CN111188034A - Preparation method of corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance - Google Patents
Preparation method of corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance Download PDFInfo
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- CN111188034A CN111188034A CN201911329517.4A CN201911329517A CN111188034A CN 111188034 A CN111188034 A CN 111188034A CN 201911329517 A CN201911329517 A CN 201911329517A CN 111188034 A CN111188034 A CN 111188034A
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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
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
Abstract
The invention discloses a preparation method of a corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance, which relates to the field of metal material surface modification and comprises the following steps: 1) designing the components of the medium-entropy alloy: the medium entropy alloy comprises the following components in atomic percentage: cr 20-50%, Co 20-50%, Ni 20-50%, the total percentage is 100%; 2) pretreatment of the medium-entropy alloy: smelting the medium entropy alloy, and then obtaining powder in an atomization mode; 3) cladding matrix pretreatment: polishing the surface of the cladding substrate to be smooth, cleaning and drying; 4) laser cladding: and melting the medium-entropy alloy on the surface of the cladding substrate by combining a laser and a powder feeding method to obtain the medium-entropy alloy laser cladding coating. The medium-entropy alloy laser cladding coating prepared by the invention has good low-temperature mechanical property and corrosion resistance, the metallurgical quality of the cladding layer is good, the tissue distribution is uniform, the related elements are less, the configuration is simple, the applicability is wide, and the use is convenient and efficient.
Description
Technical Field
The invention relates to the field of metal material surface modification, in particular to a corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance and a preparation method thereof.
Background
The traditional alloy mainly comprises one or two elements, and then other trace elements are added to improve the structure and the performance of the alloy, such as iron-carbon alloy, aluminum alloy, copper alloy and the like. The addition of alloy elements can improve various performance indexes of the alloy, such as strength, toughness, corrosion resistance, wear resistance, electromagnetic property and the like, so that the alloy can meet engineering requirements. However, the addition of too many alloy element types often leads to the formation of complex brittle amorphous intermetallic compounds in the system, so that the alloy performance is deteriorated, and therefore, the traditional alloy design thought is always limited to the mode of single principal element.
The multicomponent alloy is a new alloy design field of metallurgy research, different from traditional alloy, the multicomponent alloy is an alloy composed of 3-6 metal elements with equal molar ratio or nearly equal molar ratio, which provides wide composition space for designing new material with good mechanical property. Among them, high-entropy alloys and medium-entropy alloys have attracted much attention in the scientific community because they have effects of "diffusion retardation" and the like, can ideally exhibit a simple structure and properties determined by a plurality of elements arranged in a single lattice in common, and thus exhibit many specific properties such as good strength and toughness, high-temperature strength, wear resistance, corrosion resistance and the like.
The CrCoNi intermediate entropy alloy as the earliest proposed intermediate entropy alloy has excellent low-temperature mechanical properties as high-entropy alloy with the same FCC type crystal structure, and has higher obdurability matching than the FCC type high-entropy alloy. At present, domestic experts do a great deal of research on the performance of the alloy, but the performance is mostly improved, most of the preparation methods are casting, and the application of the medium-entropy alloy is limited to a certain extent. The Chinese invention patent CN 108866417A utilizes the addition of Mn element in the medium entropy alloy CoCrNi system to improve the tensile strength and the elongation. The invention of Chinese patent CN 108998714A utilizes vacuum melting face-centered cubic (FCC) single-phase CoCrNi master alloy-vacuum melting body-centered cubic (BCC) single-phase AlTiNi master alloy, master alloy and master alloy remelting suction casting-homogenizing annealing-aging treatment-solid solution treatment to obtain FCC + BCC two-phase entropy alloy.
The laser cladding technology is a novel surface modification and additive manufacturing technology, a cladding material and a substrate surface layer material are simultaneously melted, cooled and solidified by utilizing a high-energy laser beam, and the laser cladding technology has the characteristics of precision, controllability, small influence on the substrate material, firm metallurgical bonding between the cladding layer and the substrate and the like, thereby being widely applied to scientific research and industrial production. The medium entropy alloy is introduced into the field of material surface, and the excellent performance of the medium entropy alloy is used for material surface modification, so that the medium entropy alloy has very important practical significance, the application range of the medium entropy alloy in the industrial field can be greatly expanded, the service life of the medium entropy alloy is prolonged, and the full-period cost is reduced.
Therefore, the technical personnel in the field are dedicated to develop a preparation method of the corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance, so that the medium-entropy alloy coating has good low-temperature mechanical property and corrosion resistance, the cladding layer has good metallurgical quality and uniform tissue distribution, and the related elements are fewer, the configuration is simple, the applicability is wide, the use is convenient and efficient.
Disclosure of Invention
In view of the above defects in the prior art, the technical problem to be solved by the invention is how to prepare a corrosion-resistant intermediate-entropy alloy coating with good low-temperature performance, and the corrosion-resistant intermediate-entropy alloy coating has the advantages of fewer related elements, simple configuration, wide applicability, firm combination of the coating and a substrate, and simple, convenient and controllable preparation method.
In order to realize the aim, the invention provides a preparation method of a corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance, which comprises the following steps:
(1) and designing the components of the medium-entropy alloy: the medium entropy alloy comprises the following components in atomic percentage: cr 20-50%, Co 20-50%, Ni 20-50%, the total percentage is 100%;
(2) and pretreating the medium-entropy alloy: smelting the medium entropy alloy and then atomizing to obtain powder;
(3) and cladding matrix pretreatment: polishing the surface of the cladding substrate to be smooth, cleaning and drying;
(4) and laser cladding: and melting the medium-entropy alloy on the surface of the cladding substrate by combining a laser and a powder feeding method to obtain the medium-entropy alloy laser cladding coating.
Further, the powder of the medium entropy alloy in the step (2) needs to be dried and sieved.
Furthermore, the particle size of the medium entropy alloy powder is 53-150 μm.
Further, the step (4) is specifically that the medium-entropy alloy powder is filled into a laser cladding powder feeding device, is blown to the surface of the cladding substrate by using a powder feeding method and using a protective gas as a powder carrying gas, and is fused, metallurgically bonded and solidified to form the medium-entropy alloy laser cladding coating on the cladding substrate under the high-temperature action of laser.
Further, the parameters of the laser in the laser cladding are as follows: the laser power is 2000-2500W, the scanning speed is 7-8mm/s, and the spot diameter is 7.4 mm.
Further, the flow of argon protective gas in the laser cladding powder feeding process is 10-15L/min, and the powder feeding speed is 28-32 g/min.
Furthermore, the laser cladding adopts a multi-cladding method, and the lap joint rate is 20-30%.
Further, the medium entropy alloy laser cladding coating is of a single-phase FCC structure, and the hardness is 250-300 HV.
The invention also provides a corrosion-resistant laser cladding entropy-medium alloy coating with good low-temperature performance, wherein the entropy-medium alloy comprises the following components in atomic percentage: 20-50% of Cr, 20-50% of Co and 20-50% of Ni, wherein the total percentage is 100%.
Further, the medium entropy alloy laser cladding coating has a single-phase FCC structure, the hardness is 250-300HV, and the thickness is 2.2-2.5 mm.
The technical effects are as follows:
(1) the medium-entropy alloy coating is prepared by adopting a laser cladding method, and by means of the rapid heating and melting of laser and the rapid cooling of the steel matrix under the heat absorption effect, the composition analysis can be reduced, and the medium-entropy alloy coating with uniform components and tissues can be obtained; and the laser cladding process is simple, and the application of the medium entropy alloy in the field of surface engineering can be promoted.
(2) The medium-entropy alloy material has reasonable proportion of Cr, Co and Ni elements, simple alloy structure and single-phase FCC structure, and the 'retardation effect' of the medium-entropy alloy can delay or even prevent the diffusion of dissimilar materials in the cladding process, effectively inhibit the formation of intermetallic compounds, ensure that the coating structure is uniform and compact and has fewer defects.
(3) The medium entropy alloy has a single-phase FCC structure, the FCC series multicomponent alloy has good plastic deformation capability and good low-temperature mechanical property, the ductility of the medium entropy alloy is enhanced along with the reduction of temperature, and the medium entropy alloy laser cladding coating can be applied in a wider temperature range.
(4) The medium entropy alloy has high content of Cr element, and a certain proportion of Cr exists in a surface oxidation layer2O3The oxide film is compact and is combined with the coating more tightly, the corrosion resistance can be improved, and the cladding substrate is effectively protected.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
FIG. 2 is a powder morphology of a medium entropy alloy in accordance with a preferred embodiment of the present invention;
FIG. 3 is a metallographic structure of a cross section of a medium entropy alloy laser cladding coating according to a preferred embodiment of the invention;
FIG. 4 is an XRD analysis pattern of a medium entropy alloy laser cladding coating in accordance with a preferred embodiment of the present invention;
FIG. 5 is a microhardness profile of a medium entropy alloy laser cladding coating in accordance with a preferred embodiment of the present invention;
FIG. 6 is a graph of a low temperature mechanical tensile test of a medium entropy alloy laser cladding coating in accordance with a preferred embodiment of the present invention;
FIG. 7 is a potentiodynamic polarization curve test chart of the medium entropy alloy laser cladding coating according to a preferred embodiment of the invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example one
FIG. 1 is a schematic flow chart of a preparation method of a corrosion-resistant intermediate entropy alloy laser cladding coating with good low-temperature performance, which comprises the following steps: 1) designing the components of the medium-entropy alloy; 2) pretreating the medium-entropy alloy; 3) cladding matrix pretreatment; 4) preparing the medium entropy alloy laser cladding coating by laser cladding.
In this example, the preparation method is as follows:
1) the medium entropy alloy laser cladding coating comprises the following components in atomic percentage of Cr 33%, Co 33% and Ni 34%;
2) weighing and preparing raw materials according to the atomic percentages of the components, smelting the medium-entropy alloy material, then obtaining medium-entropy alloy powder in an atomization mode, drying, and sieving to obtain 53-150 mu m powder, wherein the shape of the powder is shown in figure 2.
3) The Q235 steel plate is selected as a cladding substrate, the size of the substrate is 200mm multiplied by 150mm multiplied by 20mm, the surface of the substrate is ground by a grinding machine before cladding, and then the substrate is cleaned by acetone and dried by blowing.
4) According to laser cladding parameters: carrying out cladding at a scanning speed of 8mm/s, a laser power of 2500W, a powder feeding rate of 28g/min and a spot diameter of 7.4 mm. The whole laser cladding process is carried out under the protection of argon, and the flow of the argon protection gas is 12L/min. The lap joint rate is 20 percent by adopting a multi-pass cladding method.
And carrying out metallographic observation, microhardness test, low-temperature tensile test and electrochemical corrosion test on the mid-entropy alloy laser cladding coating.
As shown in figure 3, the macroscopic morphology of the coating is shown, after laser cladding, the thickness of the obtained coating is about 2.5mm, no defects such as cracks, air holes, inclusions and the like exist in the coating, and the cladding layer and the matrix are well combined.
As shown in fig. 4, which is an XRD analysis pattern of the coating, the coating has a single-phase FCC structure.
As shown in FIG. 5, the hardness of the coating is approximately about 250 HV and 300HV as a whole, and the hardness is uniformly distributed.
As shown in fig. 6, which is a low-temperature mechanical test chart of the coating, the yield strength, the tensile strength and the elongation are all improved along with the decrease of the temperature, and the medium-entropy alloy laser cladding coating has good mechanical properties under the low-temperature condition.
As shown in FIG. 7, the corrosion resistance of the coating is shown, in 3.5 wt% NaCl solution, the corrosion current of the cladding coating is 9.86 x 10-7 mu Acm-2, the self-corrosion potential is-0.275V (SHE), in 0.5mol/L H2SO4 solution, the corrosion current of the cladding coating is 1.29 x 10-5 mu Acm-2, the self-corrosion potential is 0.191V (SHE), and the corrosion resistance is good. In 3.5 wt% NaCl solution and 0.5mol/L H2SO4 solution, the corrosion current of the cladding layer is 2-3 orders of magnitude lower than that of the substrate, and the corrosion potential is obviously higher than that of the substrate, thus proving that the corrosion resistance is good.
Example two
In this embodiment, a specific preparation method of the intermediate entropy alloy laser cladding coating is as follows:
1) the medium entropy alloy laser cladding coating comprises the following components in atomic percentage of Cr 33%, Co 33% and Ni 34%;
2) weighing and preparing raw materials according to the atomic percentages of the components, smelting the medium-entropy alloy material, then obtaining medium-entropy alloy powder in an atomization mode, drying, and sieving to obtain 53-150 mu m powder, wherein the shape of the powder is shown in figure 2.
3) The selected 9Ni steel plate is used as a cladding substrate, the size of the substrate is 200mm multiplied by 150mm multiplied by 20mm, the surface of the substrate is ground by a grinding machine before cladding, and then the substrate is cleaned by acetone and dried by blowing.
4) According to laser cladding parameters: 7mm/s of scanning speed, 2500W of laser power, 32g/min of powder feeding speed and 7.4mm of spot diameter. The whole laser cladding process is carried out under the protection of argon, and the flow of the argon protection gas is 15L/min. The lap joint rate is 30 percent by adopting a multi-pass cladding method.
EXAMPLE III
In this embodiment, a specific preparation method of the intermediate entropy alloy laser cladding coating is as follows:
1) the medium entropy alloy laser cladding coating comprises the following components in atomic percentage of Cr 30%, Co 20% and Ni 50%;
2) weighing and preparing raw materials according to the atomic percentages of the components, smelting the medium-entropy alloy material, then obtaining medium-entropy alloy powder in an atomization mode, drying, and sieving to obtain 53-150 mu m powder.
3) The selected 9Ni steel plate is used as a cladding substrate, the size of the substrate is 200mm multiplied by 150mm multiplied by 20mm, the surface of the substrate is ground by a grinding machine before cladding, and then the substrate is cleaned by acetone and dried by blowing.
4) According to laser cladding parameters: 7mm/s of scanning speed, 2200W of laser power, 28g/min of powder feeding speed and 7.4mm of spot diameter. The whole laser cladding process is carried out under the protection of argon, and the flow of the argon protection gas is 12L/min. The lap joint rate is 30 percent by adopting a multi-pass cladding method.
Example four
In this embodiment, a specific preparation method of the intermediate entropy alloy laser cladding coating is as follows:
1) the medium entropy alloy laser cladding coating comprises the following components in atomic percentage of Cr 50%, Co 20% and Ni 30%;
2) weighing and preparing raw materials according to the atomic percentages of the components, smelting the medium-entropy alloy material, then obtaining medium-entropy alloy powder in an atomization mode, drying, and sieving to obtain 53-150 mu m powder.
3) The selected 9Ni steel plate is used as a cladding substrate, the size of the substrate is 200mm multiplied by 150mm multiplied by 20mm, the surface of the substrate is ground by a grinding machine before cladding, and then the substrate is cleaned by acetone and dried by blowing.
4) According to laser cladding parameters: the scanning speed is 7mm/s, the laser power is 2800W, the powder feeding rate is 30g/min, and the spot diameter is 7.4 mm. The whole laser cladding process is carried out under the protection of argon, and the flow of the argon protection gas is 15L/min. The lap joint rate is 20 percent by adopting a multi-pass cladding method.
EXAMPLE five
In this embodiment, a specific preparation method of the intermediate entropy alloy laser cladding coating is as follows:
1) the medium entropy alloy laser cladding coating comprises the following components in atomic percentage of Cr 30%, Co 50% and Ni 20%;
2) weighing and preparing raw materials according to the atomic percentages of the components, smelting the medium-entropy alloy material, then obtaining medium-entropy alloy powder in an atomization mode, drying, and sieving to obtain 53-150 mu m powder.
3) The selected 9Ni steel plate is used as a cladding substrate, the size of the substrate is 200mm multiplied by 150mm multiplied by 20mm, the surface of the substrate is ground by a grinding machine before cladding, and then the substrate is cleaned by acetone and dried by blowing.
4) According to laser cladding parameters: 7mm/s of scanning speed, 2200W of laser power, 28g/min of powder feeding speed and 7.4mm of spot diameter. The whole laser cladding process is carried out under the protection of argon, and the flow of the argon protection gas is 12L/min. The lap joint rate is 20 percent by adopting a multi-pass cladding method.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (10)
1. A preparation method of a corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance is characterized by comprising the following steps:
(1) and designing the components of the medium-entropy alloy: the medium entropy alloy comprises the following components in atomic percentage: cr 20-50%, Co 20-50%, Ni 20-50%, the total percentage is 100%;
(2) and pretreating the medium-entropy alloy: smelting the medium entropy alloy and then atomizing to obtain powder;
(3) and cladding matrix pretreatment: polishing the surface of the cladding substrate to be smooth, cleaning and drying;
(4) and laser cladding: and melting the medium-entropy alloy on the surface of the cladding substrate by combining a laser and a powder feeding method to obtain the medium-entropy alloy laser cladding coating.
2. The method according to claim 1, wherein the powder of the intermediate entropy alloy in the step (2) is dried and sieved.
3. The preparation method according to claim 1, wherein the particle size of the medium entropy alloy powder is 53-150 μm.
4. The preparation method according to any one of claims 1 to 3, wherein the step (4) is specifically to put the medium-entropy alloy powder into a laser cladding powder feeding device, and blow the medium-entropy alloy powder onto the surface of the cladding substrate by using a shielding gas as a powder carrying gas through a powder feeding method, so that the medium-entropy alloy powder is melted, metallurgically bonded, solidified and clad on the cladding substrate to form the medium-entropy alloy laser cladding coating through the high-temperature action of laser.
5. The method of claim 4, wherein the parameters of the laser in the laser cladding are: the laser power is 2000-2500W, the scanning speed is 7-8mm/s, and the spot diameter is 7.4 mm.
6. The preparation method of claim 5, wherein the flow of the argon shield gas in the laser cladding powder feeding process is 10-15L/min, and the powder feeding rate is 28-32 g/min.
7. The method of claim 6, wherein the laser cladding is a multi-pass cladding method, and the overlapping rate is 20-30%.
8. The method for preparing the alloy of claim 1, wherein the medium entropy alloy laser cladding coating has a single-phase FCC structure and a hardness of 250-300 HV.
9. The corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance is characterized in that the medium-entropy alloy comprises the following components in atomic percentage: cr 20-50%, Co 20-50%, Ni 20-50%, the total percentage is 100%.
10. The corrosion-resistant medium-entropy alloy laser cladding coating with good low-temperature performance is characterized by being of a single-phase FCC structure, having the hardness of 250-300HV and the thickness of 2.2-2.5 mm.
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| CN111705237A (en) * | 2020-06-03 | 2020-09-25 | 河海大学 | Corrosion-resistant, anti-fouling and anti-cavitation copper-based intermediate entropy alloy coating for ship propeller and preparation method thereof |
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| CN113275847A (en) * | 2021-05-27 | 2021-08-20 | 中国科学院工程热物理研究所 | Marine propeller and multi-alloy composite manufacturing method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111705237A (en) * | 2020-06-03 | 2020-09-25 | 河海大学 | Corrosion-resistant, anti-fouling and anti-cavitation copper-based intermediate entropy alloy coating for ship propeller and preparation method thereof |
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| CN112410782A (en) * | 2020-11-18 | 2021-02-26 | 中国兵器科学研究院宁波分院 | Heat treatment method for laser cladding coating material |
| CN113275847A (en) * | 2021-05-27 | 2021-08-20 | 中国科学院工程热物理研究所 | Marine propeller and multi-alloy composite manufacturing method thereof |
| CN113414384A (en) * | 2021-07-02 | 2021-09-21 | 宜宾上交大新材料研究中心 | Medium-entropy alloy composite material and preparation method and application thereof |
| CN114395714A (en) * | 2021-12-20 | 2022-04-26 | 东北大学 | Ultrahigh-strength Co-based medium-entropy alloy and preparation method thereof |
| CN114875289A (en) * | 2022-04-11 | 2022-08-09 | 上海交通大学 | High-temperature-resistant radiation-resistant high-entropy alloy and preparation method thereof |
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| CN115558921A (en) * | 2022-10-14 | 2023-01-03 | 济南森峰激光科技股份有限公司 | Method for preparing titanium alloy amorphous-medium entropy-based wear-resistant material by laser cladding |
| CN115558921B (en) * | 2022-10-14 | 2024-04-12 | 山东银亿汇峰智能制造有限公司 | Method for preparing titanium alloy amorphous-medium entropy base wear-resistant material by laser cladding |
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Application publication date: 20200522 |