CN109500385B - Preparation method of nickel/graphene composite powder for laser rapid prototyping - Google Patents

Preparation method of nickel/graphene composite powder for laser rapid prototyping Download PDF

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CN109500385B
CN109500385B CN201811141155.1A CN201811141155A CN109500385B CN 109500385 B CN109500385 B CN 109500385B CN 201811141155 A CN201811141155 A CN 201811141155A CN 109500385 B CN109500385 B CN 109500385B
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nickel
graphene
solution
laser
composite powder
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CN109500385A (en
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李晓峰
刘斌
仪登豪
冯英豪
白培康
赵占勇
李忠华
王建宏
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North University of China
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    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
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    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
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    • B22F12/00—Apparatus or devices specially adapted for additive manufacturing; Auxiliary means for additive manufacturing; Combinations of additive manufacturing apparatus or devices with other processing apparatus or devices
    • B22F12/40—Radiation means
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    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention particularly relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping. The preparation method comprises the following steps: adding graphene into a dispersing agent, and performing ultrasonic dispersion to obtain a graphene dispersion liquid; dissolving a nickel source into the graphene dispersion liquid obtained in the step one; obtaining a solution A; dissolving imidazole organic ligand in a solvent to obtain a solution B; adding the solution B into the solution A; standing for at least 16h, and filtering to obtain graphene loaded with nickel particles; placing the graphene loaded with the nickel particles obtained in the step two in an aqueous solution, and adding a nickel source, a reducing agent, a complexing agent and a regulator after ultrasonic dispersion; after mixing evenly, adjusting the pH value to 8-9; reacting at 50-95 ℃ for at least 0.5 h; washing the solid after solid-liquid separation; drying to obtain nickel/graphene composite powder; the powder can be uniformly mixed with nickel powder and is used for laser cladding and selective laser melting molding. The preparation process is simple and controllable, and the obtained product has excellent performance and is convenient for large-scale industrial application in the field of laser rapid prototyping.

Description

Preparation method of nickel/graphene composite powder for laser rapid prototyping
Technical Field
The invention relates to the field of metal matrix composite materials, in particular to a preparation method of nickel/graphene composite powder for laser rapid prototyping.
Background
Various high-temperature components such as an aircraft engine, a solid rocket engine, an industrial large-scale gas turbine and the like mainly use nickel-based high-temperature alloy, mainly because nickel has a face-centered cubic structure and has a stable structure; with the further demand of the material performance in the modern aviation industry, nickel-based composite materials are widely developed and used, and gradually replace part of the nickel-based high-temperature alloy in the aviation industry. The novel metal-based composite material has the advantages of good high-temperature strength, thermal fatigue resistance, oxidation resistance, corrosion resistance and the like, and is rapidly developed at home and abroad in recent years.
Graphene has high thermal conductivity, high damping capacity, high elastic modulus, high mechanical strength and good self-lubricity, and becomes an important reinforcement of a new material with an important structure and function. The research on the related composite material taking the graphene as the reinforcement mainly focuses on the biomedical field, the energy storage material, the photoelectric material and the catalysis field, and the research on the graphene reinforced metal matrix composite material is less. If the excellent performance of the graphene is introduced into the nickel-based composite material, great influence is brought to the performance improvement of the nickel-based composite material.
At present, the problems of poor dispersion of graphene in a metal aggregate, poor wettability with a matrix metal, poor interfacial associativity and the like mainly exist in the research of graphene metal-based composite materials, and the research, development and application of the graphene metal-based composite materials are severely restricted. The surface modification of the graphene is one direction for researching the graphene metal matrix composite, and has good research prospect. The preparation method of chemical nickel-plating graphene with the public number CN 103361637A is characterized in that SnCl2 sensitization and PdCl are carried out on the graphene2Activating and carrying out graphene chemical nickel plating to obtain nickel/graphene composite powder; the public number CN 108103485A discloses a method for preparing graphene coated with metal copper or nickel on the surface, which includes preparing graphene oxide by ultrasonic mixing solution of N-methylpyrrolidone and graphite oxide, and adding the graphene oxide into chemical plating solution to obtain graphene coated with metal copper or nickel.
According to the invention, an imidazole organic compound is used as a coupler, graphene and nickel ions are connected into a whole through non-covalent bond combination, and then the nickel ions are reduced into nickel particles loaded on the graphene through a reducing agent. Thus, the electroless nickel-plated graphene is prepared.
Disclosure of Invention
The invention aims to provide a preparation method of nickel/graphene composite powder for laser rapid prototyping without using noble metal salt.
The invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, which comprises the following steps:
step one
Adding graphene into a dispersing agent, and performing ultrasonic dispersion to obtain a graphene dispersion liquid;
step two
Dissolving a nickel source in the graphene dispersion liquid obtained in the step one; obtaining a solution A;
dissolving imidazole organic ligand in a solvent to obtain a solution B;
adding the solution B into the solution A; standing for at least 16h, and filtering to obtain graphene loaded with nickel particles;
step three
Placing the graphene loaded with the nickel particles obtained in the step two into an aqueous solution, and adding a nickel source, a reducing agent, a complexing agent and a regulator after ultrasonic dispersion; after mixing evenly, adjusting the pH value to 8-9; reacting at 50-95 ℃ for at least 0.5 h; washing the solid after solid-liquid separation; and drying to obtain the nickel/graphene composite powder.
The invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, wherein in the first step, a dispersing agent is selected from at least one of deionized water, methanol and ethanol; preferably deionized water.
The invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, which comprises the following steps of; in the graphene dispersion liquid, the concentration of graphene is 9-13 mg/mL.
The invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, and in the second step, the nickel source is nickel sulfate; in the solution A, the concentration of nickel is 0.05-0.2mol/L, preferably 0.1-0.2 mol/L;
in the second step, in the solution B, the solubility of the imidazole organic ligand is 18-30 g/L; the solvent used by the solution B is at least one selected from deionized water, methanol and ethanol; preferably deionized water.
According to the preparation method of the nickel/graphene composite powder for laser rapid prototyping, the imidazole organic ligand is 2-methylimidazole.
As a preferred scheme, the invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, which comprises the following three steps; the reducing agent is selected from at least one of sodium borohydride and hydrazine hydrate; the complexing agent is selected from at least one of sodium citrate, sodium tartrate, lactic acid and oxalic acid; the regulator is at least one selected from ammonium chloride, ammonium sulfate and ammonium acetate.
As a preferred scheme, the invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, which comprises the following steps of (1) preparing nickel/graphene composite powder according to a volume ratio; solution B: solution a ═ 1-1.2: 0.6-1, dropwise adding the solution B into the solution A; and standing for 16-24h, and filtering to obtain the graphene loaded with the nickel particles.
As a preferred scheme, the preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the third step of placing the graphene loaded with nickel particles obtained in the second step into an aqueous solution, performing ultrasonic dispersion, and adding nickel sulfate hexahydrate, sodium hypophosphite, sodium citrate and ammonium chloride; after being mixed evenly, the pH value is adjusted to 8 to 9 by ammonia water; reacting for 0.5-1.5 h at 50-95 ℃; washing the solid after solid-liquid separation; and drying to obtain the nickel/graphene composite powder.
As a preferred scheme, the preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the third step of placing the graphene loaded with the nickel particles obtained in the second step into an aqueous solution, and performing ultrasonic dispersion to obtain a liquid with the concentration of the graphene loaded with the nickel particles being 3-5 g/L; then adding nickel sulfate hexahydrate, sodium hypophosphite, sodium citrate and ammonium chloride; uniformly mixing to obtain a plating solution; the concentration of nickel sulfate hexahydrate in the plating solution is 20-30g/L, the concentration of sodium hypophosphite is 15-35g/L, the concentration of sodium citrate is 15-25g/L, and the concentration of ammonium chloride is 20-30 g/L.
The invention relates to a preparation method of nickel/graphene composite powder for laser rapid prototyping, wherein the loaded nickel is uniformly distributed, the particle size of nickel particles is distributed between 500 nanometers and 3 micrometers, and the particle size of the nickel particles in the obtained product is between 500 and 800 nanometers through process optimization.
The nickel/graphene composite powder prepared by the invention; mixing the mixture with nickel powder, and performing selective laser melting to obtain a blank with a set shape; when the selective laser melting is carried out, the scanning speed is controlled to be 1000-1200mm/s, the dot spacing is controlled to be 70-90 μm, the powder spreading thickness is controlled to be 40-60 μm, and the laser power is controlled to be 240-320W. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 0.5-1.5: 99.5-99.9. The particle size of the nickel powder is 30-60 microns. The mixing is ball milling; the ball milling time is 2-12 hours; the rotating speed is 170-300 r/min; the mass ratio of the ball material is 10-30: 1.
the nickel/graphene composite powder prepared by the invention; mixing the powder with nickel powder, and carrying out laser cladding by using a synchronous powder feeding method to obtain a blank with a set shape; during laser cladding, the scanning speed is controlled to be 2-8mm/s, the laser diameter is controlled to be 2-4mm, the laser power is controlled to be 1200-1800W, and the powder feeding speed is controlled to be 6-11.1 g/min. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 0.5-1.5: 99.5-99.9. The particle size of the nickel powder is 30-60 microns. The mixing is ball milling; the ball milling time is 2-12 hours; the rotating speed is 170-300 r/min; the mass ratio of the ball material is 10-30: 1.
the hardness of the blank selectively melted by the laser is more than or equal to 380 HV. Other mechanical properties are also superior to those of similar products.
The hardness of the laser cladding blank is not less than 690 HV. Other mechanical properties are also superior to those of similar products.
Principles and advantages
Compared with the existing palladium graphene nickel plating, the palladium graphene nickel plating method has the innovation points that an imidazole organic compound is used as an organic ligand, since the imidazole group can modify graphene through a non-covalent bond, the graphene is subjected to surface modification, the good binding capacity of the imidazole group and nickel ions is realized, nickel particles are loaded on the surface of the graphene to form active sites, and then a Ni source is added again, and the nickel/graphene composite powder is prepared by reducing the reducing agent in a liquid phase system; the method abandons palladium activation used in the traditional method, reduces the cost, simultaneously carries out surface modification on the graphene, solves the problems of poor wettability and poor interface bonding with the nickel-based alloy powder in the later period, and is beneficial to uniformly mixing the graphene and the nickel-based composite powder. The obtained nickel/graphene composite powder and micron-sized nickel powder are mixed according to the mass ratio of 0.5-1.5:99.5-98.5, and then high-speed 3D printing is adopted, so that a product with excellent performance can be obtained.
Drawings
The invention is further described below with reference to the accompanying drawings:
fig. 1 is a flow chart of a preparation process of nickel/graphene composite powder.
Fig. 2 is a scanning electron microscope image of the nickel/graphene prepared in example 1.
Fig. 3 is a high power scanning electron micrograph of the nickel/graphene prepared in example 1.
Fig. 4 is a scanning electron microscope picture of the nickel/graphene prepared in comparative example 1.
The basic process flow designed by the present invention can be seen from fig. 1.
It can be seen from fig. 2 that the nickel particles in the material are uniformly distributed on the surface of the graphene.
It can be seen from fig. 3 that the particle size of the nickel particles loaded on the surface of the graphene is 500-800 nm.
It can be seen from fig. 4 that the amount of nickel particles loaded on the surface of graphene did not achieve the intended purpose of the experiment.
Detailed Description
Example 1
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) adding 1g of graphene into 500mL of deionized water, and performing ultrasonic dispersion to obtain 500mL of graphene dispersion liquid.
(2) Dissolving 10g of nickel sulfate hexahydrate in 250mL of graphene deionized water dispersion, adding 250mL of deionized water → solution A, dissolving 10.4g of 2-methylimidazole in 500mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 24 hours; and carrying out vacuum filtration on the mixed solution to obtain the graphene loaded with the nickel particles, and placing the graphene in a beaker.
(3) Ultrasonically dispersing the graphene in 500mL of water, adding 7.5g of nickel sulfate hexahydrate, 6g of sodium hypophosphite, 2.5g of sodium citrate and 7.5g of ammonium chloride, uniformly mixing, adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 90 ℃ by mechanical stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) Preparing nickel/graphene composite powder; mixing the mixture with nickel powder, and performing selective laser melting to obtain a blank with a set shape; when the selective laser melting is carried out, the scanning speed is controlled to be 1150mm/s, the dot spacing is 85 micrometers, the powder spreading thickness is 45 micrometers, and the laser power is 280W. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 0.5: 99.5. The particle size of the nickel powder is 30-60 microns. The selected area laser melting equipment adopted in the experiment is a Renyshao AM400 selected area laser melting forming machine, the laser is a fiber laser, and the nickel-based alloy is prepared on an aluminum alloy substrate; and (3) measuring the mechanical property of the nickel alloy block: the Vickers hardness is 385 HV.
(5) As shown in fig. 2, which is a scanning electron microscope image of the nickel/graphene composite powder in embodiment 1 of the present invention, it can be seen that the nickel particles in the material are uniformly distributed on the surface of the graphene, as shown in fig. 3, which is a high-power scanning electron microscope image of the nickel/graphene composite powder in embodiment 1 of the present invention, it can be seen that the particle size of the nickel particles in the material is between 500-800 nm.
Example 2
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) adding 1g of graphene into 1L of deionized water, and performing ultrasonic dispersion to obtain 1L of graphene dispersion liquid.
(2) Dissolving 16g of nickel sulfate hexahydrate in 250mL of graphene deionized water dispersion, adding 250mL of deionized water → solution A, dissolving 10g of 2-methylimidazole in 500mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 20 hours; and carrying out vacuum filtration on the mixed solution to obtain the graphene loaded with the nickel particles, and placing the graphene in a beaker.
(3) Ultrasonically dispersing the graphene in 500mL of water, adding 7.5g of nickel sulfate hexahydrate, 6g of sodium borohydride, 2.5g of sodium citrate and 7.5g of ammonium chloride, uniformly mixing, adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 80 ℃ by mechanical stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) Preparing nickel/graphene composite powder; mixing the mixture with nickel powder, and performing selective laser melting to obtain a blank with a set shape; when the selective laser melting is carried out, the scanning speed is controlled to be 1150mm/s, the dot spacing is 85 micrometers, the powder spreading thickness is 45 micrometers, and the laser power is 280W. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 1: 99.1. The particle size of the nickel powder is 30-60 microns. The selected area laser melting equipment adopted in the experiment is a Renyshao AM400 selected area laser melting forming machine, the laser is a fiber laser, and the nickel-based alloy is prepared on an aluminum alloy substrate; and (3) measuring the mechanical property of the nickel alloy block: the Vickers hardness was 395 HV.
Example 3
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) adding 1g of graphene into 1L of deionized water, and performing ultrasonic dispersion to obtain 1L of graphene dispersion liquid.
(2) Dissolving 40g of nickel sulfate hexahydrate in 250mL of graphene dispersion, adding 250mL of deionized water → solution A, dissolving 7.5g of 2-methylimidazole in 500mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 17 hours; and carrying out vacuum filtration on the mixed solution to obtain the graphene loaded with the nickel particles, and placing the graphene in a beaker.
(3) Ultrasonically dispersing the graphene in 500mL of water, adding 11g of nickel sulfate hexahydrate, 17.5g of hydrazine hydrate, 2.5g of sodium citrate and 25g of ammonium chloride, uniformly mixing, adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 75 ℃ by ultrasonic-assisted stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) Preparing nickel/graphene composite powder; mixing the mixture with nickel powder, and performing selective laser melting to obtain a blank with a set shape; when the selective laser melting is carried out, the scanning speed is controlled to be 1150mm/s, the dot spacing is 85 micrometers, the powder spreading thickness is 45 micrometers, and the laser power is 280W. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 1.5: 99.0. The particle size of the nickel powder is 30-60 microns. The selected area laser melting equipment adopted in the experiment is a Renyshao AM400 selected area laser melting forming machine, the laser is a fiber laser, and the nickel-based alloy is prepared on an aluminum alloy substrate; and (3) measuring the mechanical property of the nickel alloy block: the Vickers hardness is 385 HV.
Example 4
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) and adding 50mg of graphene into 50mL of deionized water, and performing ultrasonic dispersion to obtain 50mL of graphene dispersion liquid.
(2) Dissolving 0.8g of nickel sulfate hexahydrate in 25mL of graphene deionized water dispersion, adding 25mL of deionized water → solution A, dissolving 0.2g of 2-methylimidazole in 50mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 20 hours; and carrying out vacuum filtration on the mixed solution to obtain the graphene loaded with the nickel particles, and placing the graphene in a beaker.
(3) Ultrasonically dispersing the graphene in 100mL of water, adding 1.5g of nickel sulfate hexahydrate, 1.2g of sodium hypophosphite, 0.5g of sodium citrate and 1.5g of ammonium chloride, uniformly mixing, adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 90 ℃ by mechanical stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) Mixing the prepared nickel/graphene composite powder with nickel powder, and carrying out laser cladding by using a synchronous powder feeding method to obtain a blank with a set shape; during laser cladding, the scanning speed is controlled to be 5mm/s, the laser diameter is controlled to be 4mm, the laser power is 1500W, and the powder feeding speed is 7 g/min. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 0.5: 99.0. The particle size of the nickel powder is 77-154 microns. Preparing a nickel-based alloy on a stainless steel substrate by adopting an optical fiber coupling semiconductor laser as laser cladding equipment and an optical fiber laser as a laser; and (3) measuring the mechanical property of the nickel alloy block: the Vickers hardness was 690 HV.
Example 5
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) 100mg of graphene is added into 100mL of deionized water for ultrasonic dispersion, and 100mL of graphene dispersion liquid is prepared.
(2) Dissolving 1.8g of nickel sulfate hexahydrate in 50mL of graphene deionized water dispersion, adding 50mL of deionized water → solution A, dissolving 0.45g of 2-methylimidazole in 100mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 20 hours; and carrying out vacuum filtration on the mixed solution to obtain the graphene loaded with the nickel particles, and placing the graphene in a beaker.
(3) Ultrasonically dispersing the graphene in 200mL of water, adding 3.1g of nickel sulfate hexahydrate, 2.5g of sodium hypophosphite, 1.2g of sodium citrate and 3.2g of ammonium chloride, uniformly mixing, adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 90 ℃ by mechanical stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) Mixing the prepared nickel/graphene composite powder with nickel powder, and carrying out laser cladding by using a synchronous powder feeding method to obtain a blank with a set shape; during laser cladding, the scanning speed is controlled to be 5mm/s, the laser diameter is controlled to be 4mm, the laser power is 1500W, and the powder feeding speed is 7 g/min. Preferably, the mass ratio of the nickel/graphene composite powder to the nickel powder is 1: 99.9. The particle size of the nickel powder is 77-154 microns. Preparing a nickel-based alloy on a stainless steel substrate by adopting an optical fiber coupling semiconductor laser as laser cladding equipment and an optical fiber laser as a laser; and (3) measuring the mechanical property of the nickel alloy block: the Vickers hardness was 700 HV.
Comparative example 1
The preparation method of the nickel/graphene composite powder for laser rapid prototyping comprises the following steps:
(1) and adding 40mg of graphene into 40mL of deionized water, and performing ultrasonic dispersion to obtain 40mL of graphene dispersion liquid.
(2) Dissolving 2.4g of nickel sulfate hexahydrate in 20mL of graphene dispersion, adding 20mL of deionized water → solution A, dissolving 0.75g of 2-methylimidazole in 40mL of deionized water → solution B, slowly (dropwise) dissolving the solution B in the solution A, and standing the solution for 24 hours; graphene was observed to be uniformly dispersed in the solution.
(3) Dissolving 3.5g of hydrazine hydrate, 0.5g of sodium citrate and 5g of ammonium chloride in sequence to prepare a mixed solution, adding the mixed solution obtained in the step (2), adjusting the pH value to 8-9 by using ammonia water, reacting for 1h at 75 ℃ by mechanical stirring, filtering and washing a product to be neutral, and freeze-drying to obtain the nickel/graphene composite powder.
(4) As shown in fig. 4, which is a scanning electron micrograph of the nickel-plated graphene prepared in comparative example 4, the amount of nickel particles loaded on the graphene shown in fig. 4 is very small, and only a few nickel particles do not achieve the intended purpose of the present invention.
The present invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The above-described embodiments of the invention are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims, and not by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (6)

1. A preparation method of nickel/graphene composite powder for laser rapid prototyping is characterized by comprising the following steps of; the method comprises the following steps:
step one
Adding graphene into a dispersing agent, and performing ultrasonic dispersion to obtain a graphene dispersion liquid;
step two
Dissolving a nickel source in the graphene dispersion liquid obtained in the step one to obtain a solution A;
dissolving imidazole organic ligand in a solvent to obtain a solution B;
solution B: solution a = 1-1.2: 0.6-1, dropwise adding the solution B into the solution A; standing for 16-24h, and filtering to obtain graphene loaded with nickel ions;
step three
Placing the graphene loaded with the nickel ions obtained in the step two into an aqueous solution, and performing ultrasonic dispersion to obtain liquid with the concentration of the graphene loaded with the nickel ions being 3-5 g/L; then adding nickel sulfate hexahydrate, sodium hypophosphite, sodium citrate and ammonium chloride; mixing, and adjusting pH to 8-9 with ammonia water; obtaining a plating solution; reacting for 0.5-1.5 h at 50-95 ℃; washing the solid after solid-liquid separation; drying to obtain nickel/graphene composite powder; the concentration of nickel sulfate hexahydrate in the plating solution is 20-30g/L, the concentration of sodium hypophosphite in the plating solution is 15-35g/L, the concentration of sodium citrate in the plating solution is 15-25g/L, and the concentration of ammonium chloride in the plating solution is 20-30 g/L.
2. The method for preparing the nickel/graphene composite powder for laser rapid prototyping according to claim 1, is characterized in that:
in the first step, the dispersing agent is selected from at least one of deionized water, methanol and ethanol;
in the first step, the concentration of graphene in the graphene dispersion liquid is 9-13 mg/mL.
3. The method for preparing the nickel/graphene composite powder for laser rapid prototyping according to claim 2, characterized in that: mixing graphene and deionized water, centrifuging for 15-30min, pouring out supernatant, adding deionized water, and centrifuging for the third time; and taking out the graphene in the centrifuge tube after the third centrifugation is finished, adding deionized water, and performing ultrasonic dispersion to obtain the graphene deionized water dispersion liquid.
4. The method for preparing the nickel/graphene composite powder for laser rapid prototyping according to claim 1, is characterized in that:
in the second step, the nickel source is nickel sulfate; in the solution A, the concentration of nickel is 0.05-0.2 mol/L;
in the second step, in the solution B, the solubility of the imidazole organic ligand is 18-30 g/L; the solvent used by the solution B is at least one selected from deionized water, methanol and ethanol; the imidazole organic ligand is 2-methylimidazole.
5. The method for preparing the nickel/graphene composite powder for laser rapid prototyping according to claim 1, is characterized in that: mixing the prepared nickel/graphene composite powder with nickel powder, and performing selective laser melting to obtain a blank with a set shape; when the selective laser melting is carried out, the scanning speed is controlled to be 1000-1200mm/s, the dot spacing is controlled to be 70-90 μm, the powder spreading thickness is controlled to be 40-60 μm, and the laser power is controlled to be 240-320W.
6. The method for preparing the nickel/graphene composite powder for laser rapid prototyping according to claim 1, is characterized in that: mixing the prepared nickel/graphene composite powder with nickel powder, and carrying out laser cladding by using a synchronous powder feeding method to obtain a blank with a set shape; during laser cladding, the scanning speed is controlled to be 2-8mm/s, the laser diameter is controlled to be 2-4mm, the laser power is controlled to be 1200-1800W, and the powder feeding speed is controlled to be 6-11.1 g/min.
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