Corrosion-resistant alloy powder for additive manufacturing and preparation method thereof
By combining nanographene oxide and nanooxides in additive manufacturing alloys to form dense oxide layers, the existing additive manufacturing alloys have solved the shortcomings in corrosion resistance and significantly improved their corrosion resistance in harsh environments.
Patent Information
- Application Number
- CN202510354657.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-25
- Publication Date
- 2025-06-10
AI Technical Summary
In environments such as ships and water conservancy, there are extremely high requirements for corrosion resistance, existing additive manufacturing alloy components are insufficient to meet the application needs of Yan E.
An alloy with chromium, molybdenum, copper and iron as the main raw materials is used to form alloy powders with good barrier effects by compounding nanographene oxide, polyaniline modified nanographene, nanoyttrium oxide and nanozirconia, thereby improving its corrosion resistance.
By modifying the composite of nanographene oxide and nanooxide, a dense oxide layer is formed, which significantly improves the corrosion resistance of the alloy powder and can effectively prevent the penetration of water, oxygen and corrosive ions.
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Abstract
Description
Technical Field
[0001] This application relates to the field of 3D printing technology, and particularly to a corrosion-resistant alloy powder for additive manufacturing and a preparation method thereof. Background Art
[0002] Additive manufacturing technology, commonly known as 3D printing technology, is an advanced manufacturing process opposite to traditional machining and other "subtractive manufacturing" technologies. Based on the principle of layer-by-layer stacking, it manufactures three-dimensional entities by accumulating two-dimensional cross-sections point by point. This technology can directly convert three-dimensional digital models into solid parts, not only achieving the lightweight of part structures but also improving the composite level of part performance. Compared with traditional manufacturing technologies, additive manufacturing technology has significant advantages, including no need for molds, high flexibility, short production cycles, and no restrictions on part structures and materials. These characteristics enable additive manufacturing technology to show great application potential in fields such as personalized customization, complex structure manufacturing, and rapid prototype development. Therefore, additive manufacturing technology is regarded as one of the key representative technologies to promote the "Third Industrial Revolution" and is expected to lead the future development direction of the manufacturing industry.
[0003] With the rapid development of additive manufacturing technology in recent years, its components are increasingly widely used in aerospace, high-speed rail, ships, automobiles, military, medical implants, etc. In these fields, especially in environments with extremely high requirements for corrosion resistance such as ships and water conservancy, the demand for the corrosion resistance of additive manufacturing alloy components is particularly urgent. Summary of the Invention
[0004] In order to provide a corrosion-resistant alloy powder for additive manufacturing, this application provides a corrosion-resistant alloy powder for additive manufacturing and a preparation method thereof.
[0005] A corrosion-resistant alloy powder for additive manufacturing provided by this application adopts the following technical solution: A corrosion-resistant alloy powder for additive manufacturing, the raw materials by mass percentage include 21-23.5% chromium, 6-8% molybdenum, 1.5-2.5% copper, 0.2-0.8% polyaniline-modified nano-graphene, 0.04-0.08% nano-yttrium oxide, 0.2-0.8% nano-zirconium oxide, and the balance is iron.
[0006] Preferably, the raw materials by mass percentage include 22-22.6% chromium, 6.5-7.5% molybdenum, 1.8-2.2% copper, 0.4-0.6% polyaniline-modified nano-graphene, 0.05-0.07% nano-yttrium oxide, 0.4-0.6% nano-zirconium oxide, and the balance is iron.
[0007] Preferably, the raw materials by mass percentage include 22.3% chromium, 7% molybdenum, 2% copper, 0.5% polyaniline-modified nano-graphene, 0.06% nano-yttrium oxide, 0.5% nano-zirconia, and the balance is iron.
[0008] Preferably, the particle size of the nano-yttrium oxide is 80 - 120 nm.
[0009] Preferably, the polyaniline-modified nano-graphene is composed of the following raw materials in parts by weight: 16.1 - 24.15 parts of 85% phosphoric acid solution by mass fraction, 100 - 120 parts of distilled water, 0.5 - 1 part of aniline, 1.5 - 3 parts of nano-graphene oxide, and 3 - 4.5 parts of ammonium persulfate.
[0010] Preferably, the preparation method of the polyaniline-modified nano-graphene includes the following steps: S1. Add 1.5 - 3 parts of nano-graphene oxide to 50 - 60 parts of distilled water, and ultrasonically disperse evenly to obtain a graphene oxide dispersion; S2. Add 16.1 - 24.15 parts of 85% phosphoric acid solution by mass fraction to 50 - 60 parts of distilled water, stir evenly, add 0.5 - 1 part of aniline, and magnetically stir for 5 - 10 min; add the graphene oxide dispersion obtained in S1, and magnetically stir for 2 - 3 h; then add 3 - 4.5 parts of ammonium persulfate, magnetically stir for 1 - 2 h, ultrasonically treat the reaction solution for 2 - 4 h, filter by suction and wash until neutral, and dry in vacuum to obtain polyaniline-modified nano-graphene.
[0011] The present application also provides a preparation method of a corrosion-resistant alloy powder for additive manufacturing, adopting the following technical solution: A preparation method of a corrosion-resistant alloy powder for additive manufacturing, including the following steps: S1. Weigh each raw material by mass percentage, vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace, and then cast into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device, and perform gas atomization treatment in an inert gas environment to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nano-graphene, nano-yttrium oxide, and nano-zirconia at 80 - 120 °C for 3 - 5 h respectively, then mix and transfer to a high-energy ball mill for ball milling; screen the collected powder to obtain the corrosion-resistant alloy powder for additive manufacturing.
[0012] Preferably, the vacuum degree of the vacuum melting is less than 0.1 Pa.
[0013] Preferably, the rotation speed of the ball milling is 600 - 1000 rpm; the ball milling time is 2 - 4 h.
[0014] Preferably, the particle size of the corrosion-resistant alloy powder for additive manufacturing is less than or equal to 180 μm.
[0015] In summary, the present application includes at least one of the following beneficial technical effects: 1. By adopting the above technical solution, the present application uses chromium, molybdenum, copper, and iron as the main raw materials of the alloy. By compounding nano-graphene oxide, it can provide a good barrier for the alloy material to prevent the penetration of water, oxygen, and corrosive ions, thereby improving the corrosion resistance of the alloy powder. After modifying nano-graphene oxide with polyaniline, the dispersibility of nano-graphene oxide can be effectively improved, preventing the aggregation of nano-graphene oxide, thereby further enhancing the corrosion resistance of the alloy powder for additive manufacturing.
[0016] 2. By compounding nano-yttrium oxide and nano-zirconium oxide in the present application, nano-yttrium oxide can promote the nucleation of chromium oxide, thereby forming a denser oxide layer on the alloy surface and improving the corrosion resistance of the material in various complex environments. Detailed Embodiments
[0017] The following further elaborates on the present application in conjunction with embodiments.
[0018] The chemical reagents used in the preparation examples, embodiments, and comparative examples provided by the present invention are all commercially available products.
[0019] Preparation Example 1 S1. Add 1.5 g of nano-graphene oxide to 50 g of distilled water, and ultrasonically disperse it for 30 min at 33 kHz to obtain a graphene oxide dispersion; S2. Add 16.1 g of 85% phosphoric acid solution by mass to 50 g of distilled water. After magnetic stirring evenly, add 0.5 g of aniline and stir magnetically for 5 min; add the graphene oxide dispersion obtained in S1 and stir magnetically for 2 h; then add 3 g of ammonium persulfate, stir magnetically for 1 h, ultrasonically treat the reaction solution for 2 h, filter by suction and wash until neutral, and vacuum dry at 65 °C to obtain polyaniline-modified nano-graphene.
[0020] Preparation Example 2 S1. Add 2.25 g of nano-graphene oxide to 55 g of distilled water, and ultrasonically disperse it for 35 min at 33.5 kHz to obtain a graphene oxide dispersion; S2. Add 20.125 g of 85% phosphoric acid solution by mass to 55 g of distilled water. After magnetic stirring until homogeneous, add 0.75 g of aniline and stir magnetically for 8 min; add the graphene oxide dispersion obtained in S1 and stir magnetically for 2.5 h; then add 3.75 g of ammonium persulfate and stir magnetically for 1.5 h. After that, ultrasonically treat the reaction solution for 3 h, filter by suction and wash until neutral, and vacuum dry at 70 °C to obtain polyaniline-modified nano-graphene.
[0021] Preparation Example 3 S1. Add 3 g of nano-graphene oxide to 60 g of distilled water and ultrasonically disperse for 40 min at 34 kHz to obtain a graphene oxide dispersion; S2. Add 24.15 g of 85% phosphoric acid solution by mass to 60 g of distilled water. After magnetic stirring until homogeneous, add 1 g of aniline and stir magnetically for 10 min; add the graphene oxide dispersion obtained in S1 and stir magnetically for 3 h; then add 4.5 g of ammonium persulfate and stir magnetically for 2 h. After that, ultrasonically treat the reaction solution for 4 h, filter by suction and wash until neutral, and vacuum dry at 75 °C to obtain polyaniline-modified nano-graphene. Example 1
[0022] S1. Weigh 21% chromium, 6% molybdenum, 1.5% copper, 0.2% of the polyaniline-modified nano-graphene prepared in Preparation Example 1, 0.04% of nano-yttrium oxide with a particle size of 80 - 120 nm, 0.2% of nano-zirconia, and the balance is iron by mass percentage; melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace for vacuum melting. Put pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in turn. After the vacuum induction furnace is evacuated to 0.08 Pa, carry out melting and then cast into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 8 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nano-graphene, nano-yttrium oxide, and nano-zirconia at 80 °C for 5 h respectively, then mix and transfer them into a high-energy ball mill and carry out ball milling at a rotation speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder for additive manufacturing with a particle size less than or equal to 180 μm. Example 2
[0023] S1. Weigh 22% chromium, 6.5% molybdenum, 1.8% copper, 0.4% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.05% of nano-yttrium oxide with a particle size of 80 - 120 nm, 0.4% of nano-zirconia, and the balance is iron by mass percentage; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put the pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.08 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 8 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano-yttrium oxide, and nano-zirconia at 80 °C for 5 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotational speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder for additive manufacturing with a particle size less than or equal to 180 μm. Example 3
[0024] S1. Weigh 22.3% chromium, 7% molybdenum, 2% copper, 0.5% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.06% of nano-yttrium oxide with a particle size of 80 - 120 nm, 0.5% of nano-zirconia, and the balance is iron by mass percentage; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put the pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.08 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 8 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano-yttrium oxide, and nano-zirconia at 80 °C for 5 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotational speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder for additive manufacturing with a particle size less than or equal to 180 μm. Example 4
[0025] S1. Weigh 22.6% chromium, 7.5% molybdenum, 2.2% copper, 0.6% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.07% of nano-yttrium oxide with a particle size of 80 - 120 nm, 0.6% of nano-zirconia, and the balance being iron by mass percentage; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.08 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 8 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano-yttrium oxide, and nano-zirconia at 80 °C for 5 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotational speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder with a particle size less than or equal to 180 μm for additive manufacturing. Example 5
[0026] S1. Weigh 23.5% chromium, 8% molybdenum, 2.5% copper, 0.8% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.08% of nano-yttrium oxide with a particle size of 80 - 120 nm, 0.8% of nano-zirconia, and the balance being iron by mass percentage; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.08 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 8 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano-yttrium oxide, and nano-zirconia at 80 °C for 5 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotational speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder with a particle size less than or equal to 180 μm for additive manufacturing. Example 6
[0027] S1. Weigh 21% chromium, 6% molybdenum, 1.5% copper, 0.2% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.04% of nano yttrium oxide with a particle size of 80 - 120 nm, 0.2% of nano zirconia, and the balance is iron; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put the pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.06 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 7 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano yttrium oxide, and nano zirconia at 100 °C for 4 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotation speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder for additive manufacturing with a particle size less than or equal to 180 μm. Example 7
[0028] S1. Weigh 21% chromium, 6% molybdenum, 1.5% copper, 0.2% of the polyaniline-modified nanographene prepared in Preparation Example 1, 0.04% of nano yttrium oxide with a particle size of 80 - 120 nm, 0.2% of nano zirconia, and the balance is iron; vacuum melt the metallic iron, chromium, molybdenum, and copper using a vacuum induction furnace. Put the pure metallic iron, chromium, molybdenum, and copper into the crucible in the furnace in sequence. After the vacuum induction furnace is evacuated to 0.06 Pa, carry out melting and then cast it into a mold to obtain a master alloy rod for gas atomization; S2. Feed the master alloy rod for gas atomization into a gas atomization device and carry out gas atomization treatment in an argon environment under a pressure of 6 Pa to obtain atomized powder; S3. Dry the atomized powder obtained in S2, polyaniline-modified nanographene, nano yttrium oxide, and nano zirconia at 120 °C for 3 h respectively, then mix them and transfer them into a high-energy ball mill to carry out ball milling at a rotation speed of 600 rpm for 4 h; screen the collected powder to obtain a corrosion-resistant alloy powder for additive manufacturing with a particle size less than or equal to 180 μm. Example 8
[0029] The difference between Example 8 and Example 1 is that the polyaniline-modified nanographene used in Example 8 is from Preparation Example 2. Example 9
[0030] The difference between Example 9 and Example 1 is that the polyaniline-modified nanographene used in Example 9 is from Preparation Example 3. Example 10
[0031] Example 10 is different from Example 1 in that the rotation speed of ball milling in S3 of Example 10 is 800 rpm; the ball milling time is 3 h. Example 11
[0032] Example 11 is different from Example 1 in that the rotation speed of ball milling in S3 of Example 11 is 1000 rpm; the ball milling time is 2 h.
[0033] Comparative Example 1 Comparative Example 1 is different from Example 1 in that nano yttrium oxide is not added in Comparative Example 1.
[0034] Comparative Example 2 Comparative Example 2 is different from Example 1 in that nano zirconia is not added in Comparative Example 2.
[0035] Comparative Example 3 Comparative Example 3 is different from Example 1 in that polyaniline modified nano graphene is not added in Comparative Example 3.
[0036] Comparative Example 4 Comparative Example 4 is different from Example 1 in that the nano graphene used in Comparative Example 4 is nano graphene oxide without polyaniline modification treatment.
[0037] Performance detection test I. The DOS values of the corrosion-resistant alloy powders for additive manufacturing obtained in Examples 1-11 and Comparative Examples 1-4 were detected by the double-loop electrochemical potentiodynamic reactivation method, and the results are shown in Table 1.
[0038] The specific detection results are as follows:
[0039] It can be seen from the detection results in Table 1 that the DOS value of the corrosion-resistant alloy powder for additive manufacturing provided by the present application, which has excellent corrosion resistance, is significantly lower than that of the comparative examples, indicating that the corrosion-resistant alloy powder for additive manufacturing and its preparation method provided by the present application have excellent corrosion resistance.
[0040] This specific embodiment is only an explanation of the present application and does not limit the present application. Those skilled in the art can make modifications to this embodiment without creative contributions according to needs after reading this specification, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.
Claims
1. A corrosion-resistant alloy powder for additive manufacturing, characterized in that: The raw materials include 21-23.5% chromium, 6-8% molybdenum, 1.5-2.5% copper, 0.2-0.8% polyaniline modified nanographene, 0.04-0.08% nano yttrium oxide, 0.2-0.8% nano zirconium oxide, and the balance is iron by mass percentage.
2. The corrosion-resistant alloy powder for additive manufacturing according to claim 1, characterized in that: The raw materials include 22-22.6% chromium, 6.5-7.5% molybdenum, 1.8-2.2% copper, 0.4-0.6% polyaniline modified nanographene, 0.05-0.07% nano yttrium oxide, 0.4-0.6% nano zirconium oxide, and the balance is iron by mass percentage.
3. The corrosion-resistant alloy powder for additive manufacturing according to claim 1, characterized in that: The raw materials include 22.3% chromium, 7% molybdenum, 2% copper, 0.5% polyaniline modified nanographene, 0.06% nano yttrium oxide, 0.5% nano zirconium oxide, and the balance is iron by mass percentage.
4. A corrosion-resistant alloy powder for additive manufacturing according to claim 1, 2 or 3, characterized in that: The particle size of the nano yttrium oxide is 80-120nm.
5. A corrosion-resistant alloy powder for additive manufacturing according to claim 1, 2 or 3, characterized in that: The polyaniline-modified nanographene is composed of the following raw materials in parts by weight: 16.1-24.15 parts of 85% phosphoric acid solution, 100-120 parts of distilled water, 0.5-1 part of aniline, 1.5-3 parts of nanographene oxide, and 3-4.5 parts of ammonium persulfate.
6. The corrosion-resistant alloy powder for additive manufacturing according to claim 5, characterized in that: The preparation method of the polyaniline-modified nanographene comprises the following steps: S1. Add 1.5-3 parts of nano-graphene oxide to 50-60 parts of distilled water and disperse uniformly by ultrasonication to obtain a graphene oxide dispersion; S2. Add 16.1-24.15 parts of 85% phosphoric acid solution into 50-60 parts of distilled water, stir evenly, then add 0.5-1 parts of aniline, and stir magnetically for 5-10 minutes; add the graphene oxide dispersion obtained in S1, and stir magnetically for 2-3 hours; then add 3-4.5 parts of ammonium persulfate, stir magnetically for 1-2 hours, ultrasonically treat the reaction solution for 2-4 hours, filter and wash until neutral, and vacuum dry to obtain polyaniline-modified nanographene.
7. A method for preparing corrosion-resistant alloy powder for additive manufacturing according to claims 1-6, characterized in that: The following steps are involved: S1. Weigh each raw material by mass percentage, melt metal iron, chromium, molybdenum and copper in a vacuum induction furnace, and cast them into a mold to obtain a master alloy rod for gas atomization; S2. The master alloy rod for gas atomization is fed into a gas atomization device and atomized in an inert gas environment to obtain an atomized powder; S3. The atomized powder, polyaniline-modified nano-graphene, nano-yttrium oxide, and nano-zirconium oxide obtained in S2 are dried at 80-120° C. for 3-5 hours, respectively, and then mixed and transferred into a high-energy ball mill for ball milling; the collected powder is sieved to obtain a corrosion-resistant alloy powder for additive manufacturing.
8. The method for preparing corrosion-resistant alloy powder for additive manufacturing according to claim 7, characterized in that: The vacuum degree of the vacuum melting is less than 0.1Pa.
9. The method for preparing corrosion-resistant alloy powder for additive manufacturing according to claim 7, characterized in that: The ball milling speed is 600-1000 rpm; the ball milling time is 2-4 hours.
10. The method for preparing corrosion-resistant alloy powder for additive manufacturing according to claim 7, characterized in that: The particle size of the corrosion-resistant alloy powder used for additive manufacturing is less than or equal to 180 μm.