CN114059065A - Argon arc cladding high-entropy alloy coating and preparation method and application thereof - Google Patents
Argon arc cladding high-entropy alloy coating and preparation method and application thereof Download PDFInfo
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- CN114059065A CN114059065A CN202111371442.3A CN202111371442A CN114059065A CN 114059065 A CN114059065 A CN 114059065A CN 202111371442 A CN202111371442 A CN 202111371442A CN 114059065 A CN114059065 A CN 114059065A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
- C23C24/106—Coating with metal alloys or metal elements only
-
- 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 discloses an argon arc cladding high-entropy alloy coating, and a preparation method and application thereof. Compared with the prior art, the invention has the following advantages: (1) the method has the advantages of concentrated heat, high energy density, small alloy oxidation burning loss during cladding and good thermal stability; (2) the method can realize the rapid preparation of the high-entropy alloy coating on the surface of the 304 stainless steel, and has the advantages that the corrosion resistance of the obtained high-entropy alloy coating can be comparable to that of the 304 stainless steel, and meanwhile, the high-entropy alloy coating has good wear resistance.
Description
Technical Field
The invention belongs to the technical field of metal material surface modification, and relates to wear resistance modification aiming at a 304 stainless steel surface, in particular to an argon arc cladding high-entropy alloy coating, and a preparation method and application thereof.
Background
The 304 stainless steel, namely 18/8 austenitic stainless steel has good corrosion resistance and processing and forming performance, and is widely applied to the fields of industry, aerospace, medicine and the like. However, the application of 304 stainless steel is greatly limited due to the defects of low hardness (less than or equal to 200HV), large friction coefficient, poor wear resistance and the like, and large abrasion is inevitably generated in the using process, even the alloy is failed. The existing research shows that the wear resistance of the alloy can be effectively improved by the alloy surface strengthening technology, and the economic and efficient surface treatment technology is of great significance for expanding the application of 304 stainless steel in the field of wear-resistant materials.
The high-entropy alloy breaks through the design concept of the traditional alloy, and shows high hardness, high strength, good wear resistance and corrosion resistance on performance, so that the high-entropy alloy has wide potential application prospects as a high-strength, corrosion-resistant, high-temperature-resistant and wear-resistant material and the like in the fields of national industry, military industry and the like. The high-entropy alloy has high hardness and high wear resistance, and the application prospect of the high-entropy alloy as a wear-resistant material is widely regarded. However, in the current research, vacuum arc melting is mostly adopted to prepare small block-shaped ingots, expensive metals exist in the components of the high-entropy alloy, and the cost for preparing large high-entropy alloy ingots is higher.
The argon arc cladding technology adopts a traditional TIG welding machine, generates electric arc between a tungsten electrode and a base material, melts alloy between the base material and the tungsten electrode under the protection of inert gas argon, and forms an alloy coating on the surface of the base material after cooling and solidification. The argon arc cladding has the characteristics of concentrated heat, high energy density, small alloy oxidation burning loss during cladding, good thermal stability and the like, and the cladding layer which is in good metallurgical bonding with the matrix can be obtained due to larger fusion depth. Compared with other surface cladding technologies, the argon arc cladding technology has small size limit on workpieces, has good universality and is convenient to popularize and apply. Therefore, the argon arc cladding technology is adopted to prepare the high-entropy alloy coating, so that the synergistic advantages of excellent performance of the high-entropy alloy and strong applicability of argon arc cladding can be well exerted, the problem of processing cost is solved, and the aim of improving the wear resistance of the corresponding substrate material is fulfilled.
Disclosure of Invention
The technical problem to be solved is as follows: the 304 stainless steel has good corrosion resistance and processing and forming performance, and is widely applied in the fields of petroleum, chemical engineering, aerospace, medicine, paper making, atomic energy, ocean engineering and the like. However, 304 stainless steel has low hardness (less than or equal to 200HV), has poor wear resistance, and is easy to form a corrosion micro-battery when micro-scratches appear on the surface of a part, thereby reducing the corrosion resistance of the part. Based on the technical scheme, the invention aims to prepare a novel high-entropy alloy coating, and ensures that the obtained coating has corrosion resistance not inferior to that of 304 stainless steel and excellent wear resistance; in view of the above, the invention provides an argon arc cladding high-entropy alloy coating and a preparation method and application thereof.
The technical scheme is as follows: the preparation method of the argon arc cladding high-entropy alloy coating comprises the following steps:
s1, polishing the surface of the 304 stainless steel substrate by using a handheld angle grinder, removing oil and rust, cleaning by using analytically pure alcohol, and drying for later use;
s2, mixing Co20Cr20Fe20Mo20Ni20Mixing the high-entropy alloy powder with a polyvinyl alcohol solution at a mixing volume ratio of 10:1, adding absolute ethyl alcohol, and uniformly stirring to obtain a slurry;
s3, coating the slurry prepared in the S2 on the surface of the 304 stainless steel substrate treated in the S1 by adopting a special die, uniformly filling the slurry into a groove of the die in the coating process, and applying pressure to the alloy powder slurry in the groove by adopting a scraper to enable the upper surface of the slurry to be flush with the upper surface of the die;
s4, stripping after 15-20 minutes, then placing the 304 stainless steel substrate and the prefabricated powder slurry on the surface of the substrate in an oven, and drying for 30-40 minutes at 120 ℃ to dry and solidify the high-entropy alloy powder slurry mixed with the polyvinyl alcohol;
and S5, placing the dried and solidified alloy powder on an operation platform of an argon arc welding machine, adjusting the distance between the tungsten electrode head and the surface of the alloy powder to be 2mm, switching on a power supply, melting the alloy powder through electric arc heating under the protection of argon, and cooling to room temperature to obtain the high-entropy alloy coating.
Preferably, the polyvinyl alcohol solution in S2 is a 5% aqueous solution by mass.
Preferably, the process parameters in S5 are: the cladding current is 125-175A, the cladding speed is 60-100mm/min, and the argon flow is 10 or 12L/min.
Preferably, the process parameters in S5 are: the cladding current is 125A, the cladding speed is 60mm/min, and the argon flow is 10L/min.
The argon arc cladding high-entropy alloy coating prepared by any one of the methods.
Preferably, the hardness of the coating is as high as 585HV (mean value), which is improved by 3 times compared with the substrate.
Preferably, the coating has a volumetric wear rate of 36% of the wear rate of the substrate.
The argon arc cladding high-entropy alloy coating is applied to the surface modification of 304 stainless steel.
The argon arc cladding high-entropy alloy coating has the action principle that: the argon arc cladding technology is combined with the high-entropy alloy, the synergistic advantage of excellent performance of the high-entropy alloy and strong applicability of argon arc cladding is fully exerted, and the high-entropy alloy coating which has corrosion resistance not inferior to that of 304 stainless steel and excellent wear resistance is prepared.
Has the advantages that: (1) the method has the advantages of concentrated heat, high energy density, small alloy oxidation burning loss during cladding and good thermal stability; (2) the method can realize the rapid preparation of the high-entropy alloy coating on the surface of the 304 stainless steel, and has the positive effects that the obtained high-entropy alloy coating has good corrosion resistance and wear resistance.
Drawings
FIG. 1 is a schematic structural view of a mold;
FIG. 2 is a schematic view of an argon arc cladding test apparatus;
FIG. 3 is an X-ray diffraction pattern of the coating, wherein 3-2 represents the X-ray diffraction pattern of the coating 3-2; 2-5 represents the X-ray diffraction spectrum of coatings 2-5;
FIG. 4 is a microstructure of a high entropy alloy coating under 2-5 process parameters, FIG. 4(a) is a cross-sectional view of the coating, where CZ is a cladding region, BZ is a bonding region, HAZ is a heat affected zone, and Substrate represents a matrix, FIG. 4(c) is a metallurgical bonding zone between the coating and a Substrate, and FIGS. 4(d) and 4(b) are a coral-like dendrite structure in the coating and an enlarged view thereof, respectively.
FIG. 5 is a hardness profile of a high entropy alloy coating in an example;
FIG. 6 is a graph of the wear surface topography of the substrate and coating in an example;
FIG. 7 is the average friction coefficient (left) and the volumetric wear rate (right) of the high entropy alloy coating and silicon nitride ball to the mill in the examples;
FIG. 8 is a graph representing the corrosion resistance of the coating compared to 304 stainless steel.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit and substance of the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.
Example 1
The preparation method of the argon arc cladding high-entropy alloy coating comprises the following steps:
s1, polishing the surface of the 304 stainless steel substrate by using a handheld angle grinder, removing oil and rust, cleaning by using analytically pure alcohol, and drying for later use;
s2, mixing Co20Cr20Fe20Mo20Ni20Mixing the high-entropy alloy powder with 5% polyvinyl alcohol solution by mass percent in a volume ratio of 10:1, adding absolute ethyl alcohol, and uniformly stirring to obtain slurry;
s3, coating the slurry prepared in the S2 on the surface of the 304 stainless steel substrate treated in the S1 by adopting a mold, applying pressure to the alloy powder slurry in the groove by adopting a scraper in the coating process, and enabling the upper surface of the slurry to be flush with the upper surface of the mold while uniformly filling the mold;
s4, stripping after 15min, then placing the 304 stainless steel substrate and the prefabricated powder slurry on the surface of the substrate in an oven, and drying for 30min at 120 ℃ to dry and solidify the high-entropy alloy powder slurry mixed with the polyvinyl alcohol;
and S5, placing the dried and solidified alloy powder on an operation platform of an argon arc welding machine, adjusting the distance between the tungsten electrode head and the surface of the alloy powder to be 2mm, switching on a power supply, melting the alloy powder through electric arc heating under the protection of argon, and cooling to room temperature to obtain the high-entropy alloy coating.
Wherein, the process parameters in S5 and the alloy coating numbers prepared under the condition of the process parameters are shown in the following table:
TABLE 1 argon arc cladding Process parameters
The coating obtained from the above preparation was subjected to texture and performance analysis:
1) composition analysis of coating phase
Cutting the coating into small pieces by linear cutting, and grinding a smooth and flat plane on a water mill by using #600 water grinding abrasive paper to perform XRD analysis, wherein the scanning angle 2 theta range is 30-95 degrees, and the scanning speed is 6 degrees/min. FIG. 3 is an XRD analysis of the coatings produced under representative two parameters of the examples, wherein the process parameters for coatings 2-5 and 3-2 are shown in Table 1. The high-entropy alloy coating is composed of an FCC phase and a mu phase.
2) Coating texture observation and analysis
Cutting the coating and the base material into small blocks, and then performing water grinding and polishing by using 400#, 800#, 1000#, 1500#, 2000# water grinding sand paper. And then, etching by using aqua regia, and shooting the coating and the metallurgical bonding interface of the etched sample by using a scanning electron microscope.
FIG. 4 is a photograph of the texture of the coating at process parameters 2-5, as can be seen, as shown in FIG. 4 (a); the coating cross section area mainly comprises a Cladding area (Cladding Zone), a bonding Zone (Bounding Zone), a Heat Affected Zone (Heat Affected Zone) and a Substrate (Substrate). A metallurgical bond of the coating to the substrate is evident in the BZ region. As can be seen from fig. 4(c), the coating exhibits a strong metallurgical bond with the substrate. FIG. 4(d) is a microstructure diagram of a coating layer, wherein the cross-sectional microstructure includes coral-shaped dendrites and lamellar structures, and the structure is fine.
3) Hardness test of coating
Cutting the long-pass cladding sample into a sample with the thickness of 15 multiplied by 10mm by wire cutting, and performing water grinding and polishing by using 400#, 800#, 1000#, 1500# and 2000# water grinding sand paper. Then, aqua regia is used for corrosion, and the hardness of the cross section of the coating is measured by using a microhardness tester, wherein the specific embodiment is as follows: and measuring to the base material from the top end of the coating by taking the step length of 300 mu m as an interval, adjusting the step length interval according to the difference of the coating thickness to ensure that the number of the coating test points is about 10, the number of the base material hardness test points is about two, and counting the hardness value of each test point. The load selected in this experiment was 5N and the load hold time was 15 s.
FIG. 5 shows the microhardness distribution of the coatings of examples 1 and 2, showing that the coating hardness is higher than that of the 304 stainless steel alloy substrate, with 2-5 coating hardness averages as high as 585HV and 3-3 coating hardness averages as high as 554 HV.
4) Analysis of wear resistance of coating
And (3) cutting the long-pass cladding sample into a sample with the thickness of 15 multiplied by 10mm by linear cutting, performing reciprocating frictional wear test, and polishing the surface of the coating to be smooth and flat by using water-milled sand paper. FIG. 6 is a macroscopic wear graph after wear, with the base material having a wear scar width greater than that of most high entropy alloy coatings, and from Table 1 the comparison of wear area and coefficient of friction magnitudes also indicates that the coating is more wear resistant than the base material, and therefore the high entropy alloy coating has better wear resistance than the 304 stainless steel base material. FIG. 7 shows the bulk wear rate of 304 stainless steel substrate and the high entropy alloy coating and silicon nitride ball obtained in examples 1 and 2, and the bulk wear rate of 304 stainless steel substrate (11.11X 10)-8mm3V (N · m)) are generally higher than high entropy alloy coatings, where the volumetric wear rate of high entropy alloy coatings is minimal under 3-3 process conditions.
5) The corrosion resistance of the coating is compared with that of 304 stainless steel
FIG. 8 is a graph representing the corrosion resistance of the coating compared to 304 stainless steel. As can be seen from the zeta potential curve 4a, the three are similarThe CoCrFeMoNi coating has a wider passivation region (passivation potential range of about 1000mv) than 304 stainless steel, which indicates that the passivation film formed on the surface of the high entropy alloy coating is more protective. The pitting potentials of 304 stainless steel, coatings 3-3 and 2-5 are 0.072V, 0.928V and 0.945V, respectively, so that the CoCrFeMoNi coating has more excellent pitting resistance than 304 stainless steel. In addition, the corrosion current densities of the coatings 3-3 and 2-5 were 6.7X 10, respectively-7A/cm2And 1.1X 10-6A/cm2And the corrosion current density of 304 stainless steel is 2.2 x 10-7A/cm2Indicating that the corrosion rate of 304 stainless steel is slightly lower when corrosion begins to occur.
Claims (8)
1. The preparation method of the argon arc cladding high-entropy alloy coating is characterized by comprising the following steps of:
s1, polishing the surface of the 304 stainless steel substrate by using a handheld angle grinder, removing oil and rust, cleaning by using analytically pure alcohol, and drying for later use;
s2, mixing Co20Cr20Fe20Mo20Ni20Mixing the high-entropy alloy powder with a polyvinyl alcohol solution at a mixing volume ratio of 10:1, adding absolute ethyl alcohol, and uniformly stirring to obtain a slurry;
s3, coating the slurry prepared in the S2 on the surface of the 304 stainless steel substrate treated in the S1 by adopting a special die, uniformly filling the slurry into a groove of the die in the coating process, and applying pressure to the alloy powder slurry in the groove by adopting a scraper to enable the upper surface of the slurry to be flush with the upper surface of the die;
s4, stripping after 15-20 minutes, then placing the 304 stainless steel substrate and the prefabricated powder slurry on the surface of the substrate in an oven, and drying for 30-40 minutes at 120 ℃ to dry and solidify the high-entropy alloy powder slurry mixed with the polyvinyl alcohol;
and S5, placing the dried and solidified alloy powder on an operation platform of an argon arc welding machine, adjusting the distance between the tungsten electrode head and the surface of the alloy powder to be 2mm, switching on a power supply, melting the alloy powder through electric arc heating under the protection of argon, and cooling to room temperature to obtain the high-entropy alloy coating.
2. The method for preparing the argon arc cladding high-entropy alloy coating layer according to claim 1, wherein the polyvinyl alcohol solution in S2 is an aqueous solution with a mass percentage of 5%.
3. The preparation method of the argon arc cladding high-entropy alloy coating of claim 1, wherein the process parameters in S5 are as follows: the cladding current is 125-175A, the cladding speed is 60-100mm/min, and the argon flow is 10 or 12L/min.
4. The preparation method of the argon arc cladding high-entropy alloy coating of claim 3, wherein the process parameters in S5 are as follows: the cladding current is 125A, the cladding speed is 60mm/min, and the argon flow is 10L/min.
5. The argon arc cladding high-entropy alloy coating prepared by the method of any one of claims 1 to 4.
6. The argon arc cladding high-entropy alloy coating of claim 5, wherein the average hardness of the coating is 585HV, which is improved by 3 times compared with that of a base material.
7. The argon arc cladding high-entropy alloy coating of claim 5, wherein the volumetric wear rate of the coating is 36% of the wear rate of the base material.
8. The application of the argon arc cladding high-entropy alloy coating of claim 5 in surface modification of 304 stainless steel.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002173732A (en) * | 2000-11-29 | 2002-06-21 | Univ Qinghua | High entropy multicomponent alloy |
| CN106894015A (en) * | 2017-02-27 | 2017-06-27 | 辽宁工程技术大学 | Argon arc cladding high-entropy alloy coating and preparation method thereof |
| CN107739958A (en) * | 2017-10-24 | 2018-02-27 | 辽宁工业大学 | A kind of high-entropy alloy containing eutectic structure and preparation method thereof |
| KR20180035750A (en) * | 2018-03-22 | 2018-04-06 | 한국과학기술원 | In-situ strengthened high entropy powder, alloy thereof and method of manufacturing the same |
| CN109252162A (en) * | 2018-11-09 | 2019-01-22 | 中国石油大学(华东) | A kind of high-entropy alloy with properties of antifriction and wear resistance |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002173732A (en) * | 2000-11-29 | 2002-06-21 | Univ Qinghua | High entropy multicomponent alloy |
| CN106894015A (en) * | 2017-02-27 | 2017-06-27 | 辽宁工程技术大学 | Argon arc cladding high-entropy alloy coating and preparation method thereof |
| CN107739958A (en) * | 2017-10-24 | 2018-02-27 | 辽宁工业大学 | A kind of high-entropy alloy containing eutectic structure and preparation method thereof |
| KR20180035750A (en) * | 2018-03-22 | 2018-04-06 | 한국과학기술원 | In-situ strengthened high entropy powder, alloy thereof and method of manufacturing the same |
| CN109252162A (en) * | 2018-11-09 | 2019-01-22 | 中国石油大学(华东) | A kind of high-entropy alloy with properties of antifriction and wear resistance |
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