A particle-reinforced nickel-based metal powder and a method for producing the same

Abstract

The present application belongs to the field of metal material, and particularly relates to a kind of particle reinforced nickel-based metal powder and its preparation method. It is composed of nickel matrix metal powder and carbon-containing particles, with a ratio of 92% nickel matrix metal powder and 8% carbon-containing particles. The chemical composition of the nickel matrix metal powder and its mass percentage are as follows: C≤0.1%, 6.0% Cr, 4.5% Mo, 2.5% Nb, 1.2% B, 2.2% V, 4.5% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and unavoidable impurities. The carbon-containing particles are silicon carbide and carbon nanotube composites. The particle reinforced nickel-based metal powder has good fluidity and sphericity. After surface manufacturing and repairing using ultra-high rate laser cladding technology, the related properties of the machined surface are effectively improved.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of metal materials, and particularly relates to a kind of particle reinforced nickel-based metal powder and a preparation method thereof. BACKGROUND

[0002] Particle reinforced metal matrix composite refers to a kind of new functional material artificially added with second phase particle material into metal or alloy as matrix. The particle reinforcement includes carbide, nitride, graphite particle and oxide, etc. The preparation methods of particle reinforced metal matrix composite are generally divided into three categories: liquid phase method, solid phase method and solid-liquid two-phase mixing method. The liquid phase method is to mix and cast the composite material by adding particles into molten metal liquid through various technologies; the solid phase method is to uniformly mix particles and metal powder, and then obtain particle reinforced metal matrix composite through a series of preparation processes; the solid-liquid two-phase mixing method includes spray deposition technology and rheocasting method.

[0003] The Chinese patent application with application number 201711405737.1 discloses a kind of particle reinforced nickel-based metal powder for super high speed laser cladding, which is composed of nickel matrix metal powder and oxide or carbide particles in a certain proportion. The nickel ingot is melted by vacuum melting, and the nickel ingot is melted by using medium frequency induction heating, and the powder is obtained by using gas atomization, and then the powder is screened by particle size, and then the powder is mixed with oxide or carbide particles in a corresponding proportion in a mixer to obtain a particle reinforced nickel-based metal powder for super high speed laser cladding. However, directly mixing two or more powders may cause uneven dispersion of the powders, agglomeration of the same powder, poor flowability of the powder, and uneven cladding layer or cracks in the cladding process. SUMMARY

[0004] To solve the above problems, the present application provides a kind of particle reinforced nickel-based metal powder and a preparation method thereof, which is composed of nickel matrix metal powder and carbon-containing particles in a certain proportion, wherein the carbon-containing particles are silicon carbide and carbon nanotube composite materials. The particle reinforced nickel-based metal powder prepared has good flowability and sphericity, and after surface manufacturing and repairing by using super high speed laser cladding technology, the surface related properties after processing are effectively improved.

[0005] The technical scheme for solving the above problems is as follows:

[0006] A kind of particle reinforced nickel-based metal powder, which is composed of nickel matrix metal powder and carbon-containing particles, with a ratio of 75-95% nickel matrix metal powder and 5-25% carbon-containing particles, wherein the chemical composition of the nickel matrix metal powder and its mass percentage are C≤0.1%, 1.0-18.0% Cr, 2.0-15.0% Mo, 0.1-5.0% Nb, 0.1-3.0% B, 1.5-4.0% V, 2.0-12.0% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 0.8-1.6% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance being Ni and unavoidable impurities; the carbon-containing particles are silicon carbide and carbon nanotube composite material; preferably, 92% nickel matrix metal powder and 8% carbon-containing particles, the chemical composition of the nickel matrix metal powder and its mass percentage are C≤0.1%, 6.0% Cr, 4.5% Mo, 2.5% Nb, 1.2% B, 2.2% V, 4.5% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance being Ni and unavoidable impurities;

[0007] Further, the preparation method of the carbon-containing particles is:

[0008] S1, preparation of silicon carbide particles: weigh metal Na, Si powder and tetra-bromomethane, mix them uniformly, then put them into a high-pressure reaction kettle, keep the temperature at 220-300°C for 16-24h, preferably keep the temperature at 250°C for 18h, after the reaction is completed, naturally cool them to room temperature, wash and dry the obtained product with deionized water after impurity removal treatment to obtain silicon carbide particles;

[0009] S2, preparation of modified silicon carbide particles: ultrasonically disperse the silicon carbide particles obtained in step S1 in ethanol, add γ-aminopropyltriethoxysilane to them at room temperature, stir for 4-6h, preferably 5h, then centrifuge and wash them, disperse them in tetrahydrofuran solvent, add benzene tricarboxylic acid glycoside, stir at room temperature for 6-10h, preferably 8h, then centrifuge and wash them with water, mix them with thionyl chloride and N,N-dimethylformamide, raise the temperature to 45-55°C for 2-6h, then filter to obtain modified silicon carbide particles, preferably raise the temperature to 50°C for 4h;

[0010] S3, Preparation of amino-functionalized carbon nanotubes: carbon nanotubes are ultrasonically dispersed in toluene, and azobisisobutyronitrile is added thereto under stirring, and the reaction is carried out under an inert atmosphere for 4-6 hours, preferably for 5 hours, the reaction product is washed with toluene, and a black powder is obtained after drying; the black powder is added to a mixed solution of nickel chloride hexahydrate and tetrahydrofuran, and aluminum powder is added after ultrasonic dispersion, the reaction is completed, and the reaction product is diluted with tetrahydrofuran and filtered, and the obtained solid mixture is transferred to a reactor, dilute sulfuric acid is added thereto under stirring for 10-20 minutes, preferably for 20 minutes, and vacuum filtration is performed, and the obtained product is washed with deionized water until neutral, and amino-functionalized carbon nanotubes are obtained after drying.

[0011] S4, Preparation of carbon-containing particles: the amino-functionalized carbon nanotubes obtained in step S3 are dissolved in tetrahydrofuran together with pyridine in a reactor, and the solution is placed in an ice-water mixed bath, and the modified silicon carbide particles obtained in step S2 are added thereto, and the reaction temperature is maintained at 20-30°C and stirring is performed for 2-6 hours, preferably for 4 hours, and then the reactor is placed in an ice-water mixed bath, dilute hydrochloric acid and deionized water are added thereto, and distillation is performed under reduced pressure until a slurry is obtained, and the slurry is diluted with toluene and stirred for 10-20 minutes, preferably for 15 minutes, and then the slurry is placed in an ice-water mixed bath and stirred for 2-4 hours, preferably for 4 hours, and the solid is collected by vacuum filtration, washed with deionized water, and dried to obtain carbon-containing particles.

[0012] Further, in step S1, the step of impurity removal treatment of the obtained product is as follows: the obtained product is sequentially treated with anhydrous ethanol, hydrochloric acid, perchloric acid, and a mixed solution of hydrofluoric acid / nitric acid.

[0013] Further, in step S1, the concentration of perchloric acid is 70-75%, and reflux is performed at 150-180°C for 2-5 hours; preferably, reflux is performed at 165°C for 3 hours.

[0014] Further, in step S1, the mixed solution of hydrofluoric acid / nitric acid is a mixture of hydrofluoric acid and nitric acid in a volume ratio of 1:2-4; preferably, the volume ratio is 1:3.

[0015] Further, in step S1, the drying condition is drying in a vacuum drying oven at 55-65°C for 3-5 hours; preferably, the drying condition is drying at 60°C for 4 hours; in step S3, the drying condition of the black powder and the drying condition of the amino-functionalized carbon nanotubes are both drying in a vacuum drying oven at 50-60°C for 10-14 hours; preferably, the drying condition is drying at 55°C for 12 hours; in step S4, the drying condition of the carbon-containing particles is drying in a vacuum drying oven at 45-55°C for 6-10 hours; preferably, the drying condition is drying at 50°C for 8 hours.

[0016] Further, in step S2, the process of adding gamma-aminopropyl triethoxysilane after stirring and reaction and washing is as follows: washing with ethanol, acetone and tetrahydrofuran for 2-5 times, preferably 3 times.

[0017] The application also provides a preparation method of the particle-reinforced nickel-based metal powder, which comprises the following steps: alloying and proportioning raw materials, vacuum smelting nickel ingots, melting the nickel ingots by using a medium-frequency induction heating, powdering by using a gas atomization method, screening the obtained powder, and uniformly mixing the screened alloy composite powder and carbon-containing particles in a mixer according to a corresponding proportion.

[0018] Further, the vacuum degree of the smelting chamber is 10 -1 -10 -2 Pa, and the argon pressure of the powder spraying gas is 2.5-4 MPa.

[0019] Further, the particle-reinforced nickel-based metal powder prepared is used for surface manufacturing and repairing by using a super-high-speed laser cladding technology and corresponding processes, and the specific steps are as follows:

[0020] A1, machining the surface of the substrate;

[0021] A2, wiping the surface of the substrate with acetone to remove surface grease;

[0022] A3, planning a laser cladding path according to the geometric shape of the surface of the substrate and formulating process parameters;

[0023] A4, cladding and repairing the surface of the substrate by using a semiconductor laser cladding system;

[0024] A5, machining the repaired surface of the substrate by using a five-axis numerical control machine tool to obtain a required size.

[0025] The application has the following beneficial effects:

[0026] In the preparation of the particle reinforced nickel-based metal powder, the nickel-based metal powder and the carbon-containing particle are composed, in the preparation process of the carbon-containing particle, the silicon carbide particle is prepared first and the silicon carbide with a carbonyl chloride functional group is finally obtained through a series of reactions; and the carbon nanotube is modified to obtain the aminated carbon nanotube; finally, the silicon carbide with the carbonyl chloride functional group and the aminated carbon nanotube are further reacted to obtain the carbon-containing particle with the silicon carbide and the carbon nanotube composite; in the surface manufacturing and repairing process by using the ultra-high speed, the carbon-containing particle is added to the three-dimensional space of the entanglement, the surface or the inside of which is attached with the metal powder, which can play a role similar to a column in the metal matrix, and more energy needs to be absorbed to break the covalent bond structure in the carbon nanotube and the combination of the carbon nanotube and the metal piece when the fracture occurs, so that the reinforcing effect is achieved; in addition, the silicon carbide is combined with the carbon nanotube through the reaction, which can help the dispersion of the silicon carbide and prevent the agglomeration phenomenon caused by the uneven mixing of the direct addition, so as to affect the final surface performance. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0028] The metal sodium (S477592), silicon powder (S130843), carbon nanotube (C434681) and aluminum powder (A401395) used in the present application are purchased from Aladdin Chemical Reagent Co., Ltd., tetra bromomethane CAS: 558-13-4, gamma-aminopropyl triethoxysilane CAS: 919-30-2, tetrahydrofuran CAS: 109-99-9, benzene tricarboxylic acid glycoside CAS: 552-30-7, thionyl chloride CAS: 7719-09-7, N,N-dimethylformamide CAS: 68-12-2, azobisisobutyronitrile CAS: 78-67-1, toluene CAS: 108-88-3, nickel chloride hexahydrate CAS: 7791-20-0, and all reagents are commercially available.

[0029] Example 1

[0030] A kind of particle reinforced nickel-based metal powder, which is composed of nickel matrix metal powder and carbon-containing particles, with a ratio of 92% nickel matrix metal powder and 8% carbon-containing particles, wherein the chemical composition of the nickel matrix metal powder and its mass percentage are C≤0.1%, 6.0% Cr, 4.5% Mo, 2.5% Nb, 1.2% B, 2.2% V, 4.5% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and inevitable impurities; the carbon-containing particles are silicon carbide and carbon nanotube composite materials.

[0031] The preparation method of the carbon-containing particles is as follows:

[0032] S1, preparation of silicon carbide particles: take 3.5 parts by weight of metal Na, 1.2 parts by weight of Si powder and 15 parts by weight of tetra-bromomethane, mix them evenly, then put them into a high-pressure reaction kettle, keep the temperature at 250℃ for 18h, after the reaction is completed, cool it to room temperature naturally, wash it with deionized water after impurity removal treatment, dry it at 60℃ for 4h to obtain silicon carbide particles; wherein the impurity removal treatment step is: sequentially treat the obtained product with anhydrous ethanol, 2mol / L hydrochloric acid, 70-75% perchloric acid (refluxed at 165℃ for 3h), and a mixed solution of hydrofluoric acid / nitric acid (V / V=1 / 3);

[0033] S2, preparation of modified silicon carbide particles: ultrasonically disperse the silicon carbide particles obtained in step S1 in 30 parts by weight of ethanol, add 1.2 parts by weight of γ-aminopropyltriethoxysilane to it at room temperature, stir for 5h, then centrifuge and wash it, sequentially wash it with ethanol, acetone and tetrahydrofuran for 3 times, then disperse it in 45 parts by weight of tetrahydrofuran solvent, add 1.5 parts by weight of benzene trimesate, stir at room temperature for 8h, then centrifuge and wash it with water, mix it with 1.2 parts by weight of thionyl chloride and 45 parts by weight of N,N-dimethylformamide, then increase the temperature to 50℃ for 4h, and then filter to obtain modified silicon carbide particles;

[0034] S3, Preparation of aminated carbon nanotubes: 15 parts by weight of carbon nanotubes were ultrasonically dispersed in 80 parts by weight of toluene, 5 parts by weight of azobisisobutyronitrile was added thereto under stirring, nitrogen was introduced, and stirring reaction was performed under an inert atmosphere for 5 hours. The reaction product was washed with toluene 5 times, and dried in a vacuum drying oven at 55°C for 12 hours to obtain a black powder. The black powder was added to a mixture of 5 parts by weight of nickel chloride hexahydrate and 35 parts by weight of tetrahydrofuran, and after ultrasonic dispersion, 1.2 parts by weight of aluminum powder was added. After the reaction, the mixture was diluted with 60 parts by weight of tetrahydrofuran and filtered. The obtained solid mixture was transferred to a reactor, 2 mol / L dilute sulfuric acid was added, and stirring was performed for 20 minutes. The obtained product was washed with deionized water until neutral, and dried in a vacuum drying oven at 55°C for 12 hours to obtain aminated carbon nanotubes.

[0035] S4, Preparation of carbon-containing particles: The aminated carbon nanotubes obtained in step S3 and 8 parts by weight of pyridine were dissolved in 65 parts by weight of tetrahydrofuran in a reactor, and the solution was placed in an ice-water mixed bath. The modified silicon carbide particles obtained in step S2 were added to the solution, and after mixing, the reaction temperature was maintained at 25°C and stirring was performed for 4 hours. Then the reactor was placed in an ice-water mixed bath, 10 parts by weight of 1 mol / L hydrochloric acid and 40 parts by weight of deionized water were added thereto, and the mixture was distilled under reduced pressure to obtain a slurry. After cooling to room temperature, the slurry was diluted with 35 parts by weight of toluene and stirred for 15 minutes. The mixture was placed in an ice-water mixed bath and stirred for 4 hours. The solid was collected by vacuum filtration, washed with 75 parts by weight of deionized water, and dried in a vacuum drying oven at 50°C for 8 hours to obtain carbon-containing particles.

[0036] A method for preparing a particle-reinforced nickel-based metal powder, the method comprising: alloying raw materials, vacuum melting a nickel ingot, melting the nickel ingot using a medium-frequency induction heating method, powdering using a gas atomization method, performing particle size screening on the obtained powder, and uniformly mixing the screened alloy composite powder and carbon-containing particle material in a corresponding ratio in a mixer to obtain the particle-reinforced nickel-based metal powder. The vacuum degree of the melting chamber is 10 -2 Pa, the pressure of the powder spraying gas is 3.5 MPa, the screened alloy composite powder has a particle size range of 10-100 μm, and the carbon-containing particle has a particle size range of 10-100 μm.

[0037] The prepared particle-reinforced nickel-based metal powder is used for surface manufacturing and repairing by using a super-high-rate laser cladding technology and corresponding processes. The specific steps are as follows:

[0038] A1, machining the surface of the substrate;

[0039] A2, wiping the surface of the substrate with acetone to remove surface grease;

[0040] A3, planning a laser cladding path according to the geometric shape of the substrate surface and formulating process parameters;

[0041] A4, using a semiconductor laser cladding system to perform cladding repair on the surface of the substrate; using the following process parameters: laser power 1.2kw, spot diameter 1mm, powder feeding rate 6kg / h, laser scanning speed 25m / min, overlap rate 30%, single-layer cladding thickness 30μm, the laser cladding head has argon protection function, argon flow rate 15L / min;

[0042] A5, using a five-axis CNC machine tool to machine the repaired surface of the substrate to obtain the required size.

[0043] Example 2

[0044] Compared with Example 1, the nickel base metal powder and the carbon-containing particles have different composition ratios, the preparation process of the carbon-containing particles has different partial process parameters, the preparation method of the particle-reinforced nickel-based metal powder and the partial process parameters in the application process are different, and the rest refers to Example 1.

[0045] Specifically:

[0046] The composition ratio of the nickel base metal powder and the carbon-containing particles is: 75% of the nickel base metal powder and 25% of the carbon-containing particles, wherein the chemical composition of the nickel base metal powder and the mass percentage thereof are C≤0.1%, 18.0% Cr, 15.0% Mo, 0.1% Nb, 0.1% B, 1.5% V, 2.0% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 0.8% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and unavoidable impurities.

[0047] The partial process parameters in the preparation process of the carbon-containing particles are as follows:

[0048] S1, preparation of silicon carbide particles: take 5 parts by weight of metal Na, 2 parts by weight of Si powder, and 20 parts by weight of tetrabromomethane, mix uniformly, and then put them into a high-pressure reaction kettle, keep the temperature at 300℃ for 24h; after the reaction is completed, it is naturally cooled to room temperature, and the obtained product is treated by impurity removal, then washed with deionized water, dried at 65℃ for 5h to obtain silicon carbide particles; wherein the impurity removal treatment step is: sequentially treating the obtained product with anhydrous ethanol, 2mol / L hydrochloric acid, 70-75% perchloric acid (refluxed at 150℃ for 5h), and a mixed solution of hydrofluoric acid / nitric acid (V / V=1 / 4);

[0049] S2, Preparation of modified silicon carbide particles: The silicon carbide particles obtained in step S1 were ultrasonically dispersed in 45 parts by weight of ethanol, 2 parts by weight of γ-aminopropyl triethoxysilane was added thereto at room temperature, and the mixture was stirred for 6 hours, then centrifuged, washed, and washed with ethanol, acetone, and tetrahydrofuran in this order for 5 times. The resulting product was then dispersed in 55 parts by weight of tetrahydrofuran, 2.5 parts by weight of benzene tricarboxylic acid glycoside was added thereto, and the mixture was stirred for 10 hours at room temperature. The product was then centrifuged, washed with water, mixed with 1.2 parts by weight of thionyl chloride and 45 parts by weight of N,N-dimethylformamide, and then the temperature was raised to 55°C for 6 hours. The resulting product was then filtered to obtain modified silicon carbide particles.

[0050] S3, Preparation of aminated carbon nanotubes: 25 parts by weight of carbon nanotubes were ultrasonically dispersed in 100 parts by weight of toluene, 8 parts by weight of azobisisobutyronitrile was added thereto while stirring, and the mixture was stirred for 6 hours under a nitrogen atmosphere. The reaction product was then washed with toluene for 5 times, and dried in a vacuum drying oven at 60°C for 14 hours to obtain a black powder. The black powder was then added to a mixture of 8 parts by weight of nickel chloride hexahydrate and 45 parts by weight of tetrahydrofuran, and the mixture was ultrasonically dispersed, and then 2.5 parts by weight of aluminum powder was added thereto. The mixture was then diluted with 80 parts by weight of tetrahydrofuran and filtered. The resulting solid mixture was then transferred to a reactor, 2 mol / L dilute sulfuric acid was added thereto, and the mixture was stirred for 20 minutes. The resulting product was then washed with deionized water until neutral, and dried in a vacuum drying oven at 60°C for 14 hours to obtain aminated carbon nanotubes.

[0051] S4, Preparation of carbon-containing particles: The aminated carbon nanotubes obtained in step S3 were dissolved in 70 parts by weight of tetrahydrofuran in a reactor, and the mixture was placed in an ice-water bath. The modified silicon carbide particles obtained in step S2 were then added to the solution, and the mixture was stirred for 6 hours while maintaining the reaction temperature at 30°C. The reactor was then placed in an ice-water bath, and 15 parts by weight of 1 mol / L hydrochloric acid and 50 parts by weight of deionized water were added thereto. The mixture was then distilled under reduced pressure until a slurry was obtained. The slurry was then cooled to room temperature, diluted with 45 parts by weight of toluene, and stirred for 20 minutes. The mixture was then placed in an ice-water bath and stirred for 4 hours. The solid was then collected by vacuum filtration, washed with 90 parts by weight of deionized water, and dried in a vacuum drying oven at 55°C for 10 hours to obtain carbon-containing particles.

[0052] In the method for preparing particle-reinforced nickel-based metal powder, some process parameters are as follows: the vacuum degree of the melting chamber is 10 -2 Pa, and the argon gas pressure is 4 MPa.

[0053] The prepared particle reinforced nickel-based metal powder is used for surface manufacturing and repairing by using ultra-high rate laser cladding technology combined with corresponding process. In step A4, the following process parameters are used: laser power 1.2 kw, spot diameter 1 mm, powder feeding rate 5 kg / h, laser scanning speed 20 m / min, overlap rate 30%, single-layer cladding thickness 25 μm, and the laser cladding head has argon protection function with argon flow rate 15 L / min.

[0054] Example 3

[0055] Compared with Example 1, the nickel-based metal powder and the carbon-containing particles have different composition ratios, the carbon-containing particles have different partial process parameters in the preparation process, the particle reinforced nickel-based metal powder has different partial process parameters in the preparation method and application process, and the rest refers to Example 1.

[0056] Specifically,

[0057] The composition ratio of the nickel-based metal powder and the carbon-containing particles is: 75% of the nickel-based metal powder and 25% of the carbon-containing particles. The chemical composition and mass percentage of the nickel-based metal powder are as follows: C≤0.1%, 1.0% Cr, 2.0% Mo, 5.0% Nb, 3.0% B, 4.0% V, 12.0% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.6% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance of Ni and inevitable impurities.

[0058] The preparation method of the carbon-containing particles is as follows:

[0059] S1, preparation of silicon carbide particles: 2 parts by weight of metal Na, 0.5 parts by weight of Si powder, and 10 parts by weight of tetrabromomethane are weighed and uniformly mixed, then put into a high-pressure reaction kettle, and kept at a temperature of 220°C for 16h. After the reaction is completed, it is naturally cooled to room temperature. The obtained product is treated by impurity removal, washed with deionized water, and dried at 55°C for 3h to obtain silicon carbide particles; wherein the impurity removal treatment step is: the obtained product is sequentially treated with anhydrous ethanol, 2 mol / L hydrochloric acid, 70-75% perchloric acid (refluxed at 180°C for 2h), and a mixed solution of hydrofluoric acid / nitric acid (V / V=1 / 2);

[0060] S2, Preparation of modified silicon carbide particles: The silicon carbide particles obtained in step S1 were ultrasonically dispersed in 20 parts by weight of ethanol, 0.5 parts by weight of γ-aminopropyltriethoxysilane was added thereto at room temperature, and the mixture was stirred for 4 hours, then centrifuged, washed, and washed with ethanol, acetone, and tetrahydrofuran in this order twice, and then dispersed in 35 parts by weight of tetrahydrofuran solvent, 1 part by weight of benzene tricarboxylic acid glycoside was added thereto, and the mixture was stirred for 6 hours at room temperature, then centrifuged, washed with water, and mixed with 0.8 parts by weight of thionyl chloride and 35 parts by weight of N,N-dimethylformamide, and then the temperature was increased to 45°C, and the mixture was reacted for 2 hours, and then filtered to obtain modified silicon carbide particles;

[0061] S3, Preparation of aminated carbon nanotubes: 10 parts by weight of carbon nanotubes were ultrasonically dispersed in 60 parts by weight of toluene, 2 parts by weight of azobisisobutyronitrile was added thereto while stirring, and the mixture was stirred for 4 hours under a nitrogen atmosphere, and then the reaction product was washed with toluene 5 times, and dried in a vacuum drying oven at 50°C for 10 hours to obtain a black powder; the black powder was added to a mixture of 3 parts by weight of nickel chloride hexahydrate and 25 parts by weight of tetrahydrofuran, and then ultrasonically dispersed, and 0.8 parts by weight of aluminum powder was added thereto, and then the mixture was diluted with 45 parts by weight of tetrahydrofuran after the reaction was completed, and then filtered, and the obtained solid mixture was transferred to a reactor, 2 mol / L dilute sulfuric acid was added thereto, and stirred for 10 minutes, and then vacuum filtered, and the obtained product was washed with deionized water until neutral, and then dried in a vacuum drying oven at 50°C for 10 hours to obtain aminated carbon nanotubes.

[0062] S4, Preparation of carbon-containing particles: The aminated carbon nanotubes obtained in step S3 were dissolved in 55 parts by weight of tetrahydrofuran in a reactor, and then the mixture was placed in an ice-water mixed bath, and then the modified silicon carbide particles obtained in step S2 were added thereto, and then the mixture was stirred for 2 hours while maintaining the reaction temperature at 20°C, and then the reactor was placed in an ice-water mixed bath, and then 6 parts by weight of 1 mol / L hydrochloric acid and 25 parts by weight of deionized water were added thereto, and then the mixture was distilled under reduced pressure until a slurry was obtained, and then the mixture was cooled to room temperature, and then diluted with 30 parts by weight of toluene, and then stirred for 10 minutes, and then placed in an ice-water mixed bath, and then stirred for 2 hours, and then the solid was collected by vacuum filtration, and then washed with 65 parts by weight of deionized water, and then dried in a vacuum drying oven at 45°C for 6 hours to obtain carbon-containing particles.

[0063] In the method for preparing particle-reinforced nickel-based metal powder, some process parameters are as follows: the vacuum degree of the melting chamber is 10 -1 Pa, and the argon gas pressure of the powder spraying gas is 2.5 MPa.

[0064] The prepared particle reinforced nickel-based metal powder is used for surface manufacturing and repairing by using ultra-high rate laser cladding technology combined with corresponding process. In step A4, the following process parameters are used: laser power 1.5 kw, spot diameter 1 mm, powder feeding rate 8 kg / h, laser scanning speed 30 m / min, overlap rate 35%, single layer cladding thickness 30 μm, and the laser cladding head has argon protection function with argon flow rate 20 L / min.

[0065] Comparative Example 1

[0066] In comparison with Example 1, the carbon-containing particles added in the present comparative example are replaced by silicon carbide particles, and the rest is referred to Example 1.

[0067] Specifically, the particle reinforced nickel-based metal powder is composed of nickel matrix metal powder and silicon carbide particles, and the ratio is: 92% of nickel matrix metal powder and 8% of silicon carbide particles. The chemical composition and mass percentage of the nickel matrix metal powder are as follows: C≤0.1%, 6.0% Cr, 4.5% Mo, 2.5% Nb, 1.2% B, 2.2% V, 4.5% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and inevitable impurities.

[0068] Comparative Example 2

[0069] In comparison with Example 1, the carbon-containing particles added in the present comparative example are replaced by carbon nanotubes, and the rest is referred to Example 1.

[0070] Specifically, the particle reinforced nickel-based metal powder is composed of nickel matrix metal powder and carbon nanotubes, and the ratio is: 92% of nickel matrix metal powder and 8% of carbon nanotubes. The chemical composition and mass percentage of the nickel matrix metal powder are as follows: C≤0.1%, 6.0% Cr, 4.5% Mo, 2.5% Nb, 1.2% B, 2.2% V, 4.5% W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and inevitable impurities.

[0071] Comparative Example 3

[0072] In comparison with Example 1, the carbon-containing particles added in the present comparative example are replaced by directly adding silicon carbide particles and carbon nanotubes, and the rest is referred to Example 1.

[0073] Specifically, the particle-reinforced nickel-based metal powder is composed of nickel base metal powder, silicon carbide particles and carbon nanotubes, and the ratio is: 92% of nickel base metal powder, 4% of silicon carbide particles and 4% of carbon nanotubes, wherein the chemical composition and mass percentage of the nickel base metal powder are: C≤0.1%, 6.0% of Cr, 4.5% of Mo, 2.5% of Nb, 1.2% of B, 2.2% of V, 4.5% of W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% of Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and inevitable impurities.

[0074] Comparative Example 4

[0075] Compared with Example 1, the comparative example does not add carbon-containing particles, and the rest refers to Example 1.

[0076] Specifically, the particle-reinforced nickel-based metal powder is composed of nickel base metal powder, silicon carbide particles and carbon nanotubes, and the ratio is: 92% of nickel base metal powder, 4% of silicon carbide particles and 4% of carbon nanotubes, wherein the chemical composition and mass percentage of the nickel base metal powder are: C≤0.1%, 6.0% of Cr, 4.5% of Mo, 2.5% of Nb, 1.2% of B, 2.2% of V, 4.5% of W, Fe≤6.0%, Al≤0.6%, Ti≤0.6%, 1.0% of Mn, Co≤1.0%, P≤0.030%, S≤0.030%, and the balance is Ni and inevitable impurities.

[0077] Related tests:

[0078] The powders prepared in Examples 1-3 and Comparative Examples 1-4 were subjected to related tests, and the test performance parameters are shown in Table 1.

[0079] Table 1 Performance parameters of particle-reinforced nickel-based metal powder

[0080] Group Particle size μm Flowability s / 50 g Sphericity % D50 / μm Example 1 10-100 14 93 40 Example 2 10-100 15 92 42 Example 3 10-100 15 92 42 Comparative Example 1 10-100 18 90 43 Comparative Example 2 10-100 18 89 43 Comparative Example 3 10-100 21 89 45 Comparative Example 4 10-100 16 91 42

[0081] The surface performance after high-speed laser cladding processing of Examples 1-3 and Comparative Examples 1-4 is shown in Table 2.

[0082] Table 2 Surface performance after processing

[0083]

[0084] From the test results, it can be seen that the relevant properties of Examples 1-3 are better than those of Comparative Examples 1-4 in terms of comprehensive performance, especially in terms of wear resistance and hardness. In combination with the performance parameters of the prepared powders, it can be seen that the carbon-containing particles have good compatibility with the nickel matrix metal powder during the preparation process, and the mixing is relatively uniform. From the comparison of the test data of Examples 1-3, it can be seen that the change of parameters during the preparation process has a certain influence on the performance of the final product. From the comparison of the test data of Example 1 and Comparative Example 3, it can be seen that the performance of the mixture of the modified silicon carbide and carbon nanotubes with the nickel matrix metal powder is better than that of the mixture of the silicon carbide, carbon nanotubes and nickel matrix metal powder, which may be because the modification can help the dispersion of the silicon carbide and carbon nanotubes, avoiding the agglomeration phenomenon of the silicon carbide and carbon nanotubes after being directly added.

[0085] Silicon carbide has the characteristics of strong heat conduction, good mechanical properties, small thermal expansion coefficient, good thermal performance, stable physical and chemical properties. The introduction of silicon carbide in the process of material preparation can effectively improve the wear resistance, thereby prolonging the service life. Carbon nanotubes have excellent mechanical and chemical properties, and the composite of carbon nanotubes and materials can enhance the strength and impact resistance of the materials. In the present application, a particle reinforced nickel-based metal powder is provided, which is composed of a nickel matrix metal powder and a carbon-containing particle. In the preparation process of the carbon-containing particle, first, a high-pressure reaction kettle is used, in which sodium, silicon powder and tetrabromomethane are added, and silicon carbide particles are obtained by reaction at high temperature; secondly, γ-aminopropyl triethoxysilane is added, and after reaction, centrifugation and washing, amino-modified silicon carbide is obtained, which is dispersed in tetrahydrofuran and then reacts with benzene partial triacid glycoside, and after centrifugation and washing, carboxyl-modified silicon carbide is obtained, which is further mixed with thionyl chloride in the presence of N,N-dimethylformamide to obtain silicon carbide with carbonyl chloride functional groups; further, carbon nanotubes are dispersed in toluene, reacted with azobisisobutyronitrile, washed and dried to obtain black powder, then the remaining nickel chloride hexahydrate and tetrahydrofuran are mixed, aluminum powder is added for reaction, then diluted with tetrahydrofuran and filtered, impurities are dissolved by adding dilute sulfuric acid, and then suction filtration and washing are carried out to obtain aminated carbon nanotubes; finally, the prepared aminated carbon nanotubes and pyrrole are mixed and dissolved in tetrahydrofuran, and the obtained silicon carbide with carbonyl chloride functional groups is added to react, then dilute hydrochloric acid and deionized water are added, and after vacuum distillation, toluene dilution, low temperature treatment, vacuum filtration and washing, the carbonized silicon and carbon nanotube composite carbon-containing particles are obtained. Then in the preparation process of the particle reinforced nickel-based metal powder, the nickel matrix metal powder is mixed according to the composition ratio of each raw material, and then vacuum smelting nickel ingot is carried out, the powder is collected and sieved, the sieved alloy composite powder is uniformly mixed with the carbon-containing particles in a corresponding ratio in a mixer to obtain the particle reinforced nickel-based metal powder, and the prepared particle reinforced nickel-based metal powder is used for surface manufacturing and repair by using ultra-high-speed laser cladding technology. In this process, the silicon carbide and carbon nanotube composite carbon-containing particles are dispersed in the nickel matrix metal powder, the carbon-containing particles are entangled in three-dimensional space, and the surface or interior of the carbon-containing particles is attached with metal powder. Compared with the prior art which only contains nickel-based metal powder, in the process of surface manufacturing and repair, the added carbon-containing particles can play a role similar to a column in the metal matrix, and more energy needs to be absorbed to break the covalent bond structure in the carbon nanotube and the bonding between the carbon nanotube and the metal when fracture occurs, thereby achieving the effect of reinforcement. In addition, silicon carbide is also introduced in the preparation of the carbon-containing particle, which has good mechanical properties and small thermal expansion coefficient, and can effectively reduce the occurrence of cracking after surface repair by interacting with the carbon nanotube.Compared with directly adding carbon nanotubes and silicon carbide into nickel-based metal powder, the carbon-containing particles with silicon carbide and carbon nanotube composite are introduced, and with the lubrication of carbon nanotubes, silicon carbide can be effectively dispersed, and the agglomeration phenomenon caused by direct addition and mixing unevenness can be prevented, so as to affect the final surface performance.

[0086] It should be noted that the relational terms herein such as first and second and the like are used solely to distinguish one entity or action from another, without necessarily requiring or implying any such actual relationship or order between such entities or actions. Moreover, the terms "comprises", "comprising", or any other variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus.

[0087] Although the embodiments of the present application have been shown and described, it is to be understood that various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the present application, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A particulate reinforced nickel-based metal powder, characterized in that, The application relates to a nickel-based metal powder and carbon-containing particle composite material, which is prepared from a nickel-based metal powder and carbon-containing particles in a ratio of 75-95% of the nickel-based metal powder and 5-25% of the carbon-containing particles, wherein the chemical composition of the nickel-based metal powder and the mass percentage are as follows: C<=0.1%, 1.0-18.0% of Cr, 2.0-15.0% of Mo, 0.1-5.0% of Nb, 0.1-3.0% of B, 1.5-4.0% of V, 2.0-12.0% of W, Fe<=6.0%, Al<=0.6%, Ti<=0.6%, 0.8-1.6% of Mn, Co<=1.0%, P<=0.030%, S<=0.030%, and the balance of Ni and inevitable impurities; and the carbon-containing particles are silicon carbide and carbon nanotube composite materials. The application further relates to a preparation method of the carbon-containing particles. S1, preparation of silicon carbide particles: metal Na, Si powder and tetra-bromomethane are weighed, uniformly mixed and then put into a high-pressure reaction kettle, reaction is carried out at a temperature of 220-300 DEG C for 16-24 h, the obtained product is naturally cooled to room temperature after reaction, impurities are removed, and then the product is washed with deionized water and dried to obtain the silicon carbide particles. S2, preparation of modified silicon carbide particles: the silicon carbide particles obtained in step S1 are ultrasonically dispersed in ethanol, gamma-aminopropyl triethoxysilane is added at room temperature, stirring reaction is carried out for 4-6 h, then centrifugal washing is carried out, the product is dispersed in tetrahydrofuran solvent, benzene partial tricarboxylic acid glycoside is added, stirring reaction is carried out at room temperature for 6-10 h, then centrifugal washing is carried out, and the product is mixed with thionyl chloride and N, N-dimethylformamide, the temperature is increased to 45-55 DEG C, reaction is carried out for 2-6 h, and then the modified silicon carbide particles are obtained by filtration. S3, preparation of aminated carbon nanotubes: carbon nanotubes are ultrasonically dispersed in toluene, azobisisobutyronitrile is added under stirring, reaction is carried out under inert atmosphere for 4-6 h, the reaction product is washed with toluene, and then the black powder is obtained after drying; the black powder is added into a mixed solution of nickel chloride hexahydrate and tetrahydrofuran, aluminum powder is added after ultrasonic dispersion, the reaction product is diluted with tetrahydrofuran after reaction, and then filtration is carried out, the obtained solid mixture is transferred into a reactor, dilute sulfuric acid is added, stirring is carried out for 10-20 min, vacuum filtration is carried out, the obtained product is washed with deionized water until neutral, and then drying is carried out to obtain the aminated carbon nanotubes. S4, preparation of carbon-containing particles: the aminated carbon nanotubes obtained in step S3 and pyridine are dissolved in tetrahydrofuran in a reactor, the solution is placed in an ice-water mixed bath, the modified silicon carbide particles obtained in step S2 are added into the solution, uniform mixing is carried out, the reaction temperature is kept at 20-30 DEG C, and then stirring is carried out for 2-6 h, the reactor is placed in an ice-water mixed bath, dilute hydrochloric acid and deionized water are added into the solution, and then the solution is distilled under reduced pressure until a slurry is obtained, the slurry is diluted with toluene, stirring is carried out for 10-20 min, the slurry is placed in an ice-water mixed bath and stirred for 2-4 h, the solid is collected by vacuum filtration, washed with deionized water and dried to obtain the carbon-containing particles.

2. The particulate reinforced nickel-based metal powder of claim 1, wherein, In step S1, the step of removing impurities from the obtained product is as follows: the obtained product is sequentially treated with anhydrous ethanol, hydrochloric acid, perchloric acid and a mixed solution of hydrogen fluoride and nitric acid.

3. The particulate reinforced nickel-based metal powder of claim 2, wherein, The concentration of perchloric acid is 70-75%, and the refluxing is carried out at 150-180℃ for 2-5h.

4. The particulate reinforced nickel-based metal powder of claim 2, wherein, The mixed solution of hydrofluoric acid / nitric acid is prepared by mixing hydrofluoric acid and nitric acid in a volume ratio of 1:2-4.

5. The particulate reinforced nickel-based metal powder of claim 1 wherein, In step S1, the drying condition is drying in a vacuum drying oven at 55-65℃ for 3-5h; in step S3, the drying condition for obtaining black powder and the drying condition for obtaining amino-functionalized carbon nanotubes are both drying in a vacuum drying oven at 50-60℃ for 10-14h; and in step S4, the drying condition for obtaining carbon-containing particles is drying in a vacuum drying oven at 45-55℃ for 6-10h.

6. The particulate reinforced nickel-based metal powder of claim 1 wherein, In step S2, the washing process after adding γ-aminopropyltriethoxysilane and stirring is washing with ethanol, acetone and tetrahydrofuran for 2-5 times in turn.

7. A method of producing a particulate reinforced nickel-based metal powder according to any one of claims 1 to 6, characterized in that The preparation method is as follows: after alloying and proportioning the raw material components, vacuum melting nickel ingot is carried out, medium-frequency induction heating is applied to melt the nickel ingot, gas atomization method is used to prepare powder, the obtained powder is screened according to particle size, and the screened alloy composite powder is uniformly mixed with carbon-containing particle material in a mixer according to the corresponding proportion to obtain the product.

8. The method of claim 7, wherein the nickel-based metal powder is prepared by the steps of: The vacuum degree of the smelting chamber is 2.5-4 MPa. ​

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