CN111168057B - Nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing and preparation method and application thereof - Google Patents
Nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing and preparation method and application thereof Download PDFInfo
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0068—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only nitrides
Abstract
The invention discloses nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing and a preparation method and application thereof, and belongs to the technical field of metal additive manufacturing. The preparation method of the nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing comprises the following steps: powder mixing, powder plasma spheroidizing, redundant nano ceramic particles removal, powder size grading and mixing. The invention takes high-entropy alloy as matrix powder and nano ceramic particles as reinforcing phase particles, obtains the high-entropy alloy powder with the nano ceramic particles uniformly adhered on the surface by adopting a mode of ultrasonic dispersion and mechanical stirring, and prepares the spherical nano ceramic particle reinforced high-entropy alloy composite powder by a radio frequency plasma spheroidization technology. The preparation method of the nano-ceramic reinforced high-entropy alloy composite powder is simple in process, and the prepared powder is excellent in performance and suitable for batch production.
Description
Technical Field
The invention belongs to the technical field of metal additive manufacturing, and particularly relates to nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing, and a preparation method and application thereof.
Background
High-entropy alloys (HEAs) generally refer to a completely new multi-element alloy system composed of 4 to 13 main elements in equal or nearly equal atomic ratios and having a simple solid solution structure. Compared with the traditional alloy, the high-entropy alloy has the advantages of high entropy effect, slow diffusion effect, serious lattice distortion effect and cocktail effect, and the characteristics enable the high-entropy alloy to have excellent performance and huge potential application value in the aspects of hardness, compressive strength, thermal stability, corrosion resistance, magnetic performance, oxidation resistance and the like.
Additive Manufacturing (AM) is a technology of forming a three-dimensional solid by accumulating and superimposing materials point by point layer by layer through a discrete-accumulation principle. Compared with the traditional material reducing manufacturing technology such as machining, the technology has the advantages of high design freedom, one-step forming of complex parts, reduction of material waste and the like, and is known as a key technology for leading 'third industrial revolution'. The metal additive manufacturing technology is the most potential advanced manufacturing technology in the field of 3D printing, is widely applied in the fields of aerospace, medical instruments, military industry, automobile manufacturing and the like, and is rapidly developed. At present, the metal additive manufacturing technology mainly comprises 3 types: laser Melt Deposition (LMD), Selective Laser melt metal 3D printing (SLM), and Electron Beam Selective Electron Beam (SEBM). The metal additive manufacturing technology is used for preparing the high-entropy alloy, so that the processing procedure can be simplified and shortened, a three-dimensional complex structure can be formed at one time, the loss of raw materials is saved, and the like; meanwhile, due to the fact that the printing process is accompanied by rapid quenching, the forming probability of a second phase can be reduced, atomic diffusion is limited, and the formation of brittle intermetallic compounds is inhibited. Therefore, in recent years, the additive manufacturing of the high-entropy alloy becomes a research hotspot of domestic and foreign scientists and engineers.
In order to further improve the mechanical properties and microstructure of the high-entropy alloy manufactured by additive manufacturing, researchers try to introduce nano ceramic particles (such as TiN, TiC and Al)2O3And the like) is strengthened, and the result shows that the addition of the nano ceramic particles can improve the printing formability and the mechanical property of the product. At present, the nano ceramic reinforced high-entropy alloy spherical powder is mainly prepared by a mechanical (high-energy) ball milling method, but the powder prepared by the method has the problems of uneven dispersion of nano ceramic particles on the surface of the high-entropy alloy, poor powder sphericity and the like, directly influences the powder fluidity and the product forming performance, and is difficult to meet the requirements (such as high sphericity, narrow particle size distribution, high fluidity, apparent density and the like) of a metal additive manufacturing process on the high-performance spherical powder.
Therefore, there is a need to find a composite powder with good sphericity and nano-ceramics uniformly distributed on the surface of the high-entropy alloy.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a preparation method of nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing.
The invention also aims to provide the nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing, which is prepared by the preparation method.
The invention further aims to provide application of the nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing.
The purpose of the invention is realized by the following technical scheme:
a preparation method of nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing comprises the following steps:
(1) powder mixing: carrying out ultrasonic dispersion and mechanical stirring treatment on the high-entropy alloy powder and the nano ceramic particles to obtain high-entropy alloy powder A with the surfaces adhered with the nano ceramic particles;
(2) powder plasma spheroidizing: in an inert gas atmosphere, placing the alloy powder A obtained in the step (1) in a plasma spheroidizing device for spheroidizing, and cooling to obtain nano ceramic particle reinforced high-entropy alloy composite powder B;
(3) removing redundant nano ceramic particles: placing the composite powder B obtained in the step (2) in a solvent, stirring and settling, removing the solution, and drying in vacuum to obtain composite powder C with good adhesion;
(4) grading and mixing the powder size: and (4) performing classified screening on the composite powder C with good adhesion prepared in the step (3), and uniformly mixing the screened powder to obtain the nano ceramic particle reinforced high-entropy alloy composite spherical powder with the required particle size range.
The mass ratio of the high-entropy alloy powder to the nano ceramic particles in the step (1) is (9-22) to (1-3).
The purity of the high-entropy alloy powder is not lower than 99%; preferably 99.5 to 99.9 percent.
The purity of the nano ceramic particles is not lower than 99%; preferably 99.5 to 99.9 percent.
The particle size of the nano ceramic particles in the step (1) is 10-100 nm.
The morphology of the high-entropy alloy powder comprises at least one of irregular shape, nearly spherical shape and spherical shape.
The high-entropy alloy in the step (1) preferably comprises at least 4 of Al, Co, Cu, Cr, Fe, Ni, Mn, Ti, W, Mo, Nb, Ta, V and Zr.
The nano ceramic particles in the step (1) preferably comprise TiC, TiN and TiB2、Ti(CN)、Al2O3And SiC.
The ultrasonic dispersion frequency in the step (1) is 18-40 kHZ, the stirring speed of mechanical stirring is 30-100 r/min, and the time is 60-300 min; preferably, the frequency of ultrasonic treatment is 18-30 kHZ, the stirring speed of mechanical stirring is 60-100 r/min, and the time is 60-120 min.
The ultrasonic dispersion and mechanical stirring treatment operations are carried out simultaneously; the high-entropy alloy powder and the nano ceramic particles are subjected to ultrasonic dispersion and mechanical stirring treatment simultaneously, so that the nano ceramic particles are dispersed and simultaneously mixed with the high-entropy alloy powder.
And (3) placing the alloy powder A in the plasma spheroidizing device through carrier gas in the step (2).
The plasma torch is high-temperature inert gas plasma formed by ionizing inert gas (argon) under the action of a high-frequency power supply.
And the alloy powder A is sprayed into the plasma torch through the powder feeder.
The plasma spheroidizing process conditions in the step (2) are preferably as follows: the flow rate of the carrier gas is 0.1-1 m3H, the flow of the plasma argon is 1-3 m3The flow rate of the cooling gas is 0.5-5 m3The powder feeding rate is 1-5 kg/h; preferably, the flow rate of the carrier gas is 0.5-1 m3H, the flow of the plasma argon is 1-2 m3The flow rate of the cooling gas is 1-3 m3The powder feeding rate is 1.2-3 kg/h.
The composite powder B is rapidly melted on the surface under the action of high-temperature inert gas plasma.
The cooling in the step (2) is rapid cooling under an inert gas atmosphere.
The inert gas is preferably argon.
The solvent in the step (3) is preferably at least one of ethanol, acetone and deionized water.
The mass ratio of the composite powder B in the step (3) to the volume of the solvent is 3-10: 1.
And (4) performing stirring and settling operation in the step (3), discarding the solution, namely mixing and stirring the composite powder B and the solvent, pouring out the upper-layer solution after the powder particles are settled to the bottom, and repeating the operation for 1-3 times.
The stirring speed is 60-200 r/min, and the stirring time is 30-100 min; preferably, the stirring speed is 90-180 r/min, and the stirring time is 30-100 min.
The vacuum drying temperature in the step (3) is 80-150 ℃, and the vacuum drying time is 60-240 min; preferably, the vacuum drying temperature is 100-150 ℃, and the vacuum drying time is 120-180 min.
In the step (4), for the nano ceramic particle reinforced high-entropy alloy composite spherical powder prepared from the high-entropy alloy powder with the particle size of 15-53 microns, removing powder particles with the particle size of less than or equal to 15 microns through air flow classification, then carrying out ultrasonic vibration screening on the powder with the particle size of more than 15 microns, and removing the powder particles with the particle size of more than or equal to 53 microns to obtain the nano ceramic particle reinforced high-entropy alloy composite spherical powder with the particle size of 15-53 microns;
for the nano ceramic particle reinforced high-entropy alloy composite spherical powder prepared from the high-entropy alloy powder with the particle size of 45-105 mu m, the standard screen meshes of 325 meshes and 150 meshes are selected, and the nano ceramic particle reinforced high-entropy alloy composite spherical powder with the particle size of 45-105 mu m is obtained by ultrasonic vibration screening.
The mixing in step (4) is performed by a double motion mixing device.
The mixing speed is 60-120 r/min, and the mixing time is 1-10 h; preferably, the rotating speed is 60-90 r/min, and the time is 1-2 h.
A nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing is prepared by the preparation method.
The nano ceramic reinforced high-entropy alloy composite powder for additive manufacturing is applied to a Laser selective Melting metal 3D printing technology (SLM), an electron beam selective Melting forming technology (EBM) and a Laser Melting Deposition technology (LMD).
In the additive manufacturing process of the selective laser melting metal 3D printing technology (SLM) and the selective electron beam melting forming technology (EBM), the particle size of the high-entropy alloy powder is preferably 15-53 μm.
In the additive manufacturing process of the laser melting deposition technology, the particle size of the high-entropy alloy powder is 45-105 micrometers.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the invention takes high-entropy alloy as matrix powder and nano ceramic particles as reinforcing phase particles, obtains the high-entropy alloy powder with the nano ceramic particles uniformly adhered on the surface by adopting a mode of ultrasonic dispersion and mechanical stirring, and prepares the spherical nano ceramic particle reinforced high-entropy alloy composite powder by a radio frequency plasma spheroidization technology. Through the two-step process of ultrasonic vibration and plasma spheroidization, the prepared nano ceramic particle reinforced high-entropy alloy composite powder has extremely high sphericity (more than 98%), good powder fluidity (less than or equal to 15s/50g), low oxygen content (less than or equal to 250ppm) and narrow particle size distribution (15-53 mu m or 45-105 mu m), and meets the performance requirements of additive manufacturing on high-performance metal powder.
(2) The invention can use the high-entropy alloy powder with irregular shape as the matrix raw material, reduces the requirements on the powder raw material, is beneficial to reducing the production cost and improving the powder utilization rate.
(3) Compared with the powder prepared by the traditional mechanical ball milling method, the nano ceramic particle reinforced high-entropy alloy composite spherical powder provided by the invention is used for metal additive manufacturing and is beneficial to improving the forming precision and mechanical property of products.
(5) The preparation method of the nano-ceramic reinforced high-entropy alloy composite powder is simple in process, and the prepared powder is excellent in performance and suitable for batch production.
Drawings
FIG. 1 is an SEM topography of CoCrFeNiMn high-entropy alloy powder in example 1 of the invention.
FIG. 2 is an SEM topography of the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder in example 1 of the invention.
FIG. 3 is a laser particle size distribution diagram of the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder in example 1 of the present invention.
FIG. 4 is a SEM image of WMoNbTa high-entropy alloy powder in example 2 of the invention.
FIG. 5 is a SEM image of the high-entropy alloy composite powder of nanometer TiN enhanced WMoNbTa in example 2 of the invention.
Fig. 6 is a laser particle size distribution diagram of the nano TiN-enhanced WMoNbTa high-entropy alloy composite powder in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
The methods in the examples and comparative examples are conventional methods unless otherwise specified, and the reagents used are conventional commercially available reagents or reagents prepared by conventional methods unless otherwise specified.
Plasma spheronization equipment, TEKSPHERO-15system, tacrine, canada; the high-entropy alloy powder CoCrFeNiMn is purchased from New Material science and technology Limited of Jiangsu William, the granularity is 10-53 mu m, and the purity reaches 99.9%;
the nano TiC particles are purchased from Beijing Xinglong Yuan science and technology Limited, the particle size is 20nm, and the purity reaches 99.9 percent; the WMoNbTa high-entropy alloy powder is purchased from Jiangsu Willai New Material science and technology Limited, the granularity is 45-105 mu m, and the purity reaches 99.9%; the nanometer TiN particles are purchased from Guangzhou Hongwu materials science and technology limited, the particle size is 30nm, and the purity reaches 99.9%.
Example 1 preparation method of nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder for SLM/EBM additive manufacturing
Method and device
(1) Powder mixing: uniformly mixing high-entropy alloy powder CoCrFeNiMn (with the particle size of 15-53 mu m as shown in figure 1) and nano TiC particles (with the particle size of 20nm) through ultrasonic dispersion and mechanical stirring to obtain CoCrFeNiMn high-entropy alloy powder A with the nano TiC particles adhered to the surface; wherein, high-entropy alloy powder CoCrFeNiMn and nano TiC particles are mixed according to the mass ratio of 9: 1; the ultrasonic dispersion frequency is 18kHZ, the stirring speed of mechanical stirring is 60r/min, and the treatment time is 120 min.
(2) Powder plasma spheroidizing: spraying CoCrFeNiMn high-entropy alloy powder A with nano TiC particles adhered to the surface into a plasma torch through a carrier gas (argon) by a powder feeder, rapidly melting the surface of the powder under the action of high-temperature inert gas (argon) plasma, rapidly cooling the powder under the condition of inert atmosphere (argon), cooling and solidifying the powder into spherical powder, and entering a powder collection tank to obtain nano ceramic particle reinforced high-entropy alloy composite powder B; the plasma spheroidizing process comprises the following steps: the flow rate of the carrier gas was 0.5m3H, plasma argon flow of 1m3Flow rate of cooling gas of 1m3The powder feed rate was 1.2 kg/h;
(3) removing redundant nano ceramic particles: mixing and stirring the collected nano ceramic particle reinforced high-entropy alloy composite powder B and ethanol according to the proportion of 1:5(m/v), wherein the stirring speed is 90 r/min; stirring for 60 min; after the powder particles are settled to the bottom, pouring out the upper solution, and repeating the operation for 3 times; then, carrying out vacuum drying on the left powder, wherein the vacuum drying temperature is 100 ℃, and the vacuum drying time is 120min, so as to obtain composite powder C with good adhesion;
(4) grading and mixing the particle size: classifying and screening the particle size of the prepared composite powder C, removing powder particles with the particle size of less than or equal to 15 mu m through air flow classification, and then carrying out ultrasonic vibration screening on the powder with the particle size of more than 15 mu m to remove the powder particles with the particle size of more than or equal to 53 mu m; mixing the screened powder in a double-motion mixing device for 2 hours at the rotating speed of 60r/min to finally obtain nano TiC enhanced CoCrFeNiMn high-entropy alloy composite spherical powder with the particle size of 15-53 mu m, wherein the SEM morphology is shown in figure 2, and the laser particle size distribution is shown in figure 3; in addition, a product prepared from the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite spherical powder is detected by using a three-coordinate measuring instrument, a universal testing machine and a sliding friction coefficient tester respectively.
Second, the detection result
As can be seen from the SEM topography of the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder shown in FIG. 2, the ceramic particles are uniformly adhered to the surface of the high-entropy alloy ball after the treatment by the method of the invention because the particle size of the high-entropy alloy powder is far larger than that of the nano particles. The nano TiC reinforced CoCrFeNiMn high-entropy alloy composite powder prepared by the embodiment has high sphericity (98.6%), good powder fluidity (14.76s/50g), low oxygen content (241ppm) and narrow particle size distribution (D10/D50/D90 is 19.6 mu m/33.8 mu m/56.5 mu m), and meets the performance requirements of additive manufacturing on high-performance metal powder. By adopting the SLM forming technology, the prepared product has no defects of cracks, warping and the like, the size precision of the product is high (+/-3-5 mu m), the tensile strength is high (up to 1145MP), and the sliding friction coefficient is low (0.36).
Example 2 preparation method of nano TiN enhanced WMoNbTa high-entropy alloy composite powder for LMD additive manufacturing
Method and device
(1) Powder mixing: carrying out ultrasonic dispersion and mechanical stirring treatment on irregular-shaped WMoNbTa high-entropy alloy powder (the granularity is 45-105 mu m and is shown in figure 4) and nano TiN particles (the granularity is 30nm) at the same time to obtain WMoNbTa high-entropy alloy powder A with the nano TiN particles adhered to the surface; wherein, the WMoNbTa high-entropy alloy powder with irregular shape and the nano TiN particles are mixed according to the mass ratio of 22: 3; the ultrasonic dispersion frequency is 30kHZ, and the stirring speed of mechanical stirring is 60 r/min; the time is 90 min;
(2) Powder plasma spheroidizing: spraying WMoNbTa high-entropy alloy powder A with nano TiN particles adhered to the surface into a plasma torch through a powder feeder by carrier gas (argon), rapidly melting the surface of the powder under the action of high-temperature inert gas (argon) plasma, rapidly cooling the powder under the condition of inert atmosphere (argon), cooling and solidifying the powder into spherical powder, and entering a powder collection tank to obtain nano ceramic particle reinforced high-entropy alloy composite powder B; the plasma spheroidizing process comprises the following steps: flow rate of carrier gas 1m3H, plasma argon flow of 2m3Flow rate of cooling gas of 3m3The powder feed rate was 3 kg/h;
(3) removing redundant nano ceramic particles: mixing and stirring the collected nano ceramic particle reinforced high-entropy alloy composite powder B and deionized water according to the proportion of 1:5(m/v), wherein the stirring speed is 180 r/min; stirring for 60 min; after the powder particles are settled to the bottom, pouring out the upper solution, and repeating the operation for 2 times; then, carrying out vacuum drying on the left powder, wherein the vacuum drying temperature is 150 ℃, and the vacuum drying time is 180min, so as to obtain composite powder C with good adhesion;
(4) grading and mixing the particle size: grading and screening the granularity of the prepared composite powder C, and selecting 325-mesh and 150-mesh screens for high-entropy alloy powder with the granularity of 45-110 mu m to obtain nano TiN enhanced WMoNbTa high-entropy alloy composite spherical powder with the granularity of 45-105 mu m; mixing the screened powder in a double-motion mixing device for 1h at the rotating speed of 90r/min to finally obtain the nano TiN enhanced WMoNbTa high-entropy alloy composite spherical powder with the particle size of 45-105 mu m, wherein the SEM morphology is shown in figure 5, and the laser particle size distribution is shown in figure 6.
Second, the detection result
As can be seen from the SEM topography of the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder shown in FIG. 5, the ceramic particles are uniformly adhered to the surface of the high-entropy alloy ball after the treatment by the method disclosed by the application because the particle size of the high-entropy alloy powder is far larger than that of the nano particles. The nano TiN-enhanced WMoNbTa high-entropy alloy composite powder prepared by the embodiment has high sphericity (98%), good powder flowability (12s/50g), low oxygen content (354ppm) and narrow particle size distribution (D10/D50/D90 is 45.3 mu m/67.3 mu m/100 mu m), and meets the performance requirements of additive manufacturing on high-performance metal powder. The nano TiN-enhanced WMoNbTa high-entropy alloy composite powder is subjected to LMD forming, the powder spreading performance is good, the product has no defects such as cracks and warping, the size precision of the product is high (+/-30 mu m), the hardness Hv of the product is high (5211MPa), and the high-temperature compression strength is high (564 MPa).
Comparative example 1
This comparative example is essentially the same as example 1, except that a commercially available CoCrFeNiMn high entropy alloy powder was directly subjected to SLM forming. As a result, the prepared CoCrFeNiMn high-entropy alloy powder can be normally formed, has no defects such as cracks and the like, and has the product tensile strength of 601MPa and the sliding friction coefficient of 0.53. The reason for this phenomenon is probably that the tensile strength is low because the nano TiC ceramic particles are not added and the prepared product is not reinforced by the nano TiC particles; the sliding friction coefficient and the surface roughness form a positive correlation relationship, and the high-entropy alloy product without the nano TiC for enhancement has large surface roughness, so that the sliding friction coefficient is high.
Comparative example 2
The comparative example is basically the same as the example 1, except that the nano TiC enhanced CoCrFeNiMn high-entropy alloy composite powder prepared by performing wet ball milling treatment on the commercially available CoCrFeNiMn high-entropy alloy and the nano TiC has poor sphericity (80%), poor powder flowability (29s/50g), high oxygen content (452ppm), poor product dimensional accuracy (+/-10 mu m), tensile strength 926MP and sliding friction coefficient of 0.48. This phenomenon may be caused by the deterioration of the sphericity of the powder particles under the mutual impact of the ball milling media and the powder particles, and the exposure of the powder surface to this process may adsorb oxygen and thus cause an increase in the oxygen content. In the process of preparing the product, the powder is unevenly paved due to poor powder appearance, so that the product has poor dimensional precision, high surface roughness and high sliding friction coefficient; the increase of the oxygen content and the non-removal of the nano ceramic particle agglomerates lead to the reduction of the tensile strength and other properties of the formed piece.
Comparative example 3
This comparative example is substantially the same as example 2 except that LMD forming was directly performed on a commercially available irregular-shaped wmonibta high-entropy alloy powder, and as a result, it was found that: as the WMoNbTa high-entropy alloy powder is irregular in shape, the powder has no flowability, the powder is difficult to feed, and the powder cannot be normally fed to a forming area for forming.
Comparative example 4
The comparative example is substantially the same as example 2, except that the LMD forming was performed after directly spray-granulating the commercially available WMoNbTa high-entropy alloy powder, and as a result, the normal forming was possible without defects such as cracks, the product hardness Hv was 4458MPa, and the high-temperature compressive strength was 405 MPa. This is probably because without the addition of nano-TiN ceramic particles, the prepared article was not reinforced by nano-TiN particles, so hardness and compressive strength were reduced.
Comparative example 5
The comparative example is basically the same as example 2, except that the nano TiN enhanced WMoNbTa high entropy alloy composite powder prepared by performing wet ball milling treatment on the commercially available WMoNbTa high entropy alloy and the nano TiN has poor sphericity (75%), poor powder flowability (21.6s/50g) and high oxygen content (407 ppm). During the LMD forming process, the powder spread unevenly, the dimensional accuracy of the product is poor (+ -100 μm), the hardness Hv is 4926MPa, and the high-temperature compressive strength is 525 MPa. This is probably due to the fact that the powder particles become less spherical under the impact of the ball milling media and the powder particles with each other and that the surface exposure of the powder occurs during the process and adsorbs oxygen resulting in an increased oxygen content. In addition, the uneven powder laying caused by the poor powder appearance in the product preparation process can cause the poor product size precision; in addition, the increase of the oxygen content and the non-removal of the nano ceramic particle aggregates also cause the reduction of the properties of the formed piece, such as hardness and high-temperature compression strength.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing is characterized by comprising the following steps:
(1) powder mixing: carrying out ultrasonic dispersion and mechanical stirring treatment on the high-entropy alloy powder and the nano ceramic particles to obtain high-entropy alloy powder A with the surfaces adhered with the nano ceramic particles;
(2) powder plasma spheroidizing: in an inert gas atmosphere, placing the alloy powder A obtained in the step (1) in a plasma spheroidizing device for spheroidizing, and cooling to obtain nano ceramic particle reinforced high-entropy alloy composite powder B;
(3) removing redundant nano ceramic particles: placing the composite powder B obtained in the step (2) in a solvent, stirring and settling, removing the solution, and drying in vacuum to obtain composite powder C with good adhesion;
(4) grading and mixing the powder size: grading and screening the composite powder C with good adhesion prepared in the step (3), and uniformly mixing the screened powder to obtain nano ceramic particle reinforced high-entropy alloy composite spherical powder with the required particle size range;
Wherein the mass ratio of the high-entropy alloy powder to the nano ceramic particles in the step (1) is (9-22) to (1-3).
2. The production method according to claim 1,
the purity of the high-entropy alloy powder is not lower than 99%; the purity of the nano ceramic particles is not lower than 99%.
3. The preparation method according to claim 1, wherein the particle size of the nano ceramic particles in step (1) is 10 to 100 nm;
the morphology of the high-entropy alloy powder comprises at least one of irregular shape, nearly spherical shape and spherical shape.
4. The production method according to claim 1, wherein the high-entropy alloy in step (1) includes at least 4 of the elements Al, Co, Cu, Cr, Fe, Ni, Mn, Ti, W, Mo, Nb, Ta, V, and Zr;
the nano ceramic particles comprise TiC, TiN and TiB2、Ti(CN)、Al2O3And SiC.
5. The preparation method according to claim 1, wherein the frequency of the ultrasonic dispersion in the step (1) is 18 to 40kHZ, the stirring speed of the mechanical stirring is 30 to 100r/min, and the time is 60 to 300 min.
6. The method of claim 1, wherein the plasma spheroidizing process conditions in the step (2) are as follows: the flow rate of the carrier gas is 0.1-1 m 3H, the flow of the plasma argon is 1-3 m3Per, cooling gas flow of 0.5 to5 m3The powder feeding rate is 1-5 kg/h.
7. The method according to claim 1, wherein the solvent in step (3) is at least one of ethanol, acetone and deionized water.
8. The preparation method according to claim 1, wherein in the step (4), for the nano ceramic particle reinforced high-entropy alloy composite spherical powder prepared from the high-entropy alloy powder with the particle size of 15-53 μm, the powder particles with the particle size of less than 15 μm are removed through air flow classification, and then the powder with the particle size of more than or equal to 15 μm is subjected to ultrasonic vibration screening to remove the powder particles with the particle size of more than 53 μm, so that the nano ceramic particle reinforced high-entropy alloy composite spherical powder with the particle size of 15-53 μm is obtained;
for the nano ceramic particle reinforced high-entropy alloy composite spherical powder prepared from the high-entropy alloy powder with the particle size of 45-105 mu m, the standard screen meshes of 325 meshes and 150 meshes are selected, and the nano ceramic particle reinforced high-entropy alloy composite spherical powder with the particle size of 45-105 mu m is obtained by ultrasonic vibration screening.
9. A nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing is characterized by being prepared by the preparation method of any one of claims 1-8.
10. Use of the nano-ceramic reinforced high entropy alloy composite powder for additive manufacturing of claim 9 in selective laser melting metal 3D printing technology, selective electron beam melting forming technology and laser melting deposition technology.
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