CN116254433B - Preparation method of low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy - Google Patents
Preparation method of low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy 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
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 105
- 238000000498 ball milling Methods 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims description 27
- 239000010935 stainless steel Substances 0.000 claims description 27
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- 238000005275 alloying Methods 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 229910001325 element alloy Inorganic materials 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012856 weighed raw material Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012216 screening Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002490 spark plasma sintering Methods 0.000 claims 1
- 229910008651 TiZr Inorganic materials 0.000 abstract description 21
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 6
- 229910000601 superalloy Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 4
- 229910018580 Al—Zr Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005551 mechanical alloying Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000009977 dual effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910000816 inconels 718 Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036316 preload Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
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Abstract
The invention discloses a preparation method of a low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy, and belongs to the technical field of high-entropy alloys. Solves the problems of the prior preparation of AlMo 0.5 NbTa 0.5 The problems of uneven alloy components, poor room temperature plasticity, coarse grain size, poor applicability and low powder utilization rate exist in the TiZr high-entropy alloy process. The method comprises the following steps: 1. weighing raw materials; 2. performing primary ball milling; 3. performing secondary ball milling; 4. sieving and three-stage ball milling; 5. and (5) sintering by discharge plasma. The method is used for preparing the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy.
Description
Technical Field
The invention belongs to the technical field of high-entropy alloy.
Background
With the continuous development of the aerospace industry, a metal structural material with excellent high-temperature mechanical properties is urgently needed. The nickel-based superalloy has the advantages of high-temperature strength, high-temperature oxidation resistance, hot corrosion resistance, high-temperature fatigue resistance and the like, and has wide application prospects in the fields of aerospace and energy storage, such as jet engines and turbines; although great progress is made in the aspects of control of the structural components, performance improvement and the like of the nickel-based superalloy, and the nickel-based superalloy has been applied to the fields of aerospace, energy storage and the like, the nickel-based superalloy has not reached the extent of large-scale engineering application. The reason for this is mainly two problems: first, the density is higher (8.5 g/cm) 3 Left and right); secondly, the use at higher operating temperatures is limited by its solvus and melting temperatures. Therefore, there is a great need to develop a novel alloy material with a combination of low density and high temperature strength.
High entropy alloys using refractory elements of high melting point (e.g. NbMoTaW (V), crMo) compared to nickel-based superalloys 0.5 NbTa 0.5 TiZr and AlMo 0.5 NbTa 0.5 TiZr, etc.) has excellent high-temperature mechanical properties, and plays a role in the direction of high-temperature-resistant structural materials. Compared with other refractory high-entropy alloys, alMo prepared by the traditional arc melting method 0.5 NbTa 0.5 TiZr high-entropy alloy shows bright spots with low density and high temperature strength, and has compression yield strength as high as 2197Pa (higher than Inconel 718 by nearly 1000MPa and fracture strain as high as 4.5%) at room temperature, and has yield strength as high as 745MPa (4 times of Inconel 718) at 1000 ℃ and is considered as a substitute for nickel-based superalloy. However, the alloy prepared by arc melting has the defects of poor room temperature plasticity, coarse grain size, serious component segregation, shrinkage cavity and the like, and seriously influences the performance of the high-entropy alloy. Meanwhile, refractory elements with high melting point (such as Ta, mo, W and the like) tend to have high density, and after adding non-refractory elements with low density such as Al, si, C and the like, the traditional mechanical alloying (also known as a high-energy ball milling method) tends to have the phenomena of uneven mixing and lower efficiency in the powder preparation process; because ofTherefore, development of refractory high-entropy alloy with high strength, low density and good plasticity is urgently needed, and a new approach is provided for developing novel high-temperature-resistant alloy.
Disclosure of Invention
The invention aims to solve the problems of the existing preparation of AlMo 0.5 NbTa 0.5 The problems of uneven alloy components, poor room temperature plasticity, coarse grain size, poor applicability and low powder utilization rate exist in the TiZr high-entropy alloy process, and the preparation method of the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy is provided.
The preparation method of the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy comprises the following steps:
1. according to chemical formula Al x Mo0.5NbTa0.5TiZr y Weighing Al powder, mo powder, nb powder, ta powder, ti powder and Zr powder according to the molar ratio to obtain a weighed raw material; and chemical formula Al x Mo0.5NbTa0.5TiZr y Wherein x=0.25 to 1.5 and y=0.5 to 1;
2. under the conditions that the rotating speed is 100 rpm-200 rpm and the ball-to-material ratio is (2-5): 1, carrying out primary ball milling on the weighed raw materials for 1-6 hours to obtain primary ball-milled element alloy mixed powder;
3. under the conditions that the rotating speed is 300 rpm-400 rpm and the ball-material ratio is (6-10): 1, carrying out secondary ball milling on the element alloy mixed powder after primary ball milling for 10-50 hours to obtain alloying Al after secondary ball milling x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
4. alloying Al after secondary ball milling by utilizing screen x Mo0.5NbTa0.5TiZr y Screening the high-entropy alloy powder, carrying out three-stage ball milling on alloy particles which do not pass through a screen for 5-20 h under the conditions that the rotating speed is 200-300 rpm and the ball-to-material ratio is (6-12): 1, and then mixing the alloy powder after three-stage ball milling with the alloy powder which passes through the screen to obtain alloyed Al x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
5. alloying Al x Mo0.5NbTa0.5TiZr y Performing discharge plasma sintering on the high-entropy alloy powder to obtain Al x Mo0.5NbTa0.5TiZr y Refractory high entropy alloy, and x=0.25 to 1.5, y=0.5 to 1.
The beneficial effects of the invention are as follows:
(1) The invention provides a novel refractory high-entropy alloy Al x Mo0.5NbTa0.5TiZr y The preparation method of (x=0.25-1.5 and y=0.5-1) is characterized in that an alloy system mainly comprises a matrix phase of a BCC structure, an Al-Zr-rich phase on a grain boundary and an intragranular precipitated phase, and meanwhile, the density of the alloy system is smaller, and the preparation method combines a unique microstructure to ensure that the high-entropy alloy meets the dual requirements on normal-temperature plasticity and high-temperature strength of the material, so that the preparation method has wide application prospect;
(2) On one hand, for elements with larger melting point and density difference (especially the Al element and the Ta element of the system), the novel multistage ball milling-step powder taking technology can ensure that the components are completely and uniformly mixed, and has wide applicable component range; on the other hand, the utilization rate of the alloying powder can be obviously improved (more than 95 percent), more uniform and fine alloying powder can be obtained, and the microstructure of the material can be improved.
(3) Compared with the traditional arc melting preparation method, the refractory high-entropy alloy prepared by the method has uniform components, better compactness and fine grains (about 10 mu m), and well eliminates the component segregation.
(4) AlMo prepared by the invention 0.5 NbTa 0.5 The density of the TiZr refractory high-entropy alloy is only 7.22g/cm 3 The compressive strength at 25 ℃ is 2287MPa, the elongation is 10.4%, and the compressive strength at 1000 ℃ is 798MPa.
The invention is used for preparing the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy.
Drawings
FIG. 1 is an SEM+EDS photograph of the primary ball-milled elemental alloy powder mixture prepared in the first step of the example;
FIG. 2 is an XRD diffraction pattern of alloy powder at different times during the second-order ball milling of examples one to four and comparative experiment step three;
FIG. 3 shows a result of a secondary ball milling for 50 hours in the third step of the fourth exampleIs (are) alloyed AlMo 0.5 NbTa 0.5 SEM photographs of TiZr high-entropy alloy powder;
FIG. 4 is an SEM photograph of alloy particles not passing through a screen in step four of example four;
FIG. 5 is an SEM photograph of alloy particles passing through no screen in the fourth step of example after three-stage ball milling for 20 hours;
FIG. 6 is AlMo prepared in the fourth step five of the example 0.5 NbTa 0.5 Microscopic morphology SEM photographs of TiZr refractory high-entropy alloys;
FIG. 7 is AlMo prepared in the fourth step five of the example 0.5 NbTa 0.5 Mechanical property patterns of TiZr refractory high-entropy alloy at 25 ℃ and 1000 ℃.
Detailed Description
The first embodiment is as follows: the preparation method of the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy comprises the following steps:
1. according to chemical formula Al x Mo0.5NbTa0.5TiZr y Weighing Al powder, mo powder, nb powder, ta powder, ti powder and Zr powder according to the molar ratio to obtain a weighed raw material; and chemical formula Al x Mo0.5NbTa0.5TiZr y Wherein x=0.25 to 1.5 and y=0.5 to 1;
2. under the conditions that the rotating speed is 100 rpm-200 rpm and the ball-to-material ratio is (2-5): 1, carrying out primary ball milling on the weighed raw materials for 1-6 hours to obtain primary ball-milled element alloy mixed powder;
3. under the conditions that the rotating speed is 300 rpm-400 rpm and the ball-material ratio is (6-10): 1, carrying out secondary ball milling on the element alloy mixed powder after primary ball milling for 10-50 hours to obtain alloying Al after secondary ball milling x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
4. alloying Al after secondary ball milling by utilizing screen x Mo0.5NbTa0.5TiZr y Screening the high-entropy alloy powder, carrying out three-stage ball milling on alloy particles which do not pass through a screen for 5-20 h under the conditions that the rotating speed is 200-300 rpm and the ball-to-material ratio is (6-12): 1, and then mixing the alloy powder after three-stage ball milling with the alloy powder which passes through the screen to obtain the alloyGold-plated Al x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
5. alloying Al x Mo0.5NbTa0.5TiZr y Performing discharge plasma sintering on the high-entropy alloy powder to obtain Al x Mo0.5NbTa0.5TiZr y Refractory high entropy alloy, and x=0.25 to 1.5, y=0.5 to 1.
The beneficial effects of this concrete implementation are:
(1) The specific embodiment provides a novel refractory high-entropy alloy Al x Mo0.5NbTa0.5TiZr y The preparation method of (x=0.25-1.5 and y=0.5-1) is characterized in that an alloy system mainly comprises a matrix phase of a BCC structure, an Al-Zr-rich phase on a grain boundary and an intragranular precipitated phase, and meanwhile, the density of the alloy system is smaller, and the preparation method combines a unique microstructure to ensure that the high-entropy alloy meets the dual requirements on normal-temperature plasticity and high-temperature strength of the material, so that the preparation method has wide application prospect;
(2) On one hand, for elements with larger melting point and density difference (especially Al element and Ta element in the system of the specific embodiment), the novel multistage ball milling-step powder taking technology can ensure that the components are completely and uniformly mixed, and has wide application component range; on the other hand, the utilization rate of the alloying powder can be obviously improved (more than 95 percent), more uniform and fine alloying powder can be obtained, and the microstructure of the material can be improved.
(3) Compared with the traditional arc melting preparation method, the refractory high-entropy alloy prepared by the method has uniform components, better compactness and fine grains (about 10 mu m), and well eliminates the component segregation.
(4) AlMo prepared in this embodiment 0.5 NbTa 0.5 The density of the TiZr refractory high-entropy alloy is only 7.22g/cm 3 The compressive strength at 25 ℃ is 2287MPa, the elongation is 10.4%, and the compressive strength at 1000 ℃ is 798MPa.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the Zr powder in the first step is specifically obtained in a vacuum degree of less than 10 -3 Drying for 4h under Pa and 60 ℃. Other and embodimentsOne is the same.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the particle diameters of the Al powder, the Mo powder, the Nb powder, the Ta powder, the Ti powder and the Zr powder in the step one are all 45-48 mu m, and the purity is more than 99.5%. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the ball milling medium used in the first-stage ball milling is stainless steel grinding balls with the diameter of 6 mm. The other embodiments are the same as those of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: the ball milling medium used in the second-stage ball milling is the mixture of stainless steel grinding balls with the diameter of 6mm and stainless steel grinding balls with the diameter of 10mm, and the mass ratio of the stainless steel grinding balls with the diameter of 6mm to the stainless steel grinding balls with the diameter of 10mm is (2-5): 1. The other embodiments are the same as those of the first to fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: the ball milling medium used in the third-stage ball milling is the mixture of the stainless steel grinding ball with the diameter of 6mm and the stainless steel grinding ball with the diameter of 10mm, and the mass ratio of the stainless steel grinding ball with the diameter of 6mm to the stainless steel grinding ball with the diameter of 10mm is (1-3): 1. The other embodiments are the same as those of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: the screen mesh in the fourth step is a 100-200 mesh screen mesh. The other embodiments are the same as those of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: the discharge plasma sintering in the fifth step is specifically carried out according to the following steps: alloying Al x Mo0.5NbTa0.5TiZr y The high-entropy alloy powder is put into a die, and then is sintered for 5min to 30min under the conditions that the vacuum degree of a hearth is less than or equal to 8Pa, the temperature is 1300 ℃ to 1600 ℃ and the sintering pressure is 20MPa to 40 MPa. Which is a kind ofIt is the same as in embodiments one to seven.
Detailed description nine: this embodiment differs from one to eight of the embodiments in that: the temperature is raised to 1300-1600 ℃ at the temperature rising rate of 45-75 ℃/min. The others are the same as in embodiments one to eight.
Detailed description ten: this embodiment differs from one of the embodiments one to nine in that: the die material is high-strength graphite. The others are the same as in embodiments one to nine.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy comprises the following steps:
1. according to the chemical formula AlMo 0.5 NbTa 0.5 Weighing Al powder, mo powder, nb powder, ta powder, ti powder and Zr powder according to the molar ratio of TiZr to obtain a weighed raw material;
2. performing primary ball milling on the weighed raw materials for 6 hours by utilizing a QM-3SP4 planetary ball mill under the conditions of 200rpm of rotating speed and 3:1 of ball-material ratio to obtain element alloy mixed powder after primary ball milling;
the ball milling medium used in the primary ball milling is a stainless steel grinding ball with the diameter of 6 mm;
3. performing secondary ball milling on the element alloy mixed powder subjected to primary ball milling for 10 hours by utilizing a QM-3SP4 planetary ball mill under the conditions of a rotating speed of 350rpm and a ball-material ratio of 10:1 to obtain alloyed AlMo subjected to secondary ball milling 0.5 NbTa 0.5 TiZr high entropy alloy powder;
the ball milling medium used in the secondary ball milling is the mixture of a stainless steel grinding ball with the diameter of 6mm and a stainless steel grinding ball with the diameter of 10mm, and the mass ratio of the stainless steel grinding ball with the diameter of 6mm to the stainless steel grinding ball with the diameter of 10mm is 3:1;
4. alloying AlMo after secondary ball milling by using 100-mesh screen 0.5 NbTa 0.5 TiZr high-entropy alloy powder is screened and QM-3SP4 planetary ball mill is utilizedCarrying out three-stage ball milling on alloy particles which do not pass through a screen for 20h under the conditions of 300rpm and a ball-to-material ratio of 12:1, and then mixing alloy powder after three-stage ball milling with alloy powder which passes through the screen to obtain alloyed AlMo 0.5 NbTa 0.5 TiZr high entropy alloy powder;
the ball milling medium used in the three-stage ball milling is the mixture of a stainless steel grinding ball with the diameter of 6mm and a stainless steel grinding ball with the diameter of 10mm, and the mass ratio of the stainless steel grinding ball with the diameter of 6mm to the stainless steel grinding ball with the diameter of 10mm is 1:1;
5. (1) spraying a boron nitride mold release agent on the inner wall surface of the mold, and then alloying AlMo 0.5 NbTa 0.5 Filling TiZr high-entropy alloy powder into a die, wherein the die is a high-strength graphite die with the inner diameter of phi 40 mm;
(2) spraying a boron nitride release agent on the surface of a graphite gasket, assembling the gasket and a pressure head, applying preload by using a press machine, so that powder is tightly contacted and air in the powder is discharged, and a layer of graphite paper is arranged between the powder and the graphite gasket;
(3) heating to 450 ℃ at a heating rate of 45 ℃/min under the conditions of a hearth vacuum degree of 8Pa and a sintering pressure of 40MPa, preserving heat for 10min at the temperature of 450 ℃, heating to 1400 ℃ at a heating rate of 75 ℃/min, sintering for 20min at the temperature of 1400 ℃, cooling to room temperature, and unloading the pressure to obtain AlMo 0.5 NbTa 0.5 TiZr refractory high entropy alloy.
The Zr powder in the first step is specifically obtained in a vacuum degree of less than 10 -3 Drying for 4h under Pa and 60 ℃.
The particle diameters of the Al powder, the Mo powder, the Nb powder, the Ta powder, the Ti powder and the Zr powder in the step one are all 45-48 mu m, and the purity is more than 99.5%.
And step two to four, filling powder in a glove box filled with argon and sealing the ball milling tank.
Embodiment two: the first difference between this embodiment and the first embodiment is that: and thirdly, performing secondary ball milling on the element alloy mixed powder subjected to primary ball milling for 20 hours. The other is the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the first embodiment is that: and thirdly, performing secondary ball milling on the element alloy mixed powder subjected to primary ball milling for 30 hours. The other is the same as in the first embodiment.
Embodiment four: the first difference between this embodiment and the first embodiment is that: and thirdly, performing secondary ball milling on the element alloy mixed powder subjected to primary ball milling for 50 hours. The other is the same as in the first embodiment.
Comparison experiment: the first difference between this comparative experiment and the example is: and (3) eliminating the secondary ball milling in the third step. The other is the same as in the first embodiment.
Example one step one the mass of each metal powder was calculated from the experimentally designed molar ratio of the alloying elements, and as shown in table 1, the mass of each original powder was weighed using an electronic balance with an accuracy of 0.001 g.
Table 1 example-AlMo 0.5 NbTa 0.5 Proportioning of elements of TiZr refractory high-entropy alloy
FIG. 1 is an SEM+EDS photograph of the primary ball-milled elemental alloy powder mixture prepared in the first step of the example; as can be seen from the figure, the ball milling speed is 200rpm, and the obtained powder is uniformly distributed after ball milling for 6 hours. The alloy powder is subjected to primary ball milling at 200rpm for 6 hours, so that good homogenization treatment is obtained, and a foundation is provided for further realizing alloying.
FIG. 2 is an XRD diffraction pattern of alloy powder at different times during the second-order ball milling of examples one to four and comparative experiment step three; as can be seen from the graph, the diffraction peaks corresponding to the elements one by one can be found out from the element alloy mixed powder after primary ball milling; with the extension of the ball milling time, the intensity of each main diffraction peak is greatly weakened or even vanished, wherein diffraction peaks of Al and Ti low-melting-point elements are preferentially widened, which indicates that solid solutions are formed in the alloy powder; when the ball milling time is prolonged to 50h, the alloy powder forms a simple solid solution of the BCC structure. In addition, the mechanical alloying sequence of different alloy elements in the multi-principal element high-entropy alloy system is related to the melting point of the elements, the lower the melting point of the elements in the alloy is, the more easily alloying is, and the alloying sequence of the alloy composition elements is as follows: al-Ti-Zr-Nb-Mo-Ta.
FIG. 3 shows alloyed AlMo after secondary ball milling for 50 hours in the third step of example four 0.5 NbTa 0.5 SEM photographs of TiZr high-entropy alloy powder; FIG. 4 is an SEM photograph of alloy particles not passing through a screen in step four of example four; FIG. 5 is an SEM photograph of alloy particles passing through no screen in the fourth step of example after three-stage ball milling for 20 hours; the figure shows that the powder morphology and particle size change are obvious after mechanical alloying, the powder particles have obvious cold welding phenomenon and plastic deformation, and the powder is subjected to cold welding, fracture, refinement and finally alloying. Ball milling to 50h, wherein part of large powder particles exist in the alloyed powder, then screening the large powder particles by a 100-mesh screen (see figure 4), and performing three-stage ball milling to obtain alloy powder with uniform and fine size (see figure 5), so that the utilization rate of the alloyed powder is further improved to more than 95%, and the alloy powder particles are uniform and fine.
FIG. 6 is AlMo prepared in the fourth step five of the example 0.5 NbTa 0.5 Microscopic morphology SEM photographs of TiZr refractory high-entropy alloys; as can be seen from the graph, the prepared high-entropy alloy block material consists of a matrix phase (BCC structure), a grain boundary precipitated phase (Al-Zr-enriched phase) and an intragranular precipitated phase, the alloy structure is densified, and the grain size of the prepared alloy is about 10 mu m.
FIG. 7 is AlMo prepared in the fourth step five of the example 0.5 NbTa 0.5 Mechanical property patterns of TiZr refractory high-entropy alloy at 25 ℃ and 1000 ℃; as is clear from the graph, the compressive strength is 2287MPa and the elongation is 10.4% under the conditions of the strain rate of 0.5mm/s and the temperature of 25 ℃; at a strain rate of 0.5mm/s and 1000 DEG CUnder the condition of the pressure resistance, the pressure resistance is 798MPa.
Example four step five AlMo prepared 0.5 NbTa 0.5 The density of the TiZr refractory high-entropy alloy is only 7.22g/cm 3 Exhibiting low density characteristics.
Thus, the above demonstrates that the alloy prepared in example four has low density, excellent high temperature strength and room temperature plastic match.
Claims (10)
1. The preparation method of the low-density high-strength high-toughness AlMoNbTaTiZr refractory high-entropy alloy is characterized by comprising the following steps of:
1. according to chemical formula Al x Mo0.5NbTa0.5TiZr y Weighing Al powder, mo powder, nb powder, ta powder, ti powder and Zr powder according to the molar ratio to obtain a weighed raw material; and chemical formula Al x Mo0.5NbTa0.5TiZr y Wherein x=0.25 to 1.5 and y=0.5 to 1;
2. under the conditions that the rotating speed is 100 rpm-200 rpm and the ball-to-material ratio is (2-5): 1, carrying out primary ball milling on the weighed raw materials for 1-6 hours to obtain primary ball-milled element alloy mixed powder;
3. under the conditions that the rotating speed is 300 rpm-400 rpm and the ball-material ratio is (6-10): 1, carrying out secondary ball milling on the element alloy mixed powder after primary ball milling for 10-50 hours to obtain alloying Al after secondary ball milling x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
4. alloying Al after secondary ball milling by utilizing screen x Mo0.5NbTa0.5TiZr y Screening the high-entropy alloy powder, carrying out three-stage ball milling on alloy particles which do not pass through a screen for 5-20 h under the conditions that the rotating speed is 200-300 rpm and the ball-to-material ratio is (6-12): 1, and then mixing the alloy powder after three-stage ball milling with the alloy powder which passes through the screen to obtain alloyed Al x Mo0.5NbTa0.5TiZr y High entropy alloy powder;
5. alloying Al x Mo0.5NbTa0.5TiZr y Performing discharge plasma sintering on the high-entropy alloy powder to obtain Al x Mo0.5NbTa0.5TiZr y Refractory high entropy alloy, and x=0.25 to 1.5, y=0.5 to 1.
2. The method for producing a refractory high-entropy alloy of AlMoNbTaTiZr system having a low density and high toughness according to claim 1, wherein said Zr powder is obtained in the first step in a vacuum degree of less than 10 -3 Drying for 4h under Pa and 60 ℃.
3. The method for preparing a refractory high-entropy alloy of AlMoNbTaTiZr with low density and high strength and toughness according to claim 2, wherein the grain sizes of the Al powder, the Mo powder, the Nb powder, the Ta powder, the Ti powder and the Zr powder in the step one are 45-48 μm, and the purities are over 99.5%.
4. The method for preparing the refractory high-entropy alloy of the AlMoNbTaTiZr series with low density and high strength and toughness according to claim 1, wherein the ball milling medium used in the first-stage ball milling in the second step is a stainless steel grinding ball with the diameter of 6 mm.
5. The method for preparing the refractory high-entropy alloy of AlMoNbTaTiZr with low density and high strength and toughness according to claim 1, wherein the ball milling medium used in the second-stage ball milling in the third step is a mixture of stainless steel grinding balls with the diameter of 6mm and stainless steel grinding balls with the diameter of 10mm, and the mass ratio of the stainless steel grinding balls with the diameter of 6mm to the stainless steel grinding balls with the diameter of 10mm is (2-5): 1.
6. The method for preparing the refractory high-entropy alloy of AlMoNbTaTiZr series with low density and high strength and toughness according to claim 1, wherein the ball milling medium used in the third-stage ball milling in the fourth step is a mixture of stainless steel grinding balls with the diameter of 6mm and stainless steel grinding balls with the diameter of 10mm, and the mass ratio of the stainless steel grinding balls with the diameter of 6mm to the stainless steel grinding balls with the diameter of 10mm is (1-3): 1.
7. The method for preparing the refractory high-entropy alloy of the AlMoNbTaTiZr series with low density and high strength and toughness according to claim 1, wherein the screen mesh in the fourth step is a 100-200 mesh screen mesh.
8. The method for preparing the low-density high-strength and high-toughness AlMoNbTaTiZr refractory high-entropy alloy according to claim 1, wherein the spark plasma sintering in the fifth step is specifically performed by the following steps: alloying Al x Mo0.5NbTa0.5TiZr y The high-entropy alloy powder is put into a die, and then is sintered for 5min to 30min under the conditions that the vacuum degree of a hearth is less than or equal to 8Pa, the temperature is 1300 ℃ to 1600 ℃ and the sintering pressure is 20MPa to 40 MPa.
9. The method for preparing the low-density high-strength and high-toughness AlMoNbTaTiZr refractory high-entropy alloy according to claim 8, wherein the temperature is raised to 1300-1600 ℃ at a heating rate of 45-75 ℃/min.
10. The method for preparing the refractory high-entropy alloy of the AlMoNbTaTiZr series with low density and high strength and toughness according to claim 8, wherein the die material is high-strength graphite.
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