CN115958196A - Additive manufacturing method based on copper or copper alloy powder and copper or copper alloy profile - Google Patents
Additive manufacturing method based on copper or copper alloy powder and copper or copper alloy profile Download PDFInfo
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- CN115958196A CN115958196A CN202211503727.2A CN202211503727A CN115958196A CN 115958196 A CN115958196 A CN 115958196A CN 202211503727 A CN202211503727 A CN 202211503727A CN 115958196 A CN115958196 A CN 115958196A
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Abstract
The invention provides an additive manufacturing method based on copper or copper alloy powder, and a copper or copper alloy profile, wherein the method comprises the following steps: coating graphene on the surface of copper or copper alloy powder by using copper or copper alloy powder as a raw material and utilizing a graphene chemical vapor deposition in-situ growth technology to obtain graphene modified copper or copper alloy powder; carrying out high-energy beam additive manufacturing on graphene modified copper or copper alloy powder serving as raw material powder to prepare a copper or copper alloy profile; wherein, the high-energy beam is infrared laser with power of 1500-3000W. The additive manufacturing method comprises the steps of firstly carrying out surface modification on copper or copper alloy powder to improve the energy absorption rate of the copper or copper alloy powder, and then carrying out high-energy beam additive manufacturing on the modified copper or copper alloy powder to finally obtain the copper or copper alloy section.
Description
Technical Field
The invention relates to the technical field of metal composite materials, in particular to an additive manufacturing method based on copper or copper alloy powder and a copper or copper alloy profile.
Background
Pure copper and copper alloy have the characteristics of good thermal conductivity, electrical conductivity, corrosion resistance, plasticity and the like, and are widely applied to various industrial fields such as aerospace, electronic information, power transmission and the like, but the requirements of application ends on parts with complex structures are increased, and the requirements cannot be met by the traditional processing technology. Compared with the traditional processing method, the additive manufacturing technology can realize one-time forming of parts with complex structures, the material utilization rate is high, and die processing is not needed. Therefore, the technology has great application potential in the aspect of preparing copper-based radiators with complex function integration, heat exchangers, tail nozzles, motor windings and other parts.
At present, the additive manufacturing technology widely applied to the market is a laser 3D printing technology, the forming process based on materials such as nickel-based alloy, iron-based alloy and titanium-based alloy is relatively mature, and the performance of a printed formed part can reach or even be superior to the level of a forged piece. However, the ultra-high reflectivity of copper to infrared laser makes the absorption rate of copper to laser lower than 3%, which not only affects the endothermic melting of powder, but also causes a great deal of resource waste. Meanwhile, the ultrahigh heat-conducting property of copper makes it difficult to form an effective molten pool, and the forming property of the copper is seriously influenced.
Therefore, the additive manufacturing technology for copper or copper alloy powder is still in the research and development stage, and has a bottleneck problem which is difficult to break through, and the development and application of the additive manufacturing technology are severely limited.
Disclosure of Invention
In view of the problems in the prior art, a primary object of the present invention is to provide an additive manufacturing method based on copper or copper alloy powder, and a copper or copper alloy profile, in which the additive manufacturing method first performs surface modification on the copper or copper alloy powder to improve the energy absorption rate of the copper or copper alloy powder, and then performs high energy beam additive manufacturing on the modified copper or copper alloy powder to obtain the copper or copper alloy profile.
In order to achieve the above object, according to a first aspect of the present invention, a method of additive manufacturing based on copper or copper alloy powder is provided.
The additive manufacturing method based on copper or copper alloy powder comprises the following steps:
coating graphene on the surface of copper or copper alloy powder by using copper or copper alloy powder as a raw material and utilizing a graphene chemical vapor deposition in-situ growth technology to obtain graphene modified copper or copper alloy powder;
carrying out high-energy beam additive manufacturing by using graphene modified copper or copper alloy powder as raw material powder to prepare a copper or copper alloy section; wherein the high-energy beam is infrared laser, and the power of the infrared laser is 1500-3000W.
Further, the graphene chemical vapor deposition in-situ growth technology is that copper or copper alloy powder in a reaction chamber is vaporized into steam by using a plasma beam, and then the temperature in the reaction chamber is controlled to convert the steam into a molten liquid drop state, so that in-situ coating growth of graphene on the surface of the graphene is completed;
preferably, the temperature in the reaction chamber is controlled in a gradient way, and is controlled to be 6000-11000 ℃, 2000-6000 ℃, 200-2000 ℃ and 20-200 ℃ in sequence.
Further, the reaction chamber is filled with a protective gas and a carbon source gas, wherein: the carbon source gas is gaseous hydrocarbon, and the flow rate is 0.1 to 1slpm; the protective gas is argon, and the flow rate is 10 to 40slpm.
Furthermore, the number of the graphene layers coated on the surface of the copper or copper alloy powder is 1-5.
Further, the power of the infrared laser is 2400W.
Further, before the additive manufacturing, the method further comprises: screening the graphene modified copper or copper alloy powder, and selecting the graphene modified copper or copper alloy powder with different particle sizes to mix so as to form the raw material powder for additive manufacturing;
preferably, the particle size of the raw material powder is 15 to 50 μm.
Preferably, the particle size of the copper or copper alloy powder is 20 to 80 μm.
Further, the additive manufacturing process flow comprises:
taking a copper plate as a substrate, and carrying out sand blasting and surface cleaning treatment on the copper plate;
placing the processed substrate in a printing cabin, and preheating the substrate under a protective atmosphere;
and introducing high-energy beam flow into the printing cabin, and starting the powder feeder to perform additive manufacturing.
Furthermore, in the additive manufacturing process, the laser scanning speed is 100-600 mm/min, preferably 120mm/min; the laser scanning interval is 0.5-2 mm, preferably 1.2mm; the laser scanning layer has a thickness of 0.2 to 1mm, preferably 0.5mm.
Furthermore, the powder feeding speed is 0.1-1 r/min, preferably 0.5r/min;
the thickness of the substrate is 2-8 mm, preferably 5mm;
the oxygen content in the printing cabin is less than or equal to 200ppm;
the preheating temperature of the substrate is 100-600 ℃, and is preferably 400 ℃.
In order to achieve the above object, according to a second aspect of the present invention, there is provided a copper or copper alloy profile.
The copper or copper alloy section is obtained by adopting the additive manufacturing method based on the copper or copper alloy powder.
The obtained copper or copper alloy section bar has good quality and high precision, and the mechanical, electric, heat-conducting and wear-resisting properties of the section bar can be improved to a certain extent due to the doping of the graphene.
The invention provides a method for realizing complete coating of graphene on the surface of copper or copper alloy powder by a chemical vapor deposition method, and the method reduces the reflectivity of the powder to laser by surface modification and promotes the absorption of energy; meanwhile, high-energy beam flows such as laser beams, electron beams, ion beams and the like are adopted to realize additive manufacturing of copper or copper alloy powder.
The method has the advantages of short process flow, high efficiency, high molding quality and wide application prospect.
Compared with the prior art, the invention has the following beneficial effects:
1. by the plasma enhanced chemical vapor deposition technology, the complete coating of high-quality graphene on the surface of copper or copper alloy can be realized, the sphericity of copper or copper alloy powder can be improved, and the flowability of the powder is greatly improved. The sphericity of the graphene modified copper or copper alloy powder is higher than 99%.
2. The physical property of the copper or copper alloy powder is modified by the coating of the graphene, an effective molten pool can be quickly formed under high-energy beam flows such as laser beams, ion beams, electron beams and the like due to the great reduction of the reflectivity, and the range of a heat affected zone is reduced, so that the one-step molding of high-quality complex parts is realized. The laser absorption rate of the graphene modified copper or copper alloy powder is higher than 60%, and the laser absorption rate of the pure copper powder is only 3% -5%.
3. The doping of the graphene improves the mechanical property, the heat conduction property, the electric conduction property and the wear resistance of the formed part to a certain degree. The pure copper section finally obtained in the present invention had a tensile strength of 250MPa, a thermal conductivity of 410W/m.k, an electric conductivity of 104.3 IACS, and a friction coefficient of 0.2.
Drawings
Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:
FIG. 1a is an SEM image of pure copper powder in an example provided by the present invention;
fig. 1b is an SEM picture of graphene-modified copper powder in an embodiment provided by the present invention;
fig. 2 is an appearance and a raman spectrum of graphene-modified copper powder in an embodiment of the present invention; wherein a, b and c are appearance morphology graphs of the graphene modified copper powder; d is a Raman spectrogram of the graphene modified copper powder;
fig. 3 is a picture of a pure copper profile prepared in an example provided by the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art.
The method is based on the graphene chemical vapor deposition in-situ growth technology on the surface of copper or copper alloy, realizes the complete coating of high-quality graphene on the surface of copper or copper alloy, modifies the physical properties of copper or copper alloy powder, greatly promotes the absorption of the copper or copper alloy powder on energy, quickly forms an effective molten pool under high-energy beam flow, and reduces the range of a heat affected zone, thereby ensuring the smooth performance of the additive manufacturing process and simultaneously improving the surface precision of a formed part.
The additive manufacturing method based on copper or copper alloy powder comprises the following specific steps:
(1) Completely coating graphene on the surface of copper or copper alloy powder by using copper or copper alloy powder as a raw material and utilizing a graphene chemical vapor deposition in-situ growth technology to obtain graphene modified copper or copper alloy powder.
In the step, the graphene chemical vapor deposition in-situ growth technology is that copper or copper alloy powder in a reaction chamber is vaporized into steam by using a plasma beam, and then the temperature in the reaction chamber is controlled to convert the steam into a molten liquid drop state, so that the in-situ coating growth of graphene on the surface of the graphene is completed; wherein the temperature in the reaction chamber is controlled in a gradient way, and is controlled to be 6000-11000 ℃, 2000-6000 ℃, 200-2000 ℃ and 20-200 ℃ in sequence; the reaction chamber is filled with protective gas and carbon source gas, the carbon source gas is gaseous hydrocarbon, and the flow rate is 0.1 to 1slpm; the protective gas is argon, and the flow rate is 10-40 slpm.
The number of the graphene layers coated on the surface of the copper or copper alloy powder can be 1-5, and the graphene layers are selected according to actual needs and are not particularly limited.
The particle size of the copper or copper alloy powder is in the range of 20-80 μm, and the application is wide.
(2) Screening graphene modified copper or copper alloy powder, and selecting graphene modified copper or copper alloy powder with different particle sizes to mix in proportion so as to improve the apparent density of the graphene modified copper or copper alloy powder; and then placing the mixed powder into a powder feeder to be used as raw material powder for additive manufacturing.
In the present invention, the raw material powder used for additive manufacturing is a mixed powder of graphene-modified copper or copper alloy powder having a particle size of 15 to 50 μm after screening.
(3) The copper plate is used as a substrate for additive manufacturing, and sand blasting is carried out on the copper plate to reduce the surface light reflection performance of the copper plate; then the surface of the glass is cleaned by alcohol so as to remove oil stains, water stains and the like on the surface of the glass.
Wherein the thickness of the substrate is 2 to 8mm, preferably 5mm.
(4) And (3) placing the processed substrate in a printing cabin, filling argon gas into the printing cabin to reduce the oxygen content in the printing cabin, and then preheating the substrate at the preheating temperature of 100-600 ℃, preferably 400 ℃.
In the step, the oxygen content in the printing chamber is less than or equal to 200ppm.
(5) Introducing high-energy beam flow into the printing cabin, starting the powder feeder to feed powder at the powder feeding speed of 0.1-1 r/min, and selecting parameters such as the powder feeding speed, the high-energy beam flow power, the scanning speed, the scanning interval and the like to perform additive manufacturing on the copper or copper alloy powder.
Wherein, the high-energy beam is infrared laser, and the power of the infrared laser is 1500-3000W; the laser scanning speed is 100-600 mm/min, the laser scanning interval is 0.5-2 mm, and the laser scanning layer thickness is 0.2-1 mm.
In a preferred embodiment of the present invention, the power of the infrared laser is 2400W.
In a preferred embodiment of the present invention, the laser scanning speed is 120mm/min.
As a preferred embodiment of the present invention, the laser scanning pitch is 1.2mm.
In a preferred embodiment of the present invention, the laser scanning layer has a thickness of 0.5mm.
In a preferred embodiment of the present invention, the powder feeding speed is 0.5r/min.
(6) And after printing is finished, obtaining a copper or copper alloy molded part, taking out the molded part after the molded part is cooled, and recovering the residual powder.
The additive manufacturing method based on copper or copper alloy powder in the present invention will be described in detail below by specific examples.
Example 1:
3D printing additive manufacturing method of graphene modified copper powder
(1) Selecting copper powder with the purity of 99.9% and the granularity of 20-80 microns as a raw material, and completely coating 1-5 layers of graphene on the surface of the copper powder by using a plasma enhanced chemical vapor in-situ growth technology as shown in figure 1a to obtain graphene modified copper powder as shown in figure 1 b. Wherein, the flow rate of methane in the reaction chamber in the plasma enhanced chemical vapor in-situ growth technology is 0.5slpm, the flow rate of argon is 30slpm, and the gradient temperature control is controlled at 6000-11000 ℃, 2000-6000 ℃, 200-2000 ℃ and 20-200 ℃ in sequence.
Fig. 2a, 2b, and 2c are all appearance and appearance diagrams of the obtained graphene modified copper powder, and fig. 2d is a raman spectrogram of the graphene modified copper powder, from which it can also be seen that graphene completely covers the surface of the copper powder, and the surface of the copper powder can cover single-layer or multi-layer graphene.
(2) And (3) loading the graphene modified copper powder with the particle size of 15-50 mu m after screening into a powder feeder to be used as raw material powder for additive manufacturing.
(3) Carrying out sand blasting on the surface of a copper substrate with the thickness of 5mm to reduce the surface reflectivity of the copper substrate; then the surface of the glass is cleaned by alcohol so as to remove oil stains, water stains and the like on the surface of the glass.
(4) The printing chamber was filled with argon gas to an oxygen content of less than 200ppm, and the copper substrate was preheated to 400 ℃.
(5) And introducing infrared laser into the printing cabin, starting the powder feeder to feed powder at the powder feeding speed of 0.5r/min, and printing. Wherein the infrared laser power is 2400W, the laser scanning speed is 120mm/min, the laser scanning interval is 1.2mm, and the laser scanning layer thickness is 0.5mm.
(6) And after printing is finished, taking out the formed part after the formed part is cooled, and recovering the residual powder.
As a result of examination, as shown in FIG. 3, the pure copper section finally obtained in example 1 had a tensile strength of 250MPa, a thermal conductivity of 410W/m.k, an electric conductivity of 104.3% IACS, and a friction coefficient of 0.2.
Example 2:
3D printing additive manufacturing method of graphene modified copper-chromium alloy powder
(1) Selecting copper-chromium alloy powder with the purity of 90% and the granularity of 30-80 microns as a raw material, and completely coating 1-5 layers of graphene on the surface of the copper-chromium alloy powder by using a plasma enhanced chemical vapor in-situ growth technology to obtain graphene modified copper-chromium alloy powder. Wherein the flow rate of methane in the reaction chamber is 0.4slpm, the flow rate of argon is 20slpm, and the gradient temperature control is sequentially controlled at 6000-11000 ℃, 2000-6000 ℃, 200-2000 ℃ and 20-200 ℃.
(2) And (3) loading the graphene modified copper-chromium alloy powder with the particle size of 15-50 mu m after screening into a powder feeder to be used as raw material powder for additive manufacturing.
(3) Carrying out sand blasting on the surface of a copper substrate with the thickness of 5mm to reduce the surface light reflection; then the surface of the glass is cleaned by alcohol so as to remove oil stains, water stains and the like on the surface of the glass.
(4) The printing chamber was filled with argon gas to an oxygen content of less than 200ppm, and the copper substrate was preheated to 400 ℃.
(5) And introducing infrared laser into the printing cabin, starting the powder feeder to feed powder at the powder feeding speed of 0.6r/min, and printing. Wherein the infrared laser power is 2500W, the laser scanning speed is 150mm/min, the laser scanning interval is 1.2mm, and the laser scanning layer thickness is 0.5mm.
(6) And after printing is finished, taking out the formed part after the formed part is cooled, and recovering the residual powder.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (10)
1. A method of additive manufacturing based on copper or copper alloy powder, comprising the steps of:
coating graphene on the surface of copper or copper alloy powder by using copper or copper alloy powder as a raw material and utilizing a graphene chemical vapor deposition in-situ growth technology to obtain graphene modified copper or copper alloy powder;
carrying out high-energy beam additive manufacturing by using graphene modified copper or copper alloy powder as raw material powder to prepare a copper or copper alloy section; the high-energy beam is infrared laser, and the power of the infrared laser is 1500-3000W.
2. The additive manufacturing method based on copper or copper alloy powder according to claim 1, wherein the graphene chemical vapor deposition in-situ growth technique is to vaporize the copper or copper alloy powder in the reaction chamber into steam by using a plasma beam, and then control the temperature in the reaction chamber to convert the steam into a molten liquid droplet state, so as to complete in-situ cladding growth of graphene on the surface of the graphene;
preferably, the temperature in the reaction chamber is controlled in a gradient way, and is controlled to be 6000-11000 ℃, 2000-6000 ℃, 200-2000 ℃ and 20-200 ℃ in sequence.
3. The additive manufacturing method based on copper or copper alloy powder according to claim 2, wherein the reaction chamber is filled with a protective gas and a carbon source gas, wherein: the carbon source gas is gaseous hydrocarbon, and the flow rate is 0.1 to 1slpm; the protective gas is argon, and the flow rate is 10-40 slpm.
4. The additive manufacturing method based on copper or copper alloy powder according to claim 1, wherein the number of graphene layers coated on the surface of the copper or copper alloy powder is 1 to 5.
5. The copper or copper alloy powder based additive manufacturing method according to claim 1, wherein the power of the infrared laser is 2400W.
6. The method of additive manufacturing based on copper or copper alloy powder according to claim 1, further comprising, prior to performing additive manufacturing: screening the graphene modified copper or copper alloy powder, and selecting the graphene modified copper or copper alloy powder with different particle sizes to mix so as to form the raw material powder for additive manufacturing;
preferably, the particle size of the raw material powder is 15 to 50 μm.
7. The copper or copper alloy powder based additive manufacturing method according to claim 1, wherein the additive manufacturing process flow is:
taking a copper plate as a substrate, and carrying out sand blasting and surface cleaning treatment on the copper plate;
placing the processed substrate in a printing cabin, and preheating the substrate under a protective atmosphere;
and introducing the high-energy beam flow into the printing cabin, and starting a powder feeder to perform additive manufacturing.
8. The additive manufacturing method based on copper or copper alloy powder according to claim 7, wherein the laser scanning speed during additive manufacturing is 100-600 mm/min, preferably 120mm/min; the laser scanning interval is 0.5-2 mm, preferably 1.2mm; the laser scanning layer has a thickness of 0.2 to 1mm, preferably 0.5mm.
9. The additive manufacturing method based on copper or copper alloy powder according to claim 6, wherein the powder feeding speed is 0.1-1 r/min, preferably 0.5r/min;
the thickness of the substrate is 2-8 mm, preferably 5mm;
the oxygen content in the printing cabin is less than or equal to 200ppm;
the preheating temperature of the substrate is 100-600 ℃, and is preferably 400 ℃.
10. Copper or copper alloy profile produced by the additive manufacturing method based on copper or copper alloy powder according to any one of claims 1 to 9.
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| CN202211503727.2A CN115958196A (en) | 2022-11-29 | 2022-11-29 | Additive manufacturing method based on copper or copper alloy powder and copper or copper alloy profile |
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| CN202211503727.2A CN115958196A (en) | 2022-11-29 | 2022-11-29 | Additive manufacturing method based on copper or copper alloy powder and copper or copper alloy profile |
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