CN114406185A - Composite material with surface containing high-entropy alloy coating and preparation method thereof - Google Patents
Composite material with surface containing high-entropy alloy coating and preparation method thereof Download PDFInfo
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- CN114406185A CN114406185A CN202210038561.5A CN202210038561A CN114406185A CN 114406185 A CN114406185 A CN 114406185A CN 202210038561 A CN202210038561 A CN 202210038561A CN 114406185 A CN114406185 A CN 114406185A
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- 238000000576 coating method Methods 0.000 title claims abstract description 177
- 239000011248 coating agent Substances 0.000 title claims abstract description 168
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 115
- 239000000956 alloy Substances 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 37
- 239000010959 steel Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000006260 foam Substances 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 238000010114 lost-foam casting Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 27
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000005266 casting Methods 0.000 claims description 12
- 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
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [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
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 description 31
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- 238000001755 magnetron sputter deposition Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
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- 238000005299 abrasion Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000004372 laser cladding Methods 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
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- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 238000005275 alloying Methods 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
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 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
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- 239000002699 waste material Substances 0.000 description 1
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- 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
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
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 surface containing the high-entropy alloy coating comprises the following steps: coating the coating liquid on the surface of the lost foam model, and drying to obtain a model with a coating; and then performing lost foam casting on the molten steel by adopting a coated model. The preparation method of the composite material with the surface containing the high-entropy alloy coating is simple in process, short in production period and low in cost. When the molten steel is subjected to lost foam casting, the metal powder on the surface of the lost foam model can perform metallurgical reaction with iron elements in the molten steel, a FeCoCrNi series high-entropy alloy coating is formed on the surface of a matrix formed after the molten steel is cooled in situ, the coating and the matrix have good metallurgical bonding, and cracks are not easily generated 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 small amount of alloying elements. The purpose of adding the alloy elements is mainly to meet the requirements of the alloy on certain special properties. However, the structure and performance of conventional alloys are limited by the primary elements, which, however, are essential attributes for providing a ceiling tile with improved performance. The properties of the alloy can be improved by adding specific alloy elements. For example, high chromium cast iron is one of the common metal wear-resistant materials, and its high wear resistance is mainly due to the baseThe bulk of the alloy contains a large amount of Cr7C3And (3) carbide. In order to further improve the wear resistance of the high-chromium cast iron, higher-price alloy elements such as Ti, Ni, Mo, V and the like can be added, but the method tends to increase the cost. In order to reduce the cost, a wear-resistant alloy layer can be formed on the surface of the steel by adopting various technologies, for example, a high-chromium cast iron self-melting additive layer is formed by coating carbon-containing high-chromium alloy powder on the surface of the steel by a self-melting additive technology, namely a cast-infiltration method. Since the matrix of the self-fluxing additive layer is usually austenite or ferrite with lower hardness, the alloy powder used for preparing the coating layer often needs to contain a large amount of carbon or chromium in order to improve the wear resistance of the self-fluxing additive layer. Thus, a large amount of carbides may be formed in the prepared coating. These carbides can cause a substantial reduction in the toughness of the coating, making the coating susceptible to cracking and failure under wear conditions.
Meanwhile, alloys having specific properties, for example, high-entropy alloys, have also been developed. The high-entropy alloy has a high-entropy effect, can form a solid solution structure (without intermetallic compounds) with simple and stable structure, has the phase number far lower than the phase number predicted by an equilibrium phase law, has good performance different from that of the traditional alloy due to the characteristics, can be prepared by selecting proper element components, and has excellent performances such as high strength, high hardness, high wear resistance, high temperature softening resistance and the like. Because of the large amount of expensive elements such as cobalt in the high-entropy alloy, the price of the obtained 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 fails, and waste is caused.
Therefore, the high-entropy alloy coating can be prepared on the surface of some alloys with lower price, and the cost and 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 temperature rise of the substrate, fast deposition of the coating and compact structure of the formed coating. The high-entropy alloy coating prepared by the magnetron sputtering method can present an amorphous structure in a short time, and has the defects that a nano or micron-level film can be formed, the bonding strength of the coating and a substrate 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 between the coating and the substrate, uneven coating inside and the like. The high-entropy alloy layer prepared by the surfacing method is easy to crack with a substrate.
The thicker high-entropy alloy coating can increase the service life of the workpiece to a certain extent, but the high-entropy alloy coating prepared on the surface of the steel substrate by adopting the process has some problems. The coatings prepared on the surface of the steel base by magnetron sputtering and thermal spraying are thin. Although millimeter-scale high-entropy alloy coatings can be obtained by laser cladding and surfacing technologies, cracks are easily generated between the high-entropy alloy coatings and the matrix due to the fact that large thermal stress is generated when the surfaces of workpieces are locally heated when the coatings are prepared on the surfaces of the steel substrates.
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 easily generated between the high-entropy alloy coating and a substrate when the high-entropy alloy coating with larger thickness is prepared on the surface of a steel substrate at present.
The invention also aims to provide a composite material with a high-entropy alloy coating on the surface.
In order to achieve the purpose, the preparation method of the composite material with the surface containing the high-entropy alloy coating adopts the technical scheme that:
a preparation method of a composite material with a high-entropy alloy coating on the surface comprises the following steps:
1) coating the coating liquid on the surface of the lost foam model, 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 the cobalt element, the chromium element, the nickel element and the manganese element is (5-35): 5-35: (5-35);
2) and then performing lost foam casting on the molten steel by adopting a coated model.
The preparation method of the composite material with the surface containing the high-entropy alloy coating is simple in process, short in production period and low in cost. When the molten steel is subjected to lost foam casting, the metal powder on the surface of the lost foam model can perform metallurgical reaction with iron elements in the molten steel, a FeCoCrNi series high-entropy alloy coating is formed on the surface of a matrix formed after the molten steel is cooled in situ, the coating and the matrix have good metallurgical bonding, and cracks are not easily generated between the high-entropy alloy coating and the matrix.
More preferably, the molar ratio of the cobalt element, the chromium element, the nickel element and the 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, the chromium powder, the nickel powder and the manganese powder is (20-25): 25-30): 24-26. Further preferably, the mass ratio of the cobalt powder, the chromium powder, the nickel powder and the manganese powder is (20-25): 25-30): 24.5-26): 24-25.5.
Preferably, the average particle size of the cobalt powder, the chromium powder, the nickel powder or the manganese powder is 40-80 meshes. 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 can be 40 meshes, 50 meshes, 60 meshes, 65 meshes, 70 meshes or 80 meshes; the average particle size of the nickel powder can be 40 meshes, 50 meshes, 60 meshes, 65 meshes, 70 meshes or 80 meshes; 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, the chromium powder, the nickel powder or the manganese powder is 60 meshes.
In order to obtain metal powder with uniform components, cobalt powder, chromium powder, nickel powder and manganese powder can be mixed by a ball mill, and the average particle size of the metal powder is preferably 40-80 meshes. 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 particle size of the metal powder is larger than 80 meshes, gaps among the metal powder are too small to be beneficial to infiltration of molten steel; if the average particle size of the metal powder is less than 40 meshes, the metal powder is not melted by the infiltrated molten steel. Therefore, compared with other processes, the preparation method of the composite material with the surface containing the high-entropy alloy coating has lower requirements on the particle size and the shape of the 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 mold 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 coating layer is easy to fall off due to the fact that the adhesive in the coating liquid is quickly volatilized at high temperature before compounding in the pouring process under the action of self gravity.
Preferably, in the lost foam casting process, the temperature of molten steel during casting is 1630-1680 ℃. The temperature of the molten steel is too high, and crystal grains in the substrate and the coating are larger; the temperature of the molten steel is too low to be beneficial to melting the metal powder.
Carbon in the molten steel can permeate into the coating, C atoms are easy to form carbide in situ with the strong carbide element Cr, and the mechanical property and the wear resistance of the coating can be improved. However, if 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 carbon 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. The phenolic resin and/or polyvinyl butyral are/is used as a binder, so that the metal powder can be well bonded, and can be cured after being dried, so that the metal powder can be well adhered to the lost foam model. After the molten steel is poured, the 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 metal powder can be effectively bound and solidified.
Preferably, the coating liquid further includes 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 surface containing the high-entropy alloy coating is as follows:
the composite material with the surface containing the high-entropy alloy coating 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 surface containing the high-entropy alloy coating, the high-entropy alloy coating and the matrix have good metallurgical bonding, and cracks are not easy to generate between the high-entropy alloy coating and the matrix.
By the preparation method, the high-entropy alloy coating with the thickness of 6-12 mm can be formed on the surface of the metal matrix.
Drawings
FIG. 1 is an appearance picture of a metallographic specimen obtained by etching a composite material with a high-entropy alloy coating on the surface, which is prepared in example 2, with a nital 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 after the composite material with the high-entropy alloy coating on the surface, prepared in example 2, is corroded by a nital solution;
FIG. 3 is a Scanning Electron Microscope (SEM) photograph of the high-entropy alloy coating on the surface of the metallographic sample obtained by etching the composite material with the high-entropy alloy coating on the surface, which is prepared in example 2, by using a nital solution;
fig. 4 is an XRD spectrum of the high entropy alloy coating of the composite surface with the high entropy alloy coating prepared in example 2.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
The specific embodiment of the preparation method of the composite material with the surface containing the high-entropy alloy coating is as follows:
example 1
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average granularity of 40 meshes by using a ball mill to obtain metal powder with the average granularity 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 adhesive to the solvent is 20:1: 1.5; the adhesive is organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And (3) coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 7mm, and obtaining the model with the coating after the coating liquid is dried. Then embedding the model with the coating into dry sand for vibration molding, then placing the model into a pouring cup, finally pouring and molding 30 steel liquid steel (matrix material) at 1670 ℃, naturally cooling the model, 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 10.7 mm.
Example 2
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average granularity of 60 meshes by using a ball mill to obtain metal powder with the average granularity 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 adhesive to the solvent is 22:1: 1.9; the adhesive is 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 model with the coating after the coating liquid is dried. Then embedding the model with the coating into dry sand for vibration molding, then placing the model into a pouring cup, finally pouring and molding 45 steel liquid (matrix material) with the temperature of 1650 ℃, naturally cooling the model, 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 9.1 mm.
Example 3
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average granularity of 80 meshes by using a ball mill to obtain metal powder with the average granularity 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 adhesive to the solvent is 23:1: 2.1; the adhesive is organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And (3) coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 5mm, and obtaining the model with the coating after the coating liquid is dried. Then embedding the model with the coating into dry sand for vibration molding, then placing the model into a pouring cup, finally pouring and molding 60 steel liquid (matrix material) with the temperature of 1630 ℃, 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 7.4 mm.
Example 4
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) cobalt powder, chromium powder, nickel powder and manganese powder with the average particle size of 50 meshes are uniformly mixed by a ball mill to obtain 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 adhesive to the solvent is 24:1: 2.5; the adhesive is organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And (3) coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 4mm, and obtaining the model with the coating after the coating liquid is dried. Then embedding the coated model into dry sand for vibration molding, then placing the coated model into a pouring cup, finally pouring and molding 50 steel liquid (matrix material) at the temperature of 1640 ℃, naturally cooling the molded product, and taking out the cast product, wherein the obtained cast product 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 6.0 mm.
Example 5
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average granularity of 60 meshes by using a ball mill to obtain metal powder with the average granularity 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 adhesive to the solvent is 25:1: 3; the adhesive is organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And (3) coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 8mm, and drying the coating liquid to obtain the model with the coating. Then embedding the model with the coating into dry sand for vibration molding, then placing the model into a pouring cup, finally pouring 40 steel liquid steel (matrix material) with the temperature of 1660 ℃ for molding, 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 12.0 mm.
Example 6
The preparation method of the composite material with the surface containing the high-entropy alloy coating comprises the following steps:
(1) uniformly mixing cobalt powder, chromium powder, nickel powder and manganese powder with the average particle size of 65 meshes by using a ball mill to obtain metal powder with the average particle size 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 adhesive to the solvent is 21:1: 2.3; the adhesive is organic adhesive, the organic adhesive is polyvinyl butyral, and the solvent is ethanol.
(3) And (3) coating the coating liquid on the surface of the lost foam model, wherein the thickness of the coating liquid is 5.5mm, and drying the coating liquid to obtain the model with the coating. Then embedding the model with the coating into dry sand for vibration molding, then placing the model into a pouring cup, finally pouring and molding 20 steel liquid steel (matrix material) at the temperature of 1680 ℃, naturally cooling the model, 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 8.3 mm.
Secondly, the specific examples of the composite material with the surface containing the high-entropy alloy coating are as follows:
the composite material with the high-entropy alloy coating on the surface is prepared by the preparation method of the composite material with the high-entropy alloy coating on the surface in any one of the embodiments 1 to 6.
Experimental example 1
The composite materials prepared in examples 1 to 6 and having the high-entropy alloy coating on the surface were used as test samples, and a dry friction and wear test was performed by using an HSR-2M high-speed reciprocating friction and wear tester. The test conditions were as follows: the counter-grinding coupling part is a GCr15 steel ball, the rotating speed of the counter-grinding coupling part is 600r/min, the loading load is 60N, and the abrasion time is 15 min. After the dry friction and wear test is finished, the wear resistance of the test sample is evaluated by measuring and calculating the ratio of the mass of the test sample after the dry friction and wear test to the mass before the test, and the calculated ratios of the composite materials with the high-entropy alloy coatings on the surfaces prepared in examples 1-6 are respectively A1, A2, A3, A4, A5 and A6. Then, the base materials of examples 1 to 6 were used as comparative samples, and a dry abrasion test was conducted under the same test conditions as those described above. After the test is finished, the ratio of the mass of the base material after the dry friction 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 wear resistance of the base materials in examples 1 to 6 were all set to 1, and the wear resistance of the composite materials having a high-entropy alloy coating on the surface thereof prepared in examples 1 to 6 was evaluated with respect to the base materials by calculating the ratios 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 wear resistance of composites with high entropy alloy coatings on their 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 wear resistance of the composite materials with the high-entropy alloy coatings on the surfaces prepared in examples 1 to 6 is 2.5 to 3.7 times of that of the respective base materials, the high-entropy alloy coatings in the composite materials with the high-entropy alloy coatings on the surfaces prepared in examples 1 to 6 are well combined with the base materials in the test process, and the corresponding cast-infiltration layers show good wear resistance based on the existence of carbides and the high-entropy alloy base materials.
Experimental example 2
In order to examine whether cracks appear between the high-entropy alloy coating and the base material in the preparation process, the composite material with the high-entropy alloy coating on the surface, which is prepared in example 2, is etched in a nitric acid-alcohol solution (the volume fraction of nitric acid is 4%) for 5s at room temperature, then the composite material is cleaned by alcohol, a metallographic sample corroded by the nitric acid-alcohol solution is obtained, and then the metallographic sample is respectively subjected to naked eye observation and SEM characterization, and the results are shown in fig. 1, fig. 2 and fig. 3. As can be seen from fig. 1, in the composite material with the high-entropy alloy coating on the surface 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 FIGS. 2 and 3, the high-entropy alloy coating is well bonded with the interface of the substrate, a metallurgically bonded transition layer is present at the interface, and a small amount of carbide is also present in the high-entropy alloy coating, which is beneficial to improving the wear resistance of the coating.
The high-entropy alloy coating of the composite surface having the high-entropy alloy coating prepared in example 2 was characterized by XRD, and the result is shown in fig. 4. The result shows that the XRD peak of the high-entropy alloy coating is mainly the characteristic peak 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 (9)
1. A preparation method of a composite material with a high-entropy alloy coating on the surface is characterized by comprising the following steps:
1) coating the coating liquid on the surface of the lost foam model, 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 the cobalt element, the chromium element, the nickel element and the manganese element is (5-35): 5-35: (5-35);
2) and then performing lost foam casting on the molten steel by adopting a coated model.
2. The method for preparing a composite material with a high-entropy alloy coating on the surface according to claim 1, wherein the metal powder is composed of cobalt powder, chromium powder, nickel powder and manganese powder; the mass ratio of the cobalt powder, the chromium powder, the nickel powder and the manganese powder is (20-25): (25-30): 24-26).
3. The preparation method of the composite material with the surface containing the high-entropy alloy coating as claimed in claim 1 or 2, wherein the average particle size of the metal powder is 40-80 meshes.
4. The preparation method of the composite material with the surface containing the high-entropy alloy coating as claimed in claim 1 or 2, wherein the coating thickness of the coating liquid on the surface of the lost foam model is 4-8 mm.
5. The preparation method of the composite material with the high-entropy alloy coating on the surface as claimed in claim 1 or 2, wherein the temperature of molten steel during casting in the lost foam casting process is 1630-1680 ℃.
6. The method for preparing a composite material with a high-entropy alloy coating on the surface, as claimed in claim 1 or 2, wherein the mass fraction of carbon in the molten steel is not more than 0.65%.
7. A process for the preparation of a composite material having a high entropy alloy coating on its surface as claimed in claim 1 or 2, wherein the binder is an organic binder, the organic binder being a phenolic resin and/or polyvinyl butyral; the mass ratio of the metal powder to the binder is (20-25): 1.
8. The method for preparing a composite material with a high-entropy alloy coating layer on the surface according to claim 7, 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).
9. A composite material with a surface containing a high-entropy alloy coating, which is prepared by the preparation method of the composite material with the surface containing the high-entropy alloy coating, according to any one of claims 1 to 8.
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