CN110499481B - Alloy member and method for producing same - Google Patents
Alloy member and method for producing same Download PDFInfo
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- CN110499481B CN110499481B CN201910944926.9A CN201910944926A CN110499481B CN 110499481 B CN110499481 B CN 110499481B CN 201910944926 A CN201910944926 A CN 201910944926A CN 110499481 B CN110499481 B CN 110499481B
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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
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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
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
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- C—CHEMISTRY; METALLURGY
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- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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- B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
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Abstract
The invention provides an alloy component and a preparation method thereof, wherein the alloy component takes high-entropy alloy as a matrix and takes carbon nano tubes, carbon nano fibers and rare earth nano particles as reinforcements, wherein the atomic percentage expression of the high-entropy alloy is (Fe)1/3Co1/ 3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100‑x‑yWherein L contains at least one selected from B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb, Bi, Cu, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, and 0 < x.ltoreq.60, and 0. ltoreq. y.ltoreq.40. 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, an aspect of the present invention provides an alloy member, wherein the alloy member uses a high-entropy alloy as a matrix and uses carbon nanotubes, carbon nanofibers and rare earth nanoparticles as reinforcements, and the atomic percentage expression of the high-entropy alloy is (Fe)1/3Co1/3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100-x-yWherein L contains at least one selected from B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb, Bi, Cu, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, and 0 < x.ltoreq.60, and 0. ltoreq. y.ltoreq.40.
In one aspect of the invention, the carbon nano tube, the carbon nano fiber and the rare earth nano particle are added into the high-entropy alloy matrix as the reinforcement, so that the refining effect of the rare earth nano particle on crystal grains, the improvement of the carbon nano tube on the performance of crystal boundaries, the improvement of the corrosion resistance of the crystal boundaries and the blocking effect of dislocation migration through the crystal boundaries can be fully exerted; 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, the carbon nanotubes in the crystal grains can also hinder the formation and growth of coarse columnar crystals, and certain auxiliary effect on refined crystal grains is achieved; moreover, the carbon nanofiber has a length larger than that of the carbon nanotube and can penetrate through the grain boundary and be positioned in the grains on two sides of the grain boundary, so that the tensile strength of the grain boundary can be effectively improved by utilizing the excellent tensile strength characteristic of the carbon nanofiber, and particularly when the carbon nanotube in the system has the defect of local aggregation, the problem caused by the local aggregation of the carbon nanotube can be effectively counteracted by virtue of the characteristic that the carbon nanofiber is continuously distributed in the grain boundary and the grains, so that the tensile strength of the alloy member is further improved; in addition, due to the refining effect of the rare earth nanoparticles on the crystal grains, the carbon nanofibers can penetrate through more crystal boundaries and crystal grains simultaneously, so that the strengthening effect of the carbon nanotubes can be further improved, and the mechanical property of the alloy member is further improved.
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 structural member provided by the invention, optionally, the rare earth nanoparticles are prepared from acetylacetone rare earth salt. Preferably, the rare earth acetylacetonate salt comprises at least one member selected from the group consisting of cerium acetylacetonate, yttrium acetylacetonate, lanthanum acetylacetonate, and samarium acetylacetonate. More preferably, the rare earth acetylacetonate salt is a combination of cerium acetylacetonate and yttrium acetylacetonate in equal mass. Under the condition, the rare earth nanoparticles are prepared by the reaction of the rare earth salt solution, the rare earth nanoparticles uniformly distributed on the surfaces of the carbon nano tube, the carbon nano fiber and the high-entropy alloy can be obtained, the condition that the rare earth nanoparticles are agglomerated when being directly added into the solution can be effectively prevented, the problem that the rare earth nanoparticles are easily agglomerated when the microstructures of the high-entropy alloy, the carbon nano tube and the carbon nano fiber are not damaged is solved, and the enhancement effect of the rare earth nanoparticles on the mechanical property of the alloy member is 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 nano tube is 0.05-1.00 part, the mass of the carbon nano fiber is 0.05-0.50 part, and the mass of the acetylacetone rare earth salt is 1.00-10.00 parts in parts 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 carbon nano tubes, the carbon nano fibers and the rare earth nano particles is limited within a certain range, so that the enhancement promotion effect of the reinforcement on the high-entropy alloy can be realized, the mechanical property and the like of the alloy member are improved, and the adverse effect of excessive reinforcement on the characteristics of the high-entropy alloy can be prevented or reduced.
In addition, in the alloy member provided by the present invention, optionally, the carbon nanotube is a graphitized multilayered carbon nanotube, and the carbon nanofiber is a graphitized hollow carbon nanofiber. Preferably, the carbon nanotube is a graphitized multi-layer carbon nanotube with a purity of 99% or more, and the carbon nanofiber is a graphitized hollow carbon nanofiber with a purity of 99% or more. The carbon nano tube or the carbon nano fiber can effectively improve the microstructure of the carbon nano tube or the carbon nano fiber after the graphitization treatment, thereby improving the mechanical property, the electrical property and the like of the carbon nano tube or the carbon nano fiber, and therefore, the graphitization multi-layer carbon nano tube or the graphitization hollow carbon nano fiber with the purity of more than 99 percent, in particular the graphitization multi-layer carbon nano tube with the purity of more than 99 percent is adopted as a reinforcement body, which can more effectively play a role in enhancing and promoting the high-entropy alloy, thereby more effectively improving the performance of the prepared alloy member and the like.
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 diameter of the carbon nanofiber is 150nm to 200 nm. Therefore, the 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 are enhanced.
In the alloy member provided by the present invention, the yield strength of the alloy member is 996MPa or more, the tensile strength of the alloy member is 1078MPa or more, and the elongation at break of the alloy member is 15.1% 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 reaction step of mixing and preparing composite powder containing carbon nanotubes, carbon nanofibers, rare earth nanoparticles and the pre-alloyed high-entropy alloy; 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 carbon nanofibers, the rare earth nanoparticles, and the high-entropy alloy is melted by laser heating and deposited layer by layer to form the alloy member in combination with an additive manufacturing process (e.g., 3D printing), the cost of preparing the alloy member by using the process is low because the additive manufacturing process is not limited by the manufacturing of a mold and the amount of subsequent machining is small, and the alloy member prepared by the method of the present invention can fully exert the reinforcing effect of the carbon nanotubes, the carbon nanofibers, and the rare earth nanoparticles on the high-entropy alloy, and can rapidly mold an alloy member with a complex structure, such as a large-sized structural member with a complex structure.
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 (Fe) of the high-entropy alloy1/3Co1/3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100-x-ySelecting elements in the range of L, determining corresponding atomic percentages x and y, 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.
Further, in the method for producing an alloy structural member according to the present invention, optionally, in the prealloying step, the prealloying treatment is mechanical alloying 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 damage effect of the oxidation layer on the performance of the material is prevented, 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 member according to the present invention, optionally, in the mixing reaction step, the specific steps of mixing and manufacturing the composite powder including the carbon nanotube, the carbon nanofiber, the rare earth nanoparticle, and the pre-alloyed high-entropy alloy include: mixing the carbon nano tube, the carbon nano fiber and the pre-alloyed high-entropy alloy to form a suspension, adding acetylacetone rare earth salt into the suspension, and reacting to obtain the composite powder. Therefore, the agglomeration phenomenon when the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the pre-alloyed high-entropy alloy are directly mixed can be effectively prevented, and the composite powder of the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the high-entropy alloy which are uniformly distributed can be more effectively obtained.
Further, in the method for producing an alloy structural member according to the present invention, optionally, in the mixing reaction step, a solvent used for producing the suspension of the carbon nanotubes, the carbon nanofibers, and the pre-alloyed high-entropy alloy is triethylene glycol, wherein the amount of the triethylene glycol used is: 150mL to 250mL of the triethylene glycol is used per 100g of the prealloyed high entropy alloy. Preferably, the triethylene glycol is used in the following amount: 200mL of the triethylene glycol is used per 100g of the prealloyed high-entropy alloy. In this case, triethylene glycol can be used as a medium, and rare earth nanoparticles generated on the surfaces of carbon nanotubes, carbon nanofibers and high-entropy alloys can be more effectively and conveniently obtained.
In addition, in the method for manufacturing an alloy member according to the present invention, optionally, the mixing reaction step includes: a mixing step of adding the carbon nanotubes, the carbon nanofibers and the pre-alloyed high-entropy alloy into triethylene glycol and mixing to form a suspension; a dehydration step, namely, placing the suspension at 130 ℃ and keeping the temperature for 1 to 2 hours to perform dehydration reaction; and a reaction process, namely cooling the suspension to 90 ℃, adding acetylacetone rare earth salt, keeping the temperature, stirring for 1 to 2 hours, placing the mixture in a box-type electric furnace, heating to 300 ℃ at a speed of 15 ℃/min under the condition of inert gas, keeping the temperature for 3 hours, cooling to room temperature, and drying to obtain the composite powder. Therefore, the composite powder of the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the high-entropy alloy which are uniformly distributed can be more effectively obtained.
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 showing a mixing reaction step in the method for producing an alloy structural member according to the 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 5 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 a high-entropy alloy as a matrix and carbon nanotubes, carbon nanofibers, and rare earth nanoparticles as reinforcements, wherein the atomic percentage expression of the high-entropy alloy is (Fe)1/3Co1/3Ni1/3)x(Nb1/ 2Ta1/3Cr1/6)yL100-x-yWherein L comprises a metal selected from the group consisting of B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb and BiAt least one of Cu, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, wherein x is more than 0 and less than or equal to 60, and y is more than or equal to 0 and less than or equal to 40.
In the embodiment, the carbon nano tube, the carbon nano fiber and the rare earth nano particles are simultaneously added into the high-entropy alloy matrix to serve as the reinforcement, so that on one hand, the refining effect of the rare earth nano particles on crystal grains can be fully exerted, and the effects of improving the performance of the crystal boundary, improving the corrosion resistance of the crystal boundary and hindering dislocation from migrating through the crystal boundary can be fully exerted; 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, the carbon nanotubes in the crystal grains can also hinder the formation and growth of coarse columnar crystals, and certain auxiliary effect on refined crystal grains is achieved; moreover, the carbon nanofiber has a length larger than that of the carbon nanotube and can penetrate through the grain boundary and be positioned in the grains on two sides of the grain boundary, so that the tensile strength of the grain boundary can be effectively improved by utilizing the excellent tensile strength characteristic of the carbon nanofiber, and particularly when the carbon nanotube in the system has the defect of local aggregation, the problem caused by the local aggregation of the carbon nanotube can be effectively counteracted by virtue of the characteristic that the carbon nanofiber is continuously distributed in the grain boundary and the grains, so that the tensile strength of the alloy member is further improved; in addition, due to the refining effect of the rare earth nanoparticles on the crystal grains, the carbon nanofibers can penetrate through more crystal boundaries and crystal grains simultaneously, so that the strengthening effect of the carbon nanotubes can be further improved, and the mechanical property of the alloy member is further improved.
In addition, in the present embodiment, as described above, L can be selected from elements in a plurality of groups in the periodic table, and therefore, the types of elements to be applied are wide, and the elements can be flexibly selected and matched according to characteristics such as physicochemical characteristics and market prices of 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 (Fe)1/3Co1/3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100-x-yWherein x is more than 0 and less than or equal to 60, y is more than or equal to 0 and less than or equal to 40, namely x is not equal to 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, Co and Ni, and the three elements are combined according to a certain proportion, so that the prepared alloy member has excellent mechanical properties and better ferromagnetism and the like.
Further, in the present embodiment, the expression of atomic percent (Fe) in the high-entropy alloy1/3Co1/3Ni1/3)x(Nb1/ 2Ta1/3Cr1/6)yL100-x-yIn the method, the element selection of L and the values of x and y can be obtained by thermodynamic software calculation 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 rare earth nanoparticles may be prepared from a rare earth acetylacetonate salt, and the type of the rare earth acetylacetonate salt is not particularly limited, and may be, for example, an acetylacetonate salt of an arbitrary element in the rare earth group or the like. In some examples, the rare earth acetylacetonate salt may include at least one selected from the group consisting of cerium acetylacetonate, yttrium acetylacetonate, lanthanum acetylacetonate, and samarium acetylacetonate. In other examples, the rare earth acetylacetonate salt may be a combination of cerium acetylacetonate and yttrium acetylacetonate in equal mass. Under the condition, the rare earth nanoparticles are prepared by the reaction of the rare earth salt solution, the rare earth nanoparticles uniformly distributed on the surfaces of the carbon nano tube, the carbon nano fiber and the high-entropy alloy can be obtained, the condition that the rare earth nanoparticles are agglomerated when being directly added into the solution can be effectively prevented, the problem that the rare earth nanoparticles are easily agglomerated when the microstructures of the high-entropy alloy, the carbon nano tube and the carbon nano fiber are not damaged is solved, and the enhancement effect of the rare earth nanoparticles on the mechanical property of the alloy member is improved.
In the present embodiment, the mass of the matrix and the reinforcement constituting the alloy member is not particularly limited. In some examples, the mass of the high-entropy alloy may be 100 parts by mass, the mass of the carbon nanotubes may be 0.01 to 2.00 parts by mass, the mass of the carbon nanofibers may be 0.01 to 1.00 parts by mass, and the mass of the acetylacetone rare earth salt may be 0.10 to 12.00 parts by mass. In other examples, the mass of the carbon nanotube may be 0.05 to 1.00 parts, the mass of the carbon nanofiber may be 0.05 to 0.50 parts, and the mass of the acetylacetone rare-earth salt may be 1.00 to 10.00 parts. Therefore, the adding quality of the carbon nano tubes, the carbon nano fibers and the rare earth nano particles is limited within a certain range, so that the enhancement promotion effect of the reinforcement on the high-entropy alloy can be realized, the mechanical property and the like of the alloy member are improved, and the adverse effect of excessive reinforcement 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 may be a high entropy alloy feedstock, i.e., the high entropy alloy feedstock is 100 parts by mass. In other examples, the high entropy alloy may be a pre-alloyed high entropy alloy, i.e., 100 parts by mass of the pre-alloyed high entropy alloy. 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 and the like can be more effectively met.
In the present embodiment, the yield strength of the alloy member may be 900MPa or more, for example, 996MPa or more. In some examples, the tensile strength of the alloy member may be 1000MPa or greater, such as 1078MPa or greater, and the like. In other examples, the alloy member may have an elongation at break of 15% or more, such as 15.1% 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 addition, in the present embodiment, the particle diameter of the rare earth nanoparticles is not particularly limited. In some examples, the rare earth nanoparticles can have a particle size of 20 to 200nm, such as 30nm, 40nm, 160nm, 180nm, and the like. In other examples, the rare earth nanoparticles may have a particle size of 50 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 and carbon nanofibers are not particularly limited. In some examples, the carbon nanotubes may be graphitized multilayered carbon nanotubes and the carbon nanofibers may be graphitized hollow carbon nanofibers. In other examples, the carbon nanotubes may be graphitized multilayered carbon nanotubes having a purity of 99% or more, and the carbon nanofibers may be graphitized hollow carbon nanofibers having a purity of 99% or more. The carbon nano tube or the carbon nano fiber can effectively improve the microstructure of the carbon nano tube or the carbon nano fiber after the graphitization treatment, thereby improving the mechanical property, the electrical property and the like of the carbon nano tube or the carbon nano fiber, and therefore, the graphitization multi-layer carbon nano tube or the graphitization hollow carbon nano fiber with the purity of more than 99 percent, in particular the graphitization multi-layer carbon nano tube with the purity of more than 99 percent is adopted as a reinforcement body, which can more effectively play a role in enhancing and promoting the high-entropy alloy, thereby more effectively improving the performance of the prepared alloy member and the like.
In the present embodiment, the diameters of the carbon nanotubes and the carbon nanofibers are 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, and the carbon nanofibers may have a diameter of 100nm to 250nm, such as 120nm, 135nm, 215nm, 230nm, 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, and the carbon nanofibers may have a diameter of 150nm to 200nm, such as 165nm, 175nm, 185nm, 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 reaction 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 mainstream method for preparing the high-entropy alloy component is still vacuum melting combined with subsequent mechanical processing. However, due to the limitation of the die processing technology, vacuum melting can only prepare high-entropy alloy components with limited sizes and simple shapes, the hard and wear-resistant characteristics of the high-entropy alloy undoubtedly bring greater difficulty to subsequent mechanical processing, and the accelerated wear of a cutter can also cause the reduction of processing precision, so that the application and development of the high-entropy alloy are obviously hindered by the traditional technology.
Therefore, the additive manufacturing technology can realize near-net forming of the high-entropy alloy component, is not limited by die manufacturing any more, has less subsequent machining amount, and can manufacture the high-entropy alloy component with a complex structure at lower cost, so that the key problem of hindering rapid development of the high-entropy alloy is hopefully solved. The Laser Assisted Additive Manufacturing (LAAM) technology is an efficient high-precision additive manufacturing technology which is proposed in recent years and takes high-energy Laser as a heat source, and as the energy density of the Laser is far higher than that of an electric arc, the preparation condition of the high-entropy alloy is easier to achieve, and the process window is larger.
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. However, since the ductility and toughness of the high-entropy alloy are limited, the sizes of various alloy components prepared by the laser additive manufacturing technology in the prior art are small, for example, the maximum length of the alloy components is not more than 100mm, and thus, although the high-entropy alloy has the characteristics of excellent high hardness, high toughness and the like, the formation of intergranular cracks is easily caused by the serious stress concentration problem, which brings great difficulty to the preparation of alloy components with large sizes or complex structures by the laser additive manufacturing 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 reaction step of mixing and preparing composite powder containing carbon nanotubes, carbon nanofibers, rare earth nanoparticles and the pre-alloyed high-entropy alloy; and in the additive manufacturing process, the composite powder is locally heated and melted by laser, and the alloy component is obtained through layer-by-layer deposition and solidification.
In the embodiment, the composite powder formed by the carbon nanotube, the carbon nanofiber, the rare earth nanoparticle and the high-entropy alloy is heated and melted by laser and deposited layer by layer to form the alloy component in combination with an additive manufacturing process (such as 3D printing), the cost for preparing the alloy component by adopting the process is low because the additive manufacturing process is not limited by die manufacturing and the subsequent machining amount is small, and the alloy component prepared by the method can fully play the reinforcing effect of the carbon nanotube, the carbon nanofiber and the rare earth nanoparticle on the high-entropy alloy and can quickly form the alloy component with a complex structure, such as a large-size structural component with a complex structure.
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 (Fe) of the high-entropy alloy1/3Co1/3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100-x-ySelecting elements in the range of L, determining corresponding atomic percentages x and y, 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 control software of a LAAM platform. 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 within the range of L and determining the corresponding atomic percentages x and y 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, the elements in the range of L and the values of x and y can be calculated and selected more accurately and efficiently according to the requirements of the 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, in the mixing reaction process, the specific steps of mixing and preparing the composite powder including the carbon nanotubes, the carbon nanofibers, the rare earth nanoparticles, and the pre-alloyed high-entropy alloy may be: mixing the carbon nano tube, the carbon nano fiber and the pre-alloyed high-entropy alloy to form a suspension, adding acetylacetone rare earth salt into the suspension, and reacting to obtain the composite powder. Therefore, the agglomeration phenomenon when the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the pre-alloyed high-entropy alloy are directly mixed can be effectively prevented, and the composite powder of the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the high-entropy alloy which are uniformly distributed can be more effectively obtained.
In the present embodiment, in the mixing reaction step, the solvent and the amount thereof used for preparing the suspension of the carbon nanotubes, the carbon nanofibers, and the pre-alloyed high-entropy alloy are not particularly limited. In some examples, the solvent may be triethylene glycol, wherein the amount of triethylene glycol used may be: 150mL to 250mL of triethylene glycol is used per 100g of the prealloyed high-entropy alloy. In other examples, the amount of triethylene glycol may be: 200mL of triethylene glycol is used for each 100g of prealloyed high-entropy alloy. In this case, triethylene glycol can be used as a medium, and rare earth nanoparticles generated on the surfaces of carbon nanotubes, carbon nanofibers and high-entropy alloys can be more effectively and conveniently obtained.
In the present embodiment, as shown in fig. 3, in the mixed reaction step, the mixed reaction step may include the steps of: a mixing procedure, namely adding the carbon nano tube, the carbon nano fiber and the pre-alloyed high-entropy alloy into triethylene glycol, and mixing to form a suspension; a dehydration step, namely placing the suspension at 130 ℃ and keeping the temperature for 1 to 2 hours to perform dehydration reaction; and a reaction process, namely cooling the suspension to 90 ℃, adding acetylacetone rare earth salt, keeping the temperature, stirring for 1 to 2 hours, placing the mixture in a box-type electric furnace, heating to 300 ℃ at a speed of 15 ℃/min under the condition of inert gas, keeping the temperature for 3 hours, cooling to room temperature, and drying to obtain the composite powder. Therefore, the composite powder of the carbon nano tube, the carbon nano fiber, the rare earth nano particle and the high-entropy alloy which are uniformly distributed can be more effectively obtained.
In addition, in the present embodiment, a specific process of the additive manufacturing process is not particularly limited. In some examples, the particular process of the additive manufacturing process may be a laser assisted additive manufacturing process, i.e., a LAAM process. In other examples, the additive manufacturing process may be a Laser Melting Deposition (LMD) process. Therefore, different preparation processes can be selected according to actual requirements, so that different experimental requirements and the like are met, the convenience and effectiveness of the preparation of the alloy component material are improved, the large-size and complex-structure alloy component is manufactured, particularly, the generation of intergranular cracks on a large-size structural component is effectively inhibited through grain refinement and grain boundary strengthening, the actual industrial application level is reached, the material utilization rate is relatively high, and the research, 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 this embodiment, in the additive manufacturing process, the laser may be generated by a processing platform (e.g., an LAAM platform), and other optimized parameters of the processing platform may 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 may further include: and a substrate pretreatment step of removing an oxide layer and stains on the substrate by polishing and scrubbing, and preheating the substrate, wherein the preheating temperature can be 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 may further include: 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 laser-assisted additive manufacturing method is used for manufacturing the high-entropy alloy marine propeller blade with the maximum length of 800mm, and the process flow specifically comprises the following steps:
step 1: three-dimensional modeling is carried out on the propeller blades by utilizing CAD software, then laser scanning paths of all layers are planned by utilizing CAM software, finally a processing path program of the whole part is formed, and the program is input into LAAM platform control software;
step 2: based on the calculation result of thermodynamic software, designing the atomic percent expression of the high-entropy alloy component as Fe20Co20Ni20Nb15Ta10Cr5Zr10Converting the atomic percentages of Fe, Co, Ni, Nb, Ta, Cr and Zr into mass ratios, weighing powder, wherein the purity of the powder is required to be more than 99.9%, and screening the powder by a sieve to control the particle size of the powder to be within the range of 45-105 μm before weighing the raw material powder;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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: pouring 1.25g of carbon nano tube, 0.625g of carbon nano fiber and 250g of prealloyed high-entropy alloy powder into 500mL of triethylene glycol to be mixed to form a suspension, pouring the suspension into a three-neck flask, heating to 130 ℃, keeping the temperature for 2 hours to remove moisture, cooling the dehydrated suspension to 90 ℃, adding 6g of cerium acetylacetonate and 6g of yttrium acetylacetonate, keeping the temperature and stirring for 2 hours to mix uniformly, putting the mixed solution into a box-type electric furnace, heating to 300 ℃ at the rate of 15 ℃/min under the condition of pure argon, keeping the temperature for 3 hours, naturally cooling to room temperature along with the furnace, putting a sample into a drying oven, and drying for 4 hours to obtain mixed powder to be printed;
and 5: putting the mixed powder into a powder cylinder of a powder feeder of LAAM equipment, polishing the mixed powder by using sand paper, then scrubbing the mixed powder by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, wherein the preheating time is 2 hours; setting the laser power to 3200W, the scanning speed to 600mm/min, the spot diameter to 4.5mm, the defocusing amount to 20mm, the powder feeding rate to 4.5g/min, the single-layer thickness to 1.2mm, the lap joint rate to 20%, the shielding gas to be argon gas with the purity of 99.9%, and the shielding gas flow to 20L/min, and performing laser-assisted additive manufacturing to obtain Fe20Co20Ni20Nb15Ta10Cr5Zr10Cooling the high-entropy alloy marine propeller blades for 4 hours along with the bin, and then taking out the blades;
step 6: the blade is subjected to magnetic powder and ultrasonic flaw detection, special attention needs to be paid to detection of interlamination and stress concentration areas, and the blade can be installed into a propeller to be put into use if the detection result reaches the factory qualified standard.
Example 2
The laser-assisted additive manufacturing method is used for manufacturing the high-entropy alloy marine diesel engine connecting rod with the maximum length of 1000mm in an auxiliary mode, and the process flow specifically comprises the following steps:
step 1: three-dimensional modeling is carried out on the diesel engine connecting rod by utilizing CAD software, then laser scanning paths of all layers are planned by utilizing CAM software, finally a processing path program of the whole part is formed, and the program is input into control software of an LAAM platform;
step 2: based on the calculation result of thermodynamic software, designing the atomic percent expression of the high-entropy alloy component as Fe16Co16Ni16Nb18Ta12Cr6V8Zr8Converting the atomic percentages of Fe, Co, Ni, Nb, Ta, Cr, V and Zr 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 Fe, Co, Ni, Nb, Ta, Cr, V and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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: pouring 1.75g of carbon nano tube, 1.0g of carbon nano fiber and 250g of prealloyed high-entropy alloy powder into 500mL of triethylene glycol to be mixed to form a suspension, pouring the suspension into a three-neck flask, heating to 130 ℃, keeping the temperature for 2 hours to remove moisture, cooling the dehydrated suspension to 90 ℃, adding 7.5g of cerium acetylacetonate and 7.5g of yttrium acetylacetonate, keeping the temperature and stirring for 2 hours to mix uniformly, putting the mixed solution into a box-type electric furnace, heating to 300 ℃ at the speed of 15 ℃/min under the condition of pure argon, keeping the temperature for 3 hours, naturally cooling to room temperature along with the furnace, putting a sample into a drying box, and drying for 4 hours to obtain mixed powder to be printed;
and 5: putting the mixed powder into a powder cylinder of a powder feeder of LAAM equipment, firstly polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, setting the laser power to be 3000W, the scanning speed to be 600mm/min, the spot diameter to be 4.0mm, the defocusing amount to be 17.5mm, the powder feeding speed to be 4.0g/min, the single-layer thickness to be 1.1mm, the lap joint rate to be 20%, the protective gas to be argon with the purity of 99.9%, the protective gas flow to be 20L/min, and carrying out laser-assisted additive manufacturing to obtain Fe16Co16Ni16Nb18Ta12Cr6V8Zr8High entropy sumThe connecting rod of the golden diesel engine is taken out after being cooled for 4 hours along with the cabin;
step 6: the magnetic powder and ultrasonic flaw detection is carried out on the connecting rod shaft, the detection of interlamination and stress concentration areas needs to be particularly paid attention, and if the detection result reaches the factory qualified standard, the connecting rod can be installed in a diesel engine to be put into use.
Comparative example 1
Step 1: adopting the model and the processing path constructed in the embodiment 1, and inputting the program into LAAM platform control software;
step 2: the atomic percent expression Fe of the high-entropy alloy component calculated in example 1 is adopted20Co20Ni20Nb15Ta10Cr5Zr10Weighing Fe, Co, Ni, Nb, Ta, Cr and Zr powder, wherein the purity of the powder is required to be more than 99.9%, and before weighing the raw material powder, screening the powder by a sieve to control the particle size of the powder to be within the range of 45-105 μm;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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 250g of prealloyed high-entropy alloy powder into a powder feeder powder cylinder of LAAM equipment, polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, and preheating for 2 hours; setting the laser power to 3200W, the scanning speed to 600mm/min, the spot diameter to 4.5mm, the defocusing amount to 20mm, the powder feeding rate to 4.5g/min, the single-layer thickness to 1.2mm, the lap joint rate to 20%, the shielding gas to be argon gas with the purity of 99.9%, and the shielding gas flow to 20L/min, and performing laser-assisted additive manufacturing to obtain Fe20Co20Ni20Nb15Ta10Cr5Zr10The high-entropy alloy propeller blades for the ship are taken out after being cooled for 4 hours along with the cabin.
Comparative example 2
Step 1: utilizing the model and the processing path constructed in the embodiment 2, and inputting the program into control software of an LAAM platform;
step 2: the atomic percent expression of the high-entropy alloy component calculated in example 2 is Fe16Co16Ni16Nb18Ta12Cr6V8Zr8Weighing Fe, Co, Ni, Nb, Ta, Cr, V and Zr powder, wherein the purity of the powder is required to reach 99.9%, and before weighing the raw material powder, screening the powder by a sieve to control the particle size of the powder to be within the range of 45-105 μm;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr, V and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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 LAAM equipment, firstly polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, setting the preheating time to be 2 hours, setting the laser power to be 3000W, the scanning speed to be 600mm/min, the spot diameter to be 4.0mm, the defocusing amount to be 17.5mm, the powder feeding speed to be 4.0g/min, the single-layer thickness to be 1.1mm, the lap joint rate to be 20%, the protective gas to be argon with the purity of 99.9%, the protective gas flow to be 20L/min, and carrying out laser-assisted additive manufacturing to obtain Fe16Co16Ni16Nb18Ta12Cr6V8Zr8The connecting rod of the high-entropy alloy diesel engine is taken out after being cooled for 4 hours along with the bin.
Comparative example 3
Step 1: utilizing the model and the processing path constructed in the embodiment 2, and inputting the program into control software of an LAAM platform;
step 2: the atomic percent expression of the high-entropy alloy component calculated in example 2 is Fe16Co16Ni16Nb18Ta12Cr6V8Zr8Weighing Fe, Co, Ni, Nb, Ta, Cr, V and Zr powder with purity up to 99.9%, and sieving to control the particle size of the powder to be in the range ofIn the range of 45 μm to 105 μm;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr, V and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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: pouring 1.75g of carbon nano tube and 250g of pre-alloyed high-entropy alloy powder into 500mL of triethylene glycol to be mixed to form suspension, pouring the suspension into a three-neck flask, heating to 130 ℃, keeping for 2 hours to remove moisture, and putting a sample into a drying oven to be dried for 4 hours to obtain mixed powder to be printed;
and 5: putting the mixed powder into a powder cylinder of a powder feeder of LAAM equipment, firstly polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, setting the laser power to be 3000W, the scanning speed to be 600mm/min, the spot diameter to be 4.0mm, the defocusing amount to be 17.5mm, the powder feeding speed to be 4.0g/min, the single-layer thickness to be 1.1mm, the lap joint rate to be 20%, the protective gas to be argon with the purity of 99.9%, the protective gas flow to be 20L/min, and carrying out laser-assisted additive manufacturing to obtain Fe16Co16Ni16Nb18Ta12Cr6V8Zr8The connecting rod of the high-entropy alloy diesel engine is taken out after being cooled for 4 hours along with the bin.
Comparative example 4
Step 1: utilizing the model and the processing path constructed in the embodiment 2, and inputting the program into control software of an LAAM platform;
step 2: the atomic percent expression of the high-entropy alloy component calculated in example 2 is Fe16Co16Ni16Nb18Ta12Cr6V8Zr8Weighing Fe, Co, Ni, Nb, Ta, Cr, V and Zr powder, wherein the purity of the powder is required to reach 99.9%, and before weighing the raw material powder, screening the powder by a sieve to control the particle size of the powder to be within the range of 45-105 μm;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr, V and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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: pouring 250g of prealloyed high-entropy alloy powder into 500mL of triethylene glycol, mixing to form a suspension, pouring the suspension into a three-neck flask, heating to 130 ℃, keeping the temperature for 2 hours to remove moisture, cooling the dehydrated suspension to 90 ℃, adding 7.5g of cerium acetylacetonate and 7.5g of yttrium acetylacetonate, keeping the temperature, stirring for 2 hours to mix uniformly again, putting the mixed solution into a box-type electric furnace, heating to 300 ℃ at the rate of 15 ℃/min under the condition of pure argon, keeping the temperature for 3 hours, naturally cooling to room temperature along with the furnace, putting a sample into a drying oven, and drying for 4 hours to obtain mixed powder to be printed;
and 5: putting the mixed powder into a powder cylinder of a powder feeder of LAAM equipment, firstly polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, setting the laser power to be 3000W, the scanning speed to be 600mm/min, the spot diameter to be 4.0mm, the defocusing amount to be 17.5mm, the powder feeding speed to be 4.0g/min, the single-layer thickness to be 1.1mm, the lap joint rate to be 20%, the protective gas to be argon with the purity of 99.9%, the protective gas flow to be 20L/min, and carrying out laser-assisted additive manufacturing to obtain Fe16Co16Ni16Nb18Ta12Cr6V8Zr8The connecting rod of the high-entropy alloy diesel engine is taken out after being cooled for 4 hours along with the bin.
Comparative example 5
Step 1: utilizing the model and the processing path constructed in the embodiment 2, and inputting the program into control software of an LAAM platform;
step 2: the atomic percent expression of the high-entropy alloy component calculated in example 2 is Fe16Co16Ni16Nb18Ta12Cr6V8Zr8Weighing Fe, Co, Ni, Nb, Ta, Cr, V and Zr powder, wherein the purity of the powder is required to reach 99.9%, and before weighing the raw material powder, screening the powder by a sieve to control the particle size of the powder to be within the range of 45-105 μm;
and step 3: putting the weighed Fe, Co, Ni, Nb, Ta, Cr, V and Zr element powder into a planetary high-energy ball mill for mechanical alloying, and carrying out ball milling for 5 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: pouring 1.75g of carbon nano tube and 250g of pre-alloyed high-entropy alloy powder into 500mL of triethylene glycol to be mixed to form suspension, pouring the suspension into a three-neck flask, heating to 130 ℃, keeping the temperature for 2 hours to remove moisture, cooling the dehydrated suspension to 90 ℃, adding 7.5g of cerium acetylacetonate and 7.5g of yttrium acetylacetonate, keeping the temperature and stirring for 2 hours to mix uniformly again, putting the mixed solution into a box-type electric furnace, heating to 300 ℃ at the rate of 15 ℃/min under the condition of pure argon, keeping the temperature for 3 hours, naturally cooling to room temperature along with the furnace, putting a sample into a drying oven, and drying for 4 hours to obtain mixed powder to be printed;
and 5: putting the mixed powder into a powder cylinder of a powder feeder of LAAM equipment, firstly polishing by using sand paper, then scrubbing by using acetone to remove an oxide layer and oil stains on a substrate, preheating the substrate to 175 ℃, setting the laser power to be 3000W, the scanning speed to be 600mm/min, the spot diameter to be 4.0mm, the defocusing amount to be 17.5mm, the powder feeding speed to be 4.0g/min, the single-layer thickness to be 1.1mm, the lap joint rate to be 20%, the protective gas to be argon with the purity of 99.9%, the protective gas flow to be 20L/min, and carrying out laser-assisted additive manufacturing to obtain Fe16Co16Ni16Nb18Ta12Cr6V8Zr8The connecting rod of the high-entropy alloy diesel engine is taken out after being cooled for 4 hours along with the bin.
Scanning Electron Microscope (SEM) observations were made on the blade samples prepared in example 1 and comparative example 1, and their corresponding SEM photographs are shown in fig. 5(a) and (b); mechanical property tests were performed on the connecting rod samples prepared in example 2 and comparative examples 2 to 5, and specific engineering stress-strain curves thereof are shown in fig. 6, and the related test results are shown in table 1, wherein the yield strength is the yield limit at which the material yield phenomenon occurs, but the stress value at which 0.2% residual deformation (0.2 σ) occurs 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
| Sample (I) | Yield strength (MPa) | Tensile strength (MPa) | Elongation at Break (%) |
| Example 2 | 996 | 1078 | 15.1 |
| Comparative example 2 | 780 | 839 | 11.8 |
| Comparative example 3 | 796 | 892 | 9.9 |
| Comparative example 4 | 878 | 952 | 14.0 |
| Comparative example 5 | 896 | 994 | 14.5 |
As can be seen from fig. 5(a) and (b), the blade sample prepared in example 1 (see fig. 5(a)) has a grain size finer than that of comparative example 1 (see fig. 5(b)) and is substantially free from the formation of coarse columnar crystals and the like, because carbon nanotubes, carbon nanofibers and rare earth nanoparticles are simultaneously added as reinforcing materials.
As can be seen from fig. 6 and the results in table 1, the connecting rod sample prepared in example 2 has better mechanical properties than comparative example 2 (no reinforcement added), comparative example 3 (carbon nanotube added as reinforcement only), comparative example 4 (rare earth nanoparticle added as reinforcement only) and comparative example 5 (carbon nanotube added and rare earth nanoparticle added as reinforcement only) because the carbon nanotube, the carbon nanofiber and the rare earth nanoparticle added as reinforcement are used together, the yield strength of the connecting rod sample can reach 996MPa, the tensile strength of the connecting rod sample can reach 1078MPa, and the elongation at break of the connecting rod sample can reach 15.1%.
Therefore, the carbon nano tube, the carbon nano fiber and the rare earth nano particles are added into the high-entropy alloy matrix as the reinforcement, so that on one hand, the refining effect of the rare earth nano particles on crystal grains can be fully exerted, the improvement of the performance of the carbon nano tube on the crystal boundary, the improvement of the corrosion resistance of the crystal boundary and the blocking effect of dislocation migration through the crystal boundary can be fully exerted; 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, the carbon nanotubes in the crystal grains can also hinder the formation and growth of coarse columnar crystals, and certain auxiliary effect on refined crystal grains is achieved; moreover, the carbon nanofiber has a length larger than that of the carbon nanotube and can penetrate through the grain boundary and be positioned in the grains on two sides of the grain boundary, so that the tensile strength of the grain boundary can be effectively improved by utilizing the excellent tensile strength characteristic of the carbon nanofiber, and particularly when the carbon nanotube in the system has the defect of local aggregation, the problem caused by the local aggregation of the carbon nanotube can be effectively counteracted by virtue of the characteristic that the carbon nanofiber is continuously distributed in the grain boundary and the grains, so that the tensile strength of the alloy member is further improved; in addition, due to the refining effect of the rare earth nanoparticles on the crystal grains, the carbon nanofibers can penetrate through more crystal boundaries and crystal grains simultaneously, so that the strengthening effect of the carbon nanotubes can be further improved, and the mechanical property of the alloy member is further improved.
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 (8)
1. An alloy member characterized by using a high-entropy alloy as a matrix and carbon nanotubes, carbon nanofibers and rare earth nanoparticles as reinforcements, wherein,
the expression of atomic percent of the high-entropy alloy is (Fe)1/3Co1/3Ni1/3)x(Nb1/2Ta1/3Cr1/6)yL100-x-yWherein L contains at least one selected from the group consisting of B, Mg, Al, Si, Sr, Ga, Ge, Sn, Sb, Bi, Cu, Mn, Ag, Zn, V, Ti, Zr, Mo, Hf and W, and 0 < x.ltoreq.60, 0. ltoreq. y.ltoreq.40,
the rare earth nanoparticles are prepared from acetylacetone rare earth salt,
the high-entropy alloy comprises, by mass, 100 parts of the high-entropy alloy, 0.05-1.00 part of the carbon nanotubes, 0.05-0.50 part of the carbon nanofibers, and 1.00-10.00 parts of acetylacetone rare earth salt.
2. The alloy member according to claim 1, wherein the rare earth acetylacetonate salt comprises at least one selected from the group consisting of cerium acetylacetonate, yttrium acetylacetonate, lanthanum acetylacetonate, and samarium acetylacetonate.
3. The alloy component of claim 2, wherein the rare earth acetylacetonate salt is a combination of cerium acetylacetonate and yttrium acetylacetonate of equal mass.
4. The alloy member according to claim 1, wherein the carbon nanotube is a graphitized multilayered carbon nanotube having a purity of 99% or more, and the carbon nanofiber is a graphitized hollow carbon nanofiber having a purity of 99% or more.
5. The alloy component of claim 4, wherein the carbon nanotubes have a diameter of 10nm to 50nm and the carbon nanofibers have a diameter of 150nm to 200 nm.
6. A method of producing an alloy structural member according to any one of claims 1 to 5, comprising:
a pre-alloying process, namely pre-alloying the high-entropy alloy raw material to obtain a pre-alloyed high-entropy alloy;
a mixing reaction step of mixing and preparing composite powder containing carbon nanotubes, carbon nanofibers, rare earth nanoparticles and the pre-alloyed high-entropy alloy;
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.
7. The method for producing an alloy member according to claim 6, wherein the mixing and producing the composite powder including the carbon nanotube, the carbon nanofiber, the rare earth nanoparticle, and the pre-alloyed high-entropy alloy in the mixing reaction step includes:
mixing the carbon nano tube, the carbon nano fiber and the pre-alloyed high-entropy alloy to form a suspension, adding acetylacetone rare earth salt into the suspension, and reacting to obtain the composite powder.
8. The method of making an alloy component of claim 6, 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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