CN113444955A - High-entropy alloy containing eutectic structure and preparation method thereof - Google Patents
High-entropy alloy containing eutectic structure and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 108
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 107
- 230000005496 eutectics Effects 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000003723 Smelting Methods 0.000 claims abstract description 58
- 229910000943 NiAl Inorganic materials 0.000 claims abstract description 28
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims description 31
- 238000003760 magnetic stirring Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000010586 diagram Methods 0.000 description 10
- 238000005728 strengthening Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000006023 eutectic alloy Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910001068 laves phase Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
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- 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
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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
- C22C1/023—Alloys based on nickel
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
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Abstract
本发明公开了一种含共晶组织的高熵合金按照原子百分比为(NiAl)100‑3xMoxCrxVx，7.5≤x≤10，其中，Ni、Al为等原子比；本发明还公开了该含共晶组织的高熵合金的制备方法，具体为，先按照原子比称取原料，然后对原料进行酸洗，最后在熔炼炉中进行熔炼得到含共晶组织的高熵合金。通过本发明的方法制备得到的高熵合金具有优异的强度和韧性。
The invention discloses a high-entropy alloy containing a eutectic structure according to the atomic percentage of (NiAl) 100-3xMoxCrxVx, 7.5≤x≤10, wherein Ni and Al are equal atomic ratios; the invention also discloses the eutectic-containing high-entropy alloy The preparation method of the high-entropy alloy with the microstructure is as follows: firstly, the raw materials are weighed according to the atomic ratio, then the raw materials are pickled, and finally the high-entropy alloy containing the eutectic structure is obtained by smelting in a smelting furnace. The high-entropy alloy prepared by the method of the present invention has excellent strength and toughness.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloy materials, relates to a high-entropy alloy containing eutectic structures, and further relates to a preparation method of the high-entropy alloy.
Background
For the currently researched NiAl alloy, the NiAl alloy has wide application prospect in the aerospace field because of the advantages of high melting point, low density, good thermal conductivity, excellent oxidation resistance and the like, but the application of the NiAl alloy is limited because of poor room temperature toughness and low high temperature strength. In order to improve the performance, a large amount of elements (such as Mo, Cr, V and the like are introduced into a metal phase) are added singly to form a NiAl-based eutectic alloy, the fracture toughness of the NiAl-based eutectic alloy can be obviously improved, but the high-temperature strength of the NiAl-based eutectic alloy is lower. And after Ta and Nb are added into NiAl and Laves phases are introduced, the high-temperature strength can be obviously improved, but the fracture toughness is obviously reduced. Therefore, it is difficult to obtain high strength and toughness at the same time for the current NiAl alloy.
Disclosure of Invention
The invention aims to provide a high-entropy alloy containing eutectic structures, and solves the problems of poor room-temperature toughness and low high-temperature strength of NiAl alloy in the prior art.
The invention also aims to provide a preparation method of the high-entropy alloy containing the eutectic structure.
The invention adopts the technical scheme that the high-entropy alloy containing the eutectic structure comprises (NiAl)100-3xMoxCrxVx according to the atomic percentage, wherein x is more than or equal to 7.5 and less than or equal to 10, and Ni and Al are in equal atomic ratio.
The invention adopts another technical scheme that a preparation method of a high-entropy alloy containing eutectic structures is implemented according to the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of (NiAl)100-3xMoxCrxVx and x which is more than or equal to 7.5 and less than or equal to 10;
step 2, respectively carrying out pretreatment on the surfaces of the Ni block, the Al block and the Mo wire through acid washing;
and 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain the high-entropy alloy containing the eutectic structure.
The other technical scheme of the invention is also characterized in that:
the purity of the Ni block, the purity of the Al block, the purity of the Cr sheet and the purity of the V block weighed in the step 1 are respectively 99.96%, 99.99%, 99.95% and 99.90%.
And 2, specifically, cleaning the Ni blocks by using HF, HNO3 and water in a volume ratio of 1:1: 2.0-3.0 for 10-20 min, cleaning the Al blocks by using HCl and water in a volume ratio of 1: 1.5-2.0 for 10-20 min, cleaning the Mo wires by using HNO3 and water in a volume ratio of 1: 1.5-2.0 for 5-10 min, respectively putting the Ni blocks, the Al blocks and the Mo wires into different containers after cleaning, adding alcohol to soak for 5-10 min, removing impurities and acid attached to the surfaces, and finally drying the alcohol-soaked Ni blocks, Al blocks and Mo wires for later use.
Step 3 is specifically implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 5 multiplied by 10-3Pa～4×10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni blocks, the Al blocks, the Cr sheets, the Mo wires and the V blocks, wherein the smelting current is 500-550A, the smelting time is 1-2min, then opening magnetic stirring, the magnetic stirring current is 8-10A, the magnetic stirring time is 5-6 min, and cooling after stirring is finished to obtain primary smelting alloy ingots;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 3-5 times to obtain the high-entropy alloy containing the eutectic structure.
The invention has the beneficial effects that: the invention provides a NiAl-MoCrV high-entropy alloy containing an eutectic structure, wherein the NiAl-Mo8.7Cr8.7V8.7 alloy structure is a full eutectic structure and consists of a NiAl phase and a MoCrV phase, and the structure presents a typical eutectic cell structure. The NiAl-Mo7.5Cr7.5V7.5 and NiAl-Mo8.33Cr8.33V8.33 alloys both contained a eutectic structure, and the structures contained a NiAl primary phase, indicating that they were hypoeutectic alloys. With the increase of Mo, Cr and V elements, eutectic structures still exist in the NiAl-Mo9Cr9V9 and NiAl-Mo10Cr10V10 alloy structures, and at the moment, MoCrV primary phases are also included in the structures, which indicates that the structures are hypereutectic alloys. The high-entropy alloy contains eutectic structures, so that the casting fluidity is good, most importantly, the MoCrV phase is a high-entropy phase which has high strength due to lattice distortion, and each element has a toughening effect on NiAl, so that the alloy has excellent comprehensive mechanical properties due to the toughening of the MoCrV high-entropy phase. The invention also provides a preparation method of the NiAl-MoCrV eutectic high-entropy alloy, the preparation method is simple in process, and the prepared alloy is uniform in structure components and fine in structure.
Drawings
FIG. 1a is a low power microstructure view of a NiAl-Mo7.5Cr7.5V7.5 (at%) hypoeutectic alloy prepared in example 1 of the present invention;
FIG. 1b is a high magnification microstructure view of a NiAl-Mo7.5Cr7.5V7.5 (at%) hypoeutectic alloy prepared in example 1 of the present invention;
FIG. 2a is a low-magnification microstructure of a NiAl-Mo8.33Cr8.33V8.33 (at%) hypoeutectic alloy prepared in example 2 of the present invention;
FIG. 2b is a high power microstructure of a NiAl-Mo8.33Cr8.33V8.33 (at%) hypoeutectic alloy prepared in example 2 of the present invention;
FIG. 3a is a low magnification microstructure view of a NiAl-Mo8.7Cr8.7V8.7 (at%) eutectic alloy prepared in example 3 of the invention;
FIG. 3b is a high magnification microstructure of a NiAl-Mo8.7Cr8.7V8.7 (at%) eutectic alloy prepared in example 3 of the invention;
FIG. 4a is a low-magnification microstructure of a NiAl-Mo9Cr9V9 (at%) hypereutectic alloy prepared in example 4 of the present invention;
FIG. 4b is a high power microstructure of a NiAl-Mo9Cr9V9 (at%) hypereutectic alloy prepared in example 4 of the present invention;
FIG. 5a is a low-magnification microstructure of a NiAl-Mo10Cr10V10 (at%) hypereutectic alloy prepared in example 5 of the present invention;
FIG. 5b is a high magnification microstructure of a NiAl-Mo10Cr10V10 (at%) hypereutectic alloy prepared in example 5 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a high-entropy alloy containing eutectic structures, which is characterized in that x is more than or equal to 7.5 and less than or equal to 10 according to the atomic percentage of (NiAl)100-3xMoxCrxVx, wherein the Ni and the Al are in equal atomic ratio.
The invention relates to a preparation method of a high-entropy alloy containing a eutectic structure, which is implemented according to the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of (NiAl)100-3xMoxCrxVx, wherein x is more than or equal to 7.5 and less than or equal to 10, the purity of the Ni blocks is 99.96%, the purity of the Al blocks is 99.99%, the purity of the Cr sheets is 99.90%, the purity of the Mo wires is 99.95%, and the purity of the V blocks is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and a water-cleaning Ni block in a volume ratio of 1:1: 2.0-3.0 for 10-20 min, cleaning the Al block by adopting HCl and water in a volume ratio of 1: 1.5-2.0 for 10-20 min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1: 1.5-2.0 for 5-10 min, respectively putting the Ni block, the Al block and the Mo wire into different containers after cleaning, adding alcohol to soak for 5-10 min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 5 multiplied by 10-3Pa～4×10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni blocks, the Al blocks, the Cr sheets, the Mo wires and the V blocks, wherein the smelting current is 500-550A, the smelting time is 1-2min, then opening magnetic stirring, the magnetic stirring current is 8-10A, the magnetic stirring time is 5-6 min, and cooling after stirring is finished to obtain primary smelting alloy ingots;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 3-5 times to obtain the high-entropy alloy containing the eutectic structure.
Example 1
A preparation method of a high-entropy alloy containing a eutectic structure is implemented according to the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of (NiAl-Mo7.5Cr7.5V7.5), wherein the purity of the Ni blocks is 99.96%, the purity of the Al blocks is 99.99%, the purity of the Cr sheets is 99.90%, the purity of the Mo wires is 99.95%, and the purity of the V blocks is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and water in a volume ratio of 1:1:2.0 for 10min, cleaning the Al block by adopting HCl and water in a volume ratio of 1:1.5 for 10min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1:1.5 for 5min, respectively putting the Ni block, the Al block and the Mo wire into different containers after the cleaning is finished, adding alcohol to soak for 5min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 5 multiplied by 10-3PaPa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni block, the Al block, the Cr sheet, the Mo wire and the V block, wherein the smelting current is 500A, the smelting time is 1min, then opening magnetic stirring, the magnetic stirring current is 10A, the magnetic stirring time is 6min, and cooling after the stirring is finished to obtain a primary smelting alloy ingot;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 3 times to obtain the high-entropy alloy containing the eutectic structure.
FIG. 1 is a structural diagram of a scanning electron microscope of the NiAl-Mo7.5Cr7.5V7.5 high-entropy alloy prepared in example 1, and FIG. 1(b) is a structural diagram of a high-power scanning electron microscope, wherein the structure contains eutectic lamellar structures and consists of black NiAl and gray MoCrV high-entropy phases, and the strengthening and toughening effects of the MoCrV high-entropy phases enable the alloy to have high strength and toughness. In addition, as can be seen from fig. 1(a), the black primary phase NiAl is also present in the structure, indicating that the alloy of this composition is a hypoeutectic alloy.
Example 2
A preparation method of a high-entropy alloy containing a eutectic structure is implemented according to the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of NiAl-Mo8.33Cr8.33V8.33, wherein the purity of the Ni blocks is 99.96%, the purity of the Al blocks is 99.99%, the purity of the Cr sheets is 99.90%, the purity of the Mo wires is 99.95%, and the purity of the V blocks is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and water in a volume ratio of 1:1:2.5 for 15min, cleaning the Al block by adopting HCl and water in a volume ratio of 1:1.75 for 15min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1:1.75 for 7.5min, respectively putting the Ni block, the Al block and the Mo wire into different containers after cleaning, adding alcohol for soaking for 7.5min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 5 multiplied by 10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni block, the Al block, the Cr sheet, the Mo wire and the V block, wherein the smelting current is 510A, the smelting time is 1min, then opening magnetic stirring, the magnetic stirring current is 9A, the magnetic stirring time is 6min, and cooling after the stirring is finished to obtain a primary smelting alloy ingot;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 3 times to obtain the high-entropy alloy containing the eutectic structure.
FIG. 2 is the structural diagram of a scanning electron microscope of the NiAl-Mo8.33Cr8.33V8.33 high-entropy alloy prepared in example 2, and FIG. 2(b) is the structural diagram of a high-power scanning electron microscope, wherein the structure contains eutectic lamellar structures and consists of black NiAl and gray MoCrV high-entropy phases, and the strengthening and toughening effects of the MoCrV high-entropy phases enable the alloy to have high strength and toughness. In addition, as can be seen from fig. 2(a), the black primary phase NiAl is also present in the structure, indicating that the alloy of this composition is a hypoeutectic alloy.
Example 3
A preparation method of a high-entropy alloy containing a eutectic structure is implemented according to the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of NiAl-Mo8.7Cr8.7V8.7, wherein the purity of the Ni blocks is 99.96%, the purity of the Al blocks is 99.99%, the purity of the Cr sheets is 99.90%, the purity of the Mo wires is 99.95% and the purity of the V blocks is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and water in a volume ratio of 1:1:2.5 for 15min, cleaning the Al block by adopting HCl and water in a volume ratio of 1:1.75 for 15min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1:1.75 for 7.5min, respectively putting the Ni block, the Al block and the Mo wire into different containers after cleaning, adding alcohol for soaking for 7.5min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 4.5 multiplied by 10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni block, the Al block, the Cr sheet, the Mo wire and the V block, wherein the smelting current is 520A, the smelting time is 1.5min, then opening magnetic stirring, the magnetic stirring current is 9A, the magnetic stirring time is 5.5min, and cooling after the stirring is finished to obtain a primary smelting alloy ingot;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 4 times to obtain the high-entropy alloy containing the eutectic structure.
Fig. 3 is a scanning electron microscope structure diagram of the NiAl-mo8.7cr8.7v8.7 high entropy alloy prepared in example 3, and fig. 3(b) is a high power scanning electron microscope structure diagram, the alloy structure is a full eutectic lamellar structure and consists of black NiAl and grey white MoCrV high entropy phase, the strengthening and toughening effect of the MoCrV high entropy phase will make the alloy have high strength and toughness, and in addition, the absence of black primary phase NiAl in the structure can be seen from fig. 3 (a).
Example 4
The invention relates to a preparation method of a high-entropy alloy containing a eutectic structure, which is implemented according to the following steps:
step 1, respectively weighing a Ni block, an Al block, a Cr sheet, a Mo wire and a V block according to the atomic ratio of NiAl-Mo9Cr9V9, wherein the purity of the Ni block is 99.96%, the purity of the Al block is 99.99%, the purity of the Cr sheet is 99.90%, the purity of the Mo wire is 99.95%, and the purity of the V block is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and water in a volume ratio of 1:1:2.0 for 20min, cleaning the Al block by adopting HCl and water in a volume ratio of 1:2.0 for 20min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1:2.0 for 10min, respectively putting the Ni block, the Al block and the Mo wire into different containers after cleaning, adding alcohol for soaking for 7.5min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 4.5 multiplied by 10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni block, the Al block, the Cr sheet, the Mo wire and the V block, wherein the smelting current is 530A, the smelting time is 2min, then opening magnetic stirring, the magnetic stirring current is 8A, the magnetic stirring time is 5.5min, and cooling after the stirring is finished to obtain a primary smelting alloy ingot;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 5 times to obtain the high-entropy alloy containing the eutectic structure.
FIG. 4 is a structural diagram of a scanning electron microscope of the NiAl-Mo9Cr9V9 high-entropy alloy prepared in example 4, and FIG. 4(b) is a structural diagram of a high-power scanning electron microscope, wherein the structure contains eutectic lamellar structures and consists of black NiAl and gray MoCrV high-entropy phases, and the strengthening and toughening effects of the MoCrV high-entropy phases enable the alloy to have high strength and toughness. Further, as can be seen from fig. 4(a), white primary phase MoCrV also exists in the structure, indicating that the alloy of this composition is a hypereutectic alloy.
Example 5
The invention relates to a preparation method of a high-entropy alloy containing a eutectic structure, which is implemented according to the following steps:
step 1, respectively weighing a Ni block, an Al block, a Cr sheet, a Mo wire and a V block according to the atomic ratio of NiAl-Cr10Mo10V10, wherein the purity of the Ni block is 99.96%, the purity of the Al block is 99.99%, the purity of the Cr sheet is 99.90%, the purity of the Mo wire is 99.95%, and the purity of the V block is 99.90%;
step 2, respectively pretreating the surfaces of the Ni block, the Al block and the Mo wire by acid washing, specifically, cleaning the Ni block by adopting HF, HNO3 and water in a volume ratio of 1:1:2.0 for 20min, cleaning the Al block by adopting HCl and water in a volume ratio of 1:2.0 for 20min, cleaning the Mo wire by adopting HNO3 and water in a volume ratio of 1:2.0 for 10min, respectively putting the Ni block, the Al block and the Mo wire into different containers after the cleaning is finished, adding alcohol to soak for 10min, removing impurities and acid attached to the surfaces, and finally drying the Ni block, the Al block and the Mo wire soaked by the alcohol for later use;
step 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain a high-entropy alloy containing an eutectic structure; the method is implemented according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 4 multiplied by 10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni block, the Al block, the Cr sheet, the Mo wire and the V block, wherein the smelting current is 540A, the smelting time is 2min, then opening magnetic stirring, the magnetic stirring current is 8A, the magnetic stirring time is 5min, and cooling after the stirring is finished to obtain a primary smelting alloy ingot;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 5 times to obtain the high-entropy alloy containing the eutectic structure.
FIG. 5 is a structural diagram of a scanning electron microscope of the NiAl-Mo10Cr10V10 high-entropy alloy prepared in example 5, and FIG. 5(b) is a structural diagram of a high-power scanning electron microscope, wherein the structure contains eutectic lamellar structures and consists of black NiAl and gray MoCrV high-entropy phases, and the strengthening and toughening effects of the MoCrV high-entropy phases enable the alloy to have high strength and toughness. Further, as can be seen from fig. 5(a), white primary phase MoCrV also exists in the structure, indicating that the alloy of this composition is a hypereutectic alloy.
The NiAl-MoCrV high-entropy alloy containing the eutectic structure is designed and developed, the NiAl-Mo7.5Cr7.5V7.5 and NiAl-Mo8.33Cr8.33V8.33 high-entropy alloys are hypoeutectic alloys by adjusting the content of Mo, Cr and V elements, the NiAl-Mo8.7Cr8.7V8.7 high-entropy alloys are eutectic alloys, the NiAl-Cr9Mo9V9 and NiAl-Cr10Mo10V10 high-entropy alloys are hypereutectic alloys, and the alloy has good casting fluidity due to the eutectic structure, particularly because the strengthening and toughening of the MoCrV high-entropy phase (the high-entropy phase usually has high strength due to lattice distortion, and in addition, each element also has a strengthening and toughening effect on NiAl), the alloy has excellent strengthening and toughening properties.
Claims (5)
1. The high-entropy alloy containing the eutectic structure is characterized in that x is more than or equal to 7.5 and less than or equal to 10 according to the atomic percentage of (NiAl)100-3xMoxCrxVx, wherein the Ni and the Al are in equal atomic ratio.
2. A preparation method of a high-entropy alloy containing a eutectic structure is characterized by comprising the following steps:
step 1, respectively weighing Ni blocks, Al blocks, Cr sheets, Mo wires and V blocks according to the atomic ratio of (NiAl)100-3xMoxCrxVx and x which is more than or equal to 7.5 and less than or equal to 10;
step 2, respectively carrying out pretreatment on the surfaces of the Ni block, the Al block and the Mo wire through acid washing;
and 3, smelting the raw materials by adopting high-vacuum non-consumable arc smelting to obtain the high-entropy alloy containing the eutectic structure.
3. The method for preparing a high-entropy alloy containing a eutectic structure according to claim 2, wherein the purity of the Ni blocks, the purity of the Al blocks, the purity of the Cr sheets, the purity of the Mo wires and the purity of the V blocks weighed in the step 1 are respectively 99.96%, 99.99%, 99.90%, 99.95% and 99.90%.
4. The preparation method of the high-entropy alloy containing the eutectic structure as claimed in claim 2, wherein in the step 2, HF, HNO3 and water-cleaned Ni blocks in a volume ratio of 1:1: 2.0-3.0 are adopted, cleaning is carried out for 10-20 min, HCl and water in a volume ratio of 1: 1.5-2.0 are adopted to clean Al blocks for 10-20 min, HNO3 and water in a volume ratio of 1: 1.5-2.0 are adopted to clean Mo wires for 5-10 min, after cleaning is finished, the Ni blocks, the Al blocks and the Mo wires are respectively placed into different containers, alcohol is added to soak for 5-10 min, impurities and acid attached to the surfaces are removed, and finally the alcohol-soaked Ni blocks, Al blocks and the Mo wires are dried for later use.
5. A method for preparing a high-entropy alloy containing a eutectic structure according to claim 2, wherein the step 3 is specifically performed according to the following steps:
step 3.1, vacuumizing the arc melting furnace to 5 multiplied by 10-3Pa～4×10-3Pa, introducing argon with the purity of 99.9 percent to-0.06 Mpa as protective atmosphere;
3.2, carrying out primary smelting on the Ni blocks, the Al blocks, the Cr sheets, the Mo wires and the V blocks, wherein the smelting current is 500-550A, the smelting time is 1-2min, then opening magnetic stirring, the magnetic stirring current is 8-10A, the magnetic stirring time is 5-6 min, and cooling after stirring is finished to obtain primary smelting alloy ingots;
and 3.3, overturning the primary smelting alloy ingot in the crucible by using a mechanical arm under the vacuum condition, and repeating the step 3.2 for 3-5 times to obtain the high-entropy alloy containing the eutectic structure.
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