CN116536565A - Copper-containing eutectic high-entropy alloy and preparation method and application thereof - Google Patents
Copper-containing eutectic high-entropy alloy and preparation method and application thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 171
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 165
- 239000010949 copper Substances 0.000 title claims abstract description 89
- 230000005496 eutectics Effects 0.000 title claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims description 24
- 238000003723 Smelting Methods 0.000 claims description 21
- 238000005266 casting Methods 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 229910018182 Al—Cu Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 3
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 3
- 239000010962 carbon steel Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract description 6
- 229910001431 copper ion Inorganic materials 0.000 abstract description 6
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000011780 sodium chloride Substances 0.000 abstract description 3
- 238000002791 soaking Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 238000005260 corrosion Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000007769 metal material Substances 0.000 description 7
- 239000006104 solid solution Substances 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006023 eutectic alloy Substances 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
- C22C30/02—Alloys containing less than 50% by weight of each constituent containing copper
-
- 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
- C22C1/02—Making non-ferrous alloys by melting
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- Chemical & Material Sciences (AREA)
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- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a copper-containing eutectic high-entropy alloy, a preparation method and application thereof, wherein the chemical formula of the material of the high-entropy alloy is as follows: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 29.ltoreq.a.ltoreq.50at%, 10.ltoreq.b.ltoreq.18at%, 10.ltoreq.c.ltoreq.18at%, 10.ltoreq.d.ltoreq.18at%, 17.ltoreq.e.20at%, 2.ltoreq.f.ltoreq.10at%, and a+b+c+d+e+f=100, the high-entropy alloy has a eutectic structure, and the eutectic high-entropy alloy consists of a face-centered cubic phase and a body-centered cubic phase, wherein the face-centered cubic phase provides plasticity, the body-centered cubic phase provides strength, so that the alloy maintains good plasticity while achieving high strength, and meanwhile, the alloy has copper ion precipitation capability in a 3.5wt.% NaCl solution soaking process due to the addition of copper elements.
Description
[ field of technology ]
The invention relates to the technical field of metal materials, in particular to a copper-containing eutectic high-entropy alloy, a preparation method and application thereof.
[ background Art ]
With the rapid development of the fields of aviation, aerospace, ships and the like, the demand for high-performance metal materials is more and more urgent. Conventional metallic materials tend to be based on a single element as a principal element, and performance development has tended to be a bottleneck. In recent years, high-entropy alloys have been widely focused in the field of material research due to their excellent mechanical properties and special functional properties. Despite its composition of various components, a simple single-phase solid solution structure is maintained in the as-cast state. Such as a single-phase face-centered cubic solid solution structure, a single-phase body-centered cubic solid solution structure, and the like. In general, high-entropy alloy with single-phase face-centered cubic solid solution structure shows good plasticity but lower strength; and the high-entropy alloy with the single-phase body-centered cubic solid solution structure has high strength but poor plasticity. In addition, the high-entropy alloy has the problems of poor casting fluidity and serious component segregation, and the engineering application of the high-entropy alloy is seriously restricted from developing.
In 2014, the prior art firstly proposes the concept of eutectic high-entropy alloy, designs and prepares the AlCoCrFeNi2.1 eutectic high-entropy alloy with good casting performance, the alloy consists of FCC solid solution and L12 two phases, the two phases are distributed in a lamellar mode, and the alloy has good comprehensive mechanical property and casting performance and good engineering application prospect. The eutectic high-entropy alloy has good casting performance and higher strength, so that the eutectic high-entropy alloy has great application potential when being used as a large structural member material in the field of marine engineering such as ship propellers and the like. However, metallic materials in service in marine environments where the rate of microbial corrosion is 1-2 orders of magnitude greater than that of non-biological corrosion must also be considered as an important failure mode of microbial corrosion. In seawater, the copper alloy can slowly release copper ions with certain toxicity, so that marine organisms attached to the surface of a component are eliminated, and microbial corrosion is reduced or even stopped, which is one of the most important reasons that the copper alloy can be used as a metal material with a marine structure. In order to improve the marine biofouling resistance, adding copper element into the structural metal material is the most important material design method. However, there is no research effort on copper-containing eutectic high-entropy alloys.
Therefore, in order to advance the application of eutectic high-entropy alloy in the field of ocean engineering, it is necessary to research a copper-containing eutectic high-entropy alloy, a preparation method and application thereof to solve or alleviate one or more of the above-mentioned problems.
[ invention ]
In view of the above, the invention provides a copper-containing eutectic high-entropy alloy and a preparation method and application thereof, and aims at solving the problem that the prior eutectic high-entropy alloy does not contain copper elements with sterilization function, and provides a copper-containing eutectic high-entropy alloy and a preparation method and application thereof through careful component optimization design.
In one aspect, the invention provides a eutectic high-entropy alloy containing copper, wherein the high-entropy alloy is a Ni-Fe-Co-Cr-Al-Cu eutectic high-entropy alloy containing copper, and the chemical formula of the material of the high-entropy alloy is as follows: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 29.ltoreq.a.ltoreq.50at%, 10.ltoreq.b.ltoreq.18at%, 10.ltoreq.c.ltoreq.18at%, 10.ltoreq.d.ltoreq.18at%, 17.ltoreq.e.ltoreq.20at%, 2.ltoreq.f.ltoreq.10at%, and a+b+c+d+e+f=100, the high-entropy alloy having a eutectic structure.
In aspects and any one of the possible implementations described above, there is further provided an implementation, the material of the high-entropy alloy has a chemical formula: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 38.ltoreq.a.ltoreq.48 at.%, 10.ltoreq.b.ltoreq.15 at.%, 10.ltoreq.c.ltoreq.15 at.%, 10.ltoreq.d.ltoreq.15 at.%, 18.5.ltoreq.e.ltoreq.19.5 at.%, 3.ltoreq.f.ltoreq.8 at.%, and a+b+c+d+e+f=100.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, when a=48, b=10, c=10, d=10, e=19, f=3, the eutectic high-entropy alloy chemical formula is: ni (Ni) 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 The yield strength of the alloy is 710-750MPa, the tensile strength is 9800-1100MPa, and the elongation is 7-8%.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, when a=41.5, b=12, c=12, d=10, e=18.5, f=6, the eutectic high-entropy alloy chemical formula is: ni (Ni) 41.5 Fe 12 Co 12 Cr 10 Al 18.5 Cu 6 The yield strength of the alloy is 680-720MPa, the tensile strength is 970-1050MPa, and the elongation is 8-9.5%.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, when a=30, b=15, c=15, d=15, e=19, f=6, the eutectic high-entropy alloy chemical formula is: ni (Ni) 30 Fe 15 Co 15 Cr 15 Al 19 Cu 6 The yield strength of the alloy is 550-650MPa, the tensile strength is 800-950MPa, and the elongation is 3.5-5%.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, when a=45, b=10, c=10, d=10, e=19, f=6, the eutectic high-entropy alloy chemical formula is: ni (Ni) 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 The yield strength of the alloy is 740-810MPa, the tensile strength is 1050-1200MPa, and the elongation is 8-11%.
In the aspect and any possible implementation manner described above, there is further provided an implementation manner, when a=43, b=10, c=10, d=10, e=19, f=8, the eutectic high-entropy alloy chemical formula is: ni (Ni) 43 Fe 10 Co 10 Cr 10 Al 19 Cu 8 The yield strength of the alloy is 600-720MPa, the tensile strength is 760-880MPa, and the elongation is 3.5-5%.
In the aspect and any possible implementation manner described above, there is further provided a method for preparing a eutectic high-entropy alloy containing copper element, for preparing the high-entropy alloy, where the preparation method specifically includes the following steps:
s1) batching: removing oxide skin on the surfaces of elements of the metal raw materials of Ni, fe, co, cr, al and Cu by using a mechanical grinding method, then placing the metal raw materials in different containers, adding alcohol solution, ultrasonically cleaning, taking out, drying the alcohol to obtain six raw materials after ultrasonic treatment, accurately weighing the six raw materials according to the components of the eutectic high-entropy alloy, and obtaining Ni, co, fe, cr, al, cu metal raw materials meeting the proportioning quality;
s2) alloy smelting: the steps are as followsS1) placing the metal raw materials meeting the proportioning quality into smelting equipment, and vacuumizing to 1X 10 -2 Charging argon to 0.05MPa below Pa, and switching on a power supply to perform alloy smelting for times not less than 4 times;
s3) alloy casting: and S2) after the repeated alloy smelting, casting or suction casting is carried out by using a crucible or a water-cooling copper mold, so as to obtain the copper-containing eutectic high-entropy alloy part with preset shape and size, wherein the copper-containing eutectic high-entropy alloy part is an alloy cast ingot with uniform components, and the crucible is a graphite, carbon steel and/or oxide crucible.
In aspects and any one of the possible implementations described above, there is further provided an implementation in which the high-entropy alloy has a eutectic structure with a density of 7.3-7.5g/cm 3 The tensile yield strength is 600-780MPa, the tensile strength is 800-1125MPa, and the elongation after fracture is 4-9.5%.
In the aspects and any possible implementation manner, there is further provided an implementation manner, and application of the eutectic high-entropy alloy containing copper element, wherein the eutectic high-entropy alloy containing copper is applicable to the field of ocean engineering.
Compared with the prior art, the invention can obtain the following technical effects:
(1) Compared with the existing eutectic high-entropy alloy, the alloy disclosed by the invention is added with 2% -10% of Cu element, and the antibacterial and biofouling resistance of the existing eutectic high-entropy alloy is provided.
(2) Compared with the existing high-entropy alloy, after the Cu element with the biofouling resistance function is added, the alloy still maintains the eutectic structure, so that the excellent casting performance of the eutectic alloy can be maintained.
(3) Compared with the existing copper-containing high-entropy alloy, the high-entropy alloy has excellent tensile strength and plasticity.
Of course, it is not necessary for any of the products embodying the invention to achieve all of the technical effects described above at the same time.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM back-scattered photograph of example 1 of the invention;
FIG. 2 is an SEM back-scattered photograph of example 2 of the invention;
FIG. 3 is an SEM back-scattered photograph of example 3 of the invention;
FIG. 4 is an SEM back-scattered photograph of example 4 of the invention;
FIG. 5 is an SEM back-scattered photograph of example 5 of the invention;
FIG. 6 is an engineering stress-strain curve for examples 1-5 of the present invention;
FIG. 7 is a copper ion precipitation curve of example 4 of the present invention;
FIG. 8 is a Tafel plot of example 4 of the present invention.
[ detailed description ] of the invention
For a better understanding of the technical solution of the present invention, the following detailed description of the embodiments of the present invention refers to the accompanying drawings.
It should be understood that the described embodiments are merely some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The terminology used in the embodiments of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used in this application and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
The invention provides a eutectic high-entropy alloy containing copper, which is Ni-Fe-Co-Cr-Al-Cu copper-containing eutectic high-entropy alloy, and the chemical formula of the material of the high-entropy alloy is as follows: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 29.ltoreq.a.ltoreq.50at%, 10.ltoreq.b.ltoreq.18at%, 10.ltoreq.c.ltoreq.18at%, 10.ltoreq.d.ltoreq.18at%, 17.ltoreq.e.ltoreq.20at%, 2.ltoreq.f.ltoreq.10at%, and a+b+c+d+e+f=100, the high-entropy alloy having a eutectic structure.
In a specific embodiment, the high entropy alloy material has the formula: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 38.ltoreq.a.ltoreq.48 at.%, 10.ltoreq.b.ltoreq.15 at.%, 10.ltoreq.c.ltoreq.15 at.%, 10.ltoreq.d.ltoreq.15 at.%, 18.5.ltoreq.e.ltoreq.19.5 at.%, 3.ltoreq.f.ltoreq.8 at.%, and a+b+c+d+e+f=100.
In one specific embodiment, when a=48, b=10, c=10, d=10, e=19, f=3, the eutectic high entropy alloy chemical formula is: ni (Ni) 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 The yield strength of the alloy is 710-750MPa, the tensile strength is 9800-1100MPa, and the elongation is 7-8%.
In one specific embodiment, when a=41.5, b=12, c=12, d=10, e=18.5, f=6, the eutectic high-entropy alloy chemical formula is: ni (Ni) 41.5 Fe 12 Co 12 Cr 10 Al 18.5 Cu 6 The yield strength of the alloy is 680-720MPa, the tensile strength is 970-1050MPa, and the elongation is 8-9.5%.
In one specific embodiment, when a=30, b=15, c=15, d=15, e=19, f=6, the eutectic high entropy alloy chemical formula is: ni (Ni) 30 Fe 15 Co 15 Cr 15 Al 19 Cu 6 The yield strength of the alloy is 550-650MPa, the tensile strength is 800-950MPa, and the elongation is 3.5-5%.
In one specific embodiment, when a=45, b=10, c=10, d=10, e=19, f=6, the eutectic high entropy alloy chemical formula is: ni (Ni) 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 The yield strength of the alloy is 740-810MPa, the tensile strength is 1050-1200MPa, and the elongation is 8-11%.
In one specific embodiment, when a=43, b=10, c=10, d=10, e=19, f=8, the eutectic high entropy alloyThe chemical formula is: ni (Ni) 43 Fe 10 Co 10 Cr 10 Al 19 Cu 8 The yield strength of the alloy is 600-720MPa, the tensile strength is 760-880MPa, and the elongation is 3.5-5%.
The invention also provides a preparation method of the eutectic high-entropy alloy containing copper element, which is used for preparing the high-entropy alloy, and specifically comprises the following steps:
s1) batching: removing oxide skin on the surfaces of elements of the metal raw materials of Ni, fe, co, cr, al and Cu by using a mechanical grinding method, then placing the metal raw materials in different containers, adding alcohol solution, ultrasonically cleaning, taking out, drying the alcohol to obtain six raw materials after ultrasonic treatment, accurately weighing the six raw materials according to the components of the eutectic high-entropy alloy, and obtaining Ni, co, fe, cr, al, cu metal raw materials meeting the proportioning quality;
s2) alloy smelting: putting the metal raw materials meeting the proportioning quality, which are prepared in the step S1), into smelting equipment, and vacuumizing to 1 multiplied by 10 -2 Charging argon to 0.05MPa below Pa, and switching on a power supply to perform alloy smelting for times not less than 4 times;
s3) alloy casting: and S2) after the repeated alloy smelting, casting or suction casting is carried out by using a crucible or a water-cooling copper mold, so as to obtain the copper-containing eutectic high-entropy alloy part with preset shape and size, wherein the copper-containing eutectic high-entropy alloy part is an alloy cast ingot with uniform components, and the crucible is a graphite, carbon steel and/or oxide crucible.
The high-entropy alloy has eutectic structure and density of 7.3-7.5g/cm 3 The tensile yield strength is 600-780MPa, the tensile strength is 800-1125MPa, and the elongation after fracture is 4-9.5%. The copper-containing eutectic high-entropy alloy can be applied to the field of ocean engineering
Example 1
A copper-containing eutectic high-entropy alloy material, wherein the chemical components of the high-entropy alloy are designed to be Ni according to the molar ratio 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 。
1) And (3) batching: removing oxide skin on the surface of the element from the Ni, fe, co, cr, al, cu metal raw material by using a mechanical grinding method, then placing the metal raw material in different containers, adding alcohol solution, ultrasonically cleaning, taking out, and drying alcohol to obtain six raw materials after ultrasonic treatment. And precisely weighing the components of the eutectic high-entropy alloy to obtain Ni, co, fe, cr, al, cu metal raw materials meeting the proportioning quality.
2) Alloy smelting: placing the metal raw material prepared in the step 1) into smelting equipment such as a vacuum intermediate frequency induction smelting furnace, a non-consumable vacuum arc furnace, a vacuum suspension induction smelting furnace and the like, and vacuumizing to 5 multiplied by 10 -3 And (3) filling industrial pure argon to 0.05MPa below Pa, and turning on a power supply to perform alloy smelting. Before smelting the alloy, smelting the Ti ingot to absorb residual oxygen in the furnace, and smelting the alloy raw material. In order to ensure that the components of the master alloy ingot are uniform, the alloy ingot is turned over by a turning shovel to be smelted again after each smelting, and each alloy ingot is repeatedly smelted for at least more than 4 times, so that the alloy ingot with uniform components is obtained.
3) And (3) alloy casting: vacuum melting, and suction casting into 10×10×50mm with water-cooled copper mold 3 Is a test bar of (a).
4) Microstructure characterization: ni was measured using a Zeiss Supra55 Scanning Electron Microscope (SEM) 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 The alloy morphology and microstructure were characterized and the result is shown in figure 1, which shows a typical dense lamellar eutectic structure.
5) Tensile property test: ni was tested using a CMT4105 Universal tensile tester 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 The alloy is subjected to room temperature tensile property test, and the result is shown in figure 6, wherein the yield strength of the alloy is 735MPa, the ultimate tensile strength is 1050MPa, and the elongation after break is 7.67% under engineering stress-strain conditions.
Example 2
A copper-containing eutectic high-entropy alloy material, wherein the chemical components of the high-entropy alloy are designed to be Ni according to the molar ratio 41.5 Fe 12 Co 12 Cr 10 Al 18.5 Cu 6 . The preparation method and the test method are the same as in example 1.
1) Microstructure characterization results: SEM backscattering photographs are shown in fig. 2, with typical lamellar eutectic structures.
2) The tensile property test result is shown in figure 6, the yield strength of the alloy measured under the engineering stress-strain condition is 704MPa, the ultimate tensile strength is 1017MPa, and the elongation after break is 8.80%.
Example 3
A copper-containing eutectic high-entropy alloy material, wherein the chemical components of the high-entropy alloy are designed to be Ni according to the molar ratio 30 Fe 15 Co 15 Cr 15 Al 19 Cu 6 . The preparation method, the structure and the tensile property test method are the same as those of example 1.
1) Microstructure characterization results: SEM backscattering photographs are shown in fig. 3, with typical lamellar eutectic structures.
2) Tensile property test: as a result, as shown in FIG. 6, the alloy had a yield strength of 602MPa, an ultimate tensile strength of 838MPa, and a post-fracture elongation of 5.60% measured under engineering stress-strain conditions.
3) Density testing: ni was measured by drainage 30 Fe 15 Co 15 Cr 15 Al 19 Cu 6 Alloy density of 7.31g/cm 3 。
Example 4
A copper-containing eutectic high-entropy alloy material, wherein the chemical components of the high-entropy alloy are designed to be Ni according to the molar ratio 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 . The preparation method, the structure and the tensile property test method are the same as those of example 1.
1) Microstructure characterization: SEM backscattering photographs are shown in fig. 3, with typical lamellar eutectic structures.
2) Tensile property test: as a result, as shown in FIG. 6, the alloy had a yield strength of 778MPa, an ultimate tensile strength of 1124MPa, and a post-fracture elongation of 9.47% measured under engineering stress-strain conditions.
3) Density testing: ni was measured by drainage 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 Alloy density of 7.39g/cm 3 。
4) Copper ion precipitation test: will be 8X 2mm in size 3 After immersing the alloy sheet samples in 3.5wt.% NaCl solution in a centrifuge tube for 6, 12, 24 and 48 hours, measuring the copper ion concentration in each solution by ICP-MS inductively coupled plasma mass spectrometer, and the result is shown in figure 7, it can be seen that the copper ion concentration reaches 0.04mg/cm after immersing for 48 hours 3 。
5) Electrochemical performance test: ni was tested in NaCl solution with a concentration of 3.5wt.% using a Chenhua CHI604E electrochemical workstation 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 Polarization curve of eutectic high entropy alloy, as shown in FIG. 8, self-etching current density is 1.94×10 -6 A/cm 2 The self-corrosion current density of the nickel-aluminum bronze alloy is 1.9x10 -5 A/cm 2 The high-entropy alloy of the invention is shown to have a lower corrosion rate.
Example 5
A copper-containing eutectic high-entropy alloy material, wherein the chemical components of the high-entropy alloy are designed to be Ni according to the molar ratio 43 Fe 10 Co 10 Cr 10 Al 19 Cu 8 . The preparation method, the structure and the tensile property test method are the same as those of example 1.
1) Microstructure characterization: SEM backscattering photographs are shown in fig. 5, with typical lamellar eutectic structures.
2) Tensile property test: as a result, as shown in FIG. 6, the alloy had a yield strength of 800MPa, an ultimate tensile strength of 674MPa, and a post-fracture elongation of 4.10% measured under engineering stress-strain conditions.
The eutectic high-entropy alloy has the characteristics of high strength, corrosion resistance and good casting performance, and the application background of marine environment is taken as an example, so that the eutectic high-entropy alloy has potential application scene (the propeller is mainly cast by copper alloy at present). In order to avoid biofouling corrosion caused by marine microorganisms during service, metallic materials used in marine environments often contain elemental copper. However, the enthalpy of mixing of copper and Fe, cr, co, ni and other elements commonly used in co-crystal high-entropy alloys is positive, so that the addition of copper is easy to destroy the eutectic structure. Thus, there has been no report so far on studies on copper-containing eutectic high-entropy alloys. The alloy system is characterized in that copper elements with marine fouling resistance are introduced under the premise of keeping eutectic structures and better tensile properties, the design of the copper-containing eutectic structures is realized by finely regulating and controlling the contents of Fe, cr, co and other elements with positive mixing enthalpy with Cu elements, and the influence of various elements on the microstructure, mechanical properties, corrosion resistance and biofouling resistance of the alloy is comprehensively considered during component design, so that the alloy system has the following advantages compared with the existing eutectic high-entropy alloy:
(1) Compared with the existing eutectic high-entropy alloy, the alloy disclosed by the invention is added with 2% -10% of Cu element, and the antibacterial and biofouling resistance of the existing eutectic high-entropy alloy is provided.
(2) Compared with the existing high-entropy alloy, after the Cu element with the biofouling resistance function is added, the alloy still maintains the eutectic structure, so that the excellent casting performance of the eutectic alloy can be maintained.
(3) Compared with the existing copper-containing high-entropy alloy, the high-entropy alloy has excellent tensile strength and plasticity.
The embodiment of the application provides a copper-containing eutectic high-entropy alloy, and a preparation method and application thereof. The above description of embodiments is only for aiding in understanding the method of the present application and its core ideas; meanwhile, as those skilled in the art will have modifications in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. As referred to throughout the specification and claims, the terms "comprising," including, "and" includes "are intended to be interpreted as" including/comprising, but not limited to. By "substantially" is meant that within an acceptable error range, a person skilled in the art is able to solve the technical problem within a certain error range, substantially achieving the technical effect. The description hereinafter sets forth the preferred embodiment for carrying out the present application, but is not intended to limit the scope of the present application in general, for the purpose of illustrating the general principles of the present application. The scope of the present application is defined by the appended claims.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a commodity or system comprising such elements.
It should be understood that the term "and/or" as used herein is merely one relationship describing the association of the associated objects, meaning that there may be three relationships, e.g., a and/or B, may represent: a exists alone, A and B exist together, and B exists alone. In addition, the character "/" herein generally indicates that the front and rear associated objects are an "or" relationship.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that this application is not limited to the forms disclosed herein, but is not to be construed as an exclusive use of other embodiments, and is capable of many other combinations, modifications and environments, and adaptations within the scope of the teachings described herein, through the foregoing teachings or through the knowledge or skills of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the present invention are intended to be within the scope of the appended claims.
Claims (10)
1. Eutectic high-entropy alloy containing copper elementThe method is characterized in that the high-entropy alloy is Ni-Fe-Co-Cr-Al-Cu copper-containing eutectic high-entropy alloy, and the chemical formula of the material of the high-entropy alloy is as follows: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 29.ltoreq.a.ltoreq.50at%, 10.ltoreq.b.ltoreq.18at%, 10.ltoreq.c.ltoreq.18at%, 10.ltoreq.d.ltoreq.18at%, 17.ltoreq.e.ltoreq.20at%, 2.ltoreq.f.ltoreq.10at%, and a+b+c+d+e+f=100, the high-entropy alloy having a eutectic structure.
2. The high-entropy alloy of claim 1, wherein the material of the high-entropy alloy has the formula: ni (Ni) a Fe b Co c Cr d Al e Cu f Wherein 38.ltoreq.a.ltoreq.48 at.%, 10.ltoreq.b.ltoreq.15 at.%, 10.ltoreq.c.ltoreq.15 at.%, 10.ltoreq.d.ltoreq.15 at.%, 18.5.ltoreq.e.ltoreq.19.5 at.%, 3.ltoreq.f.ltoreq.8 at.%, and a+b+c+d+e+f=100.
3. The high entropy alloy of claim 1, wherein when a = 48, b = 10, c = 10, d = 10, e = 19, f = 3, the eutectic high entropy alloy has the formula: ni (Ni) 48 Fe 10 Co 10 Cr 10 Al 19 Cu 3 The yield strength of the alloy is 710-750MPa, the tensile strength is 9800-1100MPa, and the elongation is 7-8%.
4. The high entropy alloy of claim 1, wherein when a = 41.5, b = 12, c = 12, d = 10, e = 18.5, f = 6, the eutectic high entropy alloy has the formula: ni (Ni) 41.5 Fe 12 Co 12 Cr 10 Al 18.5 Cu 6 The yield strength of the alloy is 680-720MPa, the tensile strength is 970-1050MPa, and the elongation is 8-9.5%.
5. The high entropy alloy of claim 1, wherein when a = 30, b = 15, c = 15, d = 15, e = 19, f = 6, the eutectic high entropy alloy has the formula: ni (Ni) 30 Fe 15 Co 15 Cr 15 Al 19 Cu 6 The yield strength of the alloy is 550-650MPa,the tensile strength is 800-950MPa, and the elongation is 3.5-5%.
6. The high entropy alloy of claim 1, wherein when a = 45, b = 10, c = 10, d = 10, e = 19, f = 6, the eutectic high entropy alloy has the formula: ni (Ni) 45 Fe 10 Co 10 Cr 10 Al 19 Cu 6 The yield strength of the alloy is 740-810MPa, the tensile strength is 1050-1200MPa, and the elongation is 8-11%.
7. The high entropy alloy of claim 1, wherein when a = 43, b = 10, c = 10, d = 10, e = 19, f = 8, the eutectic high entropy alloy has the formula: ni (Ni) 43 Fe 10 Co 10 Cr 10 Al 19 Cu 8 The yield strength of the alloy is 600-720MPa, the tensile strength is 760-880MPa, and the elongation is 3.5-5%.
8. A method for preparing a eutectic high entropy alloy containing copper elements, for preparing a high entropy alloy according to any of the preceding claims 1-7, characterized in that the preparation method comprises in particular the following steps:
s1) batching: removing oxide skin on the surfaces of elements of the metal raw materials of Ni, fe, co, cr, al and Cu by using a mechanical grinding method, then placing the metal raw materials in different containers, adding alcohol solution, ultrasonically cleaning, taking out, drying the alcohol to obtain six raw materials after ultrasonic treatment, accurately weighing the six raw materials according to the components of the eutectic high-entropy alloy, and obtaining Ni, co, fe, cr, al, cu metal raw materials meeting the proportioning quality;
s2) alloy smelting: putting the metal raw materials meeting the proportioning quality, which are prepared in the step S1), into smelting equipment, and vacuumizing to 1 multiplied by 10 -2 Charging argon to 0.05MPa below Pa, and switching on a power supply to perform alloy smelting for times not less than 4 times;
s3) alloy casting: and S2) after the repeated alloy smelting, casting or suction casting is carried out by using a crucible or a water-cooling copper mold, so as to obtain the copper-containing eutectic high-entropy alloy part with preset shape and size, wherein the copper-containing eutectic high-entropy alloy part is an alloy cast ingot with uniform components, and the crucible is a graphite, carbon steel and/or oxide crucible.
9. The method of claim 8, wherein the high-entropy alloy has a eutectic structure with a density of 7.3-7.5g/cm 3 The tensile yield strength is 600-780MPa, the tensile strength is 800-1125MPa, and the elongation after fracture is 4-9.5%.
10. Use of a eutectic high entropy alloy containing copper elements, characterized in that the copper-containing eutectic high entropy alloy according to any of the preceding claims 1-7 is used in the field of marine engineering.
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