Nickel-based alloy composite board and preparation method thereof

Abstract

The invention discloses a nickel-based alloy composite plate and a preparation method thereof, and belongs to the technical field of nickel-based alloys, the nickel-based alloy composite plate comprises a stainless steel bottom plate and a nickel-based alloy plate, and the nickel-based alloy plate comprises, by weight, 52-58 parts of nickel powder, 17-21 parts of molybdenum powder, 8-12 parts of copper powder, 7-9 parts of boron powder, 2-3 parts of modified hafnium carbide powder, 4-7 parts of an alloy reinforcing agent and 2-3 parts of a fluxing agent. The modified hafnium carbide prepared from hafnium oxide and nano carbon powder successfully replaces metal hafnium with high cost in the traditional process; and meanwhile, the actual adding proportion of the modified hafnium carbide in the nickel-based alloy plate is greatly reduced, the cost of industrial mass production is doubly reduced from the two aspects of raw material selection and dosage control, and the economic requirement of large-scale production is better met.

Description

Technical Field

[0001] This invention relates to the field of nickel-based alloy technology, and more specifically to a nickel-based alloy composite plate and its preparation method. Background Technology

[0002] Nickel-based alloys are widely used in high-end fields such as aerospace, petrochemicals, and integrated circuits due to their excellent mechanical properties, high temperature resistance, and corrosion resistance. Traditional nickel-based alloys typically improve their performance by adding elements such as molybdenum, copper, and boron, while hafnium (Hf), due to its high melting point of approximately 2227℃ and strong oxidation resistance, is often introduced into alloy systems to further improve the alloy's high-temperature stability and strength.

[0003] For example, Chinese patent CN119530614A discloses a nickel-based alloy composite plate and its preparation method, the formula of which includes 35-45 parts nickel powder, 10-15 parts molybdenum powder, 5-10 parts copper powder, 5-10 parts boron powder, and 3-5 parts hafnium powder. However, hafnium is not only scarce but also expensive, and its high addition amount directly leads to a significant increase in the cost of nickel-based alloys.

[0004] Therefore, those skilled in the art are dedicated to developing a nickel-based alloy composite plate and its preparation method. Summary of the Invention

[0005] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present invention is: To achieve the above objectives, the present invention provides a nickel-based alloy composite plate, comprising a stainless steel base plate and a nickel-based alloy plate, wherein the nickel-based alloy plate comprises the following components by weight: Nickel powder 52-58 parts, molybdenum powder 17-21 parts, copper powder 8-12 parts, boron powder 7-9 parts, modified hafnium carbide powder 2-3 parts, alloy reinforcing agent 4-7 parts, flux 2-3 parts.

[0006] A method for preparing the nickel-based alloy composite plate includes the following steps: S1. Preparation of modified hafnium carbide; Pretreatment: Hafnium oxide powder and nano carbon powder were mixed, nickel powder was added, and the mixture was ball-milled under an argon atmosphere to obtain mixed powder B; Pressure heat treatment: The mixed powder B is heated to 1500-1800℃, pressurized to 30-50MPa by H2 / Ar mixed gas with a volume ratio of 4:96 and kept at the temperature, cooled in the furnace and then air-cooled, ground, crushed and sieved to obtain precursor powder. Post-processing: The precursor powder was completely immersed in a mixed solution of HCl and HF, ultrasonically treated to remove surface oxides, washed with deionized water until neutral, and dried to obtain modified hafnium carbide powder. S2. Mix nickel powder, molybdenum powder, copper powder, boron powder, modified hafnium carbide powder and alloy reinforcing agent, ball mill them, and pass them through a 200-mesh sieve to obtain mixed powder C; S3. Preheat the melting furnace to 180°C under an argon atmosphere, add the mixed powder C and flux to the melting furnace, raise the temperature to 1200-1250°C and hold, continue to raise the temperature to 1600-1680°C and hold, raise the temperature to 1820-1850°C and hold, and quickly pour the mixed melt into the preheated mold to obtain the nickel-based alloy plate; S4. Using laser welding technology, a 304 stainless steel base plate that has been cleaned, ground, and passivated is combined with a nickel-based alloy plate. After cutting and polishing, a nickel-based alloy composite plate is obtained.

[0007] In a preferred embodiment of the present invention, the pretreatment step S1 specifically involves: mixing hafnium oxide powder and nano carbon powder at a molar ratio of 1:1.1-1.3, adding nickel powder accounting for 5-10% of the total reactants, and then ball milling the mixture under an argon atmosphere for 8-10 hours at a speed of 300-400 r / min and a ball-to-material ratio of 13-15:1 to obtain mixed powder B.

[0008] In a preferred embodiment of the present invention, the pressurized heat treatment step S1 specifically involves: heating the mixed powder B to 1500-1800°C at a rate of 10-15°C / min, maintaining the final temperature for 20-30 minutes, pressurizing it to 30-50 MPa with a H2 / Ar mixed gas at a volume ratio of 4:96, holding it at that temperature for 50-60 minutes, cooling it to 200°C in the furnace, then air-cooling it to 60-80°C, grinding and crushing it through a 180-200 mesh sieve to obtain the precursor powder.

[0009] In a preferred embodiment of the present invention, the post-processing step S1 specifically involves: completely immersing the precursor powder in a mixed solution of 4-5% HCl + 2-3% HF, ultrasonically treating it for 10-15 minutes to remove surface oxides, washing it with deionized water until neutral, and drying it at 40°C for 8 hours to remove water, thereby obtaining modified hafnium carbide powder.

[0010] In a preferred embodiment of the present invention, step S3 specifically involves: preheating the melting furnace to 180°C under an argon atmosphere; adding the mixed powder C and flux to the melting furnace; raising the temperature to 1200-1250°C at a rate of 10-12°C / min and holding for 15 minutes; continuing to raise the temperature to 1600-1680°C at a rate of 5-8°C / min and holding for 20 minutes; raising the temperature to 1820-1850°C at a rate of 2-4°C / min and holding for 30 minutes; and rapidly pouring the mixed melt into a mold preheated to 150°C to obtain a nickel-based alloy plate.

[0011] In a preferred embodiment of the present invention, the flux is a mixture of sodium fluoride and potassium fluoride in a molar ratio of 1.2-1.5:1.

[0012] The apparatus or method provided by this invention has the following technical effects: 1. The modified hafnium carbide prepared by hafnium oxide and nano carbon powder in this invention successfully replaces the expensive metal hafnium in the traditional process. At the same time, the actual addition ratio of modified hafnium carbide in nickel-based alloy plates is greatly reduced, which compresses the cost of industrial mass production from both the aspects of raw material selection and dosage control, and is more in line with the economic requirements of large-scale production.

[0013] 2. By introducing modified hafnium carbide into nickel-based alloy plates, this invention unexpectedly achieved a simultaneous improvement in product hardness and high-temperature resistance, breaking the common dilemma in production where "cost reduction often comes at the cost of performance compromise." Furthermore, optimization measures for existing processes—such as adding passivation treatment in key steps and adopting gradient heating melting methods—are not only easily integrated into existing production lines without significant equipment modifications, but also further enhance the hardness and high-temperature resistance of the nickel-based alloy composite plates, providing reliable process support for the stable application of products under high-temperature conditions. Detailed Implementation

[0014] The following specific examples illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific embodiments, and various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, unless otherwise specified, the following embodiments and features described therein can be combined with each other.

[0015] Example 1: This example provides a method for preparing an alloy reinforcing agent, including the following steps: Ten parts by weight of lanthanum nitrate hexahydrate were added to 54 parts by weight of deionized water and ultrasonically stirred at 60°C for 30 min. Eight parts by weight of nano-alumina were added and stirring was continued for 3 h. The mixture was filtered and dried in a vacuum drying oven at 100°C for 6 h to obtain powder A. Powder A was calcined in a muffle furnace at 830°C for 1.5 h, then placed in a ball mill jar and hard steel balls were added. The ball-to-material ratio was controlled at 10:1. After filling with high-purity argon gas, the mixture was ball-milled in a planetary ball mill for 30 min and passed through a 500-mesh sieve to obtain the alloy reinforcing agent (the above method is selected from Chinese Patent CN119530614A).

[0016] Example 2: This example provides a nickel-based alloy composite plate, including a stainless steel base plate and a nickel-based alloy plate. The nickel-based alloy plate, by weight, comprises the following components: 56 parts nickel powder, 19 parts molybdenum powder, 9 parts copper powder, 8 parts boron powder, 2 parts modified hafnium carbide powder, 5 parts alloy reinforcing agent, and 3 parts flux.

[0017] Its preparation method includes the following steps: S1. Preparation of modified hafnium carbide; Pretreatment: Hafnium oxide powder and nano carbon powder were mixed at a molar ratio of 1:1.2, and nickel powder accounting for 8% of the total reactants was added. After mixing, the mixture was ball-milled for 10 hours under an argon atmosphere at a speed of 360 r / min and a ball-to-material ratio of 14:1 to obtain mixed powder B. Pressurized heat treatment: The mixed powder B is heated to 1700℃ at a rate of 12℃ / min. After the final temperature is kept constant for 25 min, it is pressurized to 42MPa by H2 / Ar mixed gas (H2 and Ar volume ratio is 4:96), held at the temperature for 57 min, cooled to 200℃ in the furnace, and then air-cooled to 77℃. The powder is then ground and crushed and passed through a 200-mesh sieve to obtain the precursor powder. Post-processing: The precursor powder was completely immersed in a mixed solution of 5% HCl + 2% HF, ultrasonically treated for 13 min to remove surface oxides, washed with deionized water until neutral, and dried at 40℃ for 8 h to remove water, thus obtaining modified hafnium carbide powder. S2. Nickel powder, molybdenum powder, copper powder, boron powder, modified hafnium carbide powder and alloy reinforcing agent are mixed and placed in a ball mill and ball-milled for 17 hours under an argon atmosphere. The ball-to-material ratio is 8:1, the ball milling speed is 380 r / min, and the ball milling method is ball milling for 30 min and then intermittent for 10 min. The mixture is then passed through a 200-mesh sieve to obtain mixed powder C. S3. Preheat the melting furnace to 180°C under an argon atmosphere. Add the mixed powder C and flux (a mixture of sodium fluoride and potassium fluoride in a molar ratio of 1.4:1) into the melting furnace. Raise the temperature to 1220°C at a rate of 10°C / min and hold for 15 min. Continue to raise the temperature to 1630°C at a rate of 6°C / min and hold for 20 min. Finally, raise the temperature to 1840°C at a rate of 3°C / min and hold for 30 min. Quickly pour the mixed melt into a mold preheated to 150°C to obtain the nickel-based alloy plate. S4. The surfaces to be bonded, consisting of a 304 stainless steel base plate and a nickel-based alloy plate, are cleaned with anhydrous ethanol. Then, they are cross-polished at 45° using 240, 600, and 1000 grit sandpaper (to eliminate unidirectional scratches) until a roughness of 2 μm is achieved. After polishing, a passivation treatment with a 5% nitric acid + 2% hydrofluoric acid solution (25℃, 2 min) is applied to remove the surface oxide layer, resulting in a pretreated 304 stainless steel base plate and a nickel-based alloy plate. The pretreated 304 stainless steel base plate and the nickel-based alloy plate are then bonded using laser welding technology. The laser beam spot diameter is 0.2 mm, the pulse frequency is 30 Hz, the voltage is 100 V, and the welding speed is 12 mm / s. After cutting and polishing, the nickel-based alloy composite plate is obtained.

[0018] Example 3: This example provides a nickel-based alloy composite plate, including a stainless steel base plate and a nickel-based alloy plate. The nickel-based alloy plate, by weight, comprises the following components: 58 parts nickel powder, 21 parts molybdenum powder, 12 parts copper powder, 9 parts boron powder, 3 parts modified hafnium carbide powder, 7 parts alloy reinforcing agent, and 3 parts flux.

[0019] Its preparation method includes the following steps: S1. Preparation of modified hafnium carbide; Pretreatment: Hafnium oxide powder and nano carbon powder were mixed at a molar ratio of 1:1.3, and nickel powder accounting for 10% of the total reactants was added. After mixing, the mixture was ball-milled for 10 hours under an argon atmosphere at a speed of 400 r / min and a ball-to-material ratio of 15:1 to obtain mixed powder B. Pressurized heat treatment: The mixed powder B is heated to 1800℃ at a rate of 15℃ / min. After the final temperature is kept constant for 30min, it is pressurized to 50MPa by H2 / Ar mixed gas (H2 and Ar volume ratio is 4:96), held at the temperature for 60min, cooled to 200℃ in the furnace, and then air-cooled to 80℃. It is then ground and crushed and passed through a 200-mesh sieve to obtain the precursor powder. Post-processing: The precursor powder was completely immersed in a mixed solution of 5% HCl + 3% HF, ultrasonically treated for 15 min to remove surface oxides, washed with deionized water until neutral, and dried at 40℃ for 8 h to remove water, thus obtaining modified hafnium carbide powder. S2. Nickel powder, molybdenum powder, copper powder, boron powder, modified hafnium carbide powder and alloy reinforcing agent are mixed and placed in a ball mill and ball-milled for 18 hours under an argon atmosphere. The ball-to-material ratio is 8:1, the ball milling speed is 400 r / min, and the ball milling method is ball milling for 30 min and then intermittent for 10 min. The mixture is then passed through a 200-mesh sieve to obtain mixed powder C. S3. Preheat the melting furnace to 180°C under an argon atmosphere. Add the mixed powder C and flux (a mixture of sodium fluoride and potassium fluoride in a molar ratio of 1.5:1) into the melting furnace. Raise the temperature to 1250°C at a rate of 12°C / min and hold for 15 min. Continue to raise the temperature to 1680°C at a rate of 8°C / min and hold for 20 min. Finally, raise the temperature to 1850°C at a rate of 4°C / min and hold for 30 min. Quickly pour the mixed melt into a mold preheated to 150°C to obtain the nickel-based alloy plate. S4. The surfaces to be bonded, consisting of a 304 stainless steel base plate and a nickel-based alloy plate, are cleaned with anhydrous ethanol. Then, they are cross-polished at 45° using 240, 600, and 1000 grit sandpaper (to eliminate unidirectional scratches) until a roughness of 2 μm is achieved. After polishing, a passivation treatment with a 5% nitric acid + 2% hydrofluoric acid solution (25℃, 2 min) is applied to remove the surface oxide layer, resulting in a pretreated 304 stainless steel base plate and a nickel-based alloy plate. The pretreated 304 stainless steel base plate and the nickel-based alloy plate are then bonded using laser welding technology. The laser beam spot diameter is 0.2 mm, the pulse frequency is 30 Hz, the voltage is 100 V, and the welding speed is 12 mm / s. After cutting and polishing, the nickel-based alloy composite plate is obtained.

[0020] Example 4: This example provides a nickel-based alloy composite plate, including a stainless steel base plate and a nickel-based alloy plate. The nickel-based alloy plate, by weight, comprises the following components: 52 parts nickel powder, 17 parts molybdenum powder, 8 parts copper powder, 7 parts boron powder, 2 parts modified hafnium carbide powder, 4 parts alloy reinforcing agent, and 2 parts flux.

[0021] Its preparation method includes the following steps: S1. Preparation of modified hafnium carbide; Pretreatment: Hafnium oxide powder and nano carbon powder were mixed at a molar ratio of 1:1.1, and nickel powder accounting for 5% of the total reactants was added. After mixing, the mixture was ball-milled for 8 hours under an argon atmosphere at a speed of 300 r / min and a ball-to-material ratio of 13:1 to obtain mixed powder B. Pressurized heat treatment: The mixed powder B is heated to 1500℃ at a rate of 10℃ / min. After the final temperature is kept constant for 20min, it is pressurized to 30MPa by H2 / Ar mixed gas (H2 and Ar volume ratio is 4:96), held at the temperature for 50min, cooled to 200℃ in the furnace, and then air-cooled to 60℃. It is then ground and crushed and passed through a 180-mesh sieve to obtain the precursor powder. Post-processing: The precursor powder was completely immersed in a mixed solution of 4% HCl + 2% HF, ultrasonically treated for 10 min to remove surface oxides, washed with deionized water until neutral, and dried at 40℃ for 8 h to remove water, thus obtaining modified hafnium carbide powder. S2. Nickel powder, molybdenum powder, copper powder, boron powder, modified hafnium carbide powder and alloy reinforcing agent are mixed and placed in a ball mill and ball-milled for 16 hours under an argon atmosphere. The ball-to-material ratio is 8:1, the ball milling speed is 300 r / min, and the ball milling method is ball milling for 30 min and then intermittent for 10 min. The mixture is then passed through a 200-mesh sieve to obtain mixed powder C. S3. Preheat the melting furnace to 180°C under an argon atmosphere. Add the mixed powder C and flux (a mixture of sodium fluoride and potassium fluoride in a molar ratio of 1.2:1) into the melting furnace. Increase the temperature to 1200°C at a rate of 10°C / min and hold for 15 min. Continue to increase the temperature to 1600°C at a rate of 5°C / min and hold for 20 min. Finally, increase the temperature to 1820°C at a rate of 2°C / min and hold for 30 min. Quickly pour the mixed melt into a mold preheated to 150°C to obtain the nickel-based alloy plate. S4. The surfaces to be bonded, consisting of a 304 stainless steel base plate and a nickel-based alloy plate, are cleaned with anhydrous ethanol. Then, they are cross-polished at 45° using 240, 600, and 1000 grit sandpaper (to eliminate unidirectional scratches) until a roughness of 2 μm is achieved. After polishing, a passivation treatment with a 5% nitric acid + 2% hydrofluoric acid solution (25℃, 2 min) is applied to remove the surface oxide layer, resulting in a pretreated 304 stainless steel base plate and a nickel-based alloy plate. The pretreated 304 stainless steel base plate and the nickel-based alloy plate are then bonded using laser welding technology. The laser beam spot diameter is 0.2 mm, the pulse frequency is 30 Hz, the voltage is 100 V, and the welding speed is 12 mm / s. After cutting and polishing, the nickel-based alloy composite plate is obtained.

[0022] Comparative Example 1: The difference between this comparative example and Example 2 is that in S3, a gradient heating was not used, but the temperature was always increased at a rate of 15°C / min.

[0023] Comparative Example 2: The difference between this comparative example and Example 2 is that S1 was not performed, but commercially available hafnium carbide powder (purchased from Qinghe County Xingxin New Material Technology Co., Ltd.) was directly used.

[0024] Comparative Example 3: The difference between this comparative example and Example 2 is that no passivation treatment was performed in S3.

[0025] Comparative Example 4: The difference between this comparative example and Example 2 is that commercially available hafnium carbide powder was directly used, and the temperature was increased at a rate of 15°C / min throughout S3.

[0026] Comparative example: Example 1 of Chinese patent CN119530614A was selected.

[0027] Experimental example: The hardness of the nickel-based alloy composite plates prepared in Examples 2-4, the comparative example, and the control example was tested according to GB / T 7997-2014 Vickers hardness test method (25℃ room temperature and 650℃).

[0028] The results are shown in the table below: As shown in the table above, this invention utilizes hafnium oxide and nano-carbon powder to prepare modified hafnium carbide, replacing expensive hafnium. Furthermore, the amount of modified hafnium carbide added to the nickel-based alloy plate is significantly reduced, further lowering costs. While reducing costs, the addition of modified hafnium carbide to the nickel-based alloy plate unexpectedly improves the hardness and high-temperature resistance of the nickel-based alloy composite plate. Optimization of the original process (e.g., passivation treatment and gradient temperature melting) also improves the hardness and high-temperature resistance of the nickel-based alloy composite plate to varying degrees.

[0029] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A nickel-based alloy composite plate, comprising a stainless steel base plate and a nickel-based alloy plate, characterized in that, The nickel-based alloy plate comprises the following components by weight: Nickel powder 52-58 parts, molybdenum powder 17-21 parts, copper powder 8-12 parts, boron powder 7-9 parts, modified hafnium carbide powder 2-3 parts, alloy reinforcing agent 4-7 parts, flux 2-3 parts; The modified hafnium carbide powder is prepared by the following method: Pretreatment: Hafnium oxide powder and nano carbon powder were mixed, nickel powder was added, and the mixture was ball-milled under an argon atmosphere to obtain mixed powder B; Pressure heat treatment: The mixed powder B is heated to 1500-1800℃, pressurized to 30-50MPa by H2 / Ar mixed gas with a volume ratio of 4:96 and kept at the temperature, cooled in the furnace and then air-cooled, ground, crushed and sieved to obtain precursor powder. Post-processing: The precursor powder was completely immersed in a mixed solution of HCl and HF, ultrasonically treated to remove surface oxides, washed with deionized water until neutral, and dried to obtain modified hafnium carbide powder.

2. The nickel-based alloy composite plate according to claim 1, characterized in that, The pretreatment steps for the modified hafnium carbide powder are as follows: hafnium oxide powder and nano carbon powder are mixed at a molar ratio of 1:1.1-1.3, and nickel powder accounting for 5-10% of the total reactants is added. After mixing, the mixture is ball-milled for 8-10 hours under an argon atmosphere at a speed of 300-400 r / min and a ball-to-material ratio of 13-15:1 to obtain mixed powder B.

3. The nickel-based alloy composite plate according to claim 1, characterized in that, The pressurized heat treatment step of the modified hafnium carbide powder is as follows: the mixed powder B is heated to 1500-1800℃ at a rate of 10-15℃ / min, and after the final temperature is kept constant for 20-30min, it is pressurized to 30-50MPa by a H2 / Ar mixed gas with a volume ratio of 4:96, held at that temperature for 50-60min, cooled to 200℃ in the furnace, and then air-cooled to 60-80℃. The powder is then ground and crushed through a 180-200 mesh sieve to obtain the precursor powder.

4. The nickel-based alloy composite plate according to claim 1, characterized in that, The post-processing steps of the modified hafnium carbide powder are as follows: the precursor powder is completely immersed in a mixed solution of 4-5% HCl + 2-3% HF, ultrasonically treated for 10-15 minutes to remove surface oxides, washed with deionized water until neutral, and dried at 40°C for 8 hours to remove water, thereby obtaining modified hafnium carbide powder.

5. A method for preparing a nickel-based alloy composite plate as described in any one of claims 1-4, characterized in that, Includes the following steps: S1. Mix nickel powder, molybdenum powder, copper powder, boron powder, modified hafnium carbide powder and alloy reinforcing agent, ball mill them, and pass them through a 200-mesh sieve to obtain mixed powder C; S2. Preheat the melting furnace to 180°C under an argon atmosphere, add the mixed powder C and flux to the melting furnace, raise the temperature to 1200-1250°C and hold, continue to raise the temperature to 1600-1680°C and hold, raise the temperature to 1820-1850°C and hold, and quickly pour the mixed melt into the preheated mold to obtain the nickel-based alloy plate; S3. Using laser welding technology, a 304 stainless steel base plate that has been cleaned, ground, and passivated is combined with a nickel-based alloy plate. After cutting and polishing, a nickel-based alloy composite plate is obtained.

6. The method for preparing the nickel-based alloy composite plate according to claim 5, characterized in that, S3 specifically involves: preheating the melting furnace to 180°C under an argon atmosphere, adding the mixed powder C and flux to the melting furnace, raising the temperature to 1200-1250°C at a rate of 10-12°C / min and holding it for 15 minutes, continuing to raise the temperature to 1600-1680°C at a rate of 5-8°C / min and holding it for 20 minutes, raising the temperature to 1820-1850°C at a rate of 2-4°C / min and holding it for 30 minutes, and rapidly pouring the mixed melt into a mold preheated to 150°C to obtain a nickel-based alloy plate.

7. The method for preparing the nickel-based alloy composite plate according to claim 5, characterized in that, The flux is a mixture of sodium fluoride and potassium fluoride in a molar ratio of 1.2-1.5:1.

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