CN113174517B - Corrosion-resistant Al-Si alloy and additive preparation method thereof - Google Patents
Corrosion-resistant Al-Si alloy and additive preparation method thereof Download PDFInfo
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- 230000007797 corrosion Effects 0.000 title claims abstract description 113
- 239000000654 additive Substances 0.000 title claims abstract description 76
- 230000000996 additive effect Effects 0.000 title claims abstract description 76
- 229910021364 Al-Si alloy Inorganic materials 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000956 alloy Substances 0.000 claims abstract description 59
- 239000003607 modifier Substances 0.000 claims abstract description 49
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- 239000000463 material Substances 0.000 claims abstract description 34
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 21
- 238000007639 printing Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
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- 238000001816 cooling Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 238000001238 wet grinding Methods 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 11
- 230000006872 improvement Effects 0.000 abstract description 6
- 239000008187 granular material Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
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- 229910052782 aluminium Inorganic materials 0.000 abstract 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 238000003837 high-temperature calcination Methods 0.000 description 3
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- 230000008901 benefit Effects 0.000 description 2
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- 238000011056 performance test Methods 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000007873 sieving Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910018125 Al-Si Inorganic materials 0.000 description 1
- 229910018520 Al—Si Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 150000003839 salts Chemical class 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
-
- 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
- B33Y10/00—Processes of additive manufacturing
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
- C22C32/001—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 only oxides
- C22C32/0015—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 only oxides with only single oxides as main non-metallic constituents
- C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Powder Metallurgy (AREA)
Abstract
The application discloses a corrosion-resistant Al-Si alloy which comprises the following elements in percentage by mass: 3-13% of Si, 0.4-0.5% of Mg, 0.1-0.2% of Fe, 0.01-0.05% of Zn, 0.01-0.02% of N and 2.2-2.8% of a corrosion resistant modifier, the balance being Al and unavoidable impurities, the corrosion resistant modifier comprising Al having a purity of 99.99% 2 O 3 And (3) granules. According to the preparation method, the alumina particles are used as the corrosion-resistant modifier material of the aluminum alloy material, so that the structural compactness of the prepared alloy material is effectively improved, and the finally prepared Al-Si alloy material has good corrosion resistance due to the effective improvement of the compactness structure. The application also discloses a preparation method of the corrosion-resistant Al-Si alloy additive, which adopts high-power-density laser to melt and deposit the alloy powder layer by layer, so that required parts can be directly obtained, and the near net-forming of complex metal parts is realized, thereby effectively improving the efficiency of Al-Si alloy additive preparation and further reducing the cost of alloy additive preparation.
Description
Technical Field
The invention relates to the technical field of alloy additive manufacturing, in particular to a corrosion-resistant Al-Si alloy and an additive preparation method thereof.
Background
The laser additive manufacturing technology is an advanced forming technology which is based on a three-dimensional design model of a part, obtains a rapid solidification structure through layer-by-layer melting and deposition of high-power laser on an alloy material and directly completes the forming of a three-dimensional solid part. The obtained formed body has small deformation, fine solidified structure crystal grains, compact structure, more uniform chemical components, higher strength and hardness and better wear resistance. The method has the characteristics of high material utilization rate, no molding, short production period, capability of manufacturing parts with complex structures and the like, so that the method has great development potential, wide development prospect and considerable economic benefit. With the continuous development of laser additive manufacturing technology, especially the successful development of some advanced process equipment, the application of the laser additive manufacturing technology is more and more extensive.
The Al-Si aluminum alloy has a plurality of excellent performances such as small density, high specific stiffness and high specific strength, and is widely applied to the aspects of aerospace, transportation, industrial production and the like. However, due to the physical properties of the aluminum alloy, the aluminum alloy has low hardness and poor wear resistance, and cannot meet the requirements of high-performance materials, so that further application of the aluminum alloy in industry is greatly limited. When the aluminum alloy material is prepared by the laser additive manufacturing technology, the surface precision is poor, so that the corrosion resistance and various mechanical properties of the material are poor.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art.
In view of the above, the invention provides a corrosion-resistant Al-Si alloy, and the corrosion-resistant Al-Si alloy additive has good structural compactness and excellent corrosion resistance.
The invention also provides a preparation method of the corrosion-resistant Al-Si alloy additive, the preparation method of the corrosion-resistant Al-Si alloy additive is simple and convenient, the preparation efficiency of the material is improved, and the production cost is reduced.
A corrosion resistant Al-Si alloy according to an embodiment of the first aspect of the invention, the corrosion resistant Al-Si alloy consisting of elements including, in mass percent: 3 to 13% of Si, 0.4 to 0.5% of Mg, 0.1 to 0.2% of Fe, 0.01 to 0.05% of Zn, 0.01 to 0.02% of N, 2.2 to 2.8% of corrosion resistance modifier, and the balance of Al and inevitable impurities; wherein the corrosion resistance modifier comprises Al with the purity of 99.99 percent 2 O 3 And (3) particles.
According to the corrosion-resistant Al-Si alloy provided by the embodiment of the invention, the aluminum oxide particles are used as the corrosion-resistant modifier material of the aluminum alloy material, in the preparation process, the aluminum oxide particles can be effectively dispersed among the components and form a good combined structure with the aluminum alloy matrix, or a melt formed by melting is mixed and solidified into an oxide film, the other part of the aluminum oxide particles are directly deposited in the pores of the internal structure of the primary Al-Si alloy material through adsorption and meshing actions, the pores of the oxide layer on the surface of the alloy material are greatly reduced and the oxide layer is thickened through the synergistic action of the aluminum oxide particles and the primary Al-Si alloy material, the structure compactness of the prepared alloy material is effectively improved, and the finally prepared Al-Si alloy material has good corrosion resistance due to the effective improvement of the compactness structure.
The corrosion-resistant Al-Si alloy additive according to the embodiment of the invention can also have the following additional technical characteristics:
according to one embodiment of the invention, the corrosion-resistant Al-Si alloy further comprises Y particles with the same mass as Zn, the Y particles have the particle size of 200 meshes and the purity of 99%.
According to one embodiment of the invention, the corrosion-resistant Al-Si alloy further comprises 0.6wt% of Nb particles in percentage by mass, wherein the Nb particles have a particle size of 200 meshes and a purity of 99%.
According to the second aspect of the invention, the preparation method of the corrosion-resistant Al-Si alloy additive material is characterized in that the preparation steps of the corrosion-resistant Al-Si alloy additive material comprise:
s1, mixing raw materials: according to the formula, all the raw materials are stirred, mixed and preheated, the mixture is preheated for 3 to 5 hours at the temperature of between 150 and 200 ℃, and the mixture is collected;
s2, presetting a mixture: pre-arranging the mixture on the surface of an alloy substrate, placing the alloy substrate in a processing device, and introducing argon to remove air;
s3, additive preparation: and performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, naturally cooling and stopping introducing argon after the additive printing, thus preparing the corrosion-resistant Al-Si alloy additive.
According to an embodiment of the present invention, the raw material mixing step S1 further includes:
s11, activating the corrosion-resistant modifier: stirring and mixing the corrosion resistant modifier and the adhesive, carrying out wet grinding treatment and collecting to obtain the wet-ground corrosion resistant modifier, putting the wet-ground corrosion resistant modifier material into a mould, carrying out pressure forming, putting the mould into a calcining device, heating, carrying out heat preservation and calcination, and grinding and sieving with a 500-mesh sieve to obtain the activated corrosion resistant modifier.
According to an embodiment of the present invention, the temperature-increasing heating and heat-preserving calcining in step S11 adopts the following steps: heating to 1350 deg.C/min at 10 deg.C/min, maintaining for 3 hr, heating to 1650 deg.C at 5 deg.C/min, and maintaining for 5 hr.
According to one embodiment of the present invention, the adhesive of step S11 is 0.8mol/L polyvinyl alcohol solution.
According to one embodiment of the invention, the laser power in the additive printing in the step S3 is 2500W, and the scanning speed is 300-500 mm/min.
According to one embodiment of the invention, the preset thickness of the mixture in the step S2 is 0.8-1.2 mm.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, but not limiting, of the invention.
The corrosion-resistant Al-Si alloy and the additive manufacturing method thereof according to the embodiment of the invention are specifically described below.
First, according to the corrosion-resistant Al-Si alloy of the embodiment of the present invention, the corrosion-resistant Al-Si alloy additive material is composed of elements including, in mass percent: 3-13% of Si, 0.4-0.5% of Mg, 0.1-0.2% of Fe, 0.01-0.05% of Zn, 0.01-0.02% of N and 2.2-2.8% of corrosion resistant modifier, the balance being Al and unavoidable impurities; wherein the corrosion resistant modifier comprises Al with the purity of 99.99 percent 2 O 3 And (3) granules.
Therefore, according to the corrosion-resistant Al-Si alloy additive provided by the embodiment of the invention, the alumina particles are used as the corrosion-resistant modifier material of the aluminum alloy material, in the preparation process, the alumina particles can be effectively dispersed among the components and form a good bonding structure with the aluminum alloy matrix, or a melt formed by melting is mixed and solidified into an oxide film, the other part of the alumina particles are directly deposited in the pores of the internal structure of the primary Al-Si alloy material through adsorption and meshing actions, the pores of the oxide layer on the surface of the alloy material are greatly reduced and the oxide layer is thickened through the synergistic effect of the alumina particles and the primary Al-Si alloy material, the structure compactness of the prepared alloy material is effectively improved, and the finally prepared Al-Si alloy material has good corrosion resistance due to the effective improvement of the compactness structure.
According to one embodiment of the invention, the corrosion-resistant Al-Si alloy additive material further comprises Y particles with the same mass as Zn, the Y particles are 200 meshes in particle size, and the purity is 99%.
By adopting the technical scheme, the Y element is added into the Al-Si alloy material, the rare earth element Y has active chemical property, the alloy liquid phase can be purified, the gas and impurity content in the molten liquid can be reduced, the improvement of the aluminum alloy solidification process is facilitated, and the alloy solidification structure is refined.
In some embodiments of the invention, the corrosion resistant Al-Si alloy further comprises 0.6wt% Nb particles by mass, the Nb particles having a particle size of 200 mesh and a purity of 99%.
The variety of the added materials is optimized, the Nb element is optimized, the Nb can be dissolved in Al in a solid mode to achieve a solid solution strengthening effect, the added amount of Nb particles is optimized, the Nb particles can achieve a precipitation strengthening effect, the Nb particles are distributed at primary phase crystal boundaries as second phase particles, dislocation slippage is difficult, and then an alloy strengthening effect is achieved, so that the prepared alloy material has good corrosion resistance.
In a second aspect, the present application provides a method for preparing a corrosion-resistant Al-Si alloy additive material, wherein the method for preparing the corrosion-resistant Al-Si alloy additive material comprises the steps of:
s1, mixing raw materials: according to the formula, all the raw materials are stirred, mixed and preheated, the mixture is preheated for 3 to 5 hours at the temperature of between 150 and 200 ℃, and the mixture is collected;
s2, presetting a mixture: the mixture is preset on the surface of an alloy substrate, is placed in a processing device, and is introduced with argon to remove air;
s3, additive preparation: and performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, naturally cooling and stopping introducing argon after the additive printing, thus preparing the corrosion-resistant Al-Si alloy additive.
According to the technical scheme, the alloy material is prepared by laser additive, and the alloy powder is melted and deposited layer by adopting high-power-density laser in the laser additive preparation, so that required parts can be directly obtained, the near net-forming of complex metal parts is realized, the Al-Si alloy additive preparation efficiency is effectively improved, and the alloy additive preparation cost is further reduced.
According to an embodiment of the present invention, the mixing of the raw materials in step S1 further includes:
s11, activating the corrosion-resistant modifier: stirring and mixing the corrosion-resistant modifier and the adhesive, carrying out wet grinding treatment and collecting to obtain a wet-ground corrosion-resistant modifier, putting the wet-ground corrosion-resistant modifier material in a mould, carrying out pressure forming, putting in a calcining device, heating, carrying out heat preservation and calcination, and grinding and sieving with a 500-mesh sieve to obtain the activated corrosion-resistant modifier.
According to the technical scheme, the corrosion-resistant modifier material is subjected to activation treatment, and the corrosion-resistant modifier material subjected to high-temperature activation is subjected to high-temperature calcination, so that particles can be effectively refined and more disordered structures can be generated.
In some embodiments of the present invention, the heating and calcining at elevated temperature in step S11 comprises the following steps: heating to 1350 deg.C/min at 10 deg.C/min, maintaining for 3 hr, heating to 1650 deg.C at 5 deg.C/min, and maintaining for 5 hr.
In this application technical scheme, this application adopts the scheme of steady intensification to calcine the anti-corrosion modifier material, effectively improves the total stable in structure performance of anti-corrosion modifier material of activation processing process, and this application technical scheme keeps warm at 1350 ℃ simultaneously and handles, effectively calcines and makes adhesive material pyrolysis to further improved alloy material's compact structure, improved alloy material's corrosion resisting property.
Further, the adhesive in step S11 is 0.8mol/L polyvinyl alcohol solution.
In this application technical scheme, through selecting for use polyvinyl alcohol solution, not only effectively reduced the cost of production, the polyvinyl alcohol that this application adopted simultaneously can the carbomorphism under high temperature environment, effectively gets rid of impurity component after follow-up carbomorphism to alloy material's compact structure and corrosion resisting property have further been improved.
Further, the laser power in the additive printing in the step S3 is 2500W, and the scanning speed is 300-500 mm/min.
In this application technical scheme, through optimizing the scanning speed in the laser vibration material disk preparation process, improve and solidify the in-process at the molten bath, molten bath solution violently flows and probably is drawn into the molten bath with the partial protective gas in the shaping intracavity under the high-speed laser effect and form the problem of gas pocket, laser power after the optimization simultaneously can prevent that scheme laser power from when too high, can make partial low melting point alloy element in the molten bath take place to gasify, form the gas pocket after the molten bath solidifies to improve the compact structure of material, improve the corrosion resisting property of material.
Further, the preset thickness of the mixture in the step S2 is 0.8-1.2 mm.
In summary, in the corrosion-resistant Al-Si alloy additive, the alumina particles are used as the corrosion-resistant modifier material of the aluminum alloy material, during the preparation process, the alumina particles can be effectively dispersed among the components and form a good bonding structure with the aluminum alloy matrix, or the melt formed by melting is mixed and solidified into the oxide film, the other part of the alumina particles is directly deposited in the pores of the internal structure of the primary Al-Si alloy material through the adsorption and meshing actions, the pores of the oxide layer on the surface of the alloy material are greatly reduced and the oxide layer is thickened through the synergistic effect of the two, the structure compactness of the prepared alloy material is effectively improved, and the finally prepared Al-Si alloy material has good corrosion resistance due to the effective improvement of the compactness structure.
According to the technical scheme, the Y element is added into the Al-Si alloy material, and the rare earth element Y is splashed due to chemical properties, so that the alloy liquid phase can be purified, the gas and impurity content in the molten liquid can be reduced, the aluminum alloy solidification process can be improved, and the alloy solidification structure can be refined.
In addition, the corrosion-resistant modifier material is subjected to activation treatment, and the corrosion-resistant modifier material subjected to high-temperature activation can be effectively refined and promoted to generate more disordered structures through a high-temperature calcination scheme.
The corrosion-resistant Al-Si alloy and the additive manufacturing method thereof according to the embodiments of the present invention are described in detail below with reference to specific examples.
Preparation examples
Preparation of activated corrosion-resistant modifier
Preparation example 1
Stirring and mixing the corrosion resistant modifier with 0.8mol/L polyvinyl alcohol solution, carrying out wet grinding treatment and collecting to obtain the wet grinding corrosion resistant modifier, putting the wet grinding corrosion resistant modifier material into a mould, carrying out pressure forming, putting the mould into a calcining device, heating to 1350 ℃ at the speed of 10 ℃/min, keeping the temperature for 3h, then heating to 1650 ℃ at the speed of 5 ℃/min, carrying out heat preservation calcining treatment for 5h, and grinding through a 500-mesh sieve to obtain the activated corrosion resistant modifier.
Examples
Example 1
S1, mixing raw materials: 3% by mass of Si, 0.4% by mass of Mg, 0.1% by mass of Fe, 0.01% by mass of Zn, 0.01% by mass of N, 2.2% by mass of the activated corrosion resistant modifier 1, and the balance of Al, stirring and mixing the raw materials, and preheating the mixture at 150 ℃ for 3 hours, and collecting the mixture;
s2, presetting a mixture: presetting the mixture on the surface of an alloy substrate for 0.8mm, placing the alloy substrate in a processing device, and introducing argon to remove air;
s3, additive preparation: and performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, setting the laser power to 2500W and the scanning speed to 300mm/min in the additive printing, performing additive printing, naturally cooling, and stopping introducing argon gas to prepare the corrosion-resistant Al-Si alloy additive.
Example 2
S1, mixing raw materials: mixing by mass percent 8% Si, 0.5% Mg, 0.1% Fe, 0.03% Zn, 0.02% N and 2.5% activated corrosion resistant modifier 1, balance Al, and preheating at 170 ℃ for 4h, collecting the mixture;
s2, presetting a mixture: presetting the mixture on the surface of an alloy substrate for 1.0mm, placing the alloy substrate in a processing device, and introducing argon to remove air;
s3, additive preparation: and performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, setting the laser power to 2500W and the scanning speed to 400mm/min in the additive printing, performing additive printing, naturally cooling, and stopping introducing argon gas to prepare the corrosion-resistant Al-Si alloy additive.
Example 3
S1, mixing raw materials: 13% Si, 0.5% Mg, 0.2% Fe, 0.05% Zn, 0.02% N, 2.8% activated corrosion resistant modifier 1, the balance Al, by mass percent, stirring and mixing, and heat-insulating and preheating at 200 ℃ for 5 hours, collecting the mixture;
s2, presetting a mixture: the mixture is preset on the surface of an alloy substrate for 1.2mm, is placed in a processing device, and is introduced with argon to remove air;
s3, additive preparation: and performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, setting the laser power to 2500W and the scanning speed to 500mm/min in the additive printing, performing additive printing, naturally cooling, and stopping introducing argon gas to prepare the corrosion-resistant Al-Si alloy additive.
Example 4: compared with the embodiment 1, the corrosion-resistant Al-Si alloy additive is added with Y with the purity of 99 percent and the addition amount of Y of 200 meshes, and the preparation conditions and the component distribution ratio are the same as those of the embodiment 1 except that the addition amount of Y is 0.01 percent.
Example 5: compared with the embodiment 1, the corrosion-resistant Al-Si alloy additive is added with Y with the purity of 99 percent and 200 meshes in 200 meshes, the purity is 99 percent Nb, the addition amount of Y is 0.01 percent, the addition amount of Nb is 0.6 percent, and the rest preparation conditions and the component distribution ratio are the same as the embodiment 1.
Example 6: compared with the embodiment 1, the corrosion resistant modifier added in the embodiment 6 is not subjected to high temperature calcination activation treatment, and the other preparation conditions and the component ratio are the same as those in the embodiment 1.
Comparative example
Comparative example 1: compared with the example 1, the corrosion-resistant Al-Si alloy additive in the comparative example 1 is not added with the corrosion-resistant modifier, and the rest preparation conditions and the component proportion are the same as those in the example 1.
Comparative example 2: compared with the embodiment 1, in the additive manufacturing process of the comparative example 2, the scanning speed is 800mm/min, and the other manufacturing conditions and the component proportion are the same as those of the embodiment 1.
Comparative example 3: compared with the example 1, in the additive manufacturing process of the comparative example 3, the scanning speed is 200mm/min, and the rest manufacturing conditions and the component proportion are the same as those of the example 1.
Performance test
The corrosion-resistant Al-Si alloy additive materials prepared in examples 1-6 and comparative examples 1-3 are subjected to performance tests.
And (3) corrosion resistance test: the corrosion resistance of the alloy additive in 3.5wt% NaCl solution was tested using the CHI 604D electrochemical workstation.
Wherein the reference electrode adopts saturated calomel electrode, the auxiliary electrode adopts platinum electrode, the working electrode is protected by epoxy resin, and the exposed area is 1cm 2 。
The results of the experiment are as follows:
table 1: comparison of corrosion resistant Al-Si alloy additive corrosion resistance experiments of examples 1-6 and comparative examples 1-3
| Item | Salt spray resistance time/h | Self-etching current density/. Times.10 -6 A/cm 2 |
| Example 1 | 1580 | 4.16 |
| Example 2 | 1592 | 5.65 |
| Example 3 | 1586 | 5.21 |
| Example 4 | 1652 | 3.85 |
| Example 5 | 1768 | 3.77 |
| Example 6 | 1321 | 6.84 |
| Comparative example 1 | 1015 | 12.3 |
| Comparative example 2 | 1220 | 13.5 |
| Comparative example 3 | 1232 | 14.2 |
As can be seen from table 1, the corrosion-resistant Al-Si alloy additive materials prepared in examples 1 to 6 have good corrosion resistance, and in combination with the corrosion resistance of comparative example 1, it is described that in the technical solution of the present application, the alumina particles are used as the corrosion-resistant modifier material of the aluminum alloy material, during the preparation process, the alumina particles can be effectively dispersed among the components and form a good combination structure with the aluminum alloy matrix, or the melt formed by melting is mixed and solidified inside the oxide film, and another part of the alumina particles are directly deposited in the pores of the internal structure of the nascent Al-Si alloy material through adsorption and meshing actions, so that the pores of the oxide layer on the surface of the alloy material are greatly reduced and the oxide layer is made to effectively improve the structural compactness of the prepared alloy material, and the finally prepared Al-Si alloy material has good corrosion resistance due to the effective improvement of the compactness structure.
Comparing the performance of the comparative examples 2-3 with that of the example 1, and changing the scanning speed in the comparative examples 2-3 to reduce the corrosion resistance, which indicates that in the technical scheme of the application, by optimizing the scanning speed in the laser additive manufacturing process, the problem that in the molten pool solidification process, part of protective gas in a forming cavity may be rolled into the molten pool by the violent flow of molten pool solution under the action of high-speed laser to form air holes is solved, and meanwhile, the optimized laser power can prevent part of low-melting-point alloy elements in the molten pool from being gasified when the laser power of the scheme is too high, and the air holes are formed after the molten pool is solidified, so that the compact structure of the material is improved, and the corrosion resistance of the material is improved.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (6)
1. The corrosion-resistant Al-Si alloy is characterized by comprising the following elements in percentage by mass:
3～13％Si；
0.4～0.5％Mg；
0.1～0.2％Fe；
0.01～0.05％Zn；
y is equal to Zn in mass;
0.6wt％Nb；
0.01～0.02％N；
2.2 to 2.5 percent of corrosion resistant modifier;
the balance of Al and inevitable impurities;
wherein the corrosion resistant modifier is Al with the purity of 99.99 percent 2 O 3 Particles;
the preparation method of the corrosion-resistant Al-Si alloy comprises the following steps:
s1, mixing raw materials: according to the formula, stirring and mixing all the raw materials, preheating, preserving heat and preheating for 3-5 hours at the temperature of 150-200 ℃, and collecting a mixture;
s2, presetting a mixture: pre-arranging the mixture on the surface of an alloy substrate, placing the alloy substrate in a processing device, and introducing argon to remove air;
s3, additive preparation: performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, performing additive printing, naturally cooling, and stopping introducing argon gas to prepare the corrosion-resistant Al-Si alloy additive; the laser power in the additive printing is 2500W, and the scanning speed is 300-500 mm/min;
wherein the mixing of the raw materials in step S1 further comprises:
s11, activating the corrosion-resistant modifier: stirring and mixing the corrosion-resistant modifier and the adhesive, carrying out wet grinding treatment and collecting to obtain a wet-ground corrosion-resistant modifier, putting the wet-ground corrosion-resistant modifier material into a mould, carrying out pressure forming, putting the mould into a calcining device, heating, carrying out heat preservation and calcination, and grinding the mixture through a 500-mesh sieve to obtain an activated corrosion-resistant modifier; the heating and heat preservation calcining comprises the following steps: heating to 1350 deg.C/min at 10 deg.C/min, maintaining for 3 hr, heating to 1650 deg.C at 5 deg.C/min, and maintaining for 5 hr.
2. The corrosion resistant Al-Si alloy of claim 1, wherein the Y has a particle size of 200 mesh and a purity of 99%.
3. The corrosion resistant Al-Si alloy of claim 2, wherein the Nb has a grain size of 200 mesh and a purity of 99%.
4. A method for preparing the corrosion-resistant Al-Si alloy additive according to any one of claims 1 to 3, wherein the step of preparing the corrosion-resistant Al-Si alloy comprises:
s1, mixing raw materials: according to the formula, stirring and mixing all the raw materials, preheating, preserving heat and preheating for 3-5 hours at the temperature of 150-200 ℃, and collecting a mixture;
s2, presetting a mixture: pre-arranging the mixture on the surface of an alloy substrate, placing the alloy substrate in a processing device, and introducing argon to remove air;
s3, additive preparation: performing additive printing, fixing the diameter of a laser spot, adjusting the scanning interval, performing additive printing, naturally cooling, and stopping introducing argon gas to prepare the corrosion-resistant Al-Si alloy additive;
wherein the mixing of the raw materials in step S1 further comprises:
s11, activating the corrosion-resistant modifier: stirring and mixing the corrosion-resistant modifier and the adhesive, carrying out wet grinding treatment and collecting to obtain a wet-ground corrosion-resistant modifier, putting the wet-ground corrosion-resistant modifier material into a mould, carrying out pressure forming, putting the mould into a calcining device, heating, carrying out heat preservation and calcination, and grinding the mixture through a 500-mesh sieve to obtain an activated corrosion-resistant modifier; the heating and heat preservation calcining comprises the following steps: heating to 1350 deg.C/min at 10 deg.C/min, maintaining for 3 hr, heating to 1650 deg.C at 5 deg.C/min, and calcining for 5 hr.
5. The method for preparing the corrosion-resistant Al-Si alloy additive according to claim 4, wherein the binder in step S11 is 0.8mol/L polyvinyl alcohol solution.
6. The preparation method of the corrosion-resistant Al-Si alloy additive according to claim 4, wherein the preset thickness of the mixture in the step S2 is 0.8-1.2 mm.
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