High-entropy alloy coating, nickel-based interface cone with high-entropy alloy coating and preparation method

Abstract

The application belongs to the technical field of high-entropy alloys, and particularly relates to a high-entropy alloy coating, a nickel-based interface cone with the high-entropy alloy coating and a preparation method. The high-entropy alloy coating comprises 15-20% of tantalum, 10-15% of tungsten, 14-20% of nickel, 3-8% of iron, 9-13% of molybdenum, and the balance of one or more of ruthenium, platinum, zirconium and boron. The high-entropy alloy coating has a grain size of less than or equal to 5 microns, a density of greater than or equal to 99.8%, a thickness of 0.1-0.6 mm, a surface roughness of less than 0.5 microns, and a thermal conductivity of greater than or equal to 140 W / (m*K). The nickel-based interface cone with the high-entropy alloy coating prepared by the application can continuously work for greater than or equal to 80 hours under the bombardment of 4000-8000 K high-temperature plasma, does not corrode and fall off in a working environment with a pH of less than or equal to 3 or greater than or equal to 9, and the amount of impurities introduced is less than or equal to 5 ppm. In addition, compared with a nickel-based interface cone with a platinum group metal coating, the production cost of the coating of the nickel-based interface cone with the high-entropy alloy coating can be saved by 20%-30%.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high-entropy alloys, and particularly relates to a high-entropy alloy plating layer, a nickel-based interface cone with the high-entropy alloy plating layer and a preparation method. BACKGROUND

[0002] In modern analytical science, inductively coupled plasma mass spectrometer ICP-MS is a high-precision element detection and analysis instrument, and has the advantages of high efficiency and precision, simultaneous analysis of multiple elements, isotope analysis, high sensitivity and low detection limit, and thus is distinguished from the same type of detection instrument, and is an indispensable emerging trace analysis technology. In the whole system of the instrument, the interface part is mostly an interface cone structure to connect the ICP ion source and the mass spectrometer, which maintains the consistency and integrity of the ions while ensuring the effective transmission of the ions, and is an important and key component of the ICP-MS instrument, which is a combination of the high-temperature ionization characteristics of the inductively coupled plasma and the rapid scanning and sensitive performance of the mass spectrometer. The transmission characteristics of the interface cone directly affect the analysis performance of the instrument. The interface cone needs to withstand high temperature, high pressure and corrosive environment due to the need to face the high-temperature and high-speed ion source, so high requirements are put forward for the heat resistance, corrosion resistance and thermal conductivity of the interface cone material, and it is particularly important to produce and apply high-quality nickel-based interface cones to ensure the sensitivity, stability and service life of the instrument.

[0003] At present, the method for improving the performance of the nickel-based interface cone mainly prepares an oxide ceramic plating layer or a platinum group metal plating layer on the surface of the nickel-based interface cone, wherein the oxide ceramic plating layer preferentially corrodes the oxide plating layer during use, protects the nickel-based interface cone from corrosion, and thus prolongs the service life thereof. However, the ceramic material has low thermal conductivity, which affects the heat dissipation of the nickel-based interface cone, and the oxide ceramic is not resistant to acid corrosion, so the use scene is limited and the service life is limited. Although the platinum group metal plating layer has good thermal conductivity and corrosion resistance, the use cost is high, which greatly increases the single test cost. SUMMARY

[0004] In view of the problems in the prior art, the application provides a high-entropy alloy plating layer, a nickel-based interface cone with the high-entropy alloy plating layer and a preparation method, and the application specifically comprises the following steps:

[0005] A high-entropy alloy plating layer, the high-entropy alloy comprises, by mass percentage:

[0006] Tantalum: 15-20%;

[0007] Tungsten: 10-15%;

[0008] Nickel: 14-20%;

[0009] Iron: 3-8%;

[0010] Molybdenum: 9-13%;

[0011] The balance is one or more of ruthenium, platinum, zirconium, and boron;

[0012] The grain size of the high-entropy alloy coating is ≤1 μm, and the density is ≥99.8%.

[0013] Further, the thickness of the high-entropy alloy coating is 0.1-0.6 μm; and / or, the surface roughness is <0.5 μm.

[0014] Further, the thermal conductivity of the high-entropy alloy coating is ≥140 W / (m·K).

[0015] A nickel-based interface cone with the high-entropy alloy coating.

[0016] Further, the nickel-based interface cone with the high-entropy alloy coating can continuously work for ≥80 h under high-temperature plasma bombardment of 4000-8000 K.

[0017] Further, the high-entropy alloy coating on the surface of the nickel-based interface cone can work in an environment with pH≤3 or pH≥9, and the corrosion products after corrosion in a strong acid or strong alkali environment do not fall off, and the impurity introduction amount is ≤0.5 ppm.

[0018] A preparation method of the nickel-based interface cone with the high-entropy alloy coating, comprising the following steps:

[0019] S1, sputtering coating: in an inert gas atmosphere, using the high-entropy alloy as a target material, a high-entropy alloy coating is prepared on the surface of the nickel-based interface cone by magnetic sputtering;

[0020] S2, coating heat treatment: the nickel-based interface cone with the high-entropy alloy coating sputtered on the surface is subjected to vacuum heat treatment, and after the end of the heat treatment, the nickel-based interface cone with the high-entropy alloy coating is obtained.

[0021] Further, in step S1: the inert gas is argon, the pressure of the argon atmosphere is (2-5)×10 -1 Pa; and / or, the power of the magnetic sputtering is 50-80 W, and the time is 5-10 min; and / or, the magnetic sputtering power source uses a direct current power source.

[0022] Further, in step S2: the vacuum degree of the vacuum heat treatment is ≤2×10 -4 Pa, the holding temperature is 300-500℃, and the holding time is 0.5-3 h.

[0023] Further, before step S1 of sputtering coating, it further comprises: S0, pre-sputtering: using a baffle to shield the nickel-based interface cone, pre-sputtering the target material to remove the stress and surface oxide layer of the target material.

[0024] Further, the pre-sputtering in step S0 is performed in an argon atmosphere with a pressure of (1-3) x 10 -1 Pa, and / or the power of the pre-sputtering is 30-150 W, and the pre-sputtering time is 3-15 min.

[0025] Further, before the sputtering, the nickel-based interface cone is immersed and cleaned with an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:(0.8-1.2) and a total mass concentration of ≤10%, the immersion and cleaning time is 5-15 min, and the immersion and cleaning is followed by drying for 10-30 min, and the surface roughness of the nickel-based interface cone after the immersion and cleaning is 1-5 μm; and / or, before the sputtering, the nickel-based interface cone is heated to 100-250℃ and kept for 5-15 min.

[0026] The beneficial effects of the present application are:

[0027] (1) The core feature of high-entropy alloy is its high mixing entropy, which helps the alloy to form a simple solid solution structure during solidification, rather than a complex intermetallic compound. In this solid solution structure, the distribution of various alloying elements in the crystal lattice is more uniform, reducing the phenomenon of element segregation and grain boundary enrichment. In the high-entropy alloy coating of the present application, 15-20% tantalum and 10-15% tungsten are added to increase the hardness and wear resistance of the coating, and also help to improve the density of the coating. The addition of 14-20% nickel helps to form a stable solid solution structure, and also improves the toughness and corrosion resistance of the coating. The addition of 3-8% iron can further increase the strength and hardness of the coating, and the interaction of iron with other elements also helps to form a more dense microstructure. The addition of 9-13% molybdenum can significantly improve the high-temperature resistance and corrosion resistance of the coating, and also help to improve the density of the coating. Moreover, the tantalum, nickel, molybdenum and other elements in the high-entropy alloy coating of the present application can form a dense oxide film or passivation layer outside the coating, thereby making the coating have good corrosion resistance. In addition, the addition of a certain amount of one or more of ruthenium, platinum, zirconium, boron elements can further adjust the performance of the coating, for example, ruthenium and platinum have excellent corrosion resistance and high-temperature stability; the addition of zirconium can improve the strength and hardness of the coating; the addition of boron helps to form an amorphous structure, further improving the density and wear resistance of the coating. Moreover, due to the differences in atomic size and properties of tantalum, tungsten, nickel, ruthenium, iron, zirconium, molybdenum, platinum, boron and other elements, their distribution in the crystal lattice will cause lattice distortion, which not only helps to improve the strength and hardness of the coating, but also helps to promote the densification of the coating. The grain size of the high-entropy alloy coating of the present application is ≤1 μm, the density is ≥99.8%, and the thermal conductivity is ≥140 W / (m·K).

[0028] (2) The present application can remove the oxide layer and stress layer on the surface of the target material before preparing the high-entropy alloy coating layer on the magnetron sputtering surface, the oxide layer contains a large number of oxygen atoms, and after sputtering, a large number of atomic-level point defects and line defects will be generated in the coating layer, the point defects and line defects will make the atoms around the defects have a large distortion energy, reduce the conduction efficiency of the vibration, that is, affect the thermal conductivity of the coating layer, and for the same reason, the stress layer of the target material is easy to form abnormal discharge or large particles to fall on the surface of the coating layer during the sputtering process, which affects the uniformity and performance of the target material. Before magnetron sputtering, the surface of the nickel-based interface cone is cleaned with a special acidic cleaning solution, which can corrode the surface of the nickel-based interface cone, increase the surface roughness to 1-5 μm, and increase the bonding force between the subsequent coating layer and the nickel-based interface cone substrate by 50%.

[0029] (3) The present application uses the method of magnetron sputtering to prepare a coating layer on the surface of the nickel-based interface cone, and improves the magnetron sputtering process by combining the composition of the coating layer and the characteristics of the nickel-based interface cone, which can significantly enhance the adhesion between the high-entropy alloy coating layer and the nickel-based interface cone, improve the density and strength of the coating layer, reduce the surface roughness, prevent the coating layer from falling off due to impact, high temperature, corrosion and other reasons in subsequent use, and improve the performance of the nickel-based interface cone with the high-entropy alloy coating layer. In addition, the present application also performs heat treatment on the coating layer after magnetron sputtering, and designs the heat treatment temperature and time, and the appropriate heat treatment temperature and time can make the coating layer sputtered on the surface of the nickel-based interface cone fully diffuse, reduce various defects of the coating layer to ensure the performance of the coating layer. The nickel-based interface cone with the high-entropy alloy coating layer prepared by the present application can work continuously for ≥80 h under 4000-8000 K high-temperature plasma bombardment, will not corrode and fall off in a working environment with pH≤3 or pH≥9, and the impurity introduction amount is ≤0.5 ppm. In addition, the nickel-based interface cone with the high-entropy alloy coating layer according to the present application can save 20%-30% of the manufacturing cost of the coating layer compared with the nickel-based interface cone with the platinum group metal coating layer. BRIEF DESCRIPTION OF DRAWINGS

[0030] Figure 1 It is a partial enlarged schematic view of the nickel-based interface cone with the high-entropy alloy coating layer prepared by the present application. DETAILED DESCRIPTION

[0031] The present application will be described in detail below in combination with the drawings and specific embodiments. The embodiments shown below do not limit the invention content described in the claims in any way. In addition, the entire content of the constitution represented in the following embodiments is not limited to the solution necessary for the invention described in the claims.

[0032] A high-entropy alloy coating layer, the high-entropy alloy comprises, in mass percentage: tantalum 15-20%; tungsten 10-15%; nickel 14-20%; iron 3-8%; molybdenum 9-13%; and the balance being one or more of ruthenium, platinum, zirconium and boron; the high-entropy alloy coating layer has a grain size of ≤1 μm, a density of ≥99.8%, a thickness of 0.1-0.6 μm, a surface roughness of <0.5 μm, and a thermal conductivity of ≥140 W / (m·K).

[0033] Reference Figure 1 A nickel-based interface cone with the high-entropy alloy coating layer (comprising a high-entropy alloy coating layer 1 and a nickel-based interface cone 2) can continuously work for ≥80 h under 4000-8000 K high-temperature plasma bombardment and does not corrode and fall off in a working environment with pH≤3 or pH≥9, and the amount of impurities introduced is ≤0.5 ppm.

[0034] A preparation method of a nickel-based interface cone with a high-entropy alloy coating layer, comprising the following steps:

[0035] Pre-treatment of the nickel-based interface cone: using an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:(0.8-1.2) and a total mass concentration of ≤10% to soak and clean the nickel-based interface cone, the soaking and cleaning time being 5-15 min, and then drying for 10-30 min, and placing the treated nickel-based interface cone on a substrate table of a magnetron sputtering device;

[0036] S0, pre-sputtering: closing the sputtering baffle so that the baffle completely covers the top of the interface cone, the vacuum degree being ≤2×10 -4 Pa, opening the gas valve, and filling argon to 2×10 -1 Pa, closing the gas valve, and waiting until the vacuum degree reaches ≤2×10 -4 Pa, opening the gas valve and the flowmeter, controlling the argon filling rate to be 20-60 sccm, and adjusting the pressure to be maintained at 1×10 -1 Pa-3×10 -1 Pa, turning on the magnetron sputtering power supply, slowly increasing the current size, adjusting the power to be 30-150 W for pre-sputtering, and the pre-sputtering time being 3-15 min;

[0037] S1, sputtering coating: after the pre-sputtering is completed, opening the baffle, heating the substrate table, heating the nickel-based interface cone to 100-250℃ and maintaining for 5-15 min, controlling the argon filling rate to be 20-40 sccm, and adjusting the pressure to be maintained at (2-5)×10 - 1Pa, the high-entropy alloy is used as a target material to prepare a high-entropy alloy coating on the surface of the nickel-based interface cone by magnetron sputtering; the magnetron sputtering uses a direct current as a power source, the magnetron sputtering power is controlled to be 50-80 W, and the time is 5-10 min; the high-entropy alloy target material has the same composition as the high-entropy alloy coating, the purity of the target material is ≥ 99.99%, and the grain size is ≤ 10 μm;

[0038] S2, coating heat treatment: the magnetron sputtering power source is turned off, the gas exhaust valve is closed, the argon gas is stopped from being filled, and the vacuum degree is maintained to be ≤ 2 × 10 -4 Pa, the substrate table is heated for heat treatment, the holding temperature of the heat treatment is 300-500 ℃, the holding time is 0.5-3 h, and after the heat treatment is completed, the substrate table is cooled in the furnace for 5-8 h to obtain the nickel-based interface cone with the high-entropy alloy coating.

[0039] Embodiment 1

[0040] A preparation method of a nickel-based interface cone with a high-entropy alloy coating, which uses a high-entropy alloy target material as a raw material to prepare a high-entropy alloy coating on the nickel-based interface cone by a magnetron sputtering method.

[0041] The purity of the high-entropy alloy target material used in this embodiment is ≥ 99.99%, and the grain size is ≤ 10 μm. The composition and mass content include: tantalum 16%; tungsten 11%; nickel 14%; iron 5%; molybdenum 10%; and the balance of one or more of ruthenium, platinum, zirconium, and boron.

[0042] The preparation method of this embodiment includes the following steps:

[0043] Nickel-based interface cone pretreatment: the nickel-based interface cone is immersed and cleaned with an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:1 and a total mass concentration of 10%, the immersion cleaning time is 10 min, and then the treated nickel-based interface cone is dried for 20 min and placed on a substrate table of a magnetron sputtering device;

[0044] S0, pre-sputtering: the sputtering baffle is closed so that the baffle completely covers the top of the interface cone, and the vacuum degree is ≤ 2 × 10 -4 Pa, the gas exhaust valve is opened, argon gas is filled to 2 × 10 -1 Pa, the gas exhaust valve is closed, and the vacuum degree is maintained to be ≤ 2 × 10 -4 Pa, the gas exhaust valve and the flowmeter are opened, the argon gas filling rate is controlled to be 30 sccm, and the pressure is adjusted to be maintained at 2 × 10 -1 Pa, the magnetron sputtering power source is turned on, the current is slowly increased, the power is adjusted to be 110 W for pre-sputtering, and the pre-sputtering time is 8 min;

[0045] S1, sputtering film: after the pre-sputtering is finished, the shutter is opened, the substrate table is heated, the nickel-based interface cone is heated to 180 DEG C and is kept for 9 min, the argon filling rate is controlled to be 33 sccm, and the pressure is adjusted to be maintained at 3x10 -1 Pa, the high-entropy alloy is taken as a target material, the high-entropy alloy coating is prepared on the surface of the nickel-based interface cone in a magnetron sputtering mode, direct current is taken as a power supply, the magnetron sputtering power is controlled to be 65 W, and the time is 8 min;

[0046] S2, coating heat treatment: the magnetron sputtering power supply is turned off, the exhaust valve is closed, the argon filling is stopped, the vacuum degree is waited to reach 2x10 -4 Pa, the substrate table is heated, heat treatment is carried out, the heat treatment holding temperature is 400 DEG C, the holding time is 2 h, after the heat treatment is finished, the furnace is cooled for 6 h, and the nickel-based interface cone with the high-entropy alloy coating is obtained.

[0047] It is detected that the grain size of the high-entropy alloy coating prepared in the embodiment is generally less than or equal to 1 mu m, the density is more than 99.9%, the thickness is 0.5 mu m, the surface roughness is 0.4 mu m, and the thermal conductivity is 165 W / (m*K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 96 h under the high-temperature plasma bombardment of 4000-8000 K, does not fall off in the working environment of pH less than or equal to 3 or greater than or equal to 9, and the impurity introduction amount is less than 0.5 pm.

[0048] Embodiment 2

[0049] A preparation method of a nickel-based interface cone with a high-entropy alloy coating, taking a high-entropy alloy target material as a raw material, and preparing a high-entropy alloy coating on the nickel-based interface cone by a magnetron sputtering method.

[0050] The purity of the high-entropy alloy target material used in the embodiment is greater than or equal to 99.99%, and the grain size is less than or equal to 10 mu m. The composition and mass content include: 20% of tantalum, 10% of tungsten, 17% of nickel, 3% of iron, 9% of molybdenum, and the balance of one or more of ruthenium, platinum, zirconium and boron.

[0051] The preparation method of the embodiment includes the following steps:

[0052] Nickel-based interface cone pretreatment: the nickel-based interface cone is immersed and cleaned by using an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:0.8 and a total mass concentration of 9%, the immersion cleaning time is 5 min, then the nickel-based interface cone is dried for 25 min, and the treated nickel-based interface cone is placed on the substrate table of the magnetron sputtering device;

[0053] S0, pre-sputtering: the sputtering shutter is closed, so that the shutter completely covers the upper part of the interface cone, the vacuum degree is less than or equal to 2x10 -4 Pa, the exhaust valve is opened, the argon is filled to 2x10 -1Pa, close the exhaust valve, and wait until the vacuum degree reaches ≤2*10 -4 Pa, open the exhaust valve and flow meter, control the argon filling rate to be 40sccm, and adjust the pressure to be maintained at 2*10 -1 Pa, open the magnetron sputtering power supply, slowly increase the current size, adjust the power to be 80W for pre-sputtering, and the pre-sputtering time is 5min.

[0054] S1, sputtering film: after the pre-sputtering is completed, open the shutter, heat the substrate table, heat the nickel-based interface cone to 150℃, and maintain for 7min, control the argon filling rate to be 40sccm, and adjust the pressure to be maintained at 3*10 -1 Pa, the high-entropy alloy is used as a target material, and a high-entropy alloy coating is prepared on the surface of the nickel-based interface cone in a magnetron sputtering manner; the magnetron sputtering adopts a direct current as a power supply, controls the magnetron sputtering power to be 70W, and the time is 10min.

[0055] S2, coating heat treatment: close the magnetron sputtering power supply, close the exhaust valve, stop the argon filling, and wait until the vacuum degree reaches ≤2*10 -4 Pa, heat the substrate table, and perform heat treatment; the heat treatment has a holding temperature of 300℃ and a holding time of 0.5h, and after the heat treatment is completed, the furnace is cooled for 7h to obtain the nickel-based interface cone with the high-entropy alloy coating.

[0056] It is detected that the grain size of the high-entropy alloy coating prepared in the embodiment is ≤0.9μm, the density is ≥99.8%, the thickness is 0.3μm, the surface roughness is 0.2μm, and the thermal conductivity is 140W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 86h under the high-temperature plasma bombardment of 4000-8000K, does not fall off in the working environment of pH≤3 or pH≥9, and the impurity introduction amount is ≤0.5ppm.

[0057] Embodiment 3

[0058] A preparation method of a nickel-based interface cone with a high-entropy alloy coating, which uses a high-entropy alloy target material as a raw material, and prepares a high-entropy alloy coating on the nickel-based interface cone by a magnetron sputtering method.

[0059] The purity of the high-entropy alloy target material used in the embodiment is ≥99.99%, and the grain size is ≤10μm; the composition and mass content include: tantalum 17%; tungsten 15%; nickel 17%; iron 5%; molybdenum 13%; and the balance is one or more of ruthenium, platinum, zirconium, and boron.

[0060] The preparation method of the embodiment includes the following steps:

[0061] Nickel-based interface cone pretreatment: the nickel-based interface cone is immersed and cleaned with an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:1.2 and a total mass concentration of 8%, the immersion and cleaning time is 15 min, then drying for 30 min, and then placing the treated nickel-based interface cone on the substrate table of the magnetron sputtering device;

[0062] S0, pre-sputtering: the sputtering baffle is closed so that the baffle completely covers the interface cone, the vacuum degree is ≤2×10 -4 Pa, open the gas valve, and fill argon to 2×10 -1 Pa, close the gas valve, and wait until the vacuum degree reaches ≤2×10 -4 Pa, open the gas valve and flowmeter, control the argon filling rate to be 23 sccm, and adjust the pressure to be maintained at 2×10 -1 Pa, turn on the magnetron sputtering power supply, slowly increase the current size, adjust the power to be 65 W for pre-sputtering, and the pre-sputtering time is 6 min;

[0063] S1, sputtering film: after pre-sputtering, open the baffle, heat the substrate table, heat the nickel-based interface cone to 150℃, and keep the temperature for 8 min, control the argon filling rate to be 25 sccm, and adjust the pressure to be maintained at 3×10 -1 Pa, use the high-entropy alloy as the target material, and prepare a high-entropy alloy coating on the surface of the nickel-based interface cone by magnetron sputtering; the magnetron sputtering uses direct current as the power supply, controls the magnetron sputtering power to be 55 W, and the time is 12 min;

[0064] S2, coating heat treatment: close the magnetron sputtering power supply, close the gas valve, stop the argon filling, and wait until the vacuum degree reaches ≤2×10 -4 Pa, heat the substrate table, and perform heat treatment, the heat treatment temperature is 500℃, the heat treatment time is 3 h, after the end, the furnace is cooled for 7 h, and the nickel-based interface cone with a high-entropy alloy coating is obtained.

[0065] It is detected that the grain size of the high-entropy alloy coating prepared in the embodiment is ≤0.8 μm, the density is more than 99.9%, the thickness is 0.5 μm, the surface roughness is 0.3 μm, and the thermal conductivity is 170 W / (m·K). The nickel-based interface cone with a high-entropy alloy coating prepared in the embodiment can work continuously for 85 h under 4000-8000 K high-temperature plasma bombardment, does not fall off in the working environment of pH≤3 or pH≥9, and the impurity introduction amount is ≤0.5 ppm.

[0066] Example 4

[0067] A preparation method of a nickel-based interface cone with a high-entropy alloy coating, which uses a high-entropy alloy target material as raw material, and prepares a high-entropy alloy coating on the nickel-based interface cone by a magnetron sputtering method.

[0068] The purity of the high-entropy alloy target used in the embodiment is ≥99.99%, the grain size is ≤10 μm, and the composition and mass content include: tantalum 18%; tungsten 12%; nickel 16%; iron 8%; molybdenum 11%; and the balance of one or more of ruthenium, platinum, zirconium, and boron.

[0069] The preparation method of the embodiment includes the following steps:

[0070] Pre-treatment of the nickel-based interface cone: the nickel-based interface cone is immersed and cleaned using an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:1 and a total mass concentration of 8%, the immersion and cleaning time is 12 min, then the treated nickel-based interface cone is dried for 15 min and placed on a substrate table of a magnetron sputtering device;

[0071] S0, pre-sputtering: the sputtering baffle is closed so that the baffle completely covers the top of the interface cone, the vacuum degree is ≤2×10 -4 Pa, the gas exhaust valve is opened, argon is filled to 2×10 -1 Pa, the gas exhaust valve is closed, and the vacuum degree is ≤2×10 -4 Pa, the gas exhaust valve and the flowmeter are opened, the argon filling rate is controlled to be 55 sccm, and the pressure is adjusted to be maintained at 2×10 -1 Pa, the magnetron sputtering power supply is turned on, the current is slowly increased, the power is adjusted to be 95 W for pre-sputtering, and the pre-sputtering time is 10 min;

[0072] S1, sputtering film deposition: after the pre-sputtering is completed, the baffle is opened, the substrate table is heated, the nickel-based interface cone is heated to 140℃, and is kept warm for 9 min, the argon filling rate is controlled to be 30 sccm, and the pressure is adjusted to be maintained at 3×10 -1 Pa, the high-entropy alloy is used as a target material, and a high-entropy alloy coating is prepared on the surface of the nickel-based interface cone by magnetron sputtering; the magnetron sputtering uses a direct current as a power supply, the magnetron sputtering power is controlled to be 80 W, and the time is 10 min;

[0073] S2, coating heat treatment: the magnetron sputtering power supply is turned off, the gas exhaust valve is closed, the argon filling is stopped, and the vacuum degree is ≤2×10 -4 Pa, the substrate table is heated for heat treatment, the heat treatment temperature is 450℃, the heat treatment time is 1.5 h, after the heat treatment is completed, the furnace is cooled for 6 h, and the nickel-based interface cone with the high-entropy alloy coating is obtained.

[0074] The high-entropy alloy coating prepared in the embodiment has a grain size of less than or equal to 0.5 μm, a density of more than 99.9%, a thickness of 0.2 μm, a surface roughness of 0.3 μm, and a thermal conductivity of 153 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 85 h under 4000-8000 K high-temperature plasma bombardment, does not fall off in a working environment with pH less than or equal to 3 or pH greater than or equal to 9, and has an impurity introduction amount of less than or equal to 0.5 ppm.

[0075] Comparative Example 1

[0076] The difference between the comparative example and the embodiment 1 is that the mass content of tantalum in the high-entropy alloy target material used is 12%, the mass content of tungsten is 8%, and the other conditions are the same.

[0077] The high-entropy alloy coating prepared in the comparative example has a grain size of less than or equal to 1 μm, a density of 90.2%, a thickness of 0.4 μm, a surface roughness of 0.4 μm, and a thermal conductivity of 125 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the comparative example can continuously work for 55 h under 4000-8000 K high-temperature plasma bombardment, does not fall off in a working environment with pH less than or equal to 3 or pH greater than or equal to 9, and has an impurity introduction amount of less than or equal to 0.5 ppm. The comparative example shows that too low content of tantalum and tungsten in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating and decrease the thermal conductivity.

[0078] Comparative Example 2

[0079] The difference between the comparative example and the embodiment 1 is that the mass content of tantalum in the high-entropy alloy target material used is 25%, the mass content of tungsten is 20%, and the other conditions are the same.

[0080] The high-entropy alloy coating prepared in the embodiment has a grain size of less than or equal to 1 μm, a density of more than 95.7%, a thickness of 0.4 μm, a surface roughness of 0.4 μm, and a thermal conductivity of 143 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 76 h under 4000-8000 K high-temperature plasma bombardment, and falls off in a working environment with pH less than or equal to 3 or pH greater than or equal to 9. The comparative example shows that too high content of tantalum and tungsten in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating and decrease the acid and alkali corrosion resistance.

[0081] Comparative Example 3

[0082] The difference between the comparative example and the embodiment 1 is that the mass content of nickel in the high-entropy alloy target material used is 12%, the mass content of molybdenum is 8%, and the other conditions are the same.

[0083] The high-entropy alloy coating prepared in the present comparative example has a grain size of ≤1 μm, a density of 99.3%, a thickness of 0.4 μm, a surface roughness of 0.4 μm, and a thermal conductivity of 132 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the present comparative example has a continuous working time of 72 h under 4000-8000 K high-temperature plasma bombardment, and has a problem of corrosion product falling off in a working environment with pH≤3 or pH≥9. The present comparative example shows that the high content of nickel and molybdenum in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating, and can reduce the acid and alkali corrosion resistance and the thermal conductivity.

[0084] Comparative Example 4

[0085] The present comparative example differs from Example 1 in that the high-entropy alloy target used has a mass content of nickel of 23% and a mass content of molybdenum of 15%, and other conditions are the same.

[0086] The high-entropy alloy coating prepared in the present comparative example has a grain size of ≤1 μm, a density of 95.6%, a thickness of 0.4 μm, a surface roughness of 0.4 μm, and a thermal conductivity of 140 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the present comparative example has a continuous working time of 40 h under 4000-8000 K high-temperature plasma bombardment, does not have a problem of corrosion product falling off in a working environment with pH≤3 or pH≥9, and has an impurity introduction amount of ≤0.5 ppm. The present comparative example shows that the high content of nickel and molybdenum in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating, and can reduce the acid and alkali corrosion resistance.

[0087] Comparative Example 5

[0088] The present comparative example differs from Example 1 in that the high-entropy alloy target used has a mass content of iron of 1%, and other conditions are the same.

[0089] The high-entropy alloy coating prepared in the present comparative example has a grain size of ≤1 μm, a density of 98.9%, a thickness of 0.4 μm, a surface roughness of 0.6 μm, and a thermal conductivity of 132 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the present comparative example has a continuous working time of 72 h under 4000-8000 K high-temperature plasma bombardment, does not have a problem of corrosion product falling off in a working environment with pH≤3 or pH≥9, and has an impurity introduction amount of ≤0.5 ppm. The present comparative example shows that the low content of iron in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating, and can reduce the acid and alkali corrosion resistance and the thermal conductivity.

[0090] Comparative Example 6

[0091] The difference between the present comparative example and example 1 is that the mass content of iron in the high-entropy alloy target used is 10%, and other conditions are the same.

[0092] It is detected that the grain size of the high-entropy alloy coating prepared in the present comparative example is ≤1 μm, the density is 99.8%, the thickness is 0.4 μm, the surface roughness is 0.4 μm, and the thermal conductivity is 141 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the present comparative example has a continuous working time of 52 h under 4000-8000 K high-temperature plasma bombardment, and has a problem of corrosion product falling off in a working environment with pH≤3 or pH≥9. The present comparative example shows that too high content of iron in the high-entropy alloy coating can reduce the continuous working time of the nickel-based interface cone with the high-entropy alloy coating and decrease the acid and alkali corrosion resistance.

[0093] Comparative example 7

[0094] The difference between the present comparative example and example 1 is that the surface cleaning time of the nickel-based interface cone is 2 min, the surface roughness after cleaning is 0.8 μm, and other conditions are the same.

[0095] It is detected that the grain size of the high-entropy alloy coating prepared in the present example is ≤1 μm, the density is more than 99.9%, the thickness is 0.4 μm, the surface roughness is 0.5 μm, and the thermal conductivity is 143 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the present example has a continuous working time of 52 h under 4000-8000 K high-temperature plasma bombardment, and has a problem of corrosion product falling off in a working environment with pH≤3 or pH≥9. The present comparative example shows that too short cleaning time before coating of the nickel-based interface cone can reduce the surface roughness of the nickel-based interface cone before coating, further reduce the adhesion between the high-entropy alloy coating and the surface of the nickel-based interface cone, and then reduce the continuous working time of the nickel-based interface cone with the coating and decrease the acid and alkali corrosion resistance.

[0096] Comparative example 8

[0097] The difference between the present comparative example and example 1 is that no pre-sputtering treatment is performed, and other conditions are the same.

[0098] The high-entropy alloy coating prepared in the embodiment has a grain size of less than or equal to 3 microns, a density of 98.6%, a thickness of 0.4 microns, a surface roughness of 1.3 microns, and a thermal conductivity of 120 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 48 hours under high-temperature plasma bombardment of 4000-8000 K, and corrosion products will fall off in an environment with pH less than or equal to 3 or pH greater than or equal to 9. The comparative example shows that, if the magnetron sputtering target is not pre-sputtered, the alloy coating will have a high impurity content, which will reduce the thermal conductivity of the coating and reduce the continuous working time of the nickel-based interface cone with the coating and the acid and alkali corrosion resistance of the nickel-based interface cone.

[0099] Comparative Example 9

[0100] The comparative example differs from Example 1 in that the power of magnetron sputtering is 40 W and the sputtering time is 15 minutes, and other conditions are the same.

[0101] The high-entropy alloy coating prepared in the embodiment has a grain size of less than or equal to 3 microns, a density of 98.6%, a thickness of 0.4 microns, a surface roughness of 1.3 microns, and a thermal conductivity of 120 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 48 hours under high-temperature plasma bombardment of 4000-8000 K, and corrosion products will fall off in an environment with pH less than or equal to 3 or pH greater than or equal to 9. The comparative example shows that, if the magnetron sputtering target is not pre-sputtered, the alloy coating will have a high impurity content, which will reduce the thermal conductivity of the coating and reduce the continuous working time of the nickel-based interface cone with the coating and the acid and alkali corrosion resistance of the nickel-based interface cone.

[0102] Comparative Example 10

[0103] The comparative example differs from Example 1 in that the power of magnetron sputtering is 100 W and the sputtering time is 3 minutes, and other conditions are the same.

[0104] The high-entropy alloy coating prepared in the embodiment has a grain size of less than or equal to 3 microns, a density of 98.6%, a thickness of 0.4 microns, a surface roughness of 1.3 microns, and a thermal conductivity of 120 W / (m·K). The nickel-based interface cone with the high-entropy alloy coating prepared in the embodiment can continuously work for 48 hours under high-temperature plasma bombardment of 4000-8000 K, and corrosion products will fall off in an environment with pH less than or equal to 3 or pH greater than or equal to 9. The comparative example shows that, if the magnetron sputtering target is not pre-sputtered, the alloy coating will have a high impurity content, which will reduce the thermal conductivity of the coating and reduce the continuous working time of the nickel-based interface cone with the coating and the acid and alkali corrosion resistance of the nickel-based interface cone.

[0105] Comparative Example 11

[0106] The difference between the present comparative example and example 1 is that no heat treatment is performed on the plating layer, and other conditions are the same.

[0107] It is detected that the non-crystalline, density less than 95.6%, thickness of 0.4 μm, surface roughness of 1.2 μm, and thermal conductivity of 121 W / (m·K) of the high-entropy alloy plating layer prepared in the present comparative example. The nickel-based interface cone with the high-entropy alloy plating layer prepared in the present example continuously works for 32 h under the high-temperature plasma bombardment of 4000-8000 K, and corrosion product falls off in the working environment of pH≤3 or pH≥9. The present comparative example shows that the continuous working time of the nickel-based interface cone without the plating layer is low, and the acid and alkali corrosion resistance and thermal conductivity are poor.

[0108] The above description of disclosed embodiments enables a person skilled in the art to implement or use the present application. Various modifications to the embodiments will be apparent to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present application. Therefore, the present application will not be limited to the embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for producing a nickel-based interface cone with a high-entropy alloy plating layer, characterized by, Comprising the following steps: S1, sputtering: in an inert gas atmosphere, using the high-entropy alloy as a target material, a high-entropy alloy coating is prepared on the surface of the nickel-based interface cone by magnetron sputtering, the high-entropy alloy comprises, by mass percentage: Tantalum: 15-20%; Tungsten: 10-15%; Nickel: 14-20%; Iron: 3-8%; Molybdenum: 9-13%; The balance is one or more of ruthenium, platinum, zirconium, and boron; The grain size of the high-entropy alloy coating is ≤1 μm, and the density is ≥99.8%; S2, heat treatment of the plated layer: subjecting the nickel-based interface cone with the high-entropy alloy plated layer sputtered on the surface to vacuum heat treatment, and cooling after the end to obtain the nickel-based interface cone with the high-entropy alloy plated layer; the vacuum degree of the vacuum heat treatment is ≤2*10 -4 Pa, the holding temperature is 300-500 DEG C, and the holding time is 0.5-3 h.

2. The method of claim 1, wherein the nickel-based interface cone with a high-entropy alloy plating layer is prepared by the steps of: (a) preparing a nickel-based interface cone; (b) preparing a high-entropy alloy plating layer; and (c) plating the high-entropy alloy plating layer on the nickel-based interface cone. The thickness of the high-entropy alloy coating is 0.1-0.6 μm; and / or, the surface roughness is <0.5 μm.

3. The method of making a nickel-based interface cone with a high-entropy alloy plating layer according to any one of claims 1-2, wherein, The thermal conductivity of the high-entropy alloy coating is ≥140 W / (m·K).

4. The method of claim 1, wherein the nickel-based interface cone with a high-entropy alloy plating layer is prepared by the steps of: preparing a nickel-based interface cone; and plating the nickel-based interface cone with a high-entropy alloy plating layer. Step S1: the inert gas is argon, the pressure of the argon atmosphere is (2-5)×10 -1 Pa; and / or, the power of the magnetron sputtering is 50-80 W, the time is 5-10 min; and / or, the magnetron sputtering power supply adopts a direct current power supply.

5. The method of claim 1, wherein the nickel-based interface cone with high-entropy alloy plating layer is prepared by the steps of: (a) preparing a nickel-based interface cone; (b) preparing a high-entropy alloy plating layer; and (c) plating the high-entropy alloy plating layer on the nickel-based interface cone. Before step S1 sputtering, it further comprises: S0 pre-sputtering: using a baffle to shield the nickel-based interface cone, pre-sputtering the target material to remove the stress and surface oxide layer of the target material.

6. The method of claim 5, wherein the nickel-based interface cone with high-entropy alloy plating layer is prepared by the steps of: (a) preparing a nickel-based interface cone; (b) preparing a high-entropy alloy plating layer; and (c) plating the high-entropy alloy plating layer on the nickel-based interface cone. The pre-sputtering described in step S0 is carried out at a pressure of (1-3) x 10 -1 in an argon atmosphere at a pressure of (1-3) x 10 -6 Pa and / or at a power of 30-150 W for a pre-sputtering time of 3-15 min.

7. The method of making a nickel-based interface cone with a high-entropy alloy plating layer according to any one of claims 1-6, wherein, Before sputtering, it further comprises: using an acidic cleaning solution with a mass ratio of hydrochloric acid to sulfuric acid of 1:(0.8-1.2) and a total mass concentration ≤10%, the immersion cleaning time of the nickel-based interface cone is 5-15 min, and the surface roughness of the nickel-based interface cone after immersion cleaning is 1-5 μm; and / or, before sputtering, it further comprises: heating the nickel-based interface cone to 100-250℃ and maintaining for 5-15 min.

8. A nickel-based interface cone with a high-entropy alloy coating prepared by the method of any one of claims 1-3.

9. The nickel-based interface cone with high-entropy alloy plating layer according to claim 8, characterized in that, It can work continuously for ≥80 h under 4000-8000 K high-temperature plasma bombardment.

10. The nickel-based interface cone with high-entropy alloy plating layer according to claim 8, characterized in that, No corrosion shedding occurs in a working environment with pH ≤3 or pH ≥9, and the impurity introduction amount is ≤0.5 ppm.

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