Preparation method of nickel-based superalloy surface heat dredging copper-based coating
By using compressed gas to carry copper-based powder to form a coating on the surface of a nickel-based superalloy through supersonic impact, combined with annealing treatment, the problems of low adhesion and environmental pollution are solved, achieving efficient and environmentally friendly copper-based coating deposition with high adhesion strength and excellent thermal conductivity.
Patent Information
- Application Number
- CN202511420006.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-30
- Publication Date
- 2026-01-16
AI Technical Summary
Existing technologies for attaching copper coatings to nickel-based superalloy surfaces suffer from problems such as low adhesion, complex processes, high costs, and environmental pollution.
Copper-based powder is carried by compressed gas and impacted at supersonic speed onto a nickel-based superalloy substrate to form a copper-based coating. The coating is then annealed in an inert atmosphere to improve bonding strength and thermal conductivity.
It achieves efficient and environmentally friendly copper-based coating deposition, with high bonding strength, low porosity, and good thermal conductivity, avoiding oxidation and environmental pollution in traditional processes.
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Abstract
Description
TECHNICAL FIELD
[0001] The application relates to a preparation method of an alloy surface coating, in particular to a preparation method of a heat dissipation copper-based coating on a nickel-based high-temperature alloy surface. BACKGROUND
[0002] The nickel-based high-temperature alloy is widely applied in industrial production due to its excellent corrosion resistance, and with the continuous development of aerospace, the functional requirements of some mechanical workpieces are higher and higher, the heat conduction performance of the nickel-based high-temperature alloy cannot meet the market demand compared with copper, the heat dissipation coating technology is developing in the direction of large thickness, high heat conduction and multi-function integration, therefore, attaching a copper coating on the nickel-based high-temperature alloy has very important significance for the development of modern industry.
[0003] At present, the copper coating on the nickel-based high-temperature alloy substrate is mostly prepared by electroplating, due to the existence of a dense passivation protective film on the surface of the nickel-based high-temperature alloy, the adhesion between the plating layer and the substrate is reduced, therefore, the nickel-based high-temperature alloy needs to be pretreated before electroplating, and nickel is plated on the surface of the substrate as an intermediate layer, so that the manufacturing cost and period of the workpiece are increased. In the process of electroplating, cyanide is also produced, and the cyanide is complex and high in cost in the industrial wastewater treatment process, and has an impact on the environment and people's life.
[0004] Therefore, a new process which can ensure high adhesion and improve the performance of the coating has very important practical significance for the application and basic research of the coating. SUMMARY
[0005] The application aims to provide a preparation method of a heat dissipation copper-based coating on a nickel-based high-temperature alloy surface, which has high deposition efficiency and adhesion strength.
[0006] The technical scheme is as follows: The preparation method of the heat dissipation copper-based coating on the nickel-based high-temperature alloy surface comprises the following steps:
[0007] (1) compressed gas is used as accelerating gas, copper-based powder is carried by the accelerating gas, and the copper-based powder impacts the nickel-based high-temperature alloy substrate at supersonic speed in a complete solid state to be deposited on the surface of the nickel-based high-temperature alloy substrate to form a Cu-based coating;
[0008] (2) the sample obtained in the step (1) is annealed at 200-350 DEG C in an inert atmosphere for 3-6 h, so that the heat dissipation copper-based coating is prepared on the surface of the nickel-based high-temperature alloy.
[0009] In the step (1), the copper content in the copper-based powder is 85%-99.9%, and the particle size of the copper-based powder is 20-30 mu m.
[0010] The compressed gas has a pressure of 2-6 MPa and a gas temperature of 600-1200 DEG C in step (1); the compressed gas is one of N2, He, mixed gas or air; and the supersonic speed is 300-1400 m / s.
[0011] In step (1), the compressed gas carries the powder particles into the nozzle from the axial direction to generate supersonic gas-solid two-phase flow, and the distance from the nozzle to the nickel-based superalloy substrate is 10-30 cm; the scanning speed of the nozzle on the surface of the nickel-based superalloy substrate is 100-200 mm / s, and the powder feeding amount is 100-200 g / min; and one scanning of the nozzle on the substrate surface obtains the initial sample of the copper coating.
[0012] Invention principle:
[0013] The application prepares a copper coating on the surface of a nickel-based superalloy, and proves that the coating and the substrate have high deposition efficiency and bonding strength. The compressed gas (N2, He, mixed gas or air, etc.) carries the powder particles into the nozzle from the axial direction to generate supersonic (300-1400 m / s) gas-solid two-phase flow, and the powder is accelerated to impact the substrate in a complete solid state and is deposited on the substrate surface to form a coating through plastic deformation. The dense passivation film on the surface of the substrate is broken during the particle impact on the substrate, which promotes the bonding of the powder particles and the substrate, the metal solid collision welding deposition process has little thermal effect on the structure of the powder particles, has good acceleration effect on the particles, and the copper-based powder is not easy to be oxidized during the deposition process.
[0014] The coating formed on the substrate is dense and has low porosity. During the deposition process, the impact of the subsequent particles on the coating formed by the previous particles plays a ramming role, and the volume shrinkage is not obvious, which ensures low porosity, and the particles also generate local heat treatment during the high-temperature acceleration process, which makes the internal grain uniform and improves the bonding strength between the coating and the substrate. During the annealing heat treatment process of the coating, the diffusion of the structure at high temperature improves the bonding strength between the coating and the substrate. After heat treatment, the copper grains recrystallize, making the grain structure more uniform and improving the thermal conductivity of the coating.
[0015] Compared with traditional processes such as thermal spraying, electroplating, vapor plating and laser cladding, the present application directly attaches copper-based material on the surface of nickel-based superalloy by metal solid-state collision welding deposition, and exhibits multiple innovations in process, efficiency, cost and coating effect: the present application adopts low-temperature solid-state deposition, copper-based particles impact the substrate at supersonic speed (500-1200 m / s) to realize plastic deformation and achieve metallurgical bonding, which fundamentally avoids the problems of copper-based material oxidation (copper oxide content can be controlled at a very low level), substrate thermal deformation and phase change caused by high temperature (thermal spraying can reach 3000-12000 DEG C) in thermal spraying and laser cladding, and overcomes the complex processing flow and environmental pollution risk of electroplating. In terms of efficiency, the single pass spraying thickness of cold spraying can reach several millimeters (may be > 5 mm or more), the deposition rate is high, and it is suitable for rapid preparation of copper-based coating on the surface of large components. Compared with thermal spraying, the coating is dense (porosity can be < 0.5%) and has excellent performance, and can reach more than 80% of the bulk material. In terms of coating interface bonding, the bonding strength is high (can reach 30-100 MPa), the porosity is low (can be < 0.5%), and the wear resistance, corrosion resistance and heat dissipation performance can be simultaneously improved by using composite powder (such as WC-Co, diamond) or gradient structure design, realizing multi-functional integration, which is difficult to achieve by single-function electroplating or plating.
[0016] Advantages: Compared with the prior art, the present application has the following remarkable effects: (1) Cu-based coating is obtained on the substrate by metal solid-state collision welding deposition, and the sample is annealed in an inert atmosphere, which can promote the diffusion of interface elements and improve the bonding strength of the coating and the substrate. The recrystallization of the coating occurs during annealing of the sample, which makes the grains in the coating more uniform, improves the thermal conductivity and stability of the coating, and the Cu-based coating obtained by suitable temperature and holding time annealing treatment has high bonding strength and thermal conductivity. (2) The powder particles of the sprayed material are accelerated in the hot non-oxidizing gas beam, and the coating has no oxidation phenomenon and low porosity. (3) Due to the high speed of the particles when impacting the substrate, a large plastic deformation is generated, which makes the coating and the current collector tightly bonded and not easy to crack, and reaches the state of flexible bending. (4) There is no participation and emission of organic solvents and gases such as acid washing, toxic and irritating odors, which is beneficial to the protection of the environment in industrial production. BRIEF DESCRIPTION OF DRAWINGS
[0017] Figure 1 Technical principle diagram of metal solid-state collision welding deposition;
[0018] Figure 2 Actual picture of the primary part of the Cu-based coating prepared in Example 1;
[0019] Figure 3 Cross-sectional interface diagram of the Cu-based coating and the substrate prepared in Example 1;
[0020] Figure 4 The microstructure of the Cu-based coating prepared in Example 1 is shown in the figure. DETAILED DESCRIPTION
[0021] The application will be described in further detail below.
[0022] Example 1
[0023] S1, the copper-based powder is sieved and then placed in the powder feeder of the metal solid-state collision welding deposition device; the particle size of the copper-based powder is 20-30 μm.
[0024] S2, the process parameters of the metal solid-state collision welding deposition device are set as follows: the feeding gas is N2, the gas pressure is 5 MPa, the gas temperature is 800°C; the scanning speed is 100 mm / s, and the powder feeding amount is 200 g / min. The distance between the nozzle and the nickel-based superalloy substrate during the metal solid-state collision welding deposition is about 10-30 cm; the nickel-based superalloy substrate in this example is Inconel 718, and can also be Inconel 625.
[0025] S3, the feeding powder is preheated at about 80-100°C, and the feeding gas is warmed and pressurized;
[0026] S4, the metal solid-state collision welding deposition device is started, the powder is deposited on the nickel-based superalloy substrate, the nozzle is scanned back and forth on the surface of the substrate once to obtain a Cu-based coating primary part, and the thickness of the Cu-based coating is about 0.2-0.4 mm. The principle diagram of the metal solid-state collision welding deposition technology is shown in Figure 1 .
[0027] S5, the Cu-based coating primary part is placed in a box-type furnace, the box-type furnace is filled with argon, the temperature in the box-type furnace is controlled at 300°C, and the Cu-based coating primary part is annealed in the box-type furnace for 4 h under the argon atmosphere.
[0028] The actual figure of the Cu-based coating primary part prepared in Example 1 is shown in Figure 2 .
[0029] Example 2
[0030] S1, the copper-based powder is sieved and then placed in the powder feeder of the metal solid-state collision welding deposition device; the particle size of the copper-based powder is 20-30 μm.
[0031] S2, the process parameters of the metal solid-state collision welding deposition device are set as follows: the feeding gas is N2, the gas pressure is 5 MPa, the gas temperature is 800°C; the scanning speed is 100 mm / s, and the powder feeding amount is 200 g / min. The distance between the nozzle and the nickel-based superalloy substrate during the metal solid-state collision welding deposition is about 10-30 cm; the nickel-based superalloy substrate in this example is Inconel 718, and can also be Inconel 625.
[0032] S3, preheat the feed powder at about 80-100℃, and warm and pressurize the feed gas;
[0033] S4, start the metal solid-state collision welding deposition device, deposit the powder on the nickel-based superalloy substrate, and scan the nozzle on the substrate surface back and forth once to obtain a Cu-based coating primary part. The thickness of the Cu-based coating is about 0.2-0.4 mm. The principle diagram of the metal solid-state collision welding deposition technology is shown in Figure 1 .
[0034] S5, place the Cu-based coating primary part in a box furnace, fill the box furnace with argon, control the temperature in the box furnace to be 400℃, and anneal the primary part with the Cu-based coating in the box furnace for 4 h under the argon atmosphere.
[0035] Example 3
[0036] S1, screen the copper-based powder and place it in the powder feeder of the metal solid-state collision welding deposition device. The particle size of the copper-based powder is less than 30 μm.
[0037] S2, set the process parameters of the metal solid-state collision welding deposition device as follows: the feed gas is N2, the gas pressure is 5 MPa, the gas temperature is 800℃, the scanning speed is 100 mm / s, and the powder feeding amount is 200 g / min. The distance between the nozzle and the substrate during the metal solid-state collision welding deposition is about 10-30 cm.
[0038] S3, preheat the feed powder at about 80-100℃, and warm and pressurize the feed gas;
[0039] S4, start the metal solid-state collision welding deposition device, deposit the powder on the nickel-based superalloy substrate, and scan the nozzle on the substrate surface back and forth once to obtain a Cu-based coating primary part. The thickness of the Cu-based coating is about 0.2-0.4 mm. The principle diagram of the metal solid-state collision welding deposition technology is shown in Figure 1 .
[0040] S5, place the Cu-based coating primary part in a box furnace, fill the box furnace with argon, control the temperature in the box furnace to be 500℃, and anneal the primary part with the Cu-based coating in the box furnace for 4 h under the argon atmosphere.
[0041] Example 4
[0042] S1, screen the copper-based powder and place it in the powder feeder of the metal solid-state collision welding deposition device. The particle size of the copper-based powder is 20-30 μm.
[0043] S2, set the metal solid-state collision welding deposition device process parameters as follows: feeding gas is He, gas pressure 3 MPa, gas temperature is 600 DEG C; scanning rate is 100 mm / s, powder feeding amount is 200 g / min; metal solid-state collision welding deposition nozzle to the base set distance is about 10~30 cm.
[0044] S3, preheating the feed powder at about 80~100 DEG C, the feeding gas is heated and pressurized;
[0045] S4, start the metal solid-state collision welding deposition device, to the nickel-based superalloy substrate deposition powder, nozzle on the base surface back and forth each scan once get Cu-based coating primary parts, Cu-based coating thickness is about 0.2~0.4 mm. Metal solid-state collision welding deposition technology principle diagram as shown in Figure 1
[0046] S5, the Cu-based coating of the primary parts of the box furnace, make the box furnace filled with argon, in the argon atmosphere, control the temperature in the box furnace is 300 DEG C, make the Cu-based coating of the primary parts in the box furnace annealing 4 h.
[0047] The copper coating prepared by example 4 is observed by microstructure, get Figure 3 And Figure 4 From Figure 3 And Figure 4 It can be seen that the coating is dense, the coating and the substrate are combined tightly, and it is not easy to crack.
[0048] Example 5
[0049] S1, the copper-based powder is sieved and placed in the powder feeder of the metal solid-state collision welding deposition device; the particle size of the copper-based powder is 20~30 μm.
[0050] S2, set the metal solid-state collision welding deposition device process parameters as follows: feeding gas is He, gas pressure 3 MPa, gas temperature is 600 DEG C; scanning rate is 100 mm / s, powder feeding amount is 200 g / min; metal solid-state collision welding deposition nozzle to the base set distance is about 10~30 cm.
[0051] S3, preheating the feed powder at about 80~100 DEG C, the feeding gas is heated and pressurized;
[0052] S4, start the metal solid-state collision welding deposition device, to the nickel-based superalloy substrate deposition powder, nozzle on the base surface back and forth each scan once get Cu-based coating primary parts, Cu-based coating thickness is about 0.2~0.4 mm. Metal solid-state collision welding deposition technology principle diagram as shown in Figure 1
[0053] S5, the Cu-based coating of the primary parts of the box furnace, so that the box furnace filled with argon, in the argon atmosphere, control the temperature in the box furnace is 400 ℃, so that the Cu-based coating of the primary parts in the box furnace annealing 4 h.
[0054] Example 6
[0055] S1, the copper-based powder after screening is placed in the powder feeder of the metal solid-state collision welding deposition device; the particle size of the copper-based powder is 20-30 μm.
[0056] S2, the metal solid-state collision welding deposition process parameters are set as follows: the feeding gas is He, the gas pressure is 3 MPa, the gas temperature is 600 ℃; the scanning rate is 100 mm / s, the powder feeding amount is 200 g / min; the nozzle to the substrate is set to about 10-30 cm during the metal solid-state collision welding deposition.
[0057] S3, the feeding powder is preheated at about 80-100 ℃, and the feeding gas is heated and pressurized;
[0058] S4, start the metal solid-state collision welding deposition device, deposit the powder on the nickel-based superalloy substrate, the nozzle scans back and forth on the substrate surface once to obtain the Cu-based coating of the primary parts, the thickness of the Cu-based coating is about 0.2-0.4 mm. The principle diagram of the metal solid-state collision welding deposition technology is shown in Figure 1
[0059] S5, the Cu-based coating of the primary parts of the box furnace, so that the box furnace filled with argon, in the argon atmosphere, control the temperature in the box furnace is 500 ℃, so that the Cu-based coating of the primary parts in the box furnace annealing 4 h.
[0060] Comparative Example 1
[0061] Based on Example 3, different from Example 3 is that the gas pressure is 1 MPa.
[0062] Comparative Example 2
[0063] Based on Example 3, different from Example 3 is that the gas temperature is room temperature.
[0064] Comparative Example 3
[0065] Based on Example 3, different from Example 3 is that the powder feeding amount is 500 g / min.
[0066] Comparative Example 4
[0067] Based on Example 2, different from Example 2 is that no annealing heat treatment is performed.
[0068] Comparative Example 5
[0069] On the basis of Example 4, different from Example 4 is that no annealing heat treatment is performed.
[0070] The copper coating prepared in the above Examples 1-6 and Comparative Examples 1-5 is tested for performance.
[0071] The coating surface needs to be polished before testing.
[0072] The copper coating prepared is tested for hardness by using a Vickers microhardness tester, and the average value of the coating is measured; wherein the load is 100g, and the pressure maintaining time is 15s. The copper coating prepared is tested for bonding strength by using a universal tensile testing machine, and the testing method is that the coating is connected in the middle of the tensile rod by using an epoxy resin adhesive, and the bonding strength value when the coating falls off from the substrate is tested. The copper coating prepared is tested for thermal diffusivity by using a LFA467 laser thermal conductivity instrument, and the thermal conductivity of the copper coating is calculated.
[0073] The testing results are recorded in Table 1.
[0074] Table 1: Performance of the coating of each group
[0075]
[0076] From the above Table 1, it can be seen that the copper-based coating prepared by the preparation method provided in each embodiment of the present application has excellent performance, high bonding strength and thermal conductivity. The copper coating prepared by using the comparative examples has obviously poorer performance than the embodiments.
[0077] In summary, the preparation method of the nickel-based superalloy thermal diffusion copper-based coating provided by the present application has high bonding strength and thermal conductivity, because the primary parts of the Cu-based coating are obtained by cold spraying on the 1mm nickel-based superalloy substrate, and then the Cu-based coating obtained by annealing treatment at a suitable temperature and for a suitable holding time has high bonding strength and thermal conductivity.
Claims
1. A method of producing a surface heat-dissipating copper-based coating of a nickel-based superalloy, characterized in that, The method comprises the following steps: (1) using compressed gas as accelerating gas, copper-based powder is carried by the accelerating gas, and is deposited on the surface of the nickel-based superalloy substrate by plastic deformation to form a copper-based coating at supersonic speed in a complete solid state; (2) the sample obtained in step (1) is annealed at 200-350 DEG C in an inert atmosphere for 3-6 hours, so as to prepare a heat-dissipating copper-based coating on the surface of the nickel-based superalloy.
2. The method for preparing a thermally conductive copper-based coating on the surface of a nickel-based superalloy according to claim 1, characterized in that, In step (1), the copper content in the copper-based powder is 85%-99.9%.
3. The method for preparing a thermally conductive copper-based coating on a nickel-based superalloy surface according to claim 1, characterized in that, In step (1), the pressure of the compressed gas is 2-6 MPa, and the temperature is 600-1200 DEG C.
4. The method for preparing a thermally conductive copper-based coating on a nickel-based superalloy surface according to claim 1, characterized in that, In step (1), the compressed gas is one of N2, He, mixed gas or air.
5. The method of claim 1, wherein the nickel-base superalloy surface is a turbine blade or vane. 5 In step (1), the speed of the supersonic speed is 300-1400 m / s.
6. The method of claim 1, wherein the nickel-base superalloy surface is a turbine blade or vane. In step (1), the powder particles are carried into the nozzle from the axial direction by the compressed gas to generate supersonic gas-solid two-phase flow, and the distance from the nozzle to the nickel-based superalloy substrate is 10-30 cm.
7. The method of claim 6, wherein the nickel-base superalloy surface is a turbine blade or vane.
8. The method of claim 6, wherein the nickel-base superalloy surface is a turbine blade or vane. The scanning speed of the nozzle on the surface of the substrate is 100-200 mm / s, and the powder feeding amount is 100-200 g / min.
8. The method for preparing a thermally conductive copper-based coating on a nickel-based superalloy surface according to claim 1, characterized in that, In step (1), the particle size of the copper-based powder is 20-30 μm.
9. The method of claim 1, wherein the nickel-base superalloy surface is a turbine blade or vane. In step (1), the surface of the nickel-based superalloy substrate is free of a nickel layer.