CN115351296B - Method for manufacturing high-entropy alloy reinforced copper-based composite material, product and application - Google Patents

Method for manufacturing high-entropy alloy reinforced copper-based composite material, product and application Download PDF

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CN115351296B
CN115351296B CN202211085276.5A CN202211085276A CN115351296B CN 115351296 B CN115351296 B CN 115351296B CN 202211085276 A CN202211085276 A CN 202211085276A CN 115351296 B CN115351296 B CN 115351296B
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powder
entropy alloy
manufacturing
alloy
copper
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CN115351296A (en
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马劲松
于清晓
程岚
王凯萱
谢敏
来俊华
李飞
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Shanghai Union Technology Corp
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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
    • C22C1/0425—Copper-based alloys
    • 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
    • B22F10/28—Powder bed fusion, e.g. selective laser melting [SLM] or electron beam melting [EBM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
    • 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

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  • Metallurgy (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Powder Metallurgy (AREA)

Abstract

The application relates to a method for manufacturing a high-entropy alloy reinforced copper-based composite material, a product and application thereof, and belongs to the technical field of 3D printing. The application discloses a method for manufacturing a high-entropy alloy reinforced copper-based composite material, which comprises the following steps: s1, mixing iron powder, nickel powder, chromium powder, cobalt powder and manganese powder, and then sequentially carrying out mechanical alloying treatment and drying treatment to obtain high-entropy alloy powder; s2, mixing the high-entropy alloy powder with copper powder to obtain a precursor; s3, manufacturing the precursor into the monotectic alloy by adopting a laser additive manufacturing method. The method for manufacturing the high-entropy alloy reinforced copper-based composite material can improve the tensile strength and the elongation of the monotectic alloy.

Description

Method for manufacturing high-entropy alloy reinforced copper-based composite material, product and application
Technical Field
The invention relates to the technical field of 3D printing, in particular to a method for manufacturing a high-entropy alloy reinforced copper-based composite material, a product and application thereof.
Background
Conventional alloy materials have failed to meet the demanding requirements of people for high performance materials, and in recent years, multi-element alloys (MPEAs) have become a research hotspot. The multi-element alloy is also called a high-entropy alloy (HEAs), which is originally defined as an alloy formed by mixing five or more components at an equal atomic ratio or near-equal atomic ratio by smelting, sintering or the like, and is originally named as a high-entropy alloy because of the large mixed entropy of the alloys.
The high entropy alloy, which is a novel alloy without a single dominant element, is expected to greatly increase the possibility of a new structural alloy compared to conventional alloys to obtain various functional properties such as superior strength-ductility combinations, high corrosion resistance, etc. Based on the difficult problems of the induced metastable state engineering to customize deformation behavior and how to modulate the nano twin structure reinforced phase, the iron-based high-entropy alloy (FeHEA) such as FeCoCrNi system can be regarded as a candidate material with good characteristics for regulating and controlling the microstructure variable customized material, and has great potential in the induced metastable state engineering because of the relative stability and high sensitivity of the component change.
The conventional forming method of the copper alloy material includes turning forming, stamping forming, forging forming and the like. The turning process has the problem of low material utilization rate; the material utilization rate of stamping forming is high, but larger wall thickness difference is easy to form; the forging forming process is limited to the die. However, for the manufacturing and processing of the monotectic alloy which is easy to generate segregation and layering, the traditional forming process is difficult to meet the requirements of mechanical property, microstructure, size, surface precision, processing efficiency control and the like. Compared with the traditional alloy, the copper-based monotectic alloy is extremely easy to generate segregation and delamination, so that the structure performance is uneven, and the tensile strength and the elongation rate are lower.
Disclosure of Invention
One of the purposes of the present application is to provide a method, product and application for manufacturing a high-entropy alloy reinforced copper-based composite material to improve the tensile strength and elongation of a monotectic alloy.
In order to achieve the above purpose, the present application adopts the following technical scheme:
a method of making a high entropy alloy reinforced copper matrix composite comprising the steps of:
s1, mixing iron powder, nickel powder, chromium powder, cobalt powder and manganese powder, and then sequentially carrying out mechanical alloying treatment and drying treatment to obtain high-entropy alloy powder;
S2, mixing the high-entropy alloy powder with copper powder to obtain a precursor;
s3, manufacturing the precursor into the monotectic alloy by adopting a laser additive manufacturing method.
In some embodiments, the chemical composition of the precursor comprises, in mass percent: 60 to 90 percent of Cu, 2 to 8 percent of Fe, 2 to 8 percent of Co, 2.6 to 10.4 percent of Cr, 1.4 to 8.4 percent of Ni and 2 to 8 percent of Mn.
In some embodiments, the mass ratio of the high entropy alloy powder to copper powder is (3:5): (5-7).
In some embodiments, the high entropy alloy powder includes one or more of Ni 14Fe20Cr26Co20Mn20 and equimolar ratio FeCoCrNiMn.
In some embodiments, the high entropy alloy powder has a particle size of 10 to 30 μm.
In some embodiments, the high entropy alloy powder has an stacking fault energy of 3.0 to 25mJ/m 2.
In some embodiments, the mechanical alloying treatment comprises a ball milling treatment.
In some embodiments, the ball milling time is less than or equal to 16 hours.
In some embodiments, the ball milling speed is 200 to 300 revolutions per minute.
In some embodiments, the ball milling media comprises ethanol.
In some embodiments, the ball milling atmosphere comprises an argon atmosphere or an air atmosphere.
In some embodiments, the diameter of the grinding balls is 6 to 10mm.
In some embodiments, the mass ratio of the high entropy alloy powder to the grinding balls is (15-20): (1-2).
In some embodiments, step S3 comprises:
slicing a CAD model of the monotectic alloy part with the supporting structure in a layering manner, and generating a laser selective melting forming track according to slice contour information;
Vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200-300 ℃;
And according to the generated forming track, stacking the precursor layer by layer on the base material into the three-dimensional solid monotectic alloy by adopting a laser selective melting method.
In some embodiments, the process parameters for fabricating the support structure include: the wavelength of the fiber laser is 1060nm, the laser power is 100-300W, the height of the supporting structure is 2-3 mm, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, and the lap joint rate is 45-60%.
In some embodiments, the process parameters for manufacturing the monotectic alloy include: the laser power is 100-300W, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, the lap joint rate is 45-60%, the slice is formed by adopting a path mode that the laser scanning directions of two continuous layers are mutually perpendicular, and the slice is manufactured until the size reaches 150mm multiplied by 150mm or phi 150mm multiplied by 150mm monotectic alloy parts are manufactured.
The application also provides a monotectic alloy which is prepared by adopting the method for preparing the high-entropy alloy reinforced copper-based composite material.
The application also provides the monotectic alloy prepared by the method for preparing the high-entropy alloy reinforced copper-based composite material, or the application of the monotectic alloy in preparing turbine blades, heat exchangers and as aerospace materials.
Compared with the prior art, the method, the product and the application for manufacturing the high-entropy alloy reinforced copper-based composite material have the following advantages:
The high-entropy alloy powder is prepared from iron powder, nickel powder, chromium powder, cobalt powder and manganese powder, the high-entropy alloy powder is mixed with the copper powder, so that the high-entropy alloy is dispersed in the copper powder, the monotectic alloy is prepared by adopting a laser additive manufacturing method, the monotectic alloy has the structure that high-entropy alloy particles generated by self-assembly through liquid phase separation are uniformly distributed in a copper-rich matrix, the monotectic alloy microstructure is obviously refined and relatively uniformly distributed, and the tensile strength and the elongation of the monotectic alloy are effectively improved.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
In the description of the present invention, unless otherwise defined, terms of art and words of art which have not been specifically described have the same meanings as commonly understood by those skilled in the art, and are common general knowledge to those skilled in the art, and methods which have not been specifically described are conventional methods which are well known to those skilled in the art. The term "plurality" in the present invention means at least two, for example, two, three, etc., unless specifically defined otherwise.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the desired properties sought to be obtained by the teachings disclosed herein. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4,5, and the like.
In the invention, the technical characteristics described in an open mode comprise a closed technical scheme composed of the listed characteristics and also comprise an open technical scheme comprising the listed characteristics.
An embodiment of the present application provides a method of manufacturing a high entropy alloy reinforced copper-based composite material, comprising the steps of:
s1, mixing iron powder, nickel powder, chromium powder, cobalt powder and manganese powder, and then sequentially carrying out mechanical alloying treatment and drying treatment to obtain high-entropy alloy powder;
s2, mixing the high-entropy alloy powder with copper powder to obtain a precursor;
S3, manufacturing the precursor into the monotectic alloy by adopting a laser additive manufacturing method.
The application can lead the SFE of the multicomponent alloy with Ni, fe, cr, co and Mn to be equivalent to or better than the low value of the traditional low SFE alloy through reasonable proportioning of Ni, fe, cr, co and Mn components. In low-fault energy (SFE) materials, the decomposition to form partial dislocations is more favored, the spacing between partial dislocations (the width of the faults) is greater, cross-slip and climb become more difficult, and thus the strength increases. However, low SFE materials are also more prone to twinning and deformation, increasing dislocation storage capability, strain hardening rate and plasticity. In order to improve the tensile strength and the elongation of the Cu-based composite material, a proper amount of Ni, fe, cr, co and Mn are added to manufacture high-entropy alloy powder, the high-entropy alloy powder is mixed with copper powder, so that the high-entropy alloy is dispersed in the copper powder, a laser material-increasing manufacturing method is adopted to manufacture the monotectic alloy, the monotectic alloy is structurally characterized in that liquid phase separation is adopted, high-entropy alloy particles generated by self-assembly are uniformly distributed in a copper-rich matrix, and the laser material-increasing manufacturing is a rapid solidification process, so that the formed monotectic alloy microstructure is obviously refined and relatively uniform in distribution, the tensile strength of the monotectic alloy reaches 400-700 MPa, the elongation reaches 8% -12%, and the high-strength high-toughness cooperative enhancement and the structural function integrated design and manufacture are realized. The tensile strength of the pure copper cast by the traditional technology is about 303MPa, the elongation is about 20.8 percent, and the copper-based monotectic alloy prepared by the traditional technology is easy to segregate. Therefore, the monotectic alloy prepared by the preparation method provided by the application is obviously superior to the traditional technology.
In some embodiments, the chemical composition of the precursor comprises, in mass percent: 60 to 90 percent of Cu, 2 to 8 percent of Fe, 2 to 8 percent of Co, 2.6 to 10.4 percent of Cr, 1.4 to 8.4 percent of Ni and 2 to 8 percent of Mn.
It will be appreciated that the sum of the mass percentages of the chemical components of the precursor is 100%, such as the chemical components of the precursor including Cu 60wt%, fe 8wt%, co 8wt%, cr 10.4wt%, ni 8.4wt% and Mn 5.2wt%, or including Cu 90wt%, fe 2wt%, co 2wt%, cr 2.6wt%, ni 1.4wt% and Mn 2wt%, or including Cu 78wt%, fe 4wt%, co 6wt%, cr 3wt%, ni 5wt% and Mn 4wt%, or including Cu 73wt%, fe 3wt%, co 5wt%, cr 6wt%, ni 7wt% and Mn 6wt%, or including Cu 85wt%, fe 2wt%, co 2.5wt%, cr 5wt%, ni 2wt% and Mn 3.5wt%, etc. According to the application, by reasonably designing the proportion of Cu, fe, co, cr, ni and Mn in the precursor, the high-entropy alloy is dispersed in the copper powder, and the monotectic alloy is manufactured by adopting laser material increase, so that the monotectic alloy microstructure is obviously refined and relatively uniform in distribution, and the tensile strength and the elongation of the monotectic alloy are improved.
In some embodiments, the mass ratio of high entropy alloy powder to copper powder is (3:5): (5-7).
It will be appreciated that the mass ratio of high entropy alloy powder to copper powder may be 3: 5. 3: 6. 3: 7. 4: 5. 4: 6. 4: 7. 5: 5. 5:6 or 5:7, etc., the mass ratio of the high-entropy alloy powder to the copper powder can also be (3:5): (5-7) other ratio.
In some embodiments, the high entropy alloy powder includes one or more of Ni 14Fe20Cr26Co20Mn20 and equimolar ratio FeCoCrNiMn.
Ni 14Fe20Cr26Co20Mn20 refers to Ni: fe: cr: co: mn=14: 20:26:20: feCoCrNiMn, equimolar ratio, means that the molar ratio of Fe, co, cr, ni, mn is 1:1:1:1:1.
In some embodiments, the high entropy alloy powder has a particle size of 10 to 30 μm.
It is understood that the particle size of the high-entropy alloy powder may be any value between 10 and 30. Mu.m, for example, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm or 30 μm, etc.
In some embodiments, the high entropy alloy powder has a stacking fault energy of 3.0 to 25mJ/m 2.
The stacking fault energy of the high-entropy alloy powder may be 3.0mJ/m2、3.5mJ/m2、4.0mJ/m2、4.5mJ/m2、5.0mJ/m2、5.5mJ/m2、6.0mJ/m2、6.5mJ/m2、7.0mJ/m2、7.5mJ/m2、8.0mJ/m2、8.5mJ/m2、9.0mJ/m2、9.5mJ/m2、10.0mJ/m2、11.0mJ/m2、12.0mJ/m2、15.0mJ/m2、20.0mJ/m2 or 25.0mJ/m 2, and the stacking fault energy of the high-entropy alloy powder may be other values between 3.0 and 25mJ/m 2.
In some embodiments, the mechanical alloying treatment comprises a ball milling treatment.
In some embodiments, the ball milling time is less than or equal to 16 hours.
It is understood that the ball milling time may be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, or the like.
In some embodiments, the ball milling speed is 200 to 300 revolutions per minute.
It will be appreciated that the ball milling speed may be 200 rpm, 210 rpm, 220 rpm, 230 rpm, 240 rpm, 250 rpm, 260 rpm, 270 rpm, 280 rpm, 290 rpm, 300 rpm, etc.
In some embodiments, the ball milling media comprises ethanol.
In some embodiments, the ball milling atmosphere is an argon atmosphere or an air atmosphere.
In some embodiments, the diameter of the grinding balls is 6 to 10mm.
It will be appreciated that the diameter of the grinding balls may be 6mm, 7mm, 8mm, 9mm or 10mm, etc.
In some embodiments, the mass ratio of high entropy alloy powder to grinding ball is (15-20): (1-2).
It will be appreciated that the mass ratio of high entropy alloy powder to grinding balls may be 15: 1. 15: 2. 16: 1. 16: 2. 17: 1. 17: 2. 18: 1. 18: 2. 19: 1. 19: 2. 20:1 or 20:2, etc.
In some embodiments, step S3 comprises:
slicing a CAD model of the monotectic alloy part with the supporting structure in a layering manner, and generating a laser selective melting forming track according to slice contour information;
Vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200-300 ℃;
and according to the generated forming track, stacking the precursor layer by layer on the substrate into the three-dimensional solid monotectic alloy by adopting a laser selective melting method.
It will be appreciated that the substrate may be heated to any value between 200 and 300 ℃, for example 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, 225 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, or 300 ℃.
In some embodiments, the process parameters for fabricating the support structure include: the wavelength of the fiber laser is 1060nm, the laser power is 100-300W, the height of the supporting structure is 2-3 mm, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, and the lap joint rate is 45-60%.
It will be appreciated that the laser power may be, for example, 100W, 110W, 120W, 130W, 140W, 150W, 160W, 170W, 180W, 190W, 200W, 220W, 240W, 260W, 280W, 300W, etc. in the process parameters for fabricating the support structure; the support structure height may be, for example, 2mm, 2.1mm, 2.2mm, 2.3mm, 2.4mm, 2.5mm, 2.6mm, 2.7mm, 2.8mm, 2.9mm, or 3mm, etc.; the laser scanning speed can be 500mm/s、600mm/s、700mm/s、800mm/s、900mm/s、1000mm/s、1100mm/s、1200mm/s、1300mm/s、1400mm/s、1500mm/s、1600mm/s、1800mm/s、2000mm/s、2200mm/s、2400mm/s or 2500mm/s, and can also be any value between 500 and 2500 mm/s; the slice thickness may be any value between 50 and 60 μm, for example 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm or 60 μm; the overlap ratio may be 45%, 46%, 47%, 48%, 49%, 50%, 52%, 54%, 56%, 58%, 60%, or the like.
In some embodiments, the process parameters for making the monotectic alloy include: the laser power is 100-300W, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, the lap joint rate is 45-60%, the slice is formed by adopting a path mode that the laser scanning directions of two continuous layers are mutually perpendicular, and the slice is manufactured until the size reaches 150mm multiplied by 150mm or phi 150mm multiplied by 150mm monotectic alloy parts are manufactured.
It will be appreciated that the laser power may be any value between 100 and 300W in the process parameters for producing the monotectic alloy, for example, 100W, 110W, 120W, 130W, 140W, 150W, 160W, 170W, 180W, 190W, 200W, 220W, 240W, 260W, 280W or 300W; the laser scanning speed may be any value between 500 and 2500mm/s, for example 500mm/s、600mm/s、700mm/s、800mm/s、900mm/s、1000mm/s、1100mm/s、1200mm/s、1300mm/s、1400mm/s、1500mm/s、1600mm/s、1800mm/s、2000mm/s、2200mm/s、2400mm/s or 2500mm/s, and the slice thickness may be any value between 50 and 60 μm, for example 50 μm, 51 μm, 52 μm, 53 μm, 54 μm, 55 μm, 56 μm, 57 μm, 58 μm, 59 μm or 60 μm; the overlap ratio may be 45%, 46%, 47%, 48%, 49%, 50%, 52%, 54%, 56%, 58%, 60%, or the like.
The application also provides a monotectic alloy which is prepared by adopting the method for preparing the high-entropy alloy reinforced copper-based composite material.
The application also provides a monotectic alloy prepared by the method for preparing the high-entropy alloy reinforced copper-based composite material, or application of the monotectic alloy in preparing turbine blades, heat exchangers and aerospace materials.
The present application will be described in further detail with reference to specific examples. The experimental parameters not specified in the following specific examples are preferentially referred to the guidelines given in the present document, and may also be referred to the experimental manuals in the art or other experimental methods known in the art, or to the experimental conditions recommended by the manufacturer. It is understood that the instruments and materials used in the following examples are more specific and in other embodiments may not be so limited. The weights of the relevant components mentioned in the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, and thus, it is within the scope of the embodiments of the present application as long as the contents of the relevant components are scaled up or down according to the embodiments of the present application.
The monotectic alloys prepared in examples 1 to 3 were subjected to tensile strength test and elongation test by stretching using a universal tensile tester.
Example 1
In the embodiment, the substrate is A3 steel, and the high-performance Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=70%) monotectic alloy is manufactured on the surface of the A3 steel by adopting a laser additive manufacturing method, wherein the manufacturing method specifically comprises the following steps:
S1, according to 14:20:26:20: weighing nickel powder, iron powder, chromium powder, cobalt powder and manganese powder according to the molar ratio of 20, mixing the nickel powder, the iron powder, the chromium powder, the cobalt powder and the manganese powder, and sequentially carrying out mechanical alloying treatment and drying treatment to obtain Ni 14Fe20Cr26Co20Mn20 high-entropy alloy powder;
The technological parameters of mechanical alloying are as follows: the rotating speed of the high-energy ball mill is 240 revolutions per minute, the ball milling atmosphere is argon, and the mass ratio of the stainless steel grinding ball to the Ni 14Fe20Cr26Co20Mn20 high-entropy alloy powder is 15:1, ball milling for 60 hours by adopting a method of ball milling for 40 minutes and then suspending for 10 minutes, wherein the diameter of a stainless steel ball is 8mm, and the particle size of high-entropy alloy powder Ni 14Fe20Cr26Co20Mn20 after ball milling is 30 mu m;
S2, mixing copper powder with Ni 14Fe20Cr26Co20Mn20 according to a mass ratio of 7:3, mixing uniformly by adopting a ball mill to obtain a precursor;
S3, slicing the monotectic alloy part CAD model with the supporting structure in a layering manner, and generating a series of laser selective melting forming tracks according to slice contour information; vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200 ℃; according to the generated forming track, stacking the precursor on the A3 steel substrate layer by layer into Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=70%) monotectic alloy of a three-dimensional entity by adopting a laser selective melting method;
The process parameters for manufacturing the support structure are as follows: the wavelength of the fiber laser is 1060nm, the laser power P=200W, the height of the supporting structure is 2mm, the laser scanning speed is 500mm/s, the thickness of the layered slice is 50 μm, and the lap joint rate is 50%;
Technological parameters for manufacturing the monotectic alloy parts: the laser power P=200W, the laser scanning speed is 2500mm/s, the layering slice thickness is 50 mu m, the lap joint rate is 50%, the slice is formed by adopting a path mode that the laser scanning directions between two continuous layers are mutually perpendicular, until the manufacturing of the monotectic alloy part with the size of 150mm multiplied by 150mm or phi 150mm multiplied by 150mm is completed.
The performance of Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=70%) monotectic alloy detection is: the tensile strength is 700MPa, the elongation is 12%, the high-entropy alloy particles generated by liquid phase separation and self-assembly are uniformly distributed in the copper-rich matrix, the structure is compact, no air holes and cracks are generated, and metallurgical bonding is formed with the matrix A3 steel.
Example 2
In the embodiment, the substrate is A3 steel, and the high-performance Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=50%) monotectic alloy is manufactured on the surface of the A3 steel by adopting a laser additive manufacturing method, wherein the manufacturing method specifically comprises the following steps:
S1, according to 14:20:26:20: weighing nickel powder, iron powder, chromium powder, cobalt powder and manganese powder according to the molar ratio of 20, mixing the nickel powder, the iron powder, the chromium powder, the cobalt powder and the manganese powder, and sequentially carrying out mechanical alloying treatment and drying treatment to obtain Ni 14Fe20Cr26Co20Mn20 high-entropy alloy powder;
The mechanical alloying process parameters are as follows: the rotating speed of the high-energy ball mill is 240 revolutions per minute, the ball milling atmosphere is argon, and the mass ratio of the stainless steel ball to the Ni 14Fe20Cr26Co20Mn20 high-entropy alloy powder is 15:1, ball milling for 60 hours by adopting a method of ball milling for 40 minutes and then suspending for 10 minutes, wherein the particle size of the special copper-iron-based alloy powder after ball milling is 30 mu m;
S2, mixing copper powder with Ni 14Fe20Cr26Co20Mn20 according to a mass ratio of 5:5, mixing uniformly by adopting a ball mill to obtain a precursor;
S3, slicing the monotectic alloy part CAD model with the supporting structure in a layering manner, and generating a series of laser selective melting forming tracks according to slice contour information; vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200 ℃; according to the generated forming track, stacking the precursor on the A3 steel substrate layer by layer into Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=50%) monotectic alloy of a three-dimensional entity by adopting a laser selective melting method;
The process parameters for manufacturing the support structure are as follows: the wavelength of the fiber laser is 1060nm, the laser power P=200W, the height of the supporting structure is 2mm, the laser scanning speed is 500mm/s, the thickness of the layered slice is 50 μm, and the lap joint rate is 50%;
Technological parameters for manufacturing the monotectic alloy parts: the laser power P=200W, the laser scanning speed is 2500mm/s, the layering slice thickness is 50 mu m, the lap joint rate is 50%, the slice is formed by adopting a path mode that the laser scanning directions between two continuous layers are mutually perpendicular, until the manufacturing of the monotectic alloy part with the size of 150mm multiplied by 150mm or phi 150mm multiplied by 150mm is completed.
The performance of Cu x(Ni14Fe20Cr26Co20Mn20)1-x (x=50%) monotectic alloy detection is: the tensile strength is 400MPa, the elongation is 8%, high-entropy alloy particles generated by liquid phase separation and self-assembly are uniformly distributed in a copper-rich matrix, a Fe-rich dendrite structure exists, the microstructure is compact, no air holes and cracks exist, and metallurgical bonding is formed with matrix A3 steel.
Example 3
In the embodiment, the substrate is A3 steel, and the high-performance Cu x(NiFeCrCoMn)1-x (x=70%) monotectic alloy is manufactured on the surface of the A3 steel by adopting a laser additive manufacturing method, wherein the manufacturing method specifically comprises the following steps:
S1, according to 1:1:1:1:1, mixing iron powder, cobalt powder, chromium powder, nickel powder and manganese powder, and then sequentially carrying out mechanical alloying treatment and drying treatment to obtain FeCoCrNiMn high-entropy alloy powder with an equimolar ratio, wherein the molar ratio of Fe, co, cr, ni, mn is 1:1:1:1:1, a step of;
The mechanical alloying process parameters are as follows: the rotating speed of the high-energy ball mill is 240 revolutions per minute, the ball milling atmosphere is argon, and the mass ratio of the stainless steel ball to FeCoCrNiMn high-entropy alloy powder with the equimolar ratio is 15:1, ball milling for 60 hours by adopting a method of ball milling for 40 minutes and then suspending for 10 minutes, wherein the particle size of the special copper-iron-based alloy powder after ball milling is 30 mu m;
s2, mixing Cu powder with FeCoCrNiMn in an equimolar ratio according to a mass ratio of 7:3, mixing uniformly by adopting a ball mill to obtain a precursor;
S3, slicing the monotectic alloy part CAD model with the supporting structure in a layering manner, and generating a series of laser selective melting forming tracks according to slice contour information; vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200 ℃; according to the generated forming track, stacking the precursor on the A3 steel substrate layer by layer into Cu x(NiFeCrCoMn)1-x (x=70%) monotectic alloy of a three-dimensional entity by adopting a laser selective melting method;
The process parameters for manufacturing the support structure are as follows: the wavelength of the fiber laser is 1060nm, the laser power P=200W, the height of the supporting structure is 2mm, the laser scanning speed is 500mm/s, the thickness of the layered slice is 50 μm, and the lap joint rate is 50%;
Technological parameters for manufacturing the monotectic alloy parts: the laser power P=200W, the laser scanning speed is 2500mm/s, the layering slice thickness is 50 mu m, the lap joint rate is 50%, the slice is formed by adopting a path mode that the laser scanning directions between two continuous layers are mutually perpendicular, until the manufacturing of the monotectic alloy part with the size of 150mm multiplied by 150mm or phi 150mm multiplied by 150mm is completed.
The performance of Cu x(NiFeCrCoMn)1-x (x=70%) monotectic alloy detection is: the tensile strength is 450MPa, the elongation is 9%, high-entropy alloy particles generated by liquid phase separation and self-assembly are uniformly distributed in a copper-rich matrix, a Fe-rich dendrite structure exists, the microstructure is compact, no air holes and cracks exist, and metallurgical bonding is formed with matrix A3 steel.
The tensile strength of the pure copper cast by the traditional method is about 303MPa, and the elongation is about 20.8%. The tensile strength of the copper-based monotectic alloy prepared in the embodiments 1-3 provided by the application reaches 400-700 MPa, the elongation reaches 8% -12%, and the high-entropy alloy particles can be uniformly distributed in a copper-rich matrix, have a Fe-rich dendrite structure, have a compact microstructure, and have no pores and cracks. Therefore, the manufacturing method of the application can improve the tensile strength and the elongation of the copper-based monotectic alloy, and ensure the uniformity of the distribution of the high-entropy alloy in the copper-rich matrix without segregation.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims (10)

1. A method of making a high entropy alloy reinforced copper matrix composite comprising the steps of:
S1, mixing iron powder, nickel powder, chromium powder, cobalt powder and manganese powder, and then sequentially carrying out mechanical alloying treatment and drying treatment to obtain high-entropy alloy powder; the stacking fault energy of the high-entropy alloy powder is 3.0-25 mJ/m 2;
S2, mixing the high-entropy alloy powder with copper powder to obtain a precursor; the chemical components of the precursor comprise the following components in percentage by mass: 60-90 wt% of Cu, 2-8 wt% of Fe, 2-8 wt% of Co, 2.6-10.4 wt% of Cr, 1.4-8.4 wt% of Ni and 2-8 wt% of Mn;
S3, manufacturing the precursor into a monotectic alloy by adopting a laser additive manufacturing method;
The step S3 comprises the following steps:
slicing a CAD model of the monotectic alloy part with the supporting structure in a layering manner, and generating a laser selective melting forming track according to slice contour information;
Vacuumizing a laser selective melting working chamber, and heating a substrate with the surface subjected to rust removal and sand blasting to 200-300 ℃;
according to the generated forming track, stacking the precursor layer by layer on the base material into a three-dimensional entity monotectic alloy by adopting a laser selective melting method;
The process parameters for manufacturing the support structure include: the wavelength of the fiber laser is 1060nm, the laser power is 100-300W, the height of the supporting structure is 2-3 mm, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, and the lap joint rate is 45-60%;
The technological parameters for manufacturing the monotectic alloy comprise: the laser power is 100-300W, the laser scanning speed is 500-2500 mm/s, the layering slice thickness is 50-60 mu m, the lap joint rate is 45-60%, and the slice is formed by adopting a path mode that the laser scanning directions of two continuous layers are mutually perpendicular until the manufacturing of the monotectic alloy part with the size of 150mm multiplied by 150mm or phi 150mm multiplied by 150mm is completed.
2. The method of manufacturing a high entropy alloy strengthened copper-based composite according to claim 1, wherein the chemical composition of the precursor comprises, in mass percent: cu 78wt%, fe 4wt%, co 6wt%, cr 3wt%, ni 5wt% and Mn 4wt%.
3. The method for manufacturing a high-entropy alloy reinforced copper-based composite material according to claim 1, wherein the mass ratio of the high-entropy alloy powder to the copper powder is (3-5): (5-7).
4. The method of making a high entropy alloy strengthened copper-based composite according to claim 1, wherein the high entropy alloy powder comprises one or more of Ni 14Fe20Cr26Co20Mn20 and equimolar ratio FeCoCrNiMn.
5. The method of manufacturing a high-entropy alloy-reinforced copper-based composite material according to claim 1, wherein the particle size of the high-entropy alloy powder is 10-30 μm.
6. The method of manufacturing a high entropy alloy strengthened copper-based composite according to claim 1, wherein the mechanical alloying treatment comprises a ball milling treatment, the process conditions of which are characterized by at least one of:
(1) The ball milling time is less than or equal to 16 hours;
(2) The ball milling rotating speed is 200-300 rpm;
(3) The ball milling medium comprises ethanol;
(4) The ball milling atmosphere comprises argon atmosphere or air atmosphere;
(5) The diameter of the grinding ball is 6-10 mm;
(6) The mass ratio of the high-entropy alloy powder to the grinding ball is (15-20): (1-2).
7. The method of manufacturing a high-entropy alloy-reinforced copper-based composite according to any one of claims 1 to 6, wherein the process parameters for manufacturing the monotectic alloy include: the laser power is 200W, the laser scanning speed is 2500mm/s, the thickness of the layered slice is 50 mu m, and the lap joint rate is 50%.
8. The method of manufacturing a high-entropy alloy reinforced copper-based composite according to any one of claims 1 to 6, wherein the process parameters for manufacturing the support structure include: the wavelength of the fiber laser is 1060nm, the laser power is 200W, the height of the supporting structure is 2mm, the laser scanning speed is 500mm/s, the thickness of the layered slice is 50 mu m, and the lap joint rate is 50%.
9. A monotectic alloy characterized by being prepared by the method for manufacturing the high-entropy alloy reinforced copper-based composite material according to any one of claims 1 to 8.
10. The use of a monotectic alloy produced by the method for producing a high-entropy alloy-reinforced copper-based composite material according to any one of claims 1 to 8 or the monotectic alloy according to claim 9 for producing turbine blades, heat exchangers and as an aerospace material.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108103381A (en) * 2018-01-25 2018-06-01 华南理工大学 A kind of high-strength F eCoNiCrMn high-entropy alloys and preparation method thereof

Family Cites Families (9)

* Cited by examiner, † Cited by third party
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JP6388277B2 (en) * 2014-07-25 2018-09-12 日立金属株式会社 Method for manufacturing alloy structure
CN107900335A (en) * 2017-11-21 2018-04-13 大连交通大学 A kind of laser 3D printing method of high-entropy alloy
CN112296335B (en) * 2019-07-23 2022-06-07 暨南大学 Method for melting and forming block nanometer twin crystal copper-based composite material by selective laser
US11820070B2 (en) * 2019-11-14 2023-11-21 Rolls-Royce Corporation Fused filament fabrication of high entropy alloys
KR102462801B1 (en) * 2020-11-24 2022-11-04 충남대학교산학협력단 High Entropy Alloy Phase Filament Reinforced Copper-Based High Entropy Alloy And Method for Manufacturing The Same
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CN113385689A (en) * 2021-06-03 2021-09-14 广东工业大学 High-entropy alloy and preparation method and application thereof
CN114855055B (en) * 2022-05-31 2022-11-15 广东工业大学 Low-crack-sensitivity high-entropy alloy powder material and preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108103381A (en) * 2018-01-25 2018-06-01 华南理工大学 A kind of high-strength F eCoNiCrMn high-entropy alloys and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
高熵合金增强铜基复合材料的制备及性能研究;杨博;中国优秀硕士学位论文全文数据库工程科技Ⅰ辑(第2020 年 第08期期);第B020-95页 *

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