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CN111411319B - Method for preparing nitride-enhanced high-entropy alloy coating by plasma cladding - Google Patents

Method for preparing nitride-enhanced high-entropy alloy coating by plasma cladding Download PDF

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CN111411319B
CN111411319B CN202010133033.9A CN202010133033A CN111411319B CN 111411319 B CN111411319 B CN 111411319B CN 202010133033 A CN202010133033 A CN 202010133033A CN 111411319 B CN111411319 B CN 111411319B
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powder
cladding
entropy alloy
mixed
gas
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CN111411319A (en
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徐洪洋
卢金斌
冯杰
孙嘉孚
顾圣浩
张海霞
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Hefei Wisdom Dragon Machinery Design Co ltd
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Suzhou University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134Plasma spraying
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C4/00Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06Metallic material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a method for preparing a nitride enhanced high-entropy alloy coating by plasma cladding, which comprises the steps of heating and cladding mixed powder consisting of Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti in a certain proportion on the surface of low-carbon steel under the protection of argon gas mixed with 8-12% of nitrogen gas by using a plasma beam, wherein the mixed gas is used as protective gas and ion gas, nitrogen in the mixed gas is ionized and activated in the cladding process and reacts with Cr, Al and Ti in a molten pool to form fine nitrides, and primary Cr is generated due to the hysteresis effect of high-entropy alloy in the cladding process7C3Has the characteristic of fine crystal grains, and finally is dispersed and distributed in the high-entropy alloy with nitride to form the alloy consisting of CrN, AlN, TiN and Cr7C3And the reinforced AlCoCrCuNiTi high-entropy alloy coating.

Description

Method for preparing nitride-enhanced high-entropy alloy coating by plasma cladding
Technical Field
The invention belongs to the field of high-energy beam surface treatment, and particularly relates to a method for preparing a wear-resistant composite coating by plasma cladding.
Background
The low-carbon steel is carbon steel with the carbon content of less than 0.25 percent, the annealing structure of the low-carbon steel is ferrite and a small amount of pearlite, the low-carbon steel has the characteristics of lower strength and hardness, better plasticity and toughness, good cold formability and good weldability, and has been widely applied to the fields of petrochemical industry, automobile manufacturing, aerospace, ships and the like. However, low carbon steel has low hardness and poor wear resistance, so that the application of the low carbon steel is limited to a certain extent. The hardness and the wear resistance of the low-carbon steel can be improved by cladding the high-entropy alloy coating on the surface of the low-carbon steel. The high-entropy alloy is formed by alloying more than five components according to equal atomic ratio or close to the equal atomic ratio, the high-entropy alloy can form a solid solution to realize solid solution strengthening, so that the high-entropy alloy has excellent mechanical properties such as high hardness, high toughness, high wear resistance and corrosion resistance, high strength and the like which are incomparable with the traditional alloy, and is particularly suitable for preparing a coating, and nitrides such as CrN (1750 HV), AlN (1300 HV), TiN (2300 HV) and the like are added in the high-entropy alloy coating and are dispersedly distributed on the high-entropy alloy coating, so that the hardness and the wear resistance of the high-entropy alloy coating are more favorably enhanced. The plasma cladding is to coat the alloy powder on the surface of the low-carbon steel substrate, heat and clad the alloy powder by using plasma beams, and form the wear-resistant coating after cooling. The plasma cladding equipment is simple, good in reliability, capable of saving cost and wide in application. In the cladding process, a small amount of N2 is mixed in inert Ar gas, nitrogen is ionized and activated, and then the nitrogen reacts with Cr, Al and Ti in a molten pool to form nitrides CrN, AlN and TiN, so that the hardness and the wear resistance of the coating can be further improved.
Disclosure of Invention
The invention adopts plasma cladding to clad the mixed powder consisting of the self-melting alloy with low melting point and the simple substance metal powder, can realize alloying in the cladding process to form the high-entropy alloy, adopts pure argon as the protective gas and the ionized gas in the past, and adopts a proper amount of nitrogen as the working gas to ensure that nitrogen in the mixed gas reacts with Cr, Al and Ti in a molten pool after being ionized and activated to form fine and dispersed nitride, so as to prepare the nitride-reinforced high-entropy alloy coating, thereby being beneficial to further improving the hardness and the wear resistance of the coating.
The manufacturing method adopted by the invention comprises the following process steps:
the method comprises the following steps of firstly, selecting a low-carbon steel surface to be cladded as a matrix, pretreating the surface of the low-carbon steel matrix, polishing the surface of the matrix to be cladded by using a grinding wheel or abrasive paper to remove rust and oxides, and removing oil stains on the surface of the matrix by using alcohol or acetone.
Step two, mixing Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti according to a certain proportion to form mixed powder, and performing ball milling and mixing by using a ball mill, wherein the particle size of the used powder is 40-280 mu m, the mass percentages of the components of Ni-Cr-B-Si are 15-18 of Cr, 2.5-4.5 of B, 3-4.5 of Si, 0.6-1 of C and the balance of Ni; the mass percentages of the components of Co-Cr-B-Si are 15-18% of Cr, 2.5-4.5% of B, 3-4.5% of Si, 0.6-1% of C and the balance of Co; the purities of the Cu powder and the Al powder are both higher than 99.5%; the purity of the Ti powder is higher than 99 percent; the mixed powder comprises the following components in percentage by mass: 24-30: 18-26: 8-12. Ball milling and mixing: ball milling and mixing are carried out by adopting a steel ball milling tank, wherein the mass ratio of grinding balls to mixed powder is 2.4-3.0: 1, a vacuum valve is opened after sealing, vacuum pumping is carried out for 20-40 minutes, the ball milling tank is placed into a planetary ball mill, the rotating speed is 260-280 r/min, the inversion frequency is 30-50 Hz, and the ball milling and mixing time is 50-70 minutes.
And step three, mixing the mixed powder and the pressure-sensitive adhesive according to a weight ratio of 1: 1.1-1.5 to prepare cladding powder, coating the cladding powder on the surface of the low-carbon steel substrate, wherein the coating thickness is 0.7-1.3 cm, the coating width is 0.8-1 cm, and drying for 1.5-2 h at 120-140 ℃.
Step four, heating the cladding powder by adopting plasma beams for cladding, wherein the technological parameters are set as follows: argon mixed with 8-12% of nitrogen is used as protective gas and ionized gas, the cladding parameter current is 100-150A, the working voltage is 20-50V, the scanning speed is 3-6 mm/s, and the flow of the mixed gas used as the protective gas is 0.8-1.4 m3The flow rate of the mixture gas as the ionized gas is 0.9 to 1.5m3The distance between the nozzle and the surface to be treated is 0.8-1.2 cm.
The invention has the beneficial effects that:
(1) the invention utilizes the ionization activation of nitrogen in the mixed gas, the nitrogen can react with Cr, Al and Ti in a molten pool to form fine and dispersed nitride, and the primary Cr is generated due to the delayed diffusion effect of the high-entropy alloy7C3The crystal grains are fine and can be dispersed and distributed in the high-entropy alloy with nitride, which is beneficial to improving the wear resistance and forms a high-entropy alloy consisting of CrN, AlN, TiN and Cr7C3The reinforced AlCoCrCuNiTi high-entropy alloy coating has high hardness, good toughness and good wear resistance.
(2) The high-entropy alloy is adopted as the matrix of the wear-resistant coating, and the special characteristics of low diffusion speed and insensitivity to component change can be fully utilized, so that the coating has higher toughness, strength and wear resistance.
(3) The invention uses the original commonly used Ni-Cr-B-Si and Co-Cr-B-Si self-melting alloy powder, has the advantages of low melting point, uniform components and low cost, has better intersolubility of Fe, Ni and Co, and is easy to realize alloying.
Detailed Description
Example 1:
selecting the surface of Q255 steel to be clad as a matrix, pretreating the surface of the matrix, polishing the surface of the matrix to be clad by using a grinding wheel or abrasive paper to remove rust and oxides, and removing oil stains on the surface of the matrix by using alcohol or acetone.
Step two, mixing Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti according to a certain proportion to form mixed powder, and performing ball milling and mixing by using a ball mill, wherein the particle size of the used powder is 40-280 mu m, the mass percentages of the components of Ni-Cr-B-Si are 15-18 of Cr, 2.5-4.5 of B, 3-4.5 of Si, 0.6-1 of C and the balance of Ni; the mass percentages of the components of Co-Cr-B-Si are 15-18% of Cr, 2.5-4.5% of B, 3-4.5% of Si, 0.6-1% of C and the balance of Co; the purities of the Cu powder and the Al powder are both higher than 99.5%; the purity of the Ti powder is higher than 99 percent; the mixed powder comprises the following components in percentage by mass: 26:26:24:12:12. Ball-milling and mixing the mixed powder by adopting a steel ball-milling tank, wherein the mass ratio of the grinding balls to the mixed powder is 2.4:1, sealing, opening a vacuum valve, vacuumizing for 20 minutes, putting the ball-milling tank into a planetary ball mill, rotating at 260 r/min, inverting at 50 Hz, and ball-milling and mixing for 70 minutes.
And step three, mixing the mixed powder and the pressure-sensitive adhesive according to the weight ratio of 1:1.1 to prepare cladding powder, coating the cladding powder on the surface of a Q255 steel substrate, wherein the coating thickness is 1.3 cm, the coating width is 0.8 cm, and drying for 2 h at 140 ℃.
Step four, heating the cladding powder by adopting plasma beams for cladding, wherein the technological parameters are set as follows: argon mixed with 8 percent of nitrogen is used as protective gas and ionized gas, the cladding parameter current is 130A, the working voltage is 50V, the scanning speed is 3 mm/s, and the flow of the mixed gas used as the protective gas is 1.4 m3H, the flow rate of the mixture as ionized gas is 1.5m3The distance of the nozzle from the surface to be treated was 1.2 cm.
As a result, it was found that CrN, AlN, TiN, Cr were formed on the surface of the Q255 substrate7C3The strengthened AlCoCrCuNiTi high-entropy alloy coating is combined with a substrate in a chemical metallurgy manner, wherein the strengthened phase is fine and is distributed basically uniformly, the appearance of the coating is smooth, the coating basically has no defects such as air holes and cracks, the thickness of the coating is about 550 mu m, and the wear resistance is improved by 5.6 times.
Example 2:
selecting the surface of Q195 steel to be clad as a matrix, pretreating the surface of the matrix, polishing the surface of the matrix to be clad by using a grinding wheel or abrasive paper to remove rust and oxides, and removing oil stains on the surface of the matrix by using alcohol or acetone.
Step two, mixing Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti according to a certain proportion to form mixed powder, and performing ball milling and mixing by using a ball mill, wherein the particle size of the used powder is 40-280 mu m, the mass percentages of the components of Ni-Cr-B-Si are 15-18 of Cr, 2.5-4.5 of B, 3-4.5 of Si, 0.6-1 of C and the balance of Ni; the mass percentages of the components of Co-Cr-B-Si are 15-18% of Cr, 2.5-4.5% of B, 3-4.5% of Si, 0.6-1% of C and the balance of Co; the purities of the Cu powder and the Al powder are both higher than 99.5%; the purity of the Ti powder is higher than 99 percent; the mixed powder comprises the following components in percentage by mass: 28:28:24:10:10. Ball-milling and mixing the mixed powder by adopting a steel ball-milling tank, wherein the mass ratio of the grinding balls to the mixed powder is 2.7:1, sealing, opening a vacuum valve, vacuumizing for 30 minutes, putting the ball-milling tank into a planetary ball mill, rotating at 270 r/min, inverting at 40 Hz, and ball-milling and mixing for 60 minutes.
And step three, mixing the mixed powder and the pressure-sensitive adhesive according to the weight ratio of 1:1.3 to prepare cladding powder, coating the cladding powder on the surface of a Q235 steel substrate, wherein the coating thickness is 1 cm, the coating width is 0.9 cm, and drying for 1.8 h at 130 ℃.
Step four, heating the cladding powder by adopting plasma beams for cladding, wherein the technological parameters are set as follows: argon mixed with 10% nitrogen is used as protective gas and ionized gas, the cladding parameter current is 150A, the working voltage is 35V, the scanning speed is 4.5 mm/s, and the flow of the mixture used as the protective gas is 1 m3H, the flow rate of the mixture as ionized gas is 1.1 m3The distance of the nozzle from the surface to be treated is 1 cm.
As a result, it was found that CrN, AlN, TiN, Cr were formed on the surface of the Q195 substrate7C3The strengthened AlCoCrCuNiTi high-entropy alloy coating has the advantages that the cladding layer is completely metallurgically bonded with the base material, the coating is smooth in appearance and basically free of defects such as air holes and cracks, the thickness of the coating is about 470 mu m, and the wear resistance is improved by 5.3 times.
Example 3:
selecting the surface of Q215 steel to be clad as a matrix, pretreating the surface of the low-carbon steel matrix, polishing the surface of the matrix to be clad by using a grinding wheel or abrasive paper to remove rust and oxides, and removing oil stains on the surface of the matrix by using alcohol or acetone.
Step two, mixing Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti according to a certain proportion to form mixed powder, and performing ball milling and mixing by using a ball mill, wherein the particle size of the used powder is 40-280 mu m, the mass percentages of the components of Ni-Cr-B-Si are 15-18 of Cr, 2.5-4.5 of B, 3-4.5 of Si, 0.6-1 of C and the balance of Ni; the mass percentages of the components of Co-Cr-B-Si are 15-18% of Cr, 2.5-4.5% of B, 3-4.5% of Si, 0.6-1% of C and the balance of Co; the purities of the Cu powder and the Al powder are both higher than 99.5%; the purity of the Ti powder is higher than 99 percent; the mixed powder comprises the following components in percentage by mass: 30:30:22:9:9. Ball-milling and mixing the mixed powder by adopting a steel ball-milling tank, wherein the mass ratio of the grinding balls to the mixed powder is 3:1, sealing, opening a vacuum valve, vacuumizing for 40 minutes, putting the ball-milling tank into a planetary ball mill, rotating at 280 r/min, inverting at 30 Hz, and ball-milling and mixing for 50 minutes.
And step three, mixing the mixed powder and the pressure-sensitive adhesive according to the weight ratio of 1:1.5 to prepare cladding powder, coating the cladding powder on the surface of a Q215 steel substrate, wherein the coating thickness is 0.7 cm, the coating width is 1 cm, and drying for 1.5 h at 120 ℃.
Step four, heating the cladding powder by adopting plasma beams for cladding, wherein the technological parameters are set as follows: argon mixed with 12 percent of nitrogen is used as protective gas and ionized gas, the cladding parameter current is 100A, the working voltage is 20V, the scanning speed is 6 mm/s, and the flow of the mixed gas used as the protective gas is 0.8 m3H, the flow rate of the mixture as ionized gas is 0.9 m3The distance of the nozzle from the surface to be treated was 0.8 cm.
As a result, it was found that a coating of CrN, AlN, TiN, Cr was formed on the surface of the Q215 steel substrate7C3The enhanced AlCoCrCuNiTi high-entropy alloy coating has the advantages of smooth coating appearance, basically no defects such as pores, cracks and the like, low dilution rate, fine grain size of a cladding layer, high surface hardness, coating thickness of about 390 mu m and 5.1 times improvement of wear resistance.

Claims (3)

1. A method for preparing a nitride enhanced high-entropy alloy coating by plasma cladding is characterized by comprising the following process steps:
selecting a low-carbon steel surface to be clad as a matrix, pretreating the surface of the low-carbon steel matrix, polishing the surface of the matrix by using a grinding wheel or abrasive paper to remove oxides and rust, and removing oil stains on the surface of the matrix by using alcohol or acetone;
step two, mixing Ni-Cr-B-Si, Co-Cr-B-Si, Cu, Al and Ti according to a certain proportion to form mixed powder, and performing ball milling and mixing by using a ball mill, wherein the particle size of the used powder is 40-280 mu m; wherein the mass percentages of the components of Ni-Cr-B-Si are 15-18 of Cr, 2.5-4.5 of B, 3-4.5 of Si, 0.6-1 of C and the balance of Ni; the mass percentages of the components of Co-Cr-B-Si are 15-18% of Cr, 2.5-4.5% of B, 3-4.5% of Si, 0.6-1% of C and the balance of Co; the purities of the Cu powder and the Al powder are both higher than 99.5%; the purity of the Ti powder is higher than 99 percent; the mixed powder comprises the following components in percentage by mass: 24-30: 18-26: 8-12;
mixing the mixed powder and the pressure-sensitive adhesive according to the weight ratio of 1: 1.1-1.5 to prepare powder to be cladded, coating the powder on the surface of the low-carbon steel substrate, wherein the coating thickness is 0.7-1.3 cm, the width is 0.8-1 cm, and drying;
heating the cladding powder by adopting plasma beams for cladding, and cooling to obtain the wear-resistant coating; the specific process of cladding adopts argon mixed with 8-12% of nitrogen as protective gas and ionized gas, cladding parameter current is 100-150A, working voltage is 20-50V, scanning speed is 3-6 mm/s, and flow of mixed gas as protective gas is 0.8-1.4 m3The flow rate of the mixed gas as the ionized gas is 0.9-1.5 m3The distance between the nozzle and the surface to be treated is 0.8-1.2 cm.
2. The method for preparing the nitride enhanced high-entropy alloy coating by plasma cladding as claimed in claim 1, wherein: the ball milling and mixing are carried out by adopting a steel ball milling tank, wherein the mass ratio of milling balls to mixed powder is 2.4-3.0: 1, a vacuum valve is opened after sealing, vacuum pumping is carried out for 20-40 minutes, the ball milling tank is placed into a planetary ball mill, the rotating speed is 260-280 r/min, the inversion frequency is 30-50 Hz, and the ball milling and mixing time is 50-70 minutes.
3. The method for preparing the nitride enhanced high-entropy alloy coating by plasma cladding as claimed in claim 1, wherein: the drying process comprises the following steps: drying for 1.5-2 h at 120-140 ℃.
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CN112251749B (en) * 2020-10-23 2023-04-07 黑龙江科技大学 Method for preparing ceramic phase enhanced high-entropy alloy wear-resistant coating of directional array by plasma cladding
CN114284422B (en) * 2022-01-20 2024-09-10 济南大学 Suitable for CoSb3High-entropy electrode based on thermoelectric material and connection method of thermoelectric material and high-entropy electrode

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CN108118336B (en) * 2018-01-04 2019-11-01 苏州科技大学 A kind of method of plasma alloying carbide enhancing high entropy alloy coating
CN108130505B (en) * 2018-01-04 2020-05-22 苏州科技大学 Method for preparing high-entropy alloy coating by plasma beam alloying
CN108118338B (en) * 2018-01-04 2019-11-05 苏州科技大学 A kind of method of high-frequency induction heating cladding TiC enhancing high entropy alloy coating
CN108048784B (en) * 2018-01-04 2019-07-12 苏州科技大学 A kind of method that plasma thermal sprayed prepares nitride enhancing high entropy alloy coating
CN108118337B (en) * 2018-01-04 2019-11-05 苏州科技大学 A kind of method of plasma beam surface cladding TiN enhancing high entropy alloy coating
CN109402578B (en) * 2019-01-09 2020-10-09 苏州科技大学 Method for preparing high-entropy alloy coating based on reactive magnetron sputtering technology

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