Surface protection method of high-temperature alloy material used in high-temperature, high-pressure or oxygen-enriched environment

Abstract

The invention belongs to the technical field of nickel-based superalloys, and discloses a surface protection method of a superalloy material used in a high-temperature, high-pressure or oxygen-enriched environment. The method comprises the following steps: coating the surface of a high-temperature alloy material with a pure platinum coating; the high-temperature alloy material is used in at least one environment of high temperature, high pressure and oxygen enrichment; the high temperature ranges from 550 DEG C to 750 DEG C; the high pressure is 2 to 55 MPa; the rich oxygen is oxygen concentration gt; 90%. The oxygen-enriched ablation resistance of the high-temperature alloy material is improved, and the use safety of the high-temperature alloy material in a high-temperature, high-pressure and oxygen-enriched severe environment is improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of nickel-based superalloy, and more particularly relates to a surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-rich environment. BACKGROUND

[0002] Nickel-based superalloy is widely used as a hot end component of an advanced aero-engine or space engine due to its excellent high-temperature mechanical properties.

[0003] As a core hot end component of a liquid oxygen kerosene rocket engine, a turbine pump needs to face an extremely harsh working environment of high temperature, high pressure and oxygen enrichment. In this environment, a metal material is prone to a combustion phenomenon similar to that of wood or nylon, which is different from general oxidation and melting and is called metal combustion. Metal combustion is often accompanied by phenomena such as rapid temperature rise, flame generation, volume reduction and intense heat release, which severely limits the use temperature of the high-temperature alloy material.

[0004] With the increase of engine thrust, the temperature and pressure of the turbine pump gradually increase, which puts higher requirements on the mechanical properties and oxygen-rich ablation resistance of the turbine pump material. Coating is an effective way to improve the oxygen-rich ablation resistance of the material. Therefore, in order to meet the use requirements of a liquid oxygen kerosene rocket engine with greater thrust, a new surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-rich environment needs to be developed. SUMMARY

[0005] The present application aims at the deficiencies of the prior art and provides a surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-rich environment. The present application improves the oxygen-rich ablation resistance of the high-temperature alloy material and improves the use safety of the high-temperature alloy material in a harsh environment of high temperature, high pressure and oxygen enrichment.

[0006] In order to achieve the above-mentioned purpose, the present application provides a surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-rich environment, which comprises the following steps: The high-temperature alloy material is a high-temperature alloy material used in at least one of a high-temperature, high-pressure and oxygen-rich environment; the high temperature is 550-750℃; the high pressure is 2-55MPa; and the oxygen enrichment is an oxygen concentration >90%.

[0007] According to the present application, preferably, the high temperature is 550-650℃; the high pressure is 2-50MPa; and the oxygen enrichment is an oxygen concentration >90%.

[0008] According to the present application, preferably, the method comprises the following steps: (1) performing surface treatment on the high-temperature alloy material; (2) The pure platinum coating is applied to the surface of the high-temperature alloy material after the surface treatment by electroplating; (3) The material coated with pure platinum coating is sequentially cleaned, dried, vacuum annealed and vacuum aged to obtain a high-temperature alloy material with pure platinum coating on the surface.

[0009] According to the present invention, preferably, the surface treatment includes sequentially performing surface oxide layer removal, surface grease removal, nitrogen drying, and surface sandblasting on the high-temperature alloy material.

[0010] In this invention, the surface oxide layer removal process is performed by a machining method known to those skilled in the art.

[0011] In this invention, the surface grease removal process is performed using an ultrasonic device. First, the high-temperature alloy material that has undergone surface oxide layer removal treatment and the ultrasonic liquid (the ultrasonic liquid is deionized water mixed with an appropriate amount of degreasing agent, the degreasing agent model is AJX-303, and the temperature of the ultrasonic liquid is 60℃±5℃) are placed into the ultrasonic device for a first ultrasonic cleaning of 10 minutes. Then, the material that has completed the first ultrasonic cleaning and industrial alcohol are placed into the ultrasonic device for a second ultrasonic cleaning of 5 minutes to obtain the high-temperature alloy material with surface grease removed.

[0012] In this invention, surface sandblasting is a surface treatment process performed on a RH-1212A sandblasting machine on a high-temperature alloy material that has been dried with nitrogen. The sandblasting parameters are: the sandblasting material is 180-240 mesh white corundum particles; the pressure is 0.3MPa-0.5MPa.

[0013] According to the present invention, preferably, the electroplating coating thickness of the pure platinum coating is 2.5-3.5 μm.

[0014] In this invention, a pure platinum coating can be obtained by electroplating on the surface of a high-temperature alloy material. The pure platinum coating of this invention is composed entirely of platinum metal.

[0015] In this invention, the combustion characteristics of metallic materials under high temperature, high pressure, and oxygen-rich environments are related to the heat of combustion of the elements. Elements with high heat of combustion release a large amount of heat, which promotes the continuous combustion of the material. After removing toxic and harmful elements, Figure 1 The heat values ​​of combustion of metallic elements are summarized, from Figure 1 It can be seen that the calorific value of Pt is higher than that of Ag and Au, but significantly lower than that of most metallic elements. Au is expensive and unsuitable as a coating material, while Ag is prone to corroding the substrate material and therefore cannot be used as a coating material either. Therefore, Pt is the preferred coating material for high-temperature alloys.

[0016] According to the application, preferably, the vacuum annealing heat treatment comprises: feeding the dried material into a vacuum annealing furnace, first keeping the dried material at 590-610 DEG C for 0.8-1.2 h, then increasing the temperature of the vacuum annealing furnace to 950-970 DEG C within 25-30 min, keeping the material in the vacuum annealing furnace at 950-970 DEG C for 1.8-2.2 h, and finally cooling the material in the vacuum annealing furnace to 15-30 DEG C.

[0017] In the application, the vacuum furnace cooling refers to that the material in the vacuum annealing furnace is slowly and naturally cooled to 15-30 DEG C together with the furnace body under vacuum.

[0018] According to the application, preferably, after the vacuum annealing heat treatment, a diffusion layer composed of platinum metal of the pure platinum coating and the high-temperature alloy material is formed between the pure platinum coating and the high-temperature alloy material, and the thickness of the diffusion layer is 9.5-10.5 mu m. Figure 2 As shown in the figure, the diffusion layer comprises intermetallic compound (Ni, Pt) 3Nb. In the application, the vacuum annealing heat treatment can improve the bonding force between the high-temperature alloy material and the pure platinum coating.

[0019] According to the application, preferably, the vacuum aging heat treatment comprises: feeding the material after the vacuum annealing heat treatment into a vacuum aging furnace, first keeping the material after the vacuum annealing heat treatment at 770-790 DEG C for 7.5-8.5 h, then decreasing the temperature of the vacuum aging furnace to 690-710 DEG C, keeping the material in the vacuum aging furnace at 690-710 DEG C for 7.5-8.5 h, and finally air cooling the material in the vacuum aging furnace to 15-30 DEG C.

[0020] In the application, the air cooling refers to that the material in the vacuum aging furnace is slowly and naturally cooled to 15-30 DEG C together with the furnace body under the condition of air.

[0021] According to the application, preferably, the high-temperature alloy material is at least one of materials for liquid oxygen kerosene rocket engine turbine pumps, gas pipeline materials and turbine ball shell materials.

[0022] According to the application, preferably, the high-temperature alloy material is at least one of nickel-based high-temperature alloy material GH4022, nickel-based high-temperature alloy material GH4169 and nickel-based high-temperature alloy material GH4061.

[0023] The beneficial effects of the technical scheme of the application are as follows: The present application can raise the combustion pressure threshold of high-temperature alloy material from 5 MPa to 10 MPa under the condition of room temperature (15-30 DEG C) and pure oxygen (oxygen concentration > 99.5%) by using a pure platinum coating with a coating thickness of only 2.5-3.5 microns. The present application improves the anti-oxygen-ablation performance of high-temperature alloy material by using the characteristic that platinum is not easy to burn in oxygen-rich environment, and significantly improves the safety and flame-retardant performance of high-temperature alloy material under high temperature (550-650 DEG C), high pressure (3.5-55 MPa) and oxygen-rich (oxygen concentration > 90%) environment.

[0024] The present application coats a pure platinum coating on the surface of high-temperature alloy material, has the characteristics of mature technology, suitable for various complex parts and scalable production, and can be widely applied.

[0025] Other features and advantages of the present application will be described in detail in the following specific embodiments. BRIEF DESCRIPTION OF DRAWINGS

[0026] The above and other objects, features and advantages of the present application will become more apparent from the following detailed description when taken in conjunction with the accompanying drawings in which:

[0027] Figure 1 The combustion heat value of metal elements is shown.

[0028] Figure 2 The microstructure of GH4022 alloy with a pure platinum coating on the surface obtained by the surface protection method of high-temperature alloy material provided in embodiment 1 under high temperature, high pressure or oxygen-rich environment is shown.

[0029] Figure 3 (a) shows the anti-oxygen combustion performance test results of GH4022 alloy with a pure platinum coating on the surface obtained in embodiment 1 and GH4022 alloy without a pure platinum coating on the surface obtained in comparative example 1 in test example 1.

[0030] Figure 3 (b) shows the combustion rate of the anti-oxygen combustion performance test of GH4022 alloy with a pure platinum coating on the surface obtained in embodiment 1 and GH4022 alloy without a pure platinum coating on the surface obtained in comparative example 1 in test example 1.

[0031] Figure 4 Figure 3 (c) shows the combustion morphology of GH4022 alloy with a pure platinum coating on the surface obtained in embodiment 1 and GH4022 alloy without a pure platinum coating on the surface obtained in comparative example 1 in test example 1 after combustion under the condition of 7 MPa.

[0032] Figure 5The anti-oxygen-enriched combustion performance test results of the surface-coated pure platinum-coated GH4022 alloy obtained in Example 1 and the surface-uncoated pure platinum-coated GH4022 alloy obtained in Comparative Example 1 in Test Example 2 are shown. DETAILED DESCRIPTION

[0033] The preferred embodiments of the present application will be described in more detail below. Although the preferred embodiments of the present application are described below, it is understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that the present application will be thorough and complete, and will fully convey the scope of the present application to those skilled in the art.

[0034] Example 1

[0035] The present embodiment provides a surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-enriched environment.

[0036] The high-temperature alloy material is a nickel-based high-temperature alloy GH4022 with a diameter of 3.17 mm and a length of 120 mm.

[0037] The method comprises: (1) removing the surface oxidation layer of the high-temperature alloy material selected in the present embodiment by mechanical processing; placing the high-temperature alloy material treated by removing the surface oxidation layer and an ultrasonic liquid (the ultrasonic liquid uses deionized water mixed with an appropriate amount of oil removal agent, the oil removal agent is model AJX-303, and the temperature of the ultrasonic liquid is 60℃±5℃) into an ultrasonic device for the first ultrasonic cleaning for 10 minutes; then, placing the material after the first ultrasonic cleaning and industrial alcohol into the ultrasonic device for the second ultrasonic cleaning for 5 minutes to obtain a high-temperature alloy material with surface oil removed; and performing surface sand blasting treatment on the high-temperature alloy material with surface oil removed after nitrogen blowing drying, wherein the surface sand blasting treatment is a surface treatment process performed on the high-temperature alloy material after nitrogen blowing drying on an RH-1212A sand blasting machine, and the sand blasting parameters are: the sand blasting material is 180-240 mesh white corundum particles; and the pressure is 0.3MPa-0.5MPa, to obtain the high-temperature alloy material after surface treatment.

[0038] (2) depositing a pure platinum coating layer with a thickness of about 3μm on the surface of the high-temperature alloy material after surface treatment in an alkaline platinum plating solution at a deposition rate of about 3μm / h.

[0039] (3) sequentially cleaning and drying (drying temperature is 60℃) the material coated with the pure platinum coating layer to obtain the material after drying; The dried material is placed in a vacuum annealing furnace and held at 590-610℃ for 1 hour. Then, the temperature of the vacuum annealing furnace is raised to 950-970℃ within 30 minutes, and the material is held at 950-970℃ for another 2 hours. Finally, the material is vacuum-cooled to room temperature (15-30℃). After the vacuum annealing heat treatment, a diffusion layer (i.e., a composite layer of platinum metal from the pure platinum coating and the high-temperature alloy material) is formed between the dried material and the high-temperature alloy material. Figure 2 The Pt annealed layer on the surface), the thickness of the diffusion layer is 10 μm; The material after vacuum annealing heat treatment is sent into a vacuum aging furnace. First, the material after vacuum annealing heat treatment is held at 770-790℃ for 8 hours. Then, the temperature of the vacuum aging furnace is lowered to 690-710℃, and the material in the vacuum aging furnace is held at 690-710℃ for another 8 hours. Finally, the material in the vacuum aging furnace is air-cooled to room temperature (15-30℃) to obtain GH4022 alloy with a pure platinum coating on the surface.

[0040] Comparative Example 1

[0041] This comparative example provides a surface protection method for high-temperature alloy materials used in high-temperature, high-pressure, or oxygen-rich environments.

[0042] The high-temperature alloy material used in this comparative example is the same as that used in Example 1.

[0043] The method includes: (1) Perform the same surface treatment as in Example 1 to obtain the surface-treated high-temperature alloy material.

[0044] (2) The surface-treated high-temperature alloy material is cleaned and dried in sequence (drying temperature is 60°C) to obtain the dried material; the dried material is subjected to the same vacuum annealing heat treatment and vacuum aging heat treatment as in Example 1 to obtain GH4022 alloy without pure platinum coating on the surface.

[0045] Test Example 1

[0046] This test example compares the GH4022 alloy with a pure platinum coating obtained in Example 1 and the GH4022 alloy without a pure platinum coating obtained in Comparative Example 1 to test their resistance to oxygen-enriched combustion. The test method is the Intensive Ignition Method (PIC method), and the test procedure of the Intensive Ignition Method (PIC method) is as follows: (1) Measure the original size of the test sample, add a combustion enhancer to one end of the test sample, wrap a NiCr resistance wire around the outside of the combustion enhancer, and connect the positive and negative poles of the ignition electrode to the two ends of the resistance wire; (2) The test sample is hung in the combustion pressure vessel, and the vessel is sealed; (3) The combustion pressure vessel is first cleaned with high-pressure pure oxygen, and the interior of the vessel is emptied of air. The cleaning process is as follows: pressurized to 3.5 MPa, and then vented to 0.1 MPa. This process is repeated three times; (4) High-pressure oxygen is injected into the combustion pressure vessel, and the predetermined test oxygen pressure is reached; (5) The high-frequency induction heating power supply is started, and the test sample is heated using a high-frequency induction heating coil; (6) After the test sample is heated to the predetermined temperature, ignition is performed, or direct ignition is performed without heating. The direct current power supply of the ignition system is started, and the NiCr resistance wire and the combustion-supporting agent are ignited using a large current. The combustion-supporting agent drives the test sample to burn, and the high-temperature molten droplets of the combustion reaction fall into the ceramic receiving cup; (7) The high-speed camera is started to capture the combustion process; (8) After the test sample stops burning, the high-frequency induction heating power supply is turned off, the vent valve is opened, and when the pressure in the pressure vessel drops to 0.1 MPa, the pressure vessel is opened, the test sample is taken out, and the remaining length is measured.

[0047] The test temperature is room temperature (15-30°C), the test environment is an oxygen concentration of >99.5%, and the test oxygen pressures are 3.5, 5, 7, 10, 15, and 20 MPa, respectively.

[0048] As shown in FIG. 3(a), the combustion pressure threshold of the GH4022 alloy without a pure platinum coating obtained in Comparative Example 1 is 5 MPa, and the combustion pressure threshold of the GH4022 alloy with a pure platinum coating obtained in Example 1 is 10 MPa. Therefore, the pure platinum coating significantly improves the oxygen-rich combustion resistance of the high-temperature alloy material.

[0049] Test Example 2

[0050] In this test example, the oxygen-rich combustion resistance of the GH4022 alloy with a pure platinum coating obtained in Example 1 and the GH4022 alloy without a pure platinum coating obtained in Comparative Example 1 is tested. The test method is the promoted ignition method (PIC method), and the test procedure of the promoted ignition method (PIC method) is the same as that of Test Example 1.

[0051] The test temperature is high temperature (640-660°C), the test environment is an oxygen concentration of 90-91%, and the test oxygen pressures are 25, 30, 35, 38, 40, 50, and 53 MPa, respectively.

[0052] As shown in FIG. 3(b), the combustion pressure threshold of the GH4022 alloy without a pure platinum coating obtained in Comparative Example 1 is 38 MPa, and the combustion pressure threshold of the GH4022 alloy with a pure platinum coating obtained in Example 1 is 53 MPa. Therefore, the pure platinum coating significantly improves the oxygen-rich combustion resistance of the high-temperature alloy material. Figure 5It can be seen that the combustion pressure threshold of the GH4022 alloy without the pure platinum coating on the surface obtained by the comparative example 1 is 50 MPa, and the combustion pressure threshold of the GH4022 alloy with the pure platinum coating on the surface obtained by the example 1 is greater than 53 MPa. It can be seen that the pure platinum coating on the surface can significantly improve the anti-oxygen-rich combustion performance of the high-temperature alloy material.

[0053] In the present application, the size of the high-temperature alloy material is 3.15-3.2 mm in diameter and ≥110 mm in height: The anti-oxygen-rich combustion performance test (test example 1) of the high-temperature alloy material with the pure platinum coating on the surface obtained by the high-temperature alloy material according to the method of the example 1 under the condition of room temperature (15-30℃) and oxygen concentration >99.5% is that the combustion pressure threshold reaches 10 MPa; The anti-oxygen-rich combustion performance test (test example 2) of the high-temperature alloy material with the pure platinum coating on the surface obtained by the high-temperature alloy material according to the method of the example 1 under the condition of high temperature (640-660℃) and oxygen concentration 90-91% is that the combustion pressure threshold exceeds 53 MPa.

[0054] The above has described the embodiments of the present application, and the above description is exemplary, not exhaustive, and is not limited to the disclosed embodiments. Many modifications and changes are obvious to those skilled in the art without departing from the scope and spirit of the described embodiments.

Claims

1. A surface protection method of a high-temperature alloy material used in a high-temperature, high-pressure or oxygen-rich environment, characterized by, The method comprises coating a pure platinum coating on the surface of the high-temperature alloy material; The high-temperature alloy material is used in at least one of high-temperature, high-pressure and oxygen-rich environments; the high-temperature is 550-750 DEG C; the high-pressure is 2-55 MPa; and the oxygen-rich environment is an oxygen concentration of > 90%.

2. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 1, wherein, The high-temperature is 550-650 DEG C; the high-pressure is 2-50 MPa; and the oxygen-rich environment is an oxygen concentration of > 90%.

3. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 1 or 2, wherein, The method comprises the following steps: (1) surface treatment of the high-temperature alloy material; (2) coating the pure platinum coating on the surface of the high-temperature alloy material after the surface treatment by electroplating; (3) sequentially cleaning, drying, vacuum annealing heat treatment and vacuum aging heat treatment of the material coated with the pure platinum coating to obtain the high-temperature alloy material coated with the pure platinum coating on the surface.

4. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 3, wherein The surface treatment comprises sequentially removing the surface oxidation layer, removing the surface grease, nitrogen blowing and surface sand blasting of the high-temperature alloy material.

5. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 3, wherein The electroplated coating thickness of the pure platinum coating is 2.5-3.5 μm.

6. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 3, wherein The vacuum annealing heat treatment comprises: feeding the dried material into a vacuum annealing furnace, first keeping the dried material at 590-610 DEG C for 0.8-1.2 h, then raising the temperature of the vacuum annealing furnace to 950-970 DEG C within 25-30 min, keeping the material in the vacuum annealing furnace at 950-970 DEG C for 1.8-2.2 h, and finally cooling the material in the vacuum annealing furnace to 15-30 DEG C.

7. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 6, wherein After the vacuum annealing heat treatment of the dried material, a diffusion layer composed of platinum metal of the pure platinum coating and the high-temperature alloy material is formed between the pure platinum coating and the high-temperature alloy material, and the thickness of the diffusion layer is 9.5-10.5 μm.

8. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 3, wherein The vacuum aging heat treatment comprises: feeding the material after the vacuum annealing heat treatment into a vacuum aging furnace, first keeping the material after the vacuum annealing heat treatment at 770-790 DEG C for 7.5-8.5 h, then lowering the temperature of the vacuum aging furnace to 690-710 DEG C, keeping the material in the vacuum aging furnace at 690-710 DEG C for 7.5-8.5 h, and finally air cooling the material in the vacuum aging furnace to 15-30 DEG C.

9. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 1, wherein, The high-temperature alloy material is at least one of a material for a liquid oxygen kerosene rocket engine turbine pump, a gas pipeline material and a turbine ball shell material.

10. The surface protection method of a high-temperature alloy material for use in a high-temperature, high-pressure, or oxygen-rich environment according to claim 1, wherein, The high-temperature alloy material is at least one of nickel-based high-temperature alloy material GH4022, nickel-based high-temperature alloy material GH4169 and nickel-based high-temperature alloy material GH4061.

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