CN114406185B - Composite material with high-entropy alloy coating on surface and preparation method thereof - Google Patents
Composite material with high-entropy alloy coating on surface and preparation method thereof Download PDFInfo
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- CN114406185B CN114406185B CN202210038561.5A CN202210038561A CN114406185B CN 114406185 B CN114406185 B CN 114406185B CN 202210038561 A CN202210038561 A CN 202210038561A CN 114406185 B CN114406185 B CN 114406185B
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- 238000000576 coating method Methods 0.000 title claims abstract description 165
- 239000011248 coating agent Substances 0.000 title claims abstract description 162
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 113
- 239000000956 alloy Substances 0.000 title claims abstract description 113
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 42
- 239000002184 metal Substances 0.000 claims abstract description 42
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000010959 steel Substances 0.000 claims abstract description 37
- 239000011159 matrix material Substances 0.000 claims abstract description 34
- 239000006260 foam Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010114 lost-foam casting Methods 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000011230 binding agent Substances 0.000 claims description 20
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical group [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 description 25
- 230000001070 adhesive effect Effects 0.000 description 25
- 239000002245 particle Substances 0.000 description 22
- 238000005266 casting Methods 0.000 description 15
- 238000002156 mixing Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000004372 laser cladding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007751 thermal spraying Methods 0.000 description 3
- 229910001018 Cast iron Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007712 rapid solidification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22C—FOUNDRY MOULDING
- B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D19/00—Casting in, on, or around objects which form part of the product
-
- 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
Abstract
The invention relates to a composite material with a high-entropy alloy coating on the surface and a preparation method thereof, belonging to the technical field of surface composite materials. The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps: coating the surface of the lost foam model with coating liquid, and drying to obtain a coated model; and then carrying out lost foam casting on the molten steel by adopting a coated model. The preparation method of the composite material with the high-entropy alloy coating on the surface has the advantages of simple process, short production period and low cost. When the molten steel is subjected to lost foam casting, metal powder on the surface of the lost foam model can perform metallurgical reaction with iron element in the molten steel, and a FeCoCrNi high-entropy alloy coating is formed on the surface of a matrix formed after the molten steel is cooled, so that good metallurgical bonding is realized between the coating and the matrix, and cracks are not easy to occur between the high-entropy alloy coating and the matrix.
Description
Technical Field
The invention relates to a composite material with a high-entropy alloy coating on the surface and a preparation method thereof, belonging to the technical field of surface composite materials.
Background
Conventional alloys generally consist of a metal element as a main element and a smaller amount of an alloying element. The purpose of adding the alloying elements is mainly to meet the requirements of the alloy for certain special properties. However, the structure and performance of the conventional alloy are limited to the main element, and thus, the basic properties of the main element set a ceiling for the performance improvement of the alloy, limited to the conventional design concept. The properties of the alloy may be improved by adding specific alloy elements. For example, high chromium cast iron is one of the common metallic wear resistant materials, the high wear resistance of which is mainly due to the presence of significant amounts of Cr in the matrix 7 C 3 Carbide. In order to further improve the wear resistance of the high-chromium cast iron, an alloy element such as Ti, ni, mo, V which is relatively expensive can be added, but this method tends to increase the cost. In order to reduce the cost, a wear-resistant alloy layer can be formed on the surface of steel by adopting various technologies, for example, a self-melting additive layer is formed by coating carbon-containing high-chromium alloy powder on the surface of steel by a self-melting additive technology, namely a casting infiltration method. Since the matrix of the self-fluxing additive layer is typically of lower hardness austenite or ferrite, a significant amount of carbon or chromium is often required in the alloy powder used to make the coating in order to increase the wear resistance of the self-fluxing additive layer. Thus, a large amount of carbide is formed in the prepared coating. These carbides cause a significant reduction in the toughness of the coating, resulting in a coating that is in wear conditionsThe lower part is easy to crack and fail.
Meanwhile, alloys having special properties, for example, high-entropy alloys, have also been developed. The high-entropy alloy has high entropy effect, can form a solid solution structure (without intermetallic compound) with simple and stable structure, has the phase number far lower than that predicted by a balance phase law, has good performance different from the traditional alloy, and can be prepared into various alloys with excellent performances such as high strength, high hardness, high wear resistance, high-temperature softening resistance and the like by selecting proper element components. Since a large amount of expensive elements such as cobalt are generally present in the high-entropy alloy, the price of the prepared high-entropy alloy block is high, and for some parts with high requirements on size, the size is changed due to abrasion, so that the whole part is invalid, and waste is caused.
Therefore, the high-entropy alloy coating can be prepared on the surface of some low-price alloys, and the cost and the resources can be reduced. The preparation method of the high-entropy alloy coating mainly comprises magnetron sputtering, laser cladding, thermal spraying, surfacing and the like. The magnetron sputtering technology has the advantages of slow substrate temperature rise, fast coating deposition and compact formed coating structure. The high-entropy alloy coating prepared by the magnetron sputtering method can be in an amorphous structure in a short time, but has the defects that only nano or micron-level films can be formed, the bonding strength of the coating and a matrix is not high, and the preparation process is complex. The laser cladding method has the characteristics of rapid melting and rapid solidification, the obtained coating and the matrix are metallurgically bonded, the bonding strength is high, the influence on the matrix material is small, but the defects of high equipment cost, easy crack generation of the coating and the like exist. The thermal spraying technology has the advantages of simple equipment, convenient operation process, low cost and the like, but also has the defects of low bonding strength of the coating and the matrix, uneven inside the coating and the like. The high-entropy alloy layer prepared by the build-up welding method is easy to crack with the matrix.
Thicker high-entropy alloy coatings can increase the service life of the workpiece to some extent, but the process has some problems when preparing high-entropy alloy coatings on steel-based surfaces. The coating prepared on the surface of the steel base by magnetron sputtering and thermal spraying is thinner. Although the laser cladding and surfacing technology can obtain a millimeter-sized high-entropy alloy coating, cracks are easy to generate between the high-entropy alloy coating and a substrate due to the fact that larger thermal stress occurs due to the fact that the surface of a workpiece is locally heated when the coating is prepared on the surface of a steel base.
Disclosure of Invention
The invention aims to provide a preparation method of a composite material with a high-entropy alloy coating on the surface, which is used for solving the problem that cracks are easy to generate between the high-entropy alloy coating and a matrix when the high-entropy alloy coating with larger thickness is prepared on the surface of a steel base at present.
It is another object of the present invention to provide a composite material having a high entropy alloy coating on the surface.
In order to achieve the above purpose, the preparation method of the composite material with the high-entropy alloy coating on the surface adopts the following technical scheme:
a preparation method of a composite material with a high-entropy alloy coating on the surface comprises the following steps:
1) Coating the surface of the lost foam model with the coating liquid, and drying to obtain a coated model; the coating liquid mainly comprises metal powder and a binder; the metal powder mainly comprises cobalt element, chromium element, nickel element and manganese element; the molar ratio of cobalt element to chromium element to nickel element to manganese element is (5-35): (5-35);
2) And then carrying out lost foam casting on the molten steel by adopting a coated model.
The preparation method of the composite material with the high-entropy alloy coating on the surface has the advantages of simple process, short production period and low cost. When the molten steel is subjected to lost foam casting, metal powder on the surface of the lost foam model can perform metallurgical reaction with iron element in the molten steel, and a FeCoCrNi high-entropy alloy coating is formed on the surface of a matrix formed after the molten steel is cooled, so that good metallurgical bonding is realized between the coating and the matrix, and cracks are not easy to occur between the high-entropy alloy coating and the matrix.
Further preferably, the molar ratio of cobalt element, chromium element, nickel element and manganese element is (20-26): (28-35): (24-27): (26-29).
Preferably, the metal powder is composed of cobalt powder, chromium powder, nickel powder and manganese powder.
Preferably, the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (20-25), the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (25-30), the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (24-26), and the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (24-26). Further preferably, the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (20-25): (25-30): (24.5-26): (24-25.5).
Preferably, the average particle size of the cobalt powder, chromium powder, nickel powder or manganese powder is 40-80 mesh. For example, the average particle size of the cobalt powder may be 40 mesh, 50 mesh, 60 mesh, 65 mesh, 70 mesh, or 80 mesh; the average particle size of the chromium powder may be 40 mesh, 50 mesh, 60 mesh, 65 mesh, 70 mesh or 80 mesh; the average particle size of the nickel powder may be 40 mesh, 50 mesh, 60 mesh, 65 mesh, 70 mesh or 80 mesh; the average particle size of the manganese powder may be 40 mesh, 50 mesh, 60 mesh, 65 mesh, 70 mesh or 80 mesh. Further preferably, the average particle size of the cobalt powder, chromium powder, nickel powder or manganese powder is 60 mesh.
In order to obtain a metal powder having a uniform composition, cobalt powder, chromium powder, nickel powder and manganese powder may be mixed by a ball mill, and preferably the metal powder has an average particle size of 40 to 80 mesh. For example, the average particle size of the metal powder may be 40 mesh, 50 mesh, 60 mesh, 65 mesh, 70 mesh, or 80 mesh. If the average granularity of the metal powder is larger than 80 meshes, gaps among the powder are too small, so that the infiltration of molten steel is not facilitated; if the average particle size of the metal powder is less than 40 mesh, the infiltrated molten steel is unfavorable to melt the metal powder. Therefore, compared with other processes, the preparation method of the composite material with the high-entropy alloy coating on the surface has lower requirements on the particle size and shape of powder and lower manufacturing cost.
Preferably, the coating thickness of the coating liquid on the surface of the lost foam model is 4-8 mm. When the coating thickness of the coating liquid on the surface of the lost foam mould is 4-8 mm, the obtained coating can be better combined with the matrix. If the coating thickness is too thin, a thicker high-entropy alloy coating cannot be formed on the surface of the substrate; if the coating thickness is too large, the adhesive in the coating liquid volatilizes rapidly at high temperature before the casting process due to the self gravity effect, so that the coating layer is easy to fall off.
Preferably, in the lost foam casting process, the temperature of molten steel casting is 1630-1680 ℃. The temperature of the molten steel is too high, and crystal grains in the matrix and the coating are larger; the molten steel is too low in temperature, which is unfavorable for melting metal powder.
Carbon in the molten steel can permeate into the coating, C atoms and strong carbide elements Cr are easy to form carbide in situ, and the mechanical property and the wear resistance of the coating can be improved. However, when the carbon content is too high, the toughness of the steel matrix is poor. Preferably, the mass fraction of carbon element in the molten steel is not more than 0.65%.
Further preferably, the mass fraction of the carbon element in the molten steel is 0.27-0.65%.
Preferably, the binder is an organic binder. Preferably, the organic binder is a phenolic resin and/or polyvinyl butyral. Phenolic resin and/or polyvinyl butyral are used as binders, so that the metal powder can be bonded better, and the metal powder can be cured after being dried and is adhered to the lost foam model better. After molten steel is poured, phenolic resin and/or polyvinyl butyral are easy to volatilize at high temperature and are not easy to remain.
Preferably, the mass ratio of the metal powder to the binder is (20-25): 1. When the mass ratio of the metal powder to the binder is in the above range, the effect of effectively binding and solidifying the metal powder is exhibited.
Preferably, the coating liquid further comprises a solvent. Preferably, the solvent is ethanol. Preferably, the mass ratio of the binder to the solvent is 1 (1.5-3).
The technical scheme adopted by the composite material with the high-entropy alloy coating on the surface is as follows:
a composite material with the surface containing the high-entropy alloy coating, which is prepared by the preparation method of the composite material with the surface containing the high-entropy alloy coating.
In the composite material with the high-entropy alloy coating on the surface, good metallurgical bonding is realized between the high-entropy alloy coating and the matrix, and cracks are not easy to generate between the high-entropy alloy coating and the matrix.
The preparation method can form the high-entropy alloy coating with the thickness of 6-12 mm on the surface of the metal matrix.
Drawings
FIG. 1 is an appearance picture of a metallographic specimen obtained by corroding a composite material with a high-entropy alloy coating on the surface and prepared in example 2 with a nitrate alcohol solution;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of the interface between the matrix of the metallographic specimen and the high-entropy alloy coating, which is obtained by corroding the composite material with the high-entropy alloy coating on the surface and prepared in example 2 by using a nitrate alcohol solution;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of a high-entropy alloy coating on the surface of a metallographic specimen obtained by corroding a composite material prepared in example 2 and having a high-entropy alloy coating on the surface thereof by a nitrate alcohol solution;
FIG. 4 is an XRD spectrum of a high entropy alloy coating on the surface of a composite material prepared in example 2 and having a high entropy alloy coating on the surface.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
1. The specific examples of the preparation method of the composite material with the high-entropy alloy coating on the surface of the composite material are as follows:
example 1
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average particle size of 40 meshes by using a ball mill to obtain metal powder with the average particle size of 40 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is 20:30:26:24.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 20:1:1.5; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 7mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring and molding 30 molten steel (matrix material) with the temperature of 1670 ℃, naturally cooling, and taking out a casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 10.7mm.
Example 2
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with average particle sizes of 60 meshes by using a ball mill to obtain metal powder with average particle sizes of 60 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the manganese powder to the nickel powder is 25:25:25:25.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 22:1:1.9; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 6mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring 45 steel liquid (matrix material) with the temperature of 1650 ℃ for molding, naturally cooling, and taking out a casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 9.1mm.
Example 3
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average particle size of 80 meshes by using a ball mill to obtain the metal powder with the average particle size of 80 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the manganese powder to the nickel powder is 23:27:26:24.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 23:1:2.1; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 5mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring and molding 60 steel liquid (matrix material) with the temperature of 1630 ℃, naturally cooling, and taking out the casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 7.4mm.
Example 4
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average particle size of 50 meshes by using a ball mill to obtain the metal powder with the average particle size of 50 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the manganese powder to the nickel powder is 24:26:24.5:25.5.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 24:1:2.5; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 4mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring and molding 50 molten steel (matrix material) with the temperature of 1640 ℃, naturally cooling, and taking out a casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 6.0mm.
Example 5
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with average particle sizes of 60 meshes by using a ball mill to obtain metal powder with average particle sizes of 60 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the manganese powder to the nickel powder is 22:26:26:24.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 25:1:3; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 8mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring 40 molten steel (matrix material) with the temperature of 1660 ℃, naturally cooling, and taking out the casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 12.0mm.
Example 6
The preparation method of the composite material with the high-entropy alloy coating on the surface comprises the following steps:
(1) And uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with average particle sizes of 65 meshes by using a ball mill to obtain metal powder with average particle sizes of 65 meshes. Wherein the mass ratio of the cobalt powder to the chromium powder to the manganese powder to the nickel powder is 23:27:25.5:24.5.
(2) And uniformly mixing the metal powder, the adhesive and the solvent to obtain the coating liquid. The mass ratio of the metal powder to the organic binder to the solvent is 21:1:2.3; the adhesive is an organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 5.5mm, and obtaining the coated model after the coating liquid is dried. And then embedding the coated model into dry sand for vibration molding, putting a pouring cup, finally pouring and molding 20 molten steel (matrix material) with the temperature of 1680 ℃, naturally cooling, and taking out a casting, wherein the obtained casting is the composite material with the high-entropy alloy coating on the surface, and the thickness of the high-entropy alloy coating on the surface of the composite material with the high-entropy alloy coating prepared in the embodiment is 8.3mm.
2. Specific examples of the composite material of the present invention having a high entropy alloy coating on the surface thereof are as follows:
the composite material with the high-entropy alloy coating on the surface of the embodiment is prepared by the preparation method of the composite material with the high-entropy alloy coating on the surface of any one of the embodiment 1 to the embodiment 6.
Experimental example 1
The composite materials prepared in examples 1 to 6, which had a high-entropy alloy coating on the surface, were used as test specimens, and dry frictional wear tests were conducted using an HSR-2M high-speed reciprocating frictional wear tester. The test conditions were as follows: the grinding parts are GCr15 steel balls, the rotating speed of the grinding parts is 600r/min, the loading load is 60N, and the abrasion time is 15min. After the dry frictional wear test is finished, the abrasion resistance of the test sample is evaluated by measuring and calculating the ratio of the mass of the test sample after the dry frictional wear test to the mass before the test, and the calculated ratios of the composite materials prepared in examples 1 to 6 and having the high-entropy alloy coating on the surface are A1, A2, A3, A4, A5 and A6 respectively. Then, dry frictional wear tests were conducted under the same test conditions as those described above, using the base materials of examples 1 to 6 as comparative samples, respectively. After the test is finished, the ratio of the mass of the base material after the dry friction and wear test to the mass before the test is measured and calculated, and the calculated ratios are respectively B1, B2, B3, B4, B5 and B6. The abrasion resistance of the matrix materials in examples 1 to 6 was set to 1, and the abrasion resistance of the composite materials prepared in examples 1 to 6, each of which had a high-entropy alloy coating on the surface, was evaluated with respect to the matrix materials by calculating the ratio of A1, A2, A3, A4, A5 and A6 to B1, B2, B3, B4, B5 and B6, respectively, and the experimental results are shown in Table 1.
Table 1 relative abrasion resistance of composites with high entropy alloy coatings on the surfaces prepared in examples 1-6
| Composite material | Relative wear resistance |
| Example 1 | 2.7 |
| Example 2 | 3.2 |
| Example 3 | 3.7 |
| Example 4 | 3.4 |
| Example 5 | 3.0 |
| Example 6 | 2.5 |
The results show that the abrasion resistance of the composite materials prepared in examples 1-6 and having the high-entropy alloy coating on the surface is 2.5-3.7 times that of the respective matrix materials, and the high-entropy alloy coating in the composite materials prepared in examples 1-6 and having the high-entropy alloy coating on the surface is well combined with the matrix during the test, and the corresponding cast-infiltration layer shows good abrasion resistance based on the existence of carbide and the high-entropy alloy matrix.
Experimental example 2
To examine whether cracks appear between the high-entropy alloy coating and the matrix material in the preparation process, the composite material prepared in example 2 and having the high-entropy alloy coating on the surface thereof was etched in a nitric acid alcohol solution (the volume fraction of nitric acid is 4%) at room temperature for 5 seconds, then washed with alcohol to obtain a metallographic specimen etched by the nitric acid alcohol solution, and then the metallographic specimen was subjected to visual observation and SEM characterization, respectively, and the results are shown in fig. 1, 2 and 3. As can be seen from fig. 1, in the composite material having the high-entropy alloy coating on the surface thereof prepared in example 2, no crack exists between the high-entropy alloy coating and the substrate, which indicates that the high-entropy alloy coating and the substrate are well bonded. As can be seen from fig. 2 and fig. 3, the high-entropy alloy coating is well bonded with the interface of the substrate, a metallurgically bonded transition layer is arranged at the interface, and a small amount of carbide is also arranged in the high-entropy alloy coating, so that the wear resistance of the coating is improved.
The high-entropy alloy coating of the composite surface prepared in example 2, which contained the high-entropy alloy coating on the surface, was characterized by XRD, and the results are shown in fig. 4. The results show that the XRD peaks of the high-entropy alloy coating are mainly characteristic peaks of the crystal structure of face-centered cubic lattice (fcc), and the coating on the surface of the composite material is the high-entropy alloy coating.
Claims (6)
1. The preparation method of the composite material with the high-entropy alloy coating on the surface is characterized by comprising the following steps of:
1) Coating the surface of the lost foam model with the coating liquid, and drying to obtain a coated model; the coating liquid mainly comprises metal powder and a binder; the metal powder consists of cobalt powder, chromium powder, nickel powder and manganese powder; the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (20-25), the mass ratio of the cobalt powder to the chromium powder to the nickel powder to the manganese powder is (25-30), the mass ratio of the cobalt powder to the chromium powder to the manganese powder is (24-26), and the average granularity of the metal powder is 40-80 meshes; the coating thickness of the coating liquid on the surface of the lost foam model is 4-8 mm;
2) Then adopting a coated model to perform lost foam casting on the molten steel; when the molten steel is subjected to lost foam casting, metal powder on the surface of the lost foam model and iron element in the molten steel are subjected to metallurgical reaction, and a FeCoCrNi high-entropy alloy coating is formed on the surface of a matrix formed after the molten steel is cooled.
2. The method for preparing a composite material with a high-entropy alloy coating on the surface according to claim 1, wherein the temperature of molten steel in the lost foam casting process is 1630-1680 ℃.
3. The method for preparing a composite material with a high-entropy alloy coating on the surface thereof according to claim 1, wherein the mass fraction of carbon element in the molten steel is not more than 0.65%.
4. The method for preparing a composite material with a high-entropy alloy coating on the surface according to claim 1, wherein the binder is an organic binder, and the organic binder is phenolic resin and/or polyvinyl butyral; the mass ratio of the metal powder to the binder is (20-25) 1.
5. The method for producing a composite material having a high-entropy alloy coating on a surface thereof according to claim 4, wherein the coating liquid further comprises a solvent; the solvent is ethanol; the mass ratio of the binder to the solvent is 1 (1.5-3).
6. A composite material having a high-entropy alloy coating on the surface, prepared by the method for preparing a composite material having a high-entropy alloy coating on the surface according to any one of claims 1 to 5.
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