CN116765380A - Shape memory high-entropy alloy powder for additive manufacturing and preparation method thereof - Google Patents
Shape memory high-entropy alloy powder for additive manufacturing and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 139
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 139
- 239000000843 powder Substances 0.000 title claims abstract description 124
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 37
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 238000003723 Smelting Methods 0.000 claims description 60
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 239000000725 suspension Substances 0.000 claims description 48
- 239000002245 particle Substances 0.000 claims description 30
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 16
- 238000005266 casting Methods 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 9
- 239000000498 cooling water Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000011068 loading method Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000006104 solid solution Substances 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 229910052755 nonmetal Inorganic materials 0.000 abstract 1
- 238000000889 atomisation Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000009689 gas atomisation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001465 metallisation Methods 0.000 description 2
- 238000009692 water atomization Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000012387 aerosolization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention discloses shape memory high-entropy alloy powder for additive manufacturing and a preparation method thereof, and relates to the technical field of high-entropy alloy and additive manufacturing, wherein the shape memory high-entropy alloy powder for additive manufacturing comprises Ni in percentage by atom: 5% -25%, ti:5% -25%, hf:5% -25%, zr:5% -25%, cu:5% -25%, the non-metal inclusion content in the shape memory high-entropy alloy powder prepared by the invention is low, the sphericity of the shape memory high-entropy alloy powder is high, the molten metal is thrown out by centrifugal force generated by high-speed rotation of a motor of a plasma rotary electrode atomizing device to form small liquid drops, and the molten liquid drops are spheroidized and solidified to form the shape memory high-entropy alloy powder under the action of the surface tension of the metal in the flight process of an atomizing chamber, so that the sphericity of the shape memory high-entropy alloy powder is ensured, and the sphericity of the shape memory high-entropy alloy powder prepared by the method is more than 0.80.
Description
Technical Field
The invention relates to the technical field of high-entropy alloy and additive manufacturing, in particular to shape memory high-entropy alloy powder for additive manufacturing and a preparation method thereof.
Background
The concept of high-entropy alloy (High Entropy Alloy, HEA) design based on the multi-principal component concept has been of interest in the last decade. HEA is generally composed of five principal elements, with a compositional ratio of between 5-35%, and recently the concept of HEA has been extended to alloys with four principal elements. The HEA has a series of excellent performances such as high yield strength and high ductility, excellent strength at low temperature and high temperature, high corrosion resistance, oxidation resistance and the like, and has great application potential in the fields of aerospace, molds, mechanical parts and the like. Cast HEA is typically vacuum induction melted or vacuum arc melted, which require repeated melting to achieve uniformity of chemical composition, but the bars produced still have significant porosity. In addition, as-cast HEA is often accompanied by defects such as phase segregation, coarse grains, non-uniform fibrous structure, etc., which can lead to deterioration of mechanical properties.
Faster solidification rates and finer microstructures based on additive manufacturing (Additive Manufacturing, AM) processes, either powder-laid or powder-fed, help address the above-described drawbacks of as-cast high-entropy alloys. The high entropy alloy powder for AM has powder characteristics different from those required for conventional powder metallurgy, and requires not only high purity of powder, low oxygen content, but also high sphericity of powder, uniform particle size distribution, and good flowability and bulk density. Therefore, it is necessary to obtain ingots with as good a defect as possible, low impurity content, uniform mass distribution and uniform tissue distribution before powdering. However, the direct contact between the crucible and the crucible cannot be avoided in the conventional vacuum induction furnace smelting and electric arc smelting, and raw material pollution in the smelting process is possibly caused.
Traditional pulverizing methods include water atomization, gas atomization, water-gas combined atomization, etc. The main disadvantage of water atomization powder preparation is that the oxygen content of the powder is difficult to control, the sphericity is poor, and the requirement of AM high purity powder is difficult to meet. The conventional method for preparing the AM powder mainly comprises the steps of aerosolization powder preparation, but the powder preparation efficiency is lower and the cost is higher. The plasma rotary electrode atomization method is firstly used for high-temperature alloy powder, and has broken through the problems of limit rotating speed and coarse particle size of prepared powder in recent years. The plasma rotary electrode atomizing powder process is to make metal or alloy into consumable electrode, the consumable electrode is melted to form liquid film under the action of coaxial plasma arc heating source, the liquid film is thrown out to form liquid drop under the action of rotating centrifugal force, the molten liquid drop is rubbed with argon in the atomizing chamber, the molten liquid drop is further crushed under the action of shear stress, and then the molten drop is cooled and solidified into spherical powder under the action of surface tension. Compared with the gas atomization technology, the technology does not directly disperse metal liquid flow for atomization by high-speed inert gas flow, and can avoid the umbrella effect in the gas atomization method, so that the sphericity of the powder is higher.
Disclosure of Invention
Aiming at the defects of the existing high-entropy alloy powder, the invention provides the shape memory high-entropy alloy powder for additive manufacturing, which has wide particle size distribution, high sphericity, low oxygen content and low impurity content, and the preparation method thereof.
A shape memory high entropy alloy powder for additive manufacturing, comprising, in atomic percent, ni:5% -25%, ti:5% -25%, hf:5% -25%, zr:5% -25%, cu:5% -25%.
Preferably, the shape memory high-entropy alloy powder for additive manufacturing comprises Ni in atomic percent: 10-25%, ti: 10-25% of Hf: 10-25%, zr: 10-25%, cu: 10-25%.
A method for preparing the shape memory high-entropy alloy powder for additive manufacturing comprises the following steps:
step 1, determining the addition amount of Ni, ti, hf, zr, cu according to the atomic percentage;
step 2, sequentially loading Ti, cu, zr, hf, ni into a vacuum suspension furnace from bottom to top, carrying out vacuum suspension smelting on raw materials in the vacuum suspension furnace for a plurality of times, fully diffusing the raw materials to form a uniform solid solution, casting the bar, and removing riser shrinkage cavities of the bar by using wire cutting after the bar is cooled;
and 3, mounting the processed bar on a continuous feeder, descending the continuous feeder at a certain speed, feeding the lower end of the bar into a plasma arc, continuously heating and smelting the bar through the plasma arc under the protection of inert gas, throwing out molten metal liquid by centrifugal force generated by high-speed rotation of a motor of a plasma rotary electrode atomizing device to form small liquid drops, cooling the liquid drops in the inert gas at a high speed, solidifying the liquid drops into spherical shape memory high-entropy alloy powder, and conveying the shape memory high-entropy alloy powder to a powder collecting tank through a powder conveying pipeline after the liquid drops are cooled by a cooling water system to obtain the shape memory high-entropy alloy powder.
Preferably, the method further comprises a step 4 of dividing and collecting the shape memory high-entropy alloy powder according to different specified particle size ranges by means of air classification or screen classification.
Preferably, the smelting step in the step 2 specifically includes: acid washing Ti, cu, zr, hf, ni, charging into a vacuum suspension furnace, and vacuumizing to 10 -3 The magnitude of the magnitude is that argon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and the smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after forming a molten pool, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, wherein the total smelting time is 30min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, and taking the blank shape memory high-entropy alloy each timeAnd (3) turning over up and down after the alloy is discharged, when the alloy is smelted for the tenth time, taking out the alloy when the alloy is cooled to a temperature of 100-150 ℃, casting the alloy into a bar, and fully diffusing the raw materials to form a uniform solid solution when the alloy is smelted for the tenth time.
Preferably, in the step 3, after the processed bar is mounted on the continuous feeder, the mechanical pump is used to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 15 pa-50 pa, and then the molecular pump is started to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 And (3) filling argon with the purity of 99.99% into the atomizing chamber as a shielding gas under Pa, so that the air pressure of the atomizing chamber reaches 0.04-0.08 MPa.
Preferably, in the step 4, the particle size of the shape memory high-entropy alloy powder is divided and collected according to the ranges of 15 μm to 53 μm, 50 μm to 150 μm, 150 μm to 250 μm and more than 250 μm.
The invention has the beneficial effects that:
the shape memory high-entropy alloy powder prepared by the method has high sphericity, the molten metal is thrown out by centrifugal force generated by high-speed rotation of a motor of a plasma rotary electrode atomizing device to form small liquid drops, and the molten liquid drops are spheroidized and solidified to form the shape memory high-entropy alloy powder under the action of the surface tension of the molten metal in the flight process of an atomizing chamber, so that the sphericity of the shape memory high-entropy alloy powder is ensured, and the sphericity of the shape memory high-entropy alloy powder prepared by the method reaches more than 0.80;
the components of the shape memory high-entropy alloy powder prepared by the invention are uniform, ten times of smelting are carried out in the preparation process, and the consistency and uniformity of the components of the shape memory high-entropy alloy powder are ensured;
the shape memory high-entropy alloy powder prepared by the method has low nonmetallic inclusion content, and because molten metal liquid drops in the preparation method are not contacted with a crucible, the introduction of nonmetallic inclusion is effectively avoided;
when the shape memory high-entropy alloy powder prepared by the invention is subjected to laser metal fusion forming on LAM-150V equipment, the shape memory high-entropy alloy powder is uniformly conveyed, a formed part has no obvious defects of air holes, cracking and the like, and the prepared part has hardness, yield strength, wide Wen Yuchao elastic energy and shape memory performance superior to those of most existing high-entropy shape memory alloy, can be widely applied to manufacturing of various precise instruments and special equipment, such as coupling devices, shock absorbers, fasteners and the like, and can even meet the light weight requirement and the low-temperature wide-temperature-range functional requirement in the aerospace field.
Drawings
FIG. 1 is a scanning electron microscope secondary electron imaging diagram of the shape memory high entropy alloy powder for additive manufacturing prepared in example 1;
FIG. 2 is a secondary electron image magnification of a scanning electron microscope of the shape memory high entropy alloy powder for additive manufacturing prepared in example 1;
FIG. 3 is a graph showing the particle size distribution of the shape memory high entropy alloy powder for additive manufacturing prepared in example 1;
FIG. 4 is an X-ray diffraction pattern of the shape memory high entropy alloy powder for additive manufacturing prepared in example 1;
fig. 5 is a graph of a differential scanning calorimeter analysis of the shape memory high entropy alloy powder for additive manufacturing prepared in example 1.
Detailed Description
Referring to fig. 1 and 5, a shape memory high-entropy alloy powder for additive manufacturing includes Ni in atomic percent: 5% -25%, ti:5% -25%, hf:5% -25%, zr:5% -25%, cu:5% -25%.
Wherein, the purity of the raw materials is: ni:99.98%, ti:99.95%, cu:99.9%, zr:99.9%, hf:99.95%.
Specifically, the shape memory high-entropy alloy powder for additive manufacturing comprises Ni in atomic percent: 10-25%, ti: 10-25% of Hf: 10-25%, zr: 10-25%, cu: 10-25%.
Referring to fig. 1 and 5, a method for preparing the shape memory high entropy alloy powder for additive manufacturing comprises the following steps:
step 1, determining the addition amount of Ni, ti, hf, zr, cu according to the atomic percentage;
step 2, sequentially loading Ti, cu, zr, hf, ni into a vacuum suspension furnace from bottom to top, carrying out vacuum suspension smelting on raw materials in the vacuum suspension furnace for a plurality of times, fully diffusing the raw materials to form a uniform solid solution, casting the bar, and removing riser shrinkage cavities of the bar by using wire cutting after the bar is cooled;
step 3, mounting the processed bar on a continuous feeder, descending the continuous feeder at a certain speed, feeding the lower end of the bar into a plasma arc, continuously heating and smelting the bar through the plasma arc under the protection of inert gas, throwing out molten metal liquid by centrifugal force generated by high-speed rotation of a motor of a plasma rotary electrode atomizing device to form small liquid drops, cooling the liquid drops in the inert gas at a high speed, solidifying the liquid drops into spherical shape memory high-entropy alloy powder, and conveying the shape memory high-entropy alloy powder to a powder collecting tank through a powder conveying pipeline after the liquid drops are cooled by a cooling water system to obtain the shape memory high-entropy alloy powder;
and 4, dividing and collecting the shape memory high-entropy alloy powder according to different specified particle size ranges in an air flow classification or screen classification mode.
Specifically, the smelting step in the step 2 specifically includes: acid washing Ti, cu, zr, hf, ni, charging into a vacuum suspension furnace, and vacuumizing to 10 -3 The magnitude of the magnitude is that argon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and the smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after forming a molten pool, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, wherein the total smelting duration is 30min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, taking out the blank shape memory high-entropy alloy, vertically overturning the blank shape memory high-entropy alloy, taking out the blank shape memory high-entropy alloy when the blank shape memory high-entropy alloy is cooled to a temperature ranging from 100 ℃ to 150 ℃ in the tenth smelting, casting the blank shape memory high-entropy alloy into bars, and fully expanding the raw materials in the tenth smeltingAnd dispersed to form a uniform solid solution.
Specifically, the diameter of the bar prepared in the step 2 is 20-50 mm.
Specifically, before the bar is installed in the step 3, the bar is required to be checked according to the drawing requirement, and foreign matters on the surface of the bar are removed.
Specifically, in the step 3, two bars are connected by threads, one end of each bar penetrates through the dynamic seal to extend into the atomization chamber, and the other end of each bar is connected with the driven shaft connector by threads.
Specifically, in the step 3, after the processed bar is mounted on the continuous feeder, the mechanical pump is used to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 15 pa-50 pa, and then the molecular pump is started to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 And (3) filling argon with the purity of 99.99% into the atomizing chamber as a shielding gas under Pa, so that the air pressure of the atomizing chamber reaches 0.04-0.08 MPa.
Specifically, in the step 3, the motor rotation speed of the plasma rotary electrode atomizing device is 20000r/min to 40000r/min.
Specifically, in the step 4, the particle size of the shape memory high-entropy alloy powder is divided and collected according to the ranges of 15-53 μm, 50-150 μm, 150-250 μm and more than 250 μm.
Example 1
Referring to fig. 1 and 5, a method for preparing the shape memory high entropy alloy powder for additive manufacturing comprises the following steps:
step 1, electrolytic Ni particles with purity of 99.98%, ti particles with purity of 99.95%, cu particles with purity of 99.9%, sponge Zr with purity of 99.95% and crystal bar Hf with purity of 99.95% are selected as raw materials, and the shape memory high-entropy alloy powder for additive manufacturing is set as Ni according to the atomic percentage: 25%, ti:16.67%, hf:16.67%, zr:16.66%, cu:25%;
step 2, firstly, pickling Ti, cu, zr, hf, ni, then sequentially loading Ti, cu, zr, hf, ni after pickling into a vacuum suspension furnace from bottom to top, and vacuumizing to 10 in the vacuum suspension furnace -3 Magnitude, makeArgon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after a molten pool is formed, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, wherein the total smelting duration is 30min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, taking out the blank shape memory high-entropy alloy, vertically overturning the blank shape memory high-entropy alloy, taking out the blank shape memory high-entropy alloy when the blank shape memory high-entropy alloy is cooled to 126 ℃ during the tenth smelting, casting the blank shape memory high-entropy alloy into a bar, and removing riser shrinkage cavities of the bar by using wire cutting;
step 3, mounting the processed bar on a continuous feeder, firstly pumping the air pressure of an atomizing chamber of a plasma rotary electrode atomizing device to 34Pa by using a mechanical pump, and then starting a molecular pump to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 Under Pa, argon with the purity of 99.99% is filled into an atomization chamber as a shielding gas, the air pressure of the atomization chamber reaches 0.06MPa, a continuous feeder descends at a certain speed, the lower end of a bar is fed into a plasma arc, under the protection of inert gas, the bar is continuously heated and smelted through the plasma arc, the rotating speed of a motor of a plasma rotary electrode atomization device is 40000r/min, molten metal liquid is thrown out by centrifugal force generated by the high-speed rotation of the motor of the plasma rotary electrode atomization device to form small liquid drops, the liquid drops are cooled in the inert gas at a high speed, and solidified into spherical shape memory high-entropy alloy powder, and the shape memory high-entropy alloy powder is conveyed to a powder collecting tank through a powder conveying pipeline after being cooled by a cooling water system, so as to obtain the shape memory high-entropy alloy powder;
and 4, dividing and collecting the particle size of the shape memory high-entropy alloy powder according to the ranges of 15-53 mu m, 50-150 mu m, 150-250 mu m and more than 250 mu m in an air flow classification or screen classification mode, and obtaining the shape memory high-entropy alloy powder (more than or equal to 60%) with the particle size of 15-53 mu m mainly through classification treatment, thereby completing the preparation process of the shape memory high-entropy alloy powder for powder bed melting.
The shape memory high-entropy alloy powder prepared by the plasma rotary electrode atomization method is spherical or nearly spherical, basically has no adhesion and has few satellite particles. The plasma rotary electrode atomization method has the advantages of high cooling rate, high surface cleanliness of single shape memory high-entropy alloy powder particles, uniform components and high sphericity. The X-ray diffraction pattern shows that the shape memory high-entropy alloy powder is a dual-phase microstructure of BCC+FCC, and the oxygen content of the shape memory high-entropy alloy powder is 368ppm and the nitrogen content of the shape memory high-entropy alloy powder is 31ppm through gas content detection.
Example two
Referring to fig. 1 and 5, a method for preparing the shape memory high entropy alloy powder for additive manufacturing comprises the following steps:
step 1, electrolytic Ni particles with purity of 99.98%, ti particles with purity of 99.95%, cu particles with purity of 99.9%, sponge Zr with purity of 99.95% and crystal bar Hf with purity of 99.95% are selected as raw materials, and the shape memory high-entropy alloy powder for additive manufacturing is set as Ni according to the atomic percentage: 20%, ti:20%, hf:20%, zr:20%, cu:20% of a base;
step 2, firstly, pickling Ti, cu, zr, hf, ni, then sequentially loading Ti, cu, zr, hf, ni after pickling into a vacuum suspension furnace from bottom to top, and vacuumizing to 10 in the vacuum suspension furnace -3 The magnitude of the magnitude is that argon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and the smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after forming a molten pool, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, wherein the total smelting duration is 30min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, taking out the blank shape memory high-entropy alloy each time, turning over the blank shape memory high-entropy alloy up and down, and cooling the blank shape memory high-entropy alloy to 1 when smelting for the tenth timeTaking out the blank shape memory high-entropy alloy at 32 ℃, casting into a bar, and removing riser shrinkage cavity of the bar by using wire cutting;
step 3, mounting the processed bar on a continuous feeder, firstly pumping the air pressure of an atomizing chamber of a plasma rotary electrode atomizing device to 36Pa by using a mechanical pump, and then starting a molecular pump to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 Under Pa, argon with the purity of 99.99% is filled into an atomization chamber as a shielding gas, the air pressure of the atomization chamber reaches 0.06MPa, a continuous feeder descends at a certain speed, the lower end of a bar is fed into a plasma arc, under the protection of inert gas, the bar is continuously heated and smelted through the plasma arc, the rotating speed of a motor of a plasma rotary electrode atomization device is 30000r/min, molten metal liquid is thrown out by centrifugal force generated by the high-speed rotation of the motor of the plasma rotary electrode atomization device to form small liquid drops, the liquid drops are cooled in the inert gas at a high speed, and solidified into spherical shape memory high-entropy alloy powder, and the shape memory high-entropy alloy powder is conveyed to a powder collecting tank through a powder conveying pipeline after being cooled by a cooling water system, so as to obtain the shape memory high-entropy alloy powder;
and 4, dividing and collecting the particle size of the shape memory high-entropy alloy powder according to the range of 15-53 mu m, 50-150 mu m, 150-250 mu m and more than 250 mu m in an air flow classification or screen classification mode, and obtaining the shape memory high-entropy alloy powder (more than or equal to 60%) with the particle size of mainly 50-150 mu m through classification treatment, thereby completing the preparation process of the shape memory high-entropy alloy powder for laser metal deposition.
The shape memory high-entropy alloy powder prepared by the plasma rotary electrode atomization method is spherical or nearly spherical, basically has no adhesion and has few satellite particles. The plasma rotary electrode atomization method has the advantages of high cooling rate, high surface cleanliness of single shape memory high-entropy alloy powder particles, uniform components and high sphericity. The X-ray diffraction pattern shows that the shape memory high-entropy alloy powder is a dual-phase microstructure of BCC+FCC, and the oxygen content of the shape memory high-entropy alloy powder is 356ppm and the nitrogen content of the shape memory high-entropy alloy powder is 42ppm through gas content detection.
Example III
Referring to fig. 1 and 5, a method for preparing the shape memory high entropy alloy powder for additive manufacturing comprises the following steps:
step 1, electrolytic Ni particles with purity of 99.98%, ti particles with purity of 99.95%, cu particles with purity of 99.9%, sponge Zr with purity of 99.95% and crystal bar Hf with purity of 99.95% are selected as raw materials, and the shape memory high-entropy alloy powder for additive manufacturing is set as Ni according to the atomic percentage: 12.5%, ti:12.5%, hf:25%, zr:25%, cu:25%;
step 2, firstly, pickling Ti, cu, zr, hf, ni, then sequentially loading Ti, cu, zr, hf, ni after pickling into a vacuum suspension furnace from bottom to top, and vacuumizing to 10 in the vacuum suspension furnace -3 The magnitude of the magnitude is that argon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and the smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after a molten pool is formed, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, wherein the total smelting duration is 30min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, taking out the blank shape memory high-entropy alloy, vertically turning over each time, taking out the blank shape memory high-entropy alloy when the blank shape memory high-entropy alloy is cooled to 134 ℃ during the tenth smelting, casting the blank shape memory high-entropy alloy into a bar, and removing riser shrinkage cavities of the bar by using wire cutting;
step 3, mounting the processed bar on a continuous feeder, firstly pumping the air pressure of an atomizing chamber of a plasma rotary electrode atomizing device to 31Pa by using a mechanical pump, and then starting a molecular pump to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 Argon with purity of 99.99% is filled into the atomizing chamber as protective gas under Pa to make the air pressure of the atomizing chamber reach 0.06MPa, the continuous feeder is lowered at a certain speed, the lower end of the bar is sent into the plasma arc, and the bar passes through under the protection of inert gasContinuously heating and smelting the bar by using a plasma arc, wherein the rotating speed of a motor of a plasma rotary electrode atomizing device is 30000r/min, and centrifugal force generated by high-speed rotation of the motor of the plasma rotary electrode atomizing device throws molten metal liquid out to form small liquid drops, the liquid drops are cooled at a high speed in inert gas and solidified into spherical shape memory high-entropy alloy powder, and the spherical shape memory high-entropy alloy powder is conveyed to a powder collecting tank through a powder conveying pipeline after being cooled by a cooling water system to obtain the shape memory high-entropy alloy powder;
and 4, dividing and collecting the particle size of the shape memory high-entropy alloy powder according to the range of 15-53 mu m, 50-150 mu m, 150-250 mu m and more than 250 mu m in an air flow classification or screen classification mode, and obtaining the shape memory high-entropy alloy powder (more than or equal to 60%) with the particle size of mainly 50-150 mu m through classification treatment, thereby completing the preparation process of the shape memory high-entropy alloy powder for laser metal deposition.
The shape memory high-entropy alloy powder prepared by the plasma rotary electrode atomization method is spherical or nearly spherical, basically has no adhesion and has few satellite particles. The plasma rotary electrode atomization method has the advantages of high cooling rate, high surface cleanliness of single shape memory high-entropy alloy powder particles, uniform components and high sphericity. The X-ray diffraction pattern shows that the shape memory high-entropy alloy powder is a dual-phase microstructure of BCC+FCC, and the oxygen content of the shape memory high-entropy alloy powder is 322ppm and the nitrogen content of the shape memory high-entropy alloy powder is 31ppm through gas content detection.
Claims (7)
1. The shape memory high-entropy alloy powder for additive manufacturing is characterized in that: the shape memory high-entropy alloy powder for additive manufacturing comprises Ni in atomic percent: 5% -25%, ti:5% -25%, hf:5% -25%, zr:5% -25%, cu:5% -25%.
2. A shape memory high entropy alloy powder for additive manufacturing as recited in claim 1, wherein: the shape memory high-entropy alloy powder for additive manufacturing comprises Ni in atomic percent: 10-25%, ti: 10-25% of Hf: 10-25%, zr: 10-25%, cu: 10-25%.
3. A method of preparing the shape memory high entropy alloy powder for additive manufacturing according to any one of claims 1-2, comprising the steps of:
step 1, determining the addition amount of Ni, ti, hf, zr, cu according to the atomic percentage;
step 2, sequentially loading Ti, cu, zr, hf, ni into a vacuum suspension furnace from bottom to top, carrying out vacuum suspension smelting on raw materials in the vacuum suspension furnace for a plurality of times, fully diffusing the raw materials to form a uniform solid solution, casting the bar, and removing riser shrinkage cavities of the bar by using wire cutting after the bar is cooled;
and 3, mounting the processed bar on a continuous feeder, descending the continuous feeder at a certain speed, feeding the lower end of the bar into a plasma arc, continuously heating and smelting the bar through the plasma arc under the protection of inert gas, throwing out molten metal liquid by centrifugal force generated by high-speed rotation of a motor of a plasma rotary electrode atomizing device to form small liquid drops, cooling the liquid drops in the inert gas at a high speed, solidifying the liquid drops into spherical shape memory high-entropy alloy powder, and conveying the shape memory high-entropy alloy powder to a powder collecting tank through a powder conveying pipeline after the liquid drops are cooled by a cooling water system to obtain the shape memory high-entropy alloy powder.
4. A method for preparing the shape memory high-entropy alloy powder for additive manufacturing as claimed in claim 3, wherein: and 4, dividing and collecting the shape memory high-entropy alloy powder according to different specified particle size ranges in an air flow classification or screen classification mode.
5. A method for preparing the shape memory high-entropy alloy powder for additive manufacturing as claimed in claim 3, wherein: the smelting step in the step 2 specifically comprises the following steps: acid washing Ti, cu, zr, hf, ni, charging into a vacuum suspension furnace, and vacuumizing to 10 -3 The magnitude of the magnitude is that argon is used for washing gas twice, argon is filled in a cabin for protection, the whole process of smelting and casting is required to be carried out in an argon protection environment, the power of a vacuum suspension furnace is set to be 100KW, and the smelting is carried out for 5min; continuously increasing the power of the vacuum suspension furnace to 150KW, and smelting for 5min; raising the power of the vacuum suspension furnace to 200KW again, and smelting for 5min; after a molten pool is formed, reducing the power of a vacuum suspension furnace to 150KW, fully smelting for 15min, cooling the vacuum suspension furnace to obtain a blank shape memory high-entropy alloy, repeating the smelting steps for ten times, taking out the blank shape memory high-entropy alloy, vertically overturning the blank shape memory high-entropy alloy, taking out the blank shape memory high-entropy alloy when the blank shape memory high-entropy alloy is cooled to a temperature of 100-150 ℃ during tenth smelting, and casting the blank shape memory high-entropy alloy into bars.
6. A method for preparing the shape memory high-entropy alloy powder for additive manufacturing as claimed in claim 3, wherein: in the step 3, after the processed bar is installed on the continuous feeder, firstly pumping the air pressure of an atomizing chamber of the plasma rotary electrode atomizing device to 15 Pa-50 Pa by using a mechanical pump, and then starting a molecular pump to pump the air pressure of the atomizing chamber of the plasma rotary electrode atomizing device to 1.0x10 -2 And (3) filling argon with the purity of 99.99% into the atomizing chamber as a shielding gas under Pa, so that the air pressure of the atomizing chamber reaches 0.04-0.08 MPa.
7. The method for preparing the shape memory high-entropy alloy powder for additive manufacturing according to claim 4, wherein the method comprises the following steps: in the step 4, the particle size of the shape memory high-entropy alloy powder is divided and collected according to the ranges of 15-53 mu m, 50-150 mu m, 150-250 mu m and more than 250 mu m.
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| EP3747573A1 (en) * | 2019-06-07 | 2020-12-09 | Commissariat à l'Energie Atomique et aux Energies Alternatives | Method for additive manufacturing of a part made of a cca nitride alloy |
| US20230033494A1 (en) * | 2019-12-16 | 2023-02-02 | The Regents Of The University Of California | Deposition of aluminum 5xxx alloy using laser engineered net shaping |
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