CN110592411A - Alloy member and method for producing same - Google Patents
Alloy member and method for producing same Download PDFInfo
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- CN110592411A CN110592411A CN201910944928.8A CN201910944928A CN110592411A CN 110592411 A CN110592411 A CN 110592411A CN 201910944928 A CN201910944928 A CN 201910944928A CN 110592411 A CN110592411 A CN 110592411A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 58
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 82
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 82
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- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 12
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 8
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 6
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- 229910052787 antimony Inorganic materials 0.000 claims abstract description 4
- 229910052796 boron Inorganic materials 0.000 claims abstract description 4
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- 229910052733 gallium Inorganic materials 0.000 claims abstract description 4
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- 229910052712 strontium Inorganic materials 0.000 claims abstract description 4
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- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 9
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- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 9
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
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- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 3
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- 150000001340 alkali metals Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/20—Direct sintering or melting
- B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/34—Process control of powder characteristics, e.g. density, oxidation or flowability
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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
- B33Y10/00—Processes of additive manufacturing
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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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- 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
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/32—Process control of the atmosphere, e.g. composition or pressure in a building chamber
- B22F10/322—Process control of the atmosphere, e.g. composition or pressure in a building chamber of the gas flow, e.g. rate or direction
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/36—Process control of energy beam parameters
- B22F10/362—Process control of energy beam parameters for preheating
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/37—Process control of powder bed aspects, e.g. density
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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
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/30—Process control
- B22F10/38—Process control to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The invention provides an alloy component and a preparation method thereofThe alloy member takes high-entropy alloy as a matrix and carbon nano tubes and rare earth nano particles as reinforcements, wherein the atomic percentage expression of the high-entropy alloy is LxMyNz(Fe2/3Nb1/ 6Ta1/6)100‑x‑y‑zWherein L contains at least one selected from among B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb and Bi, M contains at least one selected from among Cu, Co, Cr, Ni, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, N contains at least one selected from among Er, Y, Sc, Nd, Dy, Tm and Gd, and 0. ltoreq. x<100，0≤y＜45，0≤z＜10，0≤x+y+z<100. According to the present invention, it is possible to provide an alloy member in which crystal grains are refined, the material composition distribution is made more uniform, the grain boundary performance is improved, and the grain boundary corrosion resistance is improved, and a method for producing the same.
Description
Technical Field
The invention relates to the technical field of alloys, in particular to an alloy component and a preparation method thereof.
Background
Compared with the traditional alloy system taking one or two metal elements as a matrix, the high-entropy alloy containing a plurality of metal or nonmetal elements belongs to a brand-new alloy system. Due to the high-entropy effect on thermodynamics, the delayed diffusion effect on kinetics, the lattice distortion effect on a microstructure, the 'cocktail' effect on material characteristics and the like, the high-entropy alloy shows high toughness which is difficult to compare with the traditional alloy and excellent performances such as wear resistance, corrosion resistance, high temperature oxidation resistance and the like, and has the potential to become a preferred material for preparing relevant core components in the fields of aerospace, nuclear energy, ocean engineering and the like.
However, in the prior art, the alloy member is prepared by simply adopting the high-entropy alloy as a raw material, and a plurality of problems still exist, such as: the problems that the alloy elements are difficult to be uniformly mixed, the composition segregation problem deteriorates the toughness and the corrosion resistance of the alloy member, the coarseness of a grain structure causes the alloy member to be easy to generate looseness, shrinkage cavities, crack defects and the like, and the advantages of the high-entropy alloy material in the aspect of mechanical properties are difficult to express.
Disclosure of Invention
The present invention has been made in view of the above-described conventional circumstances, and an object thereof is to provide an alloy member and a method for producing the same, which can refine crystal grains, make the distribution of material components more uniform, and improve grain boundary performance and grain boundary corrosion resistance.
To this end, the invention provides an alloy component, which takes a high-entropy alloy as a matrix and takes carbon nanotubes and rare earth nanoparticles as reinforcements, wherein the atomic percentage expression of the high-entropy alloy is LxMyNz(Fe2/3Nb1/6Ta1/6)100-x-y-zWherein L contains at least one selected from among B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb and Bi, M contains at least one selected from among Cu, Co, Cr, Ni, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, N contains at least one selected from among Er, Y, Sc, Nd, Dy, Tm and Gd, and 0. ltoreq. x<100，0≤y＜45，0≤z＜10，0≤x+y+z<100。
In one aspect of the invention, by adding the carbon nanotubes and the rare earth nanoparticles as the reinforcement in the high-entropy alloy matrix, on one hand, the refining effect of the rare earth nanoparticles on crystal grains, the improvement of the performance of the carbon nanotubes on the crystal grain boundaries, the improvement of the corrosion resistance of the crystal grain boundaries and the blocking effect of dislocation migration through the crystal grain boundaries can be fully exerted, and on the other hand, the rare earth nanoparticles can promote the carbon nanotubes to be distributed in the crystal grains instead of being distributed on the crystal grain boundaries, so that the carbon nanotubes distributed in the crystal grains can further block the dislocation migration in the crystal grains, thereby being beneficial to improving the yield strength of the prepared alloy component, improving the high-temperature creep property of the alloy component and enabling the components to be more uniform; in addition, the carbon nanotubes in the crystal grains can also block the formation and growth of coarse columnar crystals and have certain auxiliary effect on refined crystal grains.
In addition, in the alloy member provided by the present invention, optionally, the purity of each element powder in the high-entropy alloy is 99.9% or more. Preferably, the particle size of each element powder in the high-entropy alloy is 45-105 μm. Therefore, the purity and the grain diameter of the high-entropy alloy matrix can be ensured to be within a certain range, and the mechanical property and the like of the prepared alloy member are improved.
In addition, in the alloy member provided by the invention, optionally, the mass of the high-entropy alloy is 100 parts, the mass of the carbon nanotube is 0.01-0.10 part, and the mass of the rare earth nanoparticle is 0.05-0.50 part by mass. Wherein the morphology of the high-entropy alloy is not particularly limited. In some examples, the high entropy alloy is a high entropy alloy feedstock, i.e., the mass of the high entropy alloy feedstock is 100 parts. In other examples, the high entropy alloy is a pre-alloyed high entropy alloy, i.e., the pre-alloyed high entropy alloy is 100 parts by mass. Therefore, the adding quality of the reinforcing body of the carbon nano tube and the rare earth nano particle is limited within a certain range, so that the reinforcing promotion effect of the reinforcing body on the high-entropy alloy can be realized, the mechanical property and the like of the alloy member can be improved, and the adverse effect of excessive amount of the reinforcing body on the characteristics of the high-entropy alloy can be prevented or reduced.
Additionally, in the alloy member provided by the present invention, optionally, the rare earth nanoparticles are rare earth oxide nanoparticles comprising a material selected from CeO2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3At least one of nanoparticles. Preferably, the rare earth nanoparticles are equal CeO in mass2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3A combination of nanoparticles. Therefore, the rare earth oxide nano material generally has the excellent characteristics of small size effect, high specific surface effect, quantum effect, special optical property and the like, and the rare earth oxide nano particles are used as one of the reinforcements, so that the enhancement and promotion effects on the high-entropy alloy can be more effectively realized, the performance of the prepared alloy member is more effectively improved, and the like.
In addition, in the alloy structural member provided by the present invention, optionally, the carbon nanotube is a graphitized multilayered carbon nanotube. Preferably, the carbon nanotube is a graphitized multi-layer carbon nanotube with a purity of 99% or more. The carbon nano tube can effectively improve the microstructure of the carbon nano tube after graphitization treatment, thereby improving the mechanical property, the electrical property and the like of the carbon nano tube, and therefore, the graphitization multi-layer carbon nano tube, especially the graphitization multi-layer carbon nano tube with the purity of more than 99 percent, is adopted as one of the reinforcements, and can more effectively play a role in enhancing and promoting the high-entropy alloy, thereby more effectively improving the properties and the like of the prepared alloy member.
In addition, in the alloy structural member provided by the present invention, optionally, the diameter of the carbon nanotube is 10nm to 50nm, and the particle size of the rare earth nanoparticle is 50nm to 150 nm. Therefore, the diameter or the grain diameter of the reinforcement is controlled within a certain range, so that the reinforcement and the high-entropy alloy material can be mixed more fully, and the compatibility and the like of the reinforcement and the high-entropy alloy material can be enhanced.
In the alloy member provided by the present invention, the alloy member may have a yield strength of 863MPa or more, a tensile strength of 965MPa or more, and an elongation at break of 10.1% or more. Therefore, the mechanical property of the alloy member can be ensured, and the practicability of the alloy member is improved so as to meet the requirements on the mechanical property when the alloy member is used in special fields such as aerospace, nuclear energy and ocean engineering.
Another aspect of the present invention provides a method of preparing an alloy structural member, including: a pre-alloying process, namely pre-alloying the high-entropy alloy raw material to obtain a pre-alloyed high-entropy alloy; a mixing procedure, namely mixing the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy to form a suspension, and dehydrating and deoxidizing to form composite powder; and the additive manufacturing process comprises the steps of locally heating and melting the composite powder by using laser, and depositing and solidifying layer by layer to obtain the alloy component.
In another aspect of the present invention, the composite powder formed by the carbon nanotubes, the rare earth nanoparticles and the high-entropy alloy is heated and melted by laser and deposited layer by layer to form the alloy member in combination with an additive manufacturing process (e.g., 3D printing), the cost of the alloy member prepared by the process is low because the additive manufacturing process is not limited by the die manufacturing and the subsequent machining amount is small, and the alloy member prepared by the method of the present invention can fully exert the reinforcing effect of the carbon nanotubes and the rare earth nanoparticles on the high-entropy alloy and can rapidly form the alloy member with a complex structure, such as a large-sized and complex-structured structural member.
In addition, in the preparation method of the alloy member provided by the present invention, optionally, before the additive manufacturing process, the method further includes: a modeling procedure, namely establishing a part model, generating a machining program and inputting the machining program into control software; a calculation step of expressing the atomic percent L of the high-entropy alloyxMyNz(Fe2/3Nb1/6Ta1/6)100-x-y-zSelecting elements in the range of L, M, N, determining corresponding atomic percentages x, y and z, and converting the atomic percentages into mass ratios corresponding to the elements; and a weighing process, wherein the high-entropy alloy raw material is composed of the powder of each element. Therefore, the structural and performance characteristics and the like of the alloy component needing to be formed can be designed according to actual requirements, and the alloy component meeting the requirements is prepared through a subsequent preparation process, so that the precision of the prepared alloy component is improved, and the practicability and stability of the alloy component are improved.
In addition, in the method for manufacturing an alloy structural member according to the present invention, optionally, in the prealloying step, the prealloying treatment is mechanical alloying by using a ball mill, and the mechanical alloying time is 4 to 7 hours. Therefore, the high-entropy alloy raw materials can be fully mixed to form pre-alloyed high-entropy alloy powder, an oxidation layer formed on the surface of the high-entropy alloy raw materials can be effectively removed, the oxidation layer is prevented from damaging the performance of the material, and the prepared alloy component is further ensured to have excellent mechanical properties and the like.
In addition, in the method for manufacturing an alloy structural member according to the present invention, optionally, the mixing step includes: a suspension preparation step, namely placing the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy into a magnetic stirrer, and adding deionized water to stir to prepare a suspension; a dehydration and deoxidation step, wherein the rotation speed of the magnetic stirrer is controlled to be 100r/min to 120r/min, and the suspension is continuously heated and stirred for 5 hours to 8 hours at the temperature of 80 ℃ to 100 ℃ so as to be dehydrated and deoxidized into mixed powder; and a drying step, namely taking out the mixed powder, and placing the mixed powder in a vacuum drying oven at 100-120 ℃ to be heated and dried for 5-8 hours to obtain the composite powder. Therefore, the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy can be fully mixed through the preparation of the suspension, the moisture, the oxygen and the like in the pre-alloyed high-entropy alloy are further effectively removed, the purity of the composite powder is improved, the carbon nano tube and the rare earth nano particles are simultaneously mixed with the high-entropy alloy material to prepare the suspension, the physical properties of the high-entropy alloy, the carbon nano tube and the rare earth nano particles can be effectively protected from being damaged, and the mechanical properties of the alloy component prepared by the suspension can be effectively improved.
In addition, in the preparation method of the alloy member provided by the present invention, optionally, the additive manufacturing process includes: an initial deposition step, wherein the composite powder is locally heated and melted by the laser, and an initial layer is formed by deposition and solidification in the range of laser power of 3000W to 3500W; and a stable deposition process, wherein the laser continuously heats and melts the composite powder locally, the laser power is gradually reduced layer by layer in a mode of 0.5W/layer to 10W/layer, and the alloy component is formed by layer-by-layer deposition and solidification. Therefore, an initial layer of the alloy component is formed under the action of larger laser power, and then the laser power is properly reduced in a layer-by-layer decreasing mode to deposit other layers, so that on the premise of ensuring that powder is melted and effectively deposited, material defects caused by overheating of deposited materials and the like can be effectively avoided, and the mechanical properties and the like of the prepared alloy component are improved.
Furthermore, in the method for manufacturing an alloy component provided by the present invention, optionally, in the additive manufacturing process, the laser is generated by a processing platform, and other optimized parameters of the processing platform include: the scanning speed is 400 mm/min-800 mm/min, the diameter of a light spot is 3.0 mm-6.0 mm, the defocusing amount is 10 mm-35 mm, the powder feeding speed is 0.5 g/min-5.0 g/min, the single-layer thickness is 1.0 mm-2.0 mm, the overlapping rate is 10% -50%, the protective gas is argon with the purity of more than 99.9%, the flow of the protective gas is 5L/min-20L/min, and the cooling time along with a warehouse is 2 hours-4 hours. Therefore, the working stability of the processing platform can be ensured, and the additive manufacturing efficiency is improved.
In addition, in the preparation method of the alloy member provided by the present invention, optionally, before the additive manufacturing process, the method further includes: and a substrate pretreatment step of removing an oxide layer and stains on the substrate by polishing and scrubbing, and carrying out a preheating treatment on the substrate, wherein the preheating temperature is 150 ℃ to 200 ℃, and the preheating time is 1 hour to 2 hours. Therefore, the substrate can be sufficiently cleaned and sufficiently preheated, when the melted powder is deposited on the substrate, the material defect caused by overlarge temperature difference and the like can be effectively avoided, and the mechanical property of the prepared alloy component is improved.
Further, in the preparation method of the alloy member provided by the present invention, optionally, after the additive manufacturing process, the method further includes: and a detection step of performing nondestructive detection on the surface and internal crack defects of the alloy member. Preferably, the nondestructive inspection includes at least one of magnetic particle inspection and ultrasonic inspection. Therefore, the quality of the prepared alloy component can be further determined, so that the alloy component can meet the qualified standard, and the alloy component can be conveniently mounted and used.
According to the present invention, it is possible to provide an alloy member in which crystal grains are refined, the material composition distribution is made more uniform, the grain boundary performance is improved, and the grain boundary corrosion resistance is improved, and a method for producing the same.
Drawings
The accompanying drawings, which form a part of the present invention, are provided to further explain the present invention, and the drawings are schematic drawings, and the ratio of the dimensions of the components to each other, the shapes of the components, and the like may be different from the actual ones. In the drawings:
FIG. 1 is a schematic flow diagram of a method of making an alloy component according to an embodiment of the invention;
FIG. 2 is another schematic flow diagram of a method of making an alloy component according to an embodiment of the invention;
FIG. 3 is a schematic flow chart illustrating a mixing step in a method for producing an alloy structural member according to an embodiment of the present invention;
fig. 4 is a schematic flow chart illustrating an additive manufacturing process in the method for manufacturing an alloy structural member according to the embodiment of the present invention;
fig. 5(a) and (b) are Scanning Electron Microscope (SEM) photographs of alloy structural members according to example 1 and comparative example 1, respectively, in the embodiment of the present invention;
fig. 6 is a tensile engineering stress-strain graph of the alloy structural members of example 2 and comparative examples 2 to 4 according to the embodiment of the present invention.
Detailed Description
It should be noted that the embodiments and features of the embodiments of the present invention may be combined with each other without conflict, and the exemplary embodiments and descriptions thereof of the present invention are provided for explaining the present invention and do not constitute an unlimited part of the present invention.
The present invention will be described in detail below with reference to the accompanying drawings in conjunction with embodiments.
The alloy component according to the embodiment may use the high-entropy alloy as a matrix, and the carbon nanotubes and the rare earth nanoparticles as reinforcements, wherein the atomic percentage expression of the high-entropy alloy may be LxMyNz(Fe2/3Nb1/6Ta1/6)100-x-y-zWherein L may contain at least one selected from among non-metallic alkali metal groups, M may contain at least one selected from among transition metal groups, and N may contain at least one selected from among rare earth metal groups. In some examples, L may include at least one selected from among B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb, and Bi, M may include at least one selected from among Cu, Co, Cr, Ni, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf, and W, N may include at least one selected from among Er, Y, Sc, Nd, Dy, Tm, and Gd, and 0 ≦ x<100，0≤y＜45，0≤z＜10，0≤x+y+z<100。
In the embodiment, by adding the carbon nanotubes and the rare earth nanoparticles as the reinforcement in the high-entropy alloy matrix, on one hand, the refining effect of the rare earth nanoparticles on crystal grains, the improvement of the performance of the carbon nanotubes on the crystal grain boundaries, the improvement of the corrosion resistance of the crystal grain boundaries and the blocking effect of dislocation migration through the crystal grain boundaries can be fully exerted, and on the other hand, the rare earth nanoparticles can promote the carbon nanotubes to be distributed in the crystal grains instead of only being distributed on the crystal grain boundaries, so that the carbon nanotubes distributed in the crystal grains can further block the dislocation migration in the crystal grains, thereby being beneficial to improving the yield strength of the prepared alloy component, improving the high-temperature creep property of the alloy component and enabling the components of the alloy component to be more uniform; in addition, the carbon nanotubes in the crystal grains can also block the formation and growth of coarse columnar crystals and have certain auxiliary effect on refined crystal grains.
In addition, in the present embodiment, as described above, L, M and N can be selected from the alkali metal non-metal group, the transition metal group and the rare earth metal group in the periodic table, respectively, and therefore, the types of elements to be applied are wide, and the elements can be flexibly selected and matched according to the physicochemical characteristics, the market price and other characteristics of the different elements, so as to meet different application requirements.
In the present embodiment, the form of the element used in the high-entropy alloy matrix is not particularly limited. In some examples, the elements employed in the high entropy alloy may be in elemental powder form. In other examples, the elements used in the high-entropy alloy may be in the form of powder of other compounds such as oxides. Therefore, different raw material forms can be set according to needs to meet different experimental requirements.
In the present embodiment, the purity and particle size of each element powder in the high-entropy alloy are not particularly limited. In some examples, the purity of each elemental powder in the high entropy alloy may be 99.9% or more. In other examples, the particle size of each elemental powder in the high entropy alloy may be 45 μm to 105 μm. Therefore, the purity and the grain diameter of the high-entropy alloy matrix can be ensured to be within a certain range, and the mechanical property and the like of the prepared alloy member are improved.
Further, in the present embodiment, the atomic percent expression of the high-entropy alloy may be LxMyNz(Fe2/3Nb1/ 6Ta1/6)100-x-y-zWherein, in the step (A),x + y + z ≠ 100, i.e., 100-x-y-z ≠ 0. In this case, when the high-entropy alloy is used as a matrix, the prepared alloy member at least contains three elements of Fe, Nb and Ta, and the three elements can simultaneously meet the requirements on high strength and low density of the alloy member according to the combination of a certain proportion, so that the prepared alloy member has more excellent performance and the like.
Further, in the present embodiment, the expression L is expressed in atomic percent of the high-entropy alloyxMyNz(Fe2/3Nb1/ 6Ta1/6)100-x-y-zIn the specification, L, M, N elements are selected, and x, y and z values can be calculated by thermodynamic software according to the specific requirements on the comprehensive performance of the alloy component. Therefore, the design of the atomic percentage expression of the high-entropy alloy can be realized more conveniently, and the requirement on the comprehensive performance of the alloy component can be met more accurately.
In the present embodiment, the mass of the high-entropy alloy is 100 parts, the mass of the carbon nanotube is 0.005 to 0.150 parts, and the mass of the rare earth nanoparticle is 0.005 to 0.550 parts by mass. In some examples, the mass of the high-entropy alloy is 100 parts, the mass of the carbon nanotubes is 0.01 to 0.10 parts, and the mass of the rare earth nanoparticles is 0.05 to 0.50 parts, in parts by mass. Therefore, the adding quality of the reinforcing body of the carbon nano tube and the rare earth nano particle is limited within a certain range, so that the reinforcing promotion effect of the reinforcing body on the high-entropy alloy can be realized, the mechanical property and the like of the alloy member can be improved, and the adverse effect of excessive amount of the reinforcing body on the characteristics of the high-entropy alloy can be prevented or reduced.
In the present embodiment, the form of the high-entropy alloy is not particularly limited in the mass ratio described above. In some examples, the high entropy alloy is a high entropy alloy feedstock, i.e., the mass of the high entropy alloy feedstock is 100 parts. In other examples, the high entropy alloy is a pre-alloyed high entropy alloy, i.e., the pre-alloyed high entropy alloy is 100 parts by mass. Therefore, the reinforcement and the matrix with different proportions can be designed according to actual requirements so as to meet different performance requirements and the like; in addition, when the mass of the pre-alloyed high-entropy alloy is taken as a reference (100 parts), the pre-alloyed high-entropy alloy is a substance which removes interference factors such as an oxide layer on the surface of a high-entropy alloy raw material, so that when the pre-alloyed high-entropy alloy is taken as the mass reference, the proportion of the reinforcement and the matrix can be more accurate, and the requirements on the performance of the alloy component can be more effectively met.
In the present embodiment, the yield strength of the alloy member may be 850MPa or more, for example, 863MPa or more. In some examples, the tensile strength may be 900MPa or greater, such as 965MPa or greater, and the like. In other examples, the alloy member may have an elongation at break of 10% or more, such as 10.1% or more. Therefore, the mechanical property of the alloy member can be ensured, and the practicability of the alloy member is improved so as to meet the requirements on the mechanical property when the alloy member is used in special fields such as aerospace, nuclear energy and ocean engineering.
In the present embodiment, the form of the rare earth nanoparticles is not particularly limited. In some examples, the rare earth nanoparticles may be elemental rare earth nanoparticles, or rare earth compound nanoparticles, such as rare earth oxide nanoparticles. In other examples, the rare earth oxide nanoparticles may include a material selected from CeO2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3At least one of the nanoparticles, for example the rare earth nanoparticles, may be of equal mass CeO2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3A combination of nanoparticles. Of course, the rare earth oxide nanoparticles may also be oxide nanoparticles of other elements corresponding to the rare earth group. The rare earth nanoparticles have a good promoting effect on grain refinement, and the rare earth nanoparticles in different forms are used as one of the reinforcements, so that different forms can be selected according to requirements to meet different experimental requirements and the like. Among them, since the rare earth oxide nano material generally has excellent characteristics of small size effect, high specific surface effect, quantum effect, special optical property and the like, the rare earth oxide nano particles can be used as one of the reinforcementsThe enhancement and promotion effect on the high-entropy alloy is more effectively realized, so that the performance of the prepared alloy component is more effectively improved, and the like.
In the present embodiment, the particle size of the rare earth nanoparticles is not particularly limited. In some examples, the rare earth nanoparticles may have a particle size of 20nm to 200nm, such as 30nm, 40nm, 160nm, 180nm, and the like. In other examples, the rare earth nanoparticles may have a particle size of 50nm to 150nm, such as 60nm, 80nm, 100nm, 120nm, and the like. Therefore, the particle size of the reinforcement is controlled within a certain range, so that the reinforcement and the high-entropy alloy matrix can be mixed more fully, and the compatibility and the like of the reinforcement and the high-entropy alloy matrix can be enhanced.
In the present embodiment, the size and structural features of the carbon nanotubes are not particularly limited. In some examples, the carbon nanotubes may be graphitized multilayered carbon nanotubes. In other examples, the carbon nanotubes may be graphitized multi-layered carbon nanotubes having a purity of 99% or more. The carbon nano tube can effectively improve the microstructure of the carbon nano tube after graphitization treatment, thereby improving the mechanical property, the electrical property and other properties of the carbon nano tube, therefore, the graphitization multi-layer carbon nano tube, especially the graphitization multi-layer carbon nano tube with the purity of more than 99 percent is adopted as one of the reinforcements, which can more effectively play a role in enhancing and promoting the high-entropy alloy, thereby more effectively improving the properties of the prepared alloy member and the like.
In the present embodiment, the diameter of the carbon nanotube is not particularly limited. In some examples, the carbon nanotubes may have a diameter of 0nm to 100nm, such as 5nm, 60nm, 75nm, 85nm, and the like. In other examples, the carbon nanotubes may also have a diameter of 10nm to 50nm, such as 20nm, 30nm, 45nm, and the like. Therefore, the diameter of the reinforcement is controlled within a certain range, so that the reinforcement and the high-entropy alloy matrix can be mixed more fully, and the compatibility and the like of the reinforcement and the high-entropy alloy matrix can be enhanced.
Fig. 1 is a schematic flow chart of a method for producing an alloy member according to an embodiment of the present invention, fig. 2 is another schematic flow chart of a method for producing an alloy member according to an embodiment of the present invention, fig. 3 is a schematic flow chart of a mixing step in a method for producing an alloy member according to an embodiment of the present invention, and fig. 4 is a schematic flow chart of an additive manufacturing step in a method for producing an alloy member according to an embodiment of the present invention.
At present, the preparation of the alloy member is mainly realized by traditional methods such as smelting and casting, casting and plastic processing, powder metallurgy and the like, but the alloy member prepared by the method still has a plurality of problems which cannot be solved, for example, various element components are difficult to be uniformly mixed, and the problem of component segregation deteriorates the obdurability and corrosion resistance of the alloy member; the grain structure formed by casting is large, and the defects of shrinkage porosity, shrinkage cavity, cracks and the like are easily generated, so that the advantages of the high-entropy alloy in the aspect of mechanical property are difficult to express; limited by the existing casting equipment, only the preparation of parts with simple geometric shapes and small sizes can be realized; in addition, the high-entropy alloy usually contains a plurality of expensive elements, and if the material is reduced by adopting the traditional processing methods such as turning, milling, planing, grinding and the like, the material is greatly wasted, the cost is greatly increased, and the deep application and the future development of the high-entropy alloy are difficult to meet.
Therefore, in recent years, a Laser Melting Deposition (LMD) technology which is a high-efficiency high-precision additive manufacturing technology using high-energy Laser as a heat source is provided, the LMD technology utilizes a rapid prototyping manufacturing technology, any shape is rapidly molded under the condition of no need of any mould and tool as a basic principle, discrete slice data of an alloy component entity model is directly prepared and molded into an alloy component with excellent performance through Laser Melting-rapid solidification layer-by-layer Deposition of materials under the drive of a computer numerical control system, and therefore the problems existing in the preparation of the alloy component by the traditional method can be effectively avoided.
In the prior art, some technical documents disclose an in-situ preparation method and a product for laser additive manufacturing of a high-entropy alloy, which can realize the preparation of a FeCoCrNiTi high-entropy alloy with the size of 20mm multiplied by 70mm multiplied by 5 mm; other technical documents disclose a method for preparing a tungsten particle reinforced metal matrix composite material based on a 3D printing technology, which can realize the preparation of tungsten particle reinforced AlCrFeNiV and AlCrFeNiVCu high-entropy alloy composite materials with the size of 20mm × 20mm × 100 mm; still other technical documents disclose a laser three-dimensional forming method of a high-entropy alloy component, which can realize the preparation of FeCoNiMnCr high-entropy alloy round tubes and blade components. However, the sizes of various alloy components prepared by the laser melting deposition technology in the prior art are small, for example, the maximum length is not more than 100mm, so that it is known that although the high-entropy alloy has excellent characteristics of high hardness, high toughness and the like, the formation of intergranular cracks is easily caused by serious stress concentration problems, which brings great difficulty to the preparation of alloy components with large sizes or complex structures by the laser melting deposition technology.
Therefore, in the present embodiment, a method for manufacturing an alloy member is provided, which can refine crystal grains, make material composition distribution more uniform, improve grain boundary performance, and improve grain boundary corrosion resistance, thereby facilitating the manufacture of an alloy member having a large size or a complicated structure.
Hereinafter, the method of producing the alloy structural member according to the present embodiment is described in detail with reference to fig. 1 to 4.
As shown in fig. 1, the method for producing an alloy structural member according to the present embodiment may include the steps of: a pre-alloying process, namely pre-alloying the high-entropy alloy raw material to obtain a pre-alloyed high-entropy alloy; a mixing procedure, namely mixing the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy to form a suspension, and dehydrating and deoxidizing to form composite powder; and the additive manufacturing process comprises the steps of locally heating and melting the composite powder by using laser, and depositing and solidifying layer by layer to obtain the alloy component.
In the embodiment, the composite powder formed by the carbon nano tube, the rare earth nano particles and the high-entropy alloy is heated and melted by laser and deposited layer by layer to form the alloy component by combining with the additive manufacturing process, and the additive manufacturing process is not limited by the manufacturing of a die and the subsequent machining amount is less, so the cost for preparing the alloy component by adopting the process is lower, and the alloy component prepared by the method can fully play the reinforcing effect of the carbon nano tube and the rare earth nano particles on the high-entropy alloy and can be used for quickly forming the alloy component with a complex structure, such as a large-size structural component with a complex structure and the like, and the alloy component with higher tensile strength, compressive load and corrosion performance can be obtained without post-heat treatment.
In addition, as shown in fig. 2, the present embodiment further includes, before the additive manufacturing step: a modeling procedure, namely establishing a part model, generating a machining program and inputting the machining program into control software; calculating procedure according to the atomic percentage expression L of the high-entropy alloyxMyNz(Fe2/3Nb1/6Ta1/6)100-x-y-zSelecting elements in the range of L, M, N, determining corresponding atomic percentages x, y and z, and converting the atomic percentages into mass ratios corresponding to the elements; and a weighing process, wherein the high-entropy alloy raw material is formed by weighing the element powder. Therefore, the structural and performance characteristics and the like of the alloy component needing to be formed can be designed according to actual requirements, and the alloy component meeting the requirements is prepared through a subsequent preparation process, so that the precision of the prepared alloy component is improved, and the practicability and stability of the alloy component are improved.
Further, in the present embodiment, in the modeling process, the tool for creating the part model may be CAD drawing software to create a spatial three-dimensional model of the alloy structural member. In some examples, the tool that generates the machining program may be CAM programming software to generate the most rational machining path program for each layer of the alloy component. In other examples, the control software may be LMD platform control software. Therefore, the accuracy of the alloy component model and the machining path thereof can be improved, and the quality of the prepared alloy component is improved.
In the present embodiment, in the calculation step, the calculation means for selecting elements in the range of L, M, N and determining the corresponding atomic percentages x, y, and z is not particularly limited. In some examples, the computational tool may be at least one of Pandat thermodynamic computing software and JMatPro thermodynamic computing software. Therefore, elements in the range of L, M, N and values of x, y and z can be calculated and selected more accurately and efficiently according to the requirements of thermodynamic performance and the like of the alloy component, and the overall preparation efficiency of the alloy component is improved.
In the present embodiment, the pre-alloying step is not particularly limited in the manner of pre-alloying treatment. In some examples, the pre-alloying treatment may be mechanical alloying using a ball mill, for example, a planetary high energy ball mill, and the time for mechanical alloying may be 4 hours to 7 hours, for example, 5 hours, 6 hours, or 6.5 hours, etc. In other examples, the pre-alloying treatment may be performed under an inert gas blanket, such as a high purity argon blanket, and the like. Therefore, the high-entropy alloy raw materials can be fully mixed to form pre-alloyed high-entropy alloy powder, an oxidation layer formed on the surface of the high-entropy alloy raw materials can be effectively removed, the oxidation layer is prevented from damaging the performance of the material, and the prepared alloy component is further ensured to have excellent mechanical properties and the like.
In the present embodiment, as shown in fig. 3, in the mixing step, the mixing step may include the steps of: a suspension preparation procedure, namely placing the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy into a magnetic stirrer, and adding deionized water to stir to prepare a suspension; a dehydration and deoxidation procedure, wherein the rotating speed of the magnetic stirrer is controlled to be 100r/min to 120r/min, and the suspension is continuously heated and stirred for 5 hours to 8 hours at the temperature of 80 ℃ to 100 ℃ so as to be dehydrated and deoxidized into mixed powder; and a drying step, namely taking out the mixed powder, and placing the mixed powder in a vacuum drying oven at 100-120 ℃ to heat and dry for 5-8 hours to obtain the composite powder. Therefore, the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy can be fully mixed through the preparation of the suspension, the moisture, the oxygen and the like in the pre-alloyed high-entropy alloy are further effectively removed, the purity of the composite powder is improved, the carbon nano tube and the rare earth nano particles are simultaneously mixed with the high-entropy alloy material to prepare the suspension, the physical properties of the high-entropy alloy, the carbon nano tube and the rare earth nano particles can be effectively protected from being damaged, and the mechanical properties of the alloy component prepared by the suspension can be effectively improved.
In addition, in the present embodiment, a specific process of the additive manufacturing process is not particularly limited. In some examples, the specific process of the additive manufacturing process may be a Laser Assisted Additive Manufacturing (LAAM) process. In other examples, the particular process of the additive manufacturing process may also be a laser melt deposition process, i.e., an LMD process. Therefore, different preparation processes can be selected according to actual requirements, so that different experimental requirements and the like are met, and the convenience and effectiveness of alloy member material preparation are improved; the LMD process is combined with the components for preparing the alloy component, so that the large-size and complex-structure alloy component can be manufactured, particularly, the intergranular cracks on the large-size structural component are effectively inhibited through grain refinement and grain boundary strengthening, the actual industrial application level is achieved, the material utilization rate is relatively high, and the research and development and manufacturing cost of the alloy component is more favorably reduced.
In this embodiment, as shown in fig. 4, the additive manufacturing process may include the steps of: an initial deposition process, wherein the composite powder is locally heated and melted by laser, and an initial layer is formed by deposition and solidification in the range of laser power of 3000W to 3500W; and (3) a stable deposition process, wherein the composite powder is continuously heated and melted by laser, the laser power is gradually reduced layer by layer in a mode of 0.5W/layer to 10W/layer, and the alloy component is formed by layer-by-layer deposition and solidification. Therefore, an initial layer of the alloy component is formed under the action of larger laser power, and then the laser power is properly reduced in a layer-by-layer decreasing mode to deposit other layers, so that on the premise of ensuring that powder is melted and effectively deposited, material defects caused by overheating of deposited materials and the like can be effectively avoided, and the mechanical properties and the like of the prepared alloy component are improved.
In addition, in the present embodiment, in the additive manufacturing process, the laser light is generated by a processing platform (for example, an LMD platform), and other optimized parameters of the processing platform include: the scanning speed is 400 mm/min-800 mm/min, the diameter of a light spot is 3.0 mm-6.0 mm, the defocusing amount is 10 mm-35 mm, the powder feeding speed is 0.5 g/min-5.0 g/min, the single-layer thickness is 1.0 mm-2.0 mm, the overlapping rate is 10% -50%, the protective gas is argon with the purity of more than 99.9%, the flow of the protective gas is 5L/min-20L/min, and the cooling time along with a warehouse is 2 hours-4 hours. Therefore, the working stability of the processing platform can be ensured, and the additive manufacturing efficiency is improved.
In addition, in the present embodiment, before the additive manufacturing process, the method further includes: and a substrate pretreatment step of removing an oxide layer and stains on the substrate by polishing and scrubbing, and carrying out a preheating treatment on the substrate, wherein the preheating temperature is 150 ℃ to 200 ℃, and the preheating time is 1 hour to 2 hours. Therefore, the substrate can be sufficiently cleaned and sufficiently preheated, when the melted powder is deposited on the substrate, the material defect caused by overlarge temperature difference and the like can be effectively avoided, and the mechanical property of the prepared alloy component is improved.
In addition, in the present embodiment, after the additive manufacturing process, the method further includes: and a detection step of performing nondestructive detection on the surface and internal crack defects of the alloy member, wherein the nondestructive detection mode is not particularly limited. In some examples, the means for non-destructive testing may include at least one of magnetic particle inspection and ultrasonic inspection. Therefore, the quality of the prepared alloy component can be further determined, so that the alloy component can meet the qualified standard, and the alloy component can be conveniently mounted and used.
In order to further illustrate the present invention, the following detailed description of the alloy structural member and the method for manufacturing the same according to the present invention will be given with reference to examples, and will fully explain the advantageous effects achieved by the present invention with reference to comparative examples.
Example 1
The manufacturing method is characterized in that the marine reducer gear with the maximum diameter of 1000mm is manufactured by laser melting deposition, and the process flow specifically comprises the following steps:
step 1: three-dimensional modeling is carried out on the marine reducer gear by using CAD software, on the basis, the laser scanning path of each layer is planned by using CAM software, and finally a processing path program of the whole part is formed and is input into LMD platform control software;
step 2: based on the calculation result of thermodynamic software, the atomic percent expression of the high-entropy alloy components is designed to be Al15Si5Fe40Nb10Ta10Cr10Hf5Er5Converting the atomic percentages of Al, Si, Fe, Nb, Ta, Cr, Hf and Er elements into mass ratios, weighing the powders, wherein the purity of the powders is required to reach 99.9%, and screening the powders by a sieve before weighing the raw material powders to control the particle size of the powders to be within the range of 45-105 μm;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Cr, Hf and Er element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4: accurately weighing the carbon nanotubes according to the mass of the pre-alloyed high-entropy alloy powder obtained in the step 3, wherein the mass ratio of the carbon nanotubes to the sum of the mass of the high-entropy alloy powder and the mass of the carbon nanotubes is 0.05 wt.%; the proportion of the rare earth nanoparticles to the sum of the mass of the high-entropy alloy powder and the mass of the rare earth nanoparticles is 0.15 wt.%, and CeO is accurately weighed2、Y2O3、La2O3、Sm2O3Rare earth oxide nanoparticles equal in mass to one another; putting the weighed carbon nano tube, rare earth oxide nano particles and high-entropy alloy powder into an ultrasonic magnetic stirrer together, pouring deionized water into the ultrasonic magnetic stirrer to form a suspension, wherein the rotating speed of the stirrer is 100r/min, the temperature of the suspension is 80 ℃, the stirring time is 5 hours, taking out the powder mixture from the stirrer, putting the powder mixture into a vacuum drying oven at 100 ℃ for 5 hours for further drying, dehydrating and deoxidizing, naturally cooling to room temperature, and storing in a dry and vacuum container for later use;
and 5: putting the mixed powder obtained in the step 4 into a powder feeding device powder cylinder of an LMD platform; removing an oxide layer and stains on the substrate by sanding and scrubbing with acetone, preheating the substrate to 200 ℃ for 1.5 hours; setting the laser power to 3000W, the scanning speed to 700mm/min, the spot diameter to 5.0mm, the defocusing amount to 15mm, the powder feeding rate to 4.0g/min, the single-layer thickness to 1.0mm, the lap-joint rate to 30%, the shielding gas to be argon with the purity of 99.9%, and the shielding gas flow to 20L/min, and carrying out laser meltingChemical deposition to obtain Al15Si5Fe40Nb10Ta10Cr10Hf5Er5A marine reducer gear is cooled for 4 hours along with a bin and then taken out;
step 6: the magnetic powder and ultrasonic flaw detection of the gear needs special attention to the detection of interlamination and stress concentration areas, and if the detection result reaches the factory qualified standard, the gear can be installed in a speed reducer for use.
Example 2
The laser melting deposition manufacturing method is used for manufacturing the rotating shaft of the aircraft landing gear with the length of 800mm, and the process flow specifically comprises the following steps:
step 1: three-dimensional modeling is carried out on the landing gear rotating shaft by utilizing CAD software, on the basis, the laser scanning path of each layer is planned by utilizing CAM software, a processing path program of the whole part is finally formed, and the program is input into LMD platform control software;
step 2: based on the calculation result of thermodynamic software, the atomic percent expression of the high-entropy alloy components is designed to be Al30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5Converting the atomic percentages of Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y elements into mass ratios, weighing the powders, wherein the purity of the powders is required to reach 99.9 percent, and controlling the particle size of the powders to be within the range of 45-105 mu m by screening through a sieve before weighing the raw material powders;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4: according to the mass of the pre-alloyed high-entropy alloy powder obtained in the step 3, the mass ratio of the carbon nano tubes to the sum of the mass of the high-entropy alloy powder and the mass of the carbon nano tubes is 0.07 wt%, and the carbon nano tubes are accurately weighed; the proportion of the rare earth nanoparticles to the sum of the mass of the high-entropy alloy powder and the mass of the rare earth nanoparticles is 0.3 wt.%, and the rare earth nanoparticles are accurately weighedCeO2、Y2O3、La2O3、Sm2O3Rare earth oxide nanoparticles equal in mass to one another; putting the weighed carbon nano tube, rare earth oxide nano particles and high-entropy alloy powder into an ultrasonic magnetic stirrer together, pouring deionized water into the ultrasonic magnetic stirrer to form a suspension, wherein the rotating speed of the stirrer is 100r/min, the temperature of the suspension is 80 ℃, the stirring time is 5 hours, the powder mixture taken out of the stirrer is put into a vacuum drying oven at 100 ℃ for 5 hours for further drying, dehydration and deoxidation, and then the powder mixture is naturally cooled to room temperature and stored in a dry and vacuum container for later use;
and 5: putting the mixed powder obtained in the step 4 into a powder feeding device powder cylinder of an LMD platform; removing an oxide layer and stains on the substrate by sanding and scrubbing with acetone, preheating the substrate to 150 ℃, wherein the preheating time is 1.5 hours; setting the laser power to 3200W, the scanning speed to 550mm/min, the spot diameter to 5.0mm, the defocusing amount to 15mm, the powder feeding rate to 3.0g/min, the single-layer thickness to 1.0mm, the lap joint rate to 30%, the shielding gas to be argon with the purity of 99.9%, and the shielding gas flow to 20L/min, and performing laser melting deposition to obtain Al30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5The rotating shaft of the aircraft landing gear is taken out after being cooled for 3 hours along with the cabin;
step 6: magnetic powder and ultrasonic flaw detection is carried out on the rotating shaft, special attention needs to be paid to detection of interlamination and stress concentration areas, and if the detection result reaches the factory qualified standard, the rotating shaft can be installed in a landing gear to be put into use.
Comparative example 1
Step 1: adopting the model and the processing program constructed in the embodiment 1, and inputting the program into LMD platform control software;
step 2: the expression Al of atomic percent of the high-entropy alloy composition of example 1 was used15Si5Fe40Nb10Ta10Cr10Hf5Er5Weighing Al, Si, Fe, Nb, Ta, Cr, Hf and Er powders with purity up to 99.9%, and sieving the powders before weighingThe sub-screening controls the powder particle size in the range of 45 μm to 105 μm;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Cr, Hf and Er element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4: putting prealloyed high-entropy alloy powder into a powder feeder powder cylinder of an LMD platform; removing an oxide layer and stains on the substrate by sanding and scrubbing with acetone, preheating the substrate to 200 ℃ for 1.5 hours; setting laser power to 3000W, scanning speed to 700mm/min, spot diameter to 5.0mm, defocusing amount to 15mm, powder feeding rate to 4.0g/min, single-layer thickness to 1.0mm, lap-joint rate to 30%, protective gas to be argon with purity of 99.9%, protective gas flow to 20L/min, and carrying out laser melting deposition to obtain Al15Si5Fe40Nb10Ta10Cr10Hf5Er5The gear of the marine speed reducer is taken out after being cooled for 4 hours along with the bin.
Comparative example 2
Step 1: adopting the model and the processing program constructed in the embodiment 2, and inputting the program into LMD platform control software;
step 2: the expression Al of atomic percent of the high-entropy alloy composition of example 2 was used30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5Converting the atomic percentages of Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y elements into mass ratios, weighing the powders, wherein the purity of the powders is required to reach 99.9 percent, and controlling the particle size of the powders to be within the range of 45-105 mu m by screening through a sieve before weighing the raw material powders;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4:putting prealloyed high-entropy alloy powder into a powder feeder powder cylinder of an LMD platform; removing an oxide layer and stains on the substrate by sanding and scrubbing with acetone, preheating the substrate to 150 ℃, wherein the preheating time is 1.5 hours; setting the laser power to 3200W, the scanning speed to 550mm/min, the spot diameter to 5.0mm, the defocusing amount to 15mm, the powder feeding rate to 3.0g/min, the single-layer thickness to 1.0mm, the lap joint rate to 30%, the shielding gas to be argon with the purity of 99.9%, and the shielding gas flow to 20L/min, and performing laser melting deposition to obtain Al30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5And the rotating shaft of the aircraft landing gear is taken out after being cooled for 3 hours along with the cabin.
Comparative example 3
Step 1: adopting the model and the processing program constructed in the embodiment 2, and inputting the program into LMD platform control software;
step 2: the expression Al of atomic percent of the high-entropy alloy composition of example 2 was used30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5Converting the atomic percentages of Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y elements into mass ratios, weighing the powders, wherein the purity of the powders is required to reach 99.9 percent, and controlling the particle size of the powders to be within the range of 45-105 mu m by screening through a sieve before weighing the raw material powders;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4: according to the mass of the pre-alloyed high-entropy alloy powder obtained in the step 3, the mass ratio of the carbon nano tubes to the sum of the mass of the high-entropy alloy powder and the mass of the carbon nano tubes is 0.07 wt%, and the carbon nano tubes are accurately weighed; putting the weighed carbon nano tube and the high-entropy alloy powder into an ultrasonic magnetic stirrer together, pouring deionized water into the ultrasonic magnetic stirrer to form a suspension, wherein the rotating speed of the stirrer is 100r/min, the temperature of the suspension is 80 ℃, the stirring time is 5 hours, the powder mixture taken out of the stirrer is put into a vacuum drying oven at 100 ℃ for 5 hours for further drying, dehydration and deoxidation, and then, the powder mixture is naturally cooled to room temperature and is stored in a dry and vacuum container for later use;
and 5: putting the mixed powder obtained in the step 4 into a powder feeder powder cylinder of an LMD platform, removing an oxide layer and stains on a substrate by sanding and scrubbing with acetone, preheating the substrate to 150 ℃, wherein the preheating time is 1.5 hours, the laser power is 3200W, the scanning speed is 550mm/min, the spot diameter is 5.0mm, the defocusing amount is 15mm, the powder feeding speed is 3.0g/min, the single-layer thickness is 1.0mm, the lap joint rate is 30%, the shielding gas is argon with the purity of 99.9%, the shielding gas flow is 20L/min, and carrying out laser melting deposition to obtain Al30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5And the rotating shaft of the aircraft landing gear is taken out after being cooled for 3 hours along with the cabin.
Comparative example 4
Step 1: adopting the model and the processing program constructed in the embodiment 2, and inputting the program into LMD platform control software;
step 2: the expression Al of atomic percent of the high-entropy alloy composition of example 2 was used30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5Converting the atomic percentages of Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y elements into mass ratios, weighing the powders, wherein the purity of the powders is required to reach 99.9 percent, and controlling the particle size of the powders to be within the range of 45-105 mu m by screening through a sieve before weighing the raw material powders;
and step 3: putting the weighed Al, Si, Fe, Nb, Ta, Ti, Zr, Mo and Y element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 6 hours under the protection of high-purity argon gas to remove an oxide layer on the surface of the powder and uniformly mix the powder so as to obtain pre-alloyed high-entropy alloy powder;
and 4, step 4: and (3) according to the mass of the pre-alloyed high-entropy alloy powder obtained in the step (3), enabling the proportion of the rare earth nanoparticles to the sum of the mass of the high-entropy alloy powder and the mass of the rare earth nanoparticles to be 0.3wt.% to obtain CeO2、Y2O3、La2O3、Sm2O3The preparation method comprises the following steps of (1) putting the weighed rare earth oxide nanoparticles and high-entropy alloy powder into an ultrasonic magnetic stirrer together, pouring deionized water into the ultrasonic magnetic stirrer to form suspension, wherein the rotating speed of the stirrer is 100r/min, the temperature of the suspension is 80 ℃, the stirring time is 5 hours, putting a powder mixture taken out of the stirrer into a vacuum drying oven at 100 ℃ for 5 hours for further drying, dehydrating and deoxidizing, naturally cooling to room temperature, and storing in a dry and vacuum container for later use;
and 5: putting the mixed powder obtained in the step 4 into a powder feeder powder cylinder of an LMD platform, removing an oxide layer and stains on a substrate by sanding and scrubbing with acetone, preheating the substrate to 150 ℃, wherein the preheating time is 1.5 hours, the laser power is 3200W, the scanning speed is 550mm/min, the spot diameter is 5.0mm, the defocusing amount is 15mm, the powder feeding speed is 3.0g/min, the single-layer thickness is 1.0mm, the lap joint rate is 30%, the shielding gas is argon with the purity of 99.9%, the shielding gas flow is 20L/min, and carrying out laser melting deposition to obtain Al30Si10Fe20Nb5Ta5Ti10Zr10Mo5Y5And the rotating shaft of the aircraft landing gear is taken out after being cooled for 3 hours along with the cabin.
Scanning Electron Microscope (SEM) observations were made on the gear samples prepared in example 1 and comparative example 1, and their corresponding SEM photographs are shown in fig. 5(a) and (b); the mechanical property test was performed on the rotating shaft samples prepared in example 2 and comparative examples 2 to 4, and the specific engineering stress-strain curves are shown in fig. 6, and the relevant test results are shown in table 1, wherein the yield strength is the yield limit of the material when the yield phenomenon occurs, but the stress value of 0.2% of residual deformation (0.2 σ) is taken as the yield limit, i.e., the yield strength, because the materials prepared in the corresponding examples and comparative examples in this embodiment do not yield significantly; the tensile strength is the maximum bearing capacity of the material under a static stretching condition; the elongation at break is the ratio of the displacement value of the material at the time of stretch breaking to the original length.
TABLE 1
As can be seen from a comparison of fig. 5(a) and (b), the gear sample prepared in example 1 (see fig. 5(a)) has a grain size finer than that in comparative example 1 (see fig. 5(b)) and is substantially free from the formation of coarse columnar crystals and the like, because carbon nanotubes and rare earth nanoparticles are added as reinforcing materials.
As can be seen from fig. 6 and the results in table 1, the rotating shaft sample prepared in example 2 has better mechanical properties than comparative example 2 (no reinforcement added), comparative example 3 (reinforcement added with only carbon nanotube) and comparative example 4 (reinforcement added with only rare earth nanoparticle) because the yield strength can reach 863MPa, the tensile strength can reach 965MPa, and the elongation at break can reach 10.1% due to the simultaneous addition of carbon nanotube and rare earth nanoparticle as the reinforcement.
Therefore, the carbon nano tubes and the rare earth nano particles are added into the high-entropy alloy matrix, so that the refining effect of the rare earth nano particles on crystal grains can be fully exerted, the performance of the carbon nano tubes on crystal boundaries is improved, the corrosion resistance of the crystal boundaries is improved, and the effect of hindering dislocation from migrating through the crystal boundaries is achieved; on the other hand, the rare earth nanoparticles can promote the carbon nanotubes to be distributed in the crystal grains instead of being distributed on the crystal boundary, so that the carbon nanotubes distributed in the crystal grains can further hinder the dislocation from migrating in the crystal grains, thereby being beneficial to improving the yield strength of the prepared alloy component, improving the high-temperature creep property of the alloy component and enabling the components of the alloy component to be more uniform; in addition, the carbon nanotubes in the crystal grains can also hinder the formation and growth of coarse columnar crystals and have certain auxiliary action on refined crystal grains, so that the mechanical property of the prepared alloy member can be fully enhanced.
Although the present invention has been disclosed above, the scope of the present invention is not limited thereto. Various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention, and these changes and modifications are intended to be within the scope of the invention.
Claims (10)
1. An alloy member characterized by using a high-entropy alloy as a matrix and carbon nanotubes and rare earth nanoparticles as reinforcements, wherein,
the atomic percentage expression of the high-entropy alloy is LxMyNz(Fe2/3Nb1/6Ta1/6)100-x-y-zWherein L contains at least one selected from among B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb and Bi, M contains at least one selected from among Cu, Co, Cr, Ni, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, N contains at least one selected from among Er, Y, Sc, Nd, Dy, Tm and Gd, and 0. ltoreq. x<100，0≤y＜45，0≤z＜10，0≤x+y+z<100。
2. The alloy member according to claim 1, wherein the mass of the high-entropy alloy is 100 parts, the mass of the carbon nanotube is 0.01 to 0.10 parts, and the mass of the rare earth nanoparticle is 0.05 to 0.50 parts, in parts by mass.
3. The alloy component of claim 2, wherein the rare earth nanoparticles are rare earth oxide nanoparticles comprising a material selected from CeO2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3At least one of nanoparticles.
4. The alloy component of claim 3, wherein the rare earth nanoparticles are mass-equivalent CeO2Nanoparticles, Y2O3Nanoparticles, La2O3Nanoparticles and Sm2O3Nano-particlesA combination of particles.
5. The alloy member according to claim 2, wherein the carbon nanotube is a graphitized multilayered carbon nanotube having a purity of 99% or more.
6. The alloy component of claim 2, wherein the carbon nanotubes have a diameter of 10nm to 50nm and the rare earth nanoparticles have a particle size of 50nm to 150 nm.
7. A method of producing an alloy structural member for producing the alloy structural member according to any one of claims 1 to 6, characterized by comprising:
a pre-alloying process, namely pre-alloying the high-entropy alloy raw material to obtain a pre-alloyed high-entropy alloy;
a mixing procedure, namely mixing the carbon nano tube, the rare earth nano particles and the pre-alloyed high-entropy alloy to form a suspension, and dehydrating and deoxidizing to form composite powder;
and the additive manufacturing process comprises the steps of locally heating and melting the composite powder by using laser, and depositing and solidifying layer by layer to obtain the alloy component.
8. The method of manufacturing an alloy structural member according to claim 7, wherein in the prealloying step, the prealloying treatment is mechanical alloying using a ball mill, and the mechanical alloying time is 4 to 7 hours.
9. The method of manufacturing an alloy structural member according to claim 7, wherein the mixing process includes:
a suspension preparation step of placing the carbon nanotubes, the rare earth nanoparticles and the pre-alloyed high-entropy alloy in a magnetic stirrer, and adding deionized water to stir to prepare the suspension;
a dehydration and deoxidation step, wherein the rotation speed of the magnetic stirrer is controlled to be 100r/min to 120r/min, and the suspension is continuously heated and stirred for 5 hours to 8 hours at the temperature of 80 ℃ to 100 ℃ so as to be dehydrated and deoxidized into mixed powder;
and a drying step, namely taking out the mixed powder, and placing the mixed powder in a vacuum drying oven at 100-120 ℃ to be heated and dried for 5-8 hours to obtain the composite powder.
10. The method of making an alloy component of claim 7, wherein the additive manufacturing process comprises:
an initial deposition step, wherein the composite powder is locally heated and melted by the laser, and an initial layer is formed by deposition and solidification in the range of laser power of 3000W to 3500W;
and a stable deposition process, wherein the laser continuously heats and melts the composite powder locally, the laser power is gradually reduced layer by layer in a mode of 0.5W/layer to 10W/layer, and the alloy component is formed by layer-by-layer deposition and solidification.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111549301A (en) * | 2020-04-21 | 2020-08-18 | 中国科学院力学研究所 | High-entropy alloy composition, high-entropy alloy film, high-entropy alloy target and preparation method of film |
| CN113023777A (en) * | 2021-01-28 | 2021-06-25 | 浙江大学 | High-conductivity A-site high-entropy nano metal oxide and preparation method thereof |
| CN113037027A (en) * | 2021-04-20 | 2021-06-25 | 温州大学 | Layered magnetic conductive iron core forming device and method based on laser melting deposition process |
| CN113695572A (en) * | 2021-08-30 | 2021-11-26 | 广东工业大学 | Preparation method of graphene-based high-entropy alloy material |
| TWI757096B (en) * | 2021-02-17 | 2022-03-01 | 明志科技大學 | High entropy alloy film and manufacturing method thereof |
| CN114737098A (en) * | 2021-01-07 | 2022-07-12 | 湖南工业大学 | Preparation method of Nb-Co-Hf-Mo-Sc-Er alloy |
| CN115029603A (en) * | 2022-06-24 | 2022-09-09 | 山东宇明月石油工程有限公司 | Laser cladding alloy material and process method thereof |
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| CN115354204A (en) * | 2022-08-26 | 2022-11-18 | 武汉纺织大学 | Grain bimodal distribution synergistic oxide dispersion strengthening and toughening high-entropy alloy and preparation thereof |
| CN115627402A (en) * | 2022-07-14 | 2023-01-20 | 河源正信硬质合金有限公司 | Complex-phase co-strengthening hard alloy and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| TW201910530A (en) * | 2017-08-02 | 2019-03-16 | 國立清華大學 | Precipitation strengthened high-entropy superalloy |
| CN109750179A (en) * | 2019-01-30 | 2019-05-14 | 河南一工钻业有限公司 | Multi-principal high-entropy alloy material and its application in drill bit processing |
| CN110004349A (en) * | 2019-02-13 | 2019-07-12 | 昆明理工大学 | A kind of carbon nanotube enhancing high-entropy alloy composite material and preparation method |
-
2019
- 2019-09-30 CN CN201910944928.8A patent/CN110592411B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170314097A1 (en) * | 2016-05-02 | 2017-11-02 | Korea Advanced Institute Of Science And Technology | High-strength and ultra heat-resistant high entropy alloy (hea) matrix composites and method of preparing the same |
| TW201910530A (en) * | 2017-08-02 | 2019-03-16 | 國立清華大學 | Precipitation strengthened high-entropy superalloy |
| CN109750179A (en) * | 2019-01-30 | 2019-05-14 | 河南一工钻业有限公司 | Multi-principal high-entropy alloy material and its application in drill bit processing |
| CN110004349A (en) * | 2019-02-13 | 2019-07-12 | 昆明理工大学 | A kind of carbon nanotube enhancing high-entropy alloy composite material and preparation method |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111549301B (en) * | 2020-04-21 | 2021-10-08 | 中国科学院力学研究所 | High-entropy alloy composition, high-entropy alloy film, high-entropy alloy target and preparation method of film |
| CN111549301A (en) * | 2020-04-21 | 2020-08-18 | 中国科学院力学研究所 | High-entropy alloy composition, high-entropy alloy film, high-entropy alloy target and preparation method of film |
| CN114737098A (en) * | 2021-01-07 | 2022-07-12 | 湖南工业大学 | Preparation method of Nb-Co-Hf-Mo-Sc-Er alloy |
| CN114737098B (en) * | 2021-01-07 | 2022-09-30 | 湖南工业大学 | Preparation method of refractory high-entropy alloy Nb-Co-Hf-Mo-Sc-Er |
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