CN112517906B - Aluminum-based composition for additive manufacturing, preparation method and application thereof - Google Patents
Aluminum-based composition for additive manufacturing, preparation method and application thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- 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
- B33Y10/00—Processes of additive manufacturing
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Abstract
The invention provides an aluminum-based composition for additive manufacturing, and a preparation method and application thereof. The aluminum-based composition comprising: an aluminum alloy having an average particle diameter of 30 μm; polystyrene coating the aluminum alloy; and silica, wherein the weight ratio of the aluminum alloy, the polystyrene and the silica is 1:0.1-0.3:0.3-0.5. Compared with the existing 7050 aluminum alloy material, the 7050 base material processed by the SLM of the aluminum-based composition has obviously improved tensile strength, because the SiC ceramic material is generated in situ in the 7050 matrix in the SLM processing process, the ceramic aluminum composite material is formed, siC has good dispersion effect in the matrix, and obvious enhancement effect is generated for the existing 7050 aluminum alloy.
Description
Technical Field
The invention relates to an aluminum-based composition, a preparation method and application thereof, in particular to an aluminum-based composition for additive manufacturing, and a preparation method and application thereof.
Background
7050 belongs to a high-strength heat-treatable alloy, and has extremely high strength, and anti-peeling corrosion and anti-stress corrosion fracture performances. The method is commonly used for the airplane structural part to be used for medium plate extrusion parts, free forging parts and die forging parts. The series of aluminum alloy is praised as the most excellent product in aluminum alloy, has high strength and is far superior to mild steel. The alloy has good mechanical properties and anode reaction. The method is mainly used in the fields of aerospace, mold processing, mechanical equipment, fixture and the like, and is particularly used for aircraft manufacturing structures and other high-stress structures with high strength and high corrosion resistance.
The additive manufacturing technology has realized two major breakthroughs in the 80 s of the 20 th century: first, the concept of additive manufacturing is deeply integrated with computer technology. Secondly, the development from the manufacture of nonmetallic materials such as early photosensitive resin to the manufacture of metallic materials is realized. With the rapid development of metal additive manufacturing technology, the technology has been manufactured by initial model and prototype, has moved to the fields of aerospace, military and the like, and has become a great motive force for promoting the progress of national defense industry in China, and aluminum-based metal materials have the advantages of low density and high strength, so that the technology becomes a focus attention in the fields of aerospace, military and the like.
Disclosure of Invention
In order to improve the metal material with more excellent performance for additive manufacturing, the invention provides an aluminum-based composition for additive manufacturing, and a preparation method and application thereof.
The present invention provides an aluminum-based composition for additive manufacturing, the aluminum-based composition comprising an aluminum alloy having an average particle size of 30 μm; polystyrene coating the aluminum alloy; and silica, wherein the weight ratio of the aluminum alloy, the polystyrene and the silica is 1:0.1-0.3:0.3-0.5.
According to embodiments of the invention, the silica may have an average particle size ranging from 0.1 μm to 0.3 μm.
According to an embodiment of the present invention, the aluminum alloy may be a 7050 model aluminum alloy.
According to an embodiment of the present invention, the aluminum-based composition may further comprise another aluminum alloy having an average particle size in the range of 1 μm to 25 μm.
According to embodiments of the invention, the weight ratio of the other aluminum alloy to the aluminum alloy may be 1:0.4-0.5.
The present invention provides a method of preparing an aluminum-based composition for additive manufacturing, the method comprising the steps of: step (1): dispersing an aluminum alloy with an average particle size of 30 μm in a mixed solution in which the volume ratio of water to ethanol is 1:3 to obtain an aluminum alloy dispersion; step (2): adding polyvinylpyrrolidone (PVP), azobisisobutyronitrile (AIBN) and styrene into the aluminum alloy dispersion, reacting for a preset time at a preset temperature, separating, and vacuum drying to obtain polystyrene coated aluminum alloy powder; and (3) a step of: mixing polystyrene-coated aluminum alloy powder with silicon dioxide to obtain an aluminum-based composition, wherein the weight ratio of the aluminum alloy to the polystyrene to the silicon dioxide is 1:0.1-0.3:0.3-0.5.
According to an embodiment of the present invention, in step (1), an aluminum alloy having an average particle diameter of 30 μm is placed in acetone and stirred for 1 hour, dried at 50 ℃ for 3 hours under a nitrogen atmosphere, and then the treated aluminum alloy is added to a mixed solution in which the volume ratio of water to ethanol is 1:3, thereby obtaining an aluminum alloy dispersion.
According to an embodiment of the present invention, in step (2), PVP, AIBN and styrene were added to the aluminum alloy dispersion, stirred under nitrogen protection for 1 hour, then placed in a water bath of 70 ℃ for stirring reaction for 8 hours, centrifuged at 12000 rpm, and then placed in a nitrogen atmosphere at 50 ℃ for 24 hours, thereby obtaining polystyrene-coated aluminum alloy powder.
The invention provides an application of an aluminum-based composition in additive manufacturing, wherein the additive manufacturing is performed by using a selective laser melting method, the thickness of the aluminum-based composition paved on a substrate is 30-50 mu m, the additive manufacturing process is performed under argon atmosphere, the power of laser is 250W, the scanning speed is 10mm/s, and the scanning interval is 2mm.
The aluminum-based composition for additive manufacturing, the preparation method and the application thereof according to the present invention have at least one of the following excellent effects:
compared with the existing 7050 aluminum alloy material, the 7050 base material processed by the SLM of the aluminum-based composition has obviously improved tensile strength, because the SiC ceramic material is generated in situ in the 7050 matrix in the SLM processing process, the ceramic aluminum composite material is formed, siC has good dispersion effect in the matrix, and obvious enhancement effect is generated for the existing 7050 aluminum alloy.
Drawings
FIG. 1 is a transmission electron microscope diagram showing example 1;
fig. 2 is a transmission electron microscope diagram showing comparative example 1; and
fig. 3 is an XRD diffractogram showing example 1.
Detailed Description
The invention provides an aluminum-based composition for additive manufacturing, which can generate SiC ceramic materials in situ in an aluminum alloy matrix in the process of using Selective Laser Melting (SLM) additive manufacturing, so that the mechanical properties of the aluminum-based materials are effectively improved. In particular, the aluminum-based composition for additive manufacturing includes an aluminum alloy, polystyrene coated with the aluminum alloy, and silica, and more particularly, the aluminum-based composition for additive manufacturing includes polystyrene coated aluminum alloy powder and silica powder.
The aluminum alloy powder is 7050-model aluminum alloy powder, the average grain diameter of the aluminum alloy powder is 30 mu m, and the average grain diameter of the silicon dioxide powder is in the range of 0.1 mu m to 0.3 mu m. The polystyrene coated aluminum alloy powder is prepared by using 7050 aluminum alloy powder as a nucleating agent through a styrene suspension polymerization method, and polymerizing styrene in a mixed solution of ethanol and water in a thermally initiated manner, so that a polystyrene film can be formed on the surface of the aluminum alloy powder after polymerization. In the present invention, the average particle diameter means D 50 。
Then, the polystyrene-coated aluminum alloy powder was mixed with the silica powder, thereby obtaining an aluminum-based composition.
In the present invention, the weight ratio of aluminum alloy, polystyrene and silica in the aluminum-based composition is 1:0.1-0.3:0.3-0.5.
In the present invention, the aluminum-based composition may be prepared according to the following steps: step (1): dispersing an aluminum alloy with an average particle size of 30 μm in a mixed solution in which the volume ratio of water to ethanol is 1:3 to obtain an aluminum alloy dispersion; step (2): adding PVP, AIBN and styrene into the aluminum alloy dispersion, reacting for a preset time at a preset temperature, separating, and vacuum drying to obtain polystyrene coated aluminum alloy powder; and (3) a step of: the polystyrene-coated aluminum alloy powder is mixed with silica to obtain an aluminum-based composition.
Specifically, in step (1), an aluminum alloy having an average particle diameter of 30 μm was placed in acetone and stirred for 1 hour, dried at 50 ℃ for 3 hours under a nitrogen atmosphere, and then the treated aluminum alloy was added to a mixed solution in which the volume ratio of water to ethanol was 1:3, thereby obtaining an aluminum alloy dispersion.
In the step (2), PVP, AIBN and styrene are added into the aluminum alloy dispersion, stirred for 1h under the protection of nitrogen, then placed in a water bath with 70 ℃ for stirring reaction for 8 h, centrifuged at 12000 r/min, and then placed in a nitrogen atmosphere for drying at 50 ℃ for 24h, thus obtaining the polystyrene-coated aluminum alloy powder.
The aluminum-based composition can be used as a powder raw material for additive manufacturing to perform additive manufacturing by using an SLM method.
In addition, 7050 aluminum alloy powder with the average particle diameter ranging from 1 mu m to 25 mu m can be added into the aluminum-based composition to reduce the pore structure in the aluminum-based composition, so that the pore structure of the product is reduced, and the mechanical property of the product is improved. Specifically, the weight ratio of the other aluminum alloy to the aluminum alloy may be 1:0.4-0.5.
In the process of using the SLM, the aluminum-based composition was laid on a substrate to a thickness of 30-50 μm, and the additive manufacturing process was under an argon atmosphere, wherein the power of the laser was 250W, the scanning speed was 10mm/s, and the scanning pitch was 2mm.
Specifically, the process is carried out in an argon atmosphere, polystyrene coated on the surface of aluminum alloy powder under high-energy laser irradiation is carbonized, siC is generated with silicon dioxide powder in the aluminum-based composition at high temperature, and the SiC is immediately embedded by surrounding melted aluminum alloy powder after the generation of the SiC, namely, siC materials are generated in situ in the aluminum alloy powder. The SiC-reinforced aluminum alloy material obtained after the temperature is reduced may also be referred to as a ceramic aluminum material.
In the process of producing SiC by SLM laser, laser power is one of the main influencing factors. The laser power is controlled to be about 250W, so that the carbonized polystyrene and the silicon dioxide powder are difficult to be induced to generate SiC due to the fact that the laser power is too low, and when the laser power is too high, the carbonized polystyrene is easy to evaporate, so that a carbon source is reduced, and the generation amount of the SiC is reduced.
In addition to the laser power, the weight ratio of the components of the aluminum-based composition also plays an important role in controlling, in particular, the polystyrene and SiO 2 The proportion of the SiO to be added in the system 2 When the amount is not too large, when SiO 2 When the amount is too large, due to SiO 2 After melting, the viscosity is larger, and SiO is easy to be generated 2 This will significantly reduce the continuous phase of the ceramic aluminum composite materialStrength. Therefore, when the weight ratio of each component of the aluminum-based composition is controlled to be 1:0.1-0.3:0.3-0.5, the SiC-reinforced aluminum alloy material with good dispersing effect can be produced, and the transmission electron microscope image can well prove the result.
Compared with the existing 7050 aluminum alloy material, the 7050 base material processed by the SLM of the aluminum-based composition has obviously improved tensile strength, because the SiC ceramic material is generated in situ in the 7050 matrix in the SLM processing process, the ceramic aluminum composite material is formed, siC has good dispersion effect in the matrix, and obvious enhancement effect is generated for the existing 7050 aluminum alloy.
The aluminum-based composition for additive manufacturing according to the present invention, and the manufacturing method and application thereof will be described below in conjunction with specific examples and comparative examples.
Example 1
Preparation of polystyrene coated 7050 aluminum alloy powder
50g of 7050 aluminum alloy powder having an average particle diameter of 30 μm was dispersed in acetone, stirred for 1 hour, and dried at 50℃for 3 hours under a nitrogen atmosphere. Adding the acetone-treated 7050 aluminum alloy powder into a mixed solution with the volume ratio of water (500 mL) to ethanol being 1:3 to form 7050 aluminum alloy powder dispersoid, adding 1g PVP, 0.15g AIBN and 5g styrene into the 7050 aluminum alloy powder dispersoid, stirring for 1h under the protection of nitrogen, then placing in a 70 ℃ water bath for stirring reaction for 8 h, centrifuging at 12000 r/min, and drying the solid at 50 ℃ for 24h under the nitrogen atmosphere to prepare the polystyrene-coated 7050 aluminum alloy powder.
The polystyrene-coated aluminum alloy powder obtained above, 125g of 7050 aluminum alloy powder having an average particle diameter of 20 μm, and 15g of silica powder having an average particle diameter of 0.3 μm (SiO 2 ) Added to a solid mixer and stirred for 30 minutes at 120 rpm to mix the above composition uniformly. The aluminum-based composition is paved on a substrate for 50 mu m, and then is subjected to additive manufacturing by using a selective laser melting method under an argon atmosphere, wherein the power of laser is 250W, and scanning is carried outThe speed was 10mm/s and the scanning pitch was 2mm.
Example 2
Preparation of polystyrene coated 7050 aluminum alloy powder
50g of 7050 aluminum alloy powder having an average particle diameter of 30 μm was dispersed in acetone, stirred for 1 hour, and dried at 50℃for 3 hours under a nitrogen atmosphere. Adding the acetone-treated 7050 aluminum alloy powder into a mixed solution with the volume ratio of water (500 mL) to ethanol being 1:3 to form a 7050 aluminum alloy powder dispersion system, adding 1g PVP, 0.3g AIBN and 11g styrene into the 7050 aluminum alloy powder dispersion system, stirring for 1h under the protection of nitrogen, then placing in a 70 ℃ water bath for stirring reaction for 8 h, centrifuging at 12000 r/min, and drying the solid at 50 ℃ for 24h under the nitrogen atmosphere to prepare the polystyrene-coated 7050 aluminum alloy powder.
The polystyrene-coated aluminum alloy powder obtained above, 100g of 7050 aluminum alloy powder having an average particle diameter of 10. Mu.m, and 25g of silica powder having an average particle diameter of 0.2. Mu.m (SiO 2 ) Added to a solid mixer and stirred for 30 minutes at 120 rpm to mix the above composition uniformly. The aluminum-based composition was laid on a substrate for 30 μm and then subjected to additive manufacturing using a selective laser melting method under an argon atmosphere, wherein the power of the laser was 250W, the scanning speed was 10mm/s, and the scanning pitch was 2mm.
Example 3
Preparation of polystyrene coated 7050 aluminum alloy powder
50g of 7050 aluminum alloy powder having an average particle diameter of 30 μm was dispersed in acetone, stirred for 1 hour, and dried at 50℃for 3 hours under a nitrogen atmosphere. Adding the 7050 aluminum alloy powder treated by the acetone into a mixed solution with the volume ratio of water (500 mL) to ethanol being 1:3 to form 7050 aluminum alloy powder dispersoid, adding 1g PVP, 0.3g AIBN and 9g styrene into the 7050 aluminum alloy powder dispersoid, stirring for 1h under the protection of nitrogen, then placing in a water bath with the temperature of 70 ℃ for stirring and reacting for 8 h, centrifuging at 12000 r/min, and drying the solid at the temperature of 50 ℃ for 24h under the nitrogen atmosphere to prepare the 7050 aluminum alloy powder coated by polystyrene.
The polystyrene-coated aluminum alloy powder obtained above, 110g of 7050 aluminum alloy powder having an average particle diameter of 25 μm, and 20g of silica powder having an average particle diameter of 0.1 μm (SiO 2 ) Added to a solid mixer and stirred for 30 minutes at 120 rpm to mix the above composition uniformly. The aluminum-based composition was laid on a substrate to 50 μm and then subjected to additive manufacturing using a selective laser melting method under an argon atmosphere, wherein the power of laser was 250W, the scanning speed was 10mm/s, and the scanning pitch was 2mm.
Example 4
Preparation of polystyrene coated 7050 aluminum alloy powder
50g of 7050 aluminum alloy powder having an average particle diameter of 30 μm was dispersed in acetone, stirred for 1 hour, and dried at 50℃for 3 hours under a nitrogen atmosphere. Adding the 7050 aluminum alloy powder treated by the acetone into a mixed solution with the volume ratio of water (500 mL) to ethanol being 1:3 to form 7050 aluminum alloy powder dispersoid, adding 1g PVP, 0.2g AIBN and 8g styrene into the 7050 aluminum alloy powder dispersoid, stirring for 1h under the protection of nitrogen, then placing in a water bath with the temperature of 70 ℃ for stirring and reacting for 8 h, centrifuging at 12000 r/min, and drying the solid at the temperature of 50 ℃ for 24h under the nitrogen atmosphere to prepare the 7050 aluminum alloy powder coated by polystyrene.
The polystyrene-coated aluminum alloy powder obtained above, 120g of 7050 aluminum alloy powder having an average particle diameter of 20. Mu.m, and 15g of silica powder having an average particle diameter of 0.3. Mu.m (SiO 2 ) To be added to a solid mixer and stirred for 30 minutes at 120 rpm to mix the above composition uniformly. The aluminum-based composition was laid on a substrate for 40 μm and then subjected to additive manufacturing using a selective laser melting method under an argon atmosphere, wherein the power of the laser was 250W, the scanning speed was 10mm/s, and the scanning pitch was 2mm.
Comparative example 1
Preparation of polystyrene coated 7050 aluminum alloy powder (PS-7050)
50g of 7050 aluminum alloy powder having an average particle diameter of 30 μm was dispersed in acetone, stirred for 1 hour, and dried at 50℃for 3 hours under a nitrogen atmosphere. Adding the 7050 aluminum alloy powder treated by the acetone into a mixed solution of water (500 mL) and ethanol in a volume ratio of 1:3 to form 7050 aluminum alloy powder dispersoid, adding 1g PVP, 0.2g AIBN and 8g styrene into the 7050 aluminum alloy powder dispersoid, stirring for 1h under the protection of nitrogen, then placing in a water bath at 70 ℃ for stirring reaction for 8 h, centrifuging at 12000 r/min, and drying the solid at 50 ℃ for 24h under the nitrogen atmosphere to prepare the 7050 aluminum alloy powder coated by polystyrene.
The polystyrene-coated aluminum alloy powder obtained above, 110g of 7050 aluminum alloy powder having an average particle diameter of 20. Mu.m, and 50g of silica powder (SiO 2 ) Added to a solid mixer and stirred for 30 minutes at 120 rpm to mix the above composition uniformly. The aluminum-based composition was laid on a substrate to 50 μm and then subjected to additive manufacturing using a selective laser melting method under an argon atmosphere, wherein the power of laser was 250W, the scanning speed was 10mm/s, and the scanning pitch was 2mm.
The texture of the SiC reinforced 7050 aluminum alloy material is observed by adopting a transmission electron microscope at a voltage of 200 kV. The samples were first ground into 0.1mm thick sheets, rolled into 3mm diameter discs, then thinned to about 30 μm using 400, 800, 1200, 2500 grit sandpaper, and then observed for the texture of SiC reinforced 7050 aluminum alloy materials using transmission electron microscopy at 200 kV.
FIGS. 1 and 2 are transmission electron micrographs of example 1 and comparative example 1, respectively, in which the black portion is SiC or SiO 2 The region can be seen from the figure, the dispersion degree of the generated ceramic material can be effectively controlled under a certain proportion, and the occurrence of agglomeration is avoided.
Tensile strength values were obtained by tensile testing of the SLM method manufactured aluminum alloy material according to the GB/T228.1-2010 national standard, and the results are shown in table 1.
Diffraction peak information of the aluminum alloy material was obtained using X-ray diffraction, wherein fig. 3 is an XRD diffraction pattern of example 1, and a diffraction peak at 38.2 ° which can be attributed to a characteristic peak of SiC, which proves the presence of SiC in the aluminum alloy material, is evident from the figure.
TABLE 1
| Sample of | Tensile Strength/Mpa |
| 7050 aluminum alloy | 552.1 |
| Example 1 | 732.1 |
| Example 2 | 653.2 |
| Example 3 | 672.3 |
| Example 4 | 705.1 |
| Comparative example 1 | 542.3 |
As can be seen from Table 1, the tensile strength of the aluminum-based material processed by the SLM of the aluminum-based composition of the invention is obviously improved compared with that of the 7050 aluminum alloy material, because the SiC ceramic material is generated in situ in the 7050 aluminum alloy matrix during the SLM processing process, the ceramic aluminum composite material is formed, and SiC has good dispersion effect in the matrix, thus obviously enhancing the 7050 aluminum alloy. In comparative example 1, a large amount of silica was generated during SLM processing, and the silica was distributed in a continuous phase, and the dispersion effect was poor, and stress concentration points were liable to occur, resulting in a decrease in strength.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (6)
1. An aluminum-based composition for additive manufacturing, the aluminum-based composition comprising:
an aluminum alloy having an average particle diameter of 30 μm;
polystyrene coating the aluminum alloy;
another aluminum alloy having an average particle diameter in the range of 1 μm to 25 μm; and
silica having an average particle diameter in the range of 0.1 μm to 0.3 μm,
wherein the weight ratio of the aluminum alloy, the polystyrene and the silicon dioxide is 1:0.1-0.3:0.3-0.5, and
the weight ratio of the other aluminum alloy to the aluminum alloy is 1:0.4-0.5.
2. The aluminum-based composition of claim 1, wherein the aluminum alloy is a 7050 model aluminum alloy.
3. A method of preparing an aluminum-based composition for additive manufacturing, the method comprising the steps of:
step (1): dispersing an aluminum alloy with an average particle size of 30 μm in a mixed solution in which the volume ratio of water to ethanol is 1:3 to obtain an aluminum alloy dispersion;
step (2): adding PVP, AIBN and styrene into the aluminum alloy dispersion, reacting for a preset time at a preset temperature, separating, and vacuum drying to obtain polystyrene coated aluminum alloy powder; and
step (3): mixing the polystyrene-coated aluminum alloy powder with another aluminum alloy with an average particle diameter ranging from 1 μm to 25 μm and silicon dioxide to obtain an aluminum-based composition, wherein the weight ratio of the aluminum alloy, the polystyrene and the silicon dioxide is 1:0.1-0.3:0.3-0.5,
wherein the weight ratio of the other aluminum alloy to the aluminum alloy is 1:0.4-0.5,
wherein the silica has an average particle diameter in the range of 0.1 μm to 0.3 μm.
4. A method according to claim 3, wherein in step (1), an aluminum alloy having an average particle diameter of 30 μm is placed in acetone and stirred for 1 hour, dried at 50 ℃ for 3 hours under a nitrogen atmosphere, and then the treated aluminum alloy is added to a mixed solution in which the volume ratio of water to ethanol is 1:3, thereby obtaining an aluminum alloy dispersion.
5. A method according to claim 3, wherein in step (2), PVP, AIBN and styrene are added to the aluminum alloy dispersion, stirred under nitrogen for 1 hour, then placed in a water bath of 70 ℃ for stirring reaction for 8 hours, centrifuged at 12000 rpm, and then placed in a nitrogen atmosphere at 50 ℃ for 24 hours, thereby obtaining polystyrene-coated aluminum alloy powder.
6. Use of an aluminium-based composition according to claim 1 in additive manufacturing, wherein the aluminium-based composition is laid down on a substrate for 30-50 μm and then subjected to laser irradiation under an argon atmosphere,
wherein, the power of the laser is 250W, the scanning speed is 10mm/s, and the scanning interval is 2mm.
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| Investigation on polyethylene supported poly(butyl methacrylate-acrylonitrile-styrene) terpolymer based gel electrolyte reinforced by doping nano-SiO2 for high voltage lithium ion battery;Weiyuan Huang et al.;《Electrochimica Acta》(第251期);全文 * |
| 超细粉体表面包覆技术综述;陈加娜等;《安徽化工》(第02期);全文 * |
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