of a small amount of recrystallized regions (R) and a large amount of non-recrystallized regions (NR, volume fraction about 91%) and that both recrystallized and non-recrystallized regions precipitate out a high density of L1 as shown in FIGS. 3a and 3b 2 Nanoparticles, as shown in fig. 3c and 3 a. In example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The KAM plot (EBSD) results for the medium entropy alloy show that the local orientation of the non-recrystallized regions is greater, and the corresponding KAM values are also higher (2.75 °), as shown in fig. 4a and 4d, with the corresponding dislocation densities being higher, and from the KAM values the dislocation density can be calculated to be-6.29 x 10 14 m -2 The dislocation density is high. In example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The tensile stress strain curve of the medium entropy alloy shows that the alloy can obtain extremely high yield strength under the condition, namely about 1500MPa, the ultimate tensile strength can reach 1747MPa, and certain plasticity (about 16%) is also maintained, as shown in figure 5. From the analysis, it was considered that in example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The high strength of the medium entropy alloy is mainly due to L1 2 Precipitation strengthening and dislocation strengthening of nano particles, thereby havingHas excellent performance.
Example 2
L1 2 The preparation method of the high-strength CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation simultaneously comprises the following steps:
step 1, polishing, clearing and drying a Co, fe, ni, ti, al, V simple substance metal raw material;
step 2, according to JMatPro software design (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe, ni are composed in equal atomic percentages, x=5.0, y=5.0, z=8.0, i.e. (CoFeNi) 82 Ti 5 Al 5 V 8 Weighing Co, fe, ni, ti, al, V elemental metal raw materials according to atomic percent;
the specific process of adopting the JMatPro software design in the step 2 is as follows: the material module of Nicke Based Superalloy is selected and then is according to (CoFeNi) 100-x-y-z Ti x Al y V z The input components, wherein Co, fe and Ni are composed according to equal atomic percentages, x=5.0, y=5.0 and z=8.0, and then the Step Temperature in the Thermodynamic Properties module is selected for calculation.
Step 3, arc melting the raw materials weighed in the step 2 to obtain (CoFeNi) 82 Ti 5 Al 5 V 8 A medium entropy alloy ingot; the method specifically comprises the following steps:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 475A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 5min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.3, turning the primary ingot in a water-cooled copper crucible, and repeating the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform tissue components 82 Ti 5 Al 5 V 8 And casting an ingot of the medium-entropy alloy.
Step 4, pair (CoFeNi) 82 Ti 5 Al 5 V 8 The intermediate-entropy alloy ingot is sequentially subjected to solid solution, primary cold rolling, low-temperature/high-temperature annealing, secondary cold rolling (if the previous step is the low-temperature annealing, the cold rolling is not performed), and aging ordering treatment to obtain L1 2 The nano particles and dislocation are reinforced simultaneously.
In the solution treatment process in the step 4: the treatment temperature is 1150 ℃ and the heat preservation time is 24 hours.
The reduction rate of the primary cold rolling process in the step 4 is 80 percent.
In the low-temperature annealing process in the step 4: the temperature is 900 ℃, and the treatment time is 30min.
The reduction ratio of the secondary cold rolling in the step 4 is 0, and the dislocation density is high because the former step is low-temperature annealing, so that the high dislocation density can be maintained without secondary rolling.
In the aging ordering treatment process in the step 4: the aging temperature is 700 ℃, and the aging time is 1h.
In example 2 of the present invention, the design was performed using JMatPro software (CoFeNi) 82 Ti 5 Al 5 V 8 The solidification path of the medium entropy alloy, as shown in FIG. 1, shows that the alloy structure will be composed of fcc matrix and L1 2 Phase composition. In example 2 (CoFeNi) 82 Ti 5 Al 5 V 8 XRD results of the medium entropy alloy are shown in FIG. 2a, indicating matrices fcc and L1 of the alloy 2 The diffraction peaks of the nanoparticles almost coincide and the fcc matrix at the (311) plane was analyzed by XRD with L1 2 Fitting patterns of nanoparticles (as shown in fig. 2 c) indicate that the lattice constants are very close and the two phases are highly coherent. In example 2 (CoFeNi) 82 Ti 5 Al 5 V 8 The OM and SEM results of the mid-entropy alloy show that the microstructure consists of a small amount of recrystallized regions (R) and a large amount of non-recrystallized regions (NR, volume fraction of about 83%) as shown in fig. 6a and 6 b. Both recrystallized and unrecrystallized regions precipitate out high density L1 2 Nanoparticles, as shown in fig. 6c and 6 c. In example 2 (CoFeNi) 82 Ti 5 Al 5 V 8 KAM plot (EBSD) results for medium entropy alloys indicate local orientation of non-recrystallized regionsLarger, corresponding KAM values are also higher (2.01 °), as shown in fig. 4b and 4e, corresponding dislocation densities are higher, from which a dislocation density of-4.60 x 10 can be calculated 14 m -2 The dislocation density is high. In example 2 (CoFeNi) 82 Ti 5 Al 5 V 8 The tensile stress strain curve of the medium-entropy alloy shows that the alloy can obtain higher yield strength under the condition of about 1142MPa, the ultimate tensile strength of 1399MPa and certain plasticity (about 15%) as shown in figure 5. From the analysis, it is considered that in example 2 (CoFeNi) 82 Ti 5 Al 5 V 8 The high strength of the medium entropy alloy is mainly due to L1 2 Precipitation strengthening and dislocation strengthening of the nanoparticles, thereby having excellent properties.
Comparative example 1
L1 2 The preparation method of the high-strength CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation simultaneously comprises the following steps:
step 1, polishing, clearing and drying a Co, fe, ni, ti, al, V simple substance metal raw material;
step 2, according to JMatPro software design (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe, ni are composed in equal atomic percentages, x=5.0, y=5.0, z=8.0, i.e. (CoFeNi) 82 Ti 5 Al 5 V 8 Weighing Co, fe, ni, ti, al, V elemental metal raw materials according to atomic percent;
the specific process of adopting the JMatPro software design is as follows: the material module of Nicke Based Superalloy is selected and then is according to (CoFeNi) 100-x-y-z Ti x Al y V z The input components, wherein Co, fe and Ni are composed according to equal atomic percentages, x=5.0, y=5.0 and z=8.0, and then the Step Temperature in the Thermodynamic Properties module is selected for calculation.
Step 3, arc melting the raw materials weighed in the step 2 to obtain (CoFeNi) 82 Ti 5 Al 5 V 8 A medium entropy alloy ingot; the method specifically comprises the following steps:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 475A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 5min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.4, turning the primary ingot in a water-cooled copper crucible, and repeating the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform tissue components 82 Ti 5 Al 5 V 8 And casting an ingot of the medium-entropy alloy.
Step 4, pair (CoFeNi) 82 Ti 5 Al 5 V 8 Sequentially carrying out solid solution treatment, primary cold rolling, low-temperature/high-temperature annealing, secondary cold rolling and aging ordering treatment on the intermediate-entropy alloy cast ingot to obtain L1 2 The nano particles and dislocation are reinforced simultaneously.
In the solution treatment process in the step 4: the treatment temperature is 1150 ℃ and the heat preservation time is 24 hours.
The reduction rate of the primary cold rolling process in the step 4 is 80 percent.
And 4, a high-temperature annealing process in the step: the temperature was 1000℃and the treatment time was 3min.
In step 4, the reduction ratio of the secondary cold rolling is 0, and unlike in example 1 (the secondary rolling is required due to the reduction of dislocation density after high temperature annealing), the secondary rolling is not performed in comparative example 1, so that the dislocation density is low, thereby greatly impairing the effect of dislocation strengthening.
And (4) an aging ordering treatment process in the step (4): the aging temperature is 700 ℃, and the aging time is 1h.
Comparative example 1 according to the invention (CoFeNi) was designed using JMatPro software 82 Ti 5 Al 5 V 8 The solidification path of the medium entropy alloy, as shown in FIG. 1, shows that the alloy structure will be composed of fcc matrix and L1 2 Phase composition. Comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 XRD results of the medium entropy alloy are shown in FIG. 2a, indicating matrices fcc and L1 of the alloy 2 Derivatization of nanoparticlesThe peaks almost coincide and the fcc matrix at the (311) plane was analyzed by XRD for L1 2 Fitting patterns of nanoparticles (as shown in fig. 2 b) indicate that the lattice constants are very close and the two phases are highly coherent. Comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The OM results of the medium entropy alloy show complete recrystallization after high temperature annealing, no unrecrystallized regions, and fine equiaxed microstructure as shown in fig. 7 a. SEM results indicate that high density L1 is precipitated in the crystal 2 Nanoparticles, as shown in fig. 7b and 7 c. Comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The result of the KAM plot (EBSD) of the medium entropy alloy shows that the local orientation of the non-recrystallized region is very small, the corresponding KAM value is also very small (0.381 °), as shown in fig. 4c and 4f, the corresponding dislocation density is high, and the dislocation density can be calculated to be-0.5229 x 10 according to the KAM value 14 m -2 As in example 1 (6.29 x 10) 14 m -2 ) And example 2 (-4.60 x 10) 14 m -2 ) The dislocation density is much lower than that. Comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The tensile stress strain curve of the mid-entropy alloy shows that the yield strength of the alloy is lower, about 772MPa, and the plasticity is better (about 46%), as shown in fig. 5. From the analysis, it was considered that in comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The dislocation density in the medium entropy alloy is low and the effect of dislocation enhancement is negligible, so in comparative example 1 (CoFeNi) 82 Ti 5 Al 5 V 8 The strengthening mechanism of the medium entropy alloy is mainly attributed to L1 2 The precipitation strengthening of the nanoparticles, without significant dislocation strengthening, is therefore lower in yield strength, as opposed to the high yield strength caused by dislocation strengthening in examples 1 and 2.
Example 3
L1 of the invention 2 Preparation method of CoFeNi-based medium entropy alloy with simultaneous strengthening of nano particles and dislocation, wherein L1 in later aging process is promoted by primary cold rolling and secondary cold rolling 2 Precipitation of nanoparticles, while maintaining a high dislocation density by low temperature annealing or low temperature aging, to finally achieve L1 2 Nanoparticles and dislocations simultaneouslyStrengthening effect.
Claims (8)
1.L1 2 A CoFeNi-based medium entropy alloy with simultaneous strengthening of nano particles and dislocation, characterized in that the alloy composition of the medium entropy alloy is (CoFeNi) 100-x-y-z Ti x Al y V z Wherein x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe and Ni are formed according to the equal atomic percentage; the medium entropy alloy has fcc matrix and L1 2 And (3) phase (C).
2. L1 as defined in claim 1 2 The preparation method of the CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation is characterized by comprising the following steps:
step 1, polishing, cleaning and blow-drying Co, fe, ni, ti, al, V raw materials;
step 2, according to (CoFeNi) 100-x-y-z Ti x Al y V z Wherein Co, fe and Ni are composed according to equal atomic percentage, x is more than or equal to 4.0 and less than or equal to 8.0,4.0, y is more than or equal to 8.0,4.0 and z is more than or equal to 8.0, and Co, fe, ni, ti, al, V elemental metal raw materials are weighed;
step 3, arc melting the raw materials to obtain (CoFeNi) 100-x-y-z Ti x Al y V z A medium entropy alloy ingot;
and step 4, sequentially carrying out solid solution treatment, primary cold rolling, annealing, secondary cold rolling and aging ordering treatment on the intermediate entropy alloy cast ingot to obtain the CoFeNi-based intermediate entropy alloy.
3. L1 as claimed in claim 2 2 The preparation method of the CoFeNi-based medium entropy alloy with the simultaneous strengthening of nano particles and dislocation is characterized by comprising the following steps of:
step 3.1, placing the raw materials weighed in the step 2 into a water-cooled copper crucible of a vacuum arc melting furnace, closing a furnace chamber, vacuumizing, and filling argon as protective gas;
step 3.2, arc melting is carried out on the raw materials in the water-cooled copper crucible, the melting current is 425-475A, after the raw materials are completely melted, electromagnetic stirring is started, after the raw materials are kept for 5-6 min, the molten metal is cooled to be solid, and a primary cast ingot is obtained;
step 3.3, turning the primary ingot in a water-cooled copper crucible, and repeating the arc melting of the step 3.2 four times to obtain a button-shaped (CoFeNi) with uniform structure components 100-x-y-z Ti x Al y V z And (3) casting a medium-entropy alloy ingot.
4. L1 as claimed in claim 2 2 The preparation method of the CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation is characterized in that in the step 4, the treatment temperature is 1150-1200 ℃ and the heat preservation time is 12-48 h during the solution treatment.
5. L1 as claimed in claim 2 2 The preparation method of the CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation simultaneously is characterized in that in the step 4, the thinning rate of one cold rolling is 60% -80%.
6. L1 as claimed in claim 2 2 The preparation method of the CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation is characterized in that in the step 4, the annealing temperature is 900-1050 ℃ and the annealing time is 3-60 min; the thinning rate of the secondary cold rolling is 0-15%.
7. The L1 of claim 6 2 The preparation method of the CoFeNi-based medium entropy alloy with the reinforced nano particles and dislocation is characterized in that if the temperature is higher than 980 ℃ during annealing, the high-temperature annealing is performed, and the dislocation is provided by secondary cold rolling; if the temperature is lower than 980 ℃ during annealing, the thinning rate of the secondary cold rolling is 0, namely the secondary cold rolling is not needed.
8. L1 as claimed in claim 2 2 The preparation method of the CoFeNi-based medium entropy alloy with the simultaneous strengthening of nano particles and dislocation is characterized in that in the step 4, in the aging ordering treatment process: the aging temperature is 600-800 ℃, and the aging time is 0.5-24 h.
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