CN110744045A - Method for in-situ synthesis of carbon nano tube on surface of aluminum alloy spherical powder - Google Patents
Method for in-situ synthesis of carbon nano tube on surface of aluminum alloy spherical powder Download PDFInfo
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- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 43
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 14
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 8
- 229910045601 alloy Inorganic materials 0.000 claims description 7
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
- C01B32/162—Preparation characterised by catalysts
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Abstract
The invention discloses a method for in-situ synthesis of carbon nanotubes on the surface of aluminum alloy spherical powder, which relates to the technical field of preparation of high-light-absorption aluminum-based powder, and comprises the following steps: s100, preparing a Ni/2024Al catalyst; s200, calcining the Ni/2024Al catalyst in a mixed gas atmosphere to obtain CNTs/2024Al-Ni composite powder. The preparation method of the invention utilizes the strong light absorption property and the nanoscale surface effect of the carbon tube to improve the absorption efficiency of the aluminum alloy powder to the laser energy, reduce the energy loss, avoid the adverse effect of high input energy on the microstructure of a sample, overcome the adverse effect of the low light absorption rate of the metal powder on the application of the 3D printing technology, simultaneously preserve the sphericity of the original powder to the maximum extent and meet the requirement of 3D printing.
Description
Technical Field
The invention relates to the technical field of preparation of high-light-absorption aluminum-based powder, in particular to a method for in-situ synthesis of carbon nanotubes on the surface of aluminum alloy spherical powder.
Background
In the field of aerospace, the light weight of engine materials is mainly reflected in the mass application of magnesium, aluminum alloy and composite materials, wherein the use of the magnesium and aluminum alloy composite materials is an important way for realizing the light weight of airplanes, and is called as 'material light weight'. The additive manufacturing technology is applied to the field of design and manufacture of aerospace complex structures, the traditional component design mode can be changed, and the concept of function-first design is realized. The structural design can be played at will as long as the requirements of the functions of the parts and the technical process of additive manufacturing are met. Therefore, the important role of additive manufacturing technology on the weight reduction of parts is not negligible. More notably, the additive manufacturing technology can realize the integrated manufacturing of the components, and the overall forming of the aerospace engine components can reduce the assembly and connection structural relation among the existing parts, thereby achieving the purpose of reducing weight. The selective laser melting technology is one of additive manufacturing technologies, and because powder undergoes a complete melting/solidification process in the forming process, the forming precision is very high, the direct precise and clean forming without a die, fast and full-compact of small and medium-sized components can be realized, the selective laser melting technology is particularly suitable for parts with complex structures, the component performance can reach the level of forgings with the same components, the requirements of precise forming and high-performance forming are met, and the selective laser melting technology is particularly suitable for the development requirement of integration of 'material-design-manufacturing' of aerospace complex components.
At present, the aluminum alloy material commonly used for the aerospace engine is 2024, and has the advantages of light density, high specific stiffness, high specific strength and the like, but the aluminum alloy material has high thermal conductivity and thermal expansion coefficient, and the problem of low powder surface absorbance in the selective laser melting forming process becomes a main technical bottleneck restricting the engineering application of the 2024 aluminum alloy material. The selective laser melting technology mainly comprises the steps that metal powder to be processed absorbs laser energy and converts the energy into heat energy for melting and forming; therefore, the efficiency of absorption of laser energy by the material plays an important role in the process. Due to the limitation of self performance, laser generates strong reflection on the surface of 2024Al alloy powder to take away most energy (standing wave nodes can be formed by the electric field of the laser near the surface of the metal powder, free electrons generate secondary waves after being forced to vibrate by an optical wave electromagnetic field, and the secondary waves cause strong reflected waves to finally cause energy loss); the phenomenon is particularly obvious for long-wave band laser (under the long-wave band, the photon energy is lower, the photon energy mainly acts on free electrons in metal, almost totally reflects and only absorbs a small amount). Therefore, when the metal powder is sintered by laser, a large amount of laser energy is required, but this causes an excessive heat input to the substrate, which causes severe influences such as a large deformation of the molded part, coarse grains, and a deteriorated structure, and seriously affects various properties of the printed part. Therefore, the absorption rate of the printing powder to laser is improved, and the problem which needs to be solved urgently in the field of 3D printing is solved.
In order to enhance the laser absorption efficiency of the metal surface, it is a common practice to coat a layer of coating with high resistivity and less free electrons on the surface of the metal material. However, the application of the method to the field of metal powder has new problems: the coating material is easy to introduce impurities and change the original components of the metal matrix, and the surface of the micron powder is coated with the coating material which is difficult to realize smooth surface and uniform thickness.
With the development of additive manufacturing technology, the selective laser melting technology of melting and molding metal powder layer by layer into metal parts by using laser has gained wide attention of domestic and foreign scholars. Therefore, it is an urgent need to develop a new method for increasing the laser energy absorption rate of metal powder. In recent years, the rapid development of the nano composite material technology provides possibility for the melting and forming of 2024 aluminum alloy in a laser selection area, replaces the traditional 2024 aluminum alloy brazing process, and provides technical support for the national defense strategic fields of space engines, national defense, war industry, weapons and missiles.
Therefore, in order to overcome the problem that the absorptivity of 2024 aluminum alloy micron powder to laser is not high in the prior art, and further causes a plurality of limitations in the application process of the selective laser melting technology, technical personnel in the field are dedicated to developing a preparation method of aluminum alloy powder and a method for in-situ synthesizing carbon nano tubes, which can not only improve the absorption efficiency of the aluminum alloy powder to laser energy by utilizing the strong light absorption property and the surface effect of the carbon tubes, but also enhance the aluminum alloy matrix by the strengthening effect of the carbon nano tubes, and can retain the sphericity of the powder to the maximum extent so as to meet the requirement of 3D printing.
Disclosure of Invention
In view of the above-mentioned defects in the prior art, the technical problem to be solved by the present invention is to provide a method for in-situ synthesizing carbon nanotubes on the surface of aluminum alloy spherical powder, which not only can improve the absorption efficiency of the aluminum alloy powder to laser energy by using the strong light-absorbing member and the surface effect of the carbon tubes, but also can enhance the aluminum alloy matrix by the reinforcing effect of the carbon nanotubes, and can maximally retain the sphericity of the powder to meet the requirement of 3D printing.
In order to achieve the above object, the present invention provides a method for in-situ synthesis of carbon nanotubes on the surface of an aluminum alloy spherical powder, the method comprising the steps of:
s100, preparing a Ni/2024Al catalyst;
s200, calcining the Ni/2024Al catalyst in a mixed gas atmosphere to obtain CNTs/2024Al-Ni composite powder.
The invention also provides a preparation method of the Ni/2024Al catalyst, which comprises the following steps:
s100, weighing 2024Al alloy powder and nickel nitrate hexahydrate, mixing in absolute ethyl alcohol, and performing ultrasonic dispersion uniformly;
s200, continuously stirring the mixture dispersed in the step S101 at 50 ℃ by using a magnetic stirrer until the absolute ethyl alcohol is completely volatilized to obtain powder;
s300, placing the powder obtained in the step S200 in a quartz boat, and calcining under the protection of protective gas atmosphere to obtain NiO/2024Al composite powder;
and S400, reducing the NiO/2024Al composite powder obtained in the S300 to obtain the Ni/2024Al catalyst.
Compared with the prior art, the invention has the technical advantages that:
the method for in-situ synthesizing the carbon nano tube on the surface of the aluminum alloy spherical powder improves the absorption efficiency of the aluminum alloy powder to laser energy by utilizing the strong light absorption property and the nano-scale surface effect of the carbon tube, reduces energy loss, avoids the adverse effect of high input energy on the microstructure of a sample, overcomes the adverse effect of low light absorption rate of metal powder on the application of a 3D printing technology, simultaneously preserves the sphericity of original powder to the maximum extent and meets the requirement of 3D printing.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a flow chart of a method for in-situ synthesis of carbon nanotubes on the surface of an aluminum alloy spherical powder according to a preferred embodiment of the present invention;
FIGS. 2(a) to 2(b) are SEM and TEM photographs of a CNTs/2024Al-Ni composite powder with a nickel content of 1.0 wt% prepared according to a preferred embodiment of the present invention, wherein FIG. 2(a) is the SEM photograph of the CNTs/2024Al-Ni composite powder with a nickel content of 1.0 wt%; FIG. 2(b) is a TEM photograph of the prepared CNTs/2024Al-Ni composite powder containing 1.0 wt.% Ni;
FIGS. 3(a) to 3(b) are SEM and TEM photographs of CNTs/2024Al-Ni composite powder with a nickel content of 2.5 wt.% prepared according to a preferred embodiment of the present invention; wherein, FIG. 3(a) is SEM photograph of the prepared CNTs/2024Al-Ni composite powder containing 1.0 wt.% of Ni; FIG. 3(b) is a TEM photograph of the prepared CNTs/2024Al-Ni composite powder containing 1.0 wt.% Ni;
FIG. 4 is a graph comparing absorbance of CNTs/2024Al-Ni composite powder prepared in example 1 and example 2 of the present invention with pure 2024 Al;
FIG. 5 is a graph showing the variation of the yield of CNTs and the nickel content according to a preferred embodiment of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to fig. 1 to 5 of the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
As shown in fig. 1, a flow chart of a method for in-situ synthesizing carbon nanotubes on the surface of aluminum alloy spherical powder according to a preferred embodiment of the present invention includes the following steps:
s100, preparing a Ni/2024Al catalyst;
s200, calcining the Ni/2024Al catalyst in a mixed gas atmosphere to obtain CNTs/2024Al-Ni composite powder.
The method for in-situ synthesizing the carbon nano tube on the surface of the aluminum alloy spherical powder improves the absorption efficiency of the aluminum alloy powder to laser energy by utilizing the strong light absorption property and the nano-scale surface effect of the carbon tube, reduces energy loss, avoids the adverse effect of high input energy on the microstructure of a sample, overcomes the adverse effect of low light absorption rate of metal powder on the application of a 3D printing technology, simultaneously preserves the sphericity of original powder to the maximum extent and meets the requirement of 3D printing.
In a preferred embodiment, the step S100 further includes:
s101, weighing 2024Al alloy powder and nickel nitrate hexahydrate, mixing in absolute ethyl alcohol to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30-40mins to fully disperse the mixture;
s102, continuously stirring the mixture dispersed in the step S101 at 50 ℃ by using a magnetic stirrer until the absolute ethyl alcohol is completely volatilized to obtain powder;
s103, placing the powder in a quartz boat in Ar/N2Calcining for 4-5h at the temperature of 200-250 ℃ under protection to obtain NiO/2024Al composite powder;
s104, reducing the NiO/2024Al composite powder for 2.0-2.5h at the temperature of 450-500 ℃ in a hydrogen atmosphere to obtain the Ni/2024Al catalyst.
In a preferred embodiment, step S200 further includes:
s201, adding the Ni/2024Al catalyst obtained in the step S100 in H2/Ar/CH4Reacting for 1-1.5h at the temperature of 650-700 ℃ under the atmosphere of mixed gas to obtain a sample;
s202, adding the sample obtained in the step S201 to N2And cooling to room temperature under the protection of/Ar, and taking out to obtain the CNTs/2024Al-Ni composite powder.
In a preferred embodiment, the mass of the 2024Al aluminum alloy powder is 18-20g, the mass of the nickel nitrate hexahydrate is 2.0-2.5g, and the time of ultrasonic dispersion is 30-40 mins.
In a preferred embodiment, H2Is 120-140sccm, Ar is 60-70sccm, CH4460 and 480 sccm.
The technical solution of the present invention is further explained with reference to the drawings and the embodiments.
Example 1
1. Weighing 18g of 2024Al alloy powder and 2.0g of nickel nitrate hexahydrate (the Ni content is 1.0 wt.%), placing in 200mL of absolute ethyl alcohol, keeping the temperature at 50 ℃ under continuous magnetic stirring until the absolute ethyl alcohol is completely volatilized, placing the obtained powder in a quartz boat, and calcining for 5 hours at 200 ℃ under the protection of nitrogen atmosphere to obtain NiO/2024Al composite powder;
2. switching the gas path to H2Heating to 450 ℃ to reduce NiO/2024Al composite powder for 2h, and reducing NiO into Ni particles to obtain catalyst Ni/2024Al composite powder;
3. gas path is switched to H2/Ar/CH4The mixed gas is heated to 650 ℃ for reaction for 1.5H at the ratio of 120sccm/60sccm/460sccm, and the gas path is switched to H2In H2Cooling to room temperature under protection to obtain CNTs/2024Al-Ni composite powder with high light absorption rate and nickel content of 1.0 wt%.
FIGS. 2(a) to 2(b) are SEM and TEM photographs of the CNTs/2024Al-Ni composite powder prepared in example 1 of the present invention and containing 1.0 wt.% nickel, wherein it can be seen from FIG. 2(a) that the prepared CNTs/2024Al-Ni composite powder maintains its original sphericity to the maximum extent, therefore, the preparation method of the present invention does not destroy the original shape of the powder, and the CNTs/2024Al-Ni composite powder satisfies the requirements of 3D printing on metal powder; as can be seen from FIG. 2(b), the CNTs/2024Al-Ni composite powder prepared in the embodiment 1 has a complete structure and uniform distribution, and can exert a good strengthening effect on a matrix.
Example 2
1. Weighing 20g of 2024Al alloy powder and 2.5g of nickel nitrate hexahydrate (Ni content is 2.5 wt.%), placing in 200mL of absolute ethyl alcohol, keeping the temperature at 50 ℃ under continuous magnetic stirring until the absolute ethyl alcohol is completely volatilized, placing the obtained powder in a quartz boat, and placing in a nitrogen atmosphere2Calcining for 4h at 250 ℃ under the protection of the catalyst to obtain NiO/2024Al composite powder;
2. switching the gas path to H2Heating to 500 ℃ and reducing for 2.5h to reduce NiO into Ni particles to obtain the catalyst Ni/2024Al composite powder;
3. gas path is switched to H2/CH4/N2Mixed gas in the proportion of140sccm/70sccm/480sccm, heating to 700 ℃ for 1H, and switching the gas path to H2In H2Cooling to room temperature under protection to obtain CNTs/2024Al-Ni composite powder with high light absorption rate and nickel content of 2.5 wt%.
FIGS. 3(a) to 3(b) are SEM and TEM photographs of CNTs/2024Al-Ni aluminum alloy powder with 1.0 wt.% Ni prepared in example 2 of the present invention, wherein it can be seen from FIG. 3(a) that the prepared CNTs/2024Al-Ni composite powder maintains its original sphericity to the maximum extent, therefore, the preparation method of the present invention does not destroy the original shape of the powder, and the CNTs/2024Al-Ni composite powder satisfies the requirements of 3D printing on metal powder; as can be seen from fig. 3(b), the nanotubes prepared in this example 1 have a complete structure and uniform distribution, and can exert a good strengthening effect on the substrate.
Fig. 4 is a comparison graph of absorbance of CNTs/2024Al-Ni aluminum alloy powder prepared in example 1 and example 2 of the present invention and pure 2024Al, and a test of absorbance of laser light in the wavelength band of 800-.
FIG. 5 is a graph showing the variation of the yield of CNTs according to the preferred embodiment of the present invention and the nickel content, from which it can be seen that the yield of CNTs increases when the nickel content increases from 0.25% to 2%, and that the yield of CNTs reaches the highest value when the nickel content is 2%; as the nickel content continues to increase from 2% to 10%, the CNTs yield decreases. Therefore, we conclude from FIG. 5 that CNTs can be obtained in different yields by adjusting the nickel content. And personalized adjustment is carried out according to the printing requirements under different conditions.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. The method for in-situ synthesizing the carbon nano tube on the surface of the aluminum alloy spherical powder comprises the following steps:
s100, preparing a Ni/2024Al catalyst;
s200, calcining the Ni/2024Al catalyst in a mixed gas atmosphere to obtain CNTs/2024Al-Ni composite powder.
2. The method of claim 1, wherein, preferably, the step S100 further comprises:
s101, weighing 2024Al alloy powder and nickel nitrate hexahydrate, mixing in absolute ethyl alcohol to obtain a mixture, and carrying out ultrasonic treatment on the mixture for 30-40mins to fully disperse the mixture;
s102, continuously stirring the mixture dispersed in the step S101 at 50 ℃ by using a magnetic stirrer until the absolute ethyl alcohol is completely volatilized to obtain powder;
s103, placing the powder in a quartz boat, and calcining for 4-5h at the temperature of 200-250 ℃ under the protection of Ar/N2 to obtain NiO/2024Al composite powder;
s104 at H2Reducing the NiO/2024Al composite powder for 2.0-2.5h at the temperature of 450-500 ℃ in the atmosphere to obtain the Ni/2024Al catalyst.
3. The method of claim 1, wherein the step S200 further comprises:
s201, adding Ni/2024Al catalyst in H2/Ar/CH4Reacting for 1-1.5h at the temperature of 650-700 ℃ under the atmosphere of mixed gas to obtain a sample;
s202, subjecting the sample obtained in the step S201 to Ar/H2And cooling to room temperature under protection, and taking out to obtain the CNTs/2024Al-Ni composite powder.
4. As in claimThe method of claim 3, wherein H in the step S2012120-140sccm, Ar 50-70sccm, CH4460 and 480 sccm.
5. A method of making a Ni/2024Al catalyst, the method comprising:
s100, weighing 2024Al alloy powder and nickel nitrate hexahydrate, mixing in absolute ethyl alcohol, and performing ultrasonic dispersion uniformly;
s200, continuously stirring the mixture dispersed in the step S101 at 50 ℃ by using a magnetic stirrer until the absolute ethyl alcohol is completely volatilized to obtain powder;
s300, placing the powder obtained in the step S200 in a quartz boat, and calcining under the protection of protective gas atmosphere to obtain NiO/2024Al composite powder;
and S400, reducing the NiO/2024Al composite powder obtained in the S300 to obtain the Ni/2024Al catalyst.
6. The preparation method of claim 5, wherein the 2024Al aluminum alloy powder in S100 is 18-20g in mass, the nickel nitrate hexahydrate is 2.0-2.5g in mass, and the ultrasonic dispersion time is 30-40 mins.
7. The method according to claim 5, wherein the protective gas in S300 is N2Ar or a mixed gas thereof.
8. The preparation method according to claim 5, wherein the calcination temperature in S300 is 200-250 ℃ and the calcination time is 4-5 h.
9. The method according to claim 5, wherein the reducing gas in S400 is H2The reduction temperature is 450-500 ℃, and the reduction reaction time is 2.0-2.5 h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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